Laminate for blister pack, blister pack

Abstract

The present invention provides: a multilayer body for blister packs, said multilayer body having excellent moisture-proof properties and preventing deterioration of the content due to ultraviolet light, while being not susceptible to the occurrence of a break during molding; and a blister pack.　A multilayer body for blister packs, said multilayer body being obtained by sequentially stacking a base material film, a first adhesive layer, an aluminum foil, a second adhesive layer and a sealant layer in this order, while being configured such that at least one of the first adhesive layer and the second adhesive layer is a cured coating film of a two-pack curable adhesive which contains a polyol composition (X) that contains a polyester polyol (A1) having a glass transition temperature of from -30°C to 80°C and a polyisocyanate composition (Y) that contains a polyisocyanate compound (B1) containing 50% by mass or less of an aliphatic isocyanate, wherein the ratio of the number of moles of isocyanate groups (NCO) contained in the polyisocyanate composition (Y) to the number of moles of hydroxyl groups (OH) contained in the polyol composition (X), namely (NCO) / (OH) is from 0.5 to 20.

Description

[Technical field]

[0001] The present invention relates to a laminate for a blister pack and a blister pack. [Background technology]

[0002] Conventionally, blister packs (also called press-through packaging or PTP packaging materials) have been known as containers for packaging items such as medicines, such as tablets and capsule preparations, and foods. A synthetic resin film is used as the container body of a blister pack, and aluminum foil is used as the lid material. A number of pockets are formed in the container body for individually storing tablets, etc. Synthetic resin films have good plasticity and excellent formability, so they are widely used as the material for the container body.

[0003] However, when the container body is made of a synthetic resin film, moisture easily penetrates the tablets, which can easily deteriorate them. In addition, most synthetic resin films are transparent, and the tablets can easily deteriorate when exposed to ultraviolet light. For this reason, a laminate of aluminum foil and a resin film is sometimes used as the material for the container body (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2004-058515 A [Patent Document 1] Special Publication No. 2008-535746 Summary of the Invention [Problem to be solved by the invention]

[0005] However, such a laminate has a problem in that peeling occurs between the aluminum foil and the resin film (particularly between the aluminum foil and the outer resin film) during the molding process of the pockets, making the laminate prone to tearing.

[0006] The present invention has been made in consideration of the above circumstances, and has an object to provide a laminate for blister packs and a blister pack which have excellent moisture resistance, prevent deterioration of the contents due to ultraviolet rays, and are less likely to break during molding. [Means for solving the problem]

[0007] That is, the present invention relates to a laminate for blister packs, which is a cured coating film of a two-component curing adhesive in which a base film, a first adhesive layer, an aluminum foil, a second adhesive layer, and a sealant layer are laminated in this order, and at least one of the first adhesive layer and the second adhesive layer comprises a polyol composition (X) containing a polyester polyol (A1) having a glass transition temperature of -30°C or more and 80°C or less, and a polyisocyanate composition (Y) containing a polyisocyanate compound (B1), in which the amount of aliphatic isocyanate in the polyisocyanate compound (B1) is 50 mass% or less, and the ratio [NCO] / [OH] of the number of moles of hydroxyl groups [OH] contained in the polyol composition (X) to the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (Y) is 0.5 or more and 20 or less, and a blister pack using the laminate. Effect of the Invention

[0008] According to the present invention, it is possible to provide a blister pack which has excellent moisture resistance, inhibits deterioration of the contents due to ultraviolet rays, and is less likely to break during molding. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <Laminate for blister packs> The laminate for blister packs of the present invention is a cured coating film of a two-component curing adhesive in which a base film, a first adhesive layer, an aluminum foil, a second adhesive layer, and a sealant layer are laminated in this order, and at least one of the first adhesive layer and the second adhesive layer contains a polyol composition (X) containing a polyester polyol (A1) having a glass transition temperature of -30°C to 80°C and a polyisocyanate compound (B1), the amount of aliphatic isocyanate in the polyisocyanate compound (B1) is 50 mass% or less, and the ratio [NCO] / [OH] of the number of moles of hydroxyl groups [OH] contained in the polyol composition (X) to the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (Y) is 0.5 to 20. Hereinafter, for convenience, this adhesive is referred to as a two-component curing adhesive (Z). In this specification, the laminate for blister packs refers to a laminate used for molding a blister pack before the contents are sealed. The configuration of the present invention will be described in detail below, taking as an example a case in which the first adhesive layer is a cured coating film of a two-component curing adhesive (Z).

[0010] (Base film) The outer layer of the laminate of the present invention (the layer disposed on the opposite side of the aluminum foil from the contents) is made of a film having excellent puncture resistance. Specific examples of the base film include polyamide film and polyester film.

[0011] The polyamide film is not particularly limited, and any of the conventionally known polyamide films can be used. For example, poly(4-aminobutyric acid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6, also poly(caprolactam)), poly(7-aminoheptanoic acid) (nylon 7), poly(8-aminooctanoic acid) (nylon 8), poly(9-aminononanoic acid) (nylon 9), poly(10-aminodecanoic acid) (nylon 10), poly(11-aminoundecanoic acid) (nylon 11), poly(12-aminododecanoic acid) (nylon 12), and the like. Homopolymers such as nylon 12, nylon 4,6, poly(hexamethylene adipamide) (nylon 6,6), poly(hexamethylene sebacamide) (nylon 6,10), poly(heptamethylene pimelamide) (nylon 7,7), poly(octamethylene suberamide) (nylon 8,8), poly(hexamethylene azelamide) (nylon 6,9), poly(nonamethylene azelamide) (nylon 9,9), poly(decamethylene azelamide) (nylon 10,9), poly(tetramethylphenyl azelamide) (nylon 11,12), Polyamides of n-dodecanedioic acid and hexamethylenediamine (nylon 6,12), Polyamides of n-dodecanedioic acid and hexamethylenediamine (nylon 12,12), Caprolactam / hexamethylene adipamide copolymers (nylon 6,6 / 6), Hexamethylene adipamide / caprolactam copolymers (nylon 6 / 6,6), Trimethylene adipamide / hexamethylene azelaamide copolymers (nylon trime 6,2 / 6,2], hexamethylene adipamide-hexamethylene-azelaamide caprolactam copolymer [nylon 6,6 / 6,9 / 6], poly(tetramethylenediamine-co-isophthalic acid) [nylon 4,I], polyhexamethylene isophthalamide [nylon 6,1], hexamethylene adipamide / hexamethylene-isophthalamide [nylon 6,6 / 6I], hexamethylene adipamide / hexamethylene terephthalamide [nylon 6,6 / 6T], poly(2,2,Examples of the polyamide copolymers include poly(2-trimethylhexamethylene terephthalamide), poly(m-xylylene adipamide) [MXD6], poly(p-xylylene adipamide), poly(hexamethylene terephthalamide), poly(dodecamethylene terephthalamide), polyamide 6T / 6I, polyamide 6 / MXDT / I, and polyamide MXDI. Nylon 6, nylon 6,6, nylon 6 / 6,6, or mixtures thereof are preferred.

[0012] Examples of the polyester film include polyethylene terephthalate and glycol-modified polyethylene terephthalate.

[0013] The thickness of the substrate film is not particularly limited, but from the viewpoint of the balance between formability and puncture resistance, it is preferably from 10 μm to 50 μm, and more preferably from 20 μm to 45 μm. The substrate film is produced by a tubular method or a tenter method, and is produced by biaxial stretching. The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching.

[0014] (aluminum foil) The aluminum foil may be a soft material made of pure aluminum or an aluminum-iron alloy. Specific examples of the alloy include alloy numbers 8079 and 8021. The thickness of the aluminum foil may be adjusted as appropriate, but is preferably 15 μm to 80 μm, more preferably 20 μm to 60 μm, from the viewpoint of the balance between formability and moisture resistance.

[0015] The aluminum foil may be chemically treated on either one or both sides. Examples of chemical treatment include undercoat treatment using a coupling agent such as a silane coupling agent or a titanium coupling agent, and chromate treatment. Examples of chromate treatment include a method of coating a composition containing, for example, phosphoric acid, at least one of chromate and chromic acid (III) salt, and at least one selected from the group consisting of a metal salt of fluoride, a nonmetal salt of fluoride, an acrylic resin, a chitosan derivative resin, and a phenol resin on the surface of the aluminum foil that has been degreased, and then drying the composition.

[0016] (Sealant layer) The sealant layer may be a polypropylene film, a polyvinyl chloride film, or a polyvinylidene chloride film. The thickness of the sealant layer is, for example, from 20 μm to 150 μm in terms of the balance between heat sealability and moldability.

[0017] (First adhesive layer) The first adhesive layer is a cured coating of the two-component curing adhesive (Z). The first adhesive layer is disposed between the polyamide film and the aluminum foil, and serves to bond them together.

[0018] The glass transition temperature of the polyester polyol (A1) is from −30° C. to 80° C. The glass transition temperature is measured as follows. Using a differential scanning calorimeter (DSC-7000 manufactured by SII Nano Technology Co., Ltd., hereafter referred to as DSC), 5 mg of sample is heated from room temperature to 200°C at 10°C / min under a nitrogen gas flow of 30 mL / min, and then cooled to -80°C at 10°C / min. The temperature is again raised to 150°C at 10°C / min to measure the DSC curve, and the intersection point between the line extending the low-temperature side baseline in the measurement results observed in the second heating process to the high-temperature side and the tangent drawn at the point where the gradient of the curve of the step-like part of the glass transition is maximum is taken as the glass transition point, and the temperature at this point is taken as the glass transition temperature. In addition, the temperature is raised to 200°C in the first heating, but this should be a temperature at which the polyester polyol (A1) is sufficiently melted, and if 200°C is insufficient, it should be adjusted appropriately. Similarly, if the cooling temperature is insufficient at -80°C (e.g., if the glass transition temperature is lower), it should be adjusted appropriately.

[0019] When the glass transition temperature of the polyester polyol (A1) is within the above range, a laminate for blister packs having an excellent balance between the wettability of the two-component curing adhesive (Z) to a substrate and the hardness of the cured coating film and excellent adhesion, formability, and heat resistance can be obtained.

[0020] The polyester polyol (A1) is a reaction product of a composition containing a polybasic acid or its derivative and a polyhydric alcohol. The polybasic acid or its derivative used in the synthesis of the polyester polyol includes aliphatic polycarboxylic acids such as malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, succinic anhydride, alkenyl succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, dimer acid, and trimer acid;

[0021] Alkyl esters of aliphatic polycarboxylic acids, such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;

[0022] alicyclic polycarboxylic acids such as 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, himic anhydride, and HET anhydride;

[0023] Aromatic polycarboxylic acids such as orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, naphthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic dianhydride, 5-sodium sulfoisophthalic acid, tetrachlorophthalic anhydride, and tetrabromophthalic anhydride;

[0024] methyl esters of aromatic polycarboxylic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate; and the like. These may be used alone or in combination of two or more.

[0025] The polyhydric alcohol used to prepare the polyester polyol (A1) may be a diol or a polyol having three or more functional groups. Examples of the diol include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol, and dimer diol;

[0026] Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;

[0027] modified polyether diols obtained by ring-opening polymerization of the aliphatic diols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether;

[0028] lactone-based polyester polyols obtained by polycondensation reaction of the aliphatic diols with various lactones such as lactanoids and ε-caprolactone;

[0029] Bisphenols such as bisphenol A and bisphenol F;

[0030] Examples of the alkylene oxide adducts include those obtained by adding ethylene oxide, propylene oxide, or the like to bisphenols such as bisphenol A and bisphenol F.

[0031] The tri- or higher functional polyols include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;

[0032] modified polyether polyols obtained by ring-opening polymerization of the aliphatic polyols with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether;

[0033] Examples of the polyol include lactone-based polyester polyols obtained by polycondensation reaction of the above-mentioned aliphatic polyols with various lactones such as ε-caprolactone.

[0034] In view of excellent heat resistance, the polybasic acid preferably contains an aromatic polybasic carboxylic acid or an alkyl ester of an aromatic polybasic carboxylic acid (hereinafter, these are collectively referred to as aromatic polybasic carboxylic acid). Of the polybasic acids, the aromatic polybasic carboxylic acid is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more. The entire amount of the polybasic acid may be an aromatic polybasic carboxylic acid.

[0035] The polyester polyol (A1) may be a polyester polyurethane polyol which is a reaction product of a composition containing a polyisocyanate compound in addition to the above-mentioned polybasic acid and polyhydric alcohol. Alternatively, the polyester polyol obtained from the above-mentioned polybasic acid and polyhydric alcohol may be urethane-extended with a polyisocyanate compound. The polyisocyanate compound used in this case may be the same as the polyisocyanate compound (B1) exemplified below, and may be used alone or in combination.

[0036] The solid content hydroxyl value of the polyester polyol (A1) is preferably 1.0 to 40.0 mgKOH / g, more preferably 1.0 to 30.0 mgKOH / g, and still more preferably 3.0 to 25.0 mgKOH / g, in order to achieve excellent adhesive strength and a crosslinking density suitable for molding.

[0037] The solid acid value of the polyester polyol (A1) is not particularly limited, but is, for example, 10 mgKOH / g or less. The lower limit is preferably as low as possible, but from the viewpoint of reactivity, it is difficult to introduce hydroxyl groups to all ends of the polyester polyol (A), and some of the ends become carboxyl groups. Therefore, the solid acid value is substantially 1.0 mgKOH / g or more, and when the reaction is controlled by using an excess of polyhydric alcohol with respect to a polybasic acid or its derivative having an aromatic ring, it is often 0.5 mgKOH / g or more. The hydroxyl value and acid value can be measured by the method described in JIS-K0070.

[0038] If the number average molecular weight (Mn) of the polyester polyol (A1) is too small, the crosslinking density may become too high, and moldability may decrease. It can be appropriately adjusted depending on the degree of the desired moldability, and as an example, it is preferably 3,000 to 100,000, more preferably 3,500 to 50,000, more preferably 4,000 to 20,000, and more preferably 5,000 to 20,000. The weight average molecular weight (Mw) of the polyester polyol (A1) is preferably 5,000 to 300,000, and more preferably 10,000 to 200,000. In this specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0039] 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℃ Developing 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

[0040] The amount of polyester polyol (A1) in the solid content of the polyol composition (X) is preferably 20% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. The entire amount of the solid content of the polyol composition (X) may be polyester polyol (A1). This makes it possible to more reliably obtain a laminate for blister packs having excellent moldability.

[0041] The polyol composition (X) may contain a polyol (A2) other than the polyester polyol (A1). Examples of the polyol (A2) include polyester polyol, polycarbonate polyol, and polyoxyalkylene-modified polyol. The number average molecular weight of these polyols (A2) is, for example, 300 to 50,000. The amount of the polyol (A2) in the solid content of the polyol composition (X) is preferably 20 mass% or less. In particular, by using a polyol having a glass transition temperature of 80°C (but not including 80°C) to 110°C or less in combination, the adhesive strength, moldability, and heat resistance are improved.

[0042] The polyisocyanate compound (B1) is not particularly limited as long as it is a compound having a plurality of isocyanate groups in one molecule. Examples of such polyisocyanate compound (B1) include polyisocyanates having an aromatic structure in the molecular structure, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and xylylene diisocyanate, and compounds in which a part of the NCO groups of these polyisocyanates are modified with carbodiimide;

[0043] Polyisocyanates with alicyclic structures in their molecular structure, such as isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), and 1,3-(isocyanatomethyl)cyclohexane;

[0044] Linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate, and compounds in which some of the NCO groups of these polyisocyanates have been modified with carbodiimide;

[0045] Examples of the polyisocyanates include isocyanurates of these polyisocyanates; allophanates of these polyisocyanates; biuret forms of these polyisocyanates; adducts of these polyisocyanates modified with trimethylolpropane; and polyurethane polyisocyanates which are reaction products of these polyisocyanates and polyols.

[0046] The polyisocyanate compound (B1) may be one of the polyisocyanates described above or a combination of two or more of them, but the amount of aliphatic isocyanate in the polyisocyanate compound (B1) is 50 mass% or less. This makes it possible to obtain a laminate for blister packs with excellent heat resistance. In this specification, the aliphatic isocyanate is a general term for polyisocyanates having an alicyclic structure in the molecular structure, linear aliphatic polyisocyanates, compounds in which a part of the NCO groups of these isocyanates are modified with carbodiimide, isocyanurates, allophanates, biuret bodies, adducts, and polyurethane polyisocyanates of these isocyanates.

[0047] The two-component curing adhesive (Z) may contain a coupling agent (C). This allows the adhesive to have better moldability. The effect of the coupling agent (C) is particularly effective when the aluminum foil has not been subjected to a chemical conversion treatment. Examples of the coupling agent (C) include a silane coupling agent (C1), a titanate-based coupling agent (C2), and an aluminum-based coupling agent (C3). The coupling agent (C) may be added to the polyol composition (X) or the polyisocyanate composition (Y). It may be added when the polyol composition (X) and the polyisocyanate composition (Y) are mixed.

[0048] Examples of the silane coupling agent (C1) 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, γ-glycidoxypropyltriethoxysilane, and glycidoxyoctyltrimethoxysilane; vinyltris(β-methoxy Examples of suitable silane coupling agents include vinyl silanes such as triethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, octenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane; polymeric epoxysilanes in which a plurality of alkoxysilyl groups and a plurality of epoxy groups are introduced into a polymer backbone, and polymeric aminosilanes in which a plurality of alkoxysilyl groups and a plurality of amino groups are introduced into a polymer backbone; and hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. These silane coupling agents (C1) can be used alone or in combination of two or more kinds.

[0049] Examples of the titanate coupling agent (C2) include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxytitanium.

[0050] Examples of the aluminum-based coupling agent (C3) include acetoalkoxyaluminum diisopropylate.

[0051] The amount of the coupling agent (C) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.7 parts by mass or more, relative to 100 parts by mass of the solid content of the polyol composition (X). This makes it possible to more reliably improve moldability. In addition, since the degree of improvement in moldability decreases when the content of the coupling agent (C) exceeds a certain amount, there is no particular restriction, but it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less, relative to 100 parts by mass of the solid content of the polyol composition (X).

[0052] The two-component curing adhesive (Z) may contain an epoxy resin. When the two-component curing adhesive (Z) contains an epoxy resin, a laminate having excellent moldability and initial adhesive strength can be obtained.

[0053] Examples of epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins such as biphenyl type epoxy resins and tetramethylbiphenyl type epoxy resins; and dicyclopentadiene-phenol addition reaction type epoxy resins. It is preferable to use an epoxy resin having a number average molecular weight (Mn) of 300 to 2,000. It is also preferable to use an epoxy resin having an epoxy equivalent of 150 to 1,000 g / equivalent. The amount of the epoxy resin blended is preferably 30 mass % or less of the solid content of the polyol composition (X).

[0054] The two-component curing adhesive (Z) may contain a tackifier. The tackifier may be added to the polyol composition (X), the polyisocyanate composition (Y), or when they are mixed. 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, and petroleum resin-based tackifiers. These may be used alone or in combination of two or more. Tackifiers having various softening points are obtained mainly depending on the molecular weight, but the softening point is preferably 50 to 160°C in terms of compatibility when mixed with other resins constituting the polyol composition (X), color tone, thermal stability, and the like. It is used in the range of 1 to 30 parts by mass (solid content) per 100 parts by mass of the solid content of the resin constituting the polyol composition (X), and preferably in the range of 3 to 20 parts by mass, and particularly preferably 5 to 20 parts by mass (solid content).

[0055] The two-component curing adhesive (Z) may contain phosphoric acid or a derivative thereof. This improves the initial adhesion and can suppress problems such as tunneling. The phosphoric acid or a derivative thereof may be added to the polyol composition (X) or the polyisocyanate composition (Y). It may be added when these are mixed.

[0056] Examples of phosphoric acids or derivatives thereof 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, diphenyl orthophosphate, and dimethyl orthophosphate. Examples of such phosphate esters include mono- and diesters of dimethyl phosphate, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite, etc.; mono- and diesters of condensed phosphoric acid and alcohols; addition products of epoxy compounds such as ethylene oxide and propylene oxide to the above-mentioned phosphoric acids; and epoxy phosphates obtained by adding the above-mentioned phosphoric acids to aliphatic or aromatic diglycidyl ethers. Two or more of these can also be used in combination.

[0057] The two-component curing adhesive (Z) may contain a ketone resin. The ketone resin is a resin obtained by reacting a ketone compound with an aldehyde in the presence of an alkaline catalyst. Examples of the ketone compound include cyclohexanone, methylcyclohexanone, acetophenone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the aldehyde include formaldehyde, acetaldehyde, n-butyl aldehyde, isobutyl aldehyde, valerianaldehyde, and dodecanal.

[0058] When the two-component curing adhesive (Z) contains a ketone resin, peeling between the base film and the aluminum foil, and between the sealant layer and the aluminum foil, is suppressed, and a laminate for blister packs with excellent formability can be obtained. The amount of the ketone resin to be added is preferably from 1 to 20 parts by mass per 100 parts by mass of the above-mentioned polyester polyol (A1).

[0059] The two-component curing adhesive (Z) may be in the form of either a solvent type or a solventless type. In the case of a solvent type, at least one of the polyol composition (X) and the polyisocyanate composition (Y) contains an organic solvent such as esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc., ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, etc., ethers such as tetrahydrofuran, dioxane, etc., aromatic hydrocarbons such as toluene, xylene, etc., halogenated hydrocarbons such as methylene chloride, ethylene chloride, etc., dimethyl sulfoxide, dimethyl sulfamide, etc., and the above-mentioned components are dissolved in the organic solvent. These organic solvents may be used as they are as reaction media during the production of the above-mentioned components, or may be added separately.

[0060] In the case of a solventless type, the adhesive does not substantially contain the organic solvents listed above. Note that if the organic solvent used as a reaction medium during the production of each component of the adhesive is not completely removed and remains, it is considered that the adhesive does not substantially contain an organic solvent.

[0061] In the case of solventless adhesives, low viscosity is important because of the property of lowering the viscosity by heating, and the molecular weight and molecular structure of the polyester polyol (A1) and the polyisocyanate compound (B1) that can be used are limited. If the structure derived from aromatic polycarboxylic acid incorporated in the polyester polyol (A1) increases or if the polyisocyanate compound (B1) has an aromatic ring, the viscosity increases and the coating suitability tends to decrease in order to make it a solventless adhesive. For this reason, it is preferable to use a solvent type.

[0062] In addition, the two-component adhesive (Z) may contain various additives such as ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, rheology control agents, defoamers, antistatic agents, and antifogging agents.

[0063] The polyol composition (X) and the polyisocyanate composition (Y) are used in such a manner that the ratio [NCO] / [OH] of the total number of moles of hydroxyl groups contained in the polyol composition (X) [OH] to the number of moles of isocyanate groups contained in the polyisocyanate composition (Y) [NCO] is in the range of 0.5 to 20. This makes it possible to obtain a laminate for blister packs with excellent moldability. In order to obtain a more excellent initial adhesive strength, [NCO] / [OH] is preferably 0.8 to 15, more preferably 0.8 to 10.

[0064] When the [NCO] / [OH] ratio becomes high, excess isocyanate compound reacts with moisture in the atmosphere to form urea bonds, improving heat resistance, but the cured coating film tends to become harder and its moldability tends to decrease. If the [NCO] / [OH] ratio is too low, the crosslink density will be low, and the heat resistance will decrease. Also, the amount of polyisocyanate compound (B1) in the two-component curing adhesive (Z) will inevitably be small, making it difficult for the two-component curing adhesive (Z) to sufficiently wet and spread over the substrate during aging, which may result in a decrease in adhesive strength.

[0065] The thickness of the first adhesive layer is preferably 0.5 μm or more and 50 μm or less, and more preferably 2 μm or more and 30 μm or less, from the viewpoint of the balance between adhesiveness and moldability.

[0066] (Second adhesive layer) The second adhesive layer is disposed between the aluminum foil and the sealant layer, and is a layer for bonding them together. The second adhesive layer is a cured coating film of an adhesive, and the adhesive used is not particularly limited as long as it is suitable for bonding the aluminum foil and the above-mentioned film, and for example, a general-purpose two-component curing adhesive made of a polyol compound and a polyisocyanate compound, or a two-component curing adhesive made of an acid-modified polyolefin and a curing agent that can react with it can be used.

[0067] The thickness of the second adhesive layer is preferably 0.5 μm or more and 50 μm or less, and more preferably 2 μm or more and 30 μm or less, from the viewpoint of the balance between adhesiveness and moldability.

[0068] (Modification) Although the above description has been given with reference to an example in which the first adhesive layer is a two-component curing adhesive (Z), the laminate for blister packs of the present invention may have a first adhesive layer that is a general-purpose two-component curing adhesive made of a polyol compound and a polyisocyanate compound, or a two-component curing adhesive made of an acid-modified polyolefin and a curing agent that can react with the first adhesive layer, and the second adhesive layer may be a cured coating film of the two-component curing adhesive (Z). Both the first adhesive layer and the second adhesive layer may be a cured coating film of the two-component curing adhesive (Z). It is preferable that the first adhesive layer is a cured coating film of the two-component curing adhesive (Z) because of its superior moldability and heat resistance, and it is more preferable that both the first adhesive layer and the second adhesive layer are cured coating films of the two-component curing adhesive (Z).

[0069] (Method of manufacturing laminate for blister pack) The method for producing the laminate for blister packs of the present invention is not particularly limited. As an example, when the two-component curing adhesive (including the two-component curing adhesive (Z)) is a solvent-based adhesive, it is produced by the following method. First, the above-mentioned two-component curing adhesive is applied to either the base film or the aluminum foil by extrusion, gravure coating, roll coating, or the like, and the organic solvent is evaporated, and then the other is laminated. Next, the two-component curing adhesive is applied to the aluminum foil, the organic solvent is evaporated, and then a sealant layer is laminated, and aging is performed at room temperature to 90°C for 2 days to 2 weeks to cure the adhesive, thereby obtaining the laminate for blister packs of the present invention. Alternatively, aging may be performed under the above-mentioned conditions after laminating the base film and the aluminum foil, and aging may be further performed after laminating the aluminum foil and the sealant layer.

[0070] When the adhesive is a solventless type, for example, a two-component curing adhesive is applied to either the base film or the aluminum foil, and then the base film and the aluminum foil are laminated together, and aging is performed for 2 days to 2 weeks at room temperature to 90° C. Next, the two-component curing adhesive is applied to the aluminum foil, and the aluminum foil and the sealant layer are laminated together, and aging is performed under the same conditions to cure the adhesive, thereby obtaining the laminate for blister packs of the present invention.

[0071] <Blister pack> The blister pack of the present invention is obtained by molding the laminate for blister packs described above. The laminate for blister packs of the present invention may be molded to have one or more pockets and a conventionally known lid material for blister packs (for example, aluminum foil coated with a heat seal agent) may be bonded to the molded laminate for blister packs of the present invention, or two laminates for blister packs of the present invention each having one or more pockets are prepared, the pockets are brought together, and the heat seal layers are heat sealed to each other. Examples of the molding method include flat plate air pressure molding, plug-assisted air pressure molding, drum vacuum molding, and plug molding. EXAMPLES

[0072] The present invention will be described in more detail below with reference to specific synthesis examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" respectively represent "parts by mass" and "% by mass" unless otherwise specified.

[0073] <Synthesis of polyester polyol> (Synthesis Example 1) Synthesis of polyester polyol (A1-1) In a flask equipped with a stirring rod, a temperature sensor, and a rectifying tube, 1102 parts of isophthalic acid, 473 parts of terephthalic acid, 1070 parts of 1,6-hexanediol, 156 parts of neopentyl glycol, and 0.46 parts of an organic titanium compound ("Orgatics TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.) were charged, and dry nitrogen was introduced into the flask while stirring, and the temperature was raised to 240°C while distilling off the generated water. Thereafter, the esterification reaction was carried out while increasing the degree of vacuum to 30 torr, and the reaction was stopped when the resin acid value became 2.00 mgKOH / g or less. After cooling to 150°C, the mixture was diluted with a mixed solution of ethyl acetate and toluene (mixture ratio 1:1) to a resin solid content of 50%, yielding a polyester polyol (A1-1') with a number average molecular weight (Mn) of 4,000, a weight average molecular weight (Mw) of 9,700, a resin hydroxyl value (solid content equivalent) of 38.8 mg KOH / g, a resin acid value (solid content equivalent) of 0.63 mg KOH / g, and a glass transition temperature (Tg) of 2.8°C.

[0074] A flask equipped with a stirring rod, a temperature sensor, and a condenser was charged with 1,000 parts of the polyester polyol (A1-1'), 25.7 parts of hexamethylene diisocyanate ("Desmodur H" manufactured by Sumika Covestro Urethane Co., Ltd.), and 0.16 parts of an organotin compound ("Neostan U-130" manufactured by Nitto Kasei Co., Ltd.), and dry nitrogen was introduced into the flask, and the mixture was heated to 75 to 78°C with stirring to carry out a chain extension reaction. The reaction was stopped when the isocyanate weight percentage reached 0.05% or less, and the mixture was diluted with a mixed solvent of ethyl acetate and toluene (mixture ratio 1:1) to a resin solid content of 50%, yielding a polyester polyol (A1-1) with a number average molecular weight (Mn) of 11,000, a weight average molecular weight (Mw) of 50,000, a resin hydroxyl value (solid content equivalent) of 3.9 mg KOH / g, a resin acid value (solid content equivalent) of 1.06 mg KOH / g, and a glass transition temperature (Tg) of 7.1°C.

[0075] (Synthesis Example 2) Synthesis of polyester polyol (A1-2) A flask equipped with a stirring rod, a temperature sensor, and a rectifying tube was charged with 1,261 parts of isophthalic acid, 540 parts of terephthalic acid, 667 parts of 1,6-hexanediol, 182 parts of neopentyl glycol, 253 parts of ethylene glycol, and 0.5 parts of an organic titanium compound ("Orgatics TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.), and dry nitrogen was introduced into the flask with stirring. The temperature was raised to 240°C while distilling off the generated water. The esterification reaction was then carried out while increasing the vacuum to 30 torr. The reaction was stopped when the resin acid value reached 2.00 mgKOH / g or less. After cooling to 150°C, the mixture was diluted with a mixed solution of ethyl acetate and toluene (mixture ratio 1:1) to a resin solid content of 50%. A polyester polyol (A1-2) having a number average molecular weight (Mn) of 6,700, a weight average molecular weight (Mw) of 17,000, a resin hydroxyl value (solid content equivalent) of 17.2 mgKOH / g, a resin acid value (solid content equivalent) of 1.58 mgKOH / g, and a glass transition temperature (Tg) of 23.6°C was obtained.

[0076] (Synthesis Example 4) Polyester polyol (A1-3) A flask equipped with a stirring rod, a temperature sensor, and a rectification tube was charged with 790.8 parts of isophthalic acid, 339.4 parts of terephthalic acid, 20.0 parts of trimellitic anhydride, 738.0 parts of 1,6-hexanediol, 107.4 parts of neopentyl glycol, and 4.0 parts of an organic titanium compound ("Orgatics TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.), and dry nitrogen was introduced into the flask, and the mixture was heated to 230-240°C with stirring to carry out an esterification reaction. The reaction was stopped when the resin acid value reached 1.50 mgKOH / g or less, and the mixture was cooled to 150°C. Then, the mixture was diluted with ethyl acetate to a resin solid content of 58%. A polyester polyol (A1-3) having a number average molecular weight (Mn) of 7,000, a weight average molecular weight (Mw) of 23,500, a resin hydroxyl value (solid content equivalent) of 22.4 mgKOH / g, a resin acid value (solid content equivalent) of 1.26 mgKOH / g, and a glass transition point (Tg) of 7.3°C was obtained.

[0077] (Synthesis Example 5) Polyester polyol (A2-1) A flask equipped with a stirring rod, a temperature sensor, and a rectifying tube was charged with 164 parts of neopentyl glycol, 1,125 parts of 1,6-hexanediol, 351 parts of terephthalic acid, 351 parts of isophthalic acid, 928 parts by weight of adipic acid, and 0.89 parts by weight of an organic titanium compound. Dry nitrogen was introduced into the flask with stirring, and the temperature was raised to 240° C. while distilling off the generated water. Thereafter, the esterification reaction was carried out while increasing the degree of vacuum to 30 torr, and the reaction was stopped when the resin acid value reached 2.00 mgKOH / g or less. After cooling to 150°C, the mixture was diluted with ethyl acetate to a resin solids content of 60% to obtain a polyester polyol (A2-1) having a number average molecular weight (Mn) of 5,200, a weight average molecular weight (Mw) of 32,000, a resin hydroxyl value (solid content equivalent) of 6.6 mgKOH / g, a resin acid value (solid content equivalent) of 1.86 mgKOH / g, and a glass transition temperature (Tg) of -43.6°C.

[0078] (Synthesis Example 6) Polyester polyol (A2-2) A flask equipped with a stirring rod, a temperature sensor, and a rectifying tube was charged with 73 parts of ethylene glycol, 223 parts of 1,2-propylene glycol, 697 parts of terephthalic acid, and 0.89 parts of an organic titanium compound, and dry nitrogen was introduced into the flask while stirring, and the temperature was raised to 240 ° C. while distilling off the generated water. Thereafter, an esterification reaction was carried out while increasing the degree of vacuum to 30 torr, and the reaction was stopped when the resin acid value became 2.00 mg KOH / g or less, and after cooling to 150 ° C., the resin was diluted with ethyl acetate to a resin solid content of 30%, and a polyester polyol (A2-2) having a number average molecular weight (Mn) of 8,400, a weight average molecular weight (Mw) of 61,300, a resin hydroxyl value (solid content equivalent) of 5.0 mg KOH / g, a resin acid value (solid content equivalent) of 4.0 mg KOH / g, and a glass transition temperature (Tg) of 84 ° C. was obtained.

[0079] <Preparation of two-component curing adhesive> Example 1 KBM-403 (a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., non-volatile content: 100%) was added to polyester polyol (A1-1) to obtain the composition (solid content) shown in Table 1, and the mixture was stirred thoroughly until the KBM-403 was completely dissolved. To this was added a trimethylolpropane adduct of toluene diisocyanate (referred to as TDI-TMP in the table; NCO%: 13.3) and ethyl acetate so that the non-volatile content was 25%, and the mixture was stirred thoroughly to produce the two-component curing adhesive of Example 1.

[0080] (Example 2) to (Example 5), (Comparative Example 1) to (Comparative Example 4) A two-component curing adhesive was prepared in the same manner as in Example 1, except that the polyester polyol used and the amount (solid content) were changed as shown in Tables 1 and 2. Among the compounds in the table, those not explained above are summarized as follows. [NCO] / [OH] is rounded to one decimal place. (TEGO Variplus AP) EVONIC, ketone-aldehyde condensation resin, hydroxyl value: 5mgKOH / g (E402-80E) Duranate E402-80E, manufactured by Asahi Kasei Corporation, adduct of hexamethylene diisocyanate, NCO%: 9.5%

[0081] <Production of laminate for blister pack> Example 1 The adhesive of Example 1 was applied at 4 g / m2 to the matte surface of an aluminum foil with a thickness of 30 μm using a dry laminator. 2 (solid content), and after volatilizing the solvent, a stretched polyamide film having a thickness of 25 μm was laminated. Next, the adhesive of Example 1 was applied to the glossy surface of the aluminum foil using a dry laminator at a rate of 4 g / m 2 After the solvent was evaporated, the film was laminated with an unstretched polypropylene film having a thickness of 40 μm and aged at 60° C. for 5 days to harden the adhesive, thereby obtaining a laminate of Example 1.

[0082] (Example 2) to (Example 5), (Comparative Example 1) to (Comparative Example 4) Laminates were obtained in the same manner as in Example 1, except that the adhesive of Example 1 was replaced with the adhesives of Examples 2 to 5 and Comparative Examples 1 to 4.

[0083] <Evaluation> (Adhesive strength) The adhesive strength between polyamide film and aluminum foil was evaluated using Shimadzu Corporation's Autograph AGS-J under the following conditions: peel speed 50mm / min, peel width 15mm, and peel form 180° peel. The higher the value, the more suitable it is for a laminate for blister packs.

[0084] (Moldability) Using a 1 ton tabletop servo press (SBN-1000) manufactured by Yamaoka Seisakusho Co., Ltd., the laminate for blister pack of the Example or Comparative Example was cut to a size of 60 x 60 mm. The polyamide film was placed on the convex side, and overhang molding was performed with a molding height of 3.5 mm using a straight mold with a free molding height, and moldability was evaluated based on the presence or absence of breakage of the aluminum foil and lifting between each layer. The punch shape of the mold used was a square with one side of 30 mm, a corner R of 2 mm, and a punch shoulder R of 1 mm, and the die hole shape of the mold used was a square with one side of 34 mm, a die hole corner R of 2 mm, a die hole shoulder R: 1 mm, and the clearance between the punch and the die hole was 0.3 mm on one side. The clearance causes a slope according to the molding height. ◯: No breakage of the aluminum foil or lifting between layers, excellent for practical use △: Pinholes were observed in the aluminum foil, but there was no break in the aluminum foil or lift between the layers, so it was within the practical range. ×: The aluminum foil is largely broken or there is lift between the layers.

[0085] (Heat resistance) The laminate of the example or comparative example was cut to a size of 60 x 60 mm, and the polyamide film was placed on the outside, and the laminate was bulged at a molding height of 3.0 mm using a free-form straight mold. A heat seal bar was applied to the flange of the resulting 30 mm square tray at 190°C for 3 seconds so as to contact the side wall, and the appearance near the boundary between the flange and the side wall on each side was confirmed, and it was evaluated whether or not there was any lift between the stretched polyamide film and the aluminum foil. Two samples were prepared, and a total of eight sides were checked, and the results were evaluated on a three-level scale as follows. ○: No lifting (excellent for practical use) △: Lifting occurs on 1 to 4 of the 8 sides (practical range) ×: Lifting occurs on 5 to 8 of the 8 sides

[0086] [Table 1]

[0087] [Table 2]

Claims

1. A base film, a first adhesive layer, an aluminum foil, a second adhesive layer, and a sealant layer are laminated in this order, At least one of the first adhesive layer and the second adhesive layer contains a polyester polyol (A1) having a glass transition temperature of -30°C or more and 80°C or less and an acid value of 10 mgKOH / g or less, a polyol composition (X) that does not contain an epoxy resin, and a polyisocyanate composition (Y) that contains a polyisocyanate compound (B1), the amount of aliphatic isocyanate in the polyisocyanate compound (B1) is 50 mass% or less, the polyisocyanate compound (B1) is a trimethylolpropane adduct of toluene diisocyanate, and the ratio [NCO] / [OH] of the number of moles of hydroxyl groups [OH] contained in the polyol composition (X) to the number of moles of isocyanate groups [NCO] contained in the polyisocyanate composition (Y) is 0.5 or more and 20 or less. A laminate for blister packs.

2. The laminate for blister packs according to claim 1, wherein the polyol composition (X) further contains a polyol (A2) having a glass transition temperature of 80° C. (but not including 80° C.) to 110° C. or less, and the blending amount of the polyester polyol (A1) in the solid content of the polyol composition (X) is 20 mass% or more.

3. 3. The laminate for blister packs according to claim 1, wherein the polyester polyol is a reaction product of a composition containing a polybasic acid or a derivative thereof and a polyhydric alcohol, and 30% by mass or more of the polybasic acid or a derivative thereof is an aromatic polycarboxylic acid.

4. The laminate for blister packs according to any one of claims 1 to 3, wherein the first adhesive layer is a cured coating film of the two-component curing adhesive.

5. The laminate for blister packs according to any one of claims 1 to 4, wherein the second adhesive layer is a cured coating film of the two-component curing adhesive.

6. The laminate for blister packs according to any one of claims 1 to 5, wherein the two-component curing adhesive contains a coupling agent (C).

7. The laminate for blister packs according to any one of claims 1 to 6, wherein the base film is either a polyamide film or a polyester film.

8. The laminate for blister packs according to any one of claims 1 to 7, wherein the sealant layer is any one of a polypropylene film, a polyvinyl chloride film, and a polyvinylidene chloride film.

9. A blister pack produced by molding the laminate for blister packs according to any one of claims 1 to 8.

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