Laminate, and packaging material

Abstract

To provide a packaging material which is suitable for storing a content having high acidity or basicity, and a laminate which is suitable for manufacturing the packaging material.SOLUTION: There are provided a laminate which includes a base material, a sealant film, and an adhesive layer arranged between the base material and the sealant film while being brought into contact with the sealant film, wherein the adhesive layer is a cured coating film of a two-pack curable type adhesive containing an acid group-containing olefin resin having a melting point of 40°C or higher and 100°C or lower, and an epoxy compound having viscosity at 70°C of 3,000 mPa s or less, film thickness of the sealant film is 20 μm or more and 200 μm or less, and the sealant film contains a polyethylene-based resin; and a packaging material formed by bag-making the laminate.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a laminate, more particularly to a laminate suitable for use as a packaging material for agricultural chemicals and the like, and to a packaging material comprising said laminate. [Background technology]

[0002] Traditionally, gusset bags made of a laminate with a paper outer layer and an aluminum foil or resin layer in the middle have been used as packaging bags for storing pesticide granules. This is to avoid health risks such as the contents leaking and being exposed if the bag breaks due to the nature of the contents, which are pesticide formulations, when dropped. For this reason, paper has been used as the main material for the packaging structure of gusset bags for pesticide formulations, taking into consideration appropriate strength, workability, and ease of handling in the packaging process. In addition, paper gusset bags have a pre-formed bottom due to their structure, and the bag maintains its self-supporting ability due to the stiffness (bending) characteristic of paper, which has the advantage of making them easy to handle in the packaging process and display at the time of sale.

[0003] In recent years, in order to improve the design when displayed, there are cases where packaging made of a resin laminate that does not use paper as a material is adopted (Patent Document 1). However, some pesticide active ingredients have high acidity or basicity and attack the resin that constitutes the laminate or the layer that bonds the resins together. When the laminate is attacked by the pesticide active ingredients, the laminate strength decreases, causing delamination between layers, or the seal strength decreases, causing the bag to break at the seal area. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2016-104725 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in consideration of the above circumstances, and has an object to provide a packaging material suitable for containing contents that are highly acidic or basic, and a laminate used in the production of such a packaging material. [Means for solving the problem]

[0006] The present invention relates to a laminate comprising a substrate, a sealant film, and an adhesive layer disposed between the substrate and the sealant film in contact with the sealant film, wherein the adhesive layer is a cured coating of a two-component curing adhesive comprising an acid group-containing olefin resin having a melting point of 40°C or more and 100°C or less and an epoxy compound having a viscosity at 70°C of 3000 mPa s or less, the sealant film having a thickness of 20 μm or more and 200 μm or less, and the sealant film comprises a polyethylene-based resin, and a packaging material obtained by making a bag from the laminate. Effect of the Invention

[0007] The laminate of the present invention can produce a packaging material suitable for containing contents having high acidity or basicity. The packaging material of the present invention can suppress deterioration of the packaging material even when contents having high acidity or basicity are contained therein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <Laminate> The laminate of the present invention includes a substrate, a sealant film, and an adhesive layer disposed between the substrate and the sealant film and in contact with the sealant film. The laminate of the present invention will be described in detail below.

[0009] (base material) The substrate may be any substrate that can ensure the strength required for packaging, and may be, for example, a film or sheet made of inorganic materials such as metals and metal oxides, or organic materials such as resins, that have excellent chemical and physical strength, can withstand the conditions for forming an inorganic oxide vapor deposition film, and can well retain the properties of the inorganic oxide vapor deposition film without impairing the properties.

[0010] Specifically, the resin may be paper, metal foil such as aluminum, stainless steel, iron, copper, nickel, or the like, polyolefin resin such as polyethylene resin or polypropylene resin, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, oriented polypropylene, K-coated oriented polypropylene, cyclic polyolefin resin, K-coated oriented nylon, polyvinyl alcohol, polyacrylonitrile, ethylene-vinyl acetate copolymer resin, ionomer resin, ethylene-(meth)acrylic acid copolymer resin, ethylene-ethyl(meth)acrylate copolymer resin, ethylene-propylene copolymer, acrylonitrile, etc. Examples of the resin that can be used include acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, methylpentene resins, polybutene resins, acid-modified polyolefin resins, polyamide resins such as various nylons, polystyrene resins, low-crystalline saturated polyesters or amorphous polyester resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene resins, polyethylene tetrafluoroethylene resins, polycarbonate resins, polyurethane resins, acetal resins, and cellulose resins.

[0011] When a paper base material is used, the tear strength is preferably 15 to 70 gf, and more preferably 20 to 50 gf according to JIS P8116. Pure white roll paper, coated paper, kraft paper, etc. can be used as such a paper base material.

[0012] It is also preferable that the metal foil has been subjected to a surface treatment such as sandblasting, polishing, degreasing, etching, surface treatment by immersion or spraying with an anti-rust agent, trivalent chromium conversion treatment, phosphate conversion treatment, sulfide conversion treatment, anodized film formation, fluororesin coating, etc., on the surface facing the contents (sealant side). This can further improve the resistance of the laminate to the contents. Among these, those subjected to trivalent chromium conversion treatment are preferable from the viewpoint of excellent adhesion retention performance (environmental deterioration resistance) and corrosion resistance. In addition, the thickness of this metal foil is preferably in the range of 10 to 100 μm from the viewpoint of corrosion prevention.

[0013] The resin film or sheet is produced by a film-forming method such as extrusion, cast molding, T-die, cutting, or inflation, in which the above-mentioned various resins are formed into a film alone, or by a multilayer co-extrusion film-forming method using two or more various resins, or by a method in which two or more resins are used and mixed before film formation. Furthermore, if necessary, the resin can be used as various resin films or sheets stretched uniaxially or biaxially using a tenter system or a tubular system.

[0014] When forming a resin film or sheet, various plastic compounding agents and additives can be added for the purpose of improving or modifying the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, slipperiness, release properties, flame retardancy, mold resistance, electrical properties, strength, etc. of the film. The amount of these additives can range from a very small amount to several tens of percent and can be added at any amount depending on the purpose. Examples of additives that can be used include lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and also modifying resins.

[0015] The adhesive layer side of the substrate is preferably subjected to a treatment for improving wettability, such as a corona treatment, an ozone treatment, or a flame treatment.

[0016] The substrate may be provided with a vapor-deposited film made of an inorganic material such as aluminum or an inorganic oxide such as silicon oxide or aluminum oxide. When a vapor-deposited film is provided, it may be provided directly on the substrate layer, or may be provided via a primer that improves adhesion between the substrate and the vapor-deposited film. If necessary, it may be provided with a light-shielding property that prevents the transmission of visible light, ultraviolet light, etc.

[0017] The deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and the composition and the formation method are not particularly limited. Examples of the formation method of the deposition film include physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum deposition method, sputtering method, and ion plating method, and chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method.

[0018] The thickness of the vapor-deposited film is, for example, 10 to 2000 Å, preferably 10 to 1000 Å. In the case of a vapor-deposited aluminum film, the thickness is preferably 10 to 600 Å, more preferably 10 to 400 Å. In the case of a vapor-deposited silicon oxide or aluminum oxide film, the thickness is preferably 10 to 500 Å, more preferably 10 to 300 Å.

[0019] A coating layer may be provided on the vapor deposition film. The coating layer may be, for example, a film made of a hydrolyzate of an alkoxide or a hydrolysis condensate of an alkoxide obtained by polycondensing an alkoxide and a water-soluble polymer by a sol-gel method in the presence of a sol-gel catalyst, an acid, water, and an organic solvent. In some cases, it may further contain a silane coupling agent.

[0020] The film thickness of the substrate can be appropriately adjusted, and is, for example, in the range of 0.1 to 300 μm, and more preferably in the range of 1 to 100 μm.

[0021] (Sealant film) The sealant film used is a film containing a resin layer having a sealant property that can be melted and fused to each other by heat. The sealant film of the present invention contains a polyethylene resin as the resin having a sealant property.

[0022] Examples of polyethylene-based resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-ethyl (meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-propylene copolymer, polyolefin-based resins in which polyethylene is modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, and other unsaturated carboxylic acids, terpolymer resins of ethylene-(meth)acrylic acid ester-unsaturated carboxylic acid, cyclic polyolefin resins, and cyclic olefin copolymers, and these can be used alone or in combination of two or more kinds.

[0023] The sealant film may be a film in which different resins are laminated. Examples of such films include a film in which a barrier resin, ethylene vinyl alcohol resin, is multi-layer extruded together with a polyethylene resin (low density polyethylene / ethylene-vinyl alcohol copolymer resin / low density polyethylene), a film in which a cyclic polyolefin copolymer is extruded with a polyethylene resin (low density polyethylene / cyclic polyolefin resin / low density polyethylene), and the like. Such films are preferable because they have excellent barrier properties against the contents. Hereinafter, such sealant films are also referred to as barrier sealants.

[0024] The surface of the sealant film may be subjected to a corona treatment, a flame treatment, an ozone treatment, or the like.

[0025] The sealant layer may contain one or more additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a flame retardant, a crosslinking agent, a colorant, and the like.

[0026] In the present invention, the thickness of the sealant film is 20 μm or more and 200 μm or less.

[0027] (Adhesive layer) The adhesive layer is disposed between the substrate and the sealant film in contact with the sealant film, and is a cured coating of a two-component curing adhesive containing a first agent and a second agent. The first agent contains an acid group-containing olefin resin as a resin, and the second agent contains an epoxy compound.

[0028] Examples of the acid group contained in the acid group-containing olefin resin include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a phosphoric acid group, etc. The acid-modified olefin resin may have only one of these groups, or may have two or more groups.

[0029] Examples of the acid group-containing olefin resin include homopolymers or copolymers of acid group-containing monomers, copolymers of acid group-containing monomers and olefin monomers, and modified polyolefins with acid group-containing monomers.

[0030] The acid group-containing monomer used to prepare the homopolymer or copolymer of the acid group-containing monomer is preferably an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride. Specific examples of the anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-octa-1,3-diketospiro[4.4]non-7-ene, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, methyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methyl-norbornene-5-ene-2,3-dicarboxylic anhydride, and norborn-5-ene-2,3-dicarboxylic anhydride.

[0031] The acid group-containing monomer used for preparing the copolymer of the acid group-containing monomer and the olefin monomer can be the same as the acid group-containing monomer used for preparing the homopolymer or copolymer of the above-mentioned acid group-containing monomer. It may be used alone or in combination of two or more kinds. It is preferable to use maleic anhydride.

[0032] The olefin monomer used to prepare the copolymer of the acid group-containing monomer and the olefin monomer includes olefins having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, vinylcyclohexane, etc. Among these, olefins having 3 to 8 carbon atoms are preferred because they provide particularly good adhesive strength, and propylene and 1-butene are more preferred, and the combined use of propylene and 1-butene is particularly preferred because the laminate of the present invention is more excellent in acid resistance and alkali resistance.

[0033] To prepare a copolymer of an acid group-containing monomer and an olefin monomer, in addition to the above-mentioned acid group-containing monomer and olefin monomer, other compounds having an ethylenically unsaturated group, such as styrene, butadiene, and isoprene, may be used in combination.

[0034] The acid group-containing monomer used for preparing the acid group-containing monomer modified polyolefin can be the same as the acid group-containing monomer used for preparing the homopolymer or copolymer of the above-mentioned acid group-containing monomer. It may be used alone or in combination of two or more kinds. It is preferable to use maleic anhydride.

[0035] Examples of polyolefins used for preparing the acid group-containing monomer modified polyolefin include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and copolymers of olefins having 2 to 8 carbon atoms with other monomers. Examples of such polyolefins include polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene resins, polypropylene, polyisobutylene, poly(1-butene), poly(4-methyl-1-pentene), polyvinylcyclohexane, α-olefin copolymers such as ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-hexene copolymers, and propylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate-methyl methacrylate copolymers, and ionomer resins. Among these, from the viewpoint of particularly good adhesive strength, a homopolymer of an olefin having 3 to 8 carbon atoms and a copolymer of two or more kinds of olefins having 3 to 8 carbon atoms are preferred, a homopolymer of propylene or a propylene-1-butene copolymer is more preferred, and a propylene-1-butene copolymer is particularly preferred since the laminate of the present invention will have better acid resistance and alkali resistance.

[0036] Methods for modifying polyolefins with acid group-containing monomers include graft modification and copolymerization.Specific examples of methods for reacting polyolefins with acid group-containing monomers by graft modification include melting polyolefins, adding acid group-containing monomers (graft monomers) thereto for graft reaction, dissolving polyolefins in a solvent to prepare a solution, adding graft monomers thereto for graft reaction, and mixing polyolefins dissolved in an organic solvent with graft monomers, heating at a temperature above the softening temperature or melting point of polyolefins, and simultaneously carrying out radical polymerization and hydrogen abstraction reaction in a molten state.

[0037] In either case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the graft reaction in the presence of a radical initiator. The graft reaction is usually carried out under conditions of 60 to 350° C. The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight per 100 parts by weight of the polyolefin before modification.

[0038] In order to improve the adhesiveness, the weight average molecular weight of the acid group-containing olefin resin is preferably 10,000 or more, more preferably 50,000 or more, and in order to ensure a suitable fluidity, the weight average molecular weight of the acid group-containing olefin resin is preferably 500,000 or less, more preferably 300,000 or less.

[0039] In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0040] Measuring device: Tosoh Corporation HLC-8320GPC Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL Detector: RI (differential refractometer) Data processing: Tosoh Corporation Multistation GPC-8020modelII Measurement conditions: Column temperature 40℃ Solvent Tetrahydrofuran Flow rate 0.35ml / min Standard: Monodisperse polystyrene Sample: 100 μl of tetrahydrofuran solution containing 0.2% by mass of resin solids filtered through a microfilter

[0041] The acid group-containing olefin resin used is crystalline and has a melting point of 40° C. or more and 100° C. or less. In this specification, the acid group-containing olefin resin is crystalline means that it has a melting point when DSC measurement is performed by the following method. The acid group-containing olefin resin preferably has a heat of fusion of 0.1 mJ / mg or more and 50 mJ / mg or less.

[0042] The melting point and heat of fusion of the acid group-containing olefin resin are measured by DSC (differential scanning calorimetry). Specifically, 5 mg of sample is cooled from room temperature to -50°C at 10°C / min under a nitrogen flow of 20 mL / min, held for 10 minutes, then heated to 200°C at 10°C / min and held for 10 minutes to remove thermal history. It is then cooled to -50°C at 10°C / min, held for 10 minutes, and heated again to 200°C at 10°C / min to measure the DSC curve. The maximum peak temperature of the endothermic curve observed in the second cooling or heating process is taken as the melting point, and the heat of fusion is calculated from the area surrounded by this maximum peak and the baseline.

[0043] Specific examples of such acid group-containing olefin resins include maleic anhydride-modified polypropylene, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylate-maleic anhydride terpolymers, etc. Commercially available acid group-containing olefin resins include the "Modic" series manufactured by Mitsubishi Chemical Corporation, the "Admer" series and "Unistole" series manufactured by Mitsui Chemicals, Inc., the "Toyotack" series manufactured by Toyobo Co., Ltd., the "Eumex" series manufactured by Sanyo Chemical Industries, Ltd., the "Rexpearl EAA" series and "Rexpearl ET" series manufactured by Japan Polyethylene Co., Ltd., the "Primacol" series manufactured by Dow Chemical Co., Ltd., the "Nucrel" series manufactured by Mitsui DuPont Polychemicals, and the "Bondine" series manufactured by Arkema, etc.

[0044] In order to make the acid-modified olefin resin less susceptible to attack by the contents and to improve its acid resistance and alkali resistance, the acid value of the acid-modified olefin resin is preferably 1 mgKOH / g or more, and more preferably 5 mgKOH / g or more, and is preferably 200 mgKOH / g or less, and more preferably 165 mgKOH / g or less.

[0045] The acid value of the first agent was measured using an FT-IR (JASCO Corporation, FT-IR4200) and was calculated by the coefficient (f) obtained from a calibration curve prepared using a chloroform solution of maleic anhydride, the stretching peak (1780 cm) of the anhydride ring of maleic anhydride in a maleic anhydride-modified polyolefin solution, and the -1 ) and the stretching peak of the carbonyl group of maleic acid (1720 cm -1 The absorbance (II) of maleic anhydride was calculated from the following formula: In the formula, the molecular weight of maleic anhydride is 98.06, and the molecular weight of potassium hydroxide is 56.11.

[0046]

number

[0047] The first agent may contain, as a resin, a resin that does not substantially have a reactive functional group (hereinafter also referred to as "other resin") in addition to the acid group-containing olefin resin. For example, by using a crystalline olefin resin in combination as the other resin, it is expected that the chemical resistance (acid resistance, alkali resistance) can be improved.

[0048] Examples of the crystalline olefin resin include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, such as ethylene, propylene, isobutylene, 1-butene, 4-methyl-1-pentene, hexene, and vinylcyclohexane, and copolymers of olefins having 2 to 8 carbon atoms with other monomers. Specific examples of the crystalline olefin resin include polyethylenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene resins, polypropylene, polyisobutylene, poly(1-butene), poly(4-methyl-1-pentene), polyvinylcyclohexane, α-olefin copolymers such as ethylene-propylene block copolymers, ethylene-propylene random copolymers, ethylene-1-butene copolymers, ethylene-4-methyl-1-pentene copolymers, and ethylene-hexene copolymers, ethylene-methyl methacrylate copolymers, and propylene-1-butene copolymers. Among these, homopolymers of olefins having 3 to 8 carbon atoms and copolymers of two or more kinds of olefins having 3 to 8 carbon atoms are preferred because they provide particularly good adhesive strength, and homopolymers or copolymers of propylene are more preferred.

[0049] The other resin has high solubility in a solvent and improves coatability, so the weight average molecular weight is preferably 2000 to 200,000. The weight average molecular weight of the other resin is more preferably 20,000 to 180,000, and even more preferably 40,000 to 160,000.

[0050] The melting point of the crystalline olefin resin is preferably 50°C to 100°C. When a crystalline olefin resin that does not have a reactive functional group is used in combination, the amount of the resin can be adjusted as appropriate. From the viewpoint of the balance between chemical resistance, heat resistance, and adhesion, it is preferable to keep the amount of the resin to 20 mass % or less of the solid content of the first agent, for example.

[0051] The second agent contains an epoxy compound having a viscosity of 5000 mPa·s or less at 70°C as a compound reactive with the acid group-containing olefin resin, a so-called curing agent. Hereinafter, this is also referred to as the first epoxy compound. The viscosity of the first epoxy compound is measured using a rotational viscometer with a cone and plate: 1°×R25. The epoxy compound is not particularly limited as long as it satisfies the above viscosity range and has an epoxy group in the molecule, and conventionally known epoxy compounds can be used. It is more preferable that the viscosity of the first epoxy compound is 3000 mPa·s or less.

[0052] Examples include polyglycidyl ether type epoxy resins of aliphatic polyols such as ethylene glycol, propylene glycol, hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, diglycerin, sorbitol, spiroglycol, or hydrogenated bisphenol A; Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, etc.; Aromatic epoxy resins such as novolac-type epoxy resins, which are glycidyl ethers of phenol novolac resins and cresol novolac resins; Polyglycidyl ethers of polyols, which are ethylene oxide or propylene oxide adducts of aromatic polyhydroxy compounds such as bisphenol A, bisphenol F, bisphenol S, and bisphenol AD; Polyglycidyl ether type epoxy resins of polyether polyols such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol; cyclic aliphatic type polyepoxy resins such as bis(3,4-epoxycyclohexylmethyl)adipate and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate; Polyglycidyl ester type epoxy resins of polycarboxylic acids such as propanetricarboxylic acid, butanetetracarboxylic acid, adipic acid, phthalic acid, terephthalic acid, and trimellitic acid; Bisepoxy resins of hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene; Epoxy resins of diene polymers such as polybutadiene or polyisoprene; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidyl paraaminophenol, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, and tetraglycidylmeta-xylylenediamine; Examples of the epoxy resin include those containing a heterocycle such as triazine or hydantoin. These epoxy resins may be used alone or in combination of two or more kinds.

[0053] The first epoxy compound is preferably an epoxy compound having two or more epoxy groups and one or more hydroxyl groups in one molecule and having a weight average molecular weight of 3,000 or less.

[0054] The second agent may contain a compound other than the first epoxy compound as a compound reactive with the acid group-containing olefin resin, but in that case, the ratio of the first epoxy compound in the compound reactive with the acid group-containing olefin resin contained in the second agent is preferably 40% by mass or more. This is preferable because the laminate of the present invention has better acid resistance and alkali resistance. The ratio of the first epoxy compound in the compound reactive with the acid group-containing olefin resin is more preferably 50% by mass or more, more preferably 80% by mass or more. The total amount of the compound reactive with the acid group-containing olefin resin may be the first epoxy compound.

[0055] The second agent may contain an epoxy compound other than the first epoxy compound (hereinafter also referred to as the second epoxy compound). The structure of the second epoxy compound may be the same as that of the first epoxy compound. When the second epoxy compound is used in addition to the first epoxy compound, the amount of the first epoxy compound is preferably 60% by mass or less, more preferably 50% by mass or less, and more preferably 20% by mass or less of the compound reactive with the acid group-containing olefin resin.

[0056] As The second agent may contain, as a compound reactive with the acid group-containing olefin resin, a polyfunctional isocyanate compound, an aziridine group-containing compound, a carbodiimide, an oxazoline, an amino resin, etc. Compounds reactive with the acid group-containing olefin resin other than the first epoxy compound and the second epoxy compound are also referred to as other compounds below.

[0057] Examples of polyfunctional isocyanate compounds include diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and hydrogenated diphenylmethane diisocyanate, and compounds derived therefrom, that is, isocyanurate bodies, adduct bodies, biuret types, uretdione bodies, allophanate bodies, prepolymers having an isocyanate residue (low polymers obtained from diisocyanates and polyols), and complexes thereof.

[0058] A compound obtained by reacting a part of the isocyanate groups of the above-mentioned polyfunctional isocyanate compound with a compound reactive with the isocyanate groups may be used as the curing agent. Examples of compounds reactive with an isocyanate group include compounds containing an amino group such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, and aniline; compounds containing a hydroxyl group such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, and phenol; compounds having an epoxy group such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, and cyclohexanedimethanol diglycidyl ether; and compounds containing a carboxylic acid such as acetic acid, butanoic acid, hexanoic acid, octanoic acid, succinic acid, adipic acid, sebacic acid, and phthalic acid.

[0059] Examples of the aziridine group-containing compound include N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), triethylenemelamine, trimethylolpropane-tri-β(2-methylaziridine)propionate, bisisophthaloyl-1-2-methylaziridine, tri-1-aziridinylphosphine oxide, and tris-1-2-methylaziridinephosphine oxide.

[0060] Examples of carbodiimides include N,N'-di-o-toluylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, N,N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N,N'-di-2,2-tert.-butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-di-cyclohexylcarbodiimide, and N,N'-di-p-toluylcarbodiimide.

[0061] Examples of oxazolines include monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, and 2,4-diphenyl-2-oxazoline, as well as 2,2'-(1,3-phenylene)-bis(2-oxazoline), 2,2'-(1,2-ethylene)-bis(2-oxazoline), 2,2'-(1,4butylene)-bis(2-oxazoline), and 2,2'-(1,4-phenylene)-bis(2-oxazoline).

[0062] Examples of the amino resin include melamine resin, benzoguanamine resin, and urea resin.

[0063] When the second agent contains other compounds, the amount of the compounds reactive with the acid group-containing olefin resin is preferably 60 mass % or less, more preferably 50 mass % or less, and even more preferably 20 mass % or less.

[0064] The amount of the compound reactive with the acid group-containing olefin resin is preferably adjusted so that the equivalent ratio (functional group (B) / functional group (A)) between the reactive functional group (A) contained in the first agent and the reactive functional group (B) contained in the second agent and capable of reacting with the functional group (A) of the first agent is in the range of 0.01 to 10, more preferably 0.01 to 5.0. This is preferable because it makes the laminate of the present invention more excellent in acid resistance and alkali resistance.

[0065] The adhesive used in the present invention preferably further contains an organic phosphorus compound. Examples of the organic phosphorus compound include organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, tris(4-butylphenyl)phosphine, diphenylphosphine, and phenylphosphine, and these compounds may be used alone or in combination of two or more.

[0066] The amount of the organic phosphorus compound is, for example, 0.01 to 5 parts by mass relative to 100 parts by mass of the resin of the first agent. This is preferable because the laminate of the present invention has better acid resistance and alkali resistance. When the amount of the organic phosphorus compound reaches a certain amount, the effect begins to saturate, so it is more preferable that the amount is 0.01 to 0.5 parts by mass, and more preferably 0.01 to 0.1 parts by mass, relative to 100 parts by mass of the resin of the first agent.

[0067] The organophosphorus compound may be blended in advance in the first or second agent, or may be added when the first and second agents are mixed.

[0068] The adhesive used in the present invention preferably further contains an imidazole compound, such as 2-methylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, etc., which may be used alone or in combination of two or more.

[0069] The amount of the imidazole compound is, for example, 0.06 parts by mass or more and 0.5 parts by mass or less relative to 100 parts by mass of the resin of the first agent. This is preferable because the laminate of the present invention has better acid resistance and alkali resistance. The amount of the imidazole compound is more preferably 0.06 parts by mass or more and 0.35 parts by mass or less, and more preferably 0.06 parts by mass or more and 0.30 parts by mass or less relative to 100 parts by mass of the resin of the first agent.

[0070] The imidazole compound may be blended in advance in the first agent, or may be added when the first agent and the second agent are mixed.

[0071] The reason why the laminate of the present invention has excellent acid resistance and alkali resistance is not clear, but is presumed to be as follows. When the contents contain compounds with high acidity or basicity, these compounds may penetrate the sealant film and attack the adhesive layer. Crystalline olefin resins have excellent resistance to such components, but if their melting point is too high, their adhesiveness is poor. If the melting point of the olefin resin is not so high, the adhesive layer melts during heat sealing to make a bag out of the laminate, and both are unsuitable as a laminate for packaging materials. In the laminate of the present invention, the adhesive layer is formed using a two-component curing adhesive containing an acid group-containing olefin resin with a melting point of 40°C to 100°C and an epoxy compound with a viscosity of 3000mPa·s or less at 70°C, thereby efficiently improving the heat resistance of the cured coating film, i.e., the adhesive layer, while maintaining the adhesiveness, and a laminate with excellent acid and alkali resistance can be obtained.

[0072] In addition to the above components, the adhesive used in the present invention preferably further contains an organic solvent. This ensures fluidity and allows the adhesive to exhibit appropriate coatability. Such organic solvents are not particularly limited as long as they can be removed by volatilization through overheating in the drying process when the adhesive is applied, and examples of such organic solvents include aromatic organic solvents such as toluene and xylene; aliphatic organic solvents such as n-hexane and n-heptane; alicyclic organic solvents such as cyclohexane and methylcyclohexane; halogenated organic solvents such as trichloroethylene, dichloroethylene, chlorobenzene and chloroform; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester-based solvents such as ethyl acetate and butyl acetate; ethanol, methanol, n-propanol, 2-propanol (isopropyl alcohol), and the like. Examples of suitable solvents include alcohol-based solvents such as diethanolamine, butanol, and hexanol; ether-based solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, and butyl carbitol; glycol ether-based solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and propylene glycol monomethyl ether; and glycol ester-based solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more.

[0073] It is preferable to use a mixed solvent of an alicyclic organic solvent and an ester solvent because it has excellent solubility of the acid group-containing resin. In particular, when an olefin resin having an acid group or an acid anhydride group is used as the acid group-containing resin, it is preferable to use a mixed solvent of methylcyclohexane and ethyl acetate because it has excellent solubility. Furthermore, in order to improve the solubility of the acid group-containing resin, a mixed solvent of an alicyclic organic solvent, an ester solvent, and an alcohol solvent may be used. In this case, isopropyl alcohol, 2-butanol, etc. are preferable as the alcohol solvent.

[0074] In order to improve the solubility of the epoxy compound, an aromatic organic solvent or a ketone solvent may be used in combination with the mixed solvent of the alicyclic organic solvent and the ester solvent. In this case, the aromatic organic solvent is preferably toluene, and the ketone solvent is preferably methyl ethyl ketone. The amount of the organic solvent used is preferably such that the ratio of the resin to the total mass of the resin and the organic solvent contained in the first agent is 5 to 30% by mass.

[0075] The adhesive used in the present invention may contain various additives, such as acid anhydrides, adhesion promoters, tackifiers, plasticizers, thermoplastic elastomers, reactive elastomers, phosphoric acid compounds, silane coupling agents, etc. The content of these additives may be appropriately adjusted within a range that does not impair the functions of the present invention.

[0076] Examples of the acid anhydride include cyclic aliphatic acid anhydrides, aromatic acid anhydrides, and unsaturated carboxylic acid anhydrides, and can be used alone or in combination of two or more. More specifically, for example, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic acid anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, polysebacic acid anhydride, poly(ethyl octadecanedioic acid) anhydride, poly(phenyl hexadecanedioic acid) anhydride, tetrahydrophthalic acid anhydride, methyl tetrahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methyl hymic acid anhydride, trialkyl tetrahydrophthalic acid anhydride, Examples of the anhydride include methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, HET anhydride, nadic anhydride, methylnadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride.

[0077] In addition, the above-mentioned compounds may be modified with glycol as the acid anhydride. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols may be used.

[0078] The amount of the acid anhydride may be adjusted as appropriate, but for example, it is 0.01 parts by mass or more, more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the resin contained in the first agent. Also, for example, the amount of the acid anhydride is 10 parts by mass or less, more preferably 8 parts by mass or less, more preferably 1.5 parts by mass or less, relative to 100 parts by mass of the resin contained in the first agent. This is preferable because it provides better adhesion between the adhesive layer and the substrate.

[0079] Examples of the adhesion promoter include tertiary amines such as triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undecene (DBU), 1,5-diazabicyclo[4.3.0]-nonene, 6-dibutylamino-1,8-diazabicyclo[5.4.0]undecene, compounds represented by the following structural formulas (5) to (15), and compounds obtained by converting these tertiary amines into amine salts with phenol, octylic acid, quaternized tetraphenylborate salts, etc., and cationic catalysts such as triallylsulfonium hexafluoroantimonate and diaryliodonium hexafluoroantimonate. These may be used alone or in combination of two or more. In the following structural formulas (5) to (15), the hydrogen atoms bonded to the carbon atoms are omitted.

[0080] [ka]

[0081] Examples of the tackifier include rosin-based or rosin ester-based tackifiers, terpene-based or terpene phenol-based tackifiers, saturated hydrocarbon resins, coumarone-based tackifiers, coumarone-indene-based tackifiers, styrene resin-based tackifiers, xylene resin-based tackifiers, phenol resin-based tackifiers, petroleum resin-based tackifiers, etc. These may be used alone or in combination of two or more.

[0082] Plasticizers include polyisoprene, polybutene, and procell oil, while thermoplastic elastomers include styrene-butadiene copolymer (SBS), hydrogenated styrene-butadiene copolymer (SEBS), SBBS, hydrogenated styrene-isoprene copolymer (SEPS), styrene block copolymer (TPS), and olefin elastomer (TPO), while reactive elastomers include those elastomers that have been acid-modified.

[0083] Examples of the phosphoric acid compound include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid; condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid; monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, Examples of such mono- and diesters include di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite, and the like; mono- and diesters of condensed phosphoric acids and alcohols; addition products of epoxy compounds such as ethylene oxide and propylene oxide to the above-mentioned phosphoric acids; and epoxy phosphoric acid esters obtained by adding the above-mentioned phosphoric acids to aliphatic or aromatic diglycidyl ethers.

[0084] Examples of silane coupling agents include aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; epoxysilanes such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, and the like.

[0085] The adhesive can be prepared by mixing the above-mentioned components. In this case, each component may be mixed at the same time to prepare an adhesive, or, for example, components other than the compound reactive with the acid group-containing olefin resin are mixed in advance to prepare a premixture, and when using the adhesive, a compound reactive with the acid group-containing olefin resin is mixed to prepare a two-liquid type adhesive, or a three-liquid type (or more) adhesive is prepared by mixing a first agent mainly composed of a resin containing an acid group-containing olefin, a second agent mainly composed of a compound reactive with the acid group-containing olefin resin, and a third agent containing other components (for example, an organic phosphorus compound and an imidazole compound) just before using the adhesive, which is preferable because it has excellent stability and workability of the adhesive.

[0086] (Configuration example) The laminate of the present invention includes a substrate, a sealant film, and an adhesive layer disposed between the substrate and the sealant film in contact with the sealant film, and the adhesive layer may be as described above. On the side of the adhesive layer opposite to the sealant film, only one substrate may be provided, or multiple substrates may be provided.

[0087] Examples of the configuration of the laminate of the present invention include: (1) PET film / adhesive layer / aluminum foil / adhesive layer / LLDPE film (2) PET film / adhesive layer / aluminum foil / adhesive layer / barrier sealant (3) PET film / adhesive layer / aluminum foil / adhesive layer / PET film / adhesive layer / LLDPE film (4) PET film / adhesive layer / aluminum foil / adhesive layer / PET film / adhesive layer / barrier sealant (5) PET film / adhesive layer / aluminum foil / adhesive layer / nylon film / adhesive layer / LLDPE film (6) PET film / adhesive layer / aluminum foil / adhesive layer / nylon film / adhesive layer / barrier sealant (7) PET film / adhesive layer / nylon film / adhesive layer / aluminum foil / adhesive layer / LLDPE film (8) PET film / adhesive layer / nylon film / adhesive layer / aluminum foil / adhesive layer / barrier sealant (9) PET film / adhesive layer / aluminum-deposited PET film / adhesive layer / nylon film / adhesive layer / LLDPE film (10) PET film / adhesive layer / aluminum-deposited PET film / adhesive layer / nylon film / adhesive layer / barrier sealant (11) OPP film / adhesive layer / aluminum-deposited PET film / adhesive layer / LLDPE film (12) OPP film / adhesive layer / aluminum-deposited PET film / adhesive layer / barrier sealant These include, but are not limited to, the following:

[0088] The adhesive layer other than the adhesive layer arranged in contact with the sealant film may be the same as the above-mentioned adhesive layer or may be different. If it is different from the above-mentioned adhesive layer, the adhesive layer can be formed using a two-liquid curing adhesive composed of a polyol composition and a polyisocyanate composition, or a two-liquid curing adhesive composed of a base material containing a polyolefin having a reactive functional group such as an acid group or a hydroxyl group, and a curing agent containing a functional group capable of reacting with the reactive functional group of the olefin resin, such as an epoxy resin or a compound such as polyisocyanate.

[0089] (Printing layer) The laminate of the present invention may have a printed layer (a desired printed pattern consisting of characters, figures, designs, symbols, etc.) at any position of the laminate. The printed layer is preferably provided on the front side (the side opposite to the contents) or back side (the side facing the contents) of the substrate that will be the outermost layer when the laminate of the present invention is made into a bag and filled with contents. The printed layer can be formed by a conventionally known method, for example, a gravure printing method, an offset printing method, a letterpress printing method, a silk screen printing method, or other printing methods.

[0090] (Method of manufacturing laminate) The laminate of the present invention is obtained by applying the above-mentioned adhesive of the present invention to one of the substrate and the sealant film, laminating the other, and curing the adhesive. After applying the adhesive, it is preferable to provide a drying step before laminating the substrate and the sealant film.

[0091] The adhesive can be applied using a gravure coater, a microgravure coater, a reverse coater, a bar coater, a roll coater, a die coater, etc. The amount of adhesive applied is such that the applied weight after drying is 0.5 to 20.0 g / m. 2 It is preferable to adjust the thickness so that it is 0.5 g / m 2 If the coating rate falls below 20.0 g / m, the continuous uniform coating property is likely to decrease. 2 If the content exceeds this range, the solvent releasability after coating will decrease, and problems such as decreased workability and residual solvent will easily occur.

[0092] The temperature of the laminating roll when laminating the substrate and the sealant film is, for example, 25° C. to 120° C., and more preferably 40° C. to 120° C. The pressure of the laminating roll is 3 to 300 kg / cm. 2 It is preferable that: In addition, after the substrate and the sealant film are bonded together, an aging step is preferably performed. The aging temperature is, for example, 25° C. to 100° C., and more preferably 60° C. to 100° C. The aging time is appropriately adjusted, and is, for example, 12 to 240 hours.

[0093] (packaging material) The packaging material of the present invention is produced by making a bag from the laminate of the present invention. Examples of the bag-making method include folding or stacking the laminate of the present invention so that the inner layer surface (sealant film surface) faces each other, and heat-sealing the peripheral edge, for example, by a side seal type, a two-sided seal type, a three-sided seal type, a four-sided seal type, an envelope seal type, a grooving seal type, a pleated seal type, a flat bottom seal type, a square bottom seal type, a gusset type, or other heat seal type. The packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. Self-supporting packaging materials (standing pouches) are also possible. Heat sealing can be performed by known methods such as bar seal, rotary roll seal, belt seal, impulse seal, high frequency seal, and ultrasonic seal.

[0094] The packaging material of the present invention is filled with contents through its opening, and the opening is then heat-sealed to produce a product using the packaging material of the present invention. The contents to be filled may include, but are not limited to, dusts, wettable powders, water dispersible granules, fine granules, fine granules, granules, tablets, floating granules contained in individual water-soluble film packages, and the like, each containing an active ingredient in agrochemicals.

[0095] The pesticide formulation contains one or more pesticide active ingredients. Specifically, the pesticidal active ingredients are organophosphorus pesticidal active ingredients such as acephate, isoxathion, cadusafos, chlorpyrifos, chlorpyrifos-methyl, dimethoate, diazinon, pirimiphos-methyl, fenitrothion, prothiofos, profenofos, phosalone, fosthiazate, malathion, mesulfenphos, methidathion, CYAP, DDVP, DEP, EPN, MPP, PAP, etc., carbamate pesticidal active ingredients such as oxamyl, carbosulfan, thiodicarb, benfuracarb, methomyl, BPMC, MIPC, NAC, etc. Insecticidal active ingredients include pyrethroid-based insecticidal active ingredients such as cyhalothrin, cyfluthrin, cypermethrin, tefluthrin, tralomethrin, bifenthrin, pyrethrins, fenvalerate, fenpropathrin, flucythrinate, fluvalinate, and permethrin; nereistoxin-based insecticidal active ingredients such as cartap, thiocyclam, and bensultap; and neonicotinoid-based insecticidal active ingredients such as imidacloprid, acetamiprid, clothianidin, dinotefuran, thiamethoxam, nitenpyram, and thiacloprid.

[0096] Examples of fungicidal active ingredients include IBP, thiuram, ziram, mancozeb, fthalide, TPN, and captan.

[0097] Examples of herbicidal active ingredients include butamiphos, MCPB, MCPP, MCPA, 2,4-PA, alachlor, phenmedipham, butachlor, pretilachlor, S-metolachlor, mefenacet, linuron, DCMU, potassium glyphosate, ammonium glyphosate, isopropylamine glyphosate, glufosinate, prometryn, atrazine, simazine, bensulfuron methyl, imazosulfuron, benzobicyclon, pentoxazone, pyrazolate, benthiocarb, bromobutide, dymron, and pyraclonil.

[0098] Since the packaging material of the present invention has excellent chemical resistance (acid resistance and alkali resistance), it can be suitably used for packaging contents that are highly acidic or basic, but it goes without saying that it can also be suitably used for other purposes. EXAMPLES

[0099] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. The blending compositions and other numerical values ​​are based on mass unless otherwise specified.

[0100] <Adjusting the adhesive> (Adhesive 1) 20 parts of GMP7550E, 0.01 parts of triphenylphosphine, and 0.2 parts of FTR-8120 were dissolved in a mixed solvent (cyclomethylhexane / ethyl acetate = 71 / 8) to a non-volatile content of 20%. Then, 0.5 parts of epoxy compound 1 was added and thoroughly stirred to prepare adhesive 1.

[0101] (Adhesive 2~6) Adhesives 2 to 6 were prepared in the same manner as adhesive 1, except that the formulation was changed to that shown in Table 1. The compounds used in preparing the adhesives are as follows. All values ​​in the table are solid contents.

[0102] (GMP7550E) Copolymer of unsaturated monomers including propylene and butene modified with maleic anhydride, melting point: 68.3℃, heat of fusion: 18.1mJ / mg, acid value: 29.4mgKOH / g (GMP7550N) Copolymer of unsaturated monomers including propylene and butene modified with maleic anhydride, melting point: 69.4℃, heat of fusion: 21.2mJ / mg, acid value: 51.2mgKOH / g (Cornova MPO A502) Copolymer of unsaturated monomers including propylene and butene modified with maleic anhydride, melting point: 155.3℃, heat of fusion: 25mJ / mg, acid value: 14.5mgKOH / g (Cornova MPO A201) Copolymer of unsaturated monomers including propylene and butene modified with maleic anhydride, solid content: 100%, melting point: 76.7℃, heat of fusion: 11.7mJ / mg, acid value: 15.7mgKOH / g (Epoxy compound 1) Polyglycidyl ether type epoxy resin of aliphatic polyol with a viscosity of 3000 mPa·s or less at 70℃ (Epoxy compound 2) Cycloaliphatic polyepoxy resin with a viscosity of 3000 mPa·s or less at 70℃ (Epoxy compound 3) Cresol novolac epoxy resin with a viscosity of more than 5000 mPa·s at 70℃ (FTR8120) Aromatic hydrocarbon resin (Mitsui Chemicals) (jER Cure YH-306) Trialkyltetrahydrophthalic anhydride (Mitsubishi Chemical)

[0103] The acid value of the acid group-containing olefin resin was measured using an FT-IR (JASCO Corporation, FT-IR4200) and was calculated by the coefficient (f) obtained from a calibration curve prepared using a chloroform solution of maleic anhydride, the stretching peak (1780 cm) of the anhydride ring of maleic anhydride in a maleic anhydride-modified polyolefin solution, and the -1 ) and the stretching peak of the carbonyl group of maleic acid (1720 cm -1 The absorbance (II) of maleic anhydride was calculated from the absorbance (II) of the maleic anhydride in the following formula: In the formula, the molecular weight of maleic anhydride was 98.06, and the molecular weight of potassium hydroxide was 56.11.

[0104]

number

[0105] [Table 1]

[0106] <Laminate> Example 1 The adhesive, which is made by mixing "Dick Dry LX-500" (DIC Corporation) as the base agent and "KW-75" (DIC Corporation) as the hardener at a weight ratio of base agent / hardener = 100 / 10, is applied to the matte surface of an aluminum foil with a thickness of 9 μm at a solid content of 3 g / m2.2 After drying at 80°C for 1 minute, a 12 μm-thick PET film was attached to the aluminum foil at 60°C. Next, adhesive 1 was applied to the glossy surface of the aluminum foil at a solid content of 3 g / m 2 After drying at 80° C. for 1 minute, the laminate was attached to an LLDPE film (film thickness: 60 μm) at 60° C. After aging at 70° C. for 3 days, a laminate of Example 1 was obtained.

[0107] (Examples 2 to 4) Laminates of Examples 2 to 4 were obtained in the same manner as in Example 1, except that adhesive 1 was replaced by adhesives 2 to 4.

[0108] (Examples 5 to 8) Laminates of Examples 5 to 8 were obtained in the same manner as in Examples 1 to 4, except that a 40 μm-thick barrier sealant (low-density polyethylene / cyclic polyolefin resin / low-density polyethylene) was used instead of the LLDPE film.

[0109] (Comparative Examples 1 to 6) Laminates of Comparative Examples 1 to 6 were obtained in the same manner except that adhesives 5 to 7 were used.

[0110] <Evaluation> (Measurement of initial adhesive strength) Using Shimadzu Corporation's Autograph AGS-J, the adhesive strength of the interface between the aluminum foil and the sealant film of the laminate was measured under the conditions of a peel speed of 300 mm / min, a peel width of 15 mm, and a peel angle of 180°. The results were evaluated according to the following criteria and summarized in the table. ○: 5N / 15mm or more △: 3N / 15mm or more, less than 5N / 15mm ×: 3N / 15mm or more or less

[0111] (acid resistance) The laminates of the examples and comparative examples were cut into 10 cm x 24 cm. The long side of the laminate was folded in half, and two sides were heat-sealed at 160°C for 1 second, after which 30 ml of citric acid aqueous solution adjusted to pH 3 was added, and the remaining side was heat-sealed to seal the three-sided seal. After standing at 50°C for 4 weeks, the pouch was opened, and the adhesive strength of the interface between the aluminum foil and the sealant film was measured in the same manner as in the measurement of the initial adhesive strength. The adhesive strength retention rate (adhesive strength after standing / initial adhesive strength) was calculated, evaluated according to the following criteria, and summarized in a table. Laminates whose initial adhesive strength was less than 3 N / 15 mm were not evaluated. ○: Adhesive strength retention rate 70% or more △: Adhesive strength retention rate is 40% or more but less than 70% ×: Adhesive strength retention rate less than 40%

[0112] (Alkaline resistance) The alkali resistance was examined in the same manner as in the acid resistance test, except that 30 ml of alkaline electrolyzed water adjusted to pH 11 was enclosed as the content. The adhesive strength retention rate (adhesive strength after standing / initial adhesive strength) was calculated, evaluated according to the following criteria, and summarized in a table. Note that no evaluation was performed on laminates whose initial adhesive strength was less than 3 N / 15 mm. ○: Adhesive strength retention rate 70% or more △: Adhesive strength retention rate is 40% or more but less than 70% ×: Adhesive strength retention rate less than 40%

[0113] [Table 2]

[0114] [Table 3]

[0115] As is clear from Tables 2 and 3, the laminate of the present invention exhibited excellent acid resistance and alkali resistance.

Claims

1. The present invention includes a substrate, a sealant film, and an adhesive layer disposed between the substrate and the sealant film and in contact with the sealant film, the adhesive layer is a cured coating film of a two-component curing adhesive containing an acid group-containing olefin resin having a melting point of 40° C. or more and 100° C. or less and an epoxy compound having a viscosity of 3000 mPa·s or less at 70° C., The thickness of the sealant film is 20 μm or more and 200 μm or less, The sealant film comprises a polyethylene resin.

2. 2. The laminate of claim 1, wherein the sealant film comprises low density polyethylene.

3. 2. The laminate according to claim 1, wherein the sealant film is a laminate of a polyethylene resin and a cyclic polyolefin resin.

4. 2. The laminate according to claim 1, wherein the sealant film is a laminate of a polyethylene resin and an ethylene-vinyl alcohol copolymer.

5. 2. The laminate according to claim 1, wherein the heat of fusion of the acid group-containing olefin resin is 0.1 mJ / mg or more and 50 mJ / mg or less.

6. The laminate of claim 1 further comprising a printed layer.

7. A packaging material comprising the laminate according to any one of claims 1 to 3.

8. A pharmaceutical packaging material comprising the laminate according to any one of claims 1 to 3.

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