WO2022107473A1 - エポキシ樹脂組成物、ガスバリア性積層体及び包装材 - Google Patents

エポキシ樹脂組成物、ガスバリア性積層体及び包装材 Download PDF

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Publication number
WO2022107473A1
WO2022107473A1 PCT/JP2021/036946 JP2021036946W WO2022107473A1 WO 2022107473 A1 WO2022107473 A1 WO 2022107473A1 JP 2021036946 W JP2021036946 W JP 2021036946W WO 2022107473 A1 WO2022107473 A1 WO 2022107473A1
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Prior art keywords
epoxy resin
gas barrier
resin composition
layer
curing agent
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PCT/JP2021/036946
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English (en)
French (fr)
Japanese (ja)
Inventor
菜穂子 小林
和起 河野
凌馬 橋本
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to JP2022563617A priority Critical patent/JPWO2022107473A1/ja
Priority to KR1020237016297A priority patent/KR20230109139A/ko
Priority to US18/036,944 priority patent/US12584011B2/en
Priority to CN202180075148.XA priority patent/CN116529084A/zh
Priority to EP21894348.8A priority patent/EP4249248A4/en
Publication of WO2022107473A1 publication Critical patent/WO2022107473A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition

Definitions

  • the present invention relates to an epoxy resin composition, a gas barrier laminate using the epoxy resin composition, and a packaging material.
  • Packaging materials used in foods, pharmaceuticals, cosmetics, precision electronic components, etc. are required to have high oxygen barrier properties and water vapor barrier properties in order to prevent deterioration of the contents. Since the oxygen barrier property of a thermoplastic plastic film is generally not so high, various gas barrier layers such as a polyvinylidene chloride (PVDC) layer and a polyvinyl alcohol (PVA) layer are formed as a means for imparting gas barrier property to the film. Or a method of depositing an inorganic substance such as alumina (Al 2 O 3 ) or silica (SiO 2 ) has been studied.
  • PVDC polyvinylidene chloride
  • PVA polyvinyl alcohol
  • the film on which the PVDC layer is formed as the gas barrier layer is transparent and exhibits good barrier properties. However, since harmful substances such as acid gas are generated when incinerated as general waste, it is desired to switch to other materials from the viewpoint of environmental consideration.
  • the film on which the PVA layer is formed exhibits excellent gas barrier properties under low humidity, but has a problem of high hygroscopicity and a sharp decrease in gas barrier properties when the relative humidity is about 70% or more.
  • the inorganic vapor-deposited film obtained by depositing an inorganic substance such as alumina or silica on a thermoplastic plastic film is transparent and has good gas barrier properties, and the above problem does not occur.
  • an inorganic substance such as alumina or silica
  • thermoplastic plastic film is transparent and has good gas barrier properties, and the above problem does not occur.
  • the inorganic thin-film film is bent, there is a problem that cracks are generated in the inorganic-deposited layer and the gas barrier property is remarkably lowered.
  • Patent Documents 1 to 3 As a method for improving the bending resistance of a gas barrier film or a laminate containing a layer on which an inorganic substance is vapor-deposited, a cured product of an epoxy resin composition containing a predetermined epoxy resin and a predetermined amine-based epoxy resin curing agent as main components.
  • Patent Documents 1 to 3 A method for forming a layer is proposed (Patent Documents 1 to 3).
  • Patent Document 4 has a predetermined base film having an inorganic vapor deposition layer and a predetermined resin cured layer composed of an epoxy resin, a predetermined epoxy resin curing agent, and a cured product of an epoxy resin composition containing non-spherical inorganic particles. It is disclosed that the layered gas barrier film has improved gas barrier properties and is also excellent in bending resistance as compared with the conventional gas barrier film having an inorganic vapor deposition layer.
  • Patent Document 5 covers a wide range of gas barrier resin compositions containing an epoxy resin, an epoxy resin curing agent, and a specific curing accelerator, and containing a predetermined amount of a predetermined skeleton structure derived from an amine in the cured product formed. It has been reported that high gas barrier properties are exhibited under the curing conditions of.
  • Patent Document 6 describes a primer composition containing a specific polyester resin in a laminated film in which at least a substrate, a primer layer, an adhesive layer, and a sealant layer are laminated in this order.
  • Patent Documents 1 to 6 disclose epoxy resin compositions using an amine-based epoxy resin curing agent, but according to recent studies by the present inventors, an epoxy resin using an amine-based epoxy resin curing agent has been disclosed. It was found that the cured product of the composition had unstable adhesion to the inorganic material.
  • the epoxy resin composition When the epoxy resin composition is applied as an intermediate layer of a gas barrier laminate, the epoxy resin composition may have a performance as an adhesive in addition to the gas barrier property.
  • the performance suitable for the coating composition is important. For example, it is required that the drying is quick, there is little sticking (blocking) after coating, and the appearance of the formed coating film is good.
  • the addition of a lubricant or the like is effective in suppressing blocking.
  • the cured product of the epoxy resin composition containing the additive tends to have a lower gas barrier property than that of the non-added epoxy resin composition.
  • the cured coating film obtained by applying the epoxy resin composition to a base material or the like may have uneven coating or the gloss may be deteriorated, resulting in deterioration of the appearance.
  • the subject of the present invention is an epoxy resin composition having high gas barrier properties and sufficient adhesiveness for practical use, and capable of forming a cured coating film having a good appearance, a gas barrier laminate and a packaging material using the epoxy resin composition. Is to provide.
  • the present inventors have found that the above problems can be solved by using an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and an epoxy resin composition containing polyalkylene glycol. That is, the present invention relates to the following [1] to [3].
  • [3] A packaging material containing the gas barrier laminate according to the above [2].
  • the epoxy resin composition of the present invention it is particularly useful as a coating composition, has high gas barrier properties and practically sufficient adhesiveness, and can form a cured coating film having a good appearance.
  • a gas barrier laminate having a base material and a cured product layer of the epoxy resin composition is suitable for various packaging material applications.
  • the epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin, an epoxy resin curing agent containing an amine-based curing agent, and polyalkylene glycol.
  • the epoxy resin composition of the present invention has high gas barrier properties and practically sufficient adhesiveness, and can form a cured coating film having a good appearance. The reason for this is not clear, but it is thought to be due to the leveling action of the polyalkylene glycol.
  • the epoxy resin composition of the present invention improves the drying rate, facilitates application to a substrate having low heat resistance, suppresses blocking, and imparts properties suitable for a coating composition, and cure coating. From the viewpoint of improving the adhesiveness of the film to inorganic substances, it is preferable to further contain an unsaturated fatty acid amide having 14 to 24 carbon atoms. It is considered that when an unsaturated fatty acid amide having 14 to 24 carbon atoms is contained in the epoxy resin composition, it exerts a function as a lubricant and contributes to improvement of drying rate and suppression of blocking.
  • the unsaturated fatty acid amide having 14 to 24 carbon atoms is considered to have an effect of relaxing the stress generated in the cured epoxy resin, and the amine-based epoxy resin curing agent is compared with the saturated fatty acid amide and the like. Highly compatible with the epoxy resin composition contained. Therefore, it is presumed that the cured product of the epoxy resin composition containing the unsaturated fatty acid amide has good adhesiveness to the inorganic substance.
  • the epoxy resin used in the epoxy resin composition of the present invention may be either a saturated or unsaturated aliphatic compound, an alicyclic compound, an aromatic compound, or a heterocyclic compound, but exhibits high gas barrier properties.
  • an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule is preferable.
  • Specific examples of the epoxy resin include an epoxy resin having a glycidylamino group derived from metaxylylene diamine, an epoxy resin having a glycidylamino group derived from paraxylylene diamine, and 1,3-bis (aminomethyl).
  • Epoxy resin with glycidylamino group derived from cyclohexane epoxy resin with glycidylamino group derived from 1,4-bis (aminomethyl) cyclohexane, epoxy resin with glycidylamino group derived from diaminodiphenylmethane, paraamino From phenol-derived glycidylamino and / or glycidyloxy group-derived epoxy resin, bisphenol A-derived glycidyloxy group-derived epoxy resin, bisphenol F-derived glycidyloxy group-derived epoxy resin, phenol novolac Included is at least one resin selected from an epoxy resin having an derived glycidyloxy group and an epoxy resin having an derived glycidyloxy group derived from resorcinol.
  • the epoxy resin is from an epoxy resin having a glycidylamino group derived from metaxylylene diamine, an epoxy resin having a glycidylamino group derived from paraxylylene diamine, and bisphenol F. It is preferable that the main component is at least one selected from the group consisting of the derived epoxy resin having a glycidyloxy group, and the main component is an epoxy resin having an glycidylamino group derived from a metaxylylene diamine. More preferred.
  • main component means that other components may be contained within a range that does not deviate from the gist of the present invention, preferably 50 to 100% by mass, more preferably 70 to 100% by mass. , More preferably 90 to 100% by mass.
  • the epoxy resin curing agent used in the epoxy resin composition of the present invention contains an amine-based curing agent from the viewpoint of exhibiting high gas barrier properties.
  • the amine-based curing agent polyamine or a modified product thereof, which has been conventionally used as an epoxy resin curing agent, can be used.
  • the amine-based curing agent is preferably a modified product of polyamine, and is at least one selected from the group consisting of the following amine-based curing agent (i) and amine-based curing agent (ii). It is more preferable to have the following amine-based curing agent (i).
  • R 1 and R 2 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.
  • the amine-based curing agent (i) is a reaction product of the following component (A) and component (B).
  • component (A) At least one selected from the group consisting of metaxylylenediamine and paraxylylenediamine
  • B At least one selected from the group consisting of unsaturated carboxylic acid represented by the following general formula (1) and its derivatives.
  • R 1 and R 2 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms.
  • the component (A) is used from the viewpoint of gas barrier property, and m-xylylenediamine is preferable from the viewpoint of gas barrier property.
  • the component (A) one type may be used alone, or two types may be mixed and used.
  • the component (B) is at least one selected from the group consisting of unsaturated carboxylic acids represented by the general formula (1) and derivatives thereof, and from the viewpoint of gas barrier properties, R 1 in the general formula (1).
  • R 1 in the 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, further preferably a hydrogen atom or a methyl group, and a hydrogen atom. Is even more preferable.
  • R 2 in the general formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • Examples of the derivative of the unsaturated carboxylic acid represented by the general formula (1) include esters, amides, acid anhydrides, and acid anhydrides of the unsaturated carboxylic acid.
  • the unsaturated carboxylic acid ester is preferably an alkyl ester, and the number of alkyl carbon atoms is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2 from the viewpoint of obtaining good reactivity.
  • Examples of the unsaturated carboxylic acid represented by the general formula (1) and its derivatives include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, ⁇ -propylacrylic acid, ⁇ -isopropylacrylic acid and ⁇ -n-butylacrylic acid.
  • Acid ⁇ -t-butylacrylic acid, ⁇ -pentylacrylic acid, ⁇ -phenylacrylic acid, ⁇ -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-pentenic acid, 4-phenyl-2-butenoic acid, katsura acid, o-methyl katsura Examples thereof include unsaturated carboxylic acids such as acid, m-methyl cinnamic acid, p-methyl cinnamic acid and 2-octenoic acid, and esters, amides, acid anhydrides, acidified products and the like thereof.
  • the component (B) is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and derivatives thereof, and acrylic acid, methacrylic acid and crotonic acid are preferable. At least one selected from the group consisting of acids and alkyl esters thereof is more preferred, more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and alkyl esters thereof, and alkyl esters of acrylic acid are more preferred. More preferably, methyl acrylate is even more preferred.
  • the component (B) one type may be used alone, or two or more types may be used in combination.
  • the reaction between the component (A) and the component (B) is at 0 to 100 ° C., more preferably 0 to 70 ° C. when an unsaturated carboxylic acid, ester or amide is used as the component (B).
  • the component (A) and the component (B) are mixed, and under the conditions of 100 to 300 ° C., preferably 130 to 250 ° C., a Michael addition reaction and an amide group forming reaction by dehydration, dealcoholization and deamine are carried out. It will be carried out by.
  • the inside of the reaction apparatus in order to complete the reaction, can be subjected to a reduced pressure treatment at the final stage of the reaction, if necessary. It can also be diluted with a non-reactive solvent, if desired.
  • a catalyst such as phosphite esters can be added as a dehydrating agent and a dealcoholizing agent.
  • the Michael addition reaction and the amide are performed. It is carried out by performing a group formation reaction.
  • the inside of the reaction apparatus in order to complete the reaction, can be subjected to a reduced pressure treatment at the final stage of the reaction, if necessary. It can also be diluted with a non-reactive solvent, if desired. Further, tertiary amines such as pyridine, picoline, lutidine and trialkylamine can be added.
  • the epoxy which is a reaction product between the component (A) and the component (B).
  • the cured product layer formed by using the resin curing agent has high gas barrier properties and good adhesiveness.
  • the reaction molar ratio [(B) / (A)] of the component (B) to the component (A) is preferably in the range of 0.3 to 1.0.
  • the reaction molar ratio is 0.3 or more, a sufficient amount of amide groups are generated in the epoxy resin curing agent, and a high level of gas barrier property and adhesiveness are exhibited.
  • the reaction molar ratio is in the range of 1.0 or less, the amount of amino groups required for the reaction with the epoxy group in the epoxy resin is sufficient, the heat resistance is excellent, and the solubility in an organic solvent or water is sufficient. Also excellent.
  • the reaction molar ratio [(B) / (A)] of the component (B) to the component (A) is 0. More preferably, it is in the range of 6.6 to 1.0.
  • the amine-based curing agent may be a reaction product consisting of only the component (A) and the component (B), the component (A) and the component (B), and the components (C), (D) and the following. It may be a reaction product with at least one compound selected from the group consisting of (E) components.
  • R 3 is a hydrogen atom, an alkyl having 1 to 7 carbon atoms which may have a hydroxyl group). Represents a group or an aryl group having 6 to 12 carbon atoms.
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a hydroxyl group, and R 3 is preferably an alkyl group having 1 to 3 carbon atoms or phenyl. It is the basis.
  • Examples of the derivative of the monovalent carboxylic acid represented by R3 - COOH include esters, amides, acid anhydrides and acidified compounds of the carboxylic acid.
  • the ester of the carboxylic acid is preferably an alkyl ester, and the alkyl carbon number is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.
  • the component (C) include monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, and benzoic acid, and derivatives thereof.
  • the component (C) may be used alone or in combination of two or more.
  • the cyclic carbonate which is the component (D)
  • the cyclic carbonate is used as necessary from the viewpoint of reducing the reactivity between the epoxy resin curing agent and the epoxy resin and improving the workability, and is used with the component (A).
  • a cyclic carbonate having a 6-membered ring or less is preferable.
  • at least one selected from the group consisting of ethylene carbonate, propylene carbonate and glycerin carbonate is preferable from the viewpoint of gas barrier property.
  • the component (D) may be used alone or in combination of two or more.
  • the monoepoxy compound as the component (E) is a monoepoxy compound having 2 to 20 carbon atoms, and is necessary from the viewpoint of reducing the reactivity between the epoxy resin curing agent and the epoxy resin and improving workability. Used. From the viewpoint of gas barrier properties, it is preferably a monoepoxy compound having 2 to 10 carbon atoms, and more preferably a compound represented by the following formula (2).
  • R 4 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, or R 5 -O—CH 2-
  • R 5 represents a phenyl group or a benzyl group.
  • Examples of the monoepoxy compound represented by the formula (2) include ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, phenylglycidyl ether, and benzyl glycidyl ether.
  • the component (E) may be used alone or in combination of two or more.
  • One kind of compound may be used alone, or two or more kinds may be used in combination.
  • the amine-based curing agent may be a reaction product obtained by further reacting with other components as long as the effects of the present invention are not impaired.
  • other components referred to here include aromatic dicarboxylic acids or derivatives thereof.
  • the amount of the "other component" used is preferably 30% by mass or less, more preferably 10% by mass or less, and 5% by mass of the total amount of the reaction components constituting the amine-based curing agent. It is more preferably% or less.
  • the reaction product of the components (A) and (B) and at least one compound selected from the group consisting of the components (C), (D) and (E) is the above (C). It is obtained by reacting at least one compound selected from the group consisting of a component, a component (D) and a component (E) with the component (A) which is a polyamine compound in combination with the component (B).
  • the components (B) to (E) may be added in any order and reacted with the component (A), or the components (B) to (E) may be mixed and the component (A) may be mixed. It may be reacted with the component.
  • the reaction between the component (A) and the component (C) can be carried out under the same conditions as the reaction between the component (A) and the component (B).
  • the component (C) When the component (C) is used, the component (B) and the component (C) may be mixed and reacted with the component (A).
  • the component (A) and the component (B) are combined. May be reacted and then the component (C) may be reacted.
  • the component (D) and / or the component (E) is used, the component (A) and the component (B) are first reacted, and then the component (D) and / or the component (E) are used. It is preferable to react with the components.
  • the component (A) and the component (D) and / or the component (E) are mixed under the condition of 25 to 200 ° C.
  • the addition reaction is carried out under the conditions of 30 to 180 ° C., preferably 40 to 170 ° C.
  • catalysts such as sodium methoxide, sodium ethoxide, and potassium t-butoxide can be used.
  • the component (D) and / or the component (E) may be melted or diluted with a non-reactive solvent, if necessary.
  • the amine-based curing agent is a reaction product of at least one compound selected from the group consisting of the components (A) and (B) and the components (C), (D) and (E).
  • the reaction molar ratio [(B) / (A)] of the component (B) to the component (A) is in the range of 0.3 to 1.0 for the same reason as described above. Is preferable, and the range is more preferably in the range of 0.6 to 1.0.
  • the reaction molar ratio of the component (C), the component (D) and the component (E) to the component (A) [ ⁇ (C) + (D) + (E) ⁇ / (A)] is 0.
  • reaction molar ratio of the components (B) to (E) to the component (A) [ ⁇ (B) + (C) + (D) + (E) ⁇ / (A)] is preferably in the range of 0.35 to 2.5, and more preferably in the range of 0.35 to 2.0.
  • the amine-based curing agent (ii) is a reaction product of epichlorohydrin and at least one selected from the group consisting of methoxylylenediamine and paraxylylenediamine.
  • the amine-based curing agent (ii) preferably contains a compound represented by the following general formula (3) as a main component.
  • the term "main component” as used herein means a component having a content of 50% by mass or more when all the constituents in the amine-based curing agent (ii) are 100% by mass.
  • A is a 1,3-phenylene group or a 1,4-phenylene group.
  • N is a number of 1 to 12.
  • A is a 1,3-phenylene group.
  • 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) are determined by GC analysis and gel filtration chromatography (GPC) analysis. Can be obtained by.
  • the amine-based curing agent (ii) is obtained by subjecting epichlorohydrin and at least one selected from the group consisting of methoxylylenediamine and paraxylylenediamine to a ring-opening addition reaction and a condensation reaction by a conventional method. ..
  • the epoxy resin curing agent used in the present invention may contain a curing agent component other than the amine-based curing agent, but 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, still more preferably 80% by mass or more, still more preferably 80% by mass or more, from the viewpoint of obtaining high gas barrier properties. It is 90% by mass or more.
  • the upper limit is 100% by mass.
  • the epoxy resin curing agent used in the present invention may further contain a coupling agent from the viewpoint of improving adhesiveness.
  • the coupling agent include a silane coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent, and the like, and a silane coupling agent is preferable from the viewpoint of improving the adhesiveness to an inorganic substance.
  • the silane coupling agent include a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, a silane coupling agent having a (meth) acrylic group, and a mercapto group. Examples thereof include a silane coupling agent having a above.
  • the content of the coupling agent in the epoxy resin curing agent is preferably 0.1 to 10 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the curing agent component in the epoxy resin curing agent. ⁇ 8 parts by mass.
  • the compounding ratio of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition may be generally within the standard compounding range when the epoxy resin reactant is produced by the reaction between the epoxy resin and the epoxy resin curing agent.
  • 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 is 0. It is preferably in the range of 2 to 12.0.
  • 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, still more preferably 0. It is in the range of 6 to 8.0, more preferably more than 1.0 and 5.0 or less, still more preferably 1.1 to 3.5.
  • the epoxy resin composition of the present invention contains polyalkylene glycol.
  • polyalkylene glycol when polyalkylene glycol is used, even in an epoxy resin composition containing an unsaturated fatty acid amide having 14 to 24 carbon atoms, deterioration of gas barrier property and gloss is suppressed, and high gas barrier property and practically sufficient adhesiveness are obtained. Moreover, an epoxy resin composition capable of forming a cured coating film having a good appearance can be obtained.
  • polyalkylene glycol examples include homopolymers or copolymers of alkylene glycols having 2 to 8 carbon atoms.
  • the alkylene glycol may be either a linear alkylene glycol or a branched alkylene glycol.
  • homopolymers of alkylene glycols having 2 to 8 carbon atoms include polyethylene glycol (PEG), polypropylene glycol (PPG), poly (oxytrimethylene) glycol [polytrimethylene ether glycol], and poly (oxybutylene).
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • poly (oxytrimethylene) glycol polytrimethylene ether glycol
  • poly (oxybutylene) poly (oxybutylene).
  • Glycol poly (oxytetramethylene) glycol [polytetramethylene ether glycol: PTMG]
  • poly (oxypentamethylene) glycol poly (oxyhexamethylene) glycol
  • poly (oxyoctamethylene) glycol and the like can be mentioned.
  • copolymer of alkylene glycol having 2 to 8 carbon atoms examples include polyoxyethylene-polyoxypropylene glycol (PEG-PPG), polyoxyethylene-polyoxytrimethylene glycol, and polyoxyethylene-polyoxybutylene glycol.
  • Polyoxyethylene-Polyoxytetramethylene Glycol PEG-PTMG
  • Polyoxyethylene-Polyoxyhexamethylene Glycol Polyoxypropylene-Polyoxytrimethylene Glycol
  • Polyoxypropylene-Polyoxybutylene Glycol Polyoxypropylene-Poly Oxytetramethylene glycol (PPG-PTMG)
  • PPG-PTMG Polyoxytrimethylene-polyoxytetramethylene glycol
  • polyoxytetramethylene-polyoxyhexamethylene glycol polyoxyethylene-polyoxypropylene-polyoxybutylene glycol
  • polyoxyethylene-poly Examples thereof include oxypropylene-polyoxytetramethylene glycol.
  • the polyalkylene glycol one kind or two or more kinds can be used. From the viewpoint of improving the gas barrier property and the appearance of the cured coating film, the polyalkylene glycol is preferably a homopolymer or a copolymer of alkylene glycol having 2 to 6 carbon atoms, and is preferably an alkylene glycol having 2 to 4 carbon atoms.
  • Polyethylene glycol polypropylene glycol, poly (oxytrimethylene) glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, polyoxyethylene-polyoxypropylene glycol, At least one selected from the group consisting of polyoxyethylene-polyoxytrimethylene glycol, polyoxyethylene-polyoxytetramethylene glycol, polyoxypropylene-polyoxytetramethylene glycol, and polyoxytrimethylene-polyoxytetramethylene glycol.
  • polyethylene glycol is even more preferable, and at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, and poly (oxytetramethylene) glycol is even more preferable, from the viewpoint of improving gas barrier properties, from the viewpoint of improving the appearance of the cured coating film, and to inorganic substances. From the viewpoint of improving adhesiveness, polyethylene glycol is even more preferable.
  • the weight average molecular weight (Mw) of the polyalkylene glycol is preferably 150 to 10,000, more preferably 200 to 10,000, still more preferably 200, from the viewpoint of improving the gas barrier property and the appearance of the cured coating film. It is 5,000, more preferably 200 to 3,000, and even more preferably from the viewpoint of improving the gas barrier property, improving the appearance of the cured coating film, suppressing blocking, and improving the adhesiveness to inorganic substances. It is 200 to 2,000, more preferably 200 to 1,500, even more preferably 200 to 1,000, and even more preferably 200 to 500.
  • the content of polyalkylene glycol in the epoxy resin composition is 100 parts by mass in total of the epoxy resin and the non-volatile content in the epoxy resin curing agent from the viewpoint of improving the gas barrier property and the appearance of the cured coating film.
  • 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 parts.
  • the epoxy resin composition of the present invention preferably contains an unsaturated fatty acid amide having 14 to 24 carbon atoms (hereinafter, also simply referred to as “unsaturated fatty acid amide”).
  • unsaturated fatty acid amide has 14 to 24 carbon atoms, and is preferably 16 to 24, more preferably 18 to 22, from the viewpoint of imparting properties suitable for the coating composition and improving the adhesiveness to the inorganic substance. be.
  • the unsaturated fatty acid constituting the unsaturated fatty acid amide may be a fatty acid having at least one unsaturated bond and having 14 to 24 carbon atoms.
  • the number of unsaturated bonds in the unsaturated fatty acid is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.
  • Examples of unsaturated fatty acids constituting unsaturated fatty acid amides include monounsaturated ones such as myristoleic acid, sapienoic acid, palmitoleic acid, oleic acid, ellagic acid, baxenoic acid, gadrain acid, eicosenoic acid, erucic acid, and nervonic acid.
  • Fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, meadic acid, eikosatrienic acid; stearidonic acid, arachidonic acid, eikosa Tetra fatty acids such as tetraenoic acid and adrenic acid; and one or a combination of two or more of these can be used.
  • diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid
  • triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, meadic acid, eikosatrienic acid; stearidonic acid, arachidonic acid, eikosa Tetra fatty acids such as tetraenoic acid
  • At least selected from the group consisting of monounsaturated fatty acids and diunsaturated fatty acids having 14 to 24 carbon atoms from the viewpoint of imparting properties suitable for the coating composition and improving the adhesiveness to inorganic substances.
  • monounsaturated fatty acids having 14 to 24 carbon atoms are more preferable, monounsaturated fatty acids having 16 to 24 carbon atoms are more preferable, and monounsaturated fatty acids having 18 to 22 carbon atoms are more preferable.
  • the unsaturated fatty acid amide used in the present invention is preferably palmitreic acid amide, oleic acid amide, eicosenoic acid amide, and erucic acid from the viewpoint of imparting properties suitable for the coating composition and improving the adhesiveness to inorganic substances. At least one selected from the group consisting of amides, more preferably at least one selected from the group consisting of oleic acid amides and erucic acid amides, and even more preferably erucic acid amides from the viewpoint of blocking inhibitory effect. ..
  • the epoxy resin composition has erucic acid amide solubility in an epoxy resin composition containing an amine-based curing agent, but is not too soluble in the epoxy resin composition as compared with oleic acid amide and the like. Alternatively, it bleeds out to the surface layer of the cured product and acts as a lubricant. Therefore, it is presumed that the epoxy resin composition containing the erucic acid amide has an improved drying rate and the above-mentioned blocking suppressing effect can be obtained.
  • the content of unsaturated fatty acid amide in the epoxy resin composition is preferably 0.1 with respect to 100 parts by mass of the total amount of the epoxy resin and the non-volatile content in the epoxy resin curing agent. ⁇ 20.0 parts by mass, more preferably 0.2 to 15.0 parts by mass, still more preferably 0.5 to 15.0 parts by mass, still more preferably 1.0 to 15.0 parts by mass, still more preferable. Is 3.0 to 10.0 parts by mass.
  • the content of the unsaturated fatty acid amide is 0.1 part by mass or more with respect to 100 parts by mass of the total amount of the epoxy resin in the epoxy resin composition and the non-volatile content in the epoxy resin curing agent, the adhesiveness to the inorganic substance is improved. It is preferable from the viewpoint of obtaining the blocking suppressing effect. Further, if it is 20.0 parts by mass or less, high gas barrier property and transparency can be maintained, and elution of the unsaturated fatty acid amide can be suppressed.
  • the epoxy resin composition of the present invention can further contain non-spherical inorganic particles.
  • non-spherical inorganic particles By containing non-spherical inorganic particles in the epoxy resin composition of the present invention, a blocking suppressing effect can be obtained when used for forming a cured product layer of a gas barrier laminated body described later, and gas barrier properties and bending resistance are obtained. Sex can also be improved.
  • the shape of the non-spherical inorganic particles may be a three-dimensional shape other than a spherical shape (substantially a perfect circular sphere), and examples thereof include a plate shape, a scale shape, a columnar shape, a chain shape, and a fibrous shape.
  • a plurality of plate-shaped and scaly-shaped inorganic particles may be laminated to form a layer.
  • plate-shaped, scaly, columnar, or chain-shaped inorganic particles are preferable, and plate-shaped, scaly, or columnar inorganic particles are more preferable, and plate-shaped.
  • scaly inorganic particles are more preferable.
  • Examples of the inorganic substance constituting the non-spherical inorganic particles include silica, alumina, mica, talc, aluminum, bentonite, smectite and the like. Among these, at least one selected from the group consisting of silica, alumina, and mica is preferable, and at least one selected from the group consisting of silica and alumina is more preferable from the viewpoint of improving gas barrier property and bending resistance. Silica is even more preferred.
  • the non-spherical inorganic particles may be surface-treated, if necessary, for the purpose of enhancing the dispersibility in the epoxy resin composition and improving the transparency of the cured product.
  • the non-spherical inorganic particles are preferably coated with an organic material, and when the epoxy resin composition is used for forming the cured product layer of the gas barrier laminate, the gas barrier property, bending resistance and transparency are improved.
  • the epoxy resin composition is used for forming the cured product layer of the gas barrier laminate, the gas barrier property, bending resistance and transparency are improved.
  • at least one selected from the group consisting of silica and alumina coated with an organic material is more preferable.
  • silica coated with an organic material is more preferable, and from the viewpoint of transparency, alumina coated with an organic material is further preferable.
  • the average particle size of the non-spherical inorganic particles is preferably 1 to 2,000 nm, more preferably 1 to 1,500 nm, still more preferably 1 to 1,000 nm, still more preferably 1 to 800 nm, still more preferably 1 to 1 to 1. It is in the range of 500 nm, more preferably 5 to 300 nm, even more preferably 5 to 200 nm, even more preferably 5 to 100 nm, and even more preferably 8 to 70 nm.
  • the average particle size is 1 nm or more, the inorganic particles can be easily prepared, and when the average particle size is 2,000 nm or less, the epoxy resin composition has a gas barrier property when used for forming a cured product layer of the gas barrier property. Both bending resistance and transparency are improved.
  • the average particle size is the average particle size of the primary particles.
  • the aspect ratio of the non-spherical inorganic particles is preferably 2 to 700, more preferably 3 to 500. When the aspect ratio is 2 or more, good gas barrier properties are likely to be exhibited.
  • the average particle size and aspect ratio of the non-spherical inorganic particles are observed using, for example, a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and are obtained from the average of three or more measured values.
  • the average particle size and aspect ratio of the non-spherical inorganic particles present in the cured product layer for example, after embedding a gas barrier laminate described later with an epoxy resin, ions in the cross section of the laminate are used using an ion milling device. It can be obtained by performing milling to prepare a cross-section observation sample, and observing and measuring the cross-section of the cured product layer portion of the obtained sample by the same method as described above.
  • the average particle size of the non-spherical inorganic particles is less than 100 nm and it is difficult to measure the average particle size by the above method, the average particle size can be measured by, for example, the BET method.
  • the content of the non-spherical inorganic particles in the epoxy resin composition is preferably 0.5 to 10.0 with respect to 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent. It is by mass, more preferably 1.0 to 8.0 parts by mass, still more preferably 1.5 to 7.5 parts by mass, and even more preferably 3.0 to 7.0 parts by mass.
  • the epoxy resin composition is used as a gas barrier laminate. When used for forming a cured product layer, the gas barrier property and the bending resistance improving effect are improved. Further, when the content is 10.0 parts by mass or less, the transparency is also good.
  • the epoxy resin composition may contain a thermosetting resin, a wetting agent, a tackifier, a defoaming agent, a curing accelerator, a rust preventive additive, a pigment, and oxygen scavenger, if necessary, as long as the effects of the present invention are not impaired. Additives such as agents may be added.
  • 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 parts by mass, based on 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent. It is 0.0 parts by mass.
  • the total content of the epoxy resin, the epoxy resin curing agent, and the polyalkylene glycol in the solid content of the epoxy resin composition is preferably 60% by mass or more, more preferably 70% by mass.
  • the above is more 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 in the epoxy resin composition excluding water and the organic solvent.
  • the epoxy resin composition may contain an organic solvent.
  • the organic solvent is preferably a non-reactive solvent. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propanol, 2-butoxyethanol, 1-methoxy-.
  • Use one or more protonic polar solvents such as 2-propanol, 1-ethoxy-2-propanol, 1-propanol, 1-propanol, ethyl acetate, butyl acetate, methylisobutylketone, toluene and the like. Can be done.
  • At least one selected from the group consisting of methanol, ethanol and ethyl acetate is preferable, and at least one selected from the group consisting of ethanol and ethyl acetate is preferable. More preferred.
  • the epoxy resin composition includes, for example, an epoxy resin, an epoxy resin curing agent, a polyalkylene glycol, an unsaturated fatty acid amide having 14 to 24 carbon atoms used as necessary, a dispersion of non-spherical inorganic particles, and other additives. It can be prepared by blending a predetermined amount of each solvent and then stirring and mixing using a known method and apparatus.
  • the cured product of the epoxy resin composition of the present invention has excellent gas barrier properties, and also has good appearance and adhesiveness to inorganic substances.
  • the cured product layer made of the cured product functions as a gas barrier layer having excellent gas barrier properties. Therefore, the epoxy resin composition of the present invention can be used for a gas barrier coating composition, a gas barrier adhesive, and the like, in addition to the gas barrier laminate described later.
  • the method of curing the epoxy resin composition of the present invention to form the cured product is not particularly limited, and a known method can be used. One embodiment will be described in the method for manufacturing a gas barrier laminate.
  • the gas barrier laminate of the present invention (hereinafter, also simply referred to as “laminate”) has a base material and a cured product layer of the epoxy resin composition (hereinafter, also simply referred to as “cured product layer”). It is a feature.
  • the gas-barrier laminate of the present invention has a high gas barrier property, a good appearance, and a laminate having a high interlayer adhesiveness between the base material and the cured product layer.
  • the materials constituting the gas barrier laminate of the present invention will be described.
  • Base material As the base material constituting the gas barrier laminate of the present invention, either an inorganic base material or an organic base material can be used.
  • the inorganic base material include metal foils such as aluminum foils.
  • a transparent plastic film is preferable.
  • the transparent plastic film include polyolefin films such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and polypropylene; polyester films such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; nylon 6, nylon.
  • Polyamide-based film such as polymethoxylen adipamide (N-MXD6); polyimide-based film; biodegradable film such as polylactic acid; polyacrylonitrile-based film; poly (meth) acrylic-based film; polystyrene-based film Polycarbonate-based film; ethylene-vinyl acetate copolymer saponified (EVOH) -based film, polyvinyl alcohol-based film and the like can be mentioned.
  • N-MXD6 polymethoxylen adipamide
  • biodegradable film such as polylactic acid; polyacrylonitrile-based film; poly (meth) acrylic-based film; polystyrene-based film
  • Polycarbonate-based film ethylene-vinyl acetate copolymer saponified (EVOH) -based film, polyvinyl alcohol-based film and the like can be mentioned.
  • EVOH ethylene-vinyl acetate copolymer saponified
  • the organic substrate is preferably a film selected from the group consisting of a polyolefin-based film, a polyester-based film, a polyamide-based film, and a polyimide-based film, and a polyolefin-based film and a film.
  • a film selected from the group consisting of polyester films is more preferable, and a polypropylene film or a polyethylene terephthalate (PET) film is further preferable.
  • PET polyethylene terephthalate
  • the film may be stretched in a uniaxial or biaxial direction.
  • the thickness of the base material can be appropriately selected depending on the intended use, and is not particularly limited, but is preferably 5 to 300 ⁇ m, more preferably 5 to 100 ⁇ m, still more preferably 5 to 50 ⁇ m, and more, from the viewpoint of gas barrier properties and strength. More preferably, it is 5 to 40 ⁇ m.
  • the base material is an organic base material
  • the thickness of the organic base material is more preferably 8 to 50 ⁇ m, still more preferably 10 to 40 ⁇ m from the viewpoint of gas barrier property and strength.
  • the cured product layer in the gas barrier laminate of the present invention is made of a cured product of the epoxy resin composition.
  • the curing method of the epoxy resin composition is not particularly limited, and it is carried out by a known method at a concentration and temperature of the epoxy resin composition sufficient to obtain the cured product.
  • the curing temperature can be selected, for example, in the range of 10 to 140 ° C.
  • the thickness of the cured product layer is preferably 0.05 ⁇ m or more, more preferably 0.08 ⁇ m or more, still more preferably 0.1 ⁇ m or more, from the viewpoint of gas barrier properties and bending resistance. Further, from the viewpoint of adhesiveness to inorganic substances and transparency, it is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 5.0 ⁇ m or less, still more preferably 2.0 ⁇ m or less, still more preferably 1.0 ⁇ m. Below, it is even more preferably 0.5 ⁇ m or less, and even more preferably 0.4 ⁇ m or less. The above thickness is the thickness per layer of the cured product layer.
  • the gas barrier laminate of the present invention may have a base material and at least one cured product layer. From the viewpoint of obtaining high gas barrier properties, it is preferable that the laminate of the present invention has at least one layer composed of an inorganic substance. Specifically, it is preferable that the layer made of an inorganic substance is the inorganic base material or an inorganic thin film layer.
  • the inorganic thin film layer is provided to impart gas barrier properties to the gas barrier laminated body, and can exhibit high gas barrier properties even if the thickness is thin.
  • the inorganic thin film layer include those made of a metal foil and those formed by a vapor deposition method, but from the viewpoint of obtaining high transparency, an inorganic thin film layer formed by a vapor deposition method is preferable.
  • the inorganic substance constituting the inorganic thin film layer is not particularly limited as long as it is an inorganic substance capable of forming a gas barrier thin film on the base material or the cured product layer, and is silicon, aluminum, magnesium, calcium, zinc, tin, nickel.
  • at least one selected from the group consisting of silicon oxide (silica), aluminum, and aluminum oxide (alumina) is preferable from the viewpoint of gas barrier properties.
  • the above-mentioned inorganic substances may be used alone or in combination of two or more.
  • the thickness of the inorganic thin film layer is preferably 5 nm or more from the viewpoint of obtaining high gas barrier properties. Further, from the viewpoint of transparency and bending resistance, it is preferably 100 nm or less, more preferably 50 nm or less. The above thickness is the thickness per layer of the inorganic thin film layer.
  • the method for forming the inorganic thin film layer is not particularly limited.
  • the vapor deposition method includes a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method or a thermochemical vapor deposition method.
  • a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method
  • a plasma chemical vapor deposition method or a thermochemical vapor deposition method examples thereof include known vapor deposition methods such as a chemical vapor deposition method such as a method and a photochemical vapor deposition method.
  • a metal foil such as an aluminum foil can be bonded to the base material to form an inorganic thin film layer.
  • the inorganic thin film layer can be formed on, for example, an organic base material or a cured product layer.
  • the gas barrier laminate of the present invention may further have one layer or two or more thermoplastic resin layers depending on the intended use.
  • the thermoplastic resin layer it is preferable to use a thermoplastic resin film, and the same transparent plastic film as that exemplified in the organic substrate can be used.
  • the transparent plastic films at least one selected from the group consisting of polyolefin-based films and polyamide-based films is preferable, and polypropylene films and nylon 6 films are selected from the viewpoint of transparency, heat resistance, and suitability for packaging foods and the like. At least one selected from the group is more preferable.
  • the surface of the thermoplastic resin film may be subjected to surface treatment such as flame treatment or corona discharge treatment.
  • thermoplastic resin film a film containing an ultraviolet absorber, a colorant, or the like, or a film having a primer layer, an ink layer, a surface protection layer, a vapor deposition layer, or the like on the surface can also be used.
  • the thickness of the thermoplastic resin layer is preferably 10 to 300 ⁇ m, more preferably 10 to 100 ⁇ m. The above thickness is the thickness per layer of the thermoplastic resin layer.
  • the gas barrier laminate of the present invention may further have an adhesive layer for laminating the thermoplastic resin layer.
  • the adhesive constituting the adhesive layer 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, but is preferably 0.1 to 30 ⁇ m, more preferably 1 to 20 ⁇ m, and even more preferably 2 to 20 ⁇ m from the viewpoint of achieving both adhesiveness and transparency. The above thickness is the thickness per layer of the adhesive layer.
  • the gas barrier laminate of the present invention may have a structure having the base material and at least one cured product layer.
  • the gas barrier laminate of the present invention preferably has a layer composed of an inorganic substance, and from the viewpoint of economy, the cured product layer is preferably one or two layers. Is preferably configured to have only one layer. Further, it is preferable that the layer made of an inorganic substance and the cured product layer are adjacent to each other.
  • the following is exemplified as a layer structure of a gas barrier laminate having a base material and a layer having one or two cured products and having a layer composed of an inorganic substance.
  • a structure having a base material and a cured product layer, and the base material being an inorganic base material (2) A structure having a base material, an inorganic thin film layer, and a cured product layer in order (3) A base material and a cured product layer (4) A structure having a base material, a cured product layer, an inorganic thin film layer, and a cured product layer in order (4)
  • the base material in the above (2), (3) and (4) is an organic base material. Is preferable. Further, it is preferable that the layer made of an inorganic substance and the cured product layer are adjacent to each other, and from the viewpoint of gas barrier properties, any of the above (1), (2) or (4) is preferable. , The configuration of (1) or (2) above is more preferable.
  • the epoxy resin composition of the present invention can form a cured coating film having a good appearance, and particularly when it contains the unsaturated fatty acid amide, it has improved drying speed, less blocking, and properties suitable for a coating composition. .. From the viewpoint of the effectiveness of this effect, the configuration of (2) or (4) above is more preferable, and the configuration of (2) is further preferable.
  • the gas barrier laminated body of the present invention has any of the above-mentioned layer configurations (1) to (4), and may further have one or two or more layers of the above-mentioned thermoplastic resin layer. However, from the viewpoint of the effectiveness of the above effects of the epoxy resin composition of the present invention, it is more preferable that the epoxy resin composition does not have a thermoplastic resin layer other than the base material.
  • Examples of the layer structure of the gas barrier laminate include the structures shown in FIGS. 1 to 9.
  • a laminated body having no thermoplastic resin layer other than the base material is referred to as “laminated body (I)”
  • a laminated body having a total number of laminated base materials and thermoplastic resin layers of 2 is “laminated”.
  • the body (II) "and 3 are called” laminated body (III) ". From the viewpoint of the effectiveness of the effect of the present invention, the laminated body (I) is more preferable.
  • FIG. 1 and 2 are schematic cross-sectional views showing an embodiment of the gas barrier laminate (I) of the present invention.
  • the gas barrier laminate 100 in FIG. 1 has a structure in which an inorganic thin film layer 2 and a cured product layer 3 are sequentially provided on a base material 1.
  • the inorganic thin film layer 2 and the cured product layer 3 are adjacent to each other.
  • the gas barrier laminate 100a in FIG. 2 has a structure in which a cured product layer 3 and an inorganic thin film layer 2 are sequentially provided on a base material 1.
  • FIGS. 3 to 6 are schematic cross-sectional views showing an embodiment of the gas barrier laminate (II) of the present invention.
  • the gas barrier laminates of FIGS. 3 to 6 have one base material and one thermoplastic resin layer (two layers in total), and the thermoplastic resin layer may be directly laminated or via an adhesive layer. May be laminated.
  • the gas barrier laminate 200 in FIG. 3 has a structure in which a thermoplastic resin layer 4 is directly laminated without an adhesive layer, and is a base material 1, an inorganic thin film layer 2, a cured product layer 3, and a thermoplastic resin layer 4. Is a structure in which is laminated in this order.
  • the gas barrier laminate 300 in FIG. 4 has a configuration in which a base material 1, an inorganic thin film layer 2, a cured product layer 3, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order.
  • the gas barrier laminated body 300a in FIG. 5 has a structure in which a base material 1, a cured product layer 3, an inorganic thin film layer 2, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order.
  • the gas barrier laminated body 300b in FIG. 6 has a structure in which a base material 1, a cured product layer 3, an inorganic thin film layer 2, a cured product layer 3, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order.
  • FIGS. 7 to 9 are schematic cross-sectional views showing an embodiment of the gas barrier laminate (III) of the present invention.
  • the gas barrier laminate of FIGS. 7 and 8 has one base material and two thermoplastic resin layers (three layers in total), and the gas barrier laminate of FIG. 9 has two base materials and is thermoplastic. It has one resin layer (three layers in total).
  • the base material 1, the inorganic thin film layer 2, the cured product layer 3, the adhesive layer 5, the thermoplastic resin layer 4, the adhesive layer 5, and the thermoplastic resin layer 4 are laminated in this order. It is a configuration.
  • the gas barrier laminate 400c of FIG. 9 has a configuration in which a base material 1, an adhesive layer 5, a base material 1c, a cured product layer 3, an adhesive layer 5, and a thermoplastic resin layer 4 are laminated in this order.
  • At least one of the base materials is preferably an inorganic base material, and examples thereof include those in which the base material 1c is an inorganic base material.
  • the thermoplastic resin layers 4 constituting the gas barrier laminate 400 or 400a may all be the same resin layer or may be different resin layers from each other.
  • the adhesive layer 5 may be a layer made of the same adhesive or a layer made of different adhesives.
  • the gas barrier laminate of the present invention is not limited to the layer structure shown in FIGS. 1 to 9. Further, the laminate of the present invention may be further laminated with an arbitrary layer such as a primer layer, an ink layer such as a printing layer, an adhesive layer, a surface protection layer, and a vapor deposition layer.
  • the method for producing the gas barrier laminate of the present invention is not particularly limited, and a known method can be used.
  • a method for producing the gas barrier laminate 100 having the configuration shown in FIG. 1 an inorganic thin film layer is formed on one side of a base material, and the epoxy resin composition for forming a cured product layer is formed on the surface on the inorganic thin film layer side.
  • examples thereof include a method of applying to a desired thickness and then curing the epoxy resin composition to form a cured product layer.
  • a cured product layer may be formed on the surface of the inorganic thin film layer by using a film in which the inorganic thin film layer is previously formed on the transparent plastic film.
  • the epoxy resin composition is applied to one side of a base material, and then the epoxy resin composition is cured to form a cured product layer, and then the cured product is formed.
  • Examples thereof include a method of forming an inorganic thin film layer on the layer.
  • Examples of the coating method for applying the epoxy resin composition include bar coat, Mayer bar coat, air knife coat, gravure coat, reverse gravure coat, micro gravure coat, micro reverse gravure coat, die coat, slot die coat, and vacuum die coat. Dip coat, spin coat, roll coat, spray coat, brush coat and the like can be mentioned.
  • a bar coat, a roll coat or a spray coat is preferable, and industrially, a gravure coat, a reverse gravure coat, a micro gravure coat, or a micro reverse gravure coat is preferable.
  • a step (drying step) of volatilizing the solvent is performed if necessary.
  • the conditions in the drying step can be appropriately selected, and for example, the drying step can be performed under the conditions of a drying temperature of 40 to 180 ° C. and a drying time of 5 to 180 seconds.
  • the drying rate is improved, so that the drying temperature can be lowered.
  • the drying temperature is preferably 40 to 120 ° C, more preferably 40 to 100 ° C, still more preferably 50 to 90 ° C.
  • 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 80 ° C.
  • 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.
  • an inorganic thin film layer is formed on a base material, the above-mentioned epoxy resin composition is applied to the inorganic thin film layer surface, and then heat is immediately applied to the coated surface.
  • examples thereof include a method in which the thermoplastic resin films constituting the plastic resin layer are bonded together by a nip roll or the like, and then the epoxy resin composition is cured by the above-mentioned method.
  • the epoxy resin composition constituting the cured product layer serves as an adhesive layer for adhering the inorganic thin film layer in the gas barrier laminate 200 and the thermoplastic resin film.
  • an adhesive constituting the adhesive layer is applied to the cured product layer surface of the gas barrier laminate 100 having the configuration shown in FIG. 1 or one surface of the thermoplastic resin film. Then, there is a method of laminating both.
  • the gas barrier laminate 300a having the configuration shown in FIG. 5 can be manufactured by the same method using the gas barrier laminate 100a having the configuration shown in FIG.
  • a method for manufacturing the gas barrier laminate 300b having the configuration shown in FIG. 6 a cured product layer is formed on the inorganic thin film layer surface of the gas barrier laminate 100a having the configuration shown in FIG. 2, and the cured product layer surface or the thermoplastic resin film is formed. Examples thereof include a method in which an adhesive constituting an adhesive layer is applied to one side, and then the two are laminated.
  • the gas barrier laminated body 400 having the configuration shown in FIG. 7 is manufactured by repeating the steps of forming the gas barrier laminated body 300 having the configuration shown in FIG. 4, applying an adhesive, attaching a thermoplastic resin film, and laminating. can.
  • the gas barrier laminate 400a having the configuration shown in FIG. 8 can be manufactured by the same method using the gas barrier laminate 300a having the configuration shown in FIG. In the gas barrier laminate 400c having the configuration of FIG.
  • the base material 1, the adhesive layer 5, and the base material 1c are laminated in this order, and then a cured product layer is formed on the surface of the base material 1c, and then the cured product layer surface,
  • a method of applying an adhesive constituting an adhesive layer to one side of a thermoplastic resin film and then laminating both thereof can be mentioned.
  • the gas barrier laminate of the present invention has excellent gas barrier properties.
  • the oxygen permeability of the gas barrier laminate (I) at 23 ° C. and 60% relative humidity varies depending on the barrier property of the substrate used, but is preferably 10 cc / (m 2 ⁇ day ⁇ atm) or less. It is preferably 2 cc / (m 2 ⁇ day ⁇ atm) or less, more preferably 1 cc / (m 2 ⁇ day ⁇ atm) or less.
  • the oxygen permeability and the water vapor permeability of the gas barrier laminate are specifically determined by the method described in Examples.
  • the gas barrier laminate of the present invention has a good appearance by having the cured product layer. Specifically, the epoxy resin composition of the present invention is less likely to cause uneven coating when the cured product layer is formed, and the surface of the cured product layer is highly glossy. The appearance (presence or absence of coating unevenness and gloss) of the gas barrier laminate can be specifically evaluated by the method described in Examples.
  • the packaging material of the present invention contains the gas barrier laminate.
  • the gas barrier laminate of the present invention has excellent gas barrier properties and bending resistance, and has a good appearance, and is therefore suitable for use as a packaging material for protecting foods, pharmaceuticals, cosmetics, precision electronic parts, and the like.
  • the packaging material of the present invention may be one in which the gas barrier laminate is used as it is as a packaging material, or another layer or a film may be further laminated.
  • the form of the packaging material can be appropriately selected depending on the article to be stored and stored, and examples thereof include a packaging film; a packaging container such as a packaging bag and a bottle; and a lid material and a sealing material for the packaging container. ..
  • the capacity of the packaging material is not particularly limited, and can be appropriately selected depending on the articles to be stored and stored.
  • ⁇ Thickness of cured product layer> The thickness of the cured product layer was measured using a multilayer film thickness measuring device (“DC-8200” manufactured by Gunze Corporation).
  • the reflectance of the surface of the cured product layer of the gas barrier laminate (I) formed in each example was measured according to JIS K5600-4-7: 1999. Incident light when light is incident on the surface of the cured product layer of the gas barrier laminate (I) at a scan mode and an incident angle of 60 ° using a gloss meter (“Elcometer 480” manufactured by elcometer Co., Ltd.). The ratio of the intensity of the reflected light to the light (reflectance;%) was measured. The higher the reflectance, the higher the gloss on the surface of the cured product layer. For the aluminum-deposited PET and the aluminum-deposited OPP of the reference example, the reflectance of the aluminum-deposited surface was measured.
  • the urethane adhesive was applied to the aluminum-deposited surface, and in the gas barrier laminates obtained in each example, the urethane adhesive was applied to the surface on the cured product layer side. No. 12 was applied and dried at 80 ° C. for 10 seconds to form an adhesive layer (thickness after drying: about 3 ⁇ m).
  • the urethane adhesive was prepared by adding 0.8 g of the curing agent "CAT-RT37” and 38.7 g of the solvent ethyl acetate to 17 g of the main agent "TM-569" manufactured by Toyo Morton Co., Ltd. and stirring well. I used the one.
  • a polypropylene film having a thickness of 50 ⁇ m (“P1146” manufactured by Toyobo Co., Ltd.) was bonded onto this with a nip roll and heated at 40 ° C. for 2 days to obtain a laminate for a peel strength test.
  • a T-type peeling test was performed at a peeling rate of 300 mm / min according to the method specified in JIS K6854-3: 1999, and the peeling strength (g / 15 mm) was measured. If the peel strength is 100 g / 15 mm or more, it is considered as acceptable.
  • Production Example 2 (Preparation of Epoxy Resin Hardener Solution B) A solution was prepared in the same manner as in Production Example 1 except that erucic acid amide was not added in Production Example 1 to obtain an epoxy resin curing agent solution B.
  • Example A (Preparation of Epoxy Resin Composition) To 3.75 g of the epoxy resin curing agent solution A obtained in Production Example 1, 29.0 g of ethanol as a diluting solvent was added and stirred well.
  • 0.10 g (the number of active amine hydrogens in the epoxy resin curing agent) 0.10 g (“TETRAD-X” manufactured by Mitsubishi Gas Chemicals Co., Ltd.) having a glycidylamino group derived from metaxylylene diamine as an epoxy resin /
  • the number of epoxy groups in the epoxy resin 3.0) and 0.007 g of polyethylene glycol (“PEG1000” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Mw 1,000) were added and stirred to prepare an epoxy resin composition. ..
  • the total amount of the epoxy resin in the epoxy resin composition and the non-volatile content in the epoxy resin curing agent solution A is 100 parts by mass, the amount of polyethylene glycol is 1.0 part by mass, and the amount of erucic acid amide is 5. It is 0.0 parts by mass.
  • Example B In Example A, the same method as in Example A was used except that the epoxy resin curing agent solution B obtained in Production Example 2 was used instead of the epoxy resin curing agent solution A obtained in Production Example 1. An epoxy resin composition was prepared.
  • Example C Epoxy resin in the same manner as in Example A, except that polytetramethylene ether glycol (PTMG, manufactured by Mitsubishi Chemical Corporation, Mw1,000) was used in place of polyethylene glycol "PEG1000" in Example A.
  • PTMG polytetramethylene ether glycol
  • Mw1,000 polytetramethylene ether glycol
  • Example D Epoxy resin composition in the same manner as in Example A, except that polyethylene glycol "PEG200” (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Mw200) was used in place of polyethylene glycol "PEG1000" in Example A. The thing was prepared.
  • polyethylene glycol "PEG200” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Mw200
  • Example E the epoxy resin composition was prepared by the same method as in Example A except that the blending amount of polyethylene glycol was changed to 0.014 g.
  • Example F the epoxy resin composition was prepared by the same method as in Example A except that the blending amount of polyethylene glycol was changed to 0.021 g.
  • Comparative Example A An epoxy resin composition was prepared in the same manner as in Example A except that polyethylene glycol was not blended in Example A.
  • Comparative Example B Epoxy resin composition in the same manner as in Example A, except that dipropylene glycol monomethyl ether (DPGME, manufactured by Tokyo Chemical Industry Co., Ltd., Mw148) was used in place of polyethylene glycol "PEG1000" in Example A. The thing was prepared.
  • DPGME dipropylene glycol monomethyl ether
  • the composition of the epoxy resin composition is shown in Table 1.
  • the blending amounts in Table 1 are the blending amounts (parts by mass) as effective components.
  • Example 1 (Preparation and evaluation of gas barrier laminate (I))
  • the epoxy resin composition obtained in Example A was applied to an aluminum-deposited surface of an aluminum-deposited PET (“MLPET” manufactured by Mitsui Chemicals Tohcello Corporation, thickness: 12 ⁇ m) in which aluminum was vapor-deposited on one side of the PET. 3 was applied.
  • the epoxy resin composition was heated in a drying oven at 80 ° C. for 30 seconds to dry (thickness after drying: 0.1 ⁇ m), and further aged at 40 ° C. for 2 days to obtain the gas barrier laminate having the configuration shown in FIG. I) was prepared.
  • Various evaluations were carried out by the above method using the obtained gas barrier laminate. The results are shown in Table 2.
  • Example 7 Except for the fact that in Example 1, the base material was changed to an aluminum-deposited OPP (“MLOP102” manufactured by Mitsui Chemicals Tohcello Corporation, thickness: 25 ⁇ m) in which aluminum was vapor-deposited on one side of biaxially stretched polypropylene (OPP).
  • OPP aluminum-deposited OPP
  • a gas barrier laminate was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Example 8 In Example 7, the epoxy resin composition used is changed to the epoxy resin composition shown in Table 2, and the epoxy resin composition is applied to the aluminum vapor-deposited OPP, and then heated and dried in a drying furnace at 80 ° C. for 60 seconds. A gas barrier laminated body was prepared and evaluated by the same method as in Example 7 except that it was allowed to be prepared. The results are shown in Table 2.
  • Example 9 Comparative Examples 3-4 In Example 7, a gas barrier laminate was prepared and evaluated in the same manner as in Example 7 except that the epoxy resin composition used was changed to the epoxy resin composition shown in Table 2. The results are shown in Table 2.
  • Table 2 shows the evaluation results of aluminum-deposited PET alone as "Reference Example 1". Further, as “Reference Example 2", the evaluation result of the aluminum-deposited OPP alone is shown.
  • the gas barrier laminate obtained by using the epoxy resin composition of this example did not show uneven coating of the epoxy resin composition, and the cured product layer was more than the gas barrier laminate of Comparative Example. Since the surface has a high reflectance, the gloss is improved, and it can be seen that the appearance is good. Further, the gas barrier laminate of this example has a good barrier property of oxygen and water vapor. Furthermore, the peel strength is also at the acceptable level.
  • Example 10 (Preparation and evaluation of gas barrier laminate (II))
  • the epoxy resin composition obtained in Example B is an aluminum-deposited OPP (“MLOP102” manufactured by Mitsui Chemicals Tosero Co., Ltd., thickness: 25 ⁇ m) in which aluminum is vapor-deposited on one side of biaxially stretched polypropylene (OPP). Bar coater No. on the surface. 8 was applied.
  • the epoxy resin composition was heated at 80 ° C. for 30 seconds to dry (thickness after drying: about 3 ⁇ m).
  • a polypropylene film having a thickness of 50 ⁇ m (“P1146” manufactured by Toyobo Co., Ltd.) was immediately bonded onto this with a nip roll and aged at 40 ° C.
  • gas barrier laminate (II) having the configuration shown in FIG. rice field.
  • oxygen permeability, water vapor permeability, and peel strength were measured by the above method.
  • peel strength a T-type peeling test was performed at a peeling rate of 300 mm / min using the gas barrier laminate (II) according to the method specified in JIS K6854-3: 1999, and the peel strength (g / 15 mm). ) was measured. The results are shown in Table 3.
  • Example 10 instead of the epoxy resin composition obtained in Example B, a urethane adhesive was applied to the aluminum-deposited surface of the aluminum-deposited OPP. No. 12 was applied and dried at 80 ° C. for 10 seconds to form an adhesive layer (thickness after drying: about 3 ⁇ m).
  • the urethane adhesive was prepared by adding 0.8 g of the curing agent "CAT-RT37" and 38.7 g of the solvent ethyl acetate to 17 g of the main agent "TM-569" manufactured by Toyo Morton Co., Ltd. and stirring well. I used the one.
  • the epoxy resin composition of the present invention exhibits high gas barrier properties even when used for forming an adhesive layer of a laminated film. Furthermore, the peel strength is also at the acceptable level.
  • Example 11 (Preparation and evaluation of gas barrier laminate (I))
  • the epoxy resin composition obtained in Example A was applied to a biaxially stretched polypropylene film (“FOR” manufactured by Futamura Chemical Co., Ltd., thickness: 20 ⁇ m) on one side of a bar coater No. 3 was applied.
  • the epoxy resin composition was heated in a drying oven at 80 ° C. for 30 seconds to dry (thickness after drying: 0.1 ⁇ m), and further aged at 40 ° C. for 2 days to form a cured product layer.
  • an aluminum-deposited layer having a thickness of 40 nm was formed on the surface of the cured product layer by a vacuum-deposited method to prepare a gas-barrier laminated body (I) having the configuration shown in FIG.
  • the oxygen permeability and the peel strength were measured by the above method. The results are shown in Table 4.
  • Example 11 the epoxy resin composition obtained in Example A was not used, and an aluminum vapor deposition layer having a thickness of 40 nm was formed on one side of a biaxially stretched polypropylene film having a thickness of 20 ⁇ m by a vacuum vapor deposition method to form a vapor deposition film.
  • the oxygen permeability and the peel strength were measured by the above method. The results are shown in Table 4.
  • Example 12 The epoxy resin composition obtained in Example A was applied to a biaxially stretched polypropylene film (“FOR” manufactured by Futamura Chemical Co., Ltd., thickness: 20 ⁇ m) on one side of a bar coater No. 3 was applied.
  • the epoxy resin composition was heated in a drying oven at 80 ° C. for 30 seconds to dry (thickness after drying: 0.1 ⁇ m), and further aged at 40 ° C. for 2 days to form a cured product layer.
  • an alumina-deposited layer having a thickness of 20 nm was formed on the surface of the cured product layer by a vacuum vapor deposition method to prepare a gas barrier laminated body (I) having the configuration shown in FIG.
  • the oxygen permeability and the peel strength were measured by the above method.
  • the results are shown in Table 4.
  • 1.05 g of the curing agent "CAT-RT85” and 25 g of the solvent ethyl acetate were added to 15 g of the main agent "AD-502" manufactured by Toyo Morton Co., Ltd. as the urethane adhesive.
  • the one prepared by stirring well was used.
  • Example 12 the epoxy resin composition obtained in Example A was not used, and an alumina vapor deposition layer having a thickness of 20 nm was formed on one side of a biaxially stretched polypropylene film having a thickness of 20 ⁇ m by a vacuum vapor deposition method to form a vapor deposition film.
  • the oxygen transmittance and the peel strength were measured by the same method as in Example 12. The results are shown in Table 4.
  • Example 13 The epoxy resin composition obtained in Example A was applied to a biaxially stretched polypropylene film (“FOR” manufactured by Futamura Chemical Co., Ltd., thickness: 20 ⁇ m) on one side of a bar coater No. 3 was applied.
  • the epoxy resin composition was heated in a drying oven at 80 ° C. for 30 seconds to dry (thickness after drying: 0.1 ⁇ m), and further aged at 40 ° C. for 2 days to form a cured product layer.
  • a silica-deposited layer having a thickness of 20 nm was formed on the surface of the cured product layer by a sputtering method to prepare a gas barrier laminated body (I) having the configuration shown in FIG.
  • the oxygen permeability and the peel strength were measured by the above method.
  • the results are shown in Table 4.
  • 1.05 g of the curing agent "CAT-RT85” and 25 g of the solvent ethyl acetate were added to 15 g of the main agent "AD-502" manufactured by Toyo Morton Co., Ltd. as the urethane adhesive.
  • the one prepared by stirring well was used.
  • Example 13 a silica-deposited layer having a thickness of 20 nm was formed on one side of a biaxially stretched polypropylene film having a thickness of 20 ⁇ m by a sputtering method without using the epoxy resin composition obtained in Example A to form a vapor-deposited film. Obtained. Using the obtained thin-film film, the oxygen transmittance and the peel strength were measured by the same method as in Example 13. The results are shown in Table 4.
  • the epoxy resin composition of the present invention can exhibit high gas barrier properties and adhesiveness as compared with the reference example even when used in the gas barrier laminate (I) having the configuration shown in FIG. Recognize.
  • the epoxy resin composition of the present invention it is particularly useful as a coating composition, has high gas barrier properties and practically sufficient adhesiveness, and can form a cured coating film having a good appearance.
  • a gas barrier laminate having a base material and a cured product layer of the epoxy resin composition is suitable for various packaging material applications.

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PCT/JP2021/036946 2020-11-18 2021-10-06 エポキシ樹脂組成物、ガスバリア性積層体及び包装材 Ceased WO2022107473A1 (ja)

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US18/036,944 US12584011B2 (en) 2020-11-18 2021-10-06 Epoxy resin composition, gas barrier laminate, and packaging material
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