Epoxy resin composition, gas barrier laminate, packaging material for retort food, deodorizing or flavor-retaining packaging material, heat-shrinkable label and method for producing the same, heat-shrinkable label and bottle having the same

Abstract

The present invention provides: an epoxy resin composition which contains an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having from 14 to 24 carbon atoms; a gas barrier multilayer body and a retort food packaging material, each of which uses this epoxy resin composition; a packaging material for deodorization or aroma retention; a deodorization or aroma retention method wherein an article containing a deodorization component or aroma retention component is sealed in the above-described packaging material; a heat shrinkable label; a method for producing this heat shrinkable label; a heat shrunk label; a bottle which has this heat shrunk label; and a method for preventing CO2 permeation.

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin composition, a gas barrier laminate using the same, a packaging material for retort foods, an odor-preventing or aroma-retaining packaging material, an odor-preventing or aroma-retaining method, a heat-shrinkable label and a method for producing the same, a heat-shrinkable label and a bottle having the same, and a method for preventing CO2 permeation. [Background technology]

[0002] Packaging materials used for foods, medicines, cosmetics, precision electronic components, etc. are required to have high oxygen and water vapor barrier properties to prevent deterioration of the contents. Furthermore, various gas barrier materials such as glass, metal, plastic, etc. are used as materials for preventing the volatilization of odorous components such as ammonia, trimethylamine, etc. In terms of gas barrier performance, glass and metal are far superior to plastic materials, but in consideration of moldability, light weight, recyclability, transparency, etc., plastic materials with barrier performance are preferred, and many gas barrier plastic materials are used.

[0003] Generally, the oxygen barrier properties of thermoplastic plastic films are not very high, so methods of imparting gas barrier properties to such films have been investigated, including forming various gas barrier layers such as polyvinylidene chloride (PVDC) layers and polyvinyl alcohol (PVA) layers, or vapor deposition of inorganic materials such as alumina (Al2O3) and silica (SiO2).

[0004] Films with a PVDC layer formed as a gas barrier layer are transparent and exhibit good barrier properties. However, when incinerated as general waste, they emit organic substances such as acidic gases, so a transition to other materials is desired from an environmental perspective. Films with a PVA layer exhibit excellent gas barrier properties under low humidity conditions, but they are highly hygroscopic, and their gas barrier properties rapidly decrease when the relative humidity exceeds about 70%.

[0005] Inorganic vapor-deposited films, which are made by vapor-depositing inorganic materials such as alumina or silica onto a thermoplastic plastic film, are transparent and have good gas barrier properties, and do not suffer from the above-mentioned problems. However, when inorganic vapor-deposited films are bent, cracks occur in the inorganic vapor-deposited layer, significantly reducing the gas barrier properties.

[0006] As a method for improving the flex resistance of a gas barrier film or laminate containing a layer on which an inorganic substance is vapor-deposited, a method for forming a layer made of a cured product of an epoxy resin composition containing a specified epoxy resin and a specified amine-based epoxy resin curing agent as main components has been proposed (Patent Documents 1 to 3). Patent Document 4 discloses that a gas barrier film having a specific layer structure, which has a base film having an inorganic vapor deposition layer and a cured resin layer made of a cured product of an epoxy resin composition containing an epoxy resin, a specific epoxy resin curing agent, and non-spherical inorganic particles, has improved gas barrier properties and also excellent flex resistance compared to conventional gas barrier films having an inorganic vapor deposition layer.

[0007] Studies have also been conducted to improve the various functions of the resulting gas barrier film by improving the epoxy resin composition used in the gas barrier film. For example, Patent Document 5 reports that a gas barrier resin composition containing an epoxy resin, an epoxy resin curing agent, and a specific curing accelerator, and containing a predetermined amount of a specific amine-derived skeletal structure in the formed cured product, exhibits high gas barrier properties over a wide range of curing conditions.

[0008] As described above, it is known that forming a gas barrier layer made of a cured product of a specific epoxy resin composition on a substrate has a significant effect of improving gas barrier properties. Furthermore, in a gas barrier film or gas barrier laminate having a laminate structure, high interlayer adhesion is also important in order to stably exhibit good gas barrier properties. In this regard, for example, Patent Document 6 discloses that in a laminate film in which at least a substrate, a primer layer, an adhesive layer, and a sealant layer are laminated in this order, a primer layer is formed using a primer composition containing a specific polyester resin, and an adhesive layer is formed using an adhesive mainly composed of an epoxy resin composition, thereby obtaining a laminate film with excellent adhesion over time that can maintain excellent lamination strength and heat seal strength even when stored for a long period of time.

[0009] However, depending on the types of substrate and epoxy resin composition used in the gas barrier film or laminate, the interlayer adhesion between the substrate and the cured layer of the epoxy resin composition may be insufficient.Patent Documents 1 to 6 disclose epoxy resin compositions using amine-based epoxy resin curing agents, but recent studies by the present inventors have found that cured products of epoxy resin compositions using amine-based epoxy resin curing agents have unstable adhesion to inorganic materials, particularly alumina. Furthermore, packaging materials for food applications may undergo heat treatment such as retort treatment, and it is important that the interlayer adhesiveness can be maintained even after retort treatment.

[0010] As a material for preventing the volatilization of odorous components such as ammonia and trimethylamine, a method (deodorizing method) has been studied in which odorous components are sealed in a bag made of a material that is a thermoplastic plastic film with an organic barrier layer provided thereon to prevent the diffusion of odors. Hereinafter, in this specification, the ability to seal in odorous components and prevent the volatilization of odors is referred to as "deodorizing property." For example, Patent Document 7 discloses a method for preventing the permeation of amine-based volatile substances by using a barrier material containing at least one layer made of a cured epoxy resin containing 40% by weight or more of a xylylenediamine skeleton structure, and provides examples of a laminate film and a bag-shaped container using the barrier material as an adhesive. Patent Document 8 discloses a bag for sealing malodorous substances, which comprises inner and outer layers made of an ethylene (co)polymer and an intermediate layer made of a barrier resin, the inner and outer layers containing an antiblocking agent and a surfactant, and which satisfies certain requirements.

[0011] However, there is a demand for further improvement in the odor-preventing properties of packaging materials such as the films and bags described in Patent Documents 7 and 8. For example, Patent Document 2 describes the thickness of the middle layer (barrier layer) of the malodorous substance sealing bag as being in the range of 0.8 to 5.0 μm, but from the standpoint of reducing the thickness of packaging materials and being economical, it is desirable to be able to obtain sufficient odor-preventing properties even with an even thinner barrier layer. Furthermore, it is preferable that these packaging materials not only have odor-preventing properties but also have the ability to contain the fragrant components of fragranced items so that they do not volatilize (hereinafter also referred to as "aroma-retaining properties"). Furthermore, the barrier layers in the technologies disclosed in Patent Documents 7 and 8 are adhesive materials that form intermediate layers of films or bags, and because they have blocking properties, they are not suitable as materials for forming surface layers (innermost or outermost layers). When using a barrier layer as an intermediate layer in a film, bag, etc., the layer structure must be at least three layers, including the barrier layer, which is disadvantageous in terms of cost.

[0012] Recently, PET bottles have been widely used as beverage containers. Many PET bottles have a plastic shrink label attached to the body of the bottle that indicates the contents. However, if the oxygen barrier properties of PET bottles are insufficient, the contents are likely to deteriorate due to oxidation. Therefore, studies are being conducted to impart gas barrier properties to shrink labels used on PET bottles. Furthermore, shrink labels have problems such as a decrease in decorativeness and gas barrier properties after shrinking, and methods for solving these problems are being investigated.

[0013] For example, Patent Document 9 discloses that a shrink label has at least one pigment-containing printing layer, one anchor coat layer, and one barrier layer on at least one side of a shrink film, with the layers laminated in the order of shrink film / printing layer / anchor coat layer / barrier layer, and the arithmetic mean roughness of the anchor coat layer surface is equal to or less than a predetermined value, and that the shrink label does not suffer from deterioration in decorative properties and gas barrier properties, such as "clouding," even after processing. Patent Document 10 discloses that a gas barrier shrink laminate film, which is made by bonding two heat-shrinkable films together with a gas barrier adhesive, does not lose its gas barrier properties even when subjected to shrink processing.

[0014] In the case of PET bottles for carbonated beverages, carbon dioxide (CO2) barrier properties are important. However, the shrinkable labels or films described in Patent Documents 9 and 10 were only evaluated for oxygen barrier properties, leaving room for improvement in CO2 barrier properties. Furthermore, the barrier layers in the shrinkable labels or films described in Patent Documents 9 and 10 are all materials that constitute intermediate layers of the shrinkable labels or films, and are not suitable as materials for forming surface layers (innermost or outermost layers). When using a barrier layer as an intermediate layer in a shrinkable label, the layer structure must be at least three layers, including the barrier layer, which is disadvantageous in terms of cost. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-300271 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-28835 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-101684 [Patent Document 4] International Publication No. 2018 / 105282 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-202753 [Patent Document 6] Japanese Patent Application Laid-Open No. 2013-203023 [Patent Document 7] Japanese Patent Application Laid-Open No. 2008-222761 [Patent Document 8] International Publication No. 2014 / 185482 [Patent Document 9] Japanese Patent Application Laid-Open No. 2008-201463 [Patent Document 10] Japanese Patent Application Laid-Open No. 2011-37156 Summary of the Invention [Problem to be solved by the invention]

[0016] The first object of the present invention is to provide an epoxy resin composition containing an amine-based curing agent as an epoxy resin curing agent, which has high gas barrier properties, particularly good adhesion to inorganic substances such as alumina, and is capable of forming a cured product that is resistant to peeling even after retort treatment and has excellent retort resistance; and to provide a gas barrier laminate and a packaging material for retort food that use the epoxy resin composition. A second object of the present invention is to provide a packaging material for deodorizing or retaining aroma, which has good deodorizing and aroma-retaining properties, can be made thin, and is also economical, and a method for deodorizing or retaining aroma. A third object of the present invention is to provide a heat-shrinkable label that has good CO2 barrier properties, excellent followability during heat shrinkage, and is also economical, a method for producing the same, a heat-shrinkable label and a bottle having the same, and a method for preventing CO2 permeation. [Means for solving the problem]

[0017] The present inventors have found that the above-mentioned problems can be solved by using an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and a specified fatty acid amide. That is, the present invention relates to the following. [1] An epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. [2] A gas barrier laminate having a substrate and a cured resin layer which is a cured product of the epoxy resin composition described in [1] above. [3] The gas barrier laminate according to [2] above, further comprising a thermoplastic resin layer. [4] A packaging material for retort food, comprising the gas barrier laminate described in [3] above. [5] A deodorizing or fragrance-retaining packaging material having a substrate and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. [6] A method for deodorizing or retaining an aroma, comprising enclosing an article containing an odorous or fragrant component in a packaging material having a substrate and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. [7] A heat-shrinkable label having a heat-shrinkable base layer and a cured layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. [8] A method for producing a heat-shrinkable label according to the above item [7], which comprises the following steps (I) and (II) in that order: Step (I): A step of applying an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a solvent to at least one surface of a heat-shrinkable substrate to form a coating layer. Step (II): A step of heating and drying the coating layer at a temperature of less than 100°C to remove the solvent. [9] A heat-shrinkable label obtained by heat-shrinking the heat-shrinkable label described in [7] above.

[10] A bottle having the heat-shrinkable label described in [9] above.

[11] A method for preventing CO2 permeation using the heat-shrinkable label described in [7] above or the heat-shrinkable label described in [9] above. [Effects of the Invention]

[0018] The epoxy resin composition of the first invention can form a cured product that has high gas barrier properties, particularly good adhesion to inorganic substances such as alumina, and is resistant to peeling even after retort treatment, resulting in excellent retort resistance. A gas barrier laminate having a cured resin layer, which is a cured product of the epoxy resin composition, formed on a substrate having at least one side made of an inorganic substance has high gas barrier properties, interlayer adhesion, and retort resistance, and is suitable for use as a packaging material for retort foods, for example. According to the second invention, it is possible to provide a packaging material for deodorizing or retaining aroma, which has good deodorizing and aroma-retaining properties, can be made thin, and is also economical. The packaging material according to the second invention can be suitably used for applications requiring deodorizing or aroma-retaining properties, such as bags for storing used disposable diapers, pet litter, waste, food waste, and other malodorous substances; packaging material for strong-smelling foods; packaging material for fragrant toiletries, cosmetics, stationery, and toys; etc. Furthermore, according to the third invention, it is possible to provide a heat-shrinkable label that has good CO2 barrier properties, excellent followability during heat shrinkage, and is economical, as well as a method for manufacturing the same, a heat-shrinkable label and a bottle having the same, and a method for preventing CO2 permeation. The heat-shrinkable label according to the third invention is suitable for use in PET bottles for carbonated water and other carbonated drinks. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a cross-sectional view showing a gas barrier laminate 100 according to an embodiment of the first invention. [Figure 2] 1 is a cross-sectional view showing a gas barrier laminate 100a according to an embodiment of the first invention. [Figure 3] 1 is a cross-sectional view showing a gas barrier laminate 200 according to an embodiment of the first invention. [Figure 4] 1 is a cross-sectional view showing a gas barrier laminate 300 according to an embodiment of the first invention. [Figure 5] FIG. 1 is a cross-sectional view showing a gas barrier laminate 300a according to an embodiment of the first invention. [Figure 6]FIG. 1 is a cross-sectional view showing a gas barrier laminate 300b according to an embodiment of the first invention. [Figure 7] 1 is a cross-sectional view showing a gas barrier laminate 400 according to an embodiment of the first invention. [Figure 8] FIG. 1 is a cross-sectional view showing a gas barrier laminate 400a according to an embodiment of the first invention. [Figure 9] FIG. 1 is a cross-sectional view showing a gas barrier laminate 400c according to an embodiment of the first invention. [Figure 10] FIG. 5 is a cross-sectional view showing an embodiment of a packaging material (packaging film) 500 according to the second invention. [Figure 11] FIG. 6 is a cross-sectional view showing an embodiment of a heat-shrinkable label 600 according to the third invention. [Figure 12] FIG. 2 is an explanatory diagram showing the attachment positions of heat-shrinkable labels on PET bottles in the evaluation of the examples. DETAILED DESCRIPTION OF THE INVENTION

[0020] [First invention: epoxy resin composition] The epoxy resin composition according to the first invention is an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. Hereinafter, the epoxy resin composition according to the first invention may also be simply referred to as "the epoxy resin composition of the present invention." The epoxy resin composition of the present invention has the above-mentioned constitution, and can form a cured product having high gas barrier properties, particularly good adhesion to inorganic substances such as alumina, and excellent retort resistance that is resistant to peeling even after retort treatment.Furthermore, the cured product thus formed has high transparency. Recent studies by the present inventors have revealed that the adhesiveness of cured epoxy resin compositions to inorganic materials, particularly alumina, is unstable, and this tendency is particularly pronounced when an amine-based epoxy resin curing agent is used. As a result of extensive research, the present inventors have found that when an unsaturated fatty acid amide having 14 to 24 carbon atoms is added to an epoxy resin composition using an amine-based epoxy resin curing agent, the adhesiveness of the cured product to alumina and the like, retort resistance, and transparency are improved. The reasons for this are unclear, but are thought to be as follows. When an unsaturated fatty acid amide having 14 to 24 carbon atoms is contained in an epoxy resin composition, it is believed to have the effect of alleviating stress generated in the cured product of the epoxy resin, and is more compatible with epoxy resin compositions containing amine-based epoxy resin curing agents than saturated fatty acid amides, etc. Therefore, it is presumed that the cured product of the epoxy resin composition of the present invention containing the unsaturated fatty acid amide will have good adhesion to inorganic materials such as alumina, good retort resistance, and good transparency.

[0021] Each component contained in the epoxy resin composition of the present invention will be described below. <Epoxy resin> The epoxy resin used in the epoxy resin composition of the present invention may be any of a saturated or unsaturated aliphatic compound, alicyclic compound, aromatic compound, or heterocyclic compound, but when consideration is given to the development of high gas barrier properties, an epoxy resin containing an aromatic ring or alicyclic structure in the molecule is preferred. Specific examples of the epoxy resin include at least one resin selected from the group consisting of epoxy resins having glycidylamino groups derived from meta-xylylenediamine, epoxy resins having glycidylamino groups derived from para-xylylenediamine, epoxy resins having glycidylamino groups derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having glycidylamino groups derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having glycidylamino groups derived from diaminodiphenylmethane, epoxy resins having glycidylamino groups and / or glycidyloxy groups derived from para-aminophenol, epoxy resins having glycidyloxy groups derived from bisphenol A, epoxy resins having glycidyloxy groups derived from bisphenol F, epoxy resins having glycidyloxy groups derived from phenol novolac, and epoxy resins having glycidyloxy groups derived from resorcinol. Two or more of the above epoxy resins can also be mixed in appropriate proportions to improve various properties such as flexibility, impact resistance, and moist heat resistance. Among the above, from the viewpoint of gas barrier properties, the deodorizing and aroma-retaining properties of the packaging material according to the second invention, and the CO2 barrier properties of the heat-shrinkable label according to the third invention, the epoxy resin is preferably one having as its main component at least one selected from the group consisting of epoxy resins having a glycidylamino group derived from meta-xylylenediamine, epoxy resins having a glycidylamino group derived from para-xylylenediamine, and epoxy resins having a glycidyloxy group derived from bisphenol F, and more preferably one having as its main component an epoxy resin having a glycidylamino group derived from meta-xylylenediamine. The term "main component" as used herein means that other components may be contained within the scope of the present invention, and preferably means 50 to 100% by mass of the total, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass.

[0022] <Epoxy resin curing agent containing amine-based curing agent> The epoxy resin curing agent used in the epoxy resin composition of the present invention contains an amine-based curing agent from the viewpoints of imparting high gas barrier properties, imparting high deodorizing and aroma-retaining properties to the packaging material of the second invention, and imparting high CO2 barrier properties to the heat-shrinkable label of the third invention. The amine-based curing agent can be a polyamine or a modified product thereof that has been conventionally used as an epoxy resin curing agent. From the viewpoint of obtaining high gas barrier properties, the odor prevention and aroma retention properties of the packaging material according to the second invention, and the CO2 barrier properties of the heat-shrinkable label according to the third invention, the amine-based curing agent is preferably a modified product of polyamine, more preferably at least one selected from the group consisting of the following amine-based curing agent (i) and amine-based curing agent (ii), and even more preferably the following amine-based curing agent (i). (i) A reaction product of the following components (A) and (B): (A) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (B) at least one selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: [ka] (In formula (1), R 1 , R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. (ii) A reaction product of epichlorohydrin with at least one member selected from the group consisting of metaxylylenediamine and paraxylylenediamine.

[0023] (Amine-based curing agent (i)) The amine-based curing agent (i) is a reaction product of the following components (A) and (B): (A) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (B) at least one selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: [ka] (In formula (1), R 1 , R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. The component (A) is used from the viewpoint of gas barrier properties, deodorizing and aroma-retaining properties of the packaging material according to the second invention, and CO2 barrier properties of the heat-shrinkable label according to the third invention, and meta-xylylenediamine is preferred from the viewpoint of gas barrier properties. One type of component (A) may be used alone, or two types may be used in combination.

[0024] The component (B) is at least one selected from the group consisting of unsaturated carboxylic acids represented by the general formula (1) and derivatives thereof, and from the viewpoint of gas barrier properties, deodorizing and aroma-retaining properties of the packaging material according to the second invention, and CO2 barrier properties of the heat-shrinkable label according to the third invention, R in the general formula (1) 1 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. In addition, from the viewpoint of gas barrier properties, deodorizing and aroma-retaining properties of the packaging material according to the second invention, and CO2 barrier properties of the heat-shrinkable label according to the third invention, R 2 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0025] Examples of the derivative of the unsaturated carboxylic acid represented by the general formula (1) include esters, amides, acid anhydrides, and acid chlorides of the unsaturated carboxylic acid. As the ester of the unsaturated carboxylic acid, alkyl esters are preferred, and from the viewpoint of obtaining good reactivity, the number of alkyl carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

[0026] Examples of the unsaturated carboxylic acid represented by the general formula (1) and its derivatives include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, α-propylacrylic acid, α-isopropylacrylic acid, α-n-butylacrylic acid, α-t-butylacrylic acid, α-pentylacrylic acid, α-phenylacrylic acid, α-benzylacrylic acid, crotonic acid, 2-pentenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-heptenoic acid, 4-methyl-2-hexenoic acid, 5-methyl-2-hexenoic acid, 4,4-dimethyl-2-pentenoic acid, 4-phenyl-2-butenoic acid, cinnamic acid, o-methylcinnamic acid, m-methylcinnamic acid, p-methylcinnamic acid, and 2-octenoic acid, as well as esters, amides, acid anhydrides, and acid chlorides thereof. Among the above, from the viewpoint of obtaining good gas barrier properties, the deodorizing and aroma-retaining properties of the packaging material according to the second invention, and the CO2 barrier properties of the heat-shrinkable label according to the third invention, component (B) is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and derivatives thereof, more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and alkyl esters thereof, even more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and alkyl esters thereof, even more preferably alkyl esters of acrylic acid, and even more preferably methyl acrylate. The component (B) may be used alone or in combination of two or more.

[0027] When an unsaturated carboxylic acid, ester, or amide is used as the component (B), the reaction between the component (A) and the component (B) is carried out by mixing the components (A) and (B) at a temperature of 0 to 100°C, more preferably 0 to 70°C, and then carrying out a Michael addition reaction and an amide group-forming reaction by dehydration, dealcoholization, and deamination at a temperature of 100 to 300°C, preferably 130 to 250°C. In this case, during the amide group-forming reaction, the inside of the reaction apparatus can be reduced in pressure at the final stage of the reaction, if necessary, to complete the reaction. Furthermore, the reaction can be diluted with a non-reactive solvent, if necessary. Furthermore, a catalyst such as a phosphite ester can be added as a dehydrating agent or dealcoholizing agent.

[0028] On the other hand, when an acid anhydride or acid chloride of an unsaturated carboxylic acid is used as component (B), the components are mixed at a temperature of 0 to 150°C, preferably 0 to 100°C, followed by the Michael addition reaction and the amide group formation reaction. In this case, during the amide group formation reaction, the reactor may be depressurized at the final stage of the reaction, if necessary, to complete the reaction. Furthermore, a non-reactive solvent may be used for dilution, if necessary. Furthermore, a tertiary amine such as pyridine, picoline, lutidine, or trialkylamine may also be added.

[0029] The amide group moiety formed by the reaction between the component (A) and the component (B) has high cohesive strength, and therefore a resin cured layer (cured product layer) formed using an epoxy resin composition containing an epoxy resin curing agent that is the reaction product of the component (A) and the component (B) has high gas barrier properties, deodorizing properties, fragrance retention properties, high CO2 barrier properties, and good adhesion.

[0030] The reaction molar ratio of component (B) to component (A) [(B) / (A)] is preferably in the range of 0.3 to 1.0. When the reaction molar ratio is 0.3 or higher, a sufficient amount of amide groups is generated in the epoxy resin curing agent, resulting in high levels of gas barrier properties, odor prevention and aroma retention for the packaging material according to the second invention, and CO2 barrier properties and adhesiveness for the heat-shrinkable label according to the third invention. On the other hand, when the reaction molar ratio is 1.0 or lower, a sufficient amount of amino groups are available to react with the epoxy groups in the epoxy resin, resulting in excellent heat resistance and solubility in organic solvents and water. When particularly considering the high gas barrier properties, deodorizing properties, fragrance retention properties, CO2 barrier properties, and excellent coating film performance of the obtained epoxy resin cured product, it is more preferable that the reaction molar ratio of the component (B) to the component (A) [(B) / (A)] is in the range of 0.6 to 1.0.

[0031] The amine curing agent may be a reaction product of the components (A) and (B) and at least one compound selected from the group consisting of the following components (C), (D), and (E): (C)R 3 At least one (R ) selected from the group consisting of monocarboxylic acids represented by —COOH and derivatives thereof 3 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may have a hydroxyl group, or an aryl group having 6 to 12 carbon atoms. (D) Cyclic carbonate (E) Monoepoxy compounds having 2 to 20 carbon atoms

[0032] The component (C), R 3 The monocarboxylic acid represented by --COOH and its derivatives are used as needed to reduce the reactivity between the epoxy resin curing agent and the epoxy resin, thereby improving workability. R 3 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may have a hydroxyl group, or an aryl group having 6 to 12 carbon atoms; R 3 is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group. Also R 3Derivatives of monocarboxylic acids represented by -COOH include, for example, esters, amides, acid anhydrides, and acid chlorides of the carboxylic acids. The esters of the carboxylic acids are preferably alkyl esters, and the number of alkyl carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2. Examples of the component (C) include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, and benzoic acid, and derivatives thereof. The component (C) may be used alone or in combination of two or more.

[0033] The cyclic carbonate of component (D) is used as needed to reduce the reactivity between the epoxy resin curing agent and the epoxy resin and improve workability, and is preferably a cyclic carbonate with a six-membered ring or smaller from the viewpoint of reactivity with component (A). Examples include ethylene carbonate, propylene carbonate, glycerin carbonate, 1,2-butylene carbonate, vinylene carbonate, 4-vinyl-1,3-dioxolan-2-one, 4-methoxymethyl-1,3-dioxolan-2-one, and 1,3-dioxan-2-one. Among these, at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and glycerin carbonate is preferred from the viewpoint of gas barrier properties. The component (D) may be used alone or in combination of two or more.

[0034] The monoepoxy compound of component (E) is a monoepoxy compound having 2 to 20 carbon atoms, and is used as needed to reduce the reactivity between the epoxy resin curing agent and the epoxy resin and improve workability. From the viewpoint of gas barrier properties, it is preferably a monoepoxy compound having 2 to 10 carbon atoms, and more preferably a compound represented by the following formula (2):

[0035] [ka] (In formula (2), R 4 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or R 5 represents -O-CH2-, and R 5 represents a phenyl group or a benzyl group. Examples of the monoepoxy compound represented by the formula (2) include ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, phenyl glycidyl ether, benzyl glycidyl ether, etc. The component (E) may be used alone or in combination of two or more.

[0036] When the component (C), component (D), or component (E) is used as the amine-based curing agent, any one compound selected from the group consisting of the components (C), (D), and (E) may be used alone, or two or more types may be used in combination.

[0037] The amine curing agent may be a reaction product obtained by reacting the components (A) to (E) with other components, as long as the effects of the present invention are not impaired. Examples of other components include aromatic dicarboxylic acids and their derivatives. However, the amount of the "other components" used is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less of the total amount of reactive components constituting the amine-based curing agent.

[0038] The reaction product of the components (A) and (B) with at least one compound selected from the group consisting of the components (C), (D), and (E) can be obtained by reacting the component (A), which is a polyamine compound, with at least one compound selected from the group consisting of the components (C), (D), and (E) in combination with the component (B). The reaction can be carried out by adding the components (B) to (E) in any order and reacting them with the component (A), or by mixing the components (B) to (E) and reacting them with the component (A). The reaction between the component (A) and the component (C) can be carried out under the same conditions as those for the reaction between the component (A) and the component (B). When the component (C) is used, the components (B) and (C) may be mixed and reacted with the component (A), or the components (A) and (B) may be reacted first, and then the component (C) may be reacted. On the other hand, when the component (D) and / or the component (E) is used, it is preferable to first react the component (A) with the component (B), and then react them with the component (D) and / or the component (E). The reaction of the component (A) with the component (D) and / or component (E) is carried out by mixing the component (A) with the component (D) and / or component (E) at 25 to 200° C. and carrying out an addition reaction at 30 to 180° C., preferably 40 to 170° C. Furthermore, a catalyst such as sodium methoxide, sodium ethoxide, or potassium t-butoxide can be used as needed. During the above reaction, in order to promote the reaction, the component (D) and / or the component (E) may be melted or diluted with a non-reactive solvent, as needed.

[0039] Even when the amine curing agent is a reaction product of the components (A) and (B) with at least one compound selected from the group consisting of the components (C), (D), and (E), the reaction molar ratio of the component (B) to the component (A) [(B) / (A)] is preferably in the range of 0.3 to 1.0, and more preferably in the range of 0.6 to 1.0, for the same reasons as above. On the other hand, the reaction molar ratio of the components (C), (D), and (E) to the component (A) [{(C) + (D) + (E)} / (A)] is preferably in the range of 0.05 to 3.1, more preferably in the range of 0.07 to 2.5, and even more preferably in the range of 0.1 to 2.0. However, from the viewpoints of gas barrier properties, deodorizing and aroma-retaining properties of the packaging material according to the second invention, CO2 barrier properties of the heat-shrinkable label according to the third invention, and coatability, the reaction molar ratio of the components (B) to (E) to the component (A), [{(B)+(C)+(D)+(E)} / (A)], is preferably in the range of 0.35 to 2.5, and more preferably in the range of 0.35 to 2.0.

[0040] (Amine-based curing agent (ii)) The amine curing agent (ii) is a reaction product of epichlorohydrin and at least one member selected from the group consisting of metaxylylenediamine and paraxylylenediamine. The amine curing agent (ii) preferably contains a compound represented by the following general formula (3) as a main component: Here, the "main component" refers to a component whose content is 50% by mass or more when the total amount of all components in the amine curing agent (ii) is taken as 100% by mass. [ka] (In formula (3), A is a 1,3-phenylene group or a 1,4-phenylene group, and n is a number from 1 to 12.) More preferably, A is a 1,3-phenylene group. The content of the compound represented by the general formula (3) in the amine curing agent (ii) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 75% by mass or more, and even more preferably 85% by mass or more, with the upper limit being 100% by mass. From the viewpoint of obtaining good curing performance as a curing agent, it is preferable that the proportion of the compound represented by the general formula (3) where n = 1 is high. The content of the compound represented by the general formula (3) where n = 1 in the amine curing agent (ii) is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. The upper limit is 100% by mass. The content of the compound represented by the general formula (3) in the amine curing agent (ii) and the composition of the compound represented by the general formula (3) can be determined by GC analysis and gel permeation chromatography (GPC) analysis.

[0041] The amine curing agent (ii) can be obtained by subjecting epichlorohydrin to an addition reaction with at least one member selected from the group consisting of metaxylylenediamine and paraxylylenediamine in a conventional manner.

[0042] The epoxy resin curing agent used in the present invention may contain curing agent components other than the amine-based curing agent, but from the viewpoint of obtaining high gas barrier properties, high deodorizing and aroma retention properties in the packaging material of the second invention, and high CO2 barrier properties in the heat-shrinkable label of the third invention, a high content of the amine-based curing agent is preferred. From the viewpoint of obtaining high gas barrier properties, the content of the amine-based curing agent in the epoxy resin curing agent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more. The upper limit is 100% by mass.

[0043] The epoxy resin curing agent used in the present invention may further contain a coupling agent from the viewpoint of improving the adhesiveness of the resulting cured product to inorganic substances. Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminate coupling agents, and from the viewpoint of improving the adhesiveness of the resulting cured product to inorganic substances, silane coupling agents are preferred. Examples of the silane coupling agent include a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, a silane coupling agent having a (meth)acrylic group, a silane coupling agent having a mercapto group, etc. Among these, at least one selected from the group consisting of a silane coupling agent having an amino group and a silane coupling agent having an epoxy group is preferred from the viewpoint of the adhesiveness of the resulting cured product to inorganic materials. When a coupling agent is used, the content of the coupling agent in the epoxy resin curing agent is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, per 100 parts by mass of the curing agent component in the epoxy resin curing agent.

[0044] The ratio of epoxy resin to epoxy resin curing agent in an epoxy resin composition may generally be within the standard range used when preparing an epoxy resin reaction product by reacting an epoxy resin with an epoxy resin curing agent. Specifically, the ratio of the number of active amine hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin (number of active amine hydrogens in the epoxy resin curing agent / number of epoxy groups in the epoxy resin) is preferably in the range of 0.2 to 12.0. From the viewpoint of forming a cured product with good adhesion to inorganic materials such as alumina and good retort resistance, the ratio (number of active amine hydrogens in the epoxy resin curing agent / number of epoxy groups in the epoxy resin) is more preferably in the range of 0.4 to 10.0, even more preferably 0.6 to 8.0, even more preferably more than 1.0 but not more than 5.0, and even more preferably 1.1 to 3.5.

[0045] <Unsaturated fatty acid amide with 14 to 24 carbon atoms> The epoxy resin composition of the present invention contains an unsaturated fatty acid amide having 14 to 24 carbon atoms (hereinafter simply referred to as "unsaturated fatty acid amide"). This allows for the formation of a cured product that has excellent adhesion to inorganic materials such as alumina, retort resistance, and transparency. The packaging material of the second invention allows for the formation of a cured product layer that has excellent deodorizing and aroma retention properties, little blocking, adhesion to the substrate, and transparency. The heat-shrinkable label of the third invention allows for the formation of a cured product layer that has little blocking, CO2 barrier properties, conformability to the substrate layer, and transparency. The unsaturated fatty acid amide has 14 to 24 carbon atoms, preferably 16 to 24, and more preferably 18 to 22, from the viewpoint of forming a cured product that exhibits little blocking, adhesion to inorganic substances such as alumina, retort resistance, CO2 barrier properties, conformability to a substrate layer, and transparency.

[0046] The unsaturated fatty acid constituting the unsaturated fatty acid amide may be a fatty acid having at least one unsaturated bond and having 14 to 24 carbon atoms. The number of unsaturated bonds in the unsaturated fatty acid is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. Examples of unsaturated fatty acids that constitute unsaturated fatty acid amides include monounsaturated fatty acids such as myristoleic acid, sapienic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, and eicosatrienoic acid; and tetra-fatty acids such as stearidonic acid, arachidonic acid, eicosatetraenoic acid, and adrenic acid. These may be used alone or in combination of two or more. Among these, from the viewpoint of forming a cured product having good adhesion to inorganic substances such as alumina, good retort resistance, and good transparency, at least one selected from the group consisting of monounsaturated fatty acids and diunsaturated fatty acids having 14 to 24 carbon atoms is preferred, monounsaturated fatty acids having 14 to 24 carbon atoms are more preferred, monounsaturated fatty acids having 16 to 24 carbon atoms are more preferred, and monounsaturated fatty acids having 18 to 22 carbon atoms are even more preferred. The unsaturated fatty acid amide used in the present invention is preferably at least one selected from the group consisting of palmitoleic acid amide, oleic acid amide, eicosenoic acid amide, and erucic acid amide, from the viewpoint of forming a cured product that is less prone to blocking and has good adhesion to inorganic substances such as alumina, retort resistance, CO2 barrier properties, conformability to a base layer, and transparency, and more preferably at least one selected from the group consisting of oleic acid amide and erucic acid amide. Erucic acid amide is even more preferred from the viewpoint of the blocking suppression effect when the epoxy resin composition is used to form the cured resin layer of a gas barrier laminate described below, or the cured product layer in the packaging material of the second invention and the heat-shrinkable label of the third invention. While erucic acid amide is soluble in epoxy resin compositions containing amine-based curing agents, its solubility in the epoxy resin composition is not too high compared to oleic acid amide, etc., and therefore it bleeds out to the surface of the epoxy resin composition or its cured product and acts as a lubricant. Therefore, it is presumed that epoxy resin compositions containing erucic acid amide have an improved drying rate and exhibit the above-mentioned blocking suppression effect.

[0047] The content of unsaturated fatty acid amide in the epoxy resin composition is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, even more preferably 0.5 to 15 parts by mass, even more preferably 1 to 15 parts by mass, even more preferably 3 to 15 parts by mass, and even more preferably 5 to 12 parts by mass, per 100 parts by mass of the epoxy resin and the non-volatile content of the epoxy resin curing agent combined. A content of unsaturated fatty acid amide of 0.1 parts by mass or more per 100 parts by mass of the epoxy resin and the non-volatile content of the epoxy resin curing agent combined is preferred from the viewpoints of forming a cured product with good adhesion to inorganic materials such as alumina and retort resistance, CO2 barrier properties, conformability to a substrate layer, and anti-blocking effects. Furthermore, a content of 20 parts by mass or less can maintain high gas barrier properties, deodorizing properties, fragrance retention, and transparency, while also suppressing leaching of the unsaturated fatty acid amide.

[0048] [Polyalkylene glycol] The epoxy resin composition may further contain a polyalkylene glycol. By using a polyalkylene glycol, even an epoxy resin composition containing an unsaturated fatty acid amide having 14 to 24 carbon atoms can form a cured product layer that has high gas barrier properties, deodorizing and fragrance retention properties, high CO2 barrier properties, and adhesiveness sufficient for practical use, as well as gloss and excellent leveling properties and a good appearance.

[0049] The polyalkylene glycol may be a homopolymer or copolymer of an alkylene glycol having a carbon number of 2 to 8. The alkylene glycol may be either a linear alkylene glycol or a branched alkylene glycol.

[0050] Specific examples of homopolymers of alkylene glycols having 2 to 8 carbon atoms include polyethylene glycol (PEG), polypropylene glycol (PPG), poly(oxytrimethylene) glycol [polytrimethylene ether glycol], poly(oxybutylene) glycol, poly(oxytetramethylene) glycol [polytetramethylene ether glycol: PTMG], poly(oxypentamethylene) glycol, poly(oxyhexamethylene) glycol, and poly(oxyoctamethylene) glycol.

[0051] Specific examples of copolymers of alkylene glycols having 2 to 8 carbon atoms include polyoxyethylene-polyoxypropylene glycol (PEG-PPG), polyoxyethylene-polyoxytrimethylene glycol, polyoxyethylene-polyoxybutylene glycol, polyoxyethylene-polyoxytetramethylene glycol (PEG-PTMG), polyoxyethylene-polyoxyhexamethylene glycol, polyoxypropylene-polyoxytrimethylene glycol, polyoxypropylene-polyoxybutylene glycol, polyoxypropylene-polyoxytetramethylene glycol (PPG-PTMG), polyoxytrimethylene-polyoxytetramethylene glycol, polyoxytetramethylene-polyoxyhexamethylene glycol, polyoxyethylene-polyoxypropylene-polyoxybutylene glycol, and polyoxyethylene-polyoxypropylene-polyoxytetramethylene glycol.

[0052] One or more types of polyalkylene glycols can be used. From the viewpoints of improving gas barrier properties, deodorizing properties, and fragrance retention, CO2 barrier properties, and improving the appearance of the cured product layer, the polyalkylene glycol is preferably a homopolymer or copolymer of alkylene glycol having 2 to 6 carbon atoms, more preferably a homopolymer or copolymer of alkylene glycol having 2 to 4 carbon atoms, and examples thereof include polyethylene glycol, polypropylene glycol, poly(oxytrimethylene) glycol, poly(oxybutylene) glycol, poly(oxytetramethylene) glycol, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxytrimethylene glycol, and poly At least one selected from the group consisting of oxyethylene-polyoxytetramethylene glycol, polyoxypropylene-polyoxytetramethylene glycol, and polyoxytrimethylene-polyoxytetramethylene glycol is more preferred, and at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and poly(oxytetramethylene) glycol is even more preferred, and from the viewpoints of improving gas barrier properties, deodorizing properties, and aroma retention, CO2 barrier properties, the appearance of the cured product layer, and the adhesion to substrates, polyethylene glycol is even more preferred.

[0053] The weight-average molecular weight (Mw) of the polyalkylene glycol is preferably 200 to 10,000, more preferably 200 to 5,000, and even more preferably 200 to 3,000, from the viewpoints of improving gas barrier properties, deodorizing properties, and fragrance retention, CO2 barrier properties, and improving the appearance of the cured material layer; and from the viewpoints of improving gas barrier properties, deodorizing properties, and fragrance retention, CO2 barrier properties, improving the appearance of the cured material layer, suppressing blocking, and improving adhesion to substrates, it is even more preferably 400 to 2,000, and even more preferably 500 to 1,500.

[0054] When polyalkylene glycol is used, the content of polyalkylene glycol in the epoxy resin composition is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 5.0 parts by mass, even more preferably 0.3 to 3.0 parts by mass, and still more preferably 0.5 to 2.0 parts by mass, relative to 100 parts by mass of the total amount of the epoxy resin and the non-volatile components in the epoxy resin curing agent, from the viewpoints of improving gas barrier properties, deodorizing properties, and aroma retention properties, CO barrier properties, and improving the appearance of the cured product layer.

[0055] <Non-spherical inorganic particles> The epoxy resin composition of the present invention may further contain non-spherical inorganic particles. By including non-spherical inorganic particles in the epoxy resin composition of the present invention, a blocking suppression effect can be obtained when the composition is used to form a cured resin layer of a gas barrier laminate described below, and the gas barrier properties and flex resistance, the odor prevention and aroma retention properties of the packaging material according to the second invention, and the CO2 barrier properties of the heat-shrinkable label according to the third invention can also be improved. The shape of the non-spherical inorganic particles may be any three-dimensional shape other than spherical (approximately perfect spherical), and examples thereof include plate-like, scale-like, columnar, chain-like, and fibrous shapes. A plurality of plate-like and scale-like inorganic particles may be stacked to form a layer. Among these, from the viewpoints of improving gas barrier properties and flex resistance, improving the deodorizing properties, aroma retention properties, and transparency of the packaging material according to the second invention, and improving the CO2 barrier properties of the heat-shrinkable label according to the third invention, plate-like, scale-like, columnar, or chain-like inorganic particles are preferred, plate-like, scale-like, or columnar inorganic particles are more preferred, and plate-like or scale-like inorganic particles are even more preferred.

[0056] Examples of inorganic substances constituting the non-spherical inorganic particles include silica, alumina, mica, talc, aluminum, bentonite, smectite, etc. Among these, from the viewpoint of improving gas barrier properties and flex resistance, at least one selected from the group consisting of silica, alumina, and mica is preferred, at least one selected from the group consisting of silica and alumina is more preferred, and silica is even more preferred. The non-spherical inorganic particles may be surface-treated as needed to enhance dispersibility in the epoxy resin composition and improve the transparency of the cured product. Among these, the non-spherical inorganic particles are preferably coated with an organic material. From the viewpoint of improving gas barrier properties, flex resistance, and transparency when the epoxy resin composition is used to form a cured resin layer of a gas barrier laminate, from the viewpoint of improving the odor resistance and aroma retention of the packaging material according to the second invention, and from the viewpoint of improving the CO2 barrier properties of the heat-shrinkable label according to the third invention, at least one selected from the group consisting of silica and alumina coated with an organic material is more preferred. From the viewpoint of improving gas barrier properties, odor resistance, aroma retention, CO2 barrier properties, and flex resistance, silica coated with an organic material is even more preferred, and from the viewpoint of transparency, alumina coated with an organic material is even more preferred.

[0057] The average particle size of the non-spherical inorganic particles is preferably 1 to 2,000 nm, more preferably 1 to 1,500 nm, even more preferably 1 to 1,000 nm, even more preferably 1 to 800 nm, even more preferably 1 to 500 nm, even more preferably 5 to 300 nm, even more preferably 5 to 200 nm, even more preferably 5 to 100 nm, and even more preferably 8 to 70 nm. An average particle size of 1 nm or more facilitates preparation of the inorganic particles. An average particle size of 2,000 nm or less improves gas barrier properties, flex resistance, and transparency when the epoxy resin composition is used to form a cured resin layer in a gas barrier laminate. Furthermore, when the composition is used to form a cured layer in a packaging material according to the second invention, the resulting packaging material exhibits good odor resistance, aroma retention, flex resistance, and transparency, and when the composition is used to form a cured layer in a heat-shrinkable label according to the third invention, the resulting packaging material exhibits good CO2 barrier properties. Note that this average particle size is the average particle size of primary particles.

[0058] When the non-spherical inorganic particles are plate-like, scaly, columnar, or fibrous, the aspect ratio of the non-spherical inorganic particles is preferably 2 to 700, more preferably 3 to 500. An aspect ratio of 2 or greater tends to exhibit favorable gas barrier properties. The average particle size and aspect ratio of the non-spherical inorganic particles can be determined, for example, by observing the particles using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) and averaging measurements taken at three or more locations. The average particle size and aspect ratio of the non-spherical inorganic particles present in the cured resin layer or cured product layer can be determined, for example, by embedding the gas barrier laminate or packaging material (described below) in epoxy resin, then subjecting the laminate or packaging material to ion milling using an ion milling device to prepare a cross-sectional observation sample, and observing and measuring the cross-section of the cured resin layer or cured product layer portion of the obtained sample in the same manner as described above. When the average particle size of the non-spherical inorganic particles is less than 100 nm and it is difficult to measure the average particle size by the above-mentioned method, the average particle size can also be measured by, for example, the BET method.

[0059] There are no particular limitations on the method for producing the non-spherical inorganic particles, and any known method can be used. In the present invention, from the viewpoints of ease of preparation of non-spherical inorganic particles, ease of incorporation into epoxy resin compositions, and dispersibility, it is preferable to prepare a dispersion of non-spherical inorganic particles and incorporate the dispersion into the epoxy resin composition. The dispersion medium for the non-spherical inorganic particle dispersion is not particularly limited, and either water or an organic solvent can be used. From the viewpoint of dispersibility of the non-spherical inorganic particles, polar solvents are preferred as the organic solvent. Examples of such organic solvents include protic polar solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-propoxy-2-propanol, and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone. From the viewpoint of dispersibility of the non-spherical inorganic particles, the dispersion medium is preferably at least one selected from the group consisting of water and protic polar solvents, and from the viewpoint of dispersibility of the particles and miscibility of the dispersion liquid with the epoxy resin composition, protic polar solvents are more preferred, and at least one selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol is even more preferred.

[0060] When non-spherical inorganic particles are used, the content of the non-spherical inorganic particles in the epoxy resin composition is preferably 0.5 to 10.0 parts by mass, more preferably 1.0 to 8.0 parts by mass, even more preferably 1.5 to 7.5 parts by mass, and even more preferably 3.0 to 7.0 parts by mass, per 100 parts by mass of the epoxy resin and the epoxy resin curing agent combined. When the content of the non-spherical inorganic particles in the epoxy resin composition is 0.5 parts by mass or more, per 100 parts by mass of the epoxy resin and the epoxy resin curing agent combined, the epoxy resin composition exhibits excellent gas barrier properties and improved flex resistance when used to form a cured resin layer in a gas barrier laminate. Furthermore, when the composition is used to form a cured product layer in a packaging material according to the second invention, the resulting packaging material exhibits excellent odor prevention, aroma retention, flex resistance, and transparency, and when used to form a cured product layer in a heat-shrinkable label according to the third invention, the resulting packaging material exhibits excellent CO2 barrier properties. Furthermore, when the content is 10.0 parts by mass or less, transparency is also improved.

[0061] The epoxy resin composition may contain additives such as a thermosetting resin, a wetting agent, a tackifier, an antifoaming agent, a curing accelerator, a rust-preventing additive, a pigment, and an oxygen scavenger, as needed, within the range that does not impair the effects of the present invention. The total content of the above additives in the epoxy resin composition is preferably 20.0 parts by mass or less, more preferably 0.001 to 15.0 parts by mass, per 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent.

[0062] However, from the viewpoint of obtaining the effects of the present invention, the total content of the epoxy resin, epoxy resin curing agent, and unsaturated fatty acid amide having 14 to 24 carbon atoms in the solid content of the epoxy resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and still more preferably 85% by mass or more, with the upper limit being 100% by mass. The "solid content of the epoxy resin composition" means the components in the epoxy resin composition excluding water and organic solvents.

[0063] The epoxy resin composition may contain an organic solvent, and the organic solvent used in the epoxy resin composition is preferably a non-reactive solvent. Specific examples thereof include polar solvents exemplified as the dispersion medium used in the dispersion of non-spherical inorganic particles, preferably protic polar solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-propoxy-2-propanol, as well as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, and the like, which may be used singly or in combination. Among the above, from the viewpoint of improving the drying rate and improving the appearance of the obtained cured resin layer or cured product layer, at least one selected from the group consisting of methanol, ethanol, and ethyl acetate is preferred, and at least one selected from the group consisting of ethanol and ethyl acetate is more preferred.

[0064] When an epoxy resin composition contains an organic solvent, the epoxy resin and the epoxy resin curing agent react with each other over time, which tends to cause precipitation in the composition and shorten its shelf life (usable time).From the viewpoint of suppressing precipitation and improving the shelf life of the epoxy resin composition, it is more preferable that the organic solvent used in the epoxy resin composition is ethanol or ethyl acetate. When the organic solvent is ethanol and ethyl acetate, from the viewpoint of improving the shelf life of the epoxy resin composition, the mass ratio of ethanol to ethyl acetate (ethanol / ethyl acetate) is preferably 95 / 5 to 55 / 45, more preferably 90 / 10 to 55 / 45, even more preferably 85 / 15 to 60 / 40, and even more preferably 75 / 25 to 65 / 35. When the epoxy resin composition contains an organic solvent, the solids concentration of the epoxy resin composition is not particularly limited, but from the viewpoint of coatability, it is usually 0.5% by mass or more, more preferably 1% by mass or more, and from the viewpoint of improving coatability and shelf life of the composition, it is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0065] <Preparation of Epoxy Resin Composition> The epoxy resin composition can be prepared, for example, by blending predetermined amounts of an epoxy resin, an epoxy resin curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a dispersion of non-spherical inorganic particles used as needed, other additives, and an organic solvent, and then stirring and mixing them using a known method and device. The order in which the components are mixed is not particularly limited, but when non-spherical inorganic particles are used, in order to improve the dispersibility of the non-spherical inorganic particles in the epoxy resin composition, it is preferable to first mix the dispersion of the non-spherical inorganic particles with the solvent component, and then add and mix the epoxy resin curing agent or a solution thereof, the unsaturated fatty acid amide, and the epoxy resin in that order. This is because the dispersibility of the non-spherical inorganic particles can be maintained in a good state by gradually increasing the solids concentration in the liquid containing the non-spherical inorganic particles from a low state.

[0066] When an epoxy resin composition contains an organic solvent, from the viewpoint of improving the degree of freedom in formulation of the epoxy resin composition, it is preferable that the method for producing the epoxy resin composition comprises, in order, a step of mixing an epoxy resin curing agent with an organic solvent to obtain an epoxy resin curing agent solution 1, a step of mixing the solution 1 with an unsaturated fatty acid amide having 14 to 24 carbon atoms to prepare an epoxy resin curing agent solution 2, and a step of mixing the solution 2 with an epoxy resin (production method 1). More preferably, the above-mentioned production method 1 includes, in order, a step of mixing an epoxy resin curing agent and an organic solvent to obtain an epoxy resin curing agent solution 1, a step of mixing the solution 1 with an unsaturated fatty acid amide having 14 to 24 carbon atoms to prepare an epoxy resin curing agent solution 2, and a step of mixing the solution 2 with an epoxy resin and an organic solvent.

[0067] The organic solvent can be any of the organic solvents exemplified for the epoxy resin composition, and is preferably at least one selected from the group consisting of methanol, ethanol, and ethyl acetate, more preferably at least one selected from the group consisting of ethanol and ethyl acetate, and even more preferably ethanol and ethyl acetate. When the organic solvents contained in the epoxy resin composition are ethanol and ethyl acetate, it is more preferable that the mass ratio of ethanol to ethyl acetate (ethanol / ethyl acetate) in the finally obtained epoxy resin composition be within the above range, from the viewpoint of improving shelf life. When the coupling agent is used as an additive, it is preferable to blend the coupling agent in the epoxy resin curing agent solution 2. When the non-spherical inorganic particles are used, it is preferable to mix a dispersion of the non-spherical inorganic particles with the epoxy resin curing agent solution 1.

[0068] In production method 1, the solids concentration of the epoxy resin curing agent solution 1 is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, from the viewpoint of the degree of freedom in blending the epoxy resin composition, and is preferably 80% by mass or less, more preferably 75% by mass or less, from the viewpoint of improving stirring efficiency. In production method 1, the solids concentration of the epoxy resin curing agent solution 2 is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and still more preferably 25% by mass or more, from the viewpoint of flexibility in formulation of the epoxy resin composition, and is preferably 70% by mass or less, more preferably 50% by mass or less, from the viewpoint of improving stirring efficiency and shelf life. The components can be mixed in a conventional manner using a known stirring device.

[0069] Furthermore, from the viewpoint of improving the production efficiency of the epoxy resin composition, it is more preferable to dissolve the unsaturated fatty acid amide having 14 to 24 carbon atoms in an organic solvent beforehand and then add it to the epoxy resin composition. More specifically, from the viewpoint of improving the efficiency of producing the epoxy resin composition and improving the flexibility of the formulation, it is more preferable to produce the epoxy resin composition of the present invention by a production method including the following steps (I) to (IV) (Production Method 2). Step (I): A step of mixing an unsaturated fatty acid amide having 14 to 24 carbon atoms with an organic solvent (i) to obtain an unsaturated fatty acid amide solution (a). Step (II): A step of mixing an epoxy resin curing agent containing an amine-based curing agent with an organic solvent (ii) to obtain an epoxy resin curing agent solution (b). Step (III): A step of mixing the unsaturated fatty acid amide solution (a) and the epoxy resin curing agent solution (b) to obtain an epoxy resin curing agent solution (c). Step (IV): A step of mixing the epoxy resin curing agent solution (c) with an epoxy resin to obtain an epoxy resin composition. According to the above-mentioned production method 2, in step (I), an unsaturated fatty acid amide having 14 to 24 carbon atoms is dissolved in an organic solvent in advance to prepare a solution (a), which is then mixed with an epoxy resin curing agent solution (b) in step (III). This makes it possible to shorten the dissolution time required to dissolve the unsaturated fatty acid amide in the epoxy resin composition, thereby improving production efficiency. The steps (I) and (II) may be carried out in this order, or the steps (II) and (I) may be carried out in this order.

[0070] [Process (I)] In step (I), an unsaturated fatty acid amide having 14 to 24 carbon atoms is mixed with an organic solvent (i) to obtain an unsaturated fatty acid amide solution (a). When the unsaturated fatty acid amide is directly added to an epoxy resin curing agent, an epoxy resin curing agent solution, or an epoxy resin composition, it may take a long time to dissolve the unsaturated fatty acid amide. However, by performing step (I), the dissolution time of the unsaturated fatty acid amide can be shortened. As the organic solvent (i), any of the organic solvents exemplified in the epoxy resin composition can be used, and at least one selected from the group consisting of methanol, ethanol, and ethyl acetate is preferred, at least one selected from the group consisting of ethanol and ethyl acetate is more preferred, and ethanol and ethyl acetate are even more preferred.

[0071] The mixing of the unsaturated fatty acid amide and the organic solvent (i) in step (I) can be carried out by a conventional method using a known stirring device. The mixing temperature in step (I) is not particularly limited, but is preferably 15°C or higher, more preferably 20°C or higher, from the viewpoint of the solubility of the unsaturated fatty acid amide, and is preferably 60°C or lower, more preferably 50°C or lower, from the viewpoint of suppressing the evaporation of the organic solvent (i).

[0072] The concentration of the unsaturated fatty acid amide in the unsaturated fatty acid amide solution (a) obtained in step (I) is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%, from the viewpoint of improving stirring efficiency and production efficiency of the epoxy resin composition.

[0073] [Step (II)] In the step (II), an epoxy resin curing agent containing an amine-based curing agent is mixed with an organic solvent (ii) to obtain an epoxy resin curing agent solution (b). As the organic solvent (ii), any of the organic solvents exemplified in the epoxy resin composition can be used, and at least one selected from the group consisting of methanol, ethanol, and ethyl acetate is preferred. From the viewpoint of the solubility of the epoxy resin curing agent containing the amine-based curing agent, the organic solvent (ii) is more preferably at least one selected from the group consisting of methanol and ethanol, and from the viewpoint of environmental safety, ethanol is even more preferred. At least a part of the organic solvent (ii) may be the reaction solvent used in the production of the amine-based curing agent.

[0074] The mixing of the epoxy resin curing agent containing an amine-based curing agent with the organic solvent (ii) in step (II) can be carried out in the same manner as in step (I). The mixing temperature is not particularly limited, but is preferably 15°C or higher, more preferably 20°C or higher, from the viewpoint of production efficiency, and is preferably 60°C or lower, more preferably 50°C or lower, from the viewpoint of suppressing thermal degradation of the epoxy resin curing agent and suppressing volatilization of the organic solvent (ii).

[0075] The concentration of the epoxy resin curing agent in the epoxy resin curing agent solution (b) obtained in step (II) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, from the viewpoint of the degree of freedom in adjusting the concentrations of the epoxy resin curing agent solution (c) obtained in step (III) and the epoxy resin composition obtained in step (IV); and is preferably 80% by mass or less, more preferably 75% by mass or less, from the viewpoint of improving stirring efficiency.

[0076] [Step (III)] In step (III), the unsaturated fatty acid amide solution (a) obtained in step (I) and the epoxy resin curing agent solution (b) obtained in step (II) are mixed to obtain an epoxy resin curing agent solution (c). In step (III), by mixing the unsaturated fatty acid amide solution (a) previously prepared in step (I) with the epoxy resin curing agent solution (b) obtained in step (II), the dissolution time of the unsaturated fatty acid amide can be shortened, and the production efficiency of the epoxy resin composition can be improved.

[0077] In step (III), an organic solvent may be further added as needed to adjust the solid content of the resulting epoxy resin curing agent solution (c). Examples of the organic solvent include the solvents exemplified above for the organic solvent (i). When the coupling agent is used as an additive, it is preferable to add the coupling agent in step (III). More specifically, in step (III), it is preferable to add the coupling agent to the unsaturated fatty acid amide solution (a) and then mix it with the epoxy resin curing agent solution (b).

[0078] The unsaturated fatty acid amide solution (a) and the epoxy resin curing agent solution (b) can be mixed in the step (III) by a conventional method using a known stirring device. In step (III), from the viewpoint of improving the solubility of the unsaturated fatty acid amide, it is preferable to adjust the liquid temperature of the unsaturated fatty acid amide solution (a) to 20°C or higher, preferably 25°C or higher, and then mix it with the epoxy resin curing agent solution (b). From the viewpoint of suppressing the evaporation of the organic solvent, the liquid temperature of the unsaturated fatty acid amide solution (a) is preferably 60°C or lower, more preferably 50°C or lower. After step (III) is carried out, cooling, filtration and other operations may be carried out as necessary.

[0079] The solids concentration of the epoxy resin curing agent solution (c) obtained in step (III) is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of the degree of freedom in adjusting the concentration of the epoxy resin composition obtained in step (IV), and is preferably 70% by mass or less, more preferably 50% by mass or less, from the viewpoint of improving stirring efficiency.

[0080] [Step (IV)] In the step (IV), the epoxy resin curing agent solution (c) and an epoxy resin are mixed to obtain an epoxy resin composition. In step (IV), an organic solvent may be further added as necessary to adjust the solids concentration of the resulting epoxy resin composition preferably within the above-mentioned range. Examples of such organic solvents include the solvents exemplified above as organic solvent (i). From the viewpoint of improving the shelf life of the epoxy resin composition, the organic solvents in the finally obtained epoxy resin composition are preferably ethanol and ethyl acetate, and the mass ratio of ethanol to ethyl acetate (ethanol / ethyl acetate) is more preferably within the above-mentioned range. The mixing of the epoxy resin curing agent solution (c) and the epoxy resin in step (IV) can be carried out in the same manner as in step (II).

[0081] <Application> A cured product of the epoxy resin composition of the present invention has excellent gas barrier properties, good adhesion to inorganic materials such as alumina, and is resistant to peeling even after retort treatment, resulting in excellent retort resistance. For example, a cured resin layer formed from the cured product functions as a gas barrier layer with excellent gas barrier properties. Therefore, the epoxy resin composition of the present invention is suitable for use in gas barrier laminates, which will be described later, as well as gas barrier packaging materials, gas barrier adhesives, and the like. Furthermore, the epoxy resin composition of the present invention is also suitable for use in forming a cured product layer constituting a packaging material according to the second invention and a cured product layer constituting a heat-shrinkable label according to the third invention. The method for curing the epoxy resin composition of the present invention to form the cured product is not particularly limited, and known methods can be used. One embodiment of such a method will be described in the section on the method for producing a gas barrier laminate.

[0082] [Gas barrier laminate] The gas barrier laminate according to the first invention is characterized by having a substrate and a cured resin layer (hereinafter simply referred to as "cured resin layer") that is a cured product of the epoxy resin composition. Hereinafter, the gas barrier laminate according to the first invention will also be simply referred to as the "(gas barrier) laminate of the present invention." The gas barrier laminate of the present invention has high gas barrier properties and is a laminate with high interlayer adhesion between the substrate and the cured resin layer. Hereinafter, the materials constituting the gas barrier laminate of the present invention will be described.

[0083] <Base material> The substrate constituting the gas barrier laminate of the present invention may be either an inorganic substrate or an organic substrate. Examples of inorganic substrates include metal foils such as aluminum foils.

[0084] The organic substrate is preferably a transparent plastic film. Examples of transparent plastic films include polyolefin films such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and polypropylene; polyester films such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polyamide films such as nylon 6, nylon 6,6, and polymethaxylene adipamide (N-MXD6); polyimide films; biodegradable films such as polylactic acid; polyacrylonitrile films; poly(meth)acrylic films; polystyrene films; polycarbonate films; saponified ethylene-vinyl acetate copolymer (EVOH) films; and polyvinyl alcohol films. Among these, from the viewpoints of transparency, strength, and heat resistance, films selected from the group consisting of polyolefin films, polyester films, polyamide films, and polyimide films are preferred as the organic substrate, with polyolefin films and polyester films being more preferred, and polypropylene films or polyethylene terephthalate (PET) films being even more preferred. The film may be uniaxially or biaxially stretched.

[0085] The thickness of the substrate can be appropriately selected depending on the application and is not particularly limited, but from the viewpoints of gas barrier properties and strength, it is preferably 5 to 300 μm, more preferably 5 to 100 μm, even more preferably 5 to 50 μm, and still more preferably 5 to 40 μm. When the substrate is an organic substrate, from the viewpoints of gas barrier properties and strength, the thickness of the organic substrate is even more preferably 8 to 50 μm, and even more preferably 10 to 40 μm.

[0086] <Cured resin layer> The cured resin layer in the gas barrier laminate of the present invention is a cured product of the above-mentioned epoxy resin composition. The method for curing the epoxy resin composition is not particularly limited, and the curing is carried out by a known method at a concentration and temperature sufficient for obtaining the cured product of the epoxy resin composition. The curing temperature can be selected, for example, from the range of 10 to 140°C.

[0087] The thickness of the cured resin layer is preferably 0.05 μm or more, more preferably 0.1 μm or more, from the viewpoints of gas barrier properties and flex resistance. Furthermore, from the viewpoints of adhesion to inorganic substances such as alumina, retort resistance, and transparency, the thickness is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 5.0 μm or less, still more preferably 2.0 μm or less, still more preferably 1.0 μm or less, still more preferably 0.5 μm or less, and still more preferably 0.4 μm or less. The above thickness is the thickness per layer of the cured resin layer.

[0088] The gas barrier laminate of the present invention may have a substrate and at least one cured resin layer. From the viewpoint of obtaining high gas barrier properties and the effectiveness of the effects of the present invention, it is preferable that the laminate has at least one layer made of an inorganic substance. Specifically, it is preferable that the layer made of an inorganic substance is the inorganic substrate or an inorganic thin film layer.

[0089] (inorganic thin film layer) The inorganic thin film layer is provided to impart gas barrier properties to the gas barrier laminate, and can exhibit high gas barrier properties even when it is thin. Examples of the inorganic thin film layer include those made of metal foil and those formed by a vapor deposition method, but from the viewpoint of obtaining high transparency, an inorganic vapor deposition layer formed by a vapor deposition method is preferred. The inorganic substance constituting the inorganic thin film layer is not particularly limited as long as it is an inorganic substance capable of forming a gas-barrier thin film on the substrate, and examples thereof include silicon, aluminum, magnesium, calcium, zinc, tin, nickel, titanium, zirconium, carbon, and oxides, carbides, nitrides, and oxynitrides thereof. Among these, at least one selected from the group consisting of silicon oxide (silica), aluminum, and aluminum oxide (alumina) is preferred from the viewpoint of gas barrier properties. At least one selected from the group consisting of silicon oxide and aluminum oxide is more preferred from the viewpoint of forming a thin film with high gas barrier properties and transparency, and silicon oxide is even more preferred from the viewpoint of gas barrier properties. Meanwhile, the cured resin layer, which is a cured product of the epoxy resin composition of the present invention, exhibits good adhesion even to inorganic thin film layers made of aluminum oxide, which has traditionally been difficult to exhibit adhesion to. Therefore, from the viewpoint of the effectiveness of the effects of the present invention, it is preferable that the inorganic substance constituting the inorganic thin film layer is aluminum oxide. The above inorganic substances may be used alone or in combination. The thickness of the inorganic thin film layer is preferably 5 nm or more from the viewpoint of obtaining high gas barrier properties. From the viewpoint of transparency and flex resistance, the thickness is preferably 100 nm or less, more preferably 50 nm or less. The above thickness is the thickness per inorganic thin film layer.

[0090] The method for forming the inorganic thin film layer is not particularly limited, and examples of vapor deposition methods include known vapor deposition methods such as physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. The inorganic thin film layer can also be formed by laminating a metal foil such as aluminum foil to the substrate. The inorganic thin film layer can be formed, for example, on an organic substrate or on a cured resin layer.

[0091] (thermoplastic resin layer) The gas barrier laminate of the present invention may further have one or more thermoplastic resin layers from the viewpoint of subjecting it to retort treatment. The thermoplastic resin layer is preferably a thermoplastic resin film, and the same transparent plastic films as those exemplified for the organic substrate can be used. Among the transparent plastic films, at least one selected from the group consisting of polyolefin films and polyamide films is preferred, and from the viewpoints of transparency, heat resistance, and suitability for packaging food, etc., at least one selected from the group consisting of polypropylene films and nylon 6 films is more preferred. The surface of the thermoplastic resin film may be subjected to a surface treatment such as flame treatment, corona discharge treatment, etc. Furthermore, the thermoplastic resin film may also be a film containing an ultraviolet absorber, a colorant, etc., or a film having a primer layer, an ink layer, a surface protective layer, a vapor deposition layer, etc. on its surface. The thickness of the thermoplastic resin layer is preferably 10 to 300 μm, more preferably 10 to 100 μm. The above thickness is the thickness per one thermoplastic resin layer.

[0092] (adhesive layer) The gas barrier laminate of the present invention may further have an adhesive layer for laminating the thermoplastic resin layer. The adhesive constituting the adhesive layer can be a known adhesive such as a urethane adhesive, an acrylic adhesive, or an epoxy adhesive. The thickness of the adhesive layer is not particularly limited, but from the viewpoint of achieving both adhesiveness and transparency, it is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and even more preferably 2 to 20 μm. The above thickness is the thickness per adhesive layer.

[0093] <Layer structure of gas barrier laminate> The gas barrier laminate of the present invention may have a structure including the base material and at least one of the cured resin layers. As described above, from the viewpoint of the effectiveness of the effects of the present invention, it is preferable that the gas barrier laminate of the present invention has a layer made of an inorganic material, and from the viewpoint of economic efficiency, it is preferable that the gas barrier laminate has one or two, preferably only one, cured resin layers. Furthermore, from the viewpoint of the effectiveness of the effects of the present invention, it is preferable that the layer made of an inorganic material and the cured resin layer are adjacent to each other. Examples of the layer structure of a gas barrier laminate having a substrate and one or two cured resin layers and a layer made of an inorganic material are given below. (1) A structure having a substrate and a cured resin layer, the substrate being an inorganic substrate (2) A structure having a substrate, an inorganic thin film layer, and a resin cured layer in this order. (3) A structure having a substrate, a cured resin layer, and an inorganic thin film layer in this order. (4) A structure having a substrate, a cured resin layer, an inorganic thin film layer, and a cured resin layer in this order. In the above (1), when there are two or more substrates, at least one of the substrates should be an inorganic substrate. The substrate in the above (2), (3), and (4) is preferably an organic substrate. From the viewpoint of the effectiveness of the effects of the present invention, it is preferable that the layer made of an inorganic material and the cured resin layer are adjacent to each other, and from the viewpoint of gas barrier properties, the above configuration of (1), (2), or (4) is more preferable, and the above configuration of (1) or (2) is more preferable. From the viewpoint of the effectiveness of the effects of the present invention and from the viewpoint of application to uses requiring retort resistance and transparency, the above configuration (2) is more preferable. The gas barrier laminate of the present invention has any one of the layer structures (1) to (4) above, and may further have one or more of the thermoplastic resin layers described above.

[0094] Preferred examples of the layer configuration of the gas barrier laminate include those shown in Figures 1 to 4. Hereinafter, in this specification, a laminate having only a substrate and no thermoplastic resin layer will be referred to as a "laminate (I)", a laminate having a total of two substrate and thermoplastic resin layers will be referred to as a "laminate (II)", and a laminate having a total of three substrate and thermoplastic resin layers will be referred to as a "laminate (III)".

[0095] 1 and 2 are cross-sectional schematic diagrams showing one embodiment of the gas barrier laminate (I) of the present invention. The gas barrier laminate 100 in Fig. 1 has a configuration in which an inorganic thin film layer 2 and a cured resin layer 3 are provided in this order on a substrate 1. In Fig. 1, the inorganic thin film layer 2 and the cured resin layer 3 are adjacent to each other. The gas barrier laminate 100a in FIG. 2 has a structure in which a cured resin layer 3 and an inorganic thin film layer 2 are provided in this order on a substrate 1.

[0096] 3 to 6 are cross-sectional schematic diagrams showing one embodiment of the gas barrier laminate (II) of the present invention. The gas barrier laminates of Fig. 3 to 6 have one base material and one thermoplastic resin layer (two layers in total), and the thermoplastic resin layers may be laminated directly or via an adhesive layer. The gas barrier laminate 200 in FIG. 3 has a configuration in which a thermoplastic resin layer 4 is directly laminated without an adhesive layer, and has a configuration in which a substrate 1, an inorganic thin film layer 2, a cured resin layer 3, and a thermoplastic resin layer 4 are laminated in this order. 4 to 6 have a configuration in which a thermoplastic resin layer 4 is laminated via an adhesive layer 5. The gas barrier laminate 300 in Fig. 4 has a configuration in which a substrate 1, an inorganic thin film layer 2, a cured resin layer 3, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order. The gas barrier laminate 300a in FIG. 5 has a structure in which a substrate 1, a cured resin layer 3, an inorganic thin film layer 2, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order. The gas barrier laminate 300b in FIG. 6 has a structure in which a substrate 1, a cured resin layer 3, an inorganic thin film layer 2, a cured resin layer 3, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order.

[0097] 7 to 9 are cross-sectional schematic diagrams showing one embodiment of the gas barrier laminate (III) of the present invention. The gas barrier laminates of Fig. 7 and Fig. 8 have one substrate layer and two thermoplastic resin layers (total of three layers), while the gas barrier laminate of Fig. 9 has two substrate layers and one thermoplastic resin layer (total of three layers). The gas barrier laminate 400 in FIG. 7 has a structure in which a substrate 1, an inorganic thin film layer 2, a cured resin layer 3, an adhesive layer 5, a thermoplastic resin layer 4, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order. The gas barrier laminate 400a in FIG. 8 has a structure in which a substrate 1, a cured resin layer 3, an inorganic thin film layer 2, an adhesive layer 5, a thermoplastic resin layer 4, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order. 9 has a configuration in which a substrate 1, an adhesive layer 5, a substrate 1c, a cured resin layer 3, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order. At least one of the substrates is preferably an inorganic substrate, and an example thereof is a substrate 1c which is an inorganic substrate. The thermoplastic resin layers 4 constituting the gas barrier laminate 400 or 400a may all be the same resin layers or different resin layers, and the adhesive layers 5 may all be layers made of the same adhesive or layers made of different adhesives.

[0098] However, the laminate of the present invention is not limited to the layer configurations shown in Figures 1 to 9. Furthermore, the laminate of the present invention may further include any layer such as a primer layer, an ink layer, an adhesive layer, a surface protection layer, or a vapor deposition layer.

[0099] <Method of manufacturing gas barrier laminate> The method for producing the gas barrier laminate of the present invention is not particularly limited, and known methods can be used. For example, a method for producing the gas barrier laminate 100 having the configuration shown in Fig. 1 includes forming an inorganic thin film layer on one side of a substrate, applying the epoxy resin composition for forming a cured resin layer to a desired thickness on the surface of the inorganic thin film layer, and then curing the epoxy resin composition to form a cured resin layer. Note that a film in which an inorganic thin film layer has been formed on a transparent plastic film may be used, and the cured resin layer may be formed on the surface of the inorganic thin film layer. The gas barrier laminate 100a having the configuration shown in FIG. 2 can be produced by applying the epoxy resin composition to one surface of a substrate, curing the epoxy resin composition to form a cured resin layer, and then forming an inorganic thin film layer on the cured resin layer. Examples of the coating method for applying the epoxy resin composition include bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, microreverse gravure coating, die coating, slot die coating, vacuum die coating, dip coating, spin coating, roll coating, spray coating, brush coating, etc. Among these, bar coating, roll coating, and spray coating are preferred, and industrially, gravure coating, reverse gravure coating, microgravure coating, and microreverse gravure coating are preferred. After the epoxy resin composition is applied, a step of volatilizing the solvent (drying step) is carried out as necessary. The conditions for the drying step can be appropriately selected, but for example, the drying step can be carried out under conditions of a drying temperature of 40 to 180°C and a drying time of 5 to 180 seconds. After the drying step, the epoxy resin composition is cured to form a cured resin layer. The curing temperature can be selected, for example, from 10 to 140° C., and preferably from 10 to 80° C. The curing time can be selected, for example, from 0.5 to 200 hours, and preferably from 2 to 100 hours.

[0100] 3, there is a method for producing the gas barrier laminate 200 by forming an inorganic thin film layer on a substrate, applying the epoxy resin composition described above to the surface of the inorganic thin film layer, and then immediately laminating a thermoplastic resin film constituting the thermoplastic resin layer onto the applied surface using a nip roll or the like, and then curing the epoxy resin composition by the method described above. In this case, the epoxy resin composition constituting the cured resin layer serves as an adhesive layer that bonds the inorganic thin film layer and the thermoplastic resin film in the gas barrier laminate 200. A method for producing the gas barrier laminate 300 having the configuration shown in Fig. 4 includes applying an adhesive that forms an adhesive layer to the cured resin layer surface of the gas barrier laminate 100 having the configuration shown in Fig. 1 or to one surface of a thermoplastic resin film, and then laminating the two together. The gas barrier laminate 300a having the configuration shown in Fig. 5 can be produced by a similar method using the gas barrier laminate 100a having the configuration shown in Fig. 2. A method for producing the gas barrier laminate 300b having the configuration shown in FIG. 6 includes forming a cured resin layer on the inorganic thin film layer surface of the gas barrier laminate 100a having the configuration shown in FIG. 2, applying an adhesive to form an adhesive layer on the cured resin layer surface or on one surface of a thermoplastic resin film, and then laminating the two together. The gas barrier laminate 400 having the configuration shown in Fig. 7 can be produced by forming the gas barrier laminate 300 having the configuration shown in Fig. 4, and then repeatedly carrying out the steps of applying an adhesive and attaching and laminating a thermoplastic resin film. The gas barrier laminate 400a having the configuration shown in Fig. 8 can be produced by a similar method using the gas barrier laminate 300a having the configuration shown in Fig. 5. The gas barrier laminate 400c having the configuration shown in FIG. 9 can be produced by laminating the substrate 1, adhesive layer 5, and substrate 1c in this order, forming a cured resin layer on the surface of substrate 1c, applying an adhesive to form an adhesive layer on the surface of the cured resin layer or on one surface of a thermoplastic resin film, and then laminating the two together.

[0101] <Properties of gas barrier laminate> The gas barrier laminate of the present invention has excellent gas barrier properties. For example, the oxygen permeability of the gas barrier laminate (II) at 23°C and a relative humidity of 60% is preferably 2 cc / m, although this varies depending on the barrier properties of the substrate used. 2 ·day·atm or less, preferably 1.5cc / m 2 ·day·atm or less, more preferably 1cc / m 2 ·day·atm or less. The oxygen permeability of the gas barrier laminate is specifically determined by the method described in the examples.

[0102] <Applications of gas barrier laminate> The gas barrier laminate of the present invention has excellent gas barrier properties and flex resistance, and is therefore suitable for use as a packaging material for protecting foods, medicines, cosmetics, precision electronic components, etc. When used as a packaging material, the gas barrier laminate of the present invention may be used as is as the packaging material, or may be further laminated with other layers or films.

[0103] The form of the packaging material can be appropriately selected depending on the item to be stored or preserved, and examples thereof include packaging films; packaging containers such as packaging bags and bottles; and lids and seals for packaging containers. Among these, packaging films and packaging bags or their lids and seals are preferred as forms suitable for retort treatment. Specific examples of packaging films or packaging bags include three-sided sealed flat bags, standing pouches, gusseted packaging bags, pillow packaging bags, multi-chamber pouches consisting of a main chamber and an auxiliary chamber with an easily peelable wall between them, and shrink film packaging. The capacity of the packaging material is not particularly limited, and can be selected appropriately depending on the items to be stored or preserved.

[0104] From the viewpoint of the effectiveness of the effects of the present invention, the use of the packaging material is preferably in applications requiring retort resistance, and packaging materials for retort foods such as bags and lids for retort foods, and in particular bags for retort foods, are more preferred. From the viewpoint of retort resistance, the packaging material for retort food includes the gas barrier laminate of the present invention, and preferably includes the laminate (II) or laminate (III). That is, the packaging material for retort food preferably includes a substrate, a cured resin layer, and one or more thermoplastic resin layers, and more preferably includes a laminate further including an inorganic thin film layer from the viewpoint of gas barrier properties. Examples of the packaging material for retort food include bags and lids for retort food that use the laminate (II) or laminate (III).

[0105] [Second invention: Odor-preventing or aroma-retaining packaging material] The odor-preventing or fragrance-retaining packaging material according to the second invention (hereinafter also referred to as "the packaging material of the present invention") comprises a substrate and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. The packaging material of the present invention has a cured product layer of an epoxy resin composition containing an amine-based curing agent, thereby achieving excellent deodorizing and fragrance retention properties. Furthermore, since the epoxy resin composition contains an unsaturated fatty acid amide having 14 to 24 carbon atoms, a two-layer structure consisting of a substrate and the cured product layer can be achieved, eliminating the need for a three-layer structure with a cured product layer of the epoxy resin composition as an intermediate layer. This allows for thinner packaging materials, which are also economical. Furthermore, the adhesion and transparency between the substrate and the cured product layer are also improved. When a cured product of an epoxy resin composition is used as an intermediate layer of a packaging material (a layer located between two substrates), the epoxy resin composition only needs to have adhesive properties in addition to deodorizing and aroma-retaining properties. On the other hand, when a cured product layer of an epoxy resin composition is used as a surface layer (an innermost layer or an outermost layer), it is important that the cured product layer exhibits minimal blocking. It is believed that the inclusion of an unsaturated fatty acid amide having 14 to 24 carbon atoms in an epoxy resin composition functions as a lubricant, thereby suppressing blocking in the resulting cured product layer. This effect also makes it possible to form a packaging material with a two-layer structure consisting of a substrate and a cured product layer. Furthermore, the unsaturated fatty acid amide is believed to have the effect of alleviating stress generated in the cured product of the epoxy resin, and is highly compatible with epoxy resin compositions containing amine-based epoxy resin curing agents, so it is presumed that the cured product of the epoxy resin composition containing the unsaturated fatty acid amide will have good adhesion to substrates and transparency.

[0106] The form of the packaging material of the present invention can be appropriately selected depending on the item to be stored or preserved, and examples thereof include packaging films, packaging containers such as packaging bags and bottles, and lids and seals for packaging containers. Among these, from the viewpoint of enhancing deodorizing properties and aroma retention, the packaging material of the present invention is preferably a bag, film, or lid, and more preferably a packaging bag. Specific examples of packaging bags include three-sided sealed flat bags, standing pouches, gusset packaging bags, pillow packaging bags, multi-chamber pouches consisting of a main chamber and a sub-chamber with an easily peelable wall between the main chamber and the sub-chamber, and shrink packaging bags. The capacity of the packaging material is not particularly limited, and can be selected appropriately depending on the items to be stored or preserved. The materials constituting the packaging material of the present invention will be described below.

[0107] <Base material> The substrate in the packaging material of the present invention can be either an inorganic substrate or an organic substrate. Examples of the inorganic substrate and the organic substrate include the same substrates as those exemplified for the gas barrier laminate of the first invention. From the viewpoints of lightness, transparency, and economy, the substrate is preferably an organic substrate, and from the viewpoints of transparency, strength, and heat resistance, one or more selected from the group consisting of polyolefins, polyesters, polyamides, and polyimides is more preferred, and polyolefins are even more preferred. When the packaging material is a film or a bag, the substrate is preferably a film-like substrate, and the film may be stretched uniaxially or biaxially. The film may have an inorganic thin film layer such as a vapor-deposited film of silica, alumina, etc., but from the viewpoint of economy, it is also possible to have a configuration without an inorganic thin film layer.

[0108] The thickness of the substrate can be appropriately selected depending on the shape of the packaging material and is not particularly limited, but from the viewpoints of deodorizing properties, aroma retention, and strength, it is preferably 5 to 300 μm, more preferably 5 to 100 μm, and even more preferably 5 to 50 μm. When the substrate is an organic substrate, from the viewpoints of deodorizing properties, aroma retention, and strength, the thickness of the organic substrate is even more preferably 8 to 50 μm, and even more preferably 10 to 40 μm.

[0109] <Cured material layer> The cured material layer in the packaging material of the present invention is a layer made of a cured product of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. The thickness of the cured material layer is preferably 0.02 μm or more, more preferably 0.05 μm or more, and even more preferably 0.08 μm or more from the viewpoints of deodorizing properties, aroma retention, and flex resistance. Furthermore, from the viewpoints of adhesion to the substrate, transparency, thinning, and economy, the thickness is preferably 1.0 μm or less, more preferably 0.6 μm or less, and even more preferably 0.5 μm or less. The above thickness is the thickness per cured material layer.

[0110] In the packaging material of the present invention, the components contained in the epoxy resin composition constituting the cured product layer and the preferred embodiments thereof are the same as those of the epoxy resin composition according to the first invention.

[0111] The method for curing the epoxy resin composition to form a cured product layer is not particularly limited, and the curing is carried out by a known method at a concentration and temperature sufficient to obtain a cured product of the epoxy resin composition. The curing temperature can be selected, for example, from the range of 10 to 140°C. Details will be described later in the section on the manufacturing method of a packaging material.

[0112] <Packaging material composition> The deodorizing or fragrance-retaining packaging material of the present invention may have a substrate and at least one layer of the cured product of the epoxy resin composition. When the packaging material of the present invention is a packaging film, it preferably has only one substrate and only one cured product layer (two-layer structure). From the viewpoint of adhesion, it is also preferable that the substrate and the cured product layer are adjacent to each other. The packaging bag is preferably made of the packaging film. In this case, either the surface of the substrate or the surface of the cured product layer may serve as the outer layer of the packaging bag. From the viewpoint of producing the packaging bag by heat-sealing the packaging film, it is preferable that the surface of the cured product layer serves as the outer layer.

[0113] A preferred layer structure of the packaging film is shown in FIG. Fig. 10 is a cross-sectional schematic diagram showing an embodiment of a packaging film 500, which is one embodiment of the packaging material of the present invention. The packaging film 500 in Fig. 10 has a configuration in which a cured material layer 502 is provided on one surface of a substrate 501, and the substrate 501 and the cured material layer 502 are adjacent to each other. However, the packaging film, which is one embodiment of the packaging material of the present invention, is not limited to the layer configuration shown in Fig. 10. Furthermore, the packaging material may further have any layer such as a primer layer, an ink layer such as a printed layer, an adhesive layer, a surface protection layer, a vapor deposition layer, or a thermoplastic resin layer (not shown) laminated between the substrate 501 and the cured material layer 502, on the surface of the substrate 501 where the cured material layer 502 is not provided, or on the upper surface of the cured material layer 502 (the surface not adjacent to the substrate 501).

[0114] The thickness of the packaging film is preferably 10 to 300 μm, more preferably 10 to 100 μm, and even more preferably 10 to 50 μm, from the viewpoints of deodorizing properties, aroma retention properties, and strength.

[0115] <Packaging material manufacturing method> The method for producing the packaging material of the present invention is not particularly limited, and known methods can be used. For example, a method for manufacturing the packaging film 500 having the configuration shown in FIG. 10 includes applying the epoxy resin composition to one side of a substrate to a desired thickness, and then curing the epoxy resin composition to form a cured layer. The method for applying the epoxy resin composition is the same as that described above. After the epoxy resin composition is applied, a step of volatilizing the solvent (drying step) is carried out as necessary. The epoxy resin composition used in the packaging material of the present invention contains an unsaturated fatty acid amide having 14 to 24 carbon atoms, which inhibits blocking and improves the drying speed, allowing the drying temperature to be lowered. When a substrate with low heat resistance is used, the drying temperature is preferably 40 to 120°C, more preferably 40 to 100°C, and even more preferably 50 to 90°C. After the drying step, the epoxy resin composition is cured to form a cured layer. The curing temperature can be selected, for example, from a range of 10 to 140° C., preferably from 10 to 100° C., and more preferably from 10 to 80° C. The curing time can be selected, for example, from a range of 0.5 to 200 hours, and preferably from 2 to 100 hours.

[0116] By processing the packaging film by a known method, various packaging containers such as packaging bags, lid materials for packaging containers, sealing materials, etc. can be obtained.

[0117] [Deodorizing or fragrance preserving method] The second invention provides a method for deodorizing or retaining an aroma, which comprises encapsulating an article containing an odorous or fragrant component in a packaging material having a substrate and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. Examples of odor components that can be deodorized by the method according to the second invention include amine-based volatile substances such as ammonia and trimethylamine, sulfur-based volatile substances such as methyl mercaptan, aldehydes, lower fatty acids or their esters, etc. Examples of aroma components that can be maintained include fragrance components such as natural fragrances and synthetic fragrances, such as limonene, geraniol, l-menthol, and derivatives thereof. Examples of items that can be enclosed in the packaging material in the method of the second invention include used disposable diapers, pet litter, dirt, food waste, and other foul-smelling substances; foods with strong odors; aromatic toiletries, cosmetics, stationery, toys, etc.

[0118] According to the method of the second invention, the above-mentioned article is enclosed in a packaging material and then sealed, which makes it difficult for odorous and fragrant components to volatilize outside the packaging material, thereby achieving excellent deodorizing and fragrance retention properties.

[0119] [Third invention: heat-shrinkable label] A heat-shrinkable label according to a third aspect of the present invention (hereinafter also simply referred to as "the label of the present invention") has a heat-shrinkable base layer and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. The heat-shrinkable label of the present invention has an excellent CO2 barrier property due to the presence of a cured layer of an epoxy resin composition containing an amine-based curing agent. Furthermore, since the epoxy resin composition contains an unsaturated fatty acid amide having 14 to 24 carbon atoms, the heat-shrinkable label does not need to have a three-layer structure in which the cured material layer is formed between two heat-shrinkable base layers, but can have a structure having only one heat-shrinkable base layer and one cured material layer. This allows the label to be made thinner, which is also economical. Furthermore, the heat-shrinkable label can be obtained with good adhesion between the heat-shrinkable base layer and the cured material layer, and with excellent followability during heat shrinkage. The reason for this is unclear, but is thought to be as follows.

[0120] When a cured product of an epoxy resin composition is used as an intermediate layer of a label (a layer located between two heat-shrinkable base layers), the epoxy resin composition only needs to have adhesive properties in addition to CO2 barrier properties. On the other hand, when a cured product layer of an epoxy resin composition is used as a surface layer (the innermost or outermost layer), it is important that there is little blocking. When an unsaturated fatty acid amide having 14 to 24 carbon atoms is added to an epoxy resin composition, it is believed to function as a lubricant and contribute to the suppression of blocking. This effect allows the label to have a structure with only one heat-shrinkable base layer and one cured product layer, thereby achieving a thinner label and improved cost efficiency. Furthermore, the unsaturated fatty acid amide is believed to have the effect of alleviating stress generated in the cured product of the epoxy resin. Therefore, it is presumed that the cured product of the epoxy resin composition containing the unsaturated fatty acid amide exhibits good adhesion to the heat-shrinkable substrate layer and excellent conformability during heat shrinkage. The unsaturated fatty acid amide has high compatibility with epoxy resin compositions containing amine-based epoxy resin curing agents, and therefore the transparency of the cured product of the epoxy resin composition is also good.

[0121] Furthermore, in the production of heat-shrinkable labels, it is preferable that the epoxy resin composition that forms the cured product layer has a fast drying rate in order to prevent the label from thermally shrinking during production. It is believed that the inclusion of an unsaturated fatty acid amide having 14 to 24 carbon atoms in the epoxy resin composition improves the drying rate due to the blocking suppression effect. This makes it possible to dry the label at low temperatures, suppressing thermal shrinkage of the label during production and enabling the production of heat-shrinkable labels with high productivity.

[0122] The materials constituting the heat-shrinkable label of the present invention will be described below. <Heat-shrinkable base layer> The substrate used in the heat-shrinkable substrate layer (hereinafter also simply referred to as "substrate layer") is a heat-shrinkable substrate that has the property of shrinking when heated, and is preferably a resin substrate from the viewpoints of heat shrinkability, flex resistance, transparency, and economy. Examples of resins constituting the heat-shrinkable base layer include polyvinyl chloride resin, polystyrene resin, polyolefin resin, polyester resin, polyamide resin, polyamideimide resin, etc. Among these, from the viewpoints of heat shrinkability, flex resistance, transparency, and economy, a resin selected from the group consisting of polyvinyl chloride resin, polystyrene resin, polyolefin resin, and polyester resin is preferred, a resin selected from the group consisting of polyvinyl chloride resin, polyolefin resin, and polyester resin is more preferred, and a polyvinyl chloride resin is even more preferred.

[0123] From the viewpoint of imparting heat shrinkability, the heat-shrinkable substrate is preferably stretched uniaxially or biaxially. As the stretching method, a conventional uniaxial stretching method, simultaneous biaxial stretching method, or sequential biaxial stretching method can be used. The stretching temperature and stretch ratio of the heat-shrinkable substrate are not particularly limited, but from the viewpoint of obtaining sufficient heat shrinkability in the resulting label and preventing breakage of the substrate during stretching, the stretching temperature is preferably 90 to 160°C, and the stretch ratio, expressed as the product of the stretch ratios in the MD direction and the TD direction, is preferably 1.5 to 25 times, more preferably 2 to 20 times (in the case of uniaxial stretching, the stretch ratio in the non-stretched direction is taken as 1 time). In order to impart sufficient heat shrinkability, it is preferable not to perform heat setting after the stretching.

[0124] The heat shrinkage rate of the heat-shrinkable substrate is preferably 1.0% or more, more preferably 2.0% or more, at least under the conditions for heat-shrinking the label, from the viewpoint of thermally shrinking the label to adhere it to the surface of the object to be adhered and enhancing the CO2 barrier property. For example, in the case of a heat-shrinkable label for PET bottles, the conditions for heat-shrinking the label refer to the heating temperature and heating time when shrink-packaging the PET bottle with the label. Furthermore, the heat shrinkage rate of the heat-shrinkable substrate after heating at 150°C for 30 seconds is preferably 1.0 to 80%, more preferably 1.0 to 50%, even more preferably 2.0 to 20%, and even more preferably 2.0 to 10%. A heat shrinkage rate of 1.0% or more ensures the heat shrinkability required for adhering the resulting label to the surface of the object to be adhered, while a heat shrinkage rate of 80% or less ensures good conformability during heat shrinkage of the cured product layer and the ink layer formed on the label. The heat shrinkage rate of the heat-shrinkable substrate is the area shrinkage rate (%) after the substrate is heated at 150° C. for 30 seconds, and can be determined specifically by the method described in the examples.

[0125] The thickness of the heat-shrinkable base layer is not particularly limited as long as it is within a range that allows heat shrinkage, but from the viewpoints of CO2 barrier properties, heat shrinkability, and label strength, it is preferably 10 to 300 μm, more preferably 15 to 100 μm, even more preferably 15 to 80 μm, and still more preferably 15 to 50 μm.

[0126] <Cured material layer> The cured material layer is a layer made of a cured material of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms. From the viewpoints of CO2 barrier properties and flex resistance, the thickness of the cured material layer is preferably 0.02 μm or more, more preferably 0.05 μm or more, even more preferably 0.08 μm or more, and even more preferably 0.1 μm or more. From the viewpoints of conformability during heat shrinkage, adhesion to the heat-shrinkable base layer, transparency, thinning, and economy, the thickness is preferably 1.0 μm or less, more preferably 0.6 μm or less, and even more preferably 0.5 μm or less. The above thickness is the thickness per cured material layer.

[0127] In the heat-shrinkable label of the present invention, the components contained in the epoxy resin composition constituting the cured product layer and the preferred embodiments thereof are the same as those of the epoxy resin composition of the first invention.

[0128] <Heat-shrinkable label composition> The label of the present invention may have a heat-shrinkable base layer and at least one layer of the cured product of the epoxy resin composition. From the viewpoint of heat shrinkability and thinning of the label, the label of the present invention preferably has only one layer of the heat-shrinkable base layer and one layer of the cured product layer. Furthermore, from the viewpoint of adhesion between the heat-shrinkable base layer and the cured product layer, it is preferable that the heat-shrinkable base layer and the cured product layer are adjacent to each other.

[0129] A preferred layer structure of the heat-shrinkable label is, for example, the structure shown in FIG. Fig. 11 is a cross-sectional view showing one embodiment of a heat-shrinkable label 600 of the present invention. The heat-shrinkable label 600 in Fig. 11 has a configuration in which a cured material layer 602 is provided on one surface of a heat-shrinkable base material layer 601, and the heat-shrinkable base material layer 601 and the cured material layer 602 are adjacent to each other. The surface of the heat-shrinkable label 600 that comes into contact with the object to be attached may be the surface on the heat-shrinkable base layer 601 side or the surface on the cured material layer 602 side.

[0130] The heat-shrinkable label 600 preferably further has an ink layer (not shown) such as a printed layer. The ink layer is a layer composed of an ink containing a colorant such as a pigment and a binder resin, and can be provided on the surface of the heat-shrinkable label 600 on the side of the heat-shrinkable base material layer 601, on the side of the cured material layer 602, or between the heat-shrinkable base material layer 601 and the cured material layer 602 in FIG. That is, when the heat-shrinkable label of the present invention has an ink layer, the layer structure may be any of heat-shrinkable substrate layer / cured layer / ink layer, ink layer / heat-shrinkable substrate layer / cured layer, or heat-shrinkable substrate layer / ink layer / cured layer. Of these, the layer structures of heat-shrinkable substrate layer / cured layer / ink layer or ink layer / heat-shrinkable substrate layer / cured layer are preferred. In the above layer structure, the surface of the heat-shrinkable label 100 that comes into contact with the object to be attached may be any surface, and may be the ink layer surface.

[0131] The ink layer does not need to be formed on the entire surface of the heat-shrinkable label, but may be formed on at least a portion of the label. From the viewpoint of providing a display function as a label, the ink layer is preferably provided with letters, a logo, a pattern, or the like, and is preferably formed by a known printing method. Examples of such printing methods include gravure printing, flexographic printing, and screen printing, with gravure printing being preferred from the viewpoint of productivity.

[0132] However, the heat-shrinkable label of the present invention is not limited to the layer configuration shown in Fig. 11. Furthermore, the label may further have any layer (not shown), such as a primer layer, an adhesive layer, a surface protection layer, or a vapor deposition layer, laminated between the heat-shrinkable base layer 601 and the cured material layer 602, on the surface of the heat-shrinkable base layer 1 on which the cured material layer 2 is not provided, or on the upper surface of the cured material layer 602 (the surface not adjacent to the heat-shrinkable base layer 601). However, as described above, it is preferable that the heat-shrinkable base layer 601 and the cured material layer 602 are adjacent to each other, and it is preferable that no primer layer or anchor coat layer is present between the heat-shrinkable base layer 601 and the cured material layer 602.

[0133] The thickness of the heat-shrinkable label is not particularly limited as long as it is heat-shrinkable, but from the viewpoints of CO2 barrier properties, heat shrinkability, and label strength, it is preferably 20 to 300 μm, more preferably 20 to 120 μm, even more preferably 20 to 100 μm, and still more preferably 20 to 60 μm.

[0134] <Heat-shrinkable label format> The heat-shrinkable label of the present invention is preferably a label that is attached to the outer surface of an object to be prevented from permeating CO2. The object is preferably a container, and the container is preferably a bottle. Typical examples of objects to which the label is attached include PET bottles for carbonated water and carbonated drinks. Specific forms of the heat-shrinkable label of the present invention include a tubular heat-shrinkable label in which both ends of a long label are sealed to form a cylindrical shape and attached to the outer surface of a container; a wrap-around heat-shrinkable label in which one end of a long label is attached to a container, the label is rolled up, and then the other end is overlapped on the other end to form a cylindrical shape; etc. Among the above, from the viewpoint of use with PET bottles, the label of the present invention is preferably a tubular heat-shrinkable label. A cylindrical heat-shrinkable label can be obtained, for example, by overlapping both ends of a long heat-shrinkable label to form a cylindrical shape, preferably with the heat-shrinkable direction being the circumferential direction, and then sealing the overlapped parts with a solvent or adhesive.

[0135] <Characteristics of heat-shrinkable labels> The heat shrinkage percentage of the heat-shrinkable label of the present invention after heating for 30 seconds at 150° C. is preferably 1.0 to 80%, more preferably 1.0 to 50%, even more preferably 2.0 to 20%, and even more preferably 2.0 to 10%. If the heat shrinkage percentage is 1.0% or more, the heat shrinkability required for closely adhering the resulting label to the surface of an object to be adhered is obtained, and if it is 80% or less, the cured product layer and the ink layer formed on the label will have good conformability during heat shrinkage. The heat shrinkage rate of the heat shrinkable label can be determined in the same manner as the heat shrinkage rate of the heat shrinkable substrate.

[0136] [Method of manufacturing heat-shrinkable labels] Although the method for producing the heat-shrinkable label of the present invention is not particularly limited, it is preferably produced by a production method having the following steps (I) and (II) in order. By using this production method, heat shrinkage of the label during production can be suppressed, and heat-shrinkable labels can be produced with high productivity. Step (I): A step of applying an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a solvent to at least one surface of a heat-shrinkable substrate to form a coating layer. Step (II): A step of heating and drying the coating layer at a temperature of less than 100°C to remove the solvent.

[0137] <Process (I)> In step (I), an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a solvent is applied to at least one surface of a heat-shrinkable substrate to form a coating layer. The heat-shrinkable substrate and the epoxy resin composition, as well as the preferred embodiments thereof, are the same as those described above. For example, in the production of a heat-shrinkable label 600 having the configuration shown in Fig. 11, the epoxy resin composition is applied to one side of a heat-shrinkable substrate to a desired thickness. Examples of coating methods for applying the epoxy resin composition include bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, microreverse gravure coating, die coating, slot die coating, vacuum die coating, dip coating, spin coating, roll coating, spray coating, and brush coating. Among these, bar coating, roll coating, and spray coating are preferred, and industrially, gravure coating, reverse gravure coating, microgravure coating, and microreverse gravure coating are preferred.

[0138] <Process (II)> In step (II), the coating layer formed in step (I) is heated and dried at a temperature of less than 100°C to remove the solvent. The epoxy resin composition used to form the coating layer has a fast drying rate due to the inclusion of an unsaturated fatty acid amide having 14 to 24 carbon atoms. This facilitates drying at a relatively low temperature, and prevents the label from thermally shrinking during production.

[0139] To prevent the label from thermally shrinking during production, the heat drying temperature in step (II) is preferably 40 to 90° C., more preferably 50 to 80° C., and even more preferably 50 to 70° C. The heat drying time is preferably 5 to 180 seconds, more preferably 10 to 120 seconds, and even more preferably 10 to 60 seconds.

[0140] After the heat drying, the epoxy resin composition is cured to form a cured layer. The curing temperature can be selected, for example, from 10 to 100° C., preferably from 10 to 80° C., and more preferably from 10 to 50° C. The curing time can be selected, for example, from 0.5 to 200 hours, and preferably from 2 to 100 hours.

[0141] When the heat-shrinkable label has the ink layer, a step of forming the ink layer can be carried out between steps (I) and (II) or after step (II). The ink layer can be formed by a known printing method such as gravure printing, flexographic printing, or screen printing.

[0142] After the above steps are carried out, the resulting label is molded into a desired shape to obtain a heat-shrinkable label in the shape of a long sheet, a cylindrical sheet, or the like.

[0143] [Heat-shrink labels, bottles] The present invention provides a heat-shrinkable label obtained by heat-shrinking the heat-shrinkable label, and a bottle having the heat-shrinkable label. The bottle having the heat-shrinkable label is preferably a PET bottle. The heat-shrinkable label may cover at least a part of the outer surface of the bottle, and preferably covers the outer peripheral side surface of the bottle.

[0144] A method for manufacturing a bottle having a heat-shrinkable label includes, for example, attaching a cylindrical heat-shrinkable label to the outer side surface of the bottle, or wrapping a long heat-shrinkable label around the bottle, and then heat-shrinking the label. The heat-shrinkable label can be heat-shrunk by a known method using a hot air dryer, a heater, steam, hot water, etc. Examples include a method in which the heat-shrinkable label is attached to an object to be attached, such as a bottle, and then the label is transported through a heated atmosphere using a hot air dryer, heater, steam, etc.; a method in which the label is immersed in hot water; etc. The heat shrinkage conditions for the heat-shrinkable label can be appropriately selected depending on the type of heat-shrinkable substrate, etc., but from the viewpoints of heat shrinkability and productivity, the heating temperature is preferably 70° C. or higher, more preferably 80° C. or higher, and even more preferably 85° C. or higher. Furthermore, from the viewpoint of suppressing thermal deterioration of the bottle and its contents, the heating temperature is preferably less than 100° C., more preferably 95° C. or lower. The heating time is preferably 0.5 to 120 seconds, more preferably 2 to 60 seconds, and even more preferably 3 to 20 seconds, from the viewpoint of suppressing thermal deterioration of the bottle and its contents and from the viewpoint of productivity.

[0145] [CO2 permeation prevention method] The present invention provides a method for preventing CO2 permeation using the heat-shrinkable label or the heat-shrinkable label. The object to which the label is to be attached, which is to prevent CO2 permeation, is preferably a container, preferably a bottle, and more preferably a PET bottle. Suitable embodiments of the CO2 permeation prevention method of the present invention include (1) a method of covering at least a portion of the outer surface of a container to be prevented from permeating with a heat-shrinkable label, and then sealing the container with a content containing CO2, or (2) a method of sealing at least a portion of the outer surface of a container to be prevented from permeating with CO2, and then sealing the container with a content containing CO2, and then covering at least a portion of the outer surface of the container with a heat-shrinkable label, etc. These methods can prevent CO2 from inside the container from permeating to the outside.

[0146] The heat-shrinkable label may cover at least a portion of the outer surface of the container, and preferably covers the outer peripheral side surface of the container. The method for covering at least a portion of the outer surface of the container with the heat-shrinkable label may be the same as the method described above for the heat-shrinkable label and bottle. Examples of contents containing CO2 include carbonated water and other carbonated drinks.

[0147] According to the CO2 permeation prevention method of the present invention, it is possible to effectively prevent CO2 sealed inside a container or other object to which a label is to be attached from permeating to the outside. [Example]

[0148] The present invention will now be described in detail with reference to examples, although the present invention is not limited to these examples in any way.

[0149] [First Invention (1): Production and Evaluation of Epoxy Resin Composition and Gas Barrier Laminate] In the present examples, measurements and evaluations were carried out by the following methods.

[0150] <Thickness of cured resin layer> The measurement was carried out using a multilayer film thickness measuring device ("DC-8200" manufactured by Gunze Co., Ltd.).

[0151] <haze> Measurements were carried out in accordance with JIS K7136:2000 using a color and turbidity simultaneous measuring instrument ("COH400" manufactured by Nippon Denshoku Industries Co., Ltd.).

[0152] <Total light transmittance> Measurements were carried out in accordance with JIS K7361-1:1997 using a color and turbidity simultaneous measuring instrument ("COH400" manufactured by Nippon Denshoku Industries Co., Ltd.).

[0153] <yi> Measurements were carried out in accordance with JIS K7373:2006 using a color and turbidity simultaneous measuring device ("COH400" manufactured by Nippon Denshoku Industries Co., Ltd.).

[0154] <Blocking> According to the method described in each example, an epoxy resin composition was applied to the alumina-vaporized surface of a 210 mm × 297 mm alumina-vaporized PET sheet ("Barrierox 1011HG (uncoated)" manufactured by Toray Advanced Film Co., Ltd., thickness: 12 μm) and dried to form a resin composition layer, which was then placed on a horizontal surface. A separately prepared 210 mm × 297 mm alumina-vaporized PET sheet was then laminated to the resin composition layer surface, with the PET side facing the resin composition layer. A 15 kg A4-sized weight was placed on top of the sheet, and the sheet was heated at 40°C for 2 days under this load to perform aging. After aging, the weight was removed, and the subsequently laminated alumina-vaporized PET sheet was manually peeled off from the cured resin layer surface. The state of blocking was evaluated according to the following criteria. A: No blocking occurs and alumina-coated PET can be easily peeled off. B: Blocking has occurred, and although the alumina-deposited PET can be peeled off, an increase in haze is observed in the gas barrier laminate after peeling. C: Blocking has occurred and the alumina-coated PET cannot be peeled off.

[0155] <Peel strength of laminate (normal state)> The laminate (II) or laminate (III) obtained in each example was subjected to a T-peel test at a peel rate of 300 mm / min according to the method specified in JIS K6854-3:1999, and the peel strength (g / 15 mm) was measured.

[0156] <Peel strength of laminate (after retort treatment)> The laminate (II) or laminate (III) obtained in each example was retorted at 121°C for 30 minutes or 130°C for 30 minutes using an autoclave for retort food ("SR-240" manufactured by Tomy Seiko Co., Ltd.), and then subjected to a T-peel test at a peel rate of 300 mm / min according to the method specified in JIS K6854-3:1999 to measure the peel strength (g / 15 mm). A higher peel strength value indicates better retort resistance. In the table, samples in which delamination occurred during the test are marked "peeled."

[0157] <Oxygen permeability (cc / (m 2 ·day·atm))> The oxygen permeability of the alumina-deposited PET used in each example and the gas barrier laminate obtained in each example was measured using an oxygen permeability measuring device (Modern Controls, "OX-TRAN2 / 21") under conditions of 23°C and a relative humidity of 60%.

[0158] <Water vapor permeability (g / (m 2 ·day))> The water vapor transmission rate of the gas barrier laminate obtained in each example was measured under conditions of 40° C. and a relative humidity of 90% using a water vapor transmission rate measuring device ("PERMATRAN-W 1 / 50" manufactured by MOCON).

[0159] Production Example 1 (Preparation of Epoxy Resin Curing Agent Solution A) A reaction vessel was charged with 1 mol of metaxylylenediamine (MXDA). The temperature was raised to 60°C under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. The temperature was raised to 165°C while distilling off the resulting methanol, and the temperature was maintained at 165°C for 2.5 hours to obtain an amine-based curing agent. Methanol was then added dropwise over 1.5 hours, and the silane coupling agent 3-aminopropyltriethoxysilane ("KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd.) was then added to obtain an epoxy resin curing agent solution A containing 62.2% by mass of the amine-based curing agent, 2.8% by mass of 3-aminopropyltriethoxysilane, and 35% by mass of methanol.

[0160] Production Example 2 (Preparation of Epoxy Resin Curing Agent Solution B) A reaction vessel was charged with 1 mol of metaxylylenediamine (MXDA). The temperature was raised to 60°C under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. The temperature was raised to 165°C while distilling off the resulting methanol, and the temperature was maintained at 165°C for 2.5 hours to obtain an amine-based curing agent. Methanol was then added dropwise over 1.5 hours to obtain an epoxy resin curing agent solution B containing 65.0% by mass of the amine-based curing agent and 35% by mass of methanol.

[0161] Example 1-1 (Preparation of Epoxy Resin Composition 1-1) 421.2 g of methanol as a dilution solvent, 433.8 g of ethyl acetate, and 7.7 g of a dispersion of organically coated plate-like alumina particles (Kawaken Fine Chemicals Co., Ltd.'s "KOS-A2EOK5-10," an ethanol dispersion with a solids concentration of 10% by mass and an average primary particle diameter of 20 nm for the alumina particles) were added and stirred thoroughly. Next, 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 was added and stirred. 5 g of an epoxy resin having glycidylamino groups derived from metaxylylenediamine (Mitsubishi Gas Chemical Company, Inc.'s "TETRAD-X") (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 1.2) and 1.54 g of erucamide (NOF Corporation's "Alflo P-10") were added and stirred to prepare Epoxy Resin Composition 1-1. The amount of erucamide blended was 10 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin in the epoxy resin composition 1-1 and the nonvolatile content in the epoxy resin curing agent solution A.

[0162] Example 1-2 (Preparation of Epoxy Resin Composition 1-2) An epoxy resin composition 1-2 was prepared in the same manner as in Example 1-1, except that the amounts of methanol and ethyl acetate used as dilution solvents were changed to 67.2 g and 79.7 g, respectively.

[0163] Example 2-1 (Preparation of Epoxy Resin Composition 2-1) An epoxy resin composition 2-1 was prepared in the same manner as in Example 1-1, except that 1.54 g of oleic acid amide ("Alflo E-10" manufactured by NOF Corporation) was used instead of erucic acid amide in Example 1-1.

[0164] Example 2-2 (Preparation of Epoxy Resin Composition 2-2) An epoxy resin composition 2-2 was prepared in the same manner as in Example 1-2, except that 1.54 g of oleic acid amide ("Alflo E-10" manufactured by NOF Corporation) was used instead of erucic acid amide in Example 1-2.

[0165] Example 3 (Preparation of Epoxy Resin Composition 3) Epoxy resin composition 3 was prepared in the same manner as in Example 1-1, except that the amounts of methanol, ethyl acetate, and erucamide were changed to 402.2 g, 414.8 g, and 0.77 g, respectively.

[0166] Example 4 (Preparation of Epoxy Resin Composition 4) 382.7 g of methanol as a dilution solvent, 388.3 g of ethyl acetate, and 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 were added and stirred. To this solution, 5 g of an epoxy resin having a glycidylamino group derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Company, Inc.) (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin=1.2) and 0.462 g of erucic acid amide were added and stirred to prepare epoxy resin composition 4.

[0167] Example 5-1 (Preparation of Epoxy Resin Composition 5-1) An epoxy resin composition 5-1 was prepared in the same manner as in Example 4, except that the amounts of methanol, ethyl acetate, and erucamide were changed to 395.8 g, 390.2 g, and 0.77 g, respectively.

[0168] Example 5-2 (Preparation of Epoxy Resin Composition 5-2) An epoxy resin composition 5-2 was prepared in the same manner as in Example 5-1, except that the amount of methanol added was changed to 121.0 g and the amount of ethyl acetate added was changed to 126.6 g.

[0169] Example 5-3 (Preparation of Epoxy Resin Composition 5-3) An epoxy resin composition 5-3 was prepared in the same manner as in Example 5-1, except that the amount of methanol added was changed to 67.2 g and the amount of ethyl acetate added was changed to 72.8 g.

[0170] Example 6 (Preparation of Epoxy Resin Composition 6) Epoxy resin composition 6 was prepared in the same manner as in Example 4, except that the amounts of methanol, ethyl acetate, and erucamide were changed to 403.3 g, 397.7 g, and 1.078 g, respectively.

[0171] Example 7 (Preparation of Epoxy Resin Composition 7) Epoxy resin composition 7 was prepared in the same manner as in Example 4, except that the amounts of methanol, ethyl acetate, and erucamide were changed to 414.8 g, 409.2 g, and 1.54 g, respectively.

[0172] Example 8 (Preparation of Epoxy Resin Composition 8) Epoxy resin composition 8 was prepared in the same manner as in Example 4, except that 0.462 g of oleic acid amide was used instead of erucic acid amide.

[0173] Example 9 (Preparation of Epoxy Resin Composition 9) Epoxy resin composition 9 was prepared in the same manner as in Example 5-1, except that 0.77 g of oleic acid amide was used instead of erucic acid amide.

[0174] Example 10 (Preparation of Epoxy Resin Composition 10) An epoxy resin composition 10 was prepared in the same manner as in Example 6, except that oleic acid amide was used instead of erucic acid amide.

[0175] Example 11 (Preparation of Epoxy Resin Composition 11) An epoxy resin composition 11 was prepared in the same manner as in Example 7, except that 1.078 g of oleic acid amide was used instead of erucic acid amide.

[0176] Example 12 (Preparation of Epoxy Resin Composition 12) 349.1 g of methanol as a dilution solvent, 337.9 g of ethyl acetate, and 6.2 g of a dispersion of organically coated plate-like alumina particles (Kawaken Fine Chemicals Co., Ltd.'s "KOS-A2EOK5-10," an ethanol dispersion, solids concentration: 10% by mass) were added and stirred thoroughly. Next, 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 was added and stirred. 2 g of an epoxy resin having glycidylamino groups derived from metaxylylenediamine (Mitsubishi Gas Chemical Co., Inc.'s "TETRAD-X") (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 3.0) and 1.24 g of erucic acid amide were added and stirred to prepare Epoxy Resin Composition 12.

[0177] Example 13 (Preparation of Epoxy Resin Composition 13) 326.4 g of methanol as a dilution solvent, 315.6 g of ethyl acetate, and 5.8 g of a dispersion of organically coated plate-like alumina particles (KOS-A2EOK5-10, manufactured by Kawaken Fine Chemicals Co., Ltd.) were added and stirred thoroughly. Next, 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 was added and stirred. 1.2 g of an epoxy resin having glycidylamino groups derived from metaxylylenediamine (TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Inc.) (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 5.0) and 1.16 g of erucic acid amide were added and stirred to prepare Epoxy Resin Composition 13.

[0178] Example 14-1 (Preparation of Epoxy Resin Composition 14-1) 318.8 g of methanol as a dilution solvent, 313.2 g of ethyl acetate, and 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 were added and stirred. To this solution, 2 g of an epoxy resin having a glycidylamino group derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Company, Inc.) (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin=3.0) and 0.62 g of erucic acid amide were added and stirred to prepare epoxy resin composition 14-1.

[0179] Example 14-2 (Preparation of Epoxy Resin Composition 14-2) An epoxy resin composition 14-2 was prepared in the same manner as in Example 14-1, except that the amount of methanol added was changed to 118.0 g and the amount of ethyl acetate added was changed to 123.6 g.

[0180] Example 14-3 (Preparation of Epoxy Resin Composition 14-3) An epoxy resin composition 14-3 was prepared in the same manner as in Example 14-1, except that the amount of methanol used was changed to 52.9 g and the amount of ethyl acetate used was changed to 58.5 g.

[0181] Example 15 (Preparation of Epoxy Resin Composition 15) 298.3 g of methanol as a dilution solvent, 292.7 g of ethyl acetate, and 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 were added and stirred. To this solution, 1.2 g of an epoxy resin having a glycidylamino group derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Company, Inc.) (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin=5.0) and 0.58 g of erucic acid amide were added and stirred to prepare Epoxy Resin Composition 15.

[0182] Example 16 (Preparation of Epoxy Resin Composition 16) An epoxy resin composition 16 was prepared in the same manner as in Example 5-1, except that 16 g of epoxy resin curing agent B was used instead of epoxy resin curing agent A in Example 5-1.

[0183] Comparative Example 1-1 (Preparation of Comparative Epoxy Resin Composition 1-1) Comparative epoxy resin composition 1-1 was prepared in the same manner as in Example 1-1, except that 1.54 g of stearic acid amide was used instead of erucic acid amide.

[0184] Comparative Example 1-2 (Preparation of Comparative Epoxy Resin Composition 1-2) Comparative epoxy resin composition 1-2 was prepared in the same manner as in Example 1-2, except that 1.54 g of stearic acid amide was used instead of erucic acid amide.

[0185] Comparative Example 2-1 (Preparation of Comparative Epoxy Resin Composition 2-1) Comparative epoxy resin composition 2-1 was prepared in the same manner as in Example 1-1, except that the amount of methanol added was changed to 383.5 g, the amount of ethyl acetate added was changed to 396.0 g, and erucamide was not added.

[0186] Comparative Example 2-2 (Preparation of Comparative Epoxy Resin Composition 2-2) Comparative epoxy resin composition 2-2 was prepared in the same manner as in Example 1-2, except that the amount of methanol used was changed to 62.5 g, the amount of ethyl acetate used was changed to 69.7 g, and erucamide was not used.

[0187] Comparative Example 3 (Preparation of Comparative Epoxy Resin Composition 3) Comparative epoxy resin composition 3 was prepared in the same manner as in Example 4, except that the amount of methanol added was changed to 371.7 g, the amount of ethyl acetate added was changed to 377.3 g, and erucamide was not added. The amounts in the table are all amounts (parts by mass) of active ingredients.

[0188] [Table 1]

[0189] Example 17 (Preparation and Evaluation of Gas Barrier Laminate (I)) The epoxy resin composition 1-2 obtained in Example 1-2 was applied to an alumina-deposited PET film ("Barrierox 1011HG (uncoated)" manufactured by Toray Advanced Film Co., Ltd., thickness: 12 μm, oxygen permeability: 2.2 cc / (m 2 The epoxy resin composition was applied to an alumina-deposited surface of a PET film (2000 psi, 1 ... (Preparation and Evaluation of Gas Barrier Laminate (II)) A urethane adhesive was applied to the resin cured layer side of the resulting gas barrier laminate (I) using a No. 12 bar coater and dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: approximately 3 μm). The urethane adhesive was prepared by adding 1.05 g of CAT-RT85 curing agent and 25 g of ethyl acetate solvent to 15 g of AD-502 base, and stirring thoroughly. A 50 μm thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was laminated onto the adhesive using nip rolls and heated at 40°C for 2 days to obtain the gas barrier laminate (II) shown in Figure 4. Using this gas barrier laminate (II), the oxygen permeability was measured by the above-mentioned method, and a peel test was carried out in the normal state and after retort treatment. The results are shown in Table 2.

[0190] Example 18, Comparative Examples 4-5 A gas barrier laminate was produced and evaluated in the same manner as in Example 17, except that the epoxy resin composition shown in Table 2 was used instead of Epoxy Resin Composition 1-2. The results are shown in Table 2.

[0191] Table 2 shows the haze and total light transmittance of alumina-deposited PET alone as "Reference Example 1," and the oxygen transmittance of a laminate in which alumina-deposited PET and a polypropylene film were bonded together with an adhesive layer without forming a resin-cured layer as "Reference Example 2."

[0192] [Table 2]

[0193] Table 2 confirms the differences in effect depending on the type of fatty acid amide. The gas barrier laminates (II) of Examples 17 and 18, which used the epoxy resin composition of the present invention, had higher peel strengths in the normal state and after retort treatment than the laminates of Comparative Example 4, which used stearic acid amide, a saturated fatty acid amide having 18 carbon atoms, instead of the unsaturated fatty acid amide, and Comparative Example 5, which used an epoxy resin composition without any fatty acid amide added; that is, they had better adhesion and retort resistance. Furthermore, the gas barrier laminates (I) had low haze and high total light transmittance, and thus had good transparency. Comparing Examples 17 and 18, Example 17, which used erucic acid amide as the unsaturated fatty acid amide, is superior to Example 18, which used oleic acid amide, in that the peel strength of the resulting gas barrier laminate (II) is higher and the blocking suppression effect of the gas barrier laminate (I) is also higher. In contrast, in Comparative Example 4, in which stearic acid amide was used as the fatty acid amide, the normal peel strength of the gas barrier laminate (II) was the same as that of Comparative Example 5, in which no fatty acid amide was added, and the adhesiveness was not improved. Furthermore, the retort resistance of the gas barrier laminate (II) was also lower than that of Examples 17 and 18, and the haze of the gas barrier laminate (I) increased and the transparency was also poor.

[0194] Examples 19 to 29 (Preparation and Evaluation of Gas Barrier Laminates (I) and (II)) Gas barrier laminates were produced and evaluated in the same manner as in Example 17, except that the epoxy resin compositions shown in Table 3 were used and the thickness of the cured resin layer formed was changed to that shown in Table 3. The results are shown in Table 3.

[0195] [Table 3]

[0196] Table 3 confirms the difference in effect depending on the type and amount of unsaturated fatty acid amide. Comparing Examples 19 to 22 with Examples 23 to 26, when oleic acid amide was used as the unsaturated fatty acid amide, no improvement in blocking of the gas barrier laminate (I) was observed even when the amount was changed from 3 to 10 parts by mass per 100 parts by mass of the total amount of epoxy resin and curing agent (Examples 23 to 26). In contrast, when erucic acid amide was used, a good blocking suppression effect was observed when the amount was 5 parts by mass or more (Examples 19 to 22). The results of Examples 19 to 22 show that the retort resistance of the gas barrier laminate (II) was equivalent even when the amount of erucamide was varied from 3 to 10 parts by mass per 100 parts by mass of the total amount of epoxy resin and curing agent. The results of Examples 20 and 27 show that the transparency and blocking-inhibiting effect of the gas barrier laminate (I) and the adhesion and retort resistance of the gas barrier laminate (II) were good, regardless of whether a silane coupling agent was added. Furthermore, the results of Examples 28 and 29 show that even when platelet-like alumina particles were further blended into the epoxy resin compositions of Examples 20 and 22, the transparency and blocking-inhibiting effect of the resulting gas barrier laminate (I) and the adhesion and retort resistance of the gas barrier laminate (II) were good.

[0197] Example 30 (Preparation and Evaluation of Gas Barrier Laminate (III)) The epoxy resin composition 1-1 obtained in Example 1-1 was applied to the alumina-deposited surface of an alumina-deposited PET film ("Barrierox 1011HG (uncoated)" manufactured by Toray Advanced Film Co., Ltd.) using a bar coater No. 3. The epoxy resin composition was dried by heating at 120°C for 60 seconds (thickness after drying: approximately 0.1 μm), and then cured by heating at 40°C for two days to produce a gas barrier laminate (I) having the configuration shown in FIG. A urethane adhesive was applied to the surface of the cured resin layer using a No. 12 bar coater and dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: approximately 3 μm). The urethane adhesive was prepared by adding 1.05 g of CAT-RT85 curing agent and 25 g of ethyl acetate solvent to 15 g of AD-502 base material and stirring thoroughly. A 15 μm-thick nylon film ("Harden Film N1202" manufactured by Toyobo Co., Ltd.) was then bonded to the surface using nip rolls. An adhesive layer was formed on the nylon film in the same manner as above (thickness after drying: approximately 3 μm), and a 50 μm-thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was then bonded to the surface using nip rolls and heated at 40°C for 2 days to obtain the gas barrier laminate (III) shown in Figure 7. The gas barrier laminate (III) was subjected to peel tests in the normal state and after retort treatment by the method described above. The results are shown in Table 4.

[0198] Examples 31 to 38, Comparative Examples 6 to 7 A gas barrier laminate (III) was produced and evaluated in the same manner as in Example 30, except that the epoxy resin composition shown in Table 4 was used instead of epoxy resin composition 1-1 and the thickness of the cured resin layer was changed to that shown in Table 4. The results are shown in Table 4.

[0199] [Table 4]

[0200] From Table 4, the following can be seen: Gas barrier laminates using the epoxy resin composition of the present invention had good adhesion and retort resistance even when configured as gas barrier laminate (III) shown in Figure 7. For some examples, a peel test was carried out after retorting under high retort conditions of 130°C for 30 minutes as well as 121°C for 30 minutes, and no delamination occurred, confirming good retort resistance. Comparisons of Examples 30 to 32 and Examples 33, 37, and 38 showed that adhesion and retort resistance were better when the ratio of the number of active amine hydrogens in the curing agent to the number of epoxy groups in the epoxy resin in the epoxy resin composition was in the range of 1.2 to 3.0. Furthermore, comparisons of Examples 33, 35, and 36 showed that the thinner the cured resin layer, the better the retort resistance. The results of Examples 33 and 34 show that the gas barrier laminate using the epoxy resin composition of the present invention had good adhesion and retort resistance, regardless of whether a silane coupling agent was added or not, even when it had the configuration of gas barrier laminate (III) shown in Figure 7.

[0201] Example 39 (Preparation and Evaluation of Gas Barrier Laminate (III)) A gas barrier laminate (III) was produced in the same manner as in Example 30, except that epoxy resin composition 5-1 obtained in Example 5-1 was used, and silica-deposited PET ("Techbarrier L" manufactured by Mitsubishi Plastics, Inc., thickness: 12 μm) in which silicon oxide (silica) was deposited on one side of PET was used instead of alumina-deposited PET. Peel tests were carried out in the normal state and after retort treatment using the same method. The results are shown in Table 5.

[0202] Examples 40 to 44, Comparative Example 8 A gas barrier laminate (III) was produced and evaluated in the same manner as in Example 39, except that the epoxy resin composition shown in Table 5 was used and the thickness of the cured resin layer was changed to that shown in Table 5. The results are shown in Table 5.

[0203] [Table 5]

[0204] Table 5 shows that the gas barrier laminate (III) using the epoxy resin composition of the present invention and silica-deposited PET also provides good retort resistance, similar to the case of using alumina-deposited PET.

[0205] Example 45 (Preparation and Evaluation of Gas Barrier Laminate (II)) The epoxy resin composition 5-1 obtained in Example 5-1 was applied to the aluminum-deposited surface of biaxially oriented polypropylene (OPP) ("MLOP102" manufactured by Mitsui Chemicals Tohcello, Inc., thickness: 25 μm), in which aluminum was vapor-deposited on one side, using a bar coater No. 3. The epoxy resin composition was dried by heating at 100°C for 30 seconds (thickness after drying: approximately 0.1 μm), and further cured by heating at 40°C for 2 days to produce a gas barrier laminate (I) having the configuration shown in FIG. A urethane adhesive was applied to the resin cured layer side of the resulting gas barrier laminate (I) using a No. 12 bar coater and dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: approximately 3 μm). The urethane adhesive was prepared by adding 1.05 g of CAT-RT85 curing agent and 25 g of ethyl acetate solvent to 15 g of AD-502 base, and stirring thoroughly. A 50 μm thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was laminated onto the adhesive using nip rolls and heated at 40°C for 2 days to obtain the gas barrier laminate (II) shown in Figure 4. The gas barrier laminate (II) was subjected to a peel test under normal conditions using the method described above. The results are shown in Table 6.

[0206] Example 46 A gas barrier laminate (II) was produced in the same manner as in Example 45, except that the thickness of the cured resin layer formed in Example 45 was changed to that shown in Table 6, and a peel test under normal conditions was carried out in the same manner as in Example 45. The results are shown in Table 6.

[0207] Example 47 A gas barrier laminate (II) was produced in the same manner as in Example 45, except that aluminum-vapor-deposited PET ("MLPET" manufactured by Mitsui Chemicals Tohcello, Inc., thickness: 12 μm) in which aluminum was vapor-deposited on one side of PET was used instead of the aluminum-vapor-deposited OPP in Example 45. A peel test under normal conditions was carried out in the same manner as in Example 45. The results are shown in Table 6.

[0208] Comparative Example 9 A gas barrier laminate was produced in the same manner as in Example 45, except that the cured resin layer was not formed, and a peel test under normal conditions was carried out using the same method as in Example 45. The results are shown in Table 6.

[0209] [Table 6]

[0210] Table 6 shows that the cured product of the epoxy resin composition of the present invention exhibits good adhesion even to aluminum.

[0211] Example 48 (Preparation and Evaluation of Gas Barrier Laminate (IIIc)) PET ("E5100" manufactured by Toyobo Co., Ltd., thickness: 12 μm) was used as the substrate, and the urethane adhesive was applied to one side of the substrate using a bar coater No. 12 and dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: approximately 3 μm). A 7 μm thick aluminum foil ("1N31" manufactured by Mitsubishi Aluminum Co., Ltd.) was then laminated onto the adhesive layer. Next, the epoxy resin composition 5-1 obtained in Example 5-1 was applied to an aluminum foil using a bar coater No. 3, dried by heating at 120°C for 60 seconds (thickness after drying: approximately 0.1 μm), and further cured by heating at 40°C for 2 days to form a cured resin layer. On the surface of the cured resin layer, an adhesive layer was formed in the same manner as above using the urethane adhesive (thickness after drying: approximately 3 μm). A 50 μm-thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was laminated thereon using nip rolls and heated at 40°C for 2 days to obtain a gas barrier laminate (IIIc) with the configuration shown in FIG. 9. This gas barrier laminate (IIIc) was subjected to peel tests in the normal state and after retort treatment by the method described above. The results are shown in Table 7.

[0212] Example 49 A gas barrier laminate (IIIc) was produced in the same manner as in Example 48, except that the epoxy resin composition 14-1 obtained in Example 14-1 was used, and peel tests were carried out in the normal state and after retort treatment in the same manner as described above. The results are shown in Table 7.

[0213] Comparative Example 10 A gas barrier laminate was produced in the same manner as in Example 48, except that the cured resin layer was not formed, and peel tests were carried out in the normal state and after retort treatment by the same method as in Example 48. The results are shown in Table 7.

[0214] [Table 7]

[0215] Example 50 (Preparation and Evaluation of Gas Barrier Laminate (Ia)) PET ("E5100" manufactured by Toyobo Co., Ltd., thickness: 12 μm) was used as the substrate, and the epoxy resin composition 5-1 obtained in Example 5-1 was applied to one side of the substrate using a bar coater No. 3. The epoxy resin composition was dried by heating at 120°C for 60 seconds (thickness after drying: approximately 0.1 μm), and then cured by heating at 40°C for 2 days to form a cured resin layer. A silica vapor deposition layer with a thickness of approximately 170 Å was formed on the surface of this cured resin layer using a vacuum deposition method, producing a gas barrier laminate (Ia) with the configuration shown in Figure 2. The oxygen permeability and water vapor permeability of the resulting gas barrier laminate (Ia) were measured using the methods described above. The results are shown in Table 8. (Preparation and Evaluation of Gas Barrier Laminate (IIa)) The urethane adhesive was applied to the silica-deposited surface of the resulting gas barrier laminate (Ia) using a bar coater No. 12 and dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: approximately 3µm). A 50µm-thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was laminated thereon using nip rolls and heated at 40°C for 2 days to obtain the gas barrier laminate (IIa) having the configuration shown in Fig. 5. The gas barrier laminate (IIa) was subjected to peel tests in the normal state and after retort treatment by the method described above. The results are shown in Table 8.

[0216] Comparative Example 11 A gas barrier laminate was produced in the same manner as in Example 50, except that no resin cured layer was formed, and the oxygen permeability and water vapor permeability were measured and peel tests were conducted in the normal state and after retort treatment using the same methods as in Example 50. The results are shown in Table 8.

[0217] Example 51 Gas barrier laminates (Ia) and (IIa) were prepared in the same manner as in Example 50, except that a biaxially oriented polypropylene film (FOR, manufactured by Futamura Chemical Co., Ltd., thickness: 20 μm) was used as the substrate instead of PET, an aluminum vapor-deposited layer was formed instead of the silica vapor-deposited layer, and the epoxy resin composition 14-1 obtained in Example 14-1 was used as the epoxy resin. The oxygen permeability and water vapor permeability were measured and a peel test under normal conditions was conducted using the same methods as in Example 50. The results are shown in Table 8.

[0218] Comparative Example 12 A gas barrier laminate was produced in the same manner as in Example 51, except that no resin cured layer was formed, and the oxygen permeability and water vapor permeability were measured and a peel test under normal conditions were carried out by the same methods as in Example 51. The results are shown in Table 8.

[0219] [Table 8]

[0220] Example 52 (Preparation and Evaluation of Gas Barrier Laminate (IIb)) A gas barrier laminate (Ia) was formed in the same manner as in Example 51. The epoxy resin composition 14-1 obtained in Example 14-1 was applied to the aluminum-deposited surface using a bar coater No. 3. The epoxy resin composition was dried by heating at 120°C for 60 seconds (thickness after drying: approximately 0.1 μm) and further cured by heating at 40°C for 2 days to form a cured resin layer. The urethane adhesive described above was applied to the cured resin layer surface using a bar coater No. 12 and dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: approximately 3 μm). A 50 μm-thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was laminated thereon using nip rolls and heated at 40°C for 2 days to obtain a gas barrier laminate (IIb) having the configuration shown in FIG. 6. The gas barrier laminate (IIb) was subjected to a peel test under normal conditions using the method described above. The results are shown in Table 9.

[0221] [Table 9]

[0222] [First Invention (2): Production of Epoxy Resin Composition and Evaluation of Shelf Life] Production Example 3 (Preparation of Epoxy Resin Curing Agent Solution C) A reaction vessel was charged with 1 mol of metaxylylenediamine (MXDA). The temperature was raised to 60°C under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. The temperature was raised to 165°C while distilling off the resulting methanol, and the temperature was maintained at 165°C for 2.5 hours to obtain an amine-based curing agent. Ethanol was then added dropwise over 1.5 hours to obtain a solution containing 65.0% by mass of amine-based curing agent and 35.0% by mass of ethanol. 90.3 g of ethanol as a dilution solvent, 158.1 g of ethyl acetate, and 188.5 g of the above solution were added and stirred, followed by 9.59 g of erucamide (NOF Corporation, "Alflo P-10") and 5.43 g of a silane coupling agent, 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., "KBE-903"), to obtain epoxy resin curing agent solution C with a solids concentration of 30.0 mass%.

[0223] Production Example 4 (Preparation of Epoxy Resin Curing Agent Solution D) In the same manner as in Production Example 3, a solution containing 65.0% by mass of an amine curing agent and 35.0% by mass of ethanol was obtained. 14.1 g of ethanol as a dilution solvent, 17.1 g of ethyl acetate, and 8.17 g of the above solution were added and stirred, followed by the addition of 0.42 g of erucic acid amide (NOF Corporation, "Alflo P-10") and 0.24 g of a silane coupling agent, 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., "KBE-903"), to obtain an epoxy resin curing agent solution D with a solids concentration of 14.7% by mass.

[0224] Example 53 (Preparation and Evaluation of Epoxy Resin Composition 17) To 2.24 g of the epoxy resin curing agent solution C obtained in Production Example 3, 37.6 g of ethanol as a dilution solvent was added and thoroughly stirred. To this mixture, 0.13 g of an epoxy resin having glycidylamino groups derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 3.0) was added and stirred to prepare Epoxy Resin Composition 17 with a solids concentration of 2.0 mass% (Production Method 1). The amount of erucic acid amide blended was 5.0 mass parts per 100 mass parts of the total amount of the epoxy resin in the epoxy resin composition and the nonvolatile content in Epoxy Resin Curing Agent Solution C. The obtained epoxy resin composition 17 was placed in a screw tube, allowed to stand in an environment at a temperature of 23°C, and visually observed, and the time until cloudiness occurred is shown in Table 10. A longer time indicates a longer shelf life.

[0225] Examples 54 to 58 (Preparation and Evaluation of Epoxy Resin Compositions 18 to 22) An epoxy resin composition was prepared in the same manner as in Example 53, except that ethanol and ethyl acetate were used instead of 37.6 g of ethanol as a dilution solvent, and the final solvent composition was blended in the mass ratio shown in Table 10. The results are shown in Table 10.

[0226] Example 59 (Preparation and Evaluation of Epoxy Resin Composition 23) To 4.57 g of the epoxy resin curing agent solution D obtained in Production Example 4, 35.3 g of ethanol as a dilution solvent was added and thoroughly stirred. 0.13 g of an epoxy resin having glycidylamino groups derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) was added as an epoxy resin and stirred (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 3.0) to prepare Epoxy Resin Composition 23 with a solids concentration of 2.0 mass% (Production Method 1). The amount of erucic acid amide blended was 5.0 mass parts per 100 mass parts of the total amount of the epoxy resin in the epoxy resin composition and the nonvolatile content in Epoxy Resin Curing Agent Solution D. The obtained epoxy resin composition 23 was placed in a screw tube, allowed to stand in an environment at a temperature of 23°C, and visually observed. The time until cloudiness occurred is shown in Table 10.

[0227] Examples 60 to 64 (Preparation and Evaluation of Epoxy Resin Compositions 24 to 28) An epoxy resin composition was prepared in the same manner as in Example 59, except that ethanol and ethyl acetate were used instead of 35.3 g of ethanol as a dilution solvent, and the final solvent composition was blended in the mass ratio shown in Table 10. The results are shown in Table 10.

[0228] [Table 10]

[0229] From Table 10, it can be seen that the shelf life of the epoxy resin composition can be improved by using an ethanol-ethyl acetate mixed system as the organic solvent in the epoxy resin composition at a predetermined mass ratio.

[0230] [First Invention (3): Production and Evaluation of Epoxy Resin Composition] Example 65 (Preparation and Evaluation of Gas Barrier Laminates (I) and (II)) A gas barrier laminate (I) having the structure shown in FIG. 1 and a gas barrier laminate (II) having the structure shown in FIG. 4 were obtained in the same manner as in Example 17, except that the epoxy resin composition 20 obtained in Example 56 (produced by Production Method 1) was used instead of the epoxy resin composition 1-1 in Example 17. Using this gas barrier laminate (I), the haze, total light transmittance, and YI, as well as the oxygen permeability and water vapor permeability were measured by the above-mentioned methods. Furthermore, a normal peel test was also carried out using the gas barrier laminate (II). The results are shown in Table 11. (Preparation and Evaluation of Gas Barrier Laminate (III)) A gas barrier laminate (III) having the configuration shown in FIG. 7 was obtained in the same manner as in Example 30, except that the epoxy resin composition 20 obtained in Example 56 was used instead of the epoxy resin composition 1-1 in Example 30. This gas barrier laminate (III) was subjected to a peel test in the normal state and after retort treatment. The results are shown in Table 11.

[0231] Example 66 Gas barrier laminates (I) to (III) were produced and evaluated as described above in the same manner as in Example 65, except that epoxy resin composition 26 (produced by production method 1) obtained in Example 62 was used instead of epoxy resin composition 20 obtained in Example 56. The results are shown in Table 11.

[0232] Example 67 (Preparation of Epoxy Resin Composition 29) (Preparation of erucic acid amide solution a) 2.85 g of erucic acid amide (NOF Corporation's "Alflo P-10") was added to 40.8 g of ethanol and 66.5 g of ethyl acetate as dilution solvents, and the mixture was heated using a band heater. When the temperature reached 20°C, stirring was started to prepare erucic acid amide solution a. (Preparation of epoxy resin hardener solution E) In the same manner as in Production Example 3, an amine-based curing agent solution containing 65.0 mass % of the amine-based curing agent and 35.0 mass % of ethanol was obtained. To the erucic acid amide solution a, 1.71 g of a silane coupling agent, 3-aminopropyltriethoxysilane ("KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd.), was added. While continuing to heat and stir, 73.6 g of the amine-based curing agent solution was added and stirred, obtaining an epoxy resin curing agent solution E with a solids concentration of 30.0 mass %. (Preparation of Epoxy Resin Composition 29) To 12.8 g of epoxy resin curing agent solution E, 216.0 g of ethanol and 220.5 g of ethyl acetate were added as dilution solvents and stirred thoroughly. To this mixture, 1.4 g of an epoxy resin ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) containing glycidylamino groups derived from metaxylylenediamine was added as the epoxy resin (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 3.0) and stirred to prepare epoxy resin composition 29 with a solids concentration of 2.0 mass% (production method 2). The amount of erucic acid amide blended was 5.0 mass parts per 100 mass parts of the total amount of the epoxy resin in the epoxy resin composition and the nonvolatile content of epoxy resin curing agent solution E.

[0233] Example 68 Gas barrier laminates (I) to (III) were produced and evaluated as described above in the same manner as in Example 65, except that epoxy resin composition 29 (produced by production method 2) obtained in Example 67 was used instead of epoxy resin composition 20 obtained in Example 56. The results are shown in Table 11. [Table 11]

[0234] Table 11 shows that the same performance can be obtained when the epoxy resin composition produced by either Production Method 1 or 2 is used in a gas barrier laminate.

[0235] [First Invention (4): Production and Evaluation of Gas Barrier Laminate (IIa)] Example 69 A biaxially oriented polypropylene film (Futamura Chemical Co., Ltd., "FOR," thickness: 20 μm) was used as the substrate, and the epoxy resin composition 23 obtained in Example 59 was applied to one side of the film using a bar coater No. 3. The epoxy resin composition was dried by heating at 120°C for 60 seconds (thickness after drying: approximately 0.1 μm), and then cured by heating at 40°C for two days to form a cured resin layer. An aluminum vapor-deposited layer with a thickness of approximately 170 Å was formed on the surface of this cured resin layer using a vacuum deposition method, and a gas barrier laminate (Ia) with the configuration shown in Figure 2 was produced. The urethane adhesive was applied to the aluminum-deposited surface of the resulting gas barrier laminate (Ia) using a bar coater No. 12 and dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: approximately 3µm). A 50µm-thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was laminated thereon using nip rolls and heated at 40°C for 2 days to obtain the gas barrier laminate (IIa) having the configuration shown in Figure 5. The gas barrier laminate (IIa) was subjected to a peel test under normal conditions using the method described above. The results are shown in Table 12.

[0236] Example 70 A gas barrier laminate (IIa) was produced in the same manner as in Example 69, except that a silica vapor-deposited layer was formed instead of the aluminum vapor-deposited layer, and a peel test under normal conditions was carried out using the same method as in Example 69. The results are shown in Table 12.

[0237] Comparative Example 13 A gas barrier laminate was produced in the same manner as in Example 70, except that the cured resin layer was not formed, and a peel test under normal conditions was carried out by the same method as in Example 70. The results are shown in Table 12.

[0238] Example 71 A gas barrier laminate (IIa) was produced in the same manner as in Example 69, except that an alumina vapor-deposited layer was formed instead of the aluminum vapor-deposited layer in Example 69, and a peel test under normal conditions was carried out in the same manner as in Example 69. The results are shown in Table 12.

[0239] Comparative Example 14 A gas barrier laminate was produced in the same manner as in Example 71, except that the cured resin layer was not formed, and a peel test under normal conditions was carried out in the same manner as in Example 71. The results are shown in Table 12.

[0240] [Table 12]

[0241] [Second invention: Manufacturing and evaluation of packaging materials] In the present examples, measurements and evaluations were carried out by the following methods.

[0242] <Blocking property evaluation> According to the method described in each example, an epoxy resin composition was applied to one side of a linear low-density polyethylene (LLDPE) film ("CMPS-017C" manufactured by Mitsui Chemicals Tohcello, Inc., 30 μm thick) and dried to form a resin composition layer, which was then placed on a horizontal surface. A separately prepared 210 mm × 297 mm LLDPE film was laminated facing the resin composition layer. A 15 kg A4-sized weight was placed on top of the film, and aging was carried out at 40°C for 2 days under this load. After aging, the weight was removed, and the subsequently laminated LLDPE film was manually peeled off from the cured layer surface. The state of blocking was evaluated according to the following criteria. A: No blocking occurs and the LLDPE film can be easily peeled off. B: Blocking has occurred, and although the LLDPE film can be peeled off, an increase in haze is observed after peeling. C: Blocking has occurred and the LLDPE film cannot be peeled off.

[0243] <Odor prevention evaluation> Two 12 cm square pieces of packaging film were cut out from each example, and the two pieces were stacked and heat-sealed on three sides to form a bag. In the case of the films of Examples X1 and X2, the cured product layer was stacked and heat-sealed so that it was the outermost layer. 2 mL of a 0.1% aqueous solution of the odorous component listed in Table 13 was placed in the resulting odor-proof bag, and the opening was heat-sealed. The odor-proof bag containing the odorous components was placed in an aluminum bag, and 1000 cc of air was injected into the bag using a syringe and stored in an environment of 23°C and 50% RH. After a certain period of time had passed, the edge of the aluminum bag was cut, and 100 cc of air inside the bag was sucked in using a detector tube, and the amount of odorous components in the air was measured and shown in Table 13. The lower the amount of odorous components detected, the less odorous components had leaked from the odor-proof bag, indicating higher odor-proofing properties.

[0244] Manufacturing Example X1 (Preparation of Epoxy Resin Hardener Solution XA) A reaction vessel was charged with 1 mol of metaxylylenediamine (MXDA). The temperature was raised to 60°C under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. The temperature was raised to 165°C while distilling off the resulting methanol, and the temperature was maintained at 165°C for 2.5 hours to obtain an amine-based curing agent. Ethanol was then added dropwise over 1.5 hours to obtain a solution containing 65.0% by mass of amine-based curing agent and 35.0% by mass of ethanol. 166.8 g of dilution solvent ethanol, 200.2 g of ethyl acetate, and 94.9 g of the above solution were added and stirred, followed by 4.64 g of erucic acid amide (NOF Corporation, "Alflow P-10") and the silane coupling agent 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., "KBE-903") and stirring to obtain epoxy resin curing agent solution XA.

[0245] Production Example X2 (Preparation of Epoxy Resin Composition X1) To 3.75 g of the epoxy resin curing agent solution XA obtained in Production Example X1, 29.0 g of ethanol as a dilution solvent was added and stirred thoroughly. 0.10 g of an epoxy resin having glycidylamino groups derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) was added as the epoxy resin and stirred (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 3.0) to prepare epoxy resin composition X1. The amount of erucic acid amide blended was 5.0 parts by mass per 100 parts by mass of the combined epoxy resin in epoxy resin composition X1 and the nonvolatile content of epoxy resin curing agent solution XA.

[0246] Example X1 (Production and evaluation of odor-proof bags) The epoxy resin composition X1 obtained in Production Example X2 was applied to a linear low-density polyethylene (LLDPE) film ("CMPS-017C" manufactured by Mitsui Chemicals Tohcello, Inc., thickness 30 μm) using a bar coater No. 3. The epoxy resin composition was dried by heating in a drying oven at 60°C for 30 seconds (thickness after drying: 0.1 μm), and further aged at 40°C for 2 days to produce a packaging film having the configuration shown in FIG. The obtained packaging film was used to prepare odor-proof bags according to the method described above in "Evaluation of odor-proofing properties," and the evaluation was carried out. The results are shown in Table 13.

[0247] Comparative Example X1 In Example X1, a linear low-density polyethylene film ("CMPS-017C" manufactured by Mitsui Chemicals Tohcello, Inc., thickness 30 μm) was used instead of the packaging film, and an odor-proof bag was prepared by the method described in the "Deodorizing Property Evaluation" above, and the evaluation was carried out. The results are shown in Table 13.

[0248] Comparative example X2 Using an upward air-cooled inflation molding machine (manufactured by Tomy Machine Industry Co., Ltd.) equipped with five extruders, a feed block, and a T-die, LLDPE (Prime Polymer Co., Ltd.'s "Evolue SP2510", MFR = 1.4) from the first extruder was discharged at 200 ° C., adhesive polyolefin (Mitsui Chemicals, Inc.'s "Admer NF518") from the second extruder was discharged at 200 ° C., LLDPE (Prime Polymer Co., Ltd.'s "Evolue SP2510", MFR = 1.4) from the third extruder was discharged at 200 ° C., adhesive polyolefin (Mitsui Chemicals, Inc.'s "Admer NF518") from the fourth extruder was discharged at 200 ° C., and LLDPE (Prime Polymer Co., Ltd.'s "Evolue SP2510", MFR = 1.4) from the fifth extruder was discharged at 200 ° C., and these were then air-cooled upward to obtain a multilayer sheet. The multilayer sheet had a layer structure of five layers of three types, consisting of an LLDPE layer / adhesive polyolefin layer / LLDPE layer / adhesive polyolefin layer / LLDPE layer from the outer layer, with the thicknesses of each layer being 11 / 5 / 4 / 5 / 11 (μm). The obtained multilayer sheet was used to prepare an odor-proof bag by the method described above in "Evaluation of odor-proof property," and the odor-proof property was evaluated. The results are shown in Table 13.

[0249] Comparative example X3 A multilayer sheet and an odor-proof bag were produced in the same manner as in Comparative Example X2, except that an ethylene-vinyl alcohol copolymer (EVOH, "ET3803RB" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene 38 mol%) was extruded from the third extruder at 200°C instead of LLDPE, and the odor-proof properties were evaluated. The results are shown in Table 13.

[0250] Example X2 The odor-preventing property was evaluated in the same manner as in Example X1, except that the odorous component in Example X1 was changed to trimethylamine. The results are shown in Table 13.

[0251] Comparative example X4 The odor-preventing property was evaluated in the same manner as in Comparative Example X1, except that the odorous component in Comparative Example X1 was changed to trimethylamine. The results are shown in Table 13.

[0252] [Table 13]

[0253] The abbreviations in Table 13 are as follows. LLDPE#30: Linear low-density polyethylene film (Mitsui Chemicals Tohcello Co., Ltd. "CMPS-017C"), thickness 30 μm LLDPE#11: Linear low-density polyethylene layer, Prime Polymer Co., Ltd. "Evolue SP2510", MFR = 1.4, layer thickness 11 μm LLDPE#4: Linear low-density polyethylene layer, Prime Polymer Co., Ltd. "Evolue SP2510", MFR = 1.4, layer thickness 4 μm Tie #5: Adhesive polyolefin layer, "Admer NF518" manufactured by Mitsui Chemicals, Inc., layer thickness 5 μm EVOH#4: Ethylene-vinyl alcohol copolymer layer, "ET3803RB" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene 38 mol%, layer thickness 4 μm

[0254] [Third Invention: Production and Evaluation of Heat-Shrinkable Labels] In the present examples, measurements and evaluations were carried out by the following methods.

[0255] <Heat shrinkage rate> A 10 cm × 10 cm square was drawn in the center of the heat-shrinkable substrate or the heat-shrinkable label of each example, and then placed in a hot air dryer and heat-treated at 150°C for 30 seconds. The area of ​​the square after heat treatment was measured, and the heat shrinkage rate (area shrinkage rate) was calculated using the following formula. Heat shrinkage rate (%) = {1 - (square area after heat shrinkage) / (square area before heat shrinkage)} x 100

[0256] <Follow-up during heat shrinkage> The cylindrical heat-shrinkable label of each example was attached to the outer peripheral side surface of a 500 mL PET bottle such that the heat-shrinkable film surface was on the inside of the cylinder. The attachment position of the label was the portion indicated by the shaded area in Fig. 2, and the lower end of the label was set at a position 0.5 cm from the bottom (placement surface) of the PET bottle. Next, the PET bottle with the heat-shrinkable label attached was immersed in hot water at 90 °C for 5 seconds to shrink the label and make it adhere tightly to the PET bottle (shrink packaging). The heat-shrinkable label after shrink packaging was visually observed to evaluate the followability during heat shrinkage. When the label adhered uniformly to the side surface of the PET bottle and no delamination was observed between the base material layer and the cured product layer, it was rated as "good". When the label did not follow the side surface shape of the PET bottle and adhered in a non-uniform state, or delamination was observed between the base material layer and the cured product layer, it was judged as "bad".

[0257] <Oxygen permeation amount> The O2 permeation amount of the bottle was measured using an oxygen permeation rate measuring device ("OX-TRAN 2 / 61" manufactured by MOCON). 30 mL of water was filled into a PET bottle subjected to shrink packaging in the same manner as described above, and nitrogen at 1 atm was circulated inside the bottle at 20 mL / min under the conditions of a temperature of 23 °C, an internal humidity of 100% RH, and an external humidity of 50% RH inside the bottle. The oxygen contained in the nitrogen after circulation inside the bottle was detected using a coulometric sensor. The smaller the value, the less the O2 permeation, indicating good O2 barrier properties.

[0258] <CO2 permeation amount> The CO2 permeation amount of the bottle was measured using a carbon dioxide permeation rate measuring device ("Permatran C10" manufactured by MOCON). 500 mL of carbonated water with a CO2 amount of 3.2 GV (carbonated water in which 3.2 L of CO2 was dissolved in 1 L of water) was sealed in a PET bottle subjected to shrink packaging in the same manner as described above, and it was left standing for 1 week in an environment of 23 °C and 50% RH. The amount of CO2 inside the bottle after standing for 1 week was quantified, and the CO2 permeation amount was calculated from this value. The smaller the value, the less the CO2 permeation, indicating good CO2 barrier properties.

[0259] <Shelf life> 500 mL of carbonated water with a CO2 content of 3.2 GV was sealed in a PET bottle shrink-wrapped in the same manner as above. This was left to stand in an environment of 23°C and 50% RH, and the CO2 content in the bottle was quantified over time using a carbon dioxide permeability measuring device (MOCON's "Permatran C10"). Table 2 shows the time required for the GV of CO2 in the carbonated water sealed in the PET bottle to reach 80% of its initial value. The longer the shelf life, the less CO2 permeation there was, indicating better CO2 barrier properties.

[0260] Production Example X3 (Preparation of Epoxy Resin Composition X2) To 3.42 g of the epoxy resin curing agent solution XA obtained in Production Example X1, 6.48 g of ethanol as a dilution solvent was added and stirred thoroughly. To this mixture, 0.10 g of an epoxy resin having glycidylamino groups derived from metaxylylenediamine ("TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Inc.) was added as the epoxy resin (number of active amine hydrogen atoms in the epoxy resin curing agent / number of epoxy groups in the epoxy resin = 3.0) and stirred to prepare epoxy resin composition X2. The amount of erucic acid amide blended was 5.0 parts by mass per 100 parts by mass of the combined epoxy resin in epoxy resin composition X2 and the nonvolatile content of epoxy resin curing agent solution XA.

[0261] Example Y1 (Preparation and Evaluation of Heat-Shrinkable Film) The epoxy resin composition X1 obtained in Production Example X2 was applied to the outer surface of a cylindrical heat-shrinkable polyvinyl chloride (PVC) film (Sanso Plastics' original PET bottle production film "Chiji〇kun," 110 mm wide (220 mm cylindrical circumference) × 175 mm long × 40 μm thick) using a bar coater No. 3. The epoxy resin composition 1 was dried by heating in a drying oven at 60°C for 30 seconds (thickness after drying: 0.1 μm), and further aged at 40°C for 2 days to produce a cylindrical heat-shrinkable label having the layer structure shown in FIG. 11. The heat-shrinkable labels thus obtained were subjected to various evaluations using the methods described above. The results are shown in Table 14.

[0262] Example Y2 A heat-shrinkable label was prepared in the same manner as in Example Y1, except that the epoxy resin composition X2 obtained in Production Example X3 was used instead of the epoxy resin composition X1 obtained in Production Example X2, and the above-mentioned evaluations were carried out. The results are shown in Table 14.

[0263] Comparative Example Y1 The PET bottles were shrink-wrapped using only the PVC tubular heat-shrinkable film as the heat-shrinkable label in the same manner as above, and the evaluations were carried out. The results are shown in Table 14.

[0264] Reference example Y1 The evaluation was carried out using PET bottles that were not shrink-wrapped with a heat-shrinkable label. The results are shown in Table 14.

[0265] [Table 14]

[0266] Table 14 shows that the bottles with the heat-shrinkable labels of this example have the same O2 barrier properties as the bottles of the comparative example and reference example, and have high CO2 barrier properties. The heat-shrinkable labels of this example also have good conformability during heat shrinkage. [Industrial Applicability]

[0267] The epoxy resin composition of the first invention can form a cured product that has high gas barrier properties, particularly good adhesion to inorganic substances such as alumina, and is resistant to peeling even after retort treatment, resulting in excellent retort resistance. A gas barrier laminate having a cured resin layer, which is a cured product of the epoxy resin composition, formed on a substrate having at least one side made of an inorganic substance has high gas barrier properties, interlayer adhesion, and retort resistance, and is suitable for use as a packaging material for retort foods, for example. According to the second invention, it is possible to provide a packaging material for deodorizing or retaining aroma, which has good deodorizing and aroma-retaining properties, can be made thin, and is also economical. The packaging material according to the second invention can be suitably used for applications requiring deodorizing or aroma-retaining properties, such as bags for storing used disposable diapers, pet litter, waste, food waste, and other malodorous substances; packaging material for strong-smelling foods; packaging material for fragrant toiletries, cosmetics, stationery, and toys; etc. Furthermore, according to the third invention, it is possible to provide a heat-shrinkable label that has good CO2 barrier properties, excellent followability during heat shrinkage, and is economical, as well as a method for manufacturing the same, a heat-shrinkable label and a bottle having the same, and a method for preventing CO2 permeation. The heat-shrinkable label according to the third invention is suitable for use in PET bottles for carbonated water and other carbonated drinks. [Explanation of symbols]

[0268] 100, 200, 300, 400 Gas barrier laminate 1 Base material 2. Inorganic thin film layer 3 Resin hardening layer 4 Thermoplastic resin film (thermoplastic resin layer) 5 Adhesive layer 500 Packaging materials (packaging film) 501 Base material 502, 602 Cured material layer 600 Heat Shrinkable Labels 601 Heat-shrinkable base layer< / yi> < / haze>

Claims

1. The composition contains an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms, The epoxy resin composition, wherein the amine-based curing agent is the following amine-based curing agent (i): (i) A reaction product of the following components (A) and (B): (A) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (B) at least one member selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: 【Chemistry 1】 (In formula (1), R １ , R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.

2. 2. The epoxy resin composition according to claim 1, wherein the content of the unsaturated fatty acid amide in the epoxy resin composition is 0.1 to 20 parts by mass per 100 parts by mass of the total amount of the epoxy resin and the non-volatile components in the epoxy resin curing agent.

3. 3. The epoxy resin composition according to claim 1, wherein the epoxy resin is mainly composed of an epoxy resin having a glycidylamino group derived from metaxylylenediamine.

4. 4. The epoxy resin composition according to claim 1, wherein the unsaturated fatty acid amide is at least one selected from the group consisting of oleamide and erucamide.

5. The epoxy resin composition according to any one of claims 1 to 4, further comprising non-spherical inorganic particles.

6. 6. The epoxy resin composition according to claim 1, wherein a ratio of the number of active amine hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is more than 1.0 and not more than 5.

0.

7. A gas barrier laminate having a substrate and a cured resin layer which is a cured product of the epoxy resin composition according to any one of claims 1 to 6.

8. The gas barrier laminate according to claim 7 , which has at least one layer made of an inorganic material.

9. The gas barrier laminate according to claim 8 , wherein the layer made of an inorganic material is an inorganic substrate.

10. The gas barrier laminate according to claim 8 , wherein the layer made of an inorganic substance is an inorganic thin film layer.

11. 11. The gas barrier laminate according to claim 10, wherein the inorganic substance in the inorganic thin film layer is at least one selected from the group consisting of silicon oxide, aluminum, and aluminum oxide.

12. 12. The gas barrier laminate according to claim 8, wherein the layer made of an inorganic substance and the cured resin layer are adjacent to each other.

13. The gas barrier laminate according to any one of claims 7 to 12, further comprising a thermoplastic resin layer.

14. The gas barrier laminate includes a substrate, a cured resin layer that is a cured product of an epoxy resin composition, and a thermoplastic resin layer, The packaging material for retort pouch foods, wherein the epoxy resin composition contains an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms, and the amine-based curing agent is the following amine-based curing agent (i): (i) A reaction product of the following components (A) and (B): (A) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (B) at least one member selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: 【Chemistry 2】 (In formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.)

15. A packaging material for deodorization or fragrance retention, comprising a substrate and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms, wherein the amine-based curing agent is the following amine-based curing agent (i): (i) A reaction product of the following components (A) and (B): (A) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (B) at least one member selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: 【Transformation 3】 (In formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.)

16. The odor-preventing or aroma-retaining packaging material according to claim 15, wherein the substrate is a film-like substrate.

17. 17. The odor-preventing or aroma-retaining packaging material according to claim 15 or 16, which comprises only one substrate and one cured product layer.

18. The odor-preventing or aroma-retaining packaging material according to any one of claims 15 to 17, wherein the thickness of the cured product layer is 0.02 to 0.6 µm.

19. The odor-preventing or aroma-retaining packaging material according to any one of claims 15 to 18, wherein the packaging material is a bag, a film, or a lid material.

20. A method for deodorizing or retaining an aroma, comprising: encapsulating an article containing an odorous component or a fragrance component in a packaging material having a substrate and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms; and wherein the amine-based curing agent is the following amine-based curing agent (i). (i) A reaction product of the following components (A) and (B): (A) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (B) at least one member selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: 【Chemistry 1】 (In formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.)

21. A heat-shrinkable label having a heat-shrinkable base layer and a cured product layer of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms, wherein the amine-based curing agent is the following amine-based curing agent (i): (i) A reaction product of the following components (A) and (B): (A) at least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine (B) at least one member selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and derivatives thereof: 【Chemistry 1】 (In formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.)

22. 22. A heat-shrinkable label according to claim 21, wherein the resin constituting the heat-shrinkable base layer is a resin selected from the group consisting of polyvinyl chloride resin, polystyrene resin, polyolefin resin, and polyester resin.

23. 23. The heat-shrinkable label according to claim 21 or 22, comprising only one heat-shrinkable base layer and one cured material layer.

24. A method for producing a heat-shrinkable label according to any one of claims 21 to 23, comprising the following steps (I) and (II) in this order: Step (I): A step of applying an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent including an amine-based curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a solvent to at least one surface of a heat-shrinkable substrate to form a coating layer. Step (II): A step of heating and drying the coating layer at a temperature of less than 100°C to remove the solvent.

25. A heat-shrinkable label obtained by heat-shrinking the heat-shrinkable label according to any one of claims 21 to 23.

26. 26. A bottle having the heat shrink label of claim 25.

27. A CO using the heat-shrinkable label according to any one of claims 21 to 23 or the heat-shrinkable label according to claim 25. ２ Transmission prevention method.

Images