JP2010012769A - Bending-resistant laminate film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate film having bending resistance, gas barrier properties and excellent adhesiveness. <P>SOLUTION: The laminate film is formed by laminating at least (1) a substrate, (2) a silica-deposition layer, alumina-deposition layer or silica-alumina-binary deposition layer, (3) an adhesive layer and (4) a sealant layer. The adhesive forming its layer includes an epoxy resin composition comprising an epoxy resin and an epoxy resin-curing agent as a main component. The curing agent is: a reaction product of (A) m-xylylenediamine or p-xylylenediamine, (B) a polyfunctional compound which forms an amide group portion by reaction with polyamine, can form an oligomer and has at least one acyl group and (D) a functional compound which forms a carbamate portion by reaction with polyamine and has at least one carbonate portion; or a reaction product of the components (A), (B) and (D), and (C) monovalent 1-8C carboxylic acid and/or its derivative. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate film. More specifically, the present invention relates to a laminate film used for packaging materials such as foods and pharmaceuticals for the purpose of preserving contents using an adhesive excellent in shielding various gases.

  In recent years, composite flexible films combining different kinds of polymer materials have become mainstream as packaging materials for reasons such as strength, product protection, workability, and advertising effects due to printing. Such a composite film is generally composed of a thermoplastic film layer as an outer layer having a role of protecting a product and a thermoplastic film layer as a sealant layer, and these are bonded to the laminate film layer. A dry laminating method in which a sealant layer is adhered by applying a coating agent, and an extrusion laminating method in which an anchor coating agent is applied to a laminating film layer and a plastic film that becomes a melted sealant layer is pressure-bonded and laminated into a film as necessary. It is done.

  The adhesives used in these methods are generally two-component polyurethane adhesives composed of a main agent having an active hydrogen group such as a hydroxyl group and a curing agent having an isocyanate group, because of its high adhesive performance. (For example, refer to Patent Documents 1 and 2.)

  However, since these two-component polyurethane adhesives are generally not so fast in their curing reaction, they are cured by aging for a long period of 1 to 5 days after bonding to ensure sufficient adhesion. There was a need to promote. In addition, since a curing agent having an isocyanate group is used, when an unreacted isocyanate group remains after curing, the residual isocyanate group reacts with moisture in the atmosphere to generate carbon dioxide. There were problems such as the generation of bubbles. On the other hand, as a method for solving these problems, polyurethane adhesives and epoxy laminate adhesives have been proposed (see, for example, Patent Documents 3 and 4).

However, since the gas barrier property of each of the above-mentioned polyurethane-based adhesives and epoxy-based laminate adhesives is not high, when a gas barrier property is required for the packaging material, a PVDC coating layer or a polyvinyl alcohol (PVA) coating layer Flexible polymer film layer to be used as various gas barrier layers and sealant layers, such as ethylene-vinyl alcohol copolymer (EVOH) film layer, polymetaxylylene adipamide film layer, inorganic vapor deposited film layer deposited with alumina, silica, etc. It is necessary to laminate separately the layer which plays the role of adhesion | attachment, such as an adhesive bond layer and an anchor coat layer (for example, refer patent document 5), and it is disadvantageous in the manufacturing cost of a laminate film, and the work process in lamination. It was a thing to wear. As a method for solving these problems, an adhesive for gas barrier laminate has been proposed (see, for example, Patent Document 6). Although the adhesive exhibits good performance in terms of gas barrier properties, adhesiveness, and chemical resistance, the curing agent used (polyamine-modified) is highly reactive with epoxy resin, so its epoxy Resin compositions have a short pot life and are required to be further improved in workability.
Japanese Patent Laid-Open No. 5-51574 JP-A-9-316422 JP 2000-154365 A WO99 / 60068 pamphlet Japanese Patent Laid-Open No. 10-71664 JP 2002-256208 A

  An object of the present invention is to provide a flexible laminate film using an epoxy resin composition that provides high gas barrier performance and a long pot life as an adhesive.

  As a result of intensive studies to solve the above problems, the present inventors have a high gas barrier property by laminating a sealant film using a specific adhesive on the silica vapor deposition layer or alumina vapor deposition layer of the base material. The present inventors have found that a flex-resistant laminate film having excellent adhesiveness can be obtained efficiently with good workability, and have led to the present invention.

２． 前記エポキシ樹脂組成物中のエポキシ樹脂及びエポキシ樹脂硬化剤の配合割合が、エポキシ樹脂中のエポキシ基に対するエポキシ樹脂硬化剤中の活性水素の当量比（活性水素／エポキシ基）として、０．２〜５．０の範囲であることを特徴とする第１項記載のラミネートフィルム。
３． （Ａ）と（Ｂ）と（Ｄ）との反応、又は（Ａ）と（Ｂ）と（Ｃ）と（Ｄ）との反応を行う際の（Ａ）の活性水素数に対する、（Ｂ）の炭素−炭素二重結合数、（Ｂ）のアシル基数の２倍、（Ｃ）のカルボキシル基及びその誘導官能基の数ならびに（Ｄ）のカーボネート部位数の和の比が、０．２５〜０．９９の範囲である第１項又は第２項記載のラミネートフィルム。
４． 前記接着剤層の酸素透過係数が、１０ｍｌ・ｍｍ／ｍ^２・ｄａｙ・ＭＰａ（２３℃６０％ＲＨ）以下である第１項〜第３項のいずれかに記載のラミネートフィルム。
５． 前記（Ａ）が、メタキシリレンジアミンである第１項〜第４項のいずれかに記載のラミネートフィルム。
６． 前記（Ｂ）多官能性化合物が、アクリル酸、メタクリル酸及び／又はそれらの誘導体である第１項〜第４項のいずれかに記載のラミネートフィルム。
７． 前記（Ｃ）炭素数１〜８の一価カルボン酸及び／又はそれらの誘導体が、蟻酸、酢酸、プロピオン酸、酪酸、乳酸、グリコール酸、安息香酸及び／又はその誘導体である第１項〜第４項のいずれかに記載のラミネートフィルム。
８． 前記（Ｄ）が、エチレンカーボネート、プロピレンカーボネート及び／又はトリメチレンカーボネートである第１項〜第４項のいずれかに記載のラミネートフィルム。
９． 前記エポキシ樹脂硬化剤が、（ａ）メタキシリレンジアミンと、（ｂ）アクリル酸、メタクリル酸及び／又はそれらの誘導体と、（ｄ）エチレンカーボネート、プロピレンカーボネート及び／又はトリメチレンカーボネートとの反応生成物である第１項〜第４項のいずれかに記載のラミネートフィルム。
１０． 前記（ａ）と（ｂ）と（ｄ）の反応モル比（（ａ）対（ｂ）対（ｄ））が１対０．７〜０．９５対０．１〜０．７の範囲である第９項記載のラミネートフィルム。
１１． 前記エポキシ樹脂が、メタキシリレンジアミンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、１，３−ビス（アミノメチル）シクロヘキサンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、ジアミノジフェニルメタンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、パラアミノフェノールから誘導されたグリシジルアミノ基及び／又はグリシジルオキシ基を有するエポキシ樹脂、ビスフェノールＡから誘導されたグリシジルオキシ基を有するエポキシ樹脂、ビスフェノールＦから誘導されたグリシジルオキシ基を有するエポキシ樹脂、フェノールノボラックから誘導されたグリシジルオキシ基を有するエポキシ樹脂及びレゾルシノールから誘導されたグリシジルオキシ基を有するエポキシ樹脂からなる群より選ばれる少なくとも１つの樹脂である第１項〜第１０項のいずれかに記載のラミネートフィルム。
１２． 前記エポキシ樹脂が、メタキシリレンジアミンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、及び／又はビスフェノールＦから誘導されたグリシジルオキシ基を有するエポキシ樹脂を主成分とするものである第１項〜第１０項のいずれかに記載のラミネートフィルム。
１３． 前記エポキシ樹脂が、メタキシリレンジアミンから誘導されたグリシジルアミノ基を有するエポキシ樹脂を主成分とするものである第１項〜第１０項のいずれかに記載のラミネートフィルム。
１４． ドライラミネート法により製造されたものである第１項〜第１３項のいずれかに記載のラミネートフィルム。 That is, the present invention is as follows.
1. A laminate film in which at least (1) a substrate, (2) a silica deposited layer, an alumina deposited layer or a silica / alumina binary deposited layer, (3) an adhesive layer and (4) a sealant layer are laminated, The adhesive forming the adhesive layer is mainly composed of an epoxy resin composition composed of an epoxy resin and an epoxy resin curing agent, and the epoxy resin curing agent includes the following (A), (B) and (D ) Or a reaction product of (A), (B), (C) and (D).
(A) Metaxylylenediamine or paraxylylenediamine (B) A polyfunctional compound having at least one acyl group capable of forming an amide group site and forming an oligomer by reaction with polyamine (C) carbon number Functionality having at least one carbonate moiety represented by formula (2) that forms a carbamate moiety represented by formula (1) by reaction with 1-8 monovalent carboxylic acid and / or its derivative (D) polyamine Compound

2. The blending ratio of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition is 0.2 to 0.2 as an equivalent ratio of active hydrogen in the epoxy resin curing agent to the epoxy group in the epoxy resin (active hydrogen / epoxy group). The laminate film as set forth in claim 1, which is in the range of 5.0.
3. (B) for the number of active hydrogens in (A) when (A), (B) and (D) are reacted or (A), (B), (C) and (D) are reacted The ratio of the sum of the number of carbon-carbon double bonds in (2), the number of acyl groups in (B), the number of carboxyl groups and its derived functional groups in (C) and the number of carbonate moieties in (D) is 0.25 to 0.25. The laminated film according to item 1 or 2, which is in the range of 0.99.
4). The laminate film according to any one of Items 1 to 3, wherein the adhesive layer has an oxygen permeability coefficient of 10 ml · mm / m ² · day · MPa (23 ° C., 60% RH) or less.
5). The laminate film according to any one of Items 1 to 4, wherein (A) is metaxylylenediamine.
6). The laminate film according to any one of Items 1 to 4, wherein the (B) polyfunctional compound is acrylic acid, methacrylic acid and / or a derivative thereof.
7). The (C) C 1-8 monovalent carboxylic acid and / or derivative thereof is formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid and / or a derivative thereof. 5. The laminate film according to any one of items 4.
8). The laminate film according to any one of Items 1 to 4, wherein (D) is ethylene carbonate, propylene carbonate and / or trimethylene carbonate.
9. The epoxy resin curing agent is a reaction product of (a) metaxylylenediamine, (b) acrylic acid, methacrylic acid and / or a derivative thereof, and (d) ethylene carbonate, propylene carbonate and / or trimethylene carbonate. The laminate film according to any one of Items 1 to 4, which is a product.
10. The reaction molar ratio ((a) to (b) to (d)) of (a), (b) and (d) is in the range of 1 to 0.7 to 0.95 to 0.1 to 0.7. The laminate film according to claim 9.
11. The epoxy resin is an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from 1,3-bis (aminomethyl) cyclohexane, or a glycidyl derived from diaminodiphenylmethane. Epoxy resin having amino group, epoxy resin having glycidylamino group and / or glycidyloxy group derived from paraaminophenol, epoxy resin having glycidyloxy group derived from bisphenol A, glycidyloxy group derived from bisphenol F An epoxy resin having a glycidyloxy group derived from phenol novolac, and an epoxy resin having a glycidyloxy group derived from resorcinol Laminate film according to any one of the items 1 to 10, wherein at least one resin selected.
12 The first to second items, wherein the epoxy resin is mainly composed of an epoxy resin having a glycidylamino group derived from metaxylylenediamine and / or an epoxy resin having a glycidyloxy group derived from bisphenol F. The laminate film according to any one of Items 10.
13. The laminate film according to any one of Items 1 to 10, wherein the epoxy resin is mainly composed of an epoxy resin having a glycidylamino group derived from metaxylylenediamine.
14 The laminate film according to any one of Items 1 to 13, which is produced by a dry lamination method.

  The laminate film of the present invention has high bending durability and has excellent gas barrier properties, laminate strength, and heat seal strength. Moreover, the laminate film of the present invention can be applied to various uses as an environmentally friendly non-halogen gas barrier material. Furthermore, the laminate film of the present invention can be advantageously obtained industrially with good workability.

  The laminate film of the present invention is a laminate in which at least a base material, a silica vapor deposition layer or an alumina vapor deposition layer, an adhesive layer and a sealant layer are laminated. The layer is used on the bag inner surface.

  The film material as a base material used in the present invention is, for example, a polyester film such as polyethylene terephthalate or polybutylene terephthalate, a polyamide film such as nylon 6, nylon 6,6, or polymetaxylylene adipamide (N-MXD6). Biodegradable films such as polylactic acid, polyolefin films such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polyacrylonitrile films, poly (meth) acrylic films, polystyrene films, polycarbonate systems Films, ethylene-vinyl alcohol copolymer (EVOH) films, polyvinyl alcohol films, papers such as cartons, metal foils such as aluminum and copper, and various materials used as these substrates Films coated with various polymers such as polyvinylidene chloride (PVDC) resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer saponified resin, acrylic resin, etc., films deposited with metals such as aluminum, A film in which an inorganic filler or the like is dispersed, a film having an oxygen scavenging function, or the like can be used.

  Moreover, an inorganic filler can be disperse | distributed also about the various polymers to coat. Examples of inorganic fillers include silica, alumina, mica, talc, aluminum flakes, and glass flakes. Layered silicates such as montmorillonite are preferred, and dispersion methods thereof include, for example, extrusion kneading and mixing into resin solutions. A conventionally known method such as a dispersion method can be used. Examples of methods for imparting oxygen scavenging functions include hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol and other low molecular organic compounds that react with oxygen, cobalt, manganese, nickel, iron And a method of using a composition containing a transition metal compound such as copper at least in part.

  The thickness of the film material is about 10 to 300 μm, preferably about 10 to 100 μm, and in the case of a plastic film, the film material may be uniaxially or biaxially stretched. In the present invention, the film material such as polyolefin and polyester is laminated as a layer other than the base material, silica vapor deposition layer or alumina vapor deposition layer, adhesive layer and sealant layer (for example, adhesive layer and sealant layer). Etc.). In this case, the film material may be silica-deposited or alumina-deposited. When laminating various materials, a plurality of adhesive layers may be provided. Moreover, you may use together adhesive agents (for example, polyurethane adhesive etc.) other than the adhesive agent in this invention.

  The silica vapor deposition layer or the alumina vapor deposition layer in the present invention is formed by vapor-depositing silica or alumina on the substrate. As a method of vapor-depositing with respect to various base materials, a physical vapor deposition method or a chemical vapor deposition method may be used. The silica vapor deposition layer or the alumina vapor deposition layer may be one in which silica and alumina are vapor-deposited.

  In the present invention, a coat layer may exist between the vapor deposition layer and the adhesive layer. Examples of the resin used as the coating layer include polyurethane resins such as polyurethane resins, polyurethane urea resins, acrylic modified urethane resins and acrylic modified urethane urea resins; vinyl chloride-vinyl acetate copolymer resins; rosins such as rosin modified maleic resins. Polyamide resins; Polyester resins; Chlorinated olefin resins such as chlorinated polypropylene resins, polyethyleneimine resins, polybutadiene resins, and organic titanium resins.

  The coating layer can be formed by dissolving these resins in a solvent such as water, methanol, ethanol, 2-propanol, ethyl acetate, methyl ethyl ketone, and toluene and applying the resin by a gravure method, a roll coating method, or the like. For the formation of the coat layer, general printing equipment that has been used for printing on conventional polymer films such as a gravure printing machine, a flexographic printing machine, and an offset printing machine can be similarly applied.

  When the coat layer is formed, the thickness is practically 0.005 to 5 μm, preferably 0.01 to 3 μm. When the thickness is less than 0.005 μm, sufficient adhesion is hardly exerted. On the other hand, when the thickness exceeds 5 μm, it is difficult to form a resin layer having a uniform thickness.

  When a curable coating layer is used, it may be a one-component type or a two-component type. However, when it is desired to impart water resistance and heat resistance, it is more practical to use a two-component type.

  In addition, an additive may be included in the above resins in order to impart other functionality to the coat layer. For example, wax, a dispersant, an antistatic agent, a surface modifier, etc. can be used for improving friction resistance, blocking prevention, slipping, heat resistance, antistatic, etc., which can be appropriately selected and used. .

  As the sealant layer in the present invention, it is preferable to use a flexible polymer film, and a polyolefin film such as a polyethylene film, a polypropylene film or an ethylene-vinyl acetate copolymer is selected in consideration of the expression of good heat sealability. It is preferable to do. The thickness of these films is practically about 10 to 300 μm, preferably about 10 to 100 μm, and the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment.

  The epoxy resin in the present invention may be any of an aliphatic compound, an alicyclic compound, an aromatic compound, or a heterocyclic compound. However, in consideration of the expression of high gas barrier properties, the aromatic moiety is located in the molecule. Is preferable, and an epoxy resin including the skeleton structure of the above formula (1) in the molecule is more preferable. Specifically, an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from 1,3-bis (aminomethyl) cyclohexane, and a glycidylamino derived from diaminodiphenylmethane Epoxy resin having glycidylamino group and / or glycidyloxy group derived from paraaminophenol, epoxy resin having glycidyloxy group derived from bisphenol A, glycidyloxy group derived from bisphenol F Epoxy resin having glycidyloxy group derived from phenol novolac, epoxy resin having glycidyloxy group derived from resorcinol, etc. can be used. Epoxy resin having glycidylamino group derived from metaxylylenediamine, epoxy resin having glycidylamino group derived from 1,3-bis (aminomethyl) cyclohexane, epoxy having glycidyloxy group derived from bisphenol F Epoxy resins having a glycidyloxy group derived from a resin and resorcinol are preferred.

  Furthermore, it is more preferable to use an epoxy resin having a glycidyloxy group derived from bisphenol F or an epoxy resin having a glycidylamino group derived from metaxylylenediamine as a main component. It is particularly preferable to use an epoxy resin having a glycidylamino group as a main component.

  Moreover, in order to improve various performances such as flexibility, impact resistance, and moist heat resistance, the above-mentioned various epoxy resins can be mixed and used at an appropriate ratio.

  The epoxy resin used in the present invention can be obtained by reaction of various alcohols, phenols and amines with epihalohydrin. For example, an epoxy resin having a glycidylamino group derived from metaxylylenediamine can be obtained by adding epichlorohydrin to metaxylylenediamine. Because metaxylylenediamine has four amino hydrogens, mono-, di-, tri-, and tetraglycidyl compounds are formed. The number of glycidyl groups can be changed by changing the reaction ratio between metaxylylenediamine and epichlorohydrin. For example, an epoxy resin having mainly four glycidyl groups can be obtained by addition reaction of about 4 times mole of epichlorohydrin to metaxylylenediamine.

  The epoxy resin is an excess of epihalohydrin with respect to various alcohols, phenols and amines in the presence of alkali such as sodium hydroxide at 20 to 140 ° C., preferably 50 to 120 ° C. for alcohols and phenols, amine In the case of a kind, it is synthesized by reacting at a temperature of 20 to 70 ° C. and separating the produced alkali halide. The number average molecular weight of the produced epoxy resin varies depending on the molar ratio of epihalohydrin to various alcohols, phenols and amines, but is about 80 to 4000, preferably about 200 to 1000, preferably about 200 to 500. It is more preferable.

The epoxy resin curing agent in the present invention is a reaction product of the following (A), (B), and (D), or a reaction product of (A), (B), (C), and (D).
(A) metaxylylenediamine or paraxylylenediamine,
(B) a polyfunctional compound having at least one acyl group capable of forming an amide group site by reaction with a polyamine and forming an oligomer;
(C) a monovalent carboxylic acid having 1 to 8 carbon atoms and / or a derivative thereof,
(D) A functional compound having at least one carbonate moiety represented by the above formula (2), which forms a carbamate moiety represented by the above formula (1) by reaction with a polyamine.

  As the (A) metaxylylenediamine or paraxylylenediamine, metaxylylenediamine is more preferable.

  Examples of the polyfunctional compound (B) include carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, succinic acid, malic acid, tartaric acid, adipic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and trimellitic acid. Examples include acids and derivatives thereof, such as esters, amides, acid anhydrides, acid chlorides, and the like, and in particular, carbon-carbon double bonds in a conjugated system with an acyl group such as acrylic acid, methacrylic acid, and derivatives thereof. What has is preferable.

  The (C) monovalent carboxylic acid having 1 to 8 carbon atoms and / or derivatives thereof include monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid, and the like. Derivatives thereof, such as esters, amides, acid anhydrides, acid chlorides and the like. These may be used in combination with the polyfunctional compound (B) to react with a polyamine. The amide group site introduced by the reaction has a high cohesive force, and the presence of the amide group site in a high proportion in the epoxy resin curing agent results in higher oxygen barrier properties and good adhesion to various film materials. Strength is obtained.

The (D) functional compound has at least one carbonate moiety that forms a carbamate moiety by reaction with a polyamine. Examples of such a compound include a chain compound having a carbonate moiety (hereinafter sometimes referred to as a chain carbonate compound) and a cyclic compound having a carbonate moiety (hereinafter sometimes referred to as a cyclic carbonate compound). Preferred examples of the chain carbonate compound and the cyclic carbonate compound include those represented by the following general formula (3) and general formula (4).

In Formula (3), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, a phenyl group, a pyridyl group, a benzothiazole group, A biphenyl group, a pyridylphenyl group, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkene group having 3 to 10 carbon atoms, and a monovalent group represented by the following general formula (5) are shown. The alkyl group and alkenyl group in R ¹ and R ² may be linear, branched, or cyclic. R ¹ and R ² may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, amino groups, and the like, and R ¹ and R ² are aromatic rings, or In the case of having a heterocyclic ring, in addition to the above, for example, an alkoxy group, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkylidine group, a thiol group, and an alkylthio group having 1 to 10 carbon atoms. And a functional group containing a sulfur atom or a nitrogen atom such as a group, an amino group, a cyano group, and an alkylamino group having 1 to 10 carbon atoms. When R ¹ and R ² have an aromatic ring or a heterocyclic ring, hetero atoms such as a nitrogen atom, an oxygen atom, and a sulfur atom may be included in the atoms constituting the ring system. The above-mentioned groups R ¹ and R ² are merely examples. For example, the group having an aromatic ring or a heterocyclic ring may be monocyclic, polycyclic, or condensed polycyclic. .

In formula (5), R ⁴ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, a phenyl group, a pyridyl group, a benzothiazole group, a biphenyl group, or a pyridylphenyl group. , A cycloalkyl group having 3 to 10 carbon atoms, a cycloalkene group having 3 to 10 carbon atoms, and a monovalent group represented by -OR ⁶ . R ⁵ is a single bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, a phenylene group, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenylene group having 3 to 10 carbon atoms, or the like. Indicates a valent group. R ⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, a phenyl group, a pyridyl group, a benzothiazole group, a biphenyl group, a pyridylphenyl group, or a carbon number of 3 to 10 And a monovalent group such as a cycloalkene group having 3 to 10 carbon atoms. The alkyl group, alkenyl group, alkylene group, and alkenylene group in R ⁴ , R ^5, and R ⁶ may be linear, branched, or cyclic. R ⁴ , R ⁵ and R ⁶ may have a substituent. Examples of the substituent include halogen atoms such as F, Cl and Br, amino groups, and the like, and R ¹ and R ² are aromatic. In the case of having a ring or a heterocyclic ring, in addition to the above, for example, an alkoxy group, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkylidine group, a thiol group, Examples thereof include a functional group containing a sulfur atom or a nitrogen atom such as 10 alkylthio groups, amino groups, cyano groups, and alkylamino groups having 1 to 10 carbon atoms. When R ⁴ , R ⁵ and R ⁶ have an aromatic ring or a heterocyclic ring, hetero atoms such as a nitrogen atom, an oxygen atom and a sulfur atom may be included in the atoms constituting the ring system. The groups R ⁴ , R ^5, and R ⁶ described above are merely examples. For example, the group having an aromatic ring or a heterocyclic ring may be monocyclic, polycyclic, or condensed polycyclic. May be.

In the formula (4), R ³ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, a phenyl group, a pyridyl group, a benzothiazole group, a biphenyl group, or a pyridylphenyl group. , A cycloalkyl group having 3 to 10 carbon atoms, a cycloalkene group having 3 to 10 carbon atoms, and a monovalent group represented by the following general formula (6). m represents an integer of 1 to 4, and k represents an integer of 0 to 2 × (m + 1). The alkyl group, alkenyl group, alkylene group, and alkenylene group in R ³ may be linear, branched, or cyclic. R ³ may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, amino groups, and the like, and R ¹ and R ² are aromatic rings or heterocyclic rings. In addition to the above, for example, an alkoxy group, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkylidine group, a thiol group, an alkylthio group having 1 to 10 carbon atoms, amino And functional groups containing a sulfur atom or a nitrogen atom such as a group, a cyano group, and an alkylamino group having 1 to 10 carbon atoms. When R ³ has an aromatic ring or a heterocyclic ring, a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom may be included in the atoms constituting the ring system. Incidentally, R ³ mentioned above is one example, for example, as the group having an aromatic ring or a heterocyclic ring, other monocyclic, polycyclic, may be any of condensed polycyclic. The plurality of R ³ may be the same or different.

In Formula (6), R ⁷ is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, a phenyl group, a pyridyl group, a benzothiazole group, a biphenyl group, a pyridylphenyl group, A monovalent group such as a cycloalkyl group having 3 to 10 carbon atoms and a cycloalkene group having 3 to 10 carbon atoms is shown. n represents an integer of 1 to 4, and l represents an integer of 0 to 2 × n. The alkyl group, alkenyl group, alkylene group, and alkenylene group in R ⁷ may be linear, branched, or cyclic. R ⁷ may have a substituent, and examples of the substituent include halogen atoms such as F, Cl and Br, amino groups, and the like, and R ¹ and R ² are aromatic rings or heterocyclic rings. In addition to the above, for example, an alkoxy group, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, an alkenyl group, an alkylidine group, a thiol group, an alkylthio group having 1 to 10 carbon atoms, amino And functional groups containing a sulfur atom or a nitrogen atom such as a group, a cyano group, and an alkylamino group having 1 to 10 carbon atoms. In the case where R ⁷ has an aromatic ring or a heterocyclic ring, the atoms constituting the ring system may contain a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. R ⁷ described above is an example, and for example, the group having an aromatic ring or a heterocyclic ring may be monocyclic, polycyclic, or condensed polycyclic. The plurality of R ⁷ may be the same or different.

  Examples of the chain carbonate compound represented by the general formula (3) include dimethyl carbonate, diethyl carbonate, 1-chloroethyl ethyl carbonate, dipropyl carbonate, allyl methyl carbonate, diallyl carbonate, diisobutyl carbonate, ethyl phenyl carbonate, and diphenyl. Carbonate, dibenzyl carbonate, ethyl-m-tolyl carbonate, ethyl-3,5-xylyl carbonate, tert-butylphenyl carbonate, tert-butyl-4-vinylphenyl carbonate, di-p-tolyl carbonate, tert-butyl- 8-quinolinyl carbonate, α-dichlorobenzyl methyl carbonate, bistrichloroethyl carbonate, 1-chloroethyl-4-chlorophenyl carbonate Bonate, tert-butyl-2,4,5-trichlorophenyl carbonate, methyl-2,3,4,6-tetrachlorophenyl carbonate, isopropyl-2,3,4,6-tetrachlorophenyl carbonate, tert-butyl-4- Formylphenyl carbonate, 1-chloroethyl-3-trifluoromethylphenyl carbonate, 4-methoxybenzylphenyl carbonate, 4-methoxyphenyl-N- (butoxycarbonyloxymethyl) carbonate, bis-nitrophenyl carbonate, bis- (2-methoxy) Carbonylphenyl) carbonate, methyl-2-methyl-6-nitrophenyl carbonate, ethyl-3-methyl-4-nitrophenyl carbonate, benzyl-4-nitrophenyl carbonate, 4-nitrate Rophenyl-2-trimethylsilylethyl carbonate, 2,4-dinitro-1-naphthylmethyl carbonate, 3,6-dichloro-2,4-dinitrophenylethyl carbonate, 2-sec-butyl-4,6-dinitrophenylpropyl carbonate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate, 4-nitrophenyl [(2S, 3s) -3-phenyl-2-oxiranyl] methyl carbonate, 2,4-dichloro-6-nitrophenyl methyl carbonate, 2-chloro-4-fluoro-5-nitrophenyl ethyl carbonate, methyl-2-methyl-4,6-dinitrophenyl carbonate, 2-chloro-4-methyl-6-nitrophenyl isopropyl carbonate, 4-chloro-3, 5-Dimethyl-2 6-Niditrophenylmethyl carbonate, 2-methylsulfonylethyl-4-nitrophenyl carbonate, ethyl-4-sulfo-1-naphthyl carbonate, 3-dimethylaminopropylethyl carbonate, ethyl-4-phenylazophenyl carbonate, 4- Chloro-3,5-dimethylphenylmethyl carbonate, 1,3-benzothiazol-2-yl-2-propynyl carbonate, isobutyl-3-oxo-3H-phenoxazin-7-yl-carbonate, 4- (iminomethylene- Sulfenyl) -2,5-dimethylphenylmethyl, 5-o-methoxycarbonyl-1,2-o- (1-methylethylidene) -α-D-xylofuranose, ethylene glycol bis- (methyl carbonate), o- Carbomethoxy-sari Tyric acid, carboxylic acid-1,1-dimethyl-2-oxopropyl ester methyl ester, carboxylic acid-di-o-tolyl ester, carboxylic acid-2-ethynylcyclohexyl ester phenyl ester, carboxylic acid-ethyl ester- (2- Oxobenzotriazol-3-yl) methyl ester, carboxylic acid-2-chloroethyl ester- (2-oxobenzotriazol-3-yl) ester, carboxylic acid-allyl ester- (2-oxobenzothiazol-3-yl) Methyl ester, carboxylic acid-hexyl ester- (2-oxobenzothiazol-3-yl) methyl ester, carboxylic acid-benzyl ester- (2-oxobenzothiazol-3-yl) methyl ester, carboxylic acid- (dinaphthalene- 1-yl) ester, dimethyl Dicarbonate, diethyl dicarbonate, di -tert- butyl dicarbonate, di -tert- amyl dicarbonate, diallyl dicarbonate, etc. dibenzyl carbonate.

  Examples of the cyclic carbonate compound represented by the general formula (4) include ethylene carbonate, propylene carbonate, vinylene carbonate, 1,3-dioxane-2-one, 4-vinyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 4-methoxymethyl-1,3-dioxolan-2-one, 4-chloro-1,3-dioxolan-2-one, 4,4-dimethyl- 5-methylene-1,3-dioxolan-2-one, (chloromethyl) ethylene carbonate, 5,5-diethyl-1,3-dioxane-2-one, 5-methyl-5-propyl-1,3-dioxane -2-one, erythritol biscarbonate, 4,5-diphenyl-1,3-dioxol-2-one, 4,6-dipheni Thieno - [3,4-d] -1,3- dioxol-2-one-5,5-dioxide and the like.

  Among the above, the chain carbonate compound represented by the general formula (3) is preferably dimethyl carbonate, diethyl carbonate, diphenyl carbonate or trimethylene carbonate, and the cyclic carbonate compound represented by the general formula (4) is ethylene carbonate. Propylene carbonate is preferred. From the viewpoint of reactivity with the polyamine, ethylene carbonate, propylene carbonate, and trimethylene carbonate are more preferable, and they may be used alone or in any mixture.

  The reaction product of (A), (B) and (D) or the reaction product of (A), (B), (C) and (D) constituting the epoxy resin curing agent in the present invention is ( It is obtained by reacting (B) and (C) and (D) or (B) and (D) with respect to A). In the reaction, (B) and (C) and (D), or (B) and (D) can be reacted in any order or mixed. First, (A) and (B) are reacted. It is preferable to make it.

  The reaction between (A) and (B) is carried out by mixing (A) and (B) under conditions of 0 to 100 ° C. when carboxylic acid, ester or amide is used as (B). It is carried out by carrying out an amide group formation reaction by dehydration, dealcoholization, and deamination under conditions of 300 ° C., preferably 130 to 250 ° C.

  In the amide group formation reaction, the inside of the reaction apparatus can be subjected to reduced pressure treatment at the final stage of the reaction as necessary in order to complete the reaction. Moreover, it can also dilute using a non-reactive solvent as needed. Furthermore, catalysts such as phosphites can be added as dehydrating agents and dealcoholizing agents.

  On the other hand, when an acid anhydride or acid chloride is used as (B), it is carried out by carrying out an amide group forming reaction after mixing at 0 to 150 ° C., preferably 0 to 100 ° C. In the amide group formation reaction, the inside of the reaction apparatus can be subjected to reduced pressure treatment at the final stage of the reaction as necessary in order to complete the reaction. Moreover, it can also dilute using a non-reactive solvent as needed. Furthermore, tertiary amines such as pyridine, picoline, lutidine and trialkylamine can be added.

  The amide group site introduced by the above reaction has a high cohesive force, and the presence of the amide group site in a high proportion in the curing agent results in higher oxygen barrier properties and base materials such as metals, concrete, and plastics. Good adhesion strength to can be obtained.

  Further, the reaction ratio of (A) and (B) is preferably such that the molar ratio ((B) / (A)) is 0.3 to 0.95. By setting the above range, a sufficient amount of amide groups are generated in the epoxy resin curing agent and the amount of amino groups necessary for reaction with the epoxy resin is ensured, so that high gas barrier properties and excellent adhesiveness are obtained. And an epoxy resin curing agent having good workability during coating can be obtained.

  The reaction between (A) and (D) is carried out by mixing (A) and (D) under the conditions of 40 to 200 ° C., and by addition reaction under the conditions of 40 to 200 ° C., preferably 60 to 180 ° C. This is carried out by performing a urethane group forming reaction. Further, a catalyst such as sodium methoxide, sodium ethoxide, or t-butoxy potassium can be used as necessary. In the carbamate site formation reaction, (D) may be melted or diluted with a non-reactive solvent as necessary to promote the reaction.

  The carbamate site introduced by the above reaction has a high cohesive force and the property of reducing the reactivity between the epoxy resin and the epoxy resin curing agent, and the presence of a high proportion of the carbamate site in the curing agent makes it more A long pot life, that is, better workability, higher oxygen barrier properties, and good adhesion strength to substrates such as metal, concrete, and plastic can be obtained.

  The reaction ratio of (A) and (D) can be any ratio in which the molar ratio ((D) / (A)) is in the range of 0.05 to 1.5. A range of 7 is preferred. By setting it as the said range, sufficient quantity of carbamate site | parts will produce | generate in a hardening | curing agent, and the favorable hardening | curing agent which expresses high gas barrier property and a long pot life can be obtained.

  The reaction between (A) and (C) can be carried out under the same conditions as the reaction between (A) and (B).

  When the reaction of (A), (B), and (D), or the reaction of (A), (B), (C), and (D) is performed, the ratio of (B), (C), and (D) is set. Although there is no limitation, the number of carbon-carbon double bonds in (B), twice the number of acyl groups in (B), the carboxyl group in (C), and the number of active hydrogens in (A) (4 per molecule) The ratio of the number of derived functional groups and the sum of the number of carbonate sites in (D) is preferably in the range of 0.25 to 0.99, and more preferably in the range of 0.25 to 0.67. By setting the above range, a sufficient amount of amide groups and carbamate sites are generated in the epoxy resin curing agent, and the amount of amino groups required for the reaction with the epoxy resin is ensured. It is possible to obtain an epoxy resin curing agent that exhibits excellent coating film performance and good workability during coating.

  The laminate film produced using the adhesive composed of the epoxy resin composition preferably has a laminate strength of 30 g / 15 mm or more immediately after lamination (before aging) at a peeling speed of 300 mm / min, 40 g / 15 mm. More preferably, it is 50 g / 15 mm or more. When the laminate strength is not sufficient, problems such as tunneling of the laminate film and winding deviation at the time of winding the film occur.

  When considering high gas barrier properties, long pot life, and good adhesion, the reaction molar ratio of (A) to (B) to (D) ((A) vs. (B) vs. (D)) 1 to 0.7 to 0.95 to 0.1 to 0.7, preferably 1 to 0.75 to 0.9 to 0.1 to 0.5, particularly preferably 1 to 0.8 to 0 It is preferable to use an epoxy resin curing agent in which the average molecular weight of the oligomer as the reaction product is increased to a range of .9 to 0.1 to 0.4.

  More preferred epoxy resin curing agents are the reaction of (a) metaxylylenediamine, (b) acrylic acid, methacrylic acid and / or their derivatives and (d) ethylene carbonate, propylene carbonate and / or trimethylene carbonate. Product. Here, the reaction molar ratio ((a) to (b) to (d)) of (a), (b) and (d) is preferably 1 to 0.7 to 0.95 to 0.1 to 0. 0.7, more preferably 1 to 0.75 to 0.9 to 0.1 to 0.5, and particularly preferably 1 to 0.8 to 0.9 to 0.1 to 0.4.

  In the present invention, the blending ratio of the epoxy resin and the epoxy resin curing agent may be a standard blending range in the case of producing an epoxy resin cured product by reaction between the epoxy resin and the epoxy resin curing agent. Specifically, the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin is 0.2 to 5.0, preferably 0.2 to 4.0, more preferably 0.3. It is the range of -3.0. By setting it as this range, favorable adhesiveness and gas barrier property can be expressed.

When the skeleton structure of the following formula (7) is contained at a high level in the cured epoxy resin, a high gas barrier property is expressed. In the present invention, the skeleton structure of the following formula (7) is included in the cured epoxy resin. Is preferably contained in an amount of 40% by weight or more. More preferably, it is 45 weight% or more, Most preferably, it is 50 weight% or more. According to the present invention, an epoxy resin cured product (adhesive layer) having an oxygen barrier property with an oxygen permeability coefficient of 10 ml · mm / (m ² · day · MPa) at 23 ° C. and 60% RH can be obtained.

  Further, in the present invention, the epoxy resin composition may include, if necessary, heat such as a polyurethane resin composition, a polyacrylic resin composition, and a polyurea resin composition within a range that does not impair the effects of the present invention. A curable resin composition may be mixed.

  The adhesive used in the present invention is mainly composed of the above epoxy resin composition. In order to help wet the surface when the adhesive is applied to various film materials, silicon or acrylic is used as necessary. A wetting agent such as a compound may be added to the epoxy resin composition. Suitable wetting agents include BYK331, BYK333, BYK340, BYK347, BYK348, BYK354, BYK380, BYK381, etc., available from Big Chemie. When adding these, the range of 0.01 weight%-2.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  Moreover, in order to improve the adhesiveness with respect to various film materials immediately after application | coating to various film materials, the adhesive agent used for this invention contains tackifiers, such as a xylene resin, a terpene resin, a phenol resin, and a rosin resin, as needed. It may be added. When adding these, the range of 0.01 weight%-5.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  In addition, for the adhesive used in the present invention, if necessary, for example, boron trifluoride amine complex such as boron trifluoride monoethylamine complex, boron trifluoride dimethyl ether complex, trifluoride for increasing low temperature curability. Boron diethyl ether complex, boron trifluoride ether complex such as boron trifluoride di-n-butyl ether complex, imidazoles such as 2-phenylimidazole, benzoic acid, salicylic acid, N-ethylmorpholine, dibutyltin dilaurate, naphthenic acid Curing accelerating catalysts such as cobalt and stannous chloride, organic solvents such as benzyl alcohol, zinc phosphate, iron phosphate, calcium molybdate, vanadium oxide, water-dispersed silica, fumed silica and other rust preventive additives, phthalocyanine series Organic pigments, organic pigments such as condensed polycyclic organic pigments, Emissions, zinc oxide, calcium carbonate, barium sulfate, alumina, may be added required percentage amount of each component of the inorganic pigments such as carbon black.

  Moreover, in order to improve various performances such as gas barrier properties, impact resistance, heat resistance, etc. of the adhesive layer formed by the adhesive used in the present invention, silica, alumina, mica, talc, aluminum flakes in the adhesive, An inorganic filler such as glass flakes may be added. In consideration of the transparency of the film, it is preferable that such an inorganic filler has a flat plate shape. When adding these, the range of 0.01 weight%-10.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  Moreover, you may add the compound etc. which have an oxygen capture | acquisition function to the adhesive agent used for this invention as needed. Examples of the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.

  Furthermore, in order to improve the adhesiveness of the adhesive layer formed by the adhesive used in the present invention to various film materials such as plastic film, metal foil, paper, etc., a silane coupling agent and a titanium coupling are included in the adhesive. A coupling agent such as an agent may be added. Suitable silane coupling agents include Silaace S310, S320, S330, S360, XS1003 available from Chisso as an amino silane coupling agent, Z-6050 available from Toray Dow Corning, Shin-Etsu Silicone Available KBE-603, KBE-903, KP-390, Silaace S510, S520, S530 available from Chisso as an epoxy silane coupling agent, Z-6040 available from Toray Dow Corning, Z- 6041, Z-6042, Z-6044, KBM-403, KBE-402, KBE-403 available from Shin-Etsu Silicone, Silaace S710 available from Chisso as a methacryloxy silane coupling agent, and the like. When adding these, the range of 0.01 weight%-5.0 weight% is preferable on the basis of the total weight of an epoxy resin composition.

  In the case of laminating using the adhesive composed of the epoxy resin composition, a known laminating method such as dry lamination, non-solvent laminating, extrusion laminating, etc. can be used. preferable.

  When the adhesive is applied to the film material and laminated, it is carried out at a concentration and temperature of the epoxy resin composition sufficient to obtain an epoxy resin cured product that will be the adhesive layer, which includes the starting material and It can vary depending on the choice of laminating method. That is, the concentration of the epoxy resin composition is about 5% by weight using a certain kind of appropriate organic solvent and / or water from the case where no solvent is used depending on the kind and molar ratio of the selected material, the laminating method, and the like. Various states can be taken up to the case where the coating liquid is prepared by diluting to the composition concentration. As the organic solvent to be used, any solvent having solubility with an adhesive can be used. For example, water-insoluble solvents such as toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, acetaldehyde, propionaldehyde, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, Glycol ethers such as 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, etc. Examples include alcohols, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

  The adhesive (coating solution) diluted with a solvent can be diluted at a concentration such that the Zahn cup (No. 3) viscosity is in the range of 5 to 30 seconds (25 ° C.). If the Zahn cup (No. 3) viscosity is less than 5 seconds, the adhesive is not sufficiently applied to the article to be coated, which causes contamination of the roll. On the other hand, when the Zahn cup (No. 3) viscosity exceeds 30 seconds, the adhesive does not sufficiently transfer to the roll, and it becomes difficult to form a uniform adhesive layer. For example, in dry lamination, the Zahn cup (No. 3) viscosity is preferably 10 to 20 seconds (25 ° C.) during use.

  In order to suppress foaming of the coating liquid when preparing the coating liquid in the present invention, an antifoaming agent such as silicon or an acrylic compound may be added to the coating liquid. Suitable antifoaming agents include BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070, BYK080, and the like, which are available from Big Chemie, with BYK065 being particularly preferred. Moreover, when adding these antifoamers, the range of 0.01 weight%-3.0 weight% is preferable on the basis of the total weight of the epoxy resin composition in a coating liquid, 0.02 weight%-2 More preferred is 0.0% by weight.

  When a solvent is used, the solvent drying temperature after application of the adhesive may vary from 20 ° C. to 140 ° C., but it is close to the boiling point of the solvent and affects the object to be coated. No temperature is desirable. When the drying temperature is less than 20 ° C., the solvent remains in the laminate film, which causes poor adhesion and odor. When the drying temperature exceeds 140 ° C., it becomes difficult to obtain a laminate film having a good appearance due to softening of the polymer film. For example, when apply | coating an adhesive agent to a stretched polypropylene film, 40 to 120 degreeC is desirable.

  Any of commonly used coating formats such as roll coating, spray coating, air knife coating, dipping, and brush coating can be used as the coating format for applying the adhesive. Roll coating or spray coating is preferred. For example, the same roll coat or spray technique and equipment as when a polyurethane adhesive component is applied to a polymer film and laminated may be applied.

Next, specific operations in each laminating method will be described. In the case of the dry laminating method, the coating liquid is applied to a film material including a substrate by a roll such as a gravure roll, and then the solvent is dried and a new film material is immediately bonded to the surface by a nip roll to form a laminated film. Obtainable. When there is a lot of solvent remaining in the laminate film, it becomes a cause of bad odor. Therefore, the amount of the remaining solvent is practically 7 mg / m ² or less, and when it is more than 7 mg / m ² , it is considered that a strange odor is felt from the film. Become. Preferably 5 mg / ^{m 2} or less in the case of strictly control the odor of the film, 3 mg / ^{m 2} or less is particularly preferred.

  In the dry laminating method, the adhesive can also be applied to the sealant layer, applied to a polyolefin film such as a polyethylene film, a polypropylene film, or an ethylene-vinyl acetate copolymer, dried, and then stretched polypropylene or a polyamide film. By laminating a base material such as a polyethylene terephthalate film, a laminate film can be produced.

  In the case of bonding by nip roll, the nip roll can be heated and bonded to 20 ° C. to 120 ° C., but 40 to 100 ° C. is desirable.

  In this case, it is desirable to complete the curing reaction by performing aging at 20 ° C. to 60 ° C. for a certain time as necessary after lamination. By performing aging for a certain period of time, a cured epoxy resin is formed with a sufficient reaction rate, and high gas barrier properties are exhibited. When the aging is 20 ° C. or less or without aging, the reaction rate of the epoxy resin composition is low, and sufficient gas barrier properties and adhesive strength cannot be obtained. Also, aging at 60 ° C. or higher can cause problems such as polymer film blocking and additive elution.

  In the case of the non-solvent laminating method, the adhesive that has been heated to about 40 ° C. to 100 ° C. in advance on the film material including the base material is applied by a roll such as a gravure roll heated to 40 ° C. to 120 ° C. Thereafter, a laminate film can be obtained by immediately laminating a new film material on the surface. In this case as well, as in the case of the dry laminating method, it is desirable to perform aging for a predetermined time after the lamination as necessary.

  In the case of the extrusion laminating method, a dilute solution of an epoxy resin and an epoxy resin curing agent, which are main components of the adhesive, with an organic solvent and / or water as an adhesion auxiliary agent (anchor coating agent) is added to the film material including the base material. After applying with a roll such as a gravure roll and drying and curing reaction of the solvent at 20 ° C. to 140 ° C., a laminate film can be obtained by laminating the polymer material melted by an extruder. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.

  These laminating methods and other laminating methods that can be generally used can be combined as necessary, and the layer structure of the laminated film can be changed depending on the application and form.

  The thickness of the adhesive layer after applying, drying, bonding and heat-treating the adhesive on various materials is 0.1 to 100 μm, preferably 0.5 to 10 μm. If the thickness is less than 0.1 μm, sufficient gas barrier properties and adhesiveness are hardly exhibited. On the other hand, if the thickness exceeds 100 μm, it is difficult to form an adhesive layer having a uniform thickness.

  The laminate film has excellent laminate strength. The laminate strength at a peeling speed of 300 mm / min after the heat treatment varies depending on the material of the base material and the sealant layer. For example, when the base material is stretched polypropylene, 80 g / 15 mm or more is preferable, and 100 g / 15 mm or more is more preferable. It is preferably 120 g / 15 mm or more. On the other hand, when the base material is stretched nylon or polyethylene terephthalate, if the sealant layer is low density polyethylene, it is preferably 600 g / 15 mm or more, more preferably 700 g / 15 mm or more, and particularly preferably 800 g / 15 mm or more. If is unstretched polypropylene, it is preferably 300 g / 15 mm or more, more preferably 400 g / 15 mm or more, and particularly preferably 500 g / 15 mm or more.

  The laminate film of the present invention can be used as a multilayer packaging material for the purpose of protecting foods and pharmaceuticals. The multilayer packaging material includes a laminate film. When used as a multi-layer packaging material, the layer structure can be changed according to the contents, use environment, and use form. That is, the laminate film of the present invention can be used as a multilayer packaging material as it is, and if necessary, a thermoplastic resin layer such as an oxygen absorbing layer or a heat sealable resin, a paper layer, a metal foil layer, etc. It can be further laminated on a laminate film. Under the present circumstances, you may laminate | stack using the adhesive agent for lamination of this invention, and may laminate | stack using another adhesive agent and an anchor coat agent.

  A packaging bag made of a soft packaging bag manufactured using the multilayer packaging material will be described. The packaging bag comprising such a soft packaging bag uses the multilayer packaging material, and the surfaces of the heat-sealable resin layer are overlapped with each other, and then the outer peripheral edge is heat-sealed and sealed. A part can be formed and manufactured. As the bag making method, for example, the multilayer packaging material is folded or overlapped so that the inner layer faces each other, and the peripheral edge thereof is, for example, a side seal type, a two-side seal type, or a three-side seal type. , Four-side seal type, envelope sticker seal type, jointed sticker seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. It is done. The packaging bag can take various forms depending on the contents, use environment, and use form. In addition, for example, a self-supporting packaging bag (standing pouch) is also possible. As a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, or an ultrasonic seal can be used.

  A packaging product using the packaging bag of the present invention can be manufactured by filling the packaging bag with the contents from the opening and then heat-sealing the opening. The contents that can be filled include rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles, dried noodles, pasta, Aseptic packaged rice, elephant rice, rice porridge, packaging rice cake, cereal foods and other staples, pickles, boiled beans, natto, miso, frozen tofu, tofu, licked rice, konjac, wild vegetable products, jams, peanut cream, salads, frozen vegetables Agricultural processed products such as potato processed products, hams, bacon, sausages, chicken processed products, livestock processed products such as corned beef, fish ham and sausages, fishery paste products, kamaboko, paste, boiled bonito, salted, smoked Seafood products such as salmon, mentaiko, peaches, tangerines, pineapples, apples, pears, Cooking of fruit such as cherries, vegetables such as corn, asparagus, mushrooms, onions, carrots, radishes, potatoes, hamburger, meatballs, marine fries, gyoza, croquettes, etc. Examples include dairy products such as finished food, butter, margarine, cheese, cream, instant creamy powder, and infant formula, liquid seasonings, retort curry, and pet food. It can also be used as a packaging material for tobacco, disposable body warmers, pharmaceuticals, cosmetics and the like.

  Examples of the present invention are shown below, but the present invention is not limited to these Examples.

<Epoxy resin curing agent A>
A reaction vessel was charged with 1 mol of metaxylylenediamine. The temperature was raised to 60 ° C. under a nitrogen stream, and 0.88 mol of methyl acrylate was added dropwise over 1 hour. While distilling off the produced methanol, the temperature was raised to 165 ° C. and maintained at 165 ° C. for 2.5 hours. Methanol was added dropwise over 1.5 hours to a solid content concentration of 65%, cooled to 65 ° C., and then 0.27 mol of crushed ethylene carbonate was added dropwise over 30 minutes and held at 65 ° C. for 5 hours to obtain an epoxy resin. Curing agent A was obtained.

<Epoxy resin curing agent B>
A reaction vessel was charged with 1 mol of metaxylylenediamine. The temperature was raised to 60 ° C. under a nitrogen stream, and 0.93 mol of methyl acrylate was added dropwise over 1 hour. While distilling off the produced methanol, the temperature was raised to 165 ° C. and maintained at 165 ° C. for 2.5 hours. Methanol was added dropwise over 1.5 hours to a solid content concentration of 65%, and after stirring and cooling, an epoxy resin curing agent B was obtained.

Moreover, the evaluation methods, such as pot life, gas barrier property, and laminate strength, are as follows.
<Pot life (hr)>
A solution (paint solution) in which an epoxy resin, an epoxy resin curing agent, and a solvent were mixed was kept at 25 ° C. The viscosity was measured every 30 minutes with Zaan Cup No. 3, and the relationship between the holding time and the Zaan cup viscosity (seconds) was examined. The time from the preparation of the coating solution until reaching the Zahn cup viscosity of 20 seconds was defined as the pot life.
<Oxygen permeability (ml / m ² · day · MPa)>
The oxygen transmission rate of the laminate film was measured under conditions of 23 ° C. and 60% relative humidity using an oxygen transmission rate measuring device (OX-TRAN ML2 / 21, manufactured by Modern Control).
<Oxygen permeability coefficient (ml · mm / m ² · day · MPa)>
The thickness of the film constituting the laminate film and the adhesive was measured with a multilayer film thickness measuring apparatus DC-8200 manufactured by Gunze Co., Ltd. The oxygen permeability coefficient of the adhesive layer was calculated from the measured oxygen permeability, film and thickness using the following formula.
1 / R ₁ = 1 / R ₂ + DFT / P + 1 / R ₃
Here, oxygen permeability of R ₁ = laminate film ^{(mm / m 2 · day ·} MPa)
R ₂ = Oxygen permeability of the film (ml / m ² · day · MPa)
R ₃ = Oxygen permeability of the film (ml / m ² · day · MPa)
DFT = Adhesive layer thickness (mm)
P = oxygen permeability coefficient of adhesive layer <laminate strength (g / 15 mm)>
Using the method specified in JISK-6854, the laminate strength of the laminate film was measured by a T-type peel test at a peel rate of 100 mm / min.
<Lamination strength after boil treatment (g / 15mm)>
Using the method specified in JISK-6854, the laminate strength of a laminate film that had been boiled at 90 ° C. for 30 minutes using Retort Food Autoclave (Tomy) was peeled at 100 mm / min by a T-type peel test. Measured with
<Oxygen permeability after bending treatment (ml / m ² · day · MPa)>
Using a gel bow flex tester (manufactured by Rigaku Corporation), the oxygen transmission rate of a laminated film to which a twist of 360 ° was added 50 times was measured under the conditions of 23 ° C. and relative humidity 60%.
<Heat seal strength (kg / 15mm)>
Using a heat seal processor (manufactured by Toyo Seiki Seisakusho Co., Ltd., thermal gradient tester), a test piece of a laminate film subjected to heat seal treatment at 150 ° C., 2 kg / cm ² , and 1 second is 300 mm / min. Evaluation was made by the pulling speed.

<Example 1>
Epoxy resin curing agent A 245 parts by weight and epoxy resin having a glycidylamino group derived from metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd .; TETRAD-X) 50 parts by weight, methanol 265 parts by weight, ethyl acetate A solution containing 39 parts by weight was prepared, and 0.1 part by weight of a silicon-based antifoaming agent (by Big Chemie; BYK065) and a silane coupling agent (by Chisso; Silaace S330) were added. A coating solution was obtained by stirring.
Adhesive was applied to the surface of the vapor-deposited side of a 12-μm thick polyethylene terephthalate film (silica vapor tech barrier L) using a gravure roll of 100 lines / inch. Then, after drying in a drying oven at 60 ° C. (near the entrance) to 90 ° C. (near the exit), a 40 μm-thick linear polyethylene film (T.U.X.MC-S, manufactured by Tosero Co., Ltd.) is 70. The laminate film was laminated with a nip roll heated to 0 ° C., wound at a winding speed of 130 m / min, and aged at 40 ° C. for 4 days to obtain a laminate film comprising a substrate / deposition layer / adhesive layer / sealant layer. The results are shown in Tables 1 and 2.

<Example 2>
Instead of a film of 12 μm thick polyethylene terephthalate film deposited with silica (Mitsubishi Resin Co., Ltd. Techbarrier L), a 12 μm thick polyethylene terephthalate film is subjected to alumina deposition, and there is a coating layer on the deposition surface. In the same manner as in Example 1 except that a film (GL-AEH manufactured by Toppan Printing Co., Ltd.) was used and Z-6050 manufactured by Toray Dow Corning Silicone Co. was used instead of Silaace S330 manufactured by Chisso Co., Ltd. A laminate film composed of a substrate / deposition layer / coat layer / adhesive layer / sealant layer was produced. The results are shown in Tables 1 and 2.

<Example 3>
Instead of a film of 12 μm thick polyethylene terephthalate film with silica vapor deposition (Techbarrier L manufactured by Mitsubishi Plastics), silica vapor deposition is performed on a 12 μm thick polyethylene terephthalate film with a coating layer on the vapor deposition surface. Substrate / deposited layer / coat layer / adhesive layer / sealant layer in the same manner as in Example 1 except that a film (Tech Barrier TXR manufactured by Mitsubishi Plastics) was used and no silane coupling agent was added. A laminate film made of The results are shown in Tables 1 and 2.

<Example 4>
Instead of a film of 12 μm thick polyethylene terephthalate film subjected to silica vapor deposition (Tech Barrier L manufactured by Mitsubishi Plastics, Inc.), a film of 15 μm thick stretched 6-nylon film subjected to silica vapor deposition (Mitsubishi Resin Co., Ltd.) ) A laminated film composed of a substrate / deposition layer / adhesive layer / sealant layer was prepared in the same manner as in Example 1 except that Tech Barrier NY) was used. The results are shown in Tables 1 and 2.

<Example 5>
Instead of a film of 12 μm thick polyethylene terephthalate film subjected to silica vapor deposition (Techbarrier L manufactured by Mitsubishi Plastics, Inc.), a silica-alumina binary vapor deposition is performed on a stretched 6-nylon film having a thickness of 15 μm. Substrate / deposition layer / coat layer / adhesive in the same manner as in Example 1 except that a film having a coating layer on the surface (Ecosial VN106 manufactured by Toyobo Co., Ltd.) was used and no silane coupling agent was added. A laminate film consisting of a layer / sealant layer was prepared. The results are shown in Tables 1 and 2.

<Example 6>
Instead of a film of 12 μm thick polyethylene terephthalate film with silica vapor deposition (Techbarrier L manufactured by Mitsubishi Plastics), silica vapor deposition is performed on a 12 μm thick polyethylene terephthalate film with a coating layer on the vapor deposition surface. Substrate / deposition layer / coat layer / adhesive layer / sealant in the same manner as in Example 1 except that a film (MOS-TBH manufactured by Oike Kogyo Co., Ltd.) was used and no silane coupling agent was added. A laminate film consisting of layers was produced. The results are shown in Tables 1 and 2.

<Example 7>
Instead of a film of 12 μm thick polyethylene terephthalate film with silica vapor deposition (Techbarrier L manufactured by Mitsubishi Plastics, Inc.), a 12 μm thick polyethylene terephthalate film was subjected to silica-alumina binary vapor deposition on the vapor deposition surface. A substrate / deposition layer / coat layer / adhesive layer / in the same manner as in Example 1 except that a film with a coat layer (Ecosial VE106 manufactured by Toyobo Co., Ltd.) was used and no silane coupling agent was added. A laminate film composed of a sealant layer was produced. The results are shown in Tables 1 and 2.

<Example 8>
Instead of a film of 12 μm thick polyethylene terephthalate film with silica vapor deposition (Techbarrier L manufactured by Mitsubishi Plastics, Inc.), a 12 μm thick polyethylene terephthalate film was subjected to silica-alumina binary vapor deposition on the vapor deposition surface. A substrate / deposition layer / coat layer / adhesive layer / in the same manner as in Example 1 except that a film having a coat layer (Ecosial VE306 manufactured by Toyobo Co., Ltd.) was used and no silane coupling agent was added. A laminate film composed of a sealant layer was produced. The results are shown in Tables 1 and 2.

<Example 9>
Instead of a film of 12 μm thick polyethylene terephthalate film subjected to silica vapor deposition (Tech Barrier L, manufactured by Mitsubishi Plastics, Inc.), a stretched 6-nylon film having a thickness of 15 μm was subjected to silica-alumina binary vapor deposition. Substrate / deposition layer / coat layer / adhesive in the same manner as in Example 1 except that a film having a coating layer on the surface (Ecosial VN406 manufactured by Toyobo Co., Ltd.) was used and no silane coupling agent was added. A laminate film consisting of a layer / sealant layer was prepared. The results are shown in Tables 1 and 2.

<Example 10>
Instead of a film of 12 μm thick polyethylene terephthalate film deposited with silica (Mitsubishi Resin Co., Ltd. Techbarrier L), a 12 μm thick polyethylene terephthalate film is subjected to alumina deposition, and there is a coating layer on the deposition surface. Substrate / deposition layer / coat layer / adhesive layer in the same manner as in Example 1 except that a film (Barrier Rocks 1011HG-CW manufactured by Toray Film Processing Co., Ltd.) was used and no silane coupling agent was added. / A laminate film consisting of a sealant layer was prepared. The results are shown in Tables 1 and 2.

<Example 11>
Instead of a film of 12 μm thick polyethylene terephthalate film deposited with silica (Mitsubishi Resin Co., Ltd. Techbarrier L), a 12 μm thick polyethylene terephthalate film is subjected to alumina deposition, and there is a coating layer on the deposition surface. Substrate / deposition layer / coat layer / adhesive layer in the same manner as in Example 1 except that a film (Barrier Rocks 1011HG-CR manufactured by Toray Film Processing Co., Ltd.) was used and no silane coupling agent was added. / A laminate film consisting of a sealant layer was prepared. The results are shown in Tables 1 and 2.

<Comparative Example 1>
Substrate / deposition layer / adhesion in the same manner as in Example 1 except that 163 parts by weight of epoxy resin curing agent B was used instead of epoxy resin curing agent A, 201 parts by weight of methanol, and 29 parts by weight of ethyl acetate. An agent layer / sealant layer was prepared. The results are shown in Tables 1 and 2.

<Comparative example 2>
As a polyurethane-based adhesive coating solution, ethyl acetate containing 50 parts by weight of a polyether component (manufactured by Toyo Morton Co., Ltd .; TM-329) and 50 parts by weight of a polyisocyanate component (manufactured by Toyo Morton Co., Ltd .; CAT-8B). A base material was prepared in the same manner as in Example 1 except that a solution (solid content concentration: 30% by weight) was prepared and used in place of the coating liquid of Example 1, and no silicon-based antifoaming agent and silane coupling agent were used. A laminate film consisting of / deposited layer / adhesive layer / sealant layer was produced. The results are shown in Tables 1 and 2.

Pot life, laminate strength, laminate strength after boil treatment, and heat seal strength were evaluated for the laminate films prepared in Examples and Comparative Examples. The results are shown in Table 1.

The oxygen transmission rate was evaluated for the laminate films prepared in Examples and Comparative Examples.

Claims (14)

A laminate film in which at least (1) a substrate, (2) a silica deposited layer, an alumina deposited layer or a silica / alumina binary deposited layer, (3) an adhesive layer and (4) a sealant layer are laminated, The adhesive forming the adhesive layer is mainly composed of an epoxy resin composition composed of an epoxy resin and an epoxy resin curing agent, and the epoxy resin curing agent includes the following (A), (B) and (D ) Or a reaction product of (A), (B), (C) and (D).
(A) Metaxylylenediamine or paraxylylenediamine (B) A polyfunctional compound having at least one acyl group capable of forming an amide group site and forming an oligomer by reaction with polyamine (C) carbon number Functionality having at least one carbonate moiety represented by formula (2) that forms a carbamate moiety represented by formula (1) by reaction with 1-8 monovalent carboxylic acid and / or its derivative (D) polyamine Compound

  The blending ratio of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition is 0.2 to 0.2 as an equivalent ratio of active hydrogen in the epoxy resin curing agent to the epoxy group in the epoxy resin (active hydrogen / epoxy group). The laminate film according to claim 1, which is in the range of 5.0.   The carbon of (B) with respect to the number of active hydrogens of (A) when the reaction of (A), (B) and (D), or the reaction of (A), (B), (C) and (D) is carried out -The ratio of the sum of the number of carbon double bonds, twice the number of acyl groups in (B), the number of carboxyl groups and derived functional groups in (C) and the number of carbonate sites in (D) is 0.25-0. The laminate film according to claim 1 or 2, which has a range of 99. The laminate film according to claim 1, wherein the adhesive layer has an oxygen permeability coefficient of 10 ml · mm / m ² · day · MPa (23 ° C., 60% RH) or less.   Said (A) is metaxylylene diamine, The laminate film in any one of Claims 1-4.   The laminate film according to any one of claims 1 to 4, wherein the (B) polyfunctional compound is acrylic acid, methacrylic acid and / or a derivative thereof.   The (C) monovalent carboxylic acid having 1 to 8 carbon atoms and / or a derivative thereof is formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, benzoic acid and / or a derivative thereof. The laminate film according to any one of the above.   The laminate film according to any one of claims 1 to 4, wherein (D) is ethylene carbonate, propylene carbonate, and / or trimethylene carbonate.   The epoxy resin curing agent is a reaction product of (a) metaxylylenediamine, (b) acrylic acid, methacrylic acid and / or a derivative thereof, and (d) ethylene carbonate, propylene carbonate and / or trimethylene carbonate. The laminate film according to claim 1, which is a product.   The reaction molar ratio ((a) to (b) to (d)) of (a), (b) and (d) is in the range of 1 to 0.7 to 0.95 to 0.1 to 0.7. The laminate film according to claim 9.   The epoxy resin is an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from 1,3-bis (aminomethyl) cyclohexane, or a glycidyl derived from diaminodiphenylmethane. Epoxy resin having amino group, epoxy resin having glycidylamino group and / or glycidyloxy group derived from paraaminophenol, epoxy resin having glycidyloxy group derived from bisphenol A, glycidyloxy group derived from bisphenol F An epoxy resin having a glycidyloxy group derived from phenol novolac, and an epoxy resin having a glycidyloxy group derived from resorcinol Laminate film according to claim 1 is at least one resin selected.   The epoxy resin is mainly composed of an epoxy resin having a glycidylamino group derived from metaxylylenediamine and / or an epoxy resin having a glycidyloxy group derived from bisphenol F. The laminate film according to any one of the above.   The laminate film according to any one of claims 1 to 10, wherein the epoxy resin is mainly composed of an epoxy resin having a glycidylamino group derived from metaxylylenediamine.   The laminate film according to any one of claims 1 to 13, which is produced by a dry lamination method.