WO2022130992A1 - ブリスターパック用積層体、ブリスターパック - Google Patents
ブリスターパック用積層体、ブリスターパック Download PDFInfo
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- WO2022130992A1 WO2022130992A1 PCT/JP2021/044186 JP2021044186W WO2022130992A1 WO 2022130992 A1 WO2022130992 A1 WO 2022130992A1 JP 2021044186 W JP2021044186 W JP 2021044186W WO 2022130992 A1 WO2022130992 A1 WO 2022130992A1
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- WO
- WIPO (PCT)
- Prior art keywords
- acid
- blister pack
- adhesive layer
- film
- laminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
- B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
- B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
- B65D75/36—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents one sheet or blank being recessed and the other formed of relatively stiff flat sheet material, e.g. blister packages, the recess or recesses being preformed
Definitions
- the present invention relates to a blister pack laminate and a blister pack.
- blister packs also referred to as press-through packaging or PTP packaging material
- containers for packaging drugs such as tablets and capsules and stored items such as foods.
- a synthetic resin film is used as the container body of the blister pack, and aluminum foil is used as the lid material.
- the container body is formed with a plurality of pockets for individually storing tablets and the like. Since the synthetic resin film has good plasticity and excellent moldability, the synthetic resin film is widely used as a material for the container body.
- Patent Documents 1 and 2 a laminate of aluminum foil and a resin film is also used as the material of the container body.
- such a laminated body has a problem that peeling occurs between the aluminum foil and the resin film (particularly the aluminum foil and the outer resin film) when the pocket is molded, and the laminated body is easily broken.
- the present invention has been made in view of such circumstances, and provides a blister pack laminate and a blister pack which are excellent in moisture resistance, prevent deterioration of the contents due to ultraviolet rays, and are less likely to break during molding.
- the purpose is to do.
- the base film, the first adhesive layer, the aluminum foil, the second adhesive layer, and the sealant layer are laminated in this order, and at least the first adhesive layer and the second adhesive layer are laminated.
- One contains a polyol composition (X) containing a polyester polyol (A1) having a glass transition temperature of ⁇ 30 ° C. or higher and 80 ° C. or lower, and a polyisocyanate composition (Y) containing a polyisocyanate compound (B1).
- the blending amount of the aliphatic isocyanate in the isocyanate compound (B1) is 50% by mass or less, and the number of moles [OH] of the hydroxyl group contained in the polyol composition (X) and the isocyanate group contained in the polyisocyanate composition (Y).
- a laminate for blister pack which is a cured coating film of a two-component curable adhesive in which the ratio [NCO] / [OH] to the number of moles [NCO] is 0.5 or more and 20 or less, is used. Regarding the blister pack that was there.
- a blister pack that has excellent moisture resistance, suppresses deterioration of the contents due to ultraviolet rays, and is less likely to break during molding.
- the base film, the first adhesive layer, the aluminum foil, the second adhesive layer, and the sealant layer are laminated in this order, and the first adhesive layer and the second adhesive layer are laminated in this order.
- At least one of the adhesive layers of the above contains a polyol composition (X) containing a polyester polyol (A1) having a glass transition temperature of ⁇ 30 ° C. or higher and 80 ° C. or lower, and a polyisocyanate compound (B1), and the polyisocyanate compound (B1).
- the blending amount of the aliphatic isocyanate to the above is 50% by mass or less, and the number of moles of hydroxylates [OH] contained in the polyol composition (X) and the number of moles of isocyanate groups contained in the polyisocyanate composition (Y) [NCO]. ] And a ratio [NCO] / [OH] of 0.5 or more and 20 or less, which is a cured coating film of a two-component curable adhesive.
- this adhesive will be referred to as a two-component curable adhesive (Z).
- the laminated body for a blister pack means a laminated body used for molding a blister pack before the contents are enclosed.
- the configuration of the present invention will be described in detail by taking as an example the case where the first adhesive layer is a cured coating film of a two-component curable adhesive (Z).
- Base film A film having excellent puncture resistance is used for the outer layer of the laminate of the present invention (the layer arranged on the side opposite to the contents with the aluminum foil sandwiched between them).
- Specific examples of the base film include a polyamide film and a polyester film.
- the polyamide film is not particularly limited, and conventionally known ones can be used, for example, poly (4-aminobutyric acid) [nylon 4], poly (6-aminohexanoic acid) [nylon 6, or poly (caprolactam)]. , Poly (7-aminoheptanoic acid) [Nylon 7], Poly (8-Aminooctanoic acid) [Nylon 8], Poly (9-Aminononanonic acid) [Nylon 9], Poly (10-Aminodecanoic acid) [Nylon 10] , Poly (11-aminoundecanic acid) [Nylon 11], Poly (12-Aminododecanic acid) [Nylon 12] and other homopolymers, Nylon 4,6, Poly (hexamethylene adipamide) [Nylon 6,6 ], Poly (Hexamethylene Sebacamide) [Nylon 6,10], Poly (Heptamethylenepimelamide) [Nylon 7,7], Poly (Octamethylenesveramide) [Nylon 8,8], Poly (
- polyester film examples include polyethylene terephthalate and glycol-modified polyethylene terephthalate.
- the film thickness of the base film is not particularly limited, but is preferably 10 ⁇ m or more and 50 ⁇ m or less, and more preferably 20 ⁇ m or more and 45 ⁇ m or less, from the viewpoint of the balance between moldability and puncture resistance.
- the base film is manufactured by the tubular method or the tenter method, and is manufactured by biaxial stretching.
- the stretching method may be simultaneous biaxial stretching or sequential biaxial stretching.
- Al foil As the aluminum foil, a soft material made of pure aluminum or an aluminum-iron alloy can be used. Specific examples of the alloy include alloy numbers 8079 and 8021.
- the film thickness of the aluminum foil can be adjusted as appropriate, but from the viewpoint of the balance between moldability and moisture resistance, it is preferably 15 ⁇ m or more and 80 ⁇ m or less, and more preferably 20 ⁇ m or more and 60 ⁇ m or less.
- the aluminum foil may be subjected to chemical conversion treatment on either one or both sides.
- the chemical conversion treatment include an undercoat treatment using a coupling agent such as a silane coupling agent and a titanium coupling agent, and a chromate treatment.
- a coupling agent such as a silane coupling agent and a titanium coupling agent
- a chromate treatment for example, phosphoric acid, at least one of chromium acid and chromium (III) salt, a metal salt of fluoride, a non-metal salt of fluoride, and an acrylic resin are applied to the surface of the degreased aluminum foil.
- a method of applying and drying a composition containing at least one selected from the group consisting of a chitosan derivative resin and a phenol resin is exemplified.
- sealant layer any one of polypropylene film, polyvinyl chloride film, and polyvinylidene chloride film is used.
- the film thickness of the sealant layer is, for example, 20 ⁇ m or more and 150 ⁇ m or less from the viewpoint of the balance between heat sealability and moldability.
- the first adhesive layer is a cured coating film of a two-component curable adhesive (Z).
- the first adhesive layer is arranged between the polyamide film and the aluminum foil, and these are also bonded together.
- the glass transition temperature of the polyester polyol (A1) is ⁇ 30 ° C. or higher and 80 ° C. or lower.
- the glass transition temperature is measured as follows. Using a differential scanning calorimetry device (DSC-7000 manufactured by SII Nanotechnology Co., Ltd., hereinafter referred to as DSC), 5 mg of the sample was heated from room temperature to 200 ° C. at 10 ° C./min under a nitrogen stream of 30 mL / min. After that, it is cooled to ⁇ 80 ° C. at 10 ° C./min.
- DSC-7000 differential scanning calorimetry device manufactured by SII Nanotechnology Co., Ltd.
- the DSC curve was measured by raising the temperature to 150 ° C at 10 ° C / min again, and the straight line extending the baseline on the low temperature side to the high temperature side in the measurement results observed in the second temperature rise step and the glass transition staircase.
- the intersection with the tangent line drawn at the point where the slope of the curve of the shaped portion is maximized is defined as the glass transition point, and the temperature at this time is defined as the glass transition temperature.
- the temperature is raised to 200 ° C. at the first temperature rise, but this may be a temperature at which the polyester polyol (A1) is sufficiently melted, and if 200 ° C. is insufficient, the temperature is appropriately adjusted.
- the cooling temperature is not sufficient at ⁇ 80 ° C. (for example, when the glass transition temperature is lower), the cooling temperature is appropriately adjusted.
- the two-component curable adhesive (Z) has an excellent balance between the wettability to the substrate and the hardness of the cured coating film, and has excellent adhesiveness and molding. It can be a laminated body for a blister pack having excellent properties and heat resistance.
- the polyester polyol (A1) is a reaction product of a composition containing a polybasic acid or a derivative thereof and a polyhydric alcohol.
- the polybasic acid or its derivative used for the synthesis of polyester polyols include malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, succinic anhydride, alkenyl succinic acid anhydride, glutaric acid, and the like.
- An aliphatic polyvalent carboxylic acid such as adipic acid, pimelli acid, suberic acid, azelaic acid, sebasic acid, fumaric acid, malonic acid, maleic anhydride, itaconic acid, dimer acid, trimeric acid;
- An aliphatic polyvalent carboxylic acid such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelic acid, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, etc.
- Alkyl esterified product of acid such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelic acid, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, etc.
- 1,1-Cyclopentanedicarboxylic acid 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Tetrahydrohydric acid anhydride, 4-methylhexahydrophthalic acid anhydride, hexahydrohydric acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydrous, hymic acid anhydride, het acid anhydride and the like.
- Group polyvalent carboxylic acid
- Examples thereof include methyl esterified products of aromatic polyvalent carboxylic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylic acid; and the like can be used alone or in combination of two or more.
- the polyhydric alcohol used for preparing the polyester polyol (A1) may be a diol or a trifunctional or higher functional polyol, and the diol may be ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2.
- Ether glycol such as polyoxyethylene glycol and polyoxypropylene glycol
- a lactone-based polyester polyol obtained by a polycondensation reaction between the aliphatic diol and various lactones such as lactanoid and ⁇ -caprolactone;
- Bisphenols such as bisphenol A and bisphenol F;
- Examples thereof include alkylene oxide adducts of bisphenol obtained by adding ethylene oxide, proprene oxide and the like to bisphenols such as bisphenol A and bisphenol F.
- Trifunctional or higher functional polyols are aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;
- Examples thereof include a lactone-based polyester polyol obtained by a polycondensation reaction between the aliphatic polyol and various lactones such as ⁇ -caprolactone.
- the polybasic acid contains an aromatic polyvalent carboxylic acid or an alkyl esterified product of an aromatic polyvalent carboxylic acid (hereinafter, these are collectively referred to as an aromatic polyvalent carboxylic acid).
- aromatic polyvalent carboxylic acid is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 60% by mass or more.
- the total amount of the polybasic acid may be an aromatic polyvalent carboxylic acid.
- 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.
- it may be a polyester polyurethane polyol obtained by urethane-extending a polyester polyol obtained from the above-mentioned polybasic acid and polyhydric alcohol with a polyisocyanate compound.
- the polyisocyanate compound used at this time the same ones as exemplified as the polyisocyanate compound (B1) described later can be used alone or in combination of two or more.
- the solid content hydroxyl value of the polyester polyol (A1) is preferably 1.0 to 40.0 mgKOH / g, preferably 1.0 to 30.0 mgKOH / g, because it has excellent adhesive strength and a crosslink density suitable for molding. It is more preferably g, and more preferably 3.0 to 25.0 mgKOH / g.
- the solid acid value of the polyester polyol (A1) is not particularly limited, but as an example, 10. It is mgKOH / g or less. It is preferable that the lower limit is as small as possible, but from the viewpoint of reactivity, it is difficult to introduce a hydroxyl group at all the ends of the polyester polyol (A), and a part of the ends becomes a carboxyl group. Therefore, when the solid content acid value is substantially 1.0 mgKOH / g or more, and the reaction is carried out by using an excessive amount of polyhydric alcohol with a polybasic acid having an aromatic ring or a derivative thereof, the production is controlled. Often, it is 0.5 mgKOH / g or more.
- the hydroxyl value and acid value can be measured by the method described in JIS-K0070.
- the number average molecular weight (Mn) of the polyester polyol (A1) is too small, the crosslink density becomes too high and the moldability may decrease. It can be appropriately adjusted depending on the degree of moldability of interest, but as an example, it is preferably 3,000 to 100,000, more preferably 3,500 to 50,000, and 4,000 to 20,000. Is more preferable, and 5,000 to 20,000 is more preferable.
- the weight average molecular weight (Mw) of the polyester polyol (A1) is preferably 5,000 to 300,000, more preferably 10,000 to 200,000. In the present 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.
- Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation Detector; RI (Differential Refractometer) Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions; Column temperature 40 ° C Developing solvent Tetrahydrofuran flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; Tetrahydrofuran solution of 0.2% by mass in terms of resin solid content filtered through a microfilter (100 ⁇ l)
- the blending amount of the polyester polyol (A1) is preferably 20% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. preferable.
- the total solid content of the polyol composition (X) may be the polyester polyol (A1). This makes it possible to more reliably obtain a laminated body for a blister pack having excellent moldability.
- the polyol composition (X) may contain a polyol (A2) other than the polyester polyol (A1).
- the polyol (A2) include polyester polyols, polycarbonate polyols, polyoxyalkylene modified polyols and the like.
- the number average molecular weight of these polyols (A2) is, for example, 300 to 50,000.
- the blending amount of the polyol (A2) is preferably 20% by mass or less.
- the combined use of a polyol having a glass transition temperature of 80 ° C. (but not including 80 ° C.) to 110 ° C. or lower improves adhesive strength, moldability, and heat resistance.
- the polyisocyanate compound (B1) is not particularly limited as long as it is a compound having a plurality of isocyanate groups in one molecule.
- Such a polyisocyanate compound (B1) has an aromatic structure in the molecular structure of tolylene diisocyanate, diphenylmethane diisocyanate, polypeptide diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, triphenylmethane triisocyanate, xylylene diisocyanate and the like.
- Linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate, compounds in which some of the NCO groups of these polyisocyanates are modified with carbodiimide;
- Isocyanurates of these polyisocyanates are reaction products of these polyisocyanates and polyols. And so on.
- the above-mentioned polyisocyanates can be used alone or in combination of two or more, but the blending amount of the aliphatic isocyanate in the polyisocyanate compound (B1) is 50% by mass. It is as follows. This makes it possible to obtain a laminated body for a blister pack having excellent heat resistance.
- the aliphatic isocyanate is a polyisocyanate having an alicyclic structure in the molecular structure, a linear aliphatic polyisocyanate, a compound obtained by modifying a part of these NCO groups with carbodiimide, and isocyanates of these isocyanates. It is a general term for nurate-form, allophanate-form, billet-form, adduct-form, and polyurethane polyisocyanate.
- the two-component curable adhesive (Z) may contain a coupling agent (C). This makes it possible to obtain an adhesive having better moldability.
- the effect of the coupling agent (C) is particularly effective when the aluminum foil is not subjected to chemical conversion treatment.
- 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 may be added to the polyisocyanate composition (Y). It may be added when mixing the polyol composition (X) and the polyisocyanate composition (Y).
- silane coupling agent (C1) examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ (aminoethyl).
- )-Aminosilanes such as ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, Epoxysilanes such as ⁇ -glycidoxypropyltriethoxysilane and glycidoxyoctyltrimethoxysilane; vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, octenyltrimethoxysilane, ⁇ -methacry Vinyl silanes such as loxypropyltrimethoxysilane and methacryoxyoctyltrimethoxysilane; polymer-type epoxysilanes in which multiple alkoxy
- silane coupling agents such as polymer-type aminosilanes into which a group has been introduced; hexamethyldisilazane, ⁇ -mercaptopropyltrimethoxysilane, 3-isocyandiapropyltriethoxysilane and the like can be mentioned.
- These silane coupling agents (C1) can be used alone or in combination of two or more.
- titanate-based coupling agent (C2) examples include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrasteer.
- Examples of the aluminum-based coupling agent (C3) include acetalkoxyaluminum diisopropyrate.
- the blending amount of the coupling agent (C) is preferably 0.1 part by mass or more, and more preferably 0.3 part by mass or more with respect to 100 parts by mass of the solid content of the polyol composition (X). , 0.5 parts by mass or more, more preferably 0.7 parts by mass or more. This makes it possible to improve the moldability more reliably. Further, since the degree of improvement in moldability decreases when the content of the coupling agent (C) exceeds a certain amount, there is no particular limitation, but the content is 10 mass with respect to 100 parts by mass of the solid content of the polyol composition (X). The amount is preferably parts or less, more preferably 8 parts by mass or less, and further preferably 5 parts by mass or less.
- the two-component curable adhesive (Z) may contain an epoxy resin. Since the two-component curable adhesive (Z) contains an epoxy resin, a laminate having excellent moldability and initial adhesive strength can be obtained.
- the epoxy resin examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resin and tetramethyl biphenyl type epoxy resin; dicyclopentadiene-phenol addition reaction type epoxy.
- examples include resin. It is preferable to use an epoxy resin having a number average molecular weight (Mn) of 300 to 2,000. Further, it is preferable to use one having an epoxy equivalent of 150 to 1,000 g / equivalent.
- the blending amount of the epoxy resin is preferably 30% by mass or less of the solid content of the polyol composition (X).
- the two-component curable adhesive (Z) may contain a tackifier.
- the tackifier may be added to the polyol composition (X), may be added to the polyisocyanate composition (Y), or may be added when mixing them.
- the tackifier include a rosin-based or rosin ester-based tackifier, a terpene-based or terpene-phenol-based tackifier, a saturated hydrocarbon resin, a kumaron-based tackifier, a kumaron inden-based tackifier, and a styrene resin-based tackifier.
- Examples thereof include an agent, a xylene resin-based tackifier, a phenol resin-based tackifier, and a petroleum resin-based tackifier. These may be used alone or in combination of two or more.
- a tackifier having various softening points can be obtained mainly depending on the molecular weight, but it is softened in terms of compatibility, color tone, thermal stability, etc. when mixed with other resins constituting the polyol composition (X).
- the point is preferably 50 to 160 ° C. It is used in the range of 1 to 30 parts by mass (solid content) with respect to 100 parts by mass of the solid content of the resin constituting the polyol composition (X), and 3 to 20 parts by mass, particularly 5 to 20 parts by mass (solid content). It is preferable to use it in a range.
- the two-component curable adhesive (Z) may contain phosphoric acids or derivatives thereof. As a result, the initial adhesiveness is improved, and troubles such as tunneling can be suppressed. Phosphoric acids or derivatives thereof may be added to the polyol composition (X) or may be added to the polyisocyanate composition (Y). These may be added when mixing.
- Examples of phosphoric acids or derivatives thereof include phosphoric acids such as hypophosphoric acid, phosphoric acid, orthophosphoric acid, and hypophosphoric acid, for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid.
- phosphoric acids such as hypophosphoric acid, phosphoric acid, orthophosphoric acid, and hypophosphoric acid
- condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid.
- Monobutyl Acid Mono-2-Ethylhexyl Phosphate, Monophenyl Hydrophosphate, Di-2-ethylhexyl Orthosphate, Diphenyl Diphenyl Phosphate Phosphate Dimethyl Phosphate, Diethyl Phosphate, Dipropyl Phosphate, Dibutyl Phosphate, Sub Monos such as di-2-ethylhexyl phosphate and diphenyl phosphite, diesterates, monos from condensed phosphoric acid and alcohols, diesterates, for example, the above phosphoric acids, for example, epoxy compounds such as ethylene oxide and propylene oxide. Examples thereof include phosphoric acid esters obtained by adding the above-mentioned phosphoric acid to an aliphatic or aromatic diglycidyl ether, and two or more of them can be used in combination.
- the two-component curable adhesive (Z) may contain a ketone resin.
- the ketone resin is a resin obtained by reacting a ketone compound and an aldehyde in the presence of an alkaline catalyst.
- the ketone compound include cyclohexanone, methylcyclohexanone, acetophenone, methyl ethyl ketone, and methyl isobutyl ketone.
- Examples of the aldehyde include formaldehyde, acetaldehyde, n-butyraldehyde, isobutyraldehyde, valerian aldehyde, dodecanal and the like.
- the two-component curable adhesive (Z) contains a ketone resin, peeling between the base film and the aluminum foil, and the sealant layer and the aluminum foil is suppressed, resulting in a blister pack laminate having excellent moldability. be able to.
- the blending amount of the ketone resin is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyester polyol (A1) described above.
- the two-component curable adhesive (Z) may be in either a solvent type or a solventless type.
- solvent type at least one of the polyol composition (X) or the polyisocyanate composition (Y) is an ester such as ethyl acetate, butyl acetate or cellosolve acetate, or a ketone such as acetone, methyl ethyl ketone, isobutyl ketone or cyclohexanone.
- ethers such as tetrahydrofuran and dioxane
- aromatic hydrocarbons such as toluene and xylene
- halogenated hydrocarbons such as methylene chloride and ethylene chloride
- organic solvents such as dimethylsulfoxide and dimethylsulfoamide.
- the solvent-free type does not substantially contain the organic solvents mentioned above. If the organic solvent used as the reaction medium for each component of the adhesive is not completely removed and remains, it is understood that the organic solvent is not substantially contained.
- the solvent-free type low viscosity is emphasized due to the characteristic that the viscosity is lowered 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 the aromatic polyvalent carboxylic acid incorporated in the polyester polyol (A1) increases, or if the polyisocyanate compound (B1) has an aromatic ring, the viscosity increases and the adhesive becomes a solvent-free adhesive. The coating suitability tends to decrease. Therefore, the solvent type is preferable.
- the two-component adhesive (Z) contains various additives such as ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, rheology control agents, defoaming agents, antistatic agents, and antifogging agents. It may be contained.
- the polyol composition (X) and the polyisocyanate composition (Y) are the total number of moles [OH] of hydroxyl groups contained in the polyol composition (X) and the molars of isocyanate groups contained in the polyisocyanate composition (Y). It is used in the range where the ratio [NCO] / [OH] to the number [NCO] is 0.5 or more and 20 or less. This makes it possible to obtain a laminated body for a blister pack having excellent moldability.
- the [NCO] / [OH] is preferably 0.8 or more and 15 or less, and more preferably 0.8 or more and 10 or less because the initial adhesive strength is more excellent.
- the film thickness of the first adhesive layer is preferably 0.5 ⁇ m or more and 50 ⁇ m or less, and more preferably 2 ⁇ m or more and 30 ⁇ m or less, from the viewpoint of the balance between adhesiveness and moldability.
- the second adhesive layer is a layer that is arranged between the aluminum foil and the sealant layer and adheres them.
- 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 adhering an aluminum foil to the above-mentioned film, for example, from a polyol compound and a polyisocyanate compound.
- a general-purpose two-component curable adhesive or a two-component curable adhesive composed of an acid-modified polyolefin and a curing agent capable of reacting with the acid-modified polyolefin can be used.
- the film thickness of the second adhesive layer is preferably 0.5 ⁇ m or more and 50 ⁇ m or less, and more preferably 2 ⁇ m or more and 30 ⁇ m or less, from the viewpoint of the balance between adhesiveness and moldability.
- the first adhesive layer is a two-component curable adhesive (Z)
- the first adhesive layer is a polyol compound and a polyisocyanate compound.
- It is a two-component curable adhesive composed of a general-purpose two-component curable adhesive consisting of, an acid-modified polyolefin, and a curing agent capable of reacting with the acid-modified polyolefin
- the second adhesive layer is a two-component curable adhesive (Z).
- Both the first adhesive layer and the second adhesive layer may be a cured coating film of the two-component curable adhesive (Z).
- the first adhesive layer is a cured coating film of a two-component curable adhesive (Z) because it is more excellent in moldability and heat resistance, and both the first adhesive layer and the second adhesive layer are 2 A cured coating film of the liquid-curable adhesive (Z) is more preferable.
- the method for producing the laminate for blister packs of the present invention is not particularly limited, but as an example, when the two-component curable adhesive (including the two-component curable adhesive (Z)) is a solvent type, the following method is used. Manufactured in. First, the above-mentioned two-component curable adhesive is applied to either the base film or the aluminum foil by an extrusion method, a gravure coating method, a roll coating method, etc. to volatilize the organic solvent, and then the other is attached. match.
- a two-component curable adhesive was applied to the aluminum foil, the organic solvent was volatilized, a sealant layer was attached, and then aging was performed at room temperature to 90 ° C. for 2 days to 2 weeks to apply the adhesive. It is cured to obtain a laminate for a blister pack of the present invention.
- the base film and the aluminum foil may be bonded and then aged under the above-mentioned conditions, and the aluminum foil and the sealant layer may be bonded and then aged.
- a two-component curable adhesive is applied to either the base film or the aluminum foil, and then the base film and the aluminum foil are bonded together at room temperature to 90 ° C. Aging for 2 days to 2 weeks. Next, a two-component curable adhesive is applied to the aluminum foil, the aluminum foil and the sealant layer are bonded together, and aging is performed under the same conditions to cure the adhesive to obtain a laminate for a blister pack of the present invention. ..
- the blister pack of the present invention is obtained by molding the above-mentioned laminate for blister packs.
- a conventionally known lid material for a blister pack (for example, an aluminum foil coated with a heat sealant) is bonded to a laminate of the present invention having one or more pockets formed by molding the laminate.
- the blister pack laminate of the present invention may be provided with one or more pockets, these pockets are matched, and the heat-sealed layers are heat-sealed. May be.
- Examples of the molding method include a flat plate type pneumatic forming method, a plug assisted pneumatic forming method, a drum type vacuum forming method, a plug forming method and the like.
- Synthesis of polyester polyol (A1-1) In a flask having a stirring rod, a temperature sensor, and a rectification tube, 1102 parts of isophthalic acid, 473 parts of terephthalic acid, 1070 parts of 1,6-hexanediol, neopentyl glycol. 156 parts and 0.46 parts of an organic titanium compound (“Organix TC-100” manufactured by Matsumoto Fine Chemical Co., Ltd.) were charged, and dry nitrogen was poured into the flask while stirring, and the temperature was raised to 240 ° C while distilling off the generated water. The temperature was raised.
- the reaction was stopped when the weight% of isocyanate became 0.05% or less, diluted with a mixed solvent of ethyl acetate / toluene (mixing ratio 1: 1) so as to have a resin solid content of 50%, and the number average.
- Molecular weight (Mn) is 11,000
- weight average molecular weight (Mw) is 50,000
- resin hydroxyl value (solid content equivalent) is 3.9 mgKOH / g
- resin acid value (solid content equivalent) is 1.06 mgKOH / g
- a polyester polyol (A1-1) having a glass transition temperature (Tg) of 7.1 ° C. was obtained.
- polyester polyol (A1-2) 1261 parts of isophthalic acid, 540 parts of terephthalic acid, 667 parts of 1,6-hexanediol, neopentyl glycol in a flask having a stirring rod, a temperature sensor and a rectification tube. 182 parts, 253 parts of ethylene glycol, and 0.5 part of an organic titanium compound (“Organic TC-100” manufactured by Matsumoto Fine Chemical Co., Ltd.) were charged, and dry nitrogen was poured into the flask with stirring to retain the generated water. The temperature was raised to 240 ° C. while leaving.
- the reaction was stopped when the resin acid value became 1.50 mgKOH / g or less, cooled to 150 ° C., diluted with ethyl acetate to a resin solid content of 58%, and had a number average molecular weight (Mn) of 7,000 and a weight.
- the average molecular weight (Mw) is 23,000
- the resin hydroxyl value (solid content equivalent) is 22.4 mgKOH / g
- the resin acid value (solid content equivalent) is 1.26 mgKOH / g
- Tg glass transition point
- a polyester polyol (A1-3) at ° C. was obtained.
- Polyester polyol (A2-1) 164 parts of neopentyl glycol, 1125 parts of 1,6-hexanediol, 351 parts of terephthalic acid, 351 parts of isophthalic acid, 928 parts by weight of adipic acid and organic titanium compound 0. 89 parts were charged, and dry nitrogen was poured into the flask with stirring, and the temperature was raised to 240 ° C. while distilling off the generated water.
- the esterification reaction was carried out while increasing the degree of vacuum to 30 torr, the reaction was stopped when the resin acid value became 2.00 mgKOH / g or less, cooled to 150 ° C., and then the resin solid content was 60% using ethyl acetate.
- the number average molecular weight (Mn) is 5,200
- the weight average molecular weight (Mw) is 32,000
- the resin hydroxyl value (solid content equivalent) is 6.6 mgKOH / g
- the resin acid value (solid content equivalent) A polyester polyol (A2-1) having a glass transition temperature (Tg) of 1.86 mgKOH / g and a glass transition temperature (Tg) of ⁇ 43.6 ° C. was obtained.
- the number average molecular weight (Mn) is 8,400, the weight average molecular weight (Mw) is 61,300, the resin hydroxyl value (solid content equivalent) is 5.0 mgKOH / g, and the resin acid value (solid content equivalent).
- Mn The number average molecular weight
- Mw weight average molecular weight
- Mw the weight average molecular weight
- resin hydroxyl value solid content equivalent
- solid content equivalent 5.0 mgKOH / g
- the resin acid value (solid content equivalent). was 4.0 mgKOH / g
- Tg glass transition temperature
- Example 1 KBM-403 (silane coupling agent non-volatile content manufactured by Shin-Etsu Chemical Co., Ltd .: 100%) is added to the polyester polyol (A1-1) so as to have the composition (solid content) shown in Table 1, and KBM-403 is completely dissolved. Toluene diisocyanate trimethylolpropane adduct (indicated as TDI-TMP in the table. NCO%: 13.3) and ethyl acetate so that the non-volatile content is 25% are added to the mixture well stirred and stirred well. Then, the two-component curable adhesive of Example 1 was prepared.
- TDI-TMP trimethylolpropane adduct
- Example 2 Example 2 to (Example 5)
- Comparative Example 1 Comparative Example 4
- a two-component curable adhesive was prepared in the same manner as in Example 1 except that the polyester polyol used and the blending amount (solid content) were changed as shown in Tables 1 and 2.
- the outline of the compounds in the table that are not explained above is as follows. Further, [NCO] / [OH] is rounded off to the second decimal place.
- EVONIC Ketone-aldehyde condensed resin, hydroxyl value: 5 mgKOH / g
- Duranate E402-80E manufactured by Asahi Kasei Corporation, hexamethylene diisocyanate adduct, NCO%: 9.5%
- Example 1 ⁇ Manufacturing of laminates for blister packs> (Example 1)
- the adhesive of Example 1 was applied at 4 g / m 2 (solid content) to the matte surface of an aluminum foil having a thickness of 30 ⁇ m using a dry laminator, the solvent was volatilized, and then a stretched polyamide film having a thickness of 25 ⁇ m was applied. I pasted them together.
- the adhesive of Example 1 was applied to the glossy surface of the aluminum foil at 4 g / m 2 using a dry laminator, the solvent was volatilized, and then the adhesive was bonded to an unstretched polypropylene film having a thickness of 40 ⁇ m at 60 ° C. After aging for 5 days, the adhesive was cured to obtain the laminate of Example 1.
- Example 2 Example 2
- Comparative Example 1 Comparative Example 4
- the clearance between the punch and the die hole is 0.3 mm on one side.
- the clearance causes an inclination according to the molding height.
- ⁇ Excellent in practical use with no breakage of aluminum foil or floating between layers
- ⁇ Pinhole shape is confirmed in aluminum foil, but there is no breakage of aluminum foil or floating between layers, and practical range
- ⁇ Aluminum foil Large breakage or floating between layers
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Abstract
Description
本発明のブリスターパック用積層体は、基材フィルムと、第一の接着層と、アルミニウム箔と、第二の接着層と、シーラント層とがこの順に積層され、第一の接着層と第二の接着層の少なくとも一方が、ガラス転移温度が-30℃以上80℃以下のポリエステルポリオール(A1)を含むポリオール組成物(X)と、ポリイソシアネート化合物(B1)を含み、ポリイソシアネート化合物(B1)に占める脂肪族イソシアネートの配合量が50質量%以下であり、ポリオール組成物(X)に含まれる水酸基のモル数[OH]とポリイソシアネート組成物(Y)に含まれるイソシアネート基のモル数[NCO]との比[NCO]/[OH]が0.5以上20以下で配合された2液硬化型接着剤の硬化塗膜である。以下では便宜上この接着剤を2液硬化型接着剤(Z)とする。なお本明細書においてブリスターパック用積層体とは、内容物が封入される前のブリスターパックの成型に用いられる積層体をいう。以下、第一の接着層が2液硬化型接着剤(Z)の硬化塗膜である場合を例に挙げて、本発明の構成について詳述する。
本発明の積層体の外層(アルミニウム箔をはさんで内容物とは反対側に配置される層)には、耐突き刺し性に優れるフィルムが用いられる。基材フィルムの具体例としては、ポリアミドフィルムやポリエステルフィルムなどが挙げられる。
基材フィルムはチューブラー法やテンター法で製造され、二軸延伸して製造される。延伸方法は同時二軸延伸であってもよいし、逐次二軸延伸であってもよい。
アルミニウム箔としては、純アルミニウムやアルミニウム-鉄系合金よりなる軟質材を用いることができる。合金の具体例としては、合金番号8079、8021等が挙げられる。アルミニウム箔の膜厚は適宜調整され得るが、成型性と防湿性とのバランスの観点から一例として15μm以上80μm以下であることが好ましく、20μm以上60μm以下であることがより好ましい。
シーラント層は、ポリプロピレンフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルムのいずれかが用いられる。シーラント層の膜厚は、ヒートシール性と成型性とのバランスの観点から、一例として20μm以上150μm以下である。
第一の接着層は、2液硬化型接着剤(Z)の硬化塗膜である。第一の接着層はポリアミドフィルムとアルミニウム箔との間に配置され、これらを貼り合わせるものでもある。
示差走査熱量測定装置(エスアイアイ・ナノテクノロジー株式会社製DSC-7000、以下DSCとする)を用い、試料5mgを30mL/minの窒素気流下で室温から10℃/minで200℃まで昇温した後、10℃/minで-80℃まで冷却する。再び10℃/minで150℃まで昇温させてDSC曲線を測定し、二度目の昇温工程で観測される測定結果における低温側のベースラインを高温側に延長した直線と、ガラス転移の階段状部分の曲線の勾配が最大になるような点で引いた接線との交点をガラス転移点とし、このときの温度をガラス転移温度とする。また、一度目の昇温で200℃まで昇温させているが、これはポリエステルポリオール(A1)が十分に溶融する温度であればよく、200℃では不十分である場合は適宜調整する。同様に、冷却温度も-80℃では不十分な場合(ガラス転移温度がより低い場合など)には適宜調整する。
カラム ;東ソー株式会社製 TSKgel 4000HXL、TSKgel 3000HXL、TSKgel 2000HXL、TSKgel 1000HXL
検出器 ;RI(示差屈折計)
データ処理;東ソー株式会社製 マルチステーションGPC-8020modelII
測定条件 ;カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 0.35ml/分
標準 ;単分散ポリスチレン
試料 ;樹脂固形分換算で0.2質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
エポキシ樹脂の配合量は、ポリオール組成物(X)の固形分の30質量%以下であることが好ましい。
ケトン樹脂の配合量は、上述したポリエステルポリオール(A1)100質量部に対して1質量部以上20質量部以下であることが好ましい。
[NCO]/[OH]が低すぎると架橋密度が低くなり、耐熱性が低下する。また、2液硬化型接着剤(Z)に占めるポリイソシアネート化合物(B1)の配合量が必然的に少なくなり、エージング時に2液硬化型接着剤(Z)が基材に十分に濡れ広がり難くなり、接着強度が低下する恐れがある。
第二の接着層は、アルミニウム箔とシーラント層との間に配置され、これらを貼り合わせる層である。第二の接着層は接着剤の硬化塗膜であり、用いられる接着剤としてはアルミニウム箔と上述したフィルムとの接着に適したものであれば特に限定されず、例えばポリオール化合物とポリイソシアネート化合物からなる汎用の2液硬化型接着剤や、酸変性ポリオレフィンと、これと反応しうる硬化剤とからなる2液硬化型接着剤を用いることができる。
上記では第一の接着層が2液硬化型接着剤(Z)である場合を例に挙げて説明したが、本発明のブリスターパック用積層体は第一の接着層がポリオール化合物とポリイソシアネート化合物からなる汎用の2液硬化型接着剤や、酸変性ポリオレフィンと、これと反応しうる硬化剤とからなる2液硬化型接着剤であり、第二の接着層が2液硬化型接着剤(Z)の硬化塗膜であってもよい。第一の接着層と第二の接着層の両方が2液硬化型接着剤(Z)の硬化塗膜であってもよい。より成型性、耐熱性に優れることから第一の接着層が2液硬化型接着剤(Z)の硬化塗膜であることが好ましく、第一の接着層と第二の接着層の両方が2液硬化型接着剤(Z)の硬化塗膜であることがより好ましい。
本発明のブリスターパック用積層体の製造方法については特に限定されないが、一例として2液硬化型接着剤(2液硬化型接着剤(Z)を含む)が溶剤型の場合は以下のような方法で製造される。まず、基材フィルムまたはアルミニウム箔のいずれか一方に、上述した2液硬化型接着剤を、押出法、グラビアコート法、ロールコート法等により塗布し、有機溶剤を揮発させた後、他方を貼り合わせる。次いで、アルミニウム箔に2液硬化型接着剤を塗布し、有機溶剤を揮発させた後、シーラント層を貼り合わせた後、室温~90℃で、2日~2週間のエージングを行い、接着剤を硬化させて本発明のブリスターパック用積層体を得る。あるいは、基材フィルムとアルミニウム箔を貼り合わせた後に上述の条件にてエージングを行い、さらにアルミニウム箔とシーラント層を貼り合わせた後にエージングを行うようにしてもよい。
本発明のブリスターパックは、上述したブリスターパック用積層体を成型して得られる。本発明のブリスターパック用積層体を成型して一つまたは複数のポケットを設けたものに、従来公知のブリスターパック用の蓋材(一例としてアルミニウム箔にヒートシール剤を塗布したもの)を貼り合わせたものであってもよいし、本発明のブリスターパック用積層体に一つまたは複数のポケットを設けたものを二つ用意し、これらのポケットを合致させ、ヒートシール層同士をヒートシールしたものであってもよい。
成型方法としては、平板式空圧成形法、プラグアシスト圧空成形法、ドラム式真空成型法、プラグ成形法等が挙げられる。
(合成例1)ポリエステルポリオール(A1-1)の合成
攪拌棒、温度センサー、精留管を有するフラスコに、イソフタル酸1102部、テレフタル酸473部、1,6-ヘキサンジオール1070部、ネオペンチルグリコール156部及び有機チタン化合物(マツモトファインケミカル株式会社製「オルガチックスTC-100」)0.46部を仕込み、攪拌しながら乾燥窒素をフラスコ内に流入させ、生成する水を留去しながら240℃まで昇温した。その後、真空度を30tоrrまで高めながらエステル化反応を行い、樹脂酸価が2.00mgKOH/g以下となったところで反応を停止させた。150℃まで冷却後、酢酸エチル・トルエン(混合比1:1)の混合溶液を用いて樹脂固形分50%になるよう希釈して、数平均分子量(Mn)が4,000、重量平均分子量(Mw)が9,700、樹脂水酸基価(固形分換算)が38.8mgKOH/g、樹脂酸価(固形分換算)が0.63mgKOH/g、ガラス転移温度(Tg)が2.8℃のポリエステルポリオール(A1-1’)を得た。
攪拌棒、温度センサー、精留管を有するフラスコに、イソフタル酸1261部、テレフタル酸540部、1,6-ヘキサンジオール667部、ネオペンチルグリコール182部、エチレングリコール253部、及び有機チタン化合物(マツモトファインケミカル株式会社製「オルガチックスTC-100」)0.5部を仕込み、攪拌しながら乾燥窒素をフラスコ内に流入させ、生成する水を留去しながら240℃まで昇温した。その後、真空度を30tоrrまで高めながらエステル化反応を行い、樹脂酸価が2.00mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、酢酸エチル・トルエン(混合比1:1)の混合溶液を用いて樹脂固形分50%になるように希釈して、数平均分子量(Mn)が6,700、重量平均分子量(Mw)が17,000、樹脂水酸基価(固形分換算)が17.2mgKOH/g、樹脂酸価(固形分換算)が1.58mgKOH/g、ガラス転移温度(Tg)が23.6℃のポリエステルポリオール(A1-2)を得た。
攪拌棒、温度センサー、精留管を有するフラスコに、イソフタル酸790.8部、テレフタル酸339.4部、無水トリメリット酸20.0部、1,6-ヘキサンジオール738.0部、ネオペンチルグリコール107.4部及び有機チタン化合物(マツモトファインケミカル株式会社製「オルガチックスTC-100」)4.0部を仕込み、乾燥窒素をフラスコ内に流入させ攪拌しながら230~240℃に加熱しエステル化反応を行った。樹脂酸価が1.50mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、酢酸エチルで樹脂固形分58%に希釈して、数平均分子量(Mn)が7,000、重量平均分子量(Mw)が23,500、樹脂水酸基価(固形分換算)が22.4mgKOH/g、樹脂酸価(固形分換算)が1.26mgKOH/g、ガラス転移点(Tg)が7.3℃のポリエステルポリオール(A1-3)を得た。
攪拌棒、温度センサー、精留管を有するフラスコに、ネオペンチルグリコール164部、1,6-ヘキサンジオール1125部、テレフタル酸351部、イソフタル酸351部、アジピン酸928重量部及び有機チタン化合物0.89部を仕込み、撹拌しながら乾燥窒素をフラスコ内に流入させ、生成する水を留去しながら240℃まで昇温させた。その後、真空度を30tоrrまで高めながらエステル化反応を行い、樹脂酸価が2.00mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、酢酸エチルを用いて樹脂固形分60%に希釈して、数平均分子量(Mn)が5,200、重量平均分子量(Mw)が32,000、樹脂水酸基価(固形分換算)が6.6mgKOH/g、樹脂酸価(固形分換算)が1.86mgKOH/g、ガラス転移温度(Tg)が-43.6℃のポリエステルポリオール(A2-1)を得た。
攪拌棒、温度センサー、精留管を有するフラスコに、エチレングリコール73部、1,2-プロピレングリコール223部、テレフタル酸697部及び有機チタン化合物0.89部を仕込み、撹拌しながら乾燥窒素をフラスコ内に流入させ、生成する水を留去しながら240℃まで昇温させた。その後、真空度を30tоrrまで高めながらエステル化反応を行い、樹脂酸価が2.00mgKOH/g以下となったところで反応を停止し、150℃まで冷却後、酢酸エチルを用いて樹脂固形分30%に希釈して、数平均分子量(Mn)が8,400、重量平均分子量(Mw)が61,300、樹脂水酸基価(固形分換算)が5.0mgKOH/g、樹脂酸価(固形分換算)が4.0mgKOH/g、ガラス転移温度(Tg)が84℃のポリエステルポリオール(A2-2)を得た。
(実施例1)
表1に示す配合(固形分)となるようにポリエステルポリオール(A1-1)にKBM-403(信越化学社製のシランカップリング剤 不揮発分:100%)を加えてKBM-403が完全溶解するまで良く攪拌したものに、トルエンジイソシアネートのトリメチロールプロパンアダクト体(表中ではTDI-TMPと標記する。NCO%:13.3)と不揮発分が25%なるように酢酸エチルを加えて良く攪拌させて、実施例1の2液硬化型接着剤を作製した。
用いるポリエステルポリオールや配合量(固形分)を表1、2のように変更した以外は実施例1と同様にして2液硬化型接着剤を調整した。なお表中における化合物のうち、上記で説明のないものの概要は以下の通りである。また、[NCO]/[OH]は小数点第2位を四捨五入している。
(TEGO Variplus AP)
EVONIC社製、ケトン-アルデヒド縮合樹脂、水酸基価:5mgKOH/g
(E402-80E)
デュラネートE402-80E、旭化成株式会社製、ヘキサメチレンジイソシアネートのアダクト体、NCO%:9.5%
(実施例1)
膜厚30μmのアルミニウム箔のマット面に、ドライラミネーターを用いて実施例1の接着剤を4g/m2(固形分)で塗布し、溶剤を揮発させた後、膜厚25μmの延伸ポリアミドフィルムを貼り合わせた。次いで、アルミニウム箔の光沢面に、ドライラミネーターを用いて実施例1の接着剤を4g/m2で塗布し、溶剤を揮発させた後、膜厚40μmの未延伸ポリプロピレンフィルムと貼り合わせ、60℃、5日間のエージングを行い、接着剤を硬化させて実施例1の積層体を得た。
実施例1の接着剤に換えて実施例2~5、比較例1~4の接着剤を用いた以外は実施例1と同様にして積層体を得た。
(接着強度)
株式会社島津製作所の「オートグラフAGS-J」を使用し、剥離速度50mm/min、剥離幅15mm、剥離形態180°剥離の条件で、ポリアミドフィルムとアルミニウム箔の接着強度を評価した。数値が高いほどブリスターパック用積層体として好適であることを示す。
株式会社山岡製作所の「1ton卓上サーボプレス(SBN-1000)」を使用し、実施例または比較例のブリスターパック用積層体を60×60mmの大きさに切断した。ポリアミドフィルムが凸側になるようにして、成形高さフリーのストレート金型にて成型高さ3.5mmにして張り出し成型を行い、アルミニウム箔の破断や、各層間の浮きの発生有無により成型性を評価した。なお、使用した金型のポンチ形状は、一辺30mmの正方形、コーナーR2mm、ポンチ肩R1mmであり、使用した金型のダイス孔形状は一片34mmの正方形、ダイス孔コーナーR2mm、ダイス孔肩R:1mmであり、ポンチとダイス孔とのクリアランスは片側0.3mmである。クリアランスにより成形高さに応じた傾斜が発生する。
〇:アルミニウム箔の破断や、各層間の浮きが無く、実用上優れる
△:アルミニウム箔にピンホール状が確認されるが、アルミニウム箔の破断や各層間の浮きは無く実用域
×:アルミニウム箔が大きく破断、もしくは各層間で浮きが発生
実施例または比較例の積層体を60×60mmの大きさに切断し、ポリアミドフィルムが外側になるようにして、成型高さフリーのストレート金型にて成型高さ3.0mmにて張り出し成型を行った。得られた30mm角型トレイのフランジ部に側壁部に接するように190℃3秒ヒートシールバーを当て、各辺のフランジ部と側壁部との境界部近傍における外観を確認し、延伸ポリアミドフィルムとアルミニウム箔との間に浮きが発生していないかを評価した。サンプルは2個作成し、計8辺について確認し、以下のようにして3段階で評価した。
○:浮きなし(実用上優れる)
△:8辺のうち1~4辺で浮き発生(実用域)
×:8辺のうち5~8辺で浮き発生
Claims (7)
- 基材フィルムと、第一の接着層と、アルミニウム箔と、第二の接着層と、シーラント層とがこの順に積層され、
前記第一の接着層と前記第二の接着層の少なくとも一方が、ガラス転移温度が-30℃以上80℃以下のポリエステルポリオール(A1)を含むポリオール組成物(X)と、ポリイソシアネート化合物(B1)を含むポリイソシアネート組成物(Y)とを含み、前記ポリイソシアネート化合物(B1)に占める脂肪族イソシアネートの配合量が50質量%以下であり、前記ポリオール組成物(X)に含まれる水酸基のモル数[OH]と前記ポリイソシアネート組成物(Y)に含まれるイソシアネート基のモル数[NCO]との比[NCO]/[OH]が0.5以上20以下で配合された2液硬化型接着剤の硬化塗膜であるブリスターパック用積層体。 - 前記第一の接着層が前記2液硬化型接着剤の硬化塗膜である請求項1に記載のブリスターパック用積層体。
- 前記第二の接着層が前記2液硬化型接着剤の硬化塗膜である請求項1または2のいずれか一項に記載のブリスターパック用積層体。
- 前記2液硬化型接着剤がカップリング剤(C)を含む請求項1~3のいずれか一項に記載のブリスターパック用積層体。
- 前記基材フィルムがポリアミドフィルム、ポリエステルフィルムのいずれかである請求項1~4のいずれか一項に記載のブリスターパック用積層体。
- 前記シーラント層が、ポリプロピレンフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルムのいずれかである請求項1~5のいずれか一項に記載のブリスターパック用積層体。
- 請求項1~6のいずれか一項に記載のブリスターパック用積層体を成型してなるブリスターパック。
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| JP2013018905A (ja) * | 2011-07-13 | 2013-01-31 | Dic Corp | 酸素バリア性接着剤用樹脂組成物、及び接着剤 |
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| JP5543408B2 (ja) * | 2011-07-06 | 2014-07-09 | Dic株式会社 | ガスバリア性ポリエステル樹脂組成物、及びガスバリア性フィルム |
| JP6323476B2 (ja) * | 2016-02-26 | 2018-05-16 | 東洋インキScホールディングス株式会社 | 電池用包装材、電池用容器および電池 |
| JP6308413B1 (ja) | 2016-09-06 | 2018-04-11 | Dic株式会社 | 接着剤、ブリスターパック用積層体及びそれを用いたブリスターパック |
| WO2018117082A1 (ja) * | 2016-12-20 | 2018-06-28 | Dic株式会社 | ポリエステルポリオール、反応型接着剤、および積層体 |
| CN110072964B (zh) * | 2016-12-20 | 2021-05-25 | Dic株式会社 | 电池用包装材料用粘接剂、电池用包装材料、电池用容器及电池 |
| TW202039762A (zh) | 2019-03-05 | 2020-11-01 | 日商Dic股份有限公司 | 接著劑、電池用包裝材用接著劑、積層體、電池用包裝材、電池用容器及電池 |
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| JP2013018905A (ja) * | 2011-07-13 | 2013-01-31 | Dic Corp | 酸素バリア性接着剤用樹脂組成物、及び接着剤 |
| JP2020040320A (ja) * | 2018-09-12 | 2020-03-19 | 大日本印刷株式会社 | 酸素吸収性積層体およびそれを用いた包装材料と包装袋 |
| JP2020172270A (ja) * | 2019-04-08 | 2020-10-22 | 昭和電工パッケージング株式会社 | シート成形容器用積層シート、シート成形容器および包装体 |
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