Epoxy resin composition, gas-barrier laminate, packaging material for retort foods, deodorizing or aroma-preserving use, heat-shrinkable label and method for producing the same, heat-shrinkable label and bottle having the same

Abstract

Epoxy resin composition, gas-barrier laminate using the same, packaging material for retort foods, packaging material for deodorization or fragrance retention, method for deodorization or fragrance retention by enclosing an article containing an odor component or a fragrance component in the packaging material, heat-shrinkable label, method for producing the same, heat-shrinkable label and bottle having the same, and method for preventing CO2 permeation; the epoxy resin composition contains: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

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, a packaging material for deodorization or fragrance retention, a deodorization or fragrance retention method, a heat-shrinkable label and a method for manufacturing the same, a heat-shrinkable label and a bottle having the same, and a method for preventing CO2 permeation. Background Art

[0002] For packaging materials for foods, drugs, cosmetics, precision electronic components, etc., high oxygen barrier properties and water vapor barrier properties are required to prevent deterioration of the contents.

[0003] In addition, as materials for preventing the volatilization of odor components such as ammonia and trimethylamine, various gas-barrier materials such as glass, metal, and plastic are used. In terms of gas-barrier performance, glass and metal are very excellent compared to plastic materials. However, considering moldability, light weight, recyclability, transparency, etc., plastic materials having barrier performance are suitable, and a large amount of gas-barrier plastic materials are used.

[0004] Since the oxygen barrier property of a thermoplastic film is generally not so high, as a means for imparting gas-barrier property to the film, methods of forming various gas-barrier layers such as a polyvinylidene chloride (PVDC) layer and a polyvinyl alcohol (PVA) layer, or methods of vapor-depositing inorganic substances such as aluminum oxide (Al2O3) and silicon dioxide (SiO2) have been studied.

[0005] A film formed with a PVDC layer as a gas-barrier layer is transparent and exhibits good gas-barrier property. However, when incinerated as general waste, organic substances such as acidic gases are generated, so it is desirable to replace it with other materials in view of the environment. A film formed with a PVA layer exhibits excellent gas-barrier property at low humidity, but has problems of high hygroscopicity and a sharp decrease in gas-barrier property when the relative humidity reaches about 70% or more.

[0006] An inorganic vapor-deposited film formed by vapor-depositing an inorganic substance such as aluminum oxide or silicon dioxide on a thermoplastic film is transparent and has good gas-barrier property, and does not cause the above problems. However, when the inorganic vapor-deposited film is bent, there is a problem that cracks are generated in the inorganic vapor-deposited layer and the gas-barrier property is significantly reduced.

[0007] As a method for improving the bending resistance of a gas-barrier film or laminate including a layer vapor-deposited with an inorganic substance, a method of forming a layer formed 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).

[0008] Patent Document 4 discloses a gas-barrier film composed of a specified layer structure, the gas-barrier film having: a base film with an inorganic vapor deposition layer, and a resin cured layer composed of a cured product of an epoxy resin composition; wherein the epoxy resin composition contains: an epoxy resin, a specified epoxy resin curing agent, and non-spherical inorganic particles; the gas-barrier film composed of the specified layer structure has improved gas-barrier properties and excellent flex resistance compared to an existing gas-barrier film with an inorganic vapor deposition layer.

[0009] Research has also been conducted to improve various functions of the obtained gas-barrier film by improving the epoxy resin composition used in the gas-barrier film. For example, Patent Document 5 reports a gas-barrier resin composition that contains an epoxy resin, an epoxy resin curing agent, and a specific curing accelerator, and contains a specified amount of a specified skeletal structure derived from an amine in the formed cured product, and this gas-barrier resin composition exhibits high gas-barrier properties under a wide range of curing conditions.

[0010] As described above, it is known that when forming a gas-barrier layer formed of a cured product of a specified epoxy resin composition on a substrate, the effect of improving the gas-barrier properties is significant.

[0011] Furthermore, in a gas-barrier film or gas-barrier laminate having a laminated structure, it is also important to have high interlayer adhesiveness in order to stably exhibit good gas-barrier properties. In this regard, for example, Patent Document 6 discloses that in a laminated film having at least a substrate, a primer layer, an adhesive layer, and a sealant layer laminated in sequence, by using a primer composition containing a specific polyester resin to form the primer layer and using an adhesive mainly composed of an epoxy resin composition to form the adhesive layer, a laminated film with excellent adhesiveness over time can be obtained, which can maintain excellent lamination strength and heat-seal strength even after long-term storage.

[0012] However, depending on the types of the substrate and the epoxy resin composition used in the gas-barrier film or laminate, the interlayer adhesiveness between the substrate and the cured product layer of the epoxy resin composition may sometimes be insufficient. Although Patent Documents 1 to 6 disclose epoxy resin compositions using amine-based epoxy resin curing agents, according to recent research by the inventors, it has been found that the cured product of an epoxy resin composition using an amine-based epoxy resin curing agent has unstable adhesiveness to inorganic substances, especially to alumina.

[0013] Moreover, in packaging materials for food applications, etc., heat treatment such as retort processing is sometimes carried out, and it is important to maintain the interlayer adhesiveness even after retort processing.

[0014] As a material for preventing the volatilization of odor components such as ammonia and trimethylamine, a method for preventing the diffusion of odors (anti-odor method) has been studied, in which the odor components are enclosed in a bag formed of a material in which a barrier layer containing an organic substance is further provided on a thermoplastic plastic film. Hereinafter, in this specification, the performance of enclosing odor components and preventing the volatilization of odors is referred to as "anti-odor property".

[0015] For example, Patent Document 7 discloses the following method: a barrier material containing at least one layer formed of a cured product of an epoxy resin containing 40% by weight or more of a phthalenediamine skeleton structure is used to prevent the permeation of amine-based volatile substances, and a laminated film and a bag-shaped container using the barrier material as an adhesive are exemplified.

[0016] Patent Document 8 discloses the following malodor-sealing bag: it includes an inner layer, an outer layer, and an intermediate layer, the inner layer and the outer layer contain ethylene (co) polymers, the intermediate layer contains a barrier resin, and an anti-blocking agent and a surfactant are contained in the inner and outer layers, and it satisfies specified characteristics.

[0017] However, it is desired to further improve the anti-odor property of packaging materials such as the films and bags described in Patent Documents 7 and 8. For example, it is described that the thickness of the intermediate layer (barrier layer) of the malodor-sealing bag described in Patent Document 2 is in the range of 0.8 to 5.0 μm, but from the viewpoints of thinning of the packaging material and economy, it is desired to obtain sufficient anti-odor property even if the barrier layer is further thinned. Moreover, for these packaging materials, it is preferable to have not only anti-odor property but also the property of enclosing in such a manner that the aroma components of the article imparting aromaticity do not volatilize (hereinafter also referred to as "aroma retention property").

[0018] Furthermore, the barrier layers in the disclosed technologies of Patent Documents 7 and 8 are all adhesive materials constituting the intermediate layer of the film or bag and have adhesiveness, so they are not suitable as materials for forming the surface layer (innermost layer or outermost layer). In the case of using the barrier layer as the intermediate layer in films, bags, etc., the layer structure must be at least a three-layer structure including the barrier layer, so it is disadvantageous in terms of cost.

[0019] In recent years, PET bottles have been widely used as beverage containers. On most PET bottles, a plastic shrink label indicating the contents is pasted so as to cover the main body of the PET bottle.

[0020] However, if the oxygen barrier property of the PET bottle is insufficient, there is a problem that the content is easily oxidized and deteriorated. Therefore, research has been conducted on imparting gas barrier property to the shrink label used on the PET bottle.

[0021] Furthermore, in the shrink label, there are also problems such as a decrease in the decorativeness, gas barrier property, etc. of the label after shrink processing, and methods for solving these problems have also been studied.

[0022] For example, Patent Document 9 discloses a shrink label having at least one layer each of a printing layer containing a pigment, an anchor coat layer, and a barrier layer on at least one side of a shrink film, and the layers are laminated in the order of shrink film / printing layer / anchor coat layer / barrier layer. The arithmetic mean roughness of the surface of the anchor coat layer is below a specified value; the shrink label also does not have a reduction in decorativeness and gas barrier properties such as "fogging" after processing.

[0023] Patent Document 10 discloses a gas barrier shrink laminated film formed by laminating two heat-shrinkable films with a gas barrier adhesive, and its gas barrier property does not decrease even when shrink processing is performed.

[0024] In the case of a PET bottle for carbonated beverages, the gas barrier property of carbon dioxide gas (CO2) becomes important. However, for the shrink labels or films described in Patent Documents 9 and 10, only the oxygen gas barrier property has been evaluated, and there is room for improvement in the CO2 gas barrier property. Moreover, the barrier layers in the shrink labels or films described in Patent Documents 9 and 10 are all materials that constitute the intermediate layer of the shrink label or film and are not suitable as materials for forming the surface layer (innermost layer or outermost layer). When the barrier layer is the intermediate layer in the shrink label, the layer structure must be at least a three-layer structure including the barrier layer, so it is disadvantageous in terms of cost.

[0025] Prior art documents

[0026] Patent documents

[0027] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-300271

[0028] Patent Document 2: Japanese Patent Application Laid-Open No. 2005-28835

[0029] Patent Document 3: Japanese Patent Application Laid-Open No. 2009-101684

[0030] Patent Document 4: International Publication No. 2018 / 105282

[0031] Patent Document 5: Japanese Patent Application Laid-Open No. 2010-202753

[0032] Patent Document 6: Japanese Patent Application Laid-Open No. 2013-203023

[0033] Patent Document 7: Japanese Patent Application Laid-Open No. 2008-222761

[0034] Patent Document 8: International Publication No. 2014 / 185482

[0035] Patent Document 9: Japanese Patent Application Laid-Open No. 2008-201463

[0036] Patent Document 10: Japanese Patent Application Laid-Open No. 2011-37156 Summary of the Invention

[0037] Problems to be Solved by the Invention

[0038] The first problem of the present invention is to provide: an epoxy resin composition containing an amine-based curing agent as an epoxy resin curing agent, a gas barrier laminate using the epoxy resin composition, and a packaging material for retort foods; wherein the epoxy resin composition can form a cured product having high gas barrier properties, particularly good adhesiveness to inorganic substances such as alumina, not easily causing peeling even after retort treatment, and excellent retort resistance.

[0039] The second problem of the present invention is to provide: a packaging material for deodorization or flavor retention having good deodorizing properties and flavor retention properties, capable of achieving thinning, and excellent in economy, and a deodorization or flavor retention method.

[0040] In addition, the third problem of the present invention is to provide: a heat-shrinkable label having good CO2 barrier properties, excellent followability and economy during heat shrinkage, a manufacturing method thereof, a heat-shrinkable label and a bottle having the same, and a method for preventing CO2 permeation.

[0041] Solutions to the Problems

[0042] The present inventors have found that: by using an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and a specified fatty acid amide, the above problems can be solved.

[0043] That is, the present invention relates to the following.

[0044] [1] An epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0045] [2] A gas barrier laminate having: a substrate; and a resin cured layer which is a cured product of the epoxy resin composition described in the above [1].

[0046] [3] The gas barrier laminate according to the above [2], further having a thermoplastic resin layer.

[0047] [4] A packaging material for retort foods, comprising the gas barrier laminate described in the above [3].

[0048] [5]A packaging material for preventing odor or retaining fragrance, comprising: a substrate and a cured product layer of an epoxy resin composition, the epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0049] [6]A method for preventing odor or retaining fragrance, which comprises enclosing an article containing an odor component or a fragrance component in a packaging material, the packaging material having: a substrate and a cured product layer of an epoxy resin composition, the epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0050] [7]A heat-shrinkable label, comprising: a heat-shrinkable substrate layer and a cured product layer of an epoxy resin composition, the epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0051] [8]A method for manufacturing the heat-shrinkable label according to [7] above, which successively comprises the following steps (I) and (II).

[0052] Step (I): A step of coating an epoxy resin composition on at least one surface of a heat-shrinkable substrate to form a coating layer, the epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a solvent.

[0053] Step (II): A step of heating and drying the aforementioned coating layer at a temperature below 100 °C to remove the solvent.

[0054] [9]A heat-shrink label obtained by heat-shrinking the heat-shrinkable label according to [7] above.

[0055]

[10] A bottle having the heat-shrink label according to [9] above.

[0056]

[11] A method for preventing CO2 permeation, which uses the heat-shrinkable label according to [7] above or the heat-shrink label according to [9] above.

[0057] Effects of the Invention

[0058] According to the epoxy resin composition which is the first invention, a cured product can be formed which has high gas barrier properties, particularly good adhesiveness to inorganic substances such as alumina, is not easily peeled off even after retort treatment, and has excellent retort resistance. The gas barrier laminate having a resin cured layer which is a cured product of the epoxy resin composition formed on a substrate composed of inorganic substances on at least one side has high gas barrier properties, interlayer adhesiveness, and retort resistance, and is suitable for use as a packaging material for retort foods, for example.

[0059] According to the second invention, there can be provided: a packaging material for preventing odor or retaining fragrance, which has good anti-odor and fragrance-retaining properties, can be made thin, and is also excellent in economy, and a method for preventing odor or retaining fragrance. The packaging material of the second invention can be suitably used for applications that require anti-odor or fragrance-retaining properties, such as bags for storing used disposable diapers, pet sand, dirt, household waste, and other malodorous substances; packaging materials for foods with strong odors; packaging materials for aromatic toiletries, cosmetics, stationery, and toys; and the like.

[0060] Furthermore, according to the third invention, there can be provided: a heat-shrinkable label having good CO2 barrier properties, excellent followability and economy during heat shrinkage, 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 of the third invention is suitable for use with PET bottles for carbonated water and other carbonated beverages. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 FIG. is a schematic cross-sectional view showing an embodiment of the gas barrier laminate 100 of the first invention.

[0062] Figure 2 FIG. is a schematic cross-sectional view showing an embodiment of the gas barrier laminate 100a of the first invention.

[0063] Figure 3 FIG. is a schematic cross-sectional view showing an embodiment of the gas barrier laminate 200 of the first invention.

[0064] Figure 4 FIG. is a schematic cross-sectional view showing an embodiment of the gas barrier laminate 300 of the first invention.

[0065] Figure 5 FIG. is a schematic cross-sectional view showing an embodiment of the gas barrier laminate 300a of the first invention

[0066] Figure 6 FIG. is a schematic cross-sectional view showing an embodiment of the gas barrier laminate 300b of the first invention.

[0067] Figure 7 FIG. is a schematic cross-sectional view showing an embodiment of the gas barrier laminate 400 of the first invention.

[0068] Figure 8 Cross-sectional schematic view showing an embodiment of the gas-barrier laminate 400a of the first invention.

[0069] Figure 9 Cross-sectional schematic view showing an embodiment of the gas-barrier laminate 400c of the first invention.

[0070] Figure 10 Cross-sectional schematic view showing an embodiment of the packaging material (packaging film) 500 of the second invention.

[0071] Figure 11 Cross-sectional schematic view showing an embodiment of the heat-shrinkable label 600 of the third invention.

[0072] Figure 12 Explanatory drawing showing the attachment site of the heat-shrinkable label to the PET bottle in the evaluation of the examples. Detailed Description

[0073] [First Invention: Epoxy Resin Composition]

[0074] The epoxy resin composition according to the first invention is an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent containing 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 will also be simply referred to as "the epoxy resin composition of the present invention".

[0075] By having the above configuration, the epoxy resin composition of the present invention can form a cured product having high gas barrier properties, particularly good adhesiveness to inorganic substances such as alumina, and is not easily peeled off even after retort treatment, and has excellent retort resistance. Furthermore, the transparency of the formed cured product becomes high.

[0076] According to recent research by the present inventors, it has been found that the adhesiveness of the cured product of the epoxy resin composition to inorganic substances, particularly to alumina, is unstable, and this tendency is particularly significant especially when an amine-based epoxy resin curing agent is used. Therefore, the present inventors have conducted in-depth research and as a result, it has been found that when an unsaturated fatty acid amide having 14 to 24 carbon atoms is added to the epoxy resin composition using an amine-based epoxy resin curing agent, the adhesiveness and retort resistance of the cured product to alumina and the like are improved, and the transparency also becomes good. The reason for this is not clear, but it is considered as follows.

[0077] It is considered that if an unsaturated fatty acid amide having 14 to 24 carbon atoms is contained in the epoxy resin composition, it exerts the effect of alleviating the stress generated in the cured product of the epoxy resin, and has higher compatibility with the epoxy resin composition containing an amine-based epoxy resin curing agent than a saturated fatty acid amide. Therefore, it is speculated that the adhesiveness, retort resistance, and transparency to inorganic substances such as alumina of the cured product of the epoxy resin composition of the present invention containing the unsaturated fatty acid amide become good.

[0078] Hereinafter, each component contained in the epoxy resin composition of the present invention will be described.

[0079] <Epoxy resin>

[0080] The epoxy resin used in the epoxy resin composition of the present invention may be any of saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, or heterocyclic compounds. However, when considering the manifestation of high gas barrier properties, an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule is preferred.

[0081] Specific examples of such epoxy resins include at least one resin selected from epoxy resins having a glycidylamino group derived from m-phenylenediamine, epoxy resins having a glycidylamino group derived from p-phenylenediamine, epoxy resins having a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from diaminodiphenylmethane, epoxy resins having a glycidylamino group and / or a glycidyl etheroxy group derived from p-aminophenol, epoxy resins having a glycidyl etheroxy group derived from bisphenol A, epoxy resins having a glycidyl etheroxy group derived from bisphenol F, epoxy resins having a glycidyl etheroxy group derived from phenol novolac, and epoxy resins having a glycidyl etheroxy group derived from resorcinol. In order to improve various properties such as flexibility, impact resistance, and heat and humidity resistance, the above epoxy resins may also be used by mixing two or more of them in a suitable ratio.

[0082] Among the above, from the viewpoints of gas barrier properties, deodorant properties and fragrance retention properties of the packaging material according to the second invention, and CO2 barrier properties of the heat-shrinkable label according to the third invention, as the epoxy resin, at least one selected from the group consisting of an epoxy resin having a glycidylamino group derived from m-phenylenediamine, an epoxy resin having a glycidylamino group derived from p-phenylenediamine, and an epoxy resin having a glycidyl etheroxy group derived from bisphenol F is preferably used as the main component, and more preferably, an epoxy resin having a glycidylamino group derived from m-phenylenediamine is used as the main component.

[0083] It should be noted that the so-called "main component" here means that other components can be included within the scope of the gist of the present invention, preferably 50 to 100% by mass of the whole, more preferably 70 to 100% by mass, and further preferably 90 to 100% by mass.

[0084] <Epoxy resin curing agent containing amine curing agent>

[0085] From the viewpoints of exhibiting high gas barrier properties, exhibiting high anti-odor properties and fragrance retention properties in the packaging material according to the second invention, and exhibiting high CO2 barrier properties in the heat-shrinkable label according to the third invention, the epoxy resin curing agent used in the epoxy resin composition of the present invention contains an amine curing agent.

[0086] As the amine curing agent, polyamines or their modified products currently used as epoxy resin curing agents can be used. From the viewpoints of obtaining high gas barrier properties, anti-odor properties and fragrance retention properties of the packaging material according to the second invention, and CO2 barrier properties of the heat-shrinkable label according to the third invention, the amine curing agent is preferably a modified product of polyamine, more preferably at least one selected from the group consisting of the following amine curing agent (i) and amine curing agent (ii), and further preferably the following amine curing agent (i).

[0087] (i) Reaction product of the following component (A) and component (B):

[0088] (A) At least one selected from the group consisting of m-xylenediamine and p-xylenediamine

[0089] (B) At least one selected from the group consisting of unsaturated carboxylic acids represented by the following general formula (1) and their derivatives

[0090]

[0091] (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.)

[0092] (ii) Reaction product of epichlorohydrin and at least one selected from the group consisting of m-xylenediamine and p-xylenediamine

[0093] (Amine curing agent (i))

[0094] Amine curing agent (i) is the reaction product of the following component (A) and component (B).

[0095] (A) At least one selected from the group consisting of m-xylenediamine and p-xylenediamine

[0096] (B) at least one selected from the group consisting of unsaturated carboxylic acids and their derivatives represented by the following general formula (1)

[0097]

[0098] (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.)

[0099] From the viewpoint of gas barrier properties, the deodorizing property and fragrance retention property of the packaging material according to the second invention, and the CO2 barrier property of the heat shrinkable label according to the third invention, the aforementioned component (A) is used. From the aspect of gas barrier properties, m-xylylenediamine is preferred. Component (A) can be used alone as one kind, or two kinds can be mixed and used.

[0100] The aforementioned component (B) is at least one selected from the group consisting of unsaturated carboxylic acids and their derivatives represented by the aforementioned general formula (1). From the viewpoints of gas barrier properties, the deodorizing property and fragrance retention property of the packaging material according to the second invention, and the CO2 barrier property of the heat shrinkable label according to the third invention, R 1 in the aforementioned general formula (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, still more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0101] In addition, from the viewpoints of gas barrier properties, the deodorizing property and fragrance retention property of the packaging material according to the second invention, and the CO2 barrier property of the heat shrinkable label according to the third invention, R 2 in the aforementioned general formula (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, still more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0102] Examples of the derivatives of the unsaturated carboxylic acid represented by the aforementioned general formula (1) include esters, amides, acid anhydrides, and acid chlorides of the unsaturated carboxylic acid. As the ester of the unsaturated carboxylic acid, an alkyl ester is preferred. From the viewpoint of obtaining good reactivity, the carbon number of the alkyl group is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 to 2.

[0103] Examples of the unsaturated carboxylic acids and their derivatives represented by the general formula (1) above include acrylic acid, methacrylic acid, α-ethylacrylic acid, α-propylacrylic acid, α-isopropylacrylic acid, α-n-butylacrylic acid, α-tert-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, 2-octenoic acid, and other unsaturated carboxylic acids and their esters, amides, acid anhydrides, acid chlorides, etc.

[0104] Among the above, from the viewpoints of obtaining good gas barrier properties, the odor-proof property and fragrance retention property of the packaging material according to the second invention, and the CO2 barrier property of the heat-shrinkable label according to the third invention, the component (B) is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and their derivatives, more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and their alkyl esters, still more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and their alkyl esters, even more preferably an alkyl ester of acrylic acid, and even more preferably methyl acrylate.

[0105] The component (B) can be used alone or in combination of two or more.

[0106] When using an unsaturated carboxylic acid, ester, or amide as the component (B), the component (A) and the component (B) are mixed under the conditions of 0 to 100°C, more preferably 0 to 70°C, and a Michael addition reaction and an amide group formation reaction using dehydration, de-alcoholization, or de-amination are carried out under the conditions of 100 to 300°C, preferably 130 to 250°C, thereby implementing the reaction between the component (A) and the component (B).

[0107] In this case, when carrying out the amide group formation reaction, in order to complete the reaction, a pressure reduction treatment can also be carried out on the inside of the reaction apparatus at the final stage of the reaction as needed. In addition, dilution can also be carried out using a non-reactive solvent as needed. Further, a catalyst such as phosphite can also be added as a dehydrating agent or a de-alcoholizing agent.

[0108] On the other hand, when an acid anhydride or an acyl chloride of an unsaturated carboxylic acid is used as the aforementioned component (B), it can be carried out by mixing under the conditions of 0 to 150°C, preferably 0 to 100°C, followed by a Michael addition reaction and an amide group formation reaction. In this case, when carrying out the amide group formation reaction, in order to complete the reaction, a reduced pressure treatment can also be carried out on the inside of the reaction apparatus at the final stage of the reaction as needed. In addition, dilution can also be carried out using a non-reactive solvent as needed. Furthermore, a tertiary amine such as pyridine, methylpyridine, dimethylpyridine, or trialkylamine can also be added.

[0109] The amide group moiety formed by the reaction of the aforementioned component (A) and the aforementioned component (B) has a high aggregation force. Therefore, a resin cured layer (cured product layer) formed using an epoxy resin composition containing an epoxy resin curing agent that is a reaction product of the component (A) and the component (B) has high gas barrier properties, anti-odor properties, fragrance retention properties, high CO2 barrier properties, and good adhesiveness.

[0110] The reaction molar ratio [(B) / (A)] of the aforementioned component (B) to the aforementioned component (A) is preferably in the range of 0.3 to 1.0. If the above reaction molar ratio is 0.3 or more, a sufficient amount of amide groups are generated in the epoxy resin curing agent, demonstrating high levels of gas barrier properties, anti-odor properties, and fragrance retention properties of the packaging material related to the second invention, CO2 barrier properties of the heat-shrinkable label related to the third invention, and adhesiveness. On the other hand, if the above reaction molar ratio is in the range of 1.0 or less, the amount of amino groups required for the reaction with the epoxy groups in the epoxy resin is sufficient, and the heat resistance is excellent, and the solubility in organic solvents and water is also excellent.

[0111] Especially considering the high gas barrier properties, anti-odor properties, and fragrance retention properties, CO2 barrier properties, and excellent coating film properties of the obtained epoxy resin cured product, the reaction molar ratio [(B) / (A)] of the aforementioned component (B) to the aforementioned component (A) is more preferably in the range of 0.6 to 1.0.

[0112] The above amine-based curing agent can be a reaction product of the aforementioned component (A) and the component (B), and further at least one compound selected from the group consisting of the following component (C), component (D), and component (E).

[0113] (C) At least one selected from the group consisting of monocarboxylic acids represented by R 3 -COOH and their derivatives (R 3 represents a hydrogen atom, an optionally hydroxy group-containing alkyl group having 1 to 7 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

[0114] (D) Cyclic carbonate

[0115] (E) A monocyclic epoxy compound having 2 to 20 carbon atoms

[0116] Regarding R as the aforementioned component (C) 3 The monocarboxylic acid represented by -COOH and its derivatives are used from the viewpoints of reducing the reactivity between the epoxy resin curing agent and the epoxy resin as needed and improving the workability.

[0117] R 3 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may optionally 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.

[0118] In addition, as the derivative of the monocarboxylic acid represented by R 3 -COOH, for example, esters, amides, acid anhydrides, and acyl chlorides of the carboxylic acid can be cited. As the ester of the carboxylic acid, an alkyl ester is preferred, and the carbon number of the alkyl group is preferably 1 to 6, more preferably 1 to 3, and further preferably 1 to 2.

[0119] As the aforementioned component (C), monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, and benzoic acid and their derivatives can be cited.

[0120] The aforementioned component (C) can be used alone or in combination of two or more.

[0121] Regarding the cyclic carbonate as the aforementioned component (D), it can be used as needed from the viewpoints of reducing the reactivity between the epoxy resin curing agent and the epoxy resin and improving the workability. From the viewpoint of reactivity with the aforementioned component (A), a cyclic carbonate having 6 or less membered rings is preferred. For example, ethylene carbonate, propylene carbonate, glycerol carbonate, 1,2-butylene carbonate, vinylene carbonate, 4-vinyl-1,3-dioxolan-2-one, 4-methoxymethyl-1,3-dioxolan-2-one, 1,3-dioxane-2-one, etc. can be cited. Among these, from the viewpoint of gas barrier properties, at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and glycerol carbonate is preferred.

[0122] The aforementioned component (D) can be used alone or in combination of two or more.

[0123] The monocyclic epoxide as the aforementioned component (E) is a monocyclic epoxide having 2 to 20 carbon atoms and can be used as needed from the viewpoints of reducing the reactivity between the epoxy resin curing agent and the epoxy resin and improving the workability. From the viewpoint of gas barrier properties, a monocyclic epoxide having 2 to 10 carbon atoms is preferred, and a compound represented by the following formula (2) is more preferred.

[0124]

[0125] (In formula (2), R 4represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or R 5 -O-CH2-, R 5 represents a phenyl group or a benzyl group.)

[0126] Examples of the monocyclic epoxide represented by the aforementioned formula (2) include ethylene oxide, propylene oxide, 1,2-epoxybutane, styrene oxide, phenyl glycidyl ether, and benzyl glycidyl ether. The aforementioned component (E) can be used alone or in combination of two or more.

[0127] When using the aforementioned amine curing agent with the aforementioned component (C), component (D), or component (E), any compound selected from the group consisting of the aforementioned component (C), component (D), and component (E) can be used alone, or two or more can be used in combination.

[0128] It should be noted that, in addition to the aforementioned components (A) to (E), the aforementioned amine curing agent can be a reaction product obtained by further reacting with other components within the range that does not impair the effects of the present invention. Examples of the so-called other components herein include aromatic dicarboxylic acids or their derivatives.

[0129] Among them, the dosage of the "other components" is preferably 30% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less of the total amount of the reaction components constituting the aforementioned amine curing agent.

[0130] The reaction product of the aforementioned component (A) and component (B) with at least one compound selected from the group consisting of the aforementioned component (C), component (D), and component (E) can be obtained by using at least one compound selected from the group consisting of the aforementioned component (C), component (D), and component (E) in combination with the aforementioned component (B) and reacting with the aforementioned component (A) as a polyamine compound. This reaction can add the aforementioned components (B) to (E) in any order and react with the aforementioned component (A), or mix the aforementioned components (B) to (E) and react with the aforementioned component (A).

[0131] The reaction of the aforementioned component (A) with the aforementioned component (C) can be carried out under the same conditions as the reaction of the aforementioned component (A) with component (B). When using the aforementioned component (C), the aforementioned component (B) and component (C) can be mixed and reacted with the aforementioned component (A), or the aforementioned component (A) can first react with component (B) and then react with the aforementioned component (C).

[0132] On the other hand, when using the aforementioned component (D) and / or component (E), it is preferred that the aforementioned component (A) first reacts with component (B) and then reacts with the aforementioned component (D) and / or component (E).

[0133] The reaction of the aforementioned component (A) with the aforementioned component (D) and / or component (E) is carried out by mixing component (A) with component (D) and / or component (E) under the condition of 25 to 200 °C, and performing an addition reaction under the condition of 30 to 180 °C, preferably 40 to 170 °C. In addition, catalysts such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide can be used as needed.

[0134] During the above reaction, in order to promote the reaction, component (D) and / or component (E) can be melted as needed, or diluted with a non-reactive solvent and then used.

[0135] When the above amine curing agent is a reaction product of the aforementioned component (A) and component (B) and further at least one compound selected from the group consisting of the aforementioned component (C), component (D), and component (E), for the same reason as above, the reaction molar ratio of component (B) to component (A) [(B) / (A)] is preferably in the range of 0.3 to 1.0, more preferably in the range of 0.6 to 1.0. On the other hand, the reaction molar ratio of the aforementioned component (C), component (D), and component (E) to 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 still more preferably in the range of 0.1 to 2.0.

[0136] Among them, from the viewpoints of gas barrier property, odor prevention property and fragrance retention property of the packaging material related to the second invention, and CO2 barrier property and coatability of the heat-shrinkable label related to the third invention, the reaction molar ratio of the aforementioned components (B) to (E) to component (A) [{(B)+(C)+(D)+(E)} / (A)] is preferably in the range of 0.35 to 2.5, more preferably in the range of 0.35 to 2.0.

[0137] (Amine curing agent (ii))

[0138] The amine curing agent (ii) is a reaction product of epichlorohydrin and at least one selected from the group consisting of m-xylylenediamine and p-xylylenediamine.

[0139] The amine curing agent (ii) preferably contains a compound represented by the following general formula (3) as a main component. Here, the so-called "main component" means that when all the constituent components in the amine curing agent (ii) are set to 100% by mass, its content is 50% by mass or more.

[0140]

[0141] (In formula (3), A is 1,3-phenylene or 1,4-phenylene. n is a number from 1 to 12.)

[0142] A is more preferably 1,3-phenylene.

[0143] In the amine-based curing agent (ii), the content of the compound represented by the above general formula (3) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 75% by mass or more, and even more preferably 85% by mass or more. In addition, the upper limit is 100% by mass.

[0144] From the viewpoint of obtaining good curing performance as a curing agent, in the compound represented by the above general formula (3), it is preferable that the proportion of the compound with n = 1 is high. As the content of the compound with n = 1 represented by the above general formula (3) in the amine-based curing agent (ii), it is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more. In addition, the upper limit is 100% by mass.

[0145] The content of the compound represented by the above general formula (3) in the amine-based curing agent (ii) and the composition of the compound represented by the above general formula (3) can be determined by GC analysis and gel filtration chromatography (GPC) analysis.

[0146] The amine-based curing agent (ii) can be obtained by subjecting epichlorohydrin to an addition reaction with at least one selected from the group consisting of m-xylylenediamine and p-xylylenediamine by a conventional method.

[0147] The epoxy resin curing agent used in the present invention may contain a curing agent component other than the amine-based curing agent. However, from the viewpoints of high gas barrier properties, high deodorizing properties and fragrance retention properties obtained in the packaging material according to the second invention, and high CO2 barrier properties obtained in the heat-shrinkable label according to the third invention, it is preferable that the content of the amine-based curing agent is high. 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, further preferably 80% by mass or more, and even more preferably 90% by mass or more. In addition, the upper limit is 100% by mass.

[0148] From the viewpoint of improving the adhesion of the obtained cured product to an inorganic substance, the epoxy resin curing agent used in the present invention may further contain a coupling agent. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc. From the viewpoint of improving the adhesion of the obtained cured product to an inorganic substance, a silane coupling agent is preferred.

[0149] As the silane coupling agent, for example, 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)acryloyl group, a silane coupling agent having a mercapto group, etc. can be cited. Among these, from the viewpoint of the adhesiveness of the obtained cured product to the inorganic substance, 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 preferable.

[0150] When using a coupling agent, 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, relative to 100 parts by mass of the curing agent component in the epoxy resin curing agent.

[0151] Regarding the mixing ratio of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition, it can generally be the standard mixing range when producing an epoxy resin reaction product by the reaction of the epoxy resin and the 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 (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin) is preferably in the range of 0.2 to 12.0. From the viewpoints of adhesiveness to inorganic substances such as alumina and formation of a cured product with good retort resistance, (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin) is more preferably 0.4 to 10.0, further preferably 0.6 to 8.0, still further preferably more than 1.0 and 5.0 or less, and still further preferably in the range of 1.1 to 3.5.

[0152] <Unsaturated fatty acid amide having 14 to 24 carbon atoms>

[0153] The epoxy resin composition of the present invention contains an unsaturated fatty acid amide having 14 to 24 carbon atoms (hereinafter, also simply referred to as "unsaturated fatty acid amide"). Thereby, a cured product having good adhesiveness, retort resistance, and transparency, particularly to inorganic substances such as alumina, can be formed. The packaging material according to the second invention can form a cured product layer having good anti-odor property, fragrance retention property, less adhesion, adhesiveness to the substrate, and transparency. The heat-shrinkable label according to the third invention can form a cured product layer having less adhesion, CO2 barrier property, followability to the substrate layer, and transparency.

[0154] The carbon number of the unsaturated fatty acid amide is 14 to 24, and from the viewpoints of forming a cured product having less adhesion, adhesiveness to inorganic substances such as alumina, retort resistance, CO2 barrier property, followability to the substrate layer, and transparency, it is preferably 16 to 24, more preferably 18 to 22.

[0155] The unsaturated fatty acid constituting the unsaturated fatty acid amide may be a fatty acid having 14 to 24 carbon atoms and at least 1 unsaturated bond. The number of unsaturated bonds in the unsaturated fatty acid is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.

[0156] Examples of the unsaturated fatty acid constituting the unsaturated fatty acid amide include monounsaturated fatty acids such as myristic acid, sapienic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icos-9-enoic acid, icosenoic acid, erucic acid, nervonic acid; diunsaturated fatty acids such as linoleic acid, icosadienoic acid, docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, icosatrienoic acid; tetraunsaturated fatty acids such as linolenic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid. One of them or a combination of two or more thereof can be used. Among these, from the viewpoint of forming a cured product having good adhesiveness to inorganic substances such as alumina, retort resistance, and 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, more preferably a monounsaturated fatty acid having 14 to 24 carbon atoms, still more preferably a monounsaturated fatty acid having 16 to 24 carbon atoms, and still more preferably a monounsaturated fatty acid having 18 to 22 carbon atoms.

[0157] From the viewpoint of forming a cured product having less adhesion, good adhesiveness to inorganic substances such as alumina, retort resistance, CO2 barrier property, followability to the substrate layer, and transparency, 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, icosene amide, and erucic acid amide, more preferably at least one selected from the group consisting of oleic acid amide and erucic acid amide. From the viewpoint of the adhesion inhibition effect when the epoxy resin composition is used for forming the resin cured layer of the gas barrier laminate, the packaging material according to the second invention, and the cured product layer in the heat shrinkable label according to the third invention described below, erucic acid amide is further preferred.

[0158] Erucic acid amide has solubility in an epoxy resin composition containing an amine-based curing agent. On the other hand, compared with oleic acid amide, etc., its solubility in the epoxy resin composition is not excessively high. Therefore, it exudes on the surface layer of the epoxy resin composition or its cured product and also functions as a lubricant. Therefore, it is presumed that the drying rate of the epoxy resin composition compounded with erucic acid amide is improved, and the above adhesion inhibition effect can be obtained.

[0159] The content of the 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, still more preferably 0.5 to 15 parts by mass, still further preferably 1 to 15 parts by mass, still further preferably 3 to 15 parts by mass, and still further preferably 5 to 12 parts by mass, based on 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent. If the content of the unsaturated fatty acid amide is 0.1 part by mass or more based on 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent in the epoxy resin composition, it is preferred from the viewpoints of forming a cured product having good adhesiveness to inorganic substances such as alumina and retort resistance, and obtaining a CO2 barrier property, followability to the substrate layer, and adhesion inhibition effect. Moreover, if it is 20 parts by mass or less, high gas barrier property, deodorant property, fragrance retention property, and transparency can be maintained, and elution of the unsaturated fatty acid amide can also be suppressed.

[0160] [Polyalkylene glycol]

[0161] The epoxy resin composition may further contain a polyalkylene glycol. When a polyalkylene glycol is used, the epoxy resin composition containing an unsaturated fatty acid amide having 14 to 24 carbon atoms also has high gas barrier property, deodorant property, fragrance retention property, high CO2 barrier property, and practically sufficient adhesiveness, and can form a cured product layer having gloss, high leveling property, and good appearance.

[0162] Examples of the polyalkylene glycol include homopolymers or copolymers of alkylene glycols having 2 to 8 carbon atoms. The alkylene glycol may be a linear alkylene glycol or a branched alkylene glycol.

[0163] Specific examples of the homopolymer of alkylene glycol having 2 to 8 carbon atoms include polyethylene glycol (PEG), polypropylene glycol (PPG), poly(oxytrimethylene) glycol [polytriethylene glycol], poly(oxybutylene) glycol, poly(oxytetramethylene) glycol [polytetramethylene ether glycol: PTMG], poly(oxypentamethylene) glycol, poly(oxyhexamethylene) glycol, poly(oxyoctamethylene) glycol, and the like.

[0164] As specific examples of the copolymer of an alkylene glycol having 2 to 8 carbon atoms, polyethylene glycol - polypropylene glycol (PEG - PPG), polyethylene glycol - polyoxymethylene glycol, polyethylene glycol - polyoxybutylene glycol, polyethylene glycol - polytetramethylene glycol (PEG - PTMG), polyethylene glycol - polyoxyhexamethylene glycol, polypropylene glycol - polyoxymethylene glycol, polypropylene glycol - polyoxybutylene glycol, polypropylene glycol - polytetramethylene glycol (PPG - PTMG), polyoxymethylene - polytetramethylene glycol, polytetramethylene - polyoxyhexamethylene glycol, polyethylene glycol - polypropylene glycol - polyoxybutylene glycol, polyethylene glycol - polypropylene glycol - polytetramethylene glycol, etc. can be cited.

[0165] One kind or two or more kinds of polyalkylene glycols can be used. From the viewpoints of improving gas barrier properties, deodorizing properties, and fragrance retention properties, CO2 barrier properties, and improving the appearance of the cured product layer, as the polyalkylene glycol, a homopolymer or copolymer of an alkylene glycol having 2 to 6 carbon atoms is preferred, a homopolymer or copolymer of an alkylene glycol having 2 to 4 carbon atoms is more preferred, and at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(oxymethylene) glycol, poly(oxybutylene) glycol, poly(polytetramethylene) glycol, polyethylene glycol - polypropylene glycol, polyethylene glycol - polyoxymethylene glycol, polyethylene glycol - polytetramethylene glycol, polypropylene glycol - polytetramethylene glycol, and polyoxymethylene - polytetramethylene glycol is further preferred. Even more preferably, at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and poly(polytetramethylene) glycol is selected. From the viewpoints of improving gas barrier properties, deodorizing properties, and fragrance retention properties, CO2 barrier properties, improving the appearance of the cured product layer, and improving the adhesiveness to the substrate, polyethylene glycol is even more preferably selected.

[0166] Regarding the weight - average molecular weight (Mw) of the polyalkylene glycol, from the viewpoints of improving gas barrier properties, deodorizing properties, and fragrance retention properties, CO2 barrier properties, and improving the appearance of the cured product layer, it is preferably 200 to 10000, more preferably 200 to 5000, and further preferably 200 to 3000. From the viewpoints of improving gas barrier properties, deodorizing properties, and fragrance retention properties, CO2 barrier properties, improving the appearance of the cured product layer, suppressing adhesion, and improving the adhesiveness to the substrate, it is even more preferably 400 to 2000, and even more preferably 500 to 1500.

[0167] In the case of using a polyalkylene glycol, with respect to the content of the polyalkylene glycol in the epoxy resin composition, from the viewpoints of improving gas barrier properties, anti-odor properties, and fragrance retention properties, from the viewpoint of CO2 barrier properties, and from the viewpoint of improving the appearance of the cured product layer, it is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 5.0 parts by mass, still more preferably 0.3 to 3.0 parts by mass, and even more preferably 0.5 to 2.0 parts by mass relative to 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent.

[0168] <Non-spherical inorganic particles>

[0169] The epoxy resin composition of the present invention may further contain non-spherical inorganic particles. By containing non-spherical inorganic particles in the epoxy resin composition of the present invention, an adhesion inhibition effect can be obtained when forming the resin cured layer of the gas barrier laminate described later, and the gas barrier properties, flexural resistance, anti-odor properties and fragrance 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.

[0170] The shape of the non-spherical inorganic particles only needs to be a three-dimensional shape other than spherical (substantially spherical), and examples thereof include plate-like, scaly, columnar, chain-like, fibrous, etc. The plate-like and scaly inorganic particles can be stacked in multiple layers to form a layer. Among these, from the viewpoints of improving gas barrier properties and flexural resistance, improving the anti-odor properties and fragrance retention properties of the packaging material according to the second invention, transparency, and improving the CO2 barrier properties of the heat-shrinkable label according to the third invention, plate-like, scaly, columnar, or chain-like inorganic particles are preferred, plate-like, scaly, or columnar inorganic particles are more preferred, and plate-like or scaly inorganic particles are even more preferred.

[0171] Examples of the inorganic substance constituting the non-spherical inorganic particles include silica, alumina, mica, talc, aluminum, bentonite, montmorillonite, etc. Among these, from the viewpoint of improving gas barrier properties and flexural 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.

[0172] For the purpose of improving the dispersibility in the epoxy resin composition and the transparency of the cured product, the above non-spherical inorganic particles may be surface-treated as needed. Among them, the non-spherical inorganic particles are preferably coated with an organic material. From the viewpoints of improving the gas barrier property, bending resistance, and transparency when the epoxy resin composition is used for forming the resin cured layer of the gas barrier laminate, improving the deodorizing property and fragrance retention property of the packaging material according to the second invention, and the CO2 barrier property 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 viewpoints of improving the gas barrier property, deodorizing property, fragrance retention property, CO2 barrier property, and bending resistance, silica coated with an organic material is further preferred, and alumina coated with an organic material is further preferred from the viewpoint of transparency.

[0173] The average particle diameter of the non-spherical inorganic particles is preferably in the range of 1 to 2000 nm, more preferably 1 to 1500 nm, further preferably 1 to 1000 nm, still further preferably 1 to 800 nm, still further preferably 1 to 500 nm, still further preferably 5 to 300 nm, still further preferably 5 to 200 nm, still further preferably 5 to 100 nm, and still further preferably 8 to 70 nm. If the average particle diameter is 1 nm or more, the preparation of the inorganic particles is easy, and if it is 2000 nm or less, the gas barrier property, bending resistance, and transparency when the epoxy resin composition is used for forming the resin cured layer of the gas barrier laminate are all improved. Moreover, the deodorizing property, fragrance retention property, bending resistance, and transparency of the packaging material when forming the cured product layer in the packaging material according to the second invention, and the CO2 barrier property when forming the cured product layer in the heat-shrinkable label according to the third invention are all improved. It should be noted that the average particle diameter is the average particle diameter of the primary particles.

[0174] 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. If the aspect ratio is 2 or more, it is easy to exhibit good gas barrier property. For the average particle diameter and aspect ratio of the non-spherical inorganic particles, for example, a scanning electron microscope (SEM) or a transmission electron microscope (TEM) can be used for observation, and the average value of the measurement values at three or more positions is obtained. It should be noted that for the average particle diameter and aspect ratio of the non-spherical inorganic particles present in the resin cured layer or the cured product layer, for example, it can be obtained by the following method: after embedding the gas barrier laminate and the epoxy resin for the packaging material described later, using an ion milling device, ion milling of the laminate, the packaging material, and the cross section is performed to prepare a cross-section observation sample, and the cross section of the resin cured layer or the cured product layer portion of the obtained sample is observed and measured by the same method as above, thereby the average particle diameter and aspect ratio can be obtained.

[0175] When the average particle diameter of the non-spherical inorganic particles is less than 100 nm and it is difficult to measure the average particle diameter by the above method, the average particle diameter can also be measured by, for example, the BET method.

[0176] There is no particular limitation on the method for producing the non-spherical inorganic particles, and known methods can be used.

[0177] From the viewpoints of ease of preparation of the non-spherical inorganic particles, ease of compounding in the epoxy resin composition, and dispersibility, it is preferred in the present invention to prepare a dispersion of the non-spherical inorganic particles and compound the dispersion in the epoxy resin composition. There is no particular limitation on the dispersion medium for the non-spherical inorganic particle dispersion, and water or an organic solvent can be used. As the organic solvent, from the viewpoint of the dispersibility of the non-spherical inorganic particles, a polar solvent is preferred, and examples thereof 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, 1-propoxy-2-propanol, and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0178] From the viewpoint of the 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. From the viewpoints of the dispersibility of the particles and the miscibility of the dispersion with the epoxy resin composition, a protic polar solvent is more preferred, and at least one selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol is further preferred.

[0179] When using the non-spherical inorganic particles, based on 100 parts by mass of the total amount of the aforementioned epoxy resin and the aforementioned epoxy resin curing agent, 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, further preferably 1.5 to 7.5 parts by mass, and even more preferably 3.0 to 7.0 parts by mass. When the content of the non-spherical inorganic particles in the epoxy resin composition is 0.5 parts by mass or more based on 100 parts by mass of the total amount of the epoxy resin and the aforementioned epoxy resin curing agent, the gas barrier property and the effect of improving the flex resistance are good when the epoxy resin composition is used for forming the resin cured layer of the gas barrier laminate. Furthermore, the anti-odor property, fragrance retention property, flex resistance, transparency of the packaging material when used for forming the cured product layer in the packaging material according to the second invention, and the CO2 barrier property when used for forming the cured product layer in the heat-shrinkable label according to the third invention are all good. In addition, when the content is 10.0 parts by mass or less, the transparency is also good.

[0180] Within the range not detrimental to the effects of the present invention, additives such as thermosetting resins, wetting agents, tackifiers, defoamers, curing accelerators, rust preventive additives, pigments, deoxidizers, etc. can be compounded in the epoxy resin composition as needed.

[0181] 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, relative to 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent.

[0182] Among them, from the viewpoint of obtaining the effects of the present invention, the total content of the epoxy resin, the epoxy resin curing agent, and the 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, further preferably 80% by mass or more, still more preferably 85% by mass or more, and the upper limit is 100% by mass. The "solid content of the epoxy resin composition" means the components other than water and organic solvents in the epoxy resin composition.

[0183] The epoxy resin composition may contain an organic solvent. As the organic solvent used in the epoxy resin composition, a non-reactive solvent is preferred. As specific examples thereof, polar solvents exemplified as dispersion media used in dispersions of non-spherical inorganic particles can be used, 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, 1-propoxy-2-propanol, etc., and one or more of ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, etc.

[0184] Among the above, from the viewpoints of improving the drying speed and making the appearance of the obtained resin cured layer or cured product layer good, 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.

[0185] When the epoxy resin composition contains an organic solvent, the epoxy resin and the epoxy resin curing agent react easily over time and precipitate is generated in the composition, and the shelf life (usable time) tends to be shortened. From the viewpoints of suppressing the generation of precipitation and improving the shelf life of the epoxy resin composition, the organic solvents used in the epoxy resin composition are further preferably ethanol and ethyl acetate.

[0186] 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, still more preferably 85 / 15 to 60 / 40, and even more preferably 75 / 25 to 65 / 35.

[0187] When the epoxy resin composition contains an organic solvent, the solid content concentration of the epoxy resin composition is not particularly limited, and from the viewpoint of coatability, it is usually 0.5% by mass or more, more preferably 1% by mass or more. Further, from the viewpoints of improving coatability and the shelf life of the composition, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0188] <Preparation of Epoxy Resin Composition>

[0189] The epoxy resin composition can be prepared, for example, by separately blending predetermined amounts of an epoxy resin, an epoxy resin curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, a dispersion of non-spherical inorganic particles, other additives, and an organic solvent, and then stirring and mixing them using known methods and apparatuses.

[0190] The order of mixing the respective components is not particularly limited. When using non-spherical inorganic particles, in order to improve the dispersibility of the non-spherical inorganic particles in the epoxy resin composition, it is preferred that: first, the dispersion of non-spherical inorganic particles and the solvent component are mixed, and then, an epoxy resin curing agent or its solution, an unsaturated fatty acid amide, and an epoxy resin are sequentially added and mixed. The reason is that by gradually increasing the solid content concentration in the liquid containing non-spherical inorganic particles from a lower state to a higher state, the dispersibility of the non-spherical inorganic particles can be maintained in a good state.

[0191] When the epoxy resin composition contains an organic solvent, from the viewpoint of improving the freedom of compounding of the epoxy resin composition, the manufacturing method of the epoxy resin composition preferably sequentially includes the following steps: 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 (Manufacturing Method 1).

[0192] More preferably, Manufacturing Method 1 sequentially includes the following steps: 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.

[0193] As the organic solvent, 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 further preferred. When the organic solvents contained in the epoxy resin composition are ethanol and ethyl acetate, from the viewpoint of improving the shelf life, it is more preferred that the mass ratio of ethanol to ethyl acetate (ethanol / ethyl acetate) in the finally obtained epoxy resin composition falls within the aforementioned range.

[0194] When using the aforementioned coupling agent as an additive, the coupling agent is preferably compounded in the epoxy resin curing agent solution 2. Moreover, when using the aforementioned non-spherical inorganic particles, it is preferred to mix the dispersion of the non-spherical inorganic particles with the epoxy resin curing agent solution 1.

[0195] In Production Method 1, regarding the solid content concentration of the epoxy resin curing agent solution 1, from the viewpoint of the freedom of compounding of the epoxy resin composition, it is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and from the viewpoint of improving the stirring efficiency, it is preferably 80% by mass or less, more preferably 75% by mass or less.

[0196] In Production Method 1, regarding the solid content concentration of the epoxy resin curing agent solution 2, from the viewpoint of the freedom of compounding of the epoxy resin composition, it is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, still more preferably 25% by mass or more, and from the viewpoints of improving the stirring efficiency and the shelf life, it is preferably 70% by mass or less, more preferably 50% by mass or less.

[0197] The mixing of each component can be carried out according to a conventional method using a publicly known stirring device.

[0198] Furthermore, from the viewpoint of improving the production efficiency of the epoxy resin composition, it is more preferred to pre-dissolve the unsaturated fatty acid amide having 14 to 24 carbon atoms in the organic solvent and then compound it into the epoxy resin composition.

[0199] More specifically, from the viewpoints of improving the production efficiency of the epoxy resin composition and the freedom of compounding, the epoxy resin composition of the present invention is more preferably produced by a production method (Production Method 2) having the following steps (I) to (IV).

[0200] 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)

[0201] 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).

[0202] Step (III): A step of mixing the unsaturated fatty acid amide solution (a) with the epoxy resin curing agent solution (b) to obtain an epoxy resin curing agent solution (c).

[0203] Step (IV): A step of mixing the epoxy resin curing agent solution (c) with an epoxy resin to obtain an epoxy resin composition.

[0204] According to the above manufacturing method 2, by preparing the solution (a) in which an unsaturated fatty acid amide having 14 to 24 carbon atoms is dissolved in an organic solvent in step (I) and then mixing it with the epoxy resin curing agent solution (b) in step (III), the dissolution time when the unsaturated fatty acid amide is dissolved in the epoxy resin composition can be shortened, and the manufacturing efficiency can be improved.

[0205] It should be noted that step (I) and step (II) can be carried out sequentially, or can be carried out in the order of step (II) and step (I).

[0206] 〔Step (I)〕

[0207] 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 the epoxy resin curing agent, the epoxy resin curing agent solution, or the epoxy resin composition, it sometimes takes a long time to dissolve the unsaturated fatty acid amide. However, by carrying out step (I), the dissolution time of the unsaturated fatty acid amide can be shortened.

[0208] As the organic solvent (i), the organic solvents exemplified in the epoxy resin composition can be used, and 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 still more preferably ethanol and ethyl acetate.

[0209] The mixing of the unsaturated fatty acid amide and the organic solvent (i) in step (I) can be carried out according to a conventional method using a known stirring device. The mixing temperature in step (I) is not particularly limited, and from the viewpoint of the solubility of the unsaturated fatty acid amide, it is preferably 15°C or higher, more preferably 20°C or higher, and from the viewpoint of suppressing the volatilization of the organic solvent (i), it is preferably 60°C or lower, more preferably 50°C or lower.

[0210] From the viewpoint of improving the stirring efficiency and the manufacturing efficiency of the epoxy resin composition, 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% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 5% by mass.

[0211] [Step (II)]

[0212] In 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).

[0213] As the organic solvent (ii), 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 an amine-based curing agent, at least one selected from the group consisting of methanol and ethanol is more preferred for the organic solvent (ii), and ethanol is still more preferred in consideration of environmental safety.

[0214] At least a part of the organic solvent (ii) can be the reaction solvent used in the production of the aforementioned amine-based curing agent.

[0215] The mixing of the epoxy resin curing agent containing an amine-based curing agent and 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, and from the viewpoint of manufacturing efficiency, it is preferably 15°C or higher, more preferably 20°C or higher, and from the viewpoints of suppressing the thermal deterioration of the epoxy resin curing agent and suppressing the volatilization of the organic solvent (ii), it is preferably 60°C or lower, more preferably 50°C or lower.

[0216] Regarding the concentration of the epoxy resin curing agent in the epoxy resin curing agent solution (b) obtained in step (II), from the viewpoint of the degree of freedom of concentration adjustment of the epoxy resin curing agent solution (c) obtained in step (III) and the epoxy resin composition obtained in step (IV), it is preferably 20% by mass or higher, more preferably 30% by mass or higher, and still more preferably 40% by mass or higher, and from the viewpoint of improving the stirring efficiency, it is preferably 80% by mass or lower, more preferably 75% by mass or lower.

[0217] [Step (III)]

[0218] In step (III), the unsaturated fatty acid amide solution (a) obtained in step (I) is mixed with the epoxy resin curing agent solution (b) obtained in step (II) to obtain an epoxy resin curing agent solution (c).

[0219] In step (III), the unsaturated fatty acid amide solution (a) prepared in advance in step (I) is mixed with the epoxy resin curing agent solution (b) obtained in step (II), so that the dissolution time of the unsaturated fatty acid amide can be shortened and the manufacturing efficiency of the epoxy resin composition can be improved.

[0220] In step (III), for the purpose of adjusting the solid content concentration of the obtained epoxy resin curing agent solution (c), an organic solvent can be further added as needed. As the organic solvent, the solvents exemplified in the aforementioned organic solvent (i) can be cited.

[0221] When the aforementioned coupling agent is used as an additive, the coupling agent is preferably compounded in step (III). More specifically, in step (III), the coupling agent is preferably compounded in the unsaturated fatty acid amide solution (a) and then mixed with the epoxy resin curing agent solution (b).

[0222] The mixing of the unsaturated fatty acid amide solution (a) and the epoxy resin curing agent solution (b) in step (III) can be carried out according to a conventional method using a known stirring device.

[0223] In step (III), from the viewpoint of not improving the solubility of the saturated 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 volatilization 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.

[0224] After step (III) is carried out, operations such as cooling and filtration can be carried out as needed.

[0225] Regarding the solid content concentration of the epoxy resin curing agent solution (c) obtained in step (III), from the viewpoint of the degree of freedom of adjusting the concentration of the epoxy resin composition obtained in step (IV), it is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. From the viewpoint of improving the stirring efficiency, it is preferably 70% by mass or lower, more preferably 50% by mass or lower.

[0226] 〔Step (IV)〕

[0227] In step (IV), the epoxy resin curing agent solution (c) is mixed with the epoxy resin to obtain an epoxy resin composition.

[0228] In step (IV), for the purpose of preferably adjusting the solid content concentration of the obtained epoxy resin composition to the aforementioned range, an organic solvent can be further added as needed. As the organic solvent, the solvents exemplified in the aforementioned organic solvent (i) can be cited.

[0229] From the viewpoint of improving the shelf life of the epoxy resin composition, it is preferable that the organic solvent in the finally obtained epoxy resin composition is ethanol and ethyl acetate, and more preferably the mass ratio of ethanol to ethyl acetate (ethanol / ethyl acetate) falls within the aforementioned range.

[0230] 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).

[0231] <Usage>

[0232] The cured product of the epoxy resin composition of the present invention has excellent gas barrier properties, good adhesiveness to inorganic substances such as alumina, is not easily peeled off even after retort treatment, and has excellent retort resistance. For example, the resin cured 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 not only for the gas barrier laminate described below, but also for gas barrier packaging materials, gas barrier adhesives, etc. Furthermore, the epoxy resin composition of the present invention is also suitable for forming the cured product layer constituting the packaging material according to the second invention and the cured product layer constituting the heat shrinkable label according to the third invention.

[0233] As a method for curing the epoxy resin composition of the present invention to form the cured product, there is no particular limitation, and a known method can be used. One embodiment thereof will be described in the manufacturing method of the gas barrier laminate.

[0234] [Gas barrier laminate]

[0235] The gas barrier laminate according to the first invention is characterized by having: a substrate; and a resin cured layer (hereinafter, also simply referred to as "resin cured layer") which is a cured product of the aforementioned 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".

[0236] The gas barrier laminate of the present invention is a laminate having high gas barrier properties and high interfacial adhesiveness between the substrate and the resin cured layer. Hereinafter, the materials constituting the gas barrier laminate of the present invention will be described.

[0237] <Substrate>

[0238] As the substrate constituting the gas barrier laminate of the present invention, an inorganic substrate or an organic substrate can be used.

[0239] As the inorganic substrate, for example, metal foils such as aluminum foil can be cited.

[0240] As the organic base material, a transparent plastic film is preferred. Examples of the transparent plastic film include polyolefin-based films such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and polypropylene; polyester-based films such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polyamide-based films such as nylon 6, nylon 6,6, and poly(m-phenylene isophthalamide) (N-MXD6); polyimide-based films; biodegradable films such as polylactic acid; polyacrylonitrile-based films; poly(meth)acrylic acid-based films; polystyrene-based films; polycarbonate-based films; ethylene-vinyl acetate copolymer saponified product (EVOH)-based films, polyvinyl alcohol-based films, and the like. Among these, from the viewpoints of transparency, strength, and heat resistance, as the organic base material, a film selected from the group consisting of polyolefin-based films, polyester-based films, polyamide-based films, and polyimide-based films is preferred, a film selected from the group consisting of polyolefin-based films and polyester-based films is more preferred, and a polypropylene film or a polyethylene terephthalate (PET) film is further preferred.

[0241] The above-mentioned film can be stretched in the uniaxial or biaxial direction.

[0242] The thickness of the base material can be appropriately selected according to the use and is not particularly limited. From the viewpoints of gas barrier property and strength, it is preferably 5 to 300 μm, more preferably 5 to 100 μm, further preferably 5 to 50 μm, and still further preferably 5 to 40 μm. When the base material is an organic base material, from the viewpoints of gas barrier property and strength, the thickness of the organic base material is still further preferably 8 to 50 μm, and still further preferably 10 to 40 μm.

[0243] <Resin cured layer>

[0244] The resin cured layer in the gas barrier laminate of the present invention is a cured product of the above-mentioned epoxy resin composition. The curing method of the epoxy resin composition is not particularly limited and is carried out according to a known method at a sufficient concentration and temperature of the epoxy resin composition required to obtain its cured product. The curing temperature can be selected, for example, in the range of 10 to 140 °C.

[0245] From the viewpoints of gas barrier property and bending resistance, the thickness of the resin cured layer is preferably 0.05 μm or more, more preferably 0.1 μm or more. In addition, from the viewpoints of adhesion to inorganic substances such as alumina, retort resistance, and transparency, it is preferably 20 μm or less, more preferably 10 μm or less, further preferably 5.0 μm or less, still further preferably 2.0 μm or less, still further preferably 1.0 μm or less, still further preferably 0.5 μm or less, still further preferably 0.4 μm or less. The above thickness is the thickness of each layer of the resin cured layer.

[0246] The gas-barrier laminate of the present invention only needs to have a base material and at least one resin cured layer. From the viewpoints of obtaining high gas-barrier properties and the effectiveness of the effects of the present invention, it preferably has at least one layer composed of an inorganic substance. Specifically, the layer composed of an inorganic substance is preferably the aforementioned inorganic base material or an inorganic thin film layer.

[0247] (Inorganic thin film layer)

[0248] 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 the thickness is thin. Examples of the inorganic thin film layer include those composed of a metal foil and those formed by a vapor deposition method. From the viewpoint of obtaining high transparency, an inorganic vapor deposition layer formed by a vapor deposition method is preferred.

[0249] The inorganic substance constituting the inorganic thin film layer is not particularly limited as long as it can form a gas-barrier thin film on the aforementioned base material, and examples thereof include silicon, aluminum, magnesium, calcium, zinc, tin, nickel, titanium, zirconium, carbon, or their oxides, carbides, nitrides, oxynitrides, etc. Among these, from the aspect of gas-barrier properties, at least one selected from the group consisting of silicon oxide (silica), aluminum, and aluminum oxide (aluminum oxide) is preferred. From the viewpoint of forming a thin film with high gas-barrier properties and transparency, at least one selected from the group consisting of silicon oxide and aluminum oxide is more preferred. From the aspect of gas-barrier properties, silicon oxide is further preferred. On the other hand, even for an inorganic thin film layer composed of aluminum oxide, which has been difficult to exhibit adhesiveness in the past, the resin cured layer, which is a cured product of the epoxy resin composition of the present invention, also exhibits good adhesiveness. Therefore, from the viewpoint of the effectiveness of the effects of the present invention, the inorganic substance constituting the inorganic thin film layer is preferably aluminum oxide. The above-mentioned inorganic substances can be used alone or in combination of two or more.

[0250] From the viewpoint of obtaining high gas-barrier properties, the thickness of the inorganic thin film layer is preferably 5 nm or more. In addition, from the viewpoints of transparency and bend resistance, it is preferably 100 nm or less, and more preferably 50 nm or less. The above thickness is the thickness of each layer of the inorganic thin film layer.

[0251] The method for forming the inorganic thin film layer is not particularly limited. For example, as the vapor deposition method, known vapor deposition methods such as physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, or chemical vapor deposition methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photo chemical vapor deposition can be mentioned. In addition, an inorganic thin film layer can also be formed by laminating a metal foil such as an aluminum foil with the aforementioned base material.

[0252] The inorganic thin film layer can be formed, for example, on an organic base material or on a resin cured layer.

[0253] (Thermoplastic resin layer)

[0254] From the perspective of steam cooking treatment and the like, the gas-barrier laminate of the present invention may further have one or two or more layers of thermoplastic resin layers.

[0255] As the thermoplastic resin layer, a thermoplastic resin film is preferably used, and the same film as the transparent plastic film exemplified in the aforementioned organic substrate can be used. Among the transparent plastic films, at least one selected from the group consisting of polyolefin-based films and polyamide-based films is preferably used, and from the viewpoints of transparency, heat resistance, and suitability for packaging foods and the like, at least one selected from the group consisting of polypropylene films and nylon 6 films is more preferably used.

[0256] Surface treatments such as flame treatment and corona discharge treatment can be applied to the surface of the thermoplastic resin film. Moreover, as the thermoplastic resin film, a film containing an ultraviolet absorber, a coloring agent, etc. can also be used; a film having a primer layer, an ink layer, a surface protective layer, a vapor deposition layer, etc. on the surface.

[0257] 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 of each layer of the thermoplastic resin layer.

[0258] (Adhesive layer)

[0259] In order to laminate the aforementioned thermoplastic resin layer, the gas-barrier laminate of the present invention may further have an adhesive layer.

[0260] As the adhesive constituting the adhesive layer, known adhesives such as urethane-based adhesives, acrylic-based adhesives, and epoxy-based adhesives can be used. The thickness of the adhesive layer is not particularly limited, and from the viewpoint of balancing adhesiveness and transparency, it is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and further preferably 2 to 20 μm. The above thickness is the thickness of each layer of the adhesive layer.

[0261] <Layer constitution of the gas-barrier laminate>

[0262] The gas-barrier laminate of the present invention only needs to have the constitution of the aforementioned substrate and at least one layer of the aforementioned resin cured layer. As described above, from the viewpoint of the effectiveness of the effects of the present invention, the gas-barrier laminate of the present invention preferably has a layer composed of an inorganic substance, and from the viewpoint of economy, it preferably has one or two layers, and preferably only has one layer of the aforementioned resin cured layer. In addition, from the viewpoint of the effectiveness of the effects of the present invention, the layer composed of an inorganic substance is preferably adjacent to the aforementioned resin cured layer.

[0263] As the layer constitution of the gas-barrier laminate having a substrate and one or two layers of resin cured layers and having a layer composed of an inorganic substance, the following are exemplified.

[0264] (1) A structure having a substrate and a resin cured layer, and the substrate being an inorganic substrate

[0265] (2) A structure sequentially including a substrate, an inorganic thin film layer, and a resin cured layer

[0266] (3) A structure sequentially including a substrate, a resin cured layer, and an inorganic thin film layer

[0267] (4) A structure sequentially including a substrate, a resin cured layer, an inorganic thin film layer, and a resin cured layer

[0268] In the above (1), when there are two or more substrates, as long as at least one substrate is an inorganic substrate.

[0269] In the above (2), (3) and (4), the substrate is preferably an organic substrate. In addition, from the viewpoint of the effectiveness of the effects of the present invention, the layer composed of an inorganic substance is preferably adjacent to the aforementioned resin cured layer. From the viewpoint of gas barrier properties, any of the above (1), (2) or (4) is more preferred, and the structure of (1) or (2) is more preferred.

[0270] From the viewpoint of the effectiveness of the effects of the present invention and the viewpoint of being applicable to applications requiring retort resistance and transparency, the structure of the above (2) is further preferred.

[0271] The gas barrier laminate of the present invention may have any layer structure among the above (1) to (4), and further, may have one layer or two or more layers of the aforementioned thermoplastic resin layer.

[0272] As a preferred layer structure of the gas barrier laminate, for example, Figures 1 to 4 The structure. Hereinafter, in this specification, a laminate having only a substrate and no thermoplastic resin layer is referred to as "laminate (I)", a laminate having a total of two layers of a substrate and a thermoplastic resin layer is referred to as "laminate (II)", and a laminate having a total of three layers is referred to as "laminate (III)".

[0273] Figure 1 and Figure 2 is a cross-sectional schematic view showing an embodiment of the gas barrier laminate (I) of the present invention. Figure 1 In the gas barrier laminate 100 in, an inorganic thin film layer 2 and a resin cured layer 3 are sequentially provided on a substrate 1. Figure 1 In, the inorganic thin film layer 2 is adjacent to the resin cured layer 3.

[0274] Figure 2 In the gas barrier laminate 100a in, a resin cured layer 3 and an inorganic thin film layer 2 are sequentially provided on a substrate 1.

[0275] Figures 3 to 6Cross-sectional schematic view showing an embodiment of the gas-barrier laminate (II) of the present invention. Figures 3 to 6 The gas-barrier laminate has a substrate and a thermoplastic resin layer, each having one layer (two layers in total), and the thermoplastic resin layer can be directly laminated or laminated with an adhesive layer interposed therebetween.

[0276] Figure 3 The gas-barrier laminate 200 in has a structure in which the thermoplastic resin layer 4 is directly laminated without an adhesive layer interposed therebetween, and has a structure in which the substrate 1, the inorganic thin film layer 2, the resin cured layer 3, and the thermoplastic resin layer 4 are laminated in sequence.

[0277] Figures 4 to 6 The gas-barrier laminates 300, 300a, and 300b in have a structure in which the thermoplastic resin layer 4 is laminated with an adhesive layer 5 interposed therebetween. Figure 4 The gas-barrier laminate 300 in has a structure in which the substrate 1, the inorganic thin film layer 2, the resin cured layer 3, the adhesive layer 5, and the thermoplastic resin layer 4 are laminated in sequence.

[0278] Figure 5 The gas-barrier laminate 300a in has a structure in which the substrate 1, the resin cured layer 3, the inorganic thin film layer 2, the adhesive layer 5, and the thermoplastic resin layer 4 are laminated in sequence.

[0279] Figure 6 The gas-barrier laminate 300b in has a structure in which the substrate 1, the resin cured layer 3, the inorganic thin film layer 2, the resin cured layer 3, the adhesive layer 5, and the thermoplastic resin layer 4 are laminated in sequence.

[0280] Figures 7 to 9 Cross-sectional schematic view showing an embodiment of the gas-barrier laminate (III) of the present invention. Figure 7 and Figure 8 The gas-barrier laminate of and has a substrate of one layer and two thermoplastic resin layers (three layers in total), Figure 9 The gas-barrier laminate of has a substrate of two layers and one thermoplastic resin layer (three layers in total).

[0281] Figure 7 The gas-barrier laminate 400 has a structure in which the substrate 1, the inorganic thin film layer 2, the resin cured layer 3, the adhesive layer 5, the thermoplastic resin layer 4, the adhesive layer 5, and the thermoplastic resin layer 4 are laminated in sequence.

[0282] Figure 8 The gas-barrier laminate 400a has a structure in which the substrate 1, the resin cured layer 3, the inorganic thin film layer 2, the adhesive layer 5, the thermoplastic resin layer 4, the adhesive layer 5, and the thermoplastic resin layer 4 are laminated in sequence.

[0283] Figure 9The gas-barrier laminate 400c has a structure in which a substrate 1, an adhesive layer 5, a substrate 1c, a resin cured layer 3, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order. It is preferable that at least one of the substrates is an inorganic substrate. For example, it can be cited that the substrate 1c is an inorganic substrate.

[0284] The thermoplastic resin layers 4 that constitute the gas-barrier laminate 400 or 400a can all be the same resin layer, or they can be different resin layers from each other. Moreover, the adhesive layer 5 can be a layer formed entirely of the same adhesive, or it can be a layer formed of different adhesives.

[0285] However, the laminate of the present invention is not limited to Figures 1 to 9 the laminate having such a layer structure. In addition, an arbitrary layer such as a primer layer, an ink layer, an adhesive layer, a surface protective layer, or a vapor deposition layer can be further laminated on the laminate of the present invention.

[0286] <Manufacturing method of gas-barrier laminate>

[0287] The manufacturing method of the gas-barrier laminate of the present invention is not particularly limited, and a known method can be used.

[0288] For example, as Figure 1 a manufacturing method of the gas-barrier laminate 100 having such a structure, the following method can be cited: an inorganic thin film layer is formed on one surface of a substrate, and the aforementioned epoxy resin composition for forming a resin cured layer is coated on the surface on the side of the inorganic thin film layer to a desired thickness, and then, the epoxy resin composition is cured to form a resin cured layer. It should be noted that a film on which an inorganic thin film layer is previously formed on a transparent plastic film can be used, and a resin cured layer is formed on the surface of this inorganic thin film layer.

[0289] As Figure 2 a manufacturing method of the gas-barrier laminate 100a having such a structure, the following method can be cited: the aforementioned epoxy resin composition is coated on one surface of a substrate, and then, the epoxy resin composition is cured to form a resin cured layer, and then, an inorganic thin film layer is formed on this resin cured layer.

[0290] As a coating method when coating the epoxy resin composition, for example, bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, micro reverse gravure coating, die coating, slot die coating, vacuum die coating, dip coating, spin coating, roll coating, spray coating, brush coating, etc. can be cited. Among these, bar coating, roll coating, or spray coating is preferable, and gravure coating, reverse gravure coating, microgravure coating, or micro reverse gravure coating is preferably used industrially.

[0291] After applying the epoxy resin composition, a step of volatilizing the solvent (drying step) is carried out as needed. The conditions in the drying step can be appropriately selected. For example, it can be carried out under the conditions of a drying temperature of 40 to 180°C and a drying time of 5 to 180 seconds.

[0292] After carrying out the drying step, the epoxy resin composition is cured to form a resin cured layer. The curing temperature can be selected within the range of, for example, 10 to 140°C, preferably in the range of 10 to 80°C. In addition, the curing time can be selected within the range of, for example, 0.5 to 200 hours, preferably in the range of 2 to 100 hours.

[0293] As Figure 3 a method for manufacturing the gas barrier laminate 200 having the

[0294] As Figure 4 a method for manufacturing the gas barrier laminate 300 having the Figure 1 following method can be cited: An inorganic thin film layer is formed on a substrate. After applying the aforementioned epoxy resin composition on the surface of the inorganic thin film, a thermoplastic resin film constituting a thermoplastic resin layer is immediately laminated on the coated surface by using a roll or the like. Then, the epoxy resin composition is cured by the aforementioned method. In this case, the epoxy resin composition constituting the resin cured layer functions as an adhesive layer for bonding the inorganic thin film layer in the gas barrier laminate 200 and the above-mentioned thermoplastic resin film. Figure 5 The gas barrier laminate 300a having the Figure 2 following structure can be manufactured in the same manner as the gas barrier laminate 100a having the

[0295] As Figure 6 a method for manufacturing the gas barrier laminate 300b having the Figure 2 following method can be cited: A resin cured layer is formed on the surface of the inorganic thin film of the gas barrier laminate 100a having the

[0296] Figure 7 The gas barrier laminate 400 having the Figure 4 following structure can be manufactured as follows: After forming the gas barrier laminate 300 having the Figure 8 The gas barrier laminate 400a having the Figure 5 following structure can be manufactured in the same manner as the gas barrier laminate 300a having the

[0297] Figure 9 As a method for forming the gas-barrier laminate 400c having the following configuration, for example, a substrate 1, an adhesive layer 5, and a substrate 1c are laminated in this order, a resin cured layer is formed on the surface of the substrate 1c, and then, an adhesive constituting the adhesive layer is coated on the surface of the resin cured layer or on one side of a thermoplastic resin film, and then, the two are laminated.

[0298] <Properties of the gas-barrier laminate>

[0299] The gas-barrier laminate of the present invention has excellent gas-barrier properties. For example, the oxygen transmission rate of the gas-barrier laminate (II) at 23°C and a relative humidity of 60% varies depending on the barrier properties of the substrate used, and is preferably 2 cc / m 2 ·day·atm or less, more preferably 1.5 cc / m 2 ·day·atm or less, and even more preferably 1 cc / m 2 ·day·atm or less.

[0300] Specifically, the oxygen transmission rate of the gas-barrier laminate can be determined by the method described in the examples.

[0301] <Uses of the gas-barrier laminate>

[0302] Since the gas-barrier laminate of the present invention has excellent gas-barrier properties and bending resistance, it is suitable for use as a packaging material for protecting foods, pharmaceuticals, cosmetics, precision electronic components, etc. When used as a packaging material, the gas-barrier laminate of the present invention can be directly used as a packaging material, or other layers and films can be further laminated and used.

[0303] The form of the packaging material can be appropriately selected according to the articles to be stored and preserved. For example, packaging films; packaging containers such as packaging bags and bottles; and lid materials and sealing materials for packaging containers can be mentioned. Among these, as a form suitable for heat sterilization treatment, packaging films, and packaging bags or their lid materials and sealing materials are preferred. Specific examples of the packaging film or the packaging bag include three-side sealed flat bags, stand-up pouches, gusseted packaging bags, pillow-shaped packaging bags, multi-chamber bags composed of a main chamber and a sub-chamber and having an easily peelable wall between the main chamber and the sub-chamber, shrink film packaging, etc.

[0304] There is no particular limitation on the capacity of the packaging material, and it can be appropriately selected according to the articles to be stored and preserved.

[0305] As a use of the packaging material, from the viewpoint of the effectiveness of the effects of the present invention, uses requiring heat sterilization resistance are preferred, and more preferably packaging materials for heat-sterilized foods such as bags and lid materials for heat-sterilized foods, and among them, bags for heat-sterilized foods are even more preferred.

[0306] From the viewpoint of retort resistance, the packaging material for retort foods preferably contains the gas barrier laminate of the present invention, and contains the aforementioned laminate (II) or laminate (III). That is, the packaging material for retort foods preferably contains a laminate having a base material, a resin cured layer, and one or more than two layers of thermoplastic resin layers, and from the viewpoint of gas barrier property, a laminate further having an inorganic thin film layer is more preferably contained. As such a packaging material for retort foods, for example, a bag, a lid material, etc. for retort foods using the aforementioned laminate (II) or laminate (III) can be cited.

[0307] [Second Invention: Packaging Material for Odor Prevention or Fragrance Retention]

[0308] The packaging material for odor prevention or fragrance retention (hereinafter also referred to as "the packaging material of the present invention") according to the second invention has: a base material, and a cured product layer of an epoxy resin composition, and the epoxy resin composition contains: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0309] The packaging material of the present invention can obtain excellent odor prevention and fragrance retention properties by having a cured product layer of an epoxy resin composition containing an amine-based curing agent. Moreover, since the epoxy resin composition contains an unsaturated fatty acid amide having 14 to 24 carbon atoms, a three-layer structure in which the cured product layer of the epoxy resin composition becomes an intermediate layer can be dispensed with, and a two-layer structure formed of a base material and the aforementioned cured product layer can be formed. Therefore, the thinning of the packaging material can be achieved, and the economy is also excellent. Furthermore, the adhesiveness and transparency between the base material and the cured product layer also become good.

[0310] When the cured product of the epoxy resin composition is applied as an intermediate layer (the layer between two base materials) of the packaging material, the epoxy resin composition can also have the performance as an adhesive in addition to odor prevention and fragrance retention properties. On the other hand, when the cured product layer of the epoxy resin composition is used for the surface layer (the innermost layer or the outermost layer), it is important that there is less adhesion.

[0311] It is considered that if the epoxy resin composition contains an unsaturated fatty acid amide having 14 to 24 carbon atoms, the function as a lubricant is exerted, and the adhesion of the obtained cured product layer can be suppressed. According to this effect, the layer structure of the packaging material can also be made into a two-layer structure formed of a base material and a cured product layer.

[0312] Moreover, it is considered that the unsaturated fatty acid amide plays a role in alleviating the stress generated in the cured product of the epoxy resin, and has high compatibility with the epoxy resin composition containing an amine-based epoxy resin curing agent. Therefore, it is speculated that the adhesiveness and transparency of the cured product of the epoxy resin composition containing the unsaturated fatty acid amide to the base material also become good.

[0313] The form of the packaging material of the present invention can be appropriately selected according to the articles to be stored and preserved. For example, packaging films; packaging containers such as packaging bags and bottles; and lid materials and sealing materials for packaging containers can be cited. Among these, from the viewpoints of improving anti-odor properties and fragrance retention properties, the packaging material of the present invention is preferably a bag, a film, or a lid material, and more preferably a packaging bag.

[0314] As specific examples of the packaging bag, a three-side sealed flat bag, a stand-up bag, a gusset packaging bag, a pillow-shaped packaging bag, a multi-chamber bag composed of a main chamber and a sub-chamber and having an easily peelable wall between the main chamber and the sub-chamber, a shrink packaging bag, etc. can be cited.

[0315] There is no particular limitation on the capacity of the packaging material, and it can be appropriately selected according to the articles to be stored and preserved.

[0316] Hereinafter, the materials constituting the packaging material of the present invention will be described.

[0317] <Base material>

[0318] As the base material in the packaging material of the present invention, an inorganic base material or an organic base material can be used. For the inorganic base material and the organic base material, those similar to the base materials exemplified in the gas barrier laminate according to the first invention can be cited.

[0319] From the viewpoints of light weight, transparency, and economy, the base material is preferably an organic base material. From the aspects of transparency, strength, and heat resistance, it is more preferably at least one selected from the group consisting of polyolefins, polyesters, polyamides, and polyimides, and further preferably a polyolefin.

[0320] When the packaging material is a film or a bag, the base material is preferably a film-shaped base material, and the film can be stretched in a uniaxial or biaxial direction. Moreover, the film can have an inorganic thin film layer such as a vapor deposition film of silicon dioxide, aluminum oxide, etc., and from the viewpoint of economy, a structure without an inorganic thin film layer can also be formed.

[0321] The thickness of the base material can be appropriately selected according to the shape of the packaging material, etc., and there is no particular limitation. From the viewpoints of anti-odor properties, fragrance retention properties, and strength, it is preferably 5 to 300 μm, more preferably 5 to 100 μm, and further preferably 5 to 50 μm. When the base material is an organic base material, from the viewpoints of anti-odor properties, fragrance retention properties, and strength, the thickness of the organic base material is further preferably 8 to 50 μm, and even more preferably 10 to 40 μm.

[0322] <Cured product layer>

[0323] The cured product layer in the packaging material of the present invention is a layer formed from a cured product of an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0324] From the viewpoints of anti-odor property, fragrance retention property, and flex resistance, the thickness of the cured product layer is preferably 0.02 μm or more, more preferably 0.05 μm or more, and still more preferably 0.08 μm or more. Further, from the viewpoints of adhesiveness to the substrate, transparency, thinning, and economy, it is preferably 1.0 μm or less, more preferably 0.6 μm or less, and still more preferably 0.5 μm or less. The above thickness is the thickness of each layer of the cured product layer.

[0325] In the packaging material of the present invention, each component contained in the epoxy resin composition constituting the cured product layer and its suitable mode are the same as those of the epoxy resin composition related to the aforementioned first invention.

[0326] The method for curing the above epoxy resin composition to form a cured product layer is not particularly limited, and it is carried out according to a known method at a sufficient concentration and temperature of the epoxy resin composition required to obtain the cured product of the epoxy resin composition. The curing temperature can be selected, for example, in the range of 10 to 140°C. Details thereof will be described later in the manufacturing method of the packaging material.

[0327] <Composition of Packaging Material>

[0328] The anti-odor or fragrance retention packaging material of the present invention only needs to have a substrate and at least one layer of the cured product layer of the aforementioned epoxy resin composition. When the packaging material of the present invention is a packaging film, a configuration having only one substrate and only one cured product layer (two-layer configuration) is preferred. Further, from the viewpoint of adhesiveness, it is preferred that the substrate is adjacent to the cured product layer.

[0329] The packaging bag is preferably composed of the above packaging film. At this time, any surface of the substrate and the cured product layer can be the outer layer of the packaging bag. From the viewpoint of manufacturing the packaging bag by heat-sealing the packaging film, it is preferred that the cured product layer surface becomes the outer layer.

[0330] As a preferred layer configuration of the above packaging film, for example, Figure 10 can be cited.

[0331] Figure 10 FIG. is a cross-sectional schematic view showing an embodiment of a packaging film 500 as an embodiment of the packaging material of the present invention. Figure 10 The packaging film 500 in has a configuration in which a cured product layer 502 is provided on one surface of a substrate 501, and the substrate 501 is adjacent to the cured product layer 502.

[0332] However, the packaging film as an embodiment of the packaging material of the present invention is not limited to Figure 10a layer former. Further, in this packaging material, a primer layer, an ink layer such as a printing layer, an adhesive layer, a surface protective layer, an arbitrary layer such as a vapor deposition layer, a thermoplastic resin layer (not shown), etc. may be further laminated between the base material 501 and the cured product layer 502, on the surface of the base material 501 where the cured product layer 502 is not provided, or on the upper surface of the cured product layer 502 (the surface not adjacent to the base material 501).

[0333] From the viewpoints of anti-odor property, fragrance retention property, and strength, the thickness of the above-mentioned packaging film is preferably 10 to 300 μm, more preferably 10 to 100 μm, and still more preferably 10 to 50 μm.

[0334] <Manufacturing method of packaging material>

[0335] The manufacturing method of the packaging material of the present invention is not particularly limited, and known methods can be used.

[0336] For example, as Figure 10 a manufacturing method of the packaging film 500 having the above-mentioned configuration, the following method can be cited: The aforementioned epoxy resin composition is coated on one side of the base material to a desired thickness, and then the epoxy resin composition is cured to form a cured product layer.

[0337] The coating method when coating the epoxy resin composition is the same as the above-mentioned.

[0338] After coating the epoxy resin composition, a step of volatilizing the solvent (drying step) is performed as needed.

[0339] Since 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, the drying speed is improved along with the adhesion inhibition effect, and thus the drying temperature can be lowered. In the case of using a base material with low heat resistance, the drying temperature is preferably 40 to 120 °C, more preferably 40 to 100 °C, and still more preferably 50 to 90 °C.

[0340] After performing the drying step, the epoxy resin composition is cured to form a cured product layer. The curing temperature can be selected, for example, in the range of 10 to 140 °C, preferably in the range of 10 to 100 °C, and more preferably in the range of 10 to 80 °C. And the curing time can be selected, for example, in the range of 0.5 to 200 hours, preferably in the range of 2 to 100 hours.

[0341] By processing the above-mentioned packaging film by a known method, various packaging containers such as packaging bags, lid materials for packaging containers, sealing materials, etc. can be obtained.

[0342] [Anti-odor or fragrance retention method]

[0343] The second invention provides an anti-odor or fragrance retention method, which seals an article containing an odor component or a fragrance component in a packaging material. The packaging material has: a substrate, and a cured product layer of an epoxy resin composition. The epoxy resin composition contains: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0344] As the odor components to be deodorized based on the method according to the second invention, amine-based volatile substances such as ammonia and trimethylamine can be cited; sulfur-based volatile substances such as methyl mercaptan; aldehydes, lower fatty acids or their esters; etc. In addition, as the fragrance components to be fragrance-retained, natural fragrances such as limonene, geraniol, l-menthol, and their derivatives, synthetic fragrances and other fragrance components can be cited.

[0345] In the method according to the second invention, as the articles sealed in the packaging material, used disposable diapers, pet sand, dirt, domestic waste, other malodorous substances can be cited; foods with strong odors; aromatic toilet articles, cosmetics, stationery, toys; etc.

[0346] According to the method according to the second invention, the above-mentioned articles are sealed in the packaging material, and then sealed, so that the odor components and fragrance components are less likely to volatilize outside the packaging material, and excellent anti-odor and fragrance retention properties are exhibited.

[0347] [Third Invention: Heat-Shrinkable Label]

[0348] The heat-shrinkable label according to the third invention (hereinafter, also simply referred to as "the label of the present invention") has: a heat-shrinkable substrate layer, and a cured product layer of an epoxy resin composition. The epoxy resin composition contains: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 14 to 24 carbon atoms.

[0349] The heat-shrinkable label of the present invention can obtain excellent CO2 barrier properties by having a cured product layer of an epoxy resin composition containing an amine-based curing agent.

[0350] Moreover, since the epoxy resin composition contains an unsaturated fatty acid amide having 14 to 24 carbon atoms, a structure having only one heat-shrinkable substrate layer and the aforementioned cured product layer can be formed without forming the heat-shrinkable label in a three-layer structure in which the cured product layer is formed between two heat-shrinkable substrate layers. Therefore, the label can be thinned, and the economy is also excellent. Furthermore, a heat-shrinkable label having good adhesion between the heat-shrinkable substrate layer and the cured product layer and excellent followability during heat shrinkage can be obtained. The reason for this is not clear, but it is considered as follows.

[0351] When a cured product of an epoxy resin composition is used as an intermediate layer of a label (a layer between two heat-shrinkable substrate layers), the epoxy resin composition only needs to have the performance as an adhesive in addition to having CO2 barrier properties. On the other hand, when the cured product layer of the epoxy resin composition is used for the surface layer (the innermost layer or the outermost layer), it is important that there is less adhesion.

[0352] It is considered that if an unsaturated fatty acid amide having 14 to 24 carbon atoms is contained in the epoxy resin composition, it exhibits the function as a lubricant, which is beneficial to suppressing adhesion. Through this effect, a structure in which the label has only one heat-shrinkable substrate layer and the aforementioned cured product layer can be formed, and thinning and economic improvement can also be achieved.

[0353] Moreover, it is considered that the unsaturated fatty acid amide plays a role in relaxing the stress generated in the cured product of the epoxy resin. Therefore, it is speculated that the adhesiveness of the cured product of the epoxy resin composition containing the unsaturated fatty acid amide to the heat-shrinkable substrate layer becomes good, and the followability during heat shrinkage is also excellent. Since the unsaturated fatty acid amide has high compatibility with the epoxy resin composition containing an amine-based epoxy resin curing agent, the transparency of the cured product of the epoxy resin composition also becomes good.

[0354] Furthermore, in the production of the heat-shrinkable label, from the viewpoint of preventing the label from thermally shrinking during production, it is preferable that the drying rate of the epoxy resin composition for forming the cured product layer is fast. It is considered that if an unsaturated fatty acid amide having 14 to 24 carbon atoms is contained in the epoxy resin composition, the drying rate is improved along with the adhesion suppression effect. Therefore, drying under low-temperature conditions becomes possible, the thermal shrinkage of the label during production is suppressed, and the heat-shrinkable label can be produced with good productivity.

[0355] Hereinafter, the materials constituting the heat-shrinkable label of the present invention will be described.

[0356] <Heat-shrinkable substrate layer>

[0357] The substrate used in the heat-shrinkable substrate layer (hereinafter, also simply referred to as "substrate layer") is a heat-shrinkable substrate having the property of shrinking by heating. From the viewpoints of heat shrinkability, bending resistance, transparency, and economy, a resin substrate is preferred.

[0358] Examples of the resin constituting the heat-shrinkable base material layer include polyvinyl chloride resin, polystyrene resin, polyolefin resin, polyester resin, polyamide resin, polyamideimide resin, etc. Among these, from the viewpoints of heat shrinkability, bend resistance, transparency, and economy, resins selected from the group consisting of polyvinyl chloride resin, polystyrene resin, polyolefin resin, and polyester resin are preferred, resins selected from the group consisting of polyvinyl chloride resin, polyolefin resin, and polyester resin are more preferred, and polyvinyl chloride resin is further preferred.

[0359] From the viewpoint of imparting heat shrinkability, the heat-shrinkable base material is preferably stretched in a uniaxial or biaxial direction. As the stretching method, a usual uniaxial stretching method, simultaneous biaxial stretching method, or sequential biaxial stretching method can be used.

[0360] There are no particular limitations on the stretching temperature and stretching ratio of the heat-shrinkable base material. From the viewpoints of obtaining sufficient heat shrinkability in the resulting label and preventing breakage of the base material during stretching, the stretching temperature is preferably 90 to 160 °C, and the stretching ratio, calculated as the product of the stretching ratios in the MD direction and TD direction, is preferably 1.5 to 25 times, more preferably 2 to 20 times (in the case of uniaxial stretching, the ratio in the non-stretched direction is set to 1 time).

[0361] Moreover, from the viewpoint of imparting sufficient heat shrinkability, it is preferred not to perform heat setting after the above stretching.

[0362] Regarding the heat shrinkage rate of the heat-shrinkable base material, from the viewpoints of causing the label to heat shrink and adhere closely to the surface of the adherend and improving the CO2 barrier property, the heat shrinkage rate under the condition of at least causing the label to heat shrink is preferably 1.0% or more, more preferably 2.0% or more. For example, in the case of a heat-shrinkable label for a PET bottle, the conditions for causing the label to heat shrink refer to the heating temperature and heating time when the label is shrink-wrapped around the PET bottle. In addition, the heat shrinkage rate of the heat-shrinkable base material after heating at 150 °C for 30 seconds is preferably 1.0 to 80%, more preferably 1.0 to 50%, further preferably 2.0 to 20%, and even more preferably 2.0 to 10%. If the above heat shrinkage rate is 1.0% or more, the heat shrinkability required for causing the resulting label to adhere closely to the surface of the adherend can be obtained, and if it is 80% or less, the followability during heat shrinkage of the cured layer and the ink layer formed on the label becomes good.

[0363] The heat shrinkage rate of the heat-shrinkable base material refers to the area shrinkage rate (%) after heating the base material at 150 °C for 30 seconds, and specifically, it can be obtained according to the method described in the examples.

[0364] The thickness of the heat-shrinkable substrate layer is not particularly limited as long as it is within the range that allows heat shrinkage. From the viewpoint of CO2 barrier properties, heat shrinkage, and label strength, it is preferably 10 to 300 μm, more preferably 15 to 100 μm, further preferably 15 to 80 μm, and further preferably 15 to 50 μm.

[0365] <Cured layer>

[0366] The cured product layer is a layer formed 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.

[0367] From the viewpoint of CO2 barrier property and bending resistance, the thickness of the cured layer is preferably 0.02 μm or more, more preferably 0.05 μm or more, further preferably 0.08 μm or more, and further preferably 0.1 μm or more. In addition, from the viewpoint of followability during heat shrinkage, adhesion to the heat shrinkable substrate layer, transparency, thinning and economy, it is preferably 1.0 μm or less, more preferably 0.6 μm or less, and further preferably 0.5 μm or less. The above thickness is the thickness of each layer of the cured layer.

[0368] In the heat-shrinkable label of the present invention, each component contained in the epoxy resin composition constituting the cured product layer and its suitable form are the same as those of the epoxy resin composition according to the first invention.

[0369] <Construction of heat shrinkable labels>

[0370] The label of the present invention only needs to have a heat-shrinkable substrate layer and at least one layer of the cured product layer of the epoxy resin composition. From the viewpoint of heat shrinkability and thinness of the label, the label of the present invention preferably has only one layer of the heat-shrinkable substrate layer and one layer of the cured product layer. Furthermore, from the viewpoint of adhesion between the heat-shrinkable substrate layer and the cured product layer, it is preferred that the heat-shrinkable substrate layer and the cured product layer are adjacent.

[0371] Preferred layer structures of the heat shrinkable label include, for example: Figure 11 composition.

[0372] Figure 11 1 is a schematic cross-sectional view showing one embodiment of a heat shrinkable label 600 of the present invention. Figure 11 The heat shrinkable label 600 in FIG. 1 has a structure in which a cured material layer 602 is provided on one surface of a heat shrinkable base layer 601 , and the heat shrinkable base layer 601 and the cured material layer 602 are adjacent to each other.

[0373] The surface of the heat shrinkable label 600 that contacts the adherend may be the surface on the heat shrinkable base material layer 601 side or the surface on the cured material layer 602 side.

[0374] The heat-shrinkable label 600 preferably further has an ink layer such as a printing layer (not shown). The ink layer is, for example, a layer composed of ink containing a colorant such as a pigment and a binder resin, and can be provided on Figure 11 the surface on the side of the heat-shrinkable base material layer 601 of the heat-shrinkable label 600 in

[0375] that, the surface on the side of the cured product layer 602, or between the heat-shrinkable base material layer 601 and the cured product layer 602.

[0376] That is, when the heat-shrinkable label of the present invention has an ink layer, its layer structure may be any of a heat-shrinkable base material layer / cured product layer / ink layer, ink layer / heat-shrinkable base material layer / cured product layer, or heat-shrinkable base material layer / ink layer / cured product layer. Among them, any layer structure of a heat-shrinkable base material layer / cured product layer / ink layer or ink layer / heat-shrinkable base material layer / cured product layer is preferred.

[0377] Two or more ink layers may be provided. It should be noted that in the above layer structure, the surface of the heat-shrinkable label 100 in contact with the adherend object can be arbitrary and may be the ink layer surface.

[0378] However, the heat-shrinkable label of the present invention is not limited to Figure 11 the layer structure described above. In addition, in this label, an arbitrary layer (not shown) such as a primer layer, an adhesive layer, a surface protection layer, a vapor deposition layer, etc. can be further laminated between the heat-shrinkable base material layer 601 and the cured product layer 602, on the surface of the heat-shrinkable base material layer 1 where the cured product layer 2 is not provided, or on the upper surface of the cured product layer 602 (the surface not adjacent to the heat-shrinkable base material layer 601).

[0379] Among them, as described above, it is preferred that the heat-shrinkable base material layer 601 is adjacent to the cured product layer 602, and it is preferred that no primer layer or anchor coat layer is contained between the heat-shrinkable base material layer 601 and the cured product layer 602.

[0380] The thickness of the heat-shrinkable label is not particularly limited as long as it is within the range capable of heat shrinkage. From the viewpoints of CO2 barrier property, heat shrinkage property, and label strength, it is preferably 20 to 300 μm, more preferably 20 to 120 μm, further preferably 20 to 100 μm, and still more preferably 20 to 60 μm.

[0381] <Morphology of the heat-shrinkable label>

[0382] The heat-shrinkable label of the present invention is preferably used by being mounted on the outer surface of an adherend object that is an object to prevent CO2 permeation. The adherend object is preferably a container, and the container is preferably a bottle. Typically, examples of the adherend object of the label include PET bottles for carbonated water and carbonated beverages.

[0383] As specific forms of the heat-shrinkable label of the present invention, there can be mentioned: a tubular heat-shrinkable label formed by sealing both ends of a long strip of label to form a tube and used by being mounted on the outer surface of a container; a heat-shrinkable label in a winding manner in which one end of a long strip of label is adhered to a container, the label is wound, and the other end is overlapped with the one end to form a tube; etc. Among the above, from the viewpoint of being used for PET bottles, the label of the present invention is preferably a tubular heat-shrinkable label.

[0384] The tubular heat-shrinkable label can be obtained, for example, as follows: for a long strip of heat-shrinkable label, both ends are overlapped to form a tube in such a manner that the direction in which heat shrinkage can preferably occur becomes the circumferential direction, and the overlapped portion is sealed with a solvent or an adhesive.

[0385] <Properties of the heat-shrinkable label>

[0386] The heat shrinkage rate of the heat-shrinkable label of the present invention is as follows: the heat shrinkage rate after heating at 150 °C for 30 seconds is preferably 1.0 to 80%, more preferably 1.0 to 50%, further preferably 2.0 to 20%, and still further preferably 2.0 to 10%. If the above heat shrinkage rate is 1.0% or more, the heat shrinkability required for the obtained label to fit on the surface of the adherend object can be obtained, and if it is 80% or less, the followability during heat shrinkage of the cured product layer and the ink layer formed on the label becomes good.

[0387] 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.

[0388] [Manufacturing method of the heat-shrinkable label]

[0389] The manufacturing method of the heat-shrinkable label of the present invention is not particularly limited, and it is preferably manufactured by a manufacturing method that sequentially includes the following steps (I) and (II). By using this manufacturing method, heat shrinkage of the label during manufacturing can be suppressed, and heat-shrinkable labels can be manufactured with good productivity.

[0390] Step (I): A step of coating an epoxy resin composition on at least one surface of a heat-shrinkable substrate to form a coating layer, the epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a solvent.

[0391] Step (II): A step of heating and drying the aforementioned coating layer at a temperature below 100°C to remove the solvent

[0392] <Step (I)>

[0393] In Step (I), an epoxy resin composition is coated on at least one surface of a heat-shrinkable substrate to form a coating layer. The epoxy resin composition contains: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, an unsaturated fatty acid amide having 14 to 24 carbon atoms, and a solvent.

[0394] The heat-shrinkable substrate and the epoxy resin composition, and their preferred embodiments are the same as those described above.

[0395] For example, in Figure 11 the production of the heat-shrinkable label 600 having the structure shown in, the aforementioned epoxy resin composition is coated on one surface of the heat-shrinkable substrate to a desired thickness. As the coating method when coating the epoxy resin composition, for example, bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, micro reverse gravure coating, die coating, slot die coating, vacuum die coating, dip coating, spin coating, roll coating, spraying, brush coating, etc. can be mentioned. Among these, bar coating, roll coating or spraying is preferred, and gravure coating, reverse gravure coating, microgravure coating, or micro reverse gravure coating is preferred industrially.

[0396] <Step (II)>

[0397] In Step (II), the aforementioned coating layer formed in Step (I) is heated and dried at a temperature below 100°C to remove the solvent. The epoxy resin composition used in the formation of the aforementioned coating layer contains an unsaturated fatty acid amide having 14 to 24 carbon atoms, so the drying speed is fast. Therefore, drying at a lower temperature is easy, and the heat shrinkage of the label during manufacturing can be suppressed.

[0398] From the viewpoint of suppressing the heat shrinkage of the label during manufacturing, the heating and drying temperature in Step (II) is preferably 40 to 90°C, more preferably 50 to 80°C, and further preferably 50 to 70°C. In addition, the heating and drying time is preferably 5 to 180 seconds, more preferably 10 to 120 seconds, and further preferably 10 to 60 seconds.

[0399] After the above heating and drying, the epoxy resin composition is cured to form a cured product layer. The curing temperature can be selected within the range of 10 to 100°C, preferably within the range of 10 to 80°C, and more preferably within the range of 10 to 50°C. Moreover, the curing time can be selected within the range of 0.5 to 200 hours, preferably within the range of 2 to 100 hours.

[0400] In the case where the heat-shrinkable label has the aforementioned ink layer, the process of forming the ink layer can be carried out between process (I) and process (II), or after process (II). The formation of the ink layer can be carried out by known printing methods such as gravure printing, flexographic printing, screen printing, etc.

[0401] After carrying out the above process, the obtained label is formed into a desired shape, and heat-shrinkable labels such as strips and cylinders can be obtained.

[0402] [Heat-shrink label, bottle]

[0403] The present invention provides: a heat-shrink label obtained by heat-shrinking the aforementioned heat-shrinkable label, and a bottle having the heat-shrink label.

[0404] The bottle having the heat-shrink label is preferably a PET bottle. The heat-shrink label only needs to cover at least a part of the outer surface of the bottle, and is preferably in a manner of covering the outer peripheral side surface of the bottle.

[0405] As a method for manufacturing a bottle having a heat-shrink label, for example, the following method can be cited: a tubular heat-shrinkable label is attached to the outer peripheral side surface of the bottle, or a long strip of heat-shrinkable label is wound, and then the label is heat-shrunk.

[0406] As a method for heat-shrinking the heat-shrinkable label, it can be carried out by a known method using a hot air dryer, a heater, steam, hot water, etc. For example, the following method can be cited: after attaching the heat-shrinkable label to an adherend such as a bottle, a method of traveling in a heating atmosphere based on a hot air dryer, a heater, steam, etc.; a method of immersing in hot water; etc.

[0407] The heat-shrink conditions of the heat-shrinkable label can be appropriately selected according to the type of the heat-shrinkable substrate, etc. From the viewpoints of heat-shrinkability and productivity, the heating temperature is preferably 70 °C or higher, more preferably 80 °C or higher, and further preferably 85 °C or higher. In addition, from the viewpoint of suppressing thermal deterioration of the bottle and its contents, the heating temperature is preferably lower than 100 °C, more preferably 95 °C or lower.

[0408] Moreover, from the viewpoints of suppressing thermal deterioration of the bottle and its contents and productivity, the heating time is preferably 0.5 to 120 seconds, more preferably 2 to 60 seconds, and further preferably 3 to 20 seconds.

[0409] [Method for preventing CO2 permeation]

[0410] The present invention provides: a method for preventing CO2 permeation using the aforementioned heat-shrinkable label or heat-shrink label.

[0411] The adherend of the label for which CO2 permeation prevention is targeted is preferably a container. The container is preferably a bottle, more preferably a PET bottle.

[0412] As a suitable mode of the method for preventing CO2 permeation according to the present invention, the following methods can be cited: Method (1), covering at least a part of the outer surface of the container to be the object of preventing CO2 permeation with a heat-shrinkable label, and then enclosing a content containing CO2 in the container and sealing it; or Method (2), enclosing a content containing CO2 in the container to be the object of preventing CO2 permeation and sealing it, and then covering at least a part of the outer surface of the container with a heat-shrinkable label; etc. According to these methods, the permeation of CO2 inside the container to the outside can be suppressed.

[0413] The heat-shrinkable label only needs to cover at least a part of the outer surface of the container, and preferably covers the outer peripheral side surface of the container. The method of covering at least a part of the outer surface of the container with a heat-shrinkable label can be carried out in the same manner as the method described in the item of the heat-shrinkable label and the bottle.

[0414] As the content containing CO2, carbonated water, other carbonated beverages, etc. can be cited.

[0415] According to the method for preventing CO2 permeation of the present invention, the permeation of CO2 enclosed inside a container or the like, which is the adherend of the label, to the outside can be effectively suppressed.

[0416] Examples

[0417] Next, the present invention will be specifically described by way of examples. However, the present invention is not limited by any of these examples.

[0418] [First Invention (1): Manufacture and Evaluation of Epoxy Resin Composition and Gas Barrier Laminate]

[0419] The measurement and evaluation in this example were carried out by the following methods.

[0420] <Thickness of Resin Curing Layer>

[0421] Measurement was carried out using a multi-layer film thickness measuring device ("DC-8200" manufactured by Gunze Co., Ltd.).

[0422] <Haze>

[0423] Measurement was carried out in accordance with JIS K7136:2000 using a color / turbidity simultaneous measuring device ("COH400" manufactured by Nippon Denshoku Industries Co., Ltd.).

[0424] <Total Light Transmittance>

[0425] Measurement was carried out in accordance with JIS K7361-1:1997 using a color / turbidity simultaneous measuring device ("COH400" manufactured by Nippon Denshoku Industries Co., Ltd.).

[0426] <YI>

[0427] In accordance with JIS K7373:2006, measurement was carried out using a color / turbidity simultaneous measuring instrument (“COH400” manufactured by Nippon Denshoku Industries Co., Ltd.).

[0428] <Adhesion>

[0429] According to the methods described in each example, an epoxy resin composition was coated on the aluminum oxide vapor-deposited surface of 210 mm × 297 mm aluminum oxide vapor-deposited PET (“Barrialox 1011HG (uncoated)” manufactured by Toray Film Products Ltd., thickness: 12 μm) and dried to form a resin composition layer, which was placed on a horizontal plane. The surface on the PET side of the above-mentioned 210 mm × 297 mm aluminum oxide vapor-deposited PET prepared separately was opposed and laminated on the resin composition layer surface. A 15 kg A4-sized heavy object was placed thereon and, in a state where a load was applied, it was cured by heating at 40°C for 2 days. After curing, the heavy object was removed, and the state of adhesion when the later-laminated aluminum oxide vapor-deposited PET was peeled from the resin cured layer surface by hand was evaluated according to the following criteria.

[0430] A: No adhesion occurred, and the aluminum oxide vapor-deposited PET could be easily peeled off.

[0431] B: Adhesion occurred. Although the aluminum oxide vapor-deposited PET could be peeled off, an increase in the haze of the gas barrier laminate after peeling was visible.

[0432] C: Adhesion occurred, and the aluminum oxide vapor-deposited PET could not be peeled off.

[0433] <Peeling strength of laminate (normal state)>

[0434] For the laminate (II) or laminate (III) obtained in each example, a T-peel test was carried out at a peel speed of 300 mm / minute according to the method specified in JIS K6854-3:1999, and the peel strength (g / 15 mm) was measured.

[0435] <Peeling strength of laminate (after retort treatment)>

[0436] For each of the obtained laminates (II) or laminates (III), using an autoclave for cooked foods (manufactured by TOMY SEIKO CO., LTD., "SR-240"), after performing a steaming treatment at 121°C for 30 minutes or at 130°C for 30 minutes, according to the method specified in JIS K6854-3:1999, a T-peel test was carried out at a peeling speed of 300 mm / minute to measure the peel strength (g / 15 mm). A large value of the peel strength indicates excellent retort resistance. It should be noted that for cases where interlayer peeling occurred during the test, it was recorded as "peeling" in the table.

[0437] <Oxygen transmission rate (cc / (m 2 ·day·atm))>

[0438] For the aluminum oxide-evaporated PET used in each example and the gas-barrier laminate obtained in each example, using an oxygen transmission rate measuring device (manufactured by CONTROL-SYA Co., Ltd., "OX-TRAN2 / 21"), the oxygen transmission rate was measured under the conditions of 23°C and a relative humidity of 60%.

[0439] <Water vapor transmission rate (g / (m 2 ·day))>

[0440] For the gas-barrier laminate obtained in each example, using a water vapor transmission rate measuring device (manufactured by MOCON, "PERMATRAN-W 1 / 50"), the water vapor transmission rate was measured under the conditions of 40°C and a relative humidity of 90%.

[0441] Production Example 1 (Preparation of Epoxy Resin Curing Agent Solution A)

[0442] 1 mol of m-xylylenediamine (MXDA) was put into a reaction vessel. While heating to 60°C under a nitrogen gas stream, 0.93 mol of methyl acrylate was added dropwise over 1 hour. While distilling off the generated methanol, the temperature was raised to 165°C and maintained at 165°C for 2.5 hours to obtain an amine-based curing agent. Methanol was added dropwise thereto over 1.5 hours, and further, 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBE-903") as a silane coupling agent was added to obtain Epoxy Resin Curing Agent Solution A in which the amine-based curing agent was 62.2% by mass, 3-aminopropyltriethoxysilane was 2.8% by mass, and methanol was 35% by mass.

[0443] Production Example 2 (Preparation of Epoxy Resin Curing Agent Solution B)

[0444] Charge 1 mol of m-xylenediamine (MXDA) into a reaction vessel. Heat it to 60°C under a nitrogen gas stream and add 0.93 mol of methyl acrylate dropwise over 1 hour. While distilling off the generated methanol, heat it to 165°C and maintain at 165°C for 2.5 hours to obtain an amine-based curing agent. Add methanol dropwise thereto over 1.5 hours to obtain an epoxy resin curing agent solution B with 65.0% by mass of the amine-based curing agent and 35% by mass of methanol.

[0445] Example 1-1 (Preparation of epoxy resin composition 1-1)

[0446] Add 421.2 g of methanol as a diluting solvent, 433.8 g of ethyl acetate, and 7.7 g of a dispersion of plate-shaped alumina particles subjected to organic coating (manufactured by Kawaken Fine Chemical Co., Ltd., "KOS-A2EOK5-10", ethanol dispersion, solid content concentration: 10% by mass, average primary particle diameter of alumina particles: 20 nm), and stir well. Then, add 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 and stir. Add 5 g of an epoxy resin having a glycidylamino group derived from m-xylenediamine as an epoxy resin (manufactured by Mitsubishi Gas Chemical Company, Inc., "TETRAD-X") (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 1.2), and 1.54 g of erucic acid amide (manufactured by NOF Corporation, "ALFLOW P-10") and stir to prepare epoxy resin composition 1-1. The compounding amount of erucic acid amide is 10 parts by mass relative to the total amount of 100 parts by mass of the epoxy resin in epoxy resin composition 1-1 and the non-volatile components in the epoxy resin curing agent solution A.

[0447] Example 1-2 (Preparation of epoxy resin composition 1-2)

[0448] In Example 1-1, change the compounding amount of methanol as a diluting solvent to 67.2 g and the compounding amount of ethyl acetate to 79.7 g, and otherwise, prepare epoxy resin composition 1-2 in the same manner as in Example 1-1.

[0449] Example 2-1 (Preparation of epoxy resin composition 2-1)

[0450] In Example 1-1, use 1.54 g of oleic acid amide (manufactured by NOF Corporation, "ALFLOW E-10") instead of erucic acid amide, and otherwise, prepare epoxy resin composition 2-1 in the same manner as in Example 1-1.

[0451] Example 2-2 (Preparation of epoxy resin composition 2-2)

[0452] In Example 1-2, 1.54 g of oleic acid amide (“ALFLOW E-10” manufactured by NOF Corporation) was used instead of erucic acid amide, and an epoxy resin composition 2-2 was prepared in the same manner as in Example 1-2 except for this.

[0453] Example 3 (Preparation of Epoxy Resin Composition 3)

[0454] In Example 1-1, the blending amount of methanol was changed to 402.2 g, the blending amount of ethyl acetate was changed to 414.8 g, and the blending amount of erucic acid amide was changed to 0.77 g. An epoxy resin composition 3 was prepared in the same manner as in Example 1-1 except for this.

[0455] Example 4 (Preparation of Epoxy Resin Composition 4)

[0456] 382.7 g of methanol, 388.3 g of ethyl acetate, which were used as dilution solvents, and 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 were added and stirred. 5 g of an epoxy resin having a glycidylamino group derived from m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc., “TETRAD-X”), which was used as an epoxy resin, and 0.462 g of erucic acid amide were added thereto and stirred to prepare an epoxy resin composition 4. (The number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 1.2)

[0457] Example 5-1 (Preparation of Epoxy Resin Composition 5-1)

[0458] In Example 4, the blending amount of methanol was changed to 395.8 g, the blending amount of ethyl acetate was changed to 390.2 g, and the blending amount of erucic acid amide was changed to 0.77 g. An epoxy resin composition 5-1 was prepared in the same manner as in Example 4 except for this.

[0459] Example 5-2 (Preparation of Epoxy Resin Composition 5-2)

[0460] In Example 5-1, the blending amount of methanol was changed to 121.0 g, the blending amount of ethyl acetate was changed to 126.6 g. An epoxy resin composition 5-2 was prepared in the same manner as in Example 5-1 except for this.

[0461] Example 5-3 (Preparation of Epoxy Resin Composition 5-3)

[0462] In Example 5-1, the blending amount of methanol was changed to 67.2 g, the blending amount of ethyl acetate was changed to 72.8 g. An epoxy resin composition 5-3 was prepared in the same manner as in Example 5-1 except for this.

[0463] Example 6 (Preparation of Epoxy Resin Composition 6)

[0464] In Example 4, the compounding amount of methanol was changed to 403.3 g, the compounding amount of ethyl acetate was changed to 397.7 g, and the compounding amount of erucamide was changed to 1.078 g. Except for this, an epoxy resin composition 6 was prepared in the same manner as in Example 4.

[0465] Example 7 (Preparation of Epoxy Resin Composition 7)

[0466] In Example 4, the compounding amount of methanol was changed to 414.8 g, the compounding amount of ethyl acetate was changed to 409.2 g, and the compounding amount of erucamide was changed to 1.54 g. Except for this, an epoxy resin composition 7 was prepared in the same manner as in Example 4.

[0467] Example 8 (Preparation of Epoxy Resin Composition 8)

[0468] In Example 4, 0.462 g of oleic acid amide was used instead of erucamide. Except for this, an epoxy resin composition 8 was prepared in the same manner as in Example 4.

[0469] Example 9 (Preparation of Epoxy Resin Composition 9)

[0470] In Example 5-1, 0.77 g of oleic acid amide was used instead of erucamide. Except for this, an epoxy resin composition 9 was prepared in the same manner as in Example 5-1.

[0471] Example 10 (Preparation of Epoxy Resin Composition 10)

[0472] In Example 6, oleic acid amide was used instead of erucamide. Except for this, an epoxy resin composition 10 was prepared in the same manner as in Example 6.

[0473] Example 11 (Preparation of Epoxy Resin Composition 11)

[0474] In Example 7, 1.078 g of oleic acid amide was used instead of erucamide. Except for this, an epoxy resin composition 11 was prepared in the same manner as in Example 7.

[0475] Example 12 (Preparation of Epoxy Resin Composition 12)

[0476] 349.1 g of methanol, 337.9 g of ethyl acetate, and 6.2 g of a dispersion of plate-shaped alumina particles subjected to organic coating (Kawaken Fine Chemical Co., Ltd.'s "KOS-A2EOK5-10", ethanol dispersion, solid content concentration: 10% by mass) were added as a diluting solvent, and the mixture was stirred well. Then, 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 was added and stirred. To this, 2 g of an epoxy resin having a glycidylamino group derived from m-xylylenediamine as an epoxy resin (Mitsubishi Gas Chemical Company, Inc.'s "TETRAD-X") (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 3.0) and 1.24 g of erucamide were added and stirred to prepare Epoxy Resin Composition 12.

[0477] Example 13 (Preparation of Epoxy Resin Composition 13)

[0478] 326.4 g of methanol, 315.6 g of ethyl acetate, and 5.8 g of a dispersion of plate-shaped alumina particles subjected to organic coating (Kawaken Fine Chemical Co., Ltd.'s "KOS-A2EOK5-10") were added as a diluting solvent, and the mixture was stirred well. Then, 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 was added and stirred. To this, 1.2 g of an epoxy resin having a glycidylamino group derived from m-xylylenediamine as an epoxy resin (Mitsubishi Gas Chemical Company, Inc.'s "TETRAD-X") (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 5.0) and 1.16 g of erucamide were added and stirred to prepare Epoxy Resin Composition 13.

[0479] Example 14-1 (Preparation of Epoxy Resin Composition 14-1)

[0480] 318.8 g of methanol, 313.2 g of ethyl acetate, and 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 were added as a diluting solvent and stirred. To this, 2 g of an epoxy resin having a glycidylamino group derived from m-xylylenediamine as an epoxy resin (Mitsubishi Gas Chemical Company, Inc.'s "TETRAD-X") (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 3.0) and 0.62 g of erucamide were added and stirred to prepare Epoxy Resin Composition 14-1.

[0481] Example 14-2 (Preparation of Epoxy Resin Composition 14-2)

[0482] In Example 14-1, the blending amount of methanol was changed to 118.0 g and the blending amount of ethyl acetate was changed to 123.6 g. Except for this, an epoxy resin composition 14-2 was prepared in the same manner as in Example 14-1.

[0483] Example 14-3 (Preparation of epoxy resin composition 14-3)

[0484] In Example 14-1, the blending amount of methanol was changed to 52.9 g and the blending amount of ethyl acetate was changed to 58.5 g. Except for this, an epoxy resin composition 14-3 was prepared in the same manner as in Example 14-1.

[0485] Example 15 (Preparation of epoxy resin composition 15)

[0486] 298.3 g of methanol, 292.7 g of ethyl acetate, which are dilution solvents, and 16 g of the epoxy resin curing agent solution A obtained in Production Example 1 were added and stirred. 1.2 g of an epoxy resin having a glycidylamino group derived from m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc., "TETRAD-X") (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 5.0) and 0.58 g of erucamide were added thereto and stirred to prepare an epoxy resin composition 15.

[0487] Example 16 (Preparation of epoxy resin composition 16)

[0488] In Example 5-1, 16 g of epoxy resin curing agent B was used instead of epoxy resin curing agent A. Except for this, an epoxy resin composition 16 was prepared in the same manner as in Example 5-1.

[0489] Comparative Example 1-1 (Preparation of comparative epoxy resin composition 1-1)

[0490] In Example 1-1, 1.54 g of stearic acid amide was used instead of erucamide. Except for this, a comparative epoxy resin composition 1-1 was prepared in the same manner as in Example 1-1.

[0491] Comparative Example 1-2 (Preparation of comparative epoxy resin composition 1-2)

[0492] In Example 1-2, 1.54 g of stearic acid amide was used instead of erucamide. Except for this, a comparative epoxy resin composition 1-2 was prepared in the same manner as in Example 1-2.

[0493] Comparative Example 2-1 (Preparation of comparative epoxy resin composition 2-1)

[0494] In Example 1-1, the compounding amount of methanol was changed to 383.5 g, the compounding amount of ethyl acetate was changed to 396.0 g, and erucic acid amide was not compounded. Except for this, Comparative Epoxy Resin Composition 2-1 was prepared in the same manner as in Example 1-1.

[0495] Comparative Example 2-2 (Preparation of Comparative Epoxy Resin Composition 2-2)

[0496] In Example 1-2, the compounding amount of methanol was changed to 62.5 g, the compounding amount of ethyl acetate was changed to 69.7 g, and erucic acid amide was not compounded. Except for this, Comparative Epoxy Resin Composition 2-2 was prepared in the same manner as in Example 1-2.

[0497] Comparative Example 3 (Preparation of Comparative Epoxy Resin Composition 3)

[0498] In Example 4, the compounding amount of methanol was changed to 371.7 g, the compounding amount of ethyl acetate was changed to 377.3 g, and erucic acid amide was not compounded. Except for this, Comparative Epoxy Resin Composition 3 was prepared in the same manner as in Example 4.

[0499] It should be noted that the compounding amounts in the table are all compounding amounts (parts by mass) as active ingredients.

[0500] [Table 1]

[0501] Table 1

[0502]

[0503] *1) Parts by mass relative to a total of 100 parts by mass of the non-volatile components in the epoxy resin and the epoxy resin curing agent solution *2) Parts by mass relative to a total of 100 parts by mass of the epoxy resin + curing agent

[0504] Example 17

[0505] (Production and Evaluation of Gas Barrier Laminate (I))

[0506] Using a rod coater No. 3, the epoxy resin composition 1-2 obtained in Example 1-2 was coated on the aluminum oxide vapor-deposited surface of PET with aluminum oxide (aluminum oxide) vapor-deposited on one side (Toray Film Products Ltd.'s "Barrialox 1011HG (uncoated)", thickness: 12 μm, oxygen permeability: 2.2 cc / (m 2 ·day·atm)). The epoxy resin composition was heated at 120 °C for 60 seconds and dried (thickness after drying: about 0.5 μm), and further cured by heating at 40 °C for 2 days to produce Figure 1The gas-barrier laminate (I) thus formed. Using the obtained gas-barrier laminate (I), the haze and total light transmittance were measured by the aforementioned method. In addition, in the same manner, after coating the epoxy resin composition on the aluminum oxide-evaporated PET, it was heated at 120 °C for 60 seconds and dried to form a resin composition layer, and then the adhesion evaluation was carried out by the aforementioned method. The results are shown in Table 2.

[0507] (Fabrication and Evaluation of Gas-Barrier Laminate (II))

[0508] In addition, using a bar coater No. 12, the urethane adhesive was coated on the surface of the obtained gas-barrier laminate (I) on the side of the resin cured layer, and dried at 80 °C for 10 seconds to form an adhesive layer (thickness after drying: about 3 μm). The urethane adhesive used was prepared by adding 1.05 g of the curing agent CAT-RT85 and 25 g of the solvent ethyl acetate to 15 g of the main agent AD-502 and stirring well. Using a roller, a polypropylene film with a thickness of 50 μm ("P1146" manufactured by Toyobo Co., Ltd.) was laminated thereon and heated at 40 °C for 2 days to obtain Figure 4 the gas-barrier laminate (II) having the configuration shown.

[0509] Using this gas-barrier laminate (II), the oxygen transmission rate was measured and the peel test after normal state and retort treatment was carried out by the aforementioned method. The results are shown in Table 2.

[0510] Example 18, Comparative Examples 4 to 5

[0511] Using the epoxy resin composition shown in Table 2 instead of the epoxy resin composition 1-2, a gas-barrier laminate was fabricated and evaluated in the same manner as in Example 17. The results are shown in Table 2.

[0512] In Table 2, as "Reference Example 1", the haze and total light transmittance of the aluminum oxide-evaporated PET alone are shown. And as "Reference Example 2", the oxygen transmission rate of the laminate formed by laminating the aluminum oxide-evaporated PET and the polypropylene film with an adhesive layer without forming a resin cured layer is shown.

[0513] [Table 2]

[0514]

[0515] In Table 2, the differences in the effects due to the types of fatty acid amides were confirmed. For the gas barrier laminates (II) of Examples 17 and 18 using the epoxy resin composition of the present invention, compared with Comparative Example 4 using stearic acid amide, a saturated fatty acid amide with 18 carbon atoms, instead of an unsaturated fatty acid amide, and the laminate of Comparative Example 5 using an epoxy resin composition without compounding a fatty acid amide, the peel strength after normal state and retort treatment was high, that is, the adhesiveness and retort resistance were good. Moreover, in the gas barrier laminate (I), the haze was low and the total light transmittance was high, and the transparency was good.

[0516] If Examples 17 and 18 are compared, Example 17 using erucic acid amide as the unsaturated fatty acid amide had a higher peel strength of the obtained gas barrier laminate (II) than Example 18 using oleic acid amide. Furthermore, it was good in that the adhesion inhibition effect in the gas barrier laminate (I) was also high.

[0517] In contrast, compared with Comparative Example 5 without compounding a fatty acid amide, Comparative Example 4 using stearic acid amide as the fatty acid amide had the same peel strength in the normal state of the gas barrier laminate (II), 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. In the gas barrier laminate (I), the haze increased and the transparency was poor.

[0518] Examples 19 to 29 (Production and evaluation of gas barrier laminates (I) and (II))

[0519] Using the epoxy resin compositions shown in Table 3 and changing the thickness of the formed resin cured layer to that described in Table 3, the gas barrier laminates were produced and evaluated in the same manner as in Example 17. The results are shown in Table 3.

[0520] [Table 3]

[0521]

[0522] In Table 3, the differences in the effects due to the types and compounding amounts of unsaturated fatty acid amides were confirmed. From the comparison between Examples 19 to 22 and Examples 23 to 26, it can be seen that when using oleic acid amide as the unsaturated fatty acid amide, even if the compounding amount was changed from 100 parts by mass of the total amount of the epoxy resin and the curing agent to 3 to 10 parts by mass, no improvement in the adhesion of the gas barrier laminate (I) was observed (Examples 23 to 26). In contrast, when using erucic acid amide, when the compounding amount was 5 parts by mass or more, the adhesion inhibition effect was good (Examples 19 to 22).

[0523] As can be seen from the results of Examples 19 to 22, even when the compounding amount of erucamide is changed from 100 parts by mass relative to the total amount of the epoxy resin and the curing agent to 3 to 10 parts by mass, the retort resistance of the gas barrier laminate (II) is the same.

[0524] As can be seen from the results of Examples 20 and 27, whether or not a silane coupling agent is added, the transparency and adhesion inhibition effect of the gas barrier laminate (I) and the adhesiveness and retort resistance of the gas barrier laminate (II) are good. Moreover, as can be seen from the results of Examples 28 and 29, when plate-like alumina particles are further compounded in the epoxy resin compositions of Examples 20 and 22, the transparency and adhesion inhibition effect of the obtained gas barrier laminate (I) and the adhesiveness and retort resistance of the gas barrier laminate (II) are also good.

[0525] Example 30 (Production and Evaluation of Gas Barrier Laminate (III))

[0526] Using a bar coater No. 3, the epoxy resin composition 1-1 obtained in Example 1-1 was coated on the aluminum oxide vapor deposition surface of aluminum oxide vapor-deposited PET ("Barrialox 1011HG (uncoated)" manufactured by Toray Film Products Ltd.). The epoxy resin composition was heated at 120 °C for 60 seconds and dried (thickness after drying: about 0.1 μm), and further cured by heating at 40 °C for 2 days to produce Figure 1 the gas barrier laminate (I) having the structure of

[0527] Using a bar coater No. 12, a urethane adhesive was coated on the surface on the side of the resin cured layer and dried at 80 °C for 10 seconds to form an adhesive layer (thickness after drying: about 3 μm). The urethane adhesive used was prepared by adding 1.05 g of a curing agent CAT-RT85 and 25 g of ethyl acetate as a solvent to 15 g of the main agent AD-502 and stirring well. A nylon film with a thickness of 15 μm ("HARDLEN film N1202" manufactured by Toyobo Co., Ltd.) was laminated thereon using a roller. After forming an adhesive layer in the same manner as described above (thickness after drying: about 3 μm) on the nylon film, a polypropylene film with a thickness of 50 μm ("P1146" manufactured by Toyobo Co., Ltd.) was laminated using a roller and heated at 40 °C for 2 days to obtain Figure 7 the gas barrier laminate (III) shown in

[0528] Using this gas barrier laminate (III), a peel test was carried out after normal state and retort treatment by the aforementioned method. The results are shown in Table 4.

[0529] Examples 31 to 38, Comparative Examples 6 to 7

[0530] Using the epoxy resin composition shown in Table 4 instead of the epoxy resin composition 1-1, and changing the resin cured layer to the thickness shown in Table 4, a gas barrier laminate (III) was produced and evaluated in the same manner as in Example 30. The results are shown in Table 4.

[0531] [Table 4]

[0532] Table 4

[0533]

[0534] *1) Parts by mass relative to a total of 100 parts by mass of the non-volatile components in the epoxy resin and the epoxy resin curing agent solution

[0535] *2) Parts by mass relative to a total of 100 parts by mass of the epoxy resin + curing agent

[0536] *3) Treatment at 121°C for 30 minutes

[0537] *4〉Treatment at 130°C for 30 minutes

[0538] Based on Table 4, the following was determined.

[0539] Even when forming the gas barrier laminate (III) having the configuration shown, the gas barrier laminate using the epoxy resin composition of the present invention has good adhesiveness and retort resistance. For some of the examples, a peel test was performed after retort treatment not only under the conditions of 121°C for 30 minutes but also under the high retort conditions of 130°C for 30 minutes, and no interlayer peeling occurred, confirming good retort resistance. Figure 7 Based on the comparison between Examples 30 to 32 and the comparison between Examples 33, 37, and 38, it can be seen that when the number of active amine hydrogens in the curing agent in the epoxy resin composition / the number of epoxy groups in the epoxy resin is in the range of 1.2 to 3.0, the adhesiveness and retort resistance are better. Moreover, based on the comparison between Examples 33, 35, and 36, when the thickness of the resin cured layer is thin, the retort resistance is good.

[0540] Based on the results of Examples 33 and 34, even when forming the gas barrier laminate (III) having the configuration shown, the gas barrier laminate using the epoxy resin composition of the present invention has good adhesiveness and retort resistance regardless of whether a silane coupling agent is added.

[0541] Based on the results of Examples 33 and 34, even when forming the gas barrier laminate (III) having the configuration shown, the gas barrier laminate using the epoxy resin composition of the present invention has good adhesiveness and retort resistance regardless of whether a silane coupling agent is added. Figure 7 Based on the results of Examples 33 and 34, even when forming the gas barrier laminate (III) having the configuration shown, the gas barrier laminate using the epoxy resin composition of the present invention has good adhesiveness and retort resistance regardless of whether a silane coupling agent is added.

[0542] Example 39 (Production and evaluation of gas barrier laminate (III))

[0543] Using the epoxy resin composition 5-1 obtained in Production Example 5-1, and using silica vapor-deposited PET (manufactured by Mitsubishi Rayon Co., Ltd., "Techbarrier L", thickness: 12 μm) with silica oxide (silicon dioxide) vapor-deposited on one side of PET instead of alumina vapor-deposited PET, a gas-barrier laminate (III) was produced in the same manner as in Example 30 except for this, and the peel test was carried out after normal state and retort treatment by the aforementioned method. The results are shown in Table 5.

[0544] Examples 40 to 44, Comparative Example 8

[0545] Using the epoxy resin compositions shown in Table 5, and changing the resin cured layer to the thickness shown in Table 5, a gas-barrier laminate (III) was produced and evaluated in the same manner as in Example 39 except for this. The results are shown in Table 5.

[0546] [Table 5]

[0547] Table 5

[0548]

[0549] *1) Parts by mass relative to a total of 100 parts by mass of the non-volatile components in the epoxy resin and the epoxy resin curing agent solution

[0550] *2) Parts by mass relative to a total of 100 parts by mass of the epoxy resin + curing agent

[0551] *4) Treatment at 130°C for 30 minutes

[0552] From Table 5, it was judged that: a gas-barrier laminate (III) using the epoxy resin composition of the present invention and using silica vapor-deposited PET can also obtain good retort resistance in the same manner as in the case of using alumina vapor-deposited PET.

[0553] Example 45 (Production and evaluation of gas-barrier laminate (II))

[0554] Using a bar coater No. 3, the epoxy resin composition 5-1 obtained in Production Example 5-1 was coated on the aluminum vapor-deposited surface of biaxially oriented polypropylene (OPP) with aluminum vapor-deposited on one side (manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., "MLOP102", thickness: 25 μm). The epoxy resin composition was heated at 100°C for 30 seconds and dried (thickness after drying: about 0.1 μm), and further cured by heating at 40°C for 2 days to produce Figure 1 a gas-barrier laminate (I) having the following constitution.

[0555] Using a bar coater No. 12, a urethane adhesive was applied to the surface on the resin cured layer side of the obtained gas-barrier laminate (I), dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: about 3 μm). As the urethane adhesive, 1.05 g of curing agent CAT-RT85 and 25 g of ethyl acetate as a solvent were added to 15 g of main agent AD-502, and the mixture was thoroughly stirred and prepared. Using a roller, a polypropylene film with a thickness of 50 μm (Toyobo Co., Ltd.'s "P1146") was laminated thereon, and heated at 40°C for 2 days to obtain Figure 4 the gas-barrier laminate (II) having the structure shown.

[0556] Using this gas-barrier laminate (II), a peel test was conducted under normal conditions by the aforementioned method. The results are shown in Table 6.

[0557] Example 46

[0558] In Example 45, the formed resin cured layer was changed to the thickness shown in Table 6. Except for this, a gas-barrier laminate (II) was produced in the same manner as in Example 45, and a peel test was conducted under normal conditions by the aforementioned method. The results are shown in Table 6.

[0559] Example 47

[0560] In Example 45, an aluminum vapor-deposited PET (Mitsui Chemicals TOHCELLO Co., Ltd.'s "MLPET", thickness: 12 μm) with aluminum vapor-deposited on one side of PET was used instead of aluminum vapor-deposited OPP. Except for this, a gas-barrier laminate (II) was produced in the same manner as in Example 45, and a peel test was conducted under normal conditions by the aforementioned method. The results are shown in Table 6.

[0561] Comparative Example 9

[0562] In Example 45, no resin cured layer was formed. Except for this, a gas-barrier laminate was produced in the same manner as in Example 45, and a peel test was conducted under normal conditions by the aforementioned method. The results are shown in Table 6.

[0563] [Table 6]

[0564] Table 6

[0565]

[0566] *1) Parts by mass relative to a total of 100 parts by mass of the non-volatile components in the epoxy resin and the epoxy resin curing agent solution

[0567] *2) Parts by mass relative to a total of 100 parts by mass of the epoxy resin + curing agent

[0568] According to Table 6, it was determined that the cured product of the epoxy resin composition of the present invention also exhibited good adhesiveness to aluminum.

[0569] Example 48 (Production and Evaluation of Gas Barrier Laminate (IIIc))

[0570] PET (manufactured by Toyobo Co., Ltd., "E5100", thickness: 12 μm) was used as the base material, and the aforementioned urethane adhesive was coated on one side thereof 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 (manufactured by Mitsubishi Aluminum Co., Ltd., "1N31") was laminated thereon.

[0571] Next, using a bar coater No. 3, the epoxy resin composition 5-1 obtained in Example 5-1 was coated on the aluminum foil, heated at 120°C for 60 seconds and dried (thickness after drying: approximately 0.1 μm), and further heated at 40°C for 2 days and cured to form a resin cured layer. Using the aforementioned urethane adhesive, an adhesive layer (thickness after drying: approximately 3 μm) was formed on the surface on the resin cured layer side in the same manner as above. Using a roller, a 50-μm-thick polypropylene film (manufactured by Toyobo Co., Ltd., "P1146") was laminated thereon and heated at 40°C for 2 days to obtain Figure 9 the gas barrier laminate (IIIc) having the configuration shown.

[0572] Using this gas barrier laminate (IIIc), a peel test was performed after normal state and retort treatment by the aforementioned method. The results are shown in Table 7.

[0573] Example 49

[0574] In Example 48, the epoxy resin composition 14-1 obtained in Example 14-1 was used, and except for this, a gas barrier laminate (IIIc) was produced in the same manner as in Example 48, and a peel test was performed after normal state and retort treatment by the aforementioned method. The results are shown in Table 7.

[0575] Comparative Example 10

[0576] In Example 48, a resin cured layer was not formed, and except for this, a gas barrier laminate was produced in the same manner as in Example 48, and a peel test was performed after normal state and retort treatment by the aforementioned method. The results are shown in Table 7.

[0577] [Table 7]

[0578] Table 7

[0579]

[0580] *1) Parts by mass relative to a total of 100 parts by mass of the non-volatile components in the epoxy resin and the epoxy resin curing agent solution

[0581] *2) Parts by mass relative to a total of 100 parts by mass of the epoxy resin + curing agent

[0582] *4) Treatment at 130°C for 30 minutes

[0583] Example 50

[0584] (Production and evaluation of the gas barrier laminate (Ia))

[0585] Using PET (manufactured by Toyobo Co., Ltd., "E5100", thickness: 12 μm) as the base material, and using a rod coater No. 3, the epoxy resin composition 5-1 obtained in Example 5-1 was coated on one side thereof. The epoxy resin composition was heated at 120°C for 60 seconds and dried (thickness after drying: about 0.1 μm), and further cured by heating at 40°C for 2 days to form a resin cured layer. Using the vacuum evaporation method, a silica evaporation coating layer with a thickness of about was formed on the resin cured layer surface to produce the gas barrier laminate (Ia) having the configuration of Figure 2 . Using the obtained gas barrier laminate (Ia), the oxygen permeability and water vapor transmission rate were measured by the aforementioned method. The results are shown in Table 8.

[0586] (Production and evaluation of the gas barrier laminate (IIa))

[0587] In addition, using a rod coater No. 12, the aforementioned urethane adhesive was coated on the silica evaporation coating surface of the obtained gas barrier laminate (Ia), dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: about 3 μm). Using a roller, a polypropylene film with a thickness of 50 μm (manufactured by Toyobo Co., Ltd., "P1146") was laminated thereon, and heated at 40°C for 2 days to obtain the gas barrier laminate (IIa) having the configuration shown in Figure 5 .

[0588] Using this gas barrier laminate (IIa), the peel test after normal state and retort treatment was carried out by the aforementioned method. The results are shown in Table 8.

[0589] Comparative Example 11

[0590] In Example 50, the resin cured layer was not formed. Except for this, a gas barrier laminate was produced in the same manner as in Example 50, and the oxygen permeability and water vapor transmission rate were measured, and the peel test after normal state and retort treatment was carried out by the aforementioned method. The results are shown in Table 8.

[0591] Example 51

[0592] As the base material, a biaxially oriented polypropylene film ("FOR" manufactured by Futamura Chemical Co., Ltd., thickness: 20 μm) was used instead of PET, an aluminum vapor deposition layer was formed instead of a silica vapor deposition layer, and the epoxy resin composition 14-1 obtained in Example 14-1 was used as the epoxy resin. Except for this, gas-barrier laminates (Ia) and (IIa) were produced in the same manner as in Example 50, and the oxygen permeability, water vapor transmission rate, and peel test under normal conditions were measured by the aforementioned methods. The results are shown in Table 8.

[0593] Comparative Example 12

[0594] In Example 51, a resin cured layer was not formed. Except for this, a gas-barrier laminate was produced in the same manner as in Example 51, and the oxygen permeability, water vapor transmission rate, and peel test under normal conditions were measured by the aforementioned methods. The results are shown in Table 8.

[0595] [Table 8]

[0596]

[0597] Example 52 (Production and Evaluation of Gas-Barrier Laminate (IIb))

[0598] A gas-barrier laminate (Ia) was formed in the same manner as in Example 51. Using a rod coater No. 3, the epoxy resin composition 14-1 obtained in Example 14-1 was coated on the aluminum vapor deposition surface. The epoxy resin composition was heated at 120 °C for 60 seconds and dried (thickness after drying: about 0.1 μm), and further cured by heating at 40 °C for 2 days to form a resin cured layer. Using a rod coater No. 12, the aforementioned urethane adhesive was coated on the resin cured layer surface and dried at 80 °C for 10 seconds to form an adhesive layer (thickness after drying: about 3 μm). Using a roller, a 50-μm-thick polypropylene film ("P1146" manufactured by Toyobo Co., Ltd.) was laminated thereon and heated at 40 °C for 2 days to obtain Figure 6 the gas-barrier laminate (IIb) having the structure shown.

[0599] Using this gas-barrier laminate (IIb), the peel test under normal conditions was carried out by the aforementioned method. The results are shown in Table 9.

[0600] [Table 9]

[0601] Table 9

[0602]

[0603] *1) Parts by mass relative to a total of 100 parts by mass of the non-volatile components in the epoxy resin and the epoxy resin curing agent solution

[0604] *2) Parts by mass relative to a total of 100 parts by mass of epoxy resin + curing agent

[0605] [First Invention (2): Manufacture of Epoxy Resin Composition and Evaluation of Shelf Life]

[0606] Production Example 3 (Preparation of Epoxy Resin Curing Agent Solution C)

[0607] Put 1 mol of m-xylenediamine (MXDA) into a reaction vessel. Heat it to 60°C under a nitrogen stream and add 0.93 mol of methyl acrylate dropwise over 1 hour. While distilling off the generated methanol, heat it to 165°C and maintain at 165°C for 2.5 hours to obtain an amine-based curing agent. Add ethanol dropwise thereto over 1.5 hours to obtain a solution containing 65.0% by mass of the amine-based curing agent and 35.0% by mass of ethanol.

[0608] Add 90.3 g of ethanol, 158.1 g of ethyl acetate as a diluting solvent, and 188.5 g of the above solution and stir. Add 9.59 g of erucamide (“ALFLOW P-10” manufactured by NOF Corporation) and 5.43 g of 3-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent and stir to obtain an epoxy resin curing agent solution C with a solid content concentration of 30.0% by mass.

[0609] Production Example 4 (Preparation of Epoxy Resin Curing Agent Solution D)

[0610] In the same manner as in Production Example 3, obtain a solution containing 65.0% by mass of the amine-based curing agent and 35.0% by mass of ethanol.

[0611] Add 14.1 g of ethanol, 17.1 g of ethyl acetate as a diluting solvent, and 8.17 g of the above solution and stir. Add 0.42 g of erucamide (“ALFLOW P-10” manufactured by NOF Corporation) and 0.24 g of 3-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent and stir to obtain an epoxy resin curing agent solution D with a solid content concentration of 14.7% by mass.

[0612] Example 53 (Preparation and Evaluation of Epoxy Resin Composition 17)

[0613] For 2.24 g of the epoxy resin curing agent solution C obtained in Production Example 3, 37.6 g of ethanol as a diluting solvent was added, and the mixture was sufficiently stirred. To this, 0.13 g of an epoxy resin having glycidylamino groups derived from m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc., "TETRAD-X") as the epoxy resin was added (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 3.0), and the mixture was stirred to prepare an epoxy resin composition 17 having a solid content concentration of 2.0% by mass (Production Method 1). The compounding amount of erucamide was 5.0 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin in the epoxy resin composition and the non-volatile components in the epoxy resin curing agent solution C.

[0614] The obtained epoxy resin composition 17 was placed in a screw-capped tube and allowed to stand in an environment at a temperature of 23°C, and visual observation was carried out. The time until turbidity occurred is shown in Table 10. The longer this time, the longer the shelf life.

[0615] Examples 54 to 58 (Preparation and evaluation of epoxy resin compositions 18 to 22)

[0616] In Example 53, 37.6 g of ethanol was replaced with ethanol and ethyl acetate, and they were compounded so that the final solvent composition became the mass ratio shown in Table 10. Except for this, the epoxy resin composition was prepared in the same manner as in Example 53, and the shelf life was evaluated. The results are shown in Table 10.

[0617] Example 59 (Preparation and evaluation of epoxy resin composition 23)

[0618] For 4.57 g of the epoxy resin curing agent solution D obtained in Production Example 4, 35.3 g of ethanol as a diluting solvent was added, and the mixture was sufficiently stirred. To this, 0.13 g of an epoxy resin having glycidylamino groups derived from m-xylylenediamine (manufactured by Mitsubishi Gas Chemical Company, Inc., "TETRAD-X") as the epoxy resin was added (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 3.0), and the mixture was stirred to prepare an epoxy resin composition 23 having a solid content concentration of 2.0% by mass (Production Method 1). The compounding amount of erucamide was 5.0 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin in the epoxy resin composition and the non-volatile components in the epoxy resin curing agent solution D.

[0619] The obtained epoxy resin composition 23 was placed in a screw-capped tube and allowed to stand in an environment at a temperature of 23°C, and visual observation was carried out. The time until turbidity occurred is shown in Table 10.

[0620] Examples 60 to 64 (Preparation and evaluation of epoxy resin compositions 24 to 28)

[0621] In Example 59, 35.3 g of ethanol used as a dilution solvent was replaced with ethanol and ethyl acetate, and compounding was carried out in such a manner that the final solvent composition became the mass ratio described in Table 10. Except for this, an epoxy resin composition was prepared in the same manner as in Example 59, and the shelf life was evaluated. The results are shown in Table 10.

[0622] [Table 10]

[0623] Table 10

[0624]

[0625] *1) Parts by mass relative to a total of 100 parts by mass of the nonvolatile components in the epoxy resin and the epoxy resin curing agent solution

[0626] *2) Parts by mass relative to a total of 100 parts by mass of the epoxy resin + curing agent

[0627] As can be seen from Table 10: By making the organic solvent in the epoxy resin composition a mixed system of ethanol - ethyl acetate and using it in a specified mass ratio, the shelf life of the epoxy resin composition was improved.

[0628] [First Invention (3): Manufacturing and Evaluation of Epoxy Resin Composition]

[0629] Example 65

[0630] (Production and Evaluation of Gas - Barrier Laminate (I) (II))

[0631] In Example 17, 20 of the epoxy resin composition obtained in Example 56 (manufactured according to Production Method 1) was used instead of the epoxy resin composition 1 - 1. Except for this, gas - barrier laminates (I) having the same Figure 1 configuration as obtained and Figure 4 gas - barrier laminates (II) having the configuration shown were obtained.

[0632] Using this gas - barrier laminate (I), the haze, total light transmittance, and YI were measured, and the oxygen permeability and water vapor transmission rate were measured by the aforementioned method. Moreover, using the gas - barrier laminate (II), a peel test under normal conditions was carried out. The results are shown in Table 11.

[0633] (Production and Evaluation of Gas - Barrier Laminate (III))

[0634] In Example 30, 20 of the epoxy resin composition obtained in Example 56 was used instead of the epoxy resin composition 1 - 1. Except for this, a gas - barrier laminate (III) having the same Figure 7 configuration as obtained was obtained.

[0635] Using the gas barrier laminate (III), a peel test was conducted under normal conditions and after retort treatment. The results are shown in Table 11.

[0636] Example 66

[0637] In Example 65, the epoxy resin composition 26 obtained in Example 62 (manufactured according to Production Method 1) was used instead of the epoxy resin composition 20 obtained in Example 56. Except for this, gas barrier laminates (I) to (III) were produced in the same manner as in Example 65, and the above-described evaluation was conducted. The results are shown in Table 11.

[0638] Example 67 (Preparation of Epoxy Resin Composition 29)

[0639] (Preparation of Erucamide Solution a)

[0640] To 40.8 g of ethanol and 66.5 g of ethyl acetate, which were used as dilution solvents, 2.85 g of erucamide (“ALFLOW P-10” manufactured by NOF Corporation) was added, and the mixture was heated using a belt heater. Stirring was started when the temperature reached 20°C to prepare erucamide solution a.

[0641] (Preparation of Epoxy Resin Curing Agent Solution E)

[0642] In the same manner as in Production Example 3, an amine-based curing agent solution having an amine-based curing agent content of 65.0% by mass and an ethanol content of 35.0% by mass was obtained.

[0643] To the above-described erucamide solution a, 1.71 g of 3-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd.), which was used as a silane coupling agent, was added. While continuously heating and stirring, 73.6 g of the above-described amine-based curing agent solution was added and stirred to obtain an epoxy resin curing agent solution E having a solid content concentration of 30.0% by mass.

[0644] (Preparation of Epoxy Resin Composition 29)

[0645] To 12.8 g of the epoxy resin curing agent solution E, 216.0 g of ethanol and 220.5 g of ethyl acetate, which were used as dilution solvents, were added and stirred well. To this, 1.4 g of an epoxy resin having glycidylamino groups derived from m-xylylenediamine (“TETRAD-X” manufactured by Mitsubishi Gas Chemical Company, Inc.) (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 3.0) was added and stirred to prepare an epoxy resin composition 29 having a solid content concentration of 2.0% by mass (Production Method 2). The compounding amount of erucamide was 5.0 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin in the epoxy resin composition and the non-volatile components in the epoxy resin curing agent solution E.

[0646] Example 68

[0647] In Example 65, the epoxy resin composition 29 obtained in Example 67 (manufactured according to Production Method 2) was used instead of the epoxy resin composition 20 obtained in Example 56, and the gas-barrier laminates (I) to (III) were produced in the same manner as in Example 65, and the above-described evaluation was performed. The results are shown in Table 11.

[0648] [Table 11]

[0649]

[0650] As can be seen from Table 11: Equivalent performance can also be obtained when the epoxy resin composition manufactured by either Production Method 1 or 2 is used for the gas-barrier laminate.

[0651] [First Invention (4): Manufacture and Evaluation of Gas-Barrier Laminate (IIa)]

[0652] Example 69

[0653] A biaxially stretched polypropylene film (“FOR” manufactured by Futamura Chemical Co., Ltd., thickness: 20 μm) was used as the substrate, and the epoxy resin composition 23 obtained in Example 59 was coated on one side thereof using a bar coater No. 3. The epoxy resin composition was heated at 120°C for 60 seconds and dried (thickness after drying: about 0.1 μm), and further cured by heating at 40°C for 2 days to form a resin cured layer. Using the vacuum evaporation method, an aluminum vapor deposition layer with a thickness of about was formed on the resin cured layer surface to produce a gas-barrier laminate (Ia) having the Figure 2 configuration.

[0654] Using a bar coater No. 12, the above-described urethane adhesive was coated on the aluminum vapor deposition surface of the obtained gas-barrier laminate (Ia), dried at 80°C for 10 seconds to form an adhesive layer (thickness after drying: about 3 μm). Using a roll, a polypropylene film with a thickness of 50 μm (“P1146” manufactured by Toyobo Co., Ltd.) was laminated thereon, and heated at 40°C for 2 days to obtain a gas-barrier laminate (IIa) having the Figure 5 configuration shown.

[0655] Using this gas-barrier laminate (IIa), the peel test was performed under normal conditions by the above-described method. The results are shown in Table 12.

[0656] Example 70

[0657] In Example 69, a silicon dioxide vapor deposition layer was formed instead of an aluminum vapor deposition layer. Except for this, an air barrier laminate (IIa) was produced in the same manner as in Example 69, and the peel test under normal conditions was carried out by the aforementioned method. The results are shown in Table 12.

[0658] Comparative Example 13

[0659] In Example 70, a resin cured layer was not formed. Except for this, an air barrier laminate was produced in the same manner as in Example 70, and the peel test under normal conditions was carried out by the aforementioned method. The results are shown in Table 12.

[0660] Example 71

[0661] In Example 69, an aluminum oxide vapor deposition layer was formed instead of an aluminum vapor deposition layer. Except for this, an air barrier laminate (IIa) was produced in the same manner as in Example 69, and the peel test under normal conditions was carried out by the aforementioned method. The results are shown in Table 12.

[0662] Comparative Example 14

[0663] In Example 71, a resin cured layer was not formed. Except for this, an air barrier laminate was produced in the same manner as in Example 71, and the peel test under normal conditions was carried out by the aforementioned method. The results are shown in Table 12.

[0664] [Table 12]

[0665] Table 12

[0666]

[0667] [Second Invention: Manufacture and Evaluation of Packaging Material]

[0668] The measurements and evaluations in this example were carried out by the following methods.

[0669] <Adhesion Evaluation>

[0670] According to the method described in each example, an epoxy resin composition was coated on one surface of a linear low-density polyethylene (LLDPE) film (manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., "CMPS-017C", thickness 30 μm) and dried to form a resin composition layer, which was placed on a horizontal plane. Another prepared LLDPE film of 210 mm × 297 mm was placed facing and laminated with this resin composition layer. While placing a weight of 15 kg in the A4 size on it and applying a load, it was cured at 40 °C for 2 days. After curing, the weight was removed, and the state of adhesion when peeling the later-laminated LLDPE film from the cured layer surface by hand was evaluated according to the following criteria.

[0671] A: No adhesion occurred, and the LLDPE film can be easily peeled off.

[0672] B: Adhesion occurred. Although the LLDPE film can be peeled off, an increase in haze can be seen after peeling.

[0673] C: Adhesion occurred, and the LLDPE film cannot be peeled off.

[0674] <Antiochic evaluation>

[0675] Cut the packaging films manufactured in each example into two pieces of 12 cm square, overlap the two films, and heat-seal three sides to form a bag shape. At this time, for the films of Example X1 and X2, overlap them in such a way that the cured layer becomes the outermost layer and perform heat-sealing. Put 2 mL of a 0.1% aqueous solution of the odor components listed in Table 13 into the obtained anti-odor bag, and heat-seal the opening.

[0676] Put the anti-odor bag containing the odor components into an aluminum bag, inject 1000 cc of air into the bag with a syringe, and store it in an environment of 23°C and 50% R.H. After a certain period of time, cut the end of the aluminum bag, use a detector tube, suck 100 cc of the air inside the bag, measure the amount of the odor components in the air, and show it in Table 13. The smaller the amount of the detected odor components, the less the odor components leaking from the anti-odor bag, and the higher the anti-odor property.

[0677] Production Example X1 (Preparation of epoxy resin curing agent solution XA)

[0678] Put 1 mol of m-xylenediamine (MXDA) into a reaction vessel. Heat it to 60°C under a nitrogen gas stream, and dropwise add 0.93 mol of methyl acrylate over 1 hour. While distilling off the generated methanol, heat it to 165°C and keep it at 165°C for 2.5 hours to obtain an amine-based curing agent. Dropwise add ethanol to it over 1.5 hours to obtain a solution containing 65.0% by mass of the amine-based curing agent and 35.0% by mass of ethanol.

[0679] Add 166.8 g of ethanol, 200.2 g of ethyl acetate, and 94.9 g of the above solution as a diluting solvent and stir. Add 4.64 g of erucamide (manufactured by NOF CORPORATION, "ALFLOW P-10") and 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBE-903") as a silane coupling agent and stir to obtain epoxy resin curing agent solution XA.

[0680] Production Example X2 (Preparation of epoxy resin composition X1)

[0681] To 3.75 g of the epoxy resin curing agent solution XA obtained in Production Example X1, 29.0 g of ethanol as a diluting solvent was added and stirred well. To this, 0.10 g of an epoxy resin having glycidylamino groups derived from m-xylylenediamine (Mitsubishi Gas Chemical Company, Inc.'s "TETRAD-X") as the epoxy resin (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 3.0) was added and stirred to prepare an epoxy resin composition X1. The compounding amount of erucamide was 5.0 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin in the epoxy resin composition X1 and the non-volatile components in the epoxy resin curing agent solution XA.

[0682] Example X1 (Production and Evaluation of Odor-Proof Bag)

[0683] Using a bar coater No. 3, the epoxy resin composition X1 obtained in Production Example X2 was coated on a linear low-density polyethylene (LLDPE) film ("CMPS-017C" manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., thickness 30 μm). The epoxy resin composition was heated in a drying oven at 60 °C for 30 seconds and dried (thickness after drying: 0.1 μm), and further cured at 40 °C for 2 days to produce Figure 10 a packaging film having the constitution of.

[0684] Using the obtained packaging film, an odor-proof bag was produced by the method described in the above-mentioned "Odor-Proof Property Evaluation" and the above-mentioned evaluation was carried out. The results are shown in Table 13.

[0685] Comparative Example X1

[0686] In Example X1, only a linear low-density polyethylene film ("CMPS-017C" manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., thickness 30 μm) was used instead of the packaging film, and an odor-proof bag was produced by the method described in the above-mentioned "Odor-Proof Property Evaluation" and the above-mentioned evaluation was carried out. The results are shown in Table 13.

[0687] Comparative Example X2

[0688] Using an upward air-cooled blown film forming machine (manufactured by Tommy Machinery Industry Co., Ltd.) equipped with 5 extruders, a feed head, and a T-die, respectively, from the first extruder, upward air-cooled LLDPE (Prime Polymer Co., Ltd.'s "Evolue SP2510", MFR = 1.4) at 200°C, from the second extruder, upward air-cooled adhesive polyolefin (Mitsui Chemicals, Inc.'s "Admer NF518") at 200°C, from the third extruder, upward air-cooled LLDPE (Prime Polymer Co., Ltd.'s "Evolue SP2510", MFR = 1.4) at 200°C, from the fourth extruder, upward air-cooled adhesive polyolefin (Mitsui Chemicals, Inc.'s "Admer NF518") at 200°C, and from the fifth extruder, upward air-cooled LLDPE (Prime Polymer Co., Ltd.'s "Evolue SP2510", MFR = 1.4) at 200°C to obtain a multilayer sheet. The layer structure of the multilayer sheet is a three-kind five-layer structure of LLDPE layer / adhesive polyolefin layer / LLDPE layer / adhesive polyolefin layer / LLDPE layer from the outer layer, and the thickness of each layer is 11 / 5 / 4 / 5 / 11 (μm).

[0689] Using the obtained multilayer sheet, an odor-proof bag was produced by the method described in the above "odor-proof evaluation", and the odor-proof evaluation was carried out. The results are shown in Table 13.

[0690] Comparative Example X3

[0691] In Comparative Example X2, ethylene-vinyl alcohol copolymer (EVOH, "ET3803RB" manufactured by Nippon Gohsei Co., Ltd., ethylene 38 mol%) was extruded from the third extruder at 200°C instead of LLDPE. Except for this, a multilayer sheet and an odor-proof bag were produced in the same manner as in Comparative Example X2, and the odor-proof evaluation was carried out. The results are shown in Table 13.

[0692] Example X2

[0693] In Example X1, the odor component was changed to trimethylamine. Except for this, the odor-proof evaluation was carried out in the same manner as in Example X1. The results are shown in Table 13.

[0694] Comparative Example X4

[0695] In Comparative Example X1, the odor component was changed to trimethylamine. Except for this, the odor-proof evaluation was carried out in the same manner as in Comparative Example X1. The results are shown in Table 13.

[0696] [Table 13]

[0697] Table 13

[0698]

[0699] *1) The diagonal part is not evaluated

[0700] The abbreviations in Table 13 are as follows.

[0701] LLDPE#30: Linear low-density polyethylene film, "CMPS-017C" manufactured by Mitsui Chemicals TOHCELLO Co., Ltd., thickness 30 μm

[0702] LLDPE#11: Linear low-density polyethylene layer, "Evolue SP2510" manufactured by Prime Polymer Co., Ltd., MFR = 1.4, layer thickness 11 μm

[0703] LLDPE#4: Linear low-density polyethylene layer, "Evolue SP2510" manufactured by Prime Polymer Co., Ltd., MFR = 1.4, layer thickness 4 μm

[0704] Tie#5: Adhesive polyolefin layer, "Admer NF518" manufactured by Mitsui Chemicals, Inc., layer thickness 5 μm

[0705] EVOH#4: Ethylene-vinyl alcohol copolymer layer, "ET3803RB" manufactured by Nippon Gohsei Chemical Industry Co., Ltd., ethylene 38 mol%, layer thickness 4 μm

[0706] [Third Invention: Manufacture and Evaluation of Heat-Shrinkable Labels]

[0707] The measurements and evaluations in this example were carried out by the following methods.

[0708] <Heat shrinkage rate>

[0709] After drawing a 10 cm × 10 cm square at the center of the heat-shrinkable substrate or the heat-shrinkable label of each example, it was put into 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 according to the following formula.

[0710] Heat shrinkage rate (%) = {1 - (area of the square after heat shrinkage) / (area of the square before heat shrinkage)} × 100

[0711] <Followability during heat shrinkage>

[0712] The tubular heat-shrinkable label of each example was installed on the outer peripheral side of a 500 mL PET bottle in such a way that the heat-shrinkable film surface was on the inner side of the cylinder. The installation position of the label wasFigure 12 The part represented by the slanted portion is such that the lower end of the label is 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 is 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 is visually observed to evaluate the followability during heat shrinkage. When the label adheres evenly to the side of the PET bottle and no delamination between the substrate layer and the cured layer is observed, it is judged as "good"; when the label does not follow the shape of the side of the PET bottle and adheres unevenly, or delamination between the substrate layer and the cured layer is visible, it is judged as "bad".

[0713] <O2 Permeation Rate>

[0714] Using an oxygen permeation rate measuring device ("OX-TRAN 2 / 61" manufactured by MOCON), the O2 permeation rate of the bottle is measured.

[0715] In a PET bottle that has been shrink-packaged in the same manner as described above, 30 mL of water is filled. Under the conditions of a temperature of 23°C, an internal humidity of 100% RH, and an external humidity of 50% RH, nitrogen gas at 1 atm is circulated inside the bottle at a rate of 20 mL / minute. The oxygen contained in the nitrogen gas circulated inside the bottle is detected using a coulometric gas sensor. The smaller the value, the less O2 permeates and the better the O2 barrier property.

[0716] <CO2 Permeation Rate>

[0717] Using a carbon dioxide gas permeability measuring device ("Permatran C10" manufactured by MOCON), the CO2 permeation rate of the bottle is measured.

[0718] In a PET bottle that has been shrink-packaged in the same manner as described above, 500 mL of carbonated water with a CO2 content of 3.2 GV (carbonated water in which 3.2 L of CO2 is dissolved in 1 L of water) is sealed and left standing in an environment of 23°C and 50% RH for 1 week. The amount of CO2 inside the bottle after standing for 1 week is quantified, and the CO2 permeation rate is calculated from this value. The smaller the value, the less CO2 permeates and the better the CO2 barrier property.

[0719] <Shelf Life>

[0720] In a PET bottle shrink-wrapped in the same manner as described above, 500 mL of carbonated water with a CO₂ content of 3.2 GV was sealed. It was left standing in an environment of 23°C and 50% RH, and the amount of CO₂ in the bottle was quantified over time using a carbon dioxide gas permeability measuring device ("Permatran C10" manufactured by MOCON). The time until the GV of CO₂ in the carbonated water sealed in the PET bottle reached 80% of the initial value is shown in Table 2. The longer the shelf life, the less CO₂ permeates, indicating better CO₂ barrier properties.

[0721] Production Example X3 (Preparation of Epoxy Resin Composition X2)

[0722] To 3.42 g of the epoxy resin curing agent solution XA obtained in Production Example X1, 6.48 g of ethanol as a diluting solvent was added and thoroughly stirred. To this, 0.10 g of an epoxy resin having glycidylamino groups derived from m-xylylenediamine as an epoxy resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., "TETRAD-X") (the number of active amine hydrogens in the epoxy resin curing agent / the number of epoxy groups in the epoxy resin = 3.0) was added and stirred to prepare Epoxy Resin Composition X2. The compounding amount of erucamide was 5.0 parts by mass with respect to a total of 100 parts by mass of the epoxy resin and the non-volatile components in the epoxy resin curing agent solution XA in Epoxy Resin Composition X2.

[0723] Example Y1 (Production and Evaluation of Heat-Shrinkable Film)

[0724] Using a rod coater No. 3, the epoxy resin composition X1 obtained in Production Example X2 was coated on the outer surface of a tubular heat-shrinkable film made of polyvinyl chloride (PVC) (original PET bottle-making film "Chijimarukun(ちぢ〇くん)" manufactured by Sun Plastic Co., Ltd., width 110 mm (total circumference of the tube 220 mm) × length 175 mm × thickness 40 μm). The epoxy resin composition 1 was heated in a drying oven at 60°C for 30 seconds and dried (thickness after drying: 0.1 μm), and further cured at 40°C for 2 days to produce a Figure 11 tubular heat-shrinkable label having a layer structure.

[0725] Using the obtained heat-shrinkable label, various evaluations were carried out in the above-described manner. The results are shown in Table 14.

[0726] Example Y2

[0727] In Example Y1, 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 otherwise, a heat-shrinkable label was produced in the same manner as in Example Y1, and the above-described evaluation was carried out. The results are shown in Table 14.

[0728] Comparative Example Y1

[0729] Using only the above-mentioned cylindrical heat-shrinkable film made of PVC as the heat-shrinkable label, the PET bottle was shrink-wrapped by the above-mentioned method, and the above-mentioned evaluation was carried out. The results are shown in Table 14.

[0730] Reference Example Y1

[0731] Using a PET bottle without shrink-wrapping based on a heat-shrinkable label, the above-mentioned evaluation was carried out. The results are shown in Table 14.

[0732] [Table 14]

[0733] Table 14

[0734]

[0735] As can be seen from Table 14, the bottle with the heat-shrinkable label of this example has the same O2 barrier property as the bottles of the comparative example and the reference example, and has a high CO2 barrier property. Moreover, the followability during heat shrinkage of the heat-shrinkable label of this example is also good.

[0736] Industrial Applicability

[0737] According to the epoxy resin composition as the first invention, a cured product having high gas barrier properties, particularly good adhesion to inorganic substances such as alumina, not easily causing peeling even after retort treatment, and excellent retort resistance can be formed. For a gas barrier laminate having a resin cured layer which is a cured product of the epoxy resin composition formed on a substrate composed of an inorganic substance on at least one side, it has high gas barrier properties, interlayer adhesion, and retort resistance, and is suitable for use as a packaging material for retort foods, for example.

[0738] According to the second invention, a packaging material for deodorization or flavor retention and a deodorization or flavor retention method having good deodorizing properties and flavor retention properties, capable of being thinned, and excellent in economy can be provided. The packaging material according to the second invention can be suitably used for applications requiring deodorizing properties or flavor retention properties, such as bags for storing used disposable diapers, pet sand, dirt, domestic waste, and other malodorous substances; packaging materials for foods with strong odors; packaging materials for fragrant toiletries, cosmetics, stationery, and toys; etc.

[0739] In addition, according to the third invention, a heat-shrinkable label having good CO2 barrier properties, excellent followability and economy during heat shrinkage, a manufacturing method thereof, a heat-shrink label and a bottle having the same, and a method for preventing CO2 permeation can be provided. The heat-shrinkable label according to the third invention is suitable for PET bottles for carbonated water and other carbonated beverages.

[0740] Explanation of Reference Numerals

[0741] 100, 200, 300, 400 Gas-barrier laminated body

[0742] 1 Substrate

[0743] 2 Inorganic thin film layer

[0744] 3 Resin cured layer

[0745] 4 Thermoplastic resin film (Thermoplastic resin layer)

[0746] 5 Adhesive layer

[0747] 500 Packaging material (Packaging film)

[0748] 501 Substrate

[0749] 502, 602 Cured product layer

[0750] 600 Heat-shrinkable label

[0751] 601 Heat-shrinkable substrate layer

Claims

1. An epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 18 to 22 carbon atoms, The content of the unsaturated fatty acid amide in the epoxy resin composition is 3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent, The amine-based curing agent is the following amine-based curing agent (i), (i) The reaction product of the following component (A) and component (B): (A) At least 1 selected from the group consisting of m-xylylenediamine and p-xylylenediamine, (B) At least 1 selected from the group consisting of the unsaturated carboxylic acid represented by the following general formula (1) and its derivatives, 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. The epoxy resin composition according to claim 1, wherein, The epoxy resin has, as a main component, an epoxy resin having a glycidylamino group derived from m-xylylenediamine.

3. The epoxy resin composition according to claim 1 or 2, wherein The unsaturated fatty acid amide is at least 1 selected from the group consisting of oleic acid amide and erucic acid amide.

4. The epoxy resin composition according to claim 1 or 2, further containing non-spherical inorganic particles.

5. The epoxy resin composition according to claim 1 or 2, wherein The ratio of the number of hydrogens of the active amine in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin exceeds 1.0 and is 5.0 or less.

6. A gas barrier laminate having: a substrate; and a resin cured layer which is a cured product of the epoxy resin composition according to any one of claims 1 to 5.

7. The gas barrier laminate according to claim 6, wherein, Having at least 1 layer of a layer composed of an inorganic substance.

8. The gas-barrier laminate according to claim 7, wherein, The layer composed of an inorganic substance is an inorganic substrate.

9. The gas-barrier laminate according to claim 7, wherein, The layer composed of an inorganic substance is an inorganic thin film layer.

10. The gas-barrier laminate according to claim 9, wherein, The inorganic substance in the inorganic thin film layer is at least 1 selected from the group consisting of silicon oxide, aluminum, and aluminum oxide.

11. The gas-barrier laminate according to any one of claims 7 to 10, wherein, The layer composed of an inorganic substance is adjacent to the resin cured layer.

12. The gas barrier laminate according to any one of claims 7 to 10, further having a thermoplastic resin layer.

13. A packaging material for retort foods, comprising the gas barrier laminate according to claim 12.

14. A packaging material for preventing odor or preserving fragrance, having: a substrate, and a cured product layer of an epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 18 to 22 carbon atoms, the content of the unsaturated fatty acid amide in the epoxy resin composition being 3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent, The amine-based curing agent is the following amine-based curing agent (i), (i) The reaction product of the following component (A) and component (B): (A) At least 1 selected from the group consisting of m-xylylenediamine and p-xylylenediamine, (B) At least 1 selected from the group consisting of the unsaturated carboxylic acid represented by the following general formula (1) and its derivatives, 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.

15. The packaging material for preventing odor or preserving fragrance according to claim 14, wherein, The substrate is a film-like substrate.

16. The packaging material for preventing odor or preserving fragrance according to claim 14 or 15, having only 1 piece of the substrate and only 1 layer of the cured product layer.

17. The packaging material for preventing odor or preserving fragrance according to claim 14 or 15, wherein, The thickness of the cured product layer is 0.02 to 0.6 μm.

18. The packaging material for preventing odor or preserving fragrance according to claim 14 or 15, wherein, The packaging material is a bag, a film, or a lid material.

19. A method for preventing odor or preserving fragrance, the method comprising enclosing an article containing an odor component or a fragrance component in a packaging material, the packaging material having: a substrate and a cured product layer of an epoxy resin composition, the epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 18 to 22 carbon atoms, the content of the unsaturated fatty acid amide in the epoxy resin composition being 3 to 10 parts by mass relative to 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent, The amine-based curing agent is the following amine-based curing agent (i), (i) The reaction product of the following component (A) and component (B): (A) At least one selected from the group consisting of m-xylenediamine and p-xylenediamine, (B) At least one selected from the group consisting of an unsaturated carboxylic acid represented by the following general formula (1) and its derivatives, 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.

20. A heat-shrinkable label having: a heat-shrinkable substrate layer and a cured product layer of an epoxy resin composition, the epoxy resin composition containing: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an unsaturated fatty acid amide having 18 to 22 carbon atoms, the content of the unsaturated fatty acid amide in the epoxy resin composition being 3 to 10 parts by mass relative to 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent, The amine-based curing agent is the following amine-based curing agent (i), (i) The reaction product of the following component (A) and component (B): (A) At least one selected from the group consisting of m-xylenediamine and p-xylenediamine, (B) At least one selected from the group consisting of an unsaturated carboxylic acid represented by the following general formula (1) and its derivatives, 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.

21. The heat-shrinkable label according to claim 20, wherein, The resin constituting the heat-shrinkable substrate layer is a resin selected from the group consisting of a polyvinyl chloride resin, a polystyrene resin, a polyolefin resin, and a polyester resin.

22. The heat-shrinkable label according to claim 20 or 21, wherein, The heat-shrinkable substrate layer and the cured product layer each have only one layer.

23. A method for manufacturing the heat-shrinkable label according to any one of claims 20 to 22, which sequentially includes the following steps (I) and (II), Step (I): A step of coating an epoxy resin composition on at least one surface of a heat-shrinkable substrate to form a coating layer; the epoxy resin composition contains: an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, an unsaturated fatty acid amide having 18 to 22 carbon atoms, and a solvent; Step (II): A step of heating and drying the coating layer at a temperature below 100 °C to remove the solvent, The content of the unsaturated fatty acid amide in the epoxy resin composition is 3 to 10 parts by mass relative to 100 parts by mass of the total amount of the non-volatile components in the epoxy resin and the epoxy resin curing agent, The amine-based curing agent is the following amine-based curing agent (i), (i) The reaction product of the following component (A) and component (B): (A) At least one selected from the group consisting of m-xylenediamine and p-xylenediamine, (B) At least one selected from the group consisting of an unsaturated carboxylic acid represented by the following general formula (1) and its derivatives, 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.

24. A heat-shrinkable label obtained by heat-shrinking the heat-shrinkable label according to any one of claims 20 to 22.

25. A bottle having the heat-shrinkable label according to claim 24.

26. A method for preventing CO2 permeation, which uses the heat-shrinkable label according to any one of claims 20 to 22 or the heat-shrinkable label according to claim 24.

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