JP6308413B1 - Adhesive, laminate for blister pack and blister pack using the same - Google Patents

Abstract

An adhesive and a substrate having a main agent containing a polyol and an epoxy compound, and a curing agent containing an isocyanate compound, wherein the solid content mass ratio of the polyol and the epoxy compound in the main agent is 100/20 to 100/60 A blister pack laminate in which a layer and a metal foil are laminated via the adhesive layer described above, and a blister pack using the blister pack laminate. The solid content mass ratio between the isocyanate compound and the polyol is preferably in the range of 1-30.

Description

  The present invention relates to a laminate for blister packs that can be suitably used for pharmaceutical packaging applications that are subjected to molding processing, and an adhesive used therefor.

2. Description of the Related Art Conventionally, containers that have been subjected to molding processing typified by blister packs are known as containers for packaging stored items such as drugs and foods such as tablets and capsule preparations. Blister packs (sometimes referred to as press-through packages or PTPs) have a lid provided with a metal foil, such as an aluminum foil, on one side of a resin film in which a plurality of pockets for accommodating stored items are formed. By doing so, each pocket part is sealed and sealed, and by pressing the back side of the pocket part, the contents in the pocket part can break through the metal foil and take out the contents from the pocket part. (For example, see Patent Documents 1 and 2). Utilizing the high light-shielding and moisture-proofing properties of metals, the stored items can be used for various things such as feeds for dogs and cats, cosmetics, medical equipment, electronic parts, etc. in addition to chemicals and foods that are expected to be stored for a long period of time. Has been. Recently, in addition to blister packs with transparent pockets and visibility, there are also known blister packs with metal foil in the pockets in the hope of higher light shielding and moisture resistance (for example, Patent Documents). 3).
Moreover, the laminated body for blister packs is the film or sheet material used for shaping | molding the blister pack before a stored item is enclosed.

  A blister pack having a metal foil also in the pocket is obtained by molding a blister pack laminate in which a metal foil and a base material such as a plastic film are laminated with an adhesive. However, at the time of the forming process, peeling may occur between the metal foil layer or the laminate and the adhesive layer, and the laminate may be broken.

  As a laminate requiring a forming process in which a metal foil and a base material such as a plastic film are laminated with an adhesive, a battery laminate is known. For example, Patent Document 4 discloses a base material layer and a barrier layer. A laminate in which a sealant layer is laminated in this order via an adhesive layer, the barrier layer is made of a metal foil, and the adhesive layer between the barrier layer and the sealant layer is a polyester polyol as a main agent. And an epoxy compound, and a urethane-based adhesive containing polyisocyanate as a curing agent, and the ratio of the main agent to the curing agent is 10: 1.269 to 10: 2.885 in terms of solid content mass ratio. A certain laminated body is described, and this laminated body is described that it is used for the packaging body used for the packaging container suitable for packaging the liquid substance which contains alcohol in high concentration.

  Patent Document 5 discloses a polyurethane adhesive for battery packaging materials containing a main agent and a curing agent, wherein the main agent has a number average molecular weight of 10,000 to 100,000 and a hydroxyl value of 1. The equivalent ratio of the isocyanate group derived from the aromatic polyisocyanate (B) contained in the curing agent to the hydroxyl group derived from the acrylic polyol (A) [NCO] / It is described that [OH] is 10 to 30, and that the adhesive can be used as an adhesive for PTP packaging.

  Patent Document 6 discloses a battery packaging material in which an outer layer side resin film layer, an outer layer side adhesive layer, a metal foil layer, an inner layer side adhesive layer, and a heat seal layer are sequentially laminated. Is formed from a polyurethane adhesive containing a main component containing a polyol component (A) and a curing agent containing a polyisocyanate component (B), and the polyol component (A) is a polyester polyol ( A1): 85 to 99% by weight, trifunctional or higher-functional alcohol component (A2): 1 to 15% by weight (provided that the total of (A1) and (A2) is 100% by weight), and the polyester Polyol (A1) is a number average molecular weight 5000 to 50000 polyester polyol composed of a polybasic acid component and a polyhydric alcohol component, wherein the polybasic acid component The equivalent ratio of the isocyanate groups contained in the curing agent to the total of the hydroxyl groups and carboxyl groups derived from the polyol (A) contained in the main agent, containing 45 to 95 mol% of the aromatic polybasic acid component in 00 mol% A battery packaging material having [NCO] / ([OH] + [COOH]) of 0.5 to 10 is described, and it is described that the adhesive can be used as an adhesive for PTP packaging. ing.

  However, none of them has been specifically evaluated as a PTP, that is, a blister pack, and no knowledge has been obtained about the application of a blister pack laminate particularly when polyamide is used as a plastic film.

JP 2013-199283 A Special table 2009-526715 Special table 2008-535746 JP-A-2015-157363 JP 2014-185317 A Japanese Patent Laying-Open No. 2015-82354

  An object of the present invention is to provide a laminate having an adhesive layer having a specific composition capable of reducing breakage of a metal foil layer and lifting of a base material layer during molding as a laminate for a blister pack that can be used as a blister pack. The purpose is to provide.

  The present inventors have a main agent containing a polyol and an epoxy compound, and a curing agent containing an isocyanate compound, and by setting the solid content mass ratio of the polyol and the epoxy compound in the main agent to a specific range, We found that the above problems could be solved.

  That is, this invention has the main ingredient containing a polyol and an epoxy compound, and the hardening | curing agent containing an isocyanate compound, The solid content mass ratio of the polyol in the said main ingredient and an epoxy compound is 100 / 20-100 / 60. Provide adhesive.

  Moreover, this invention provides the laminated body for blister packs in which the base material layer and the metal foil were laminated | stacked through the said adhesive bond layer.

  Moreover, this invention provides the medical blister pack using the laminated body for blister packs of the said description.

  By using the adhesive of the present invention as an adhesive for a laminated body for blister packs, it is possible to provide a blister pack in which breakage of the metal foil layer and lifting of the base material layer are reduced during molding.

It is a schematic diagram showing the configuration of the laminate for a blister pack of the present invention,

(Definition of terms)
In the present invention, as shown in the background art, the “blister pack” is a container for packaging stored items such as drugs and foods such as tablets and capsule preparations as disclosed in Patent Documents 1 to 3 (here, visually recognized). Whether or not there is sex. In addition, although it may also be called a press through package or PTP, in this invention, it shall call a blister pack.

(Main agent)
The main agent used in the present invention contains a polyol and an epoxy compound.

(Polyol)
As the polyol used in the present invention, any polyol used in the adhesive field can be used without any particular limitation. For example, polyalkylene polyols such as polyethylene glycol and polypropylene glycol, polyether polyols, polyester polyols, polyurethane polyols, polyester polyurethane polyols, polyether polyurethane polyols, and blends of the aforementioned polyols can be used.

  The polyether polyol can be obtained, for example, by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like, for example, by using a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin or the like as an initiator. A polyether polyol is mentioned.

  The polyester polyol is obtained by reacting a polybasic acid and a polyhydric alcohol. Any known raw material can be used as the polybasic acid. For example, dimer acid can be used. Dimer acid is a product obtained by Diels-Alder dimerization of C18 unsaturated fatty acids such as oleic acid and linoleic acid, and various products such as those obtained by adding hydrogen to saturated bonds and saturating them are commercially available. . A typical one is composed of 0 to 5% by weight of C18 monocarboxylic acid, 70 to 98% of C36 dimer acid and 0 to 30% by weight of C54 trimer acid. The dimer diol is obtained by reducing the dimer acid described above. Also, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalate Acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid And anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and polybasic acids such as dimer acid alone Or in a mixture of two or more.

  As the polyhydric alcohol, any raw material can be used as long as it is known. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol , Glycols such as triethylene glycol, polycaprolactone diol, dimer diol, bisphenol A, hydrogenated bisphenol A, propiolactone, butyro Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as kuton, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene oxide, propylene using one or more compounds having two active hydrogen atoms such as neopentyl glycol as an initiator Polyhydric alcohol components such as polyethers obtained by addition polymerization of one or more monomers such as oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene and the like by a conventional method are used. Can be used as a mixture of two or more.

  A polyurethane polyol is obtained by reacting the polyhydric alcohol and an isocyanate. Isocyanates used in the reaction, ie, urethanization, include aromatic diisocyanates (diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, prepolymers of low molecular glycols and the above aromatic diisocyanates, etc.) aliphatic Diisocyanates (1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, prepolymers of the above-mentioned aliphatic diisocyanates with low molecular weight glycols such as ethylene glycol and propylene glycol); Diisocyanate (isophorone diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, methylcyclohexylene diisocyanate , Isopropylidene dicyclohexyl over 4,4'-diisocyanate, low molecular glycols and the prepolymer an alicyclic diisocyanate); and mixtures of two or more thereof. Moreover, you may make it react with the above-mentioned polyalkylene polyol, polyether polyol, and polyester polyol, In this case, it may be used together with the said polyhydric alcohol, and it is not necessary to use it together. What was made to react is called polyester polyurethane polyol or polyether polyurethane polyol.

  Among these, a polyol having an ester skeleton such as polyester polyol and polyester polyurethane polyol is preferably used because of its excellent flexibility and moldability.

(Epoxy compound)
As an epoxy compound used in the present invention, commercially available epi-bis type, novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type And various epoxy resins such as epoxidized fatty acid ester type, polycarboxylic acid ester type, aminoglycidyl type, and resorcin type.
Epoxy resins include commercially available bisphenol-type epoxy resins, rag-type epoxy resins, cyclic oxirane-type resins, glycidyl ether-type resins, glycidyl ester-type resins, polyglycol ether-type epoxy resins, glycol ether-type epoxy resins. Various epoxy resins such as resin, epoxidized fatty acid ester type resin, polyvalent carboxylic acid ester type epoxy resin, glycidyl amine type resin, resorcin type epoxy resin and the like can be mentioned. Of these, bisphenol-type epoxy resins are preferably used because of their excellent moldability.

  In the main ingredient containing the polyol and the epoxy compound, the solid content mass ratio of the polyol and the epoxy compound is 100/20 to 100/60. Within this range, it is possible to obtain a laminate having an adhesive layer that is less prone to breakage of the metal foil layer and lifting of the base material layer during molding. The solid content mass ratio is preferably 100/20 to 100/40, and most preferably 100/20 to 100/30.

(Curing agent containing isocyanate compound)
As the isocyanate compound used in the present invention, known and commonly used isocyanate compounds can be used.
For example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanate) Polyisocyanates such as methyl) cyclohexane, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; adducts of these polyisocyanates, burettes of these polyisocyanates, or isocyanurates of these polyisocyanates Examples include isocyanate derivatives (modified products).
The polyisocyanate is not limited, but the aromatic type is better than the aliphatic type in terms of peel strength and moldability.

In the present invention, the equivalent ratio (NCO / OH) of the hydroxyl group (OH) derived from the polyol and the isocyanate group (NCO) derived from the polyisocyanate compound is not particularly limited, but is preferably in the range of 1-30. Within this range, moisture and heat resistance (65 ° C-90% / 72 hours in depth 6.5 mm deep and no floating near the boundary between the molded flange portion and the side wall portion), heat sealability (190 ° C / 3 seconds) The balance of the fact that there is no float near the boundary between the molded flange portion and the side wall portion with a depth of 6.5 mm is the best. On the other hand, if it is smaller than 1, the peel strength and heat-and-moisture resistance may be deteriorated, and if it is more than 30, the peel strength and heat sealability may be further deteriorated, more preferably 2 to 10, and more preferably 4 to 10 And the range of 4-7 is most preferred.

The adhesive of the present invention can also contain a ketone resin.
Examples of the ketone resin used in the present invention include known and commonly used ones, and formaldehyde resins, cyclohexanone / formaldehyde resins, ketone aldehyde condensation resins, and the like can be preferably used.

  The adhesive of the present invention may be either a solvent type or a solventless type. In the case of the solvent type, the solvent is used as a reaction medium during production of the main agent and the curing agent, and is further used as a diluent during coating. Examples of solvents that can be used include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferred to use ethyl acetate or methyl ethyl ketone alone or in combination. On the other hand, the solvent-free type in the present invention is an ester such as ethyl acetate, butyl acetate, cellosolve acetate, etc., which is used as a reaction medium during the production of the above main agent and curing agent, and further used as a diluent during coating. , Ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, Examples thereof include dimethylsulfamide. Of these, it usually refers to a form containing no ethyl acetate or methyl ethyl ketone.

  In the adhesive of the present invention, as another preferred embodiment, known phosphoric acids or derivatives thereof can be used in combination. Thereby, the initial adhesiveness of the adhesive is further improved, and troubles such as tunneling can be solved.

  Examples of phosphoric acids or derivatives thereof used herein include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and hypophosphoric acid, such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Condensed phosphoric acids such as monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, phosphorous acid Monopropyl, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, Dibutyl phosphate, di-2-ethylhexyl phosphite Mono-, diesterified products such as diphenyl phosphite, mono- and diesterified products from condensed phosphoric acid and alcohols, for example, those obtained by adding an epoxy compound such as ethylene oxide, propylene oxide, etc. Examples thereof include epoxy phosphate esters obtained by adding the above phosphoric acid to an aliphatic or aromatic diglycidyl ether.

  One or more of the above phosphoric acids or derivatives thereof may be used. As a method of inclusion, it may be simply mixed.

  In the adhesive of the present invention, an adhesion promoter can be used. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, epoxy resins, and the like.

  Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ. Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycine Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris (β-methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, γ-Mel Hept trimethoxysilane and the like.

  Examples of titanate coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.

  Moreover, as an aluminum coupling agent, acetoalkoxy aluminum diisopropylate etc. can be mentioned, for example.

The adhesive of the present invention may be applied by any coating method as long as it is known, but is generally applied by a gravure roll coating method. The coating amount of the adhesive is 1.5 to 5 g / ^{m 2} in terms of solid content, preferably used in coating conditions of 2 to 4 g / ^{m 2.} Usually, about 1.0~4.0g / ^{m 2} coating weight with a solvent type, a solventless type may be used in about 0.5 to 3.0 g / ^{m 2.}

The laminate for blister packs of the present invention is characterized in that a base material layer and a metal foil are laminated via the adhesive layer. As described above, the blister pack laminate in the present application is a film or sheet material used for forming a blister pack before the stored items are enclosed. The base material used in this case is a blister pack (press-through package). , PTP), food packs, and feed packs that are commonly used in food packs.
Moreover, the structure of the laminated body for blister packs of this invention WHEREIN: Even if the base material layer is adhere | attached only on the single side | surface of metal foil, the base material layer may be adhere | attached on both surfaces of metal foil. Moreover, a base material layer may be bonded together.

  The metal foil is preferably a pure aluminum foil or an aluminum alloy foil. The metal foil is preferably a semi-hard material or a soft material.

  Examples of the plastic substrate used as the substrate layer include polyamide, polyester, and polyolefin.

  Examples of the polyamide include polyamide homopolymers and copolymers. Polyamide homopolymers include 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-aminononanoic acid) [nylon 9], poly (10-aminodecanoic acid) [nylon 10], poly (11-aminoundecanoic acid) [nylon 11], And poly (12-aminododecanoic acid) [nylon 12]. Polyamide copolymers include 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 (tetramethylenediamine-co-oxalic acid) [Nylon 4,2], n-dodecanedioic acid and hexamethylenediamine polyamide [Nylon 6,12], Dodeca Examples include methylenediamine and polyamide of n-dodecanedioic acid [nylon 12, 12]. Other useful polyamide copolymers include caprolactam / hexamethylene adipamide copolymer [nylon 6,6 / 6], hexamethylene adipamide / caprolactam copolymer [nylon 6 / 6,6], Methylene adipamide / hexamethylene azelaamide copolymer [nylon trimethyl 6, 2/6, 2], hexamethylene adipamide-hexamethylene-azelayamide 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 (2,2,2-trimethylhexamethylene terephthalamide), poly (m-xylylene adipamide) [MXD6], poly (p-xylylene adipamide), poly ( Hexamethylene terephthalamide), poly (dodecamethylene terephthalamide), polyamide 6T / 6I, polyamide 6 / MXDT / I, polyamide MXDI, and the like.

  Further, other polyamides that are not particularly described in the present specification, and combinations described in the present specification may be used. Among these, as polyamide, nylon 6, nylon 6,6, nylon 6 / 6,6 or a mixture thereof is more preferable, and nylon 6 is still more preferable.

  Examples of the polyester include polyethylene terephthalate [PET] and glycol-modified polyethylene terephthalate [PETG]. The cyclic olefin copolymer [COC] is preferably a copolymer of ethylene and norbornene.

  The polyolefin is selected from the group consisting of polyethylene [PE], polypropylene [PP], polyvinyl chloride [PVC], polyvinylidene chloride [PVdC], cyclic olefin copolymer [COC], polystyrene [PS], and acrylic resin. In particular, polyethylene [PE], polyester, and polyvinyl chloride [PVC] are preferable. Examples of the polyethylene include low density polyethylene [LDPE], linear low density polyethylene [LLDPE], linear medium density polyethylene [LMDPE], linear and very low density polyethylene [VLDPE], and linear very low density polyethylene [ ULDPE] and high-density polyethylene [HDPE], and low-density polyethylene is preferred.

(Blister pack)
The blister pack of the present invention is provided with a lid on the blister pack laminate of the present invention, and a predetermined number of recesses are formed on the blister pack laminate (bottom material) of the present invention, and then each molded It can be manufactured by storing the contents such as tablets in the recess and heat-sealing the lid material to the flange part of the laminated body for blister packs, which is the bottom material, using a molding filling sealing machine for blister pack packaging. it can.

  As the lid member, one having a heat-sealable resin layer is preferable because the contained contents can be sealed by heat sealing. The heat-sealable resin layer is not particularly limited as long as the heat-sealing resin layer is a layer that is fused to the surface of the bottom material in which the contents are accommodated. For example, low-density polyethylene [LDPE], medium-density polyethylene [ MDPE], high density polyethylene [HDPE], linear low density polyethylene [LLDPE], ethylene vinyl acetate copolymer [EVA], polypropylene [PP], ethylene / acrylic acid copolymer [EAA], ethylene / methacrylic acid Copolymer [EMA], ethylene / methyl acrylate copolymer [EMAA], ethylene / ethyl acrylate copolymer [EEA], ethylene / methyl methacrylic acid copolymer [EMMA], ionomer [IO], etc. Examples include a seed or a layer containing two or more. Moreover, it is preferable that a lid | cover material contains metal layers, such as metal vapor deposition film layers, such as an aluminum layer, and a metal foil layer, from the point that low water vapor permeability is favorable, and it is more preferable that an aluminum foil layer is included.

  Furthermore, since it is excellent in light-shielding property and moisture-proof property, the structure which has a double-sided metal foil layer (aluminum foil layer) which has a metal foil layer is especially preferable for the laminated body for blister packs and the bonded lid | cover material of this invention.

  The laminated body for blister packs and blister packs of the present invention can be used not only for medical purposes, but also for foods or pet food packs. In addition, there is no decrease in adhesion strength between layers even after a long-term durability test, and since there is no appearance defect such as floating between layers, a battery used as a battery electrolyte sealing film or a battery electrode part protective film, And it can be usefully used also as a secondary battery used as a secondary battery electrolyte solution sealing film or a secondary battery electrode part protective film.

  Hereinafter, the present invention will be described in more detail with reference to examples. The notation “parts” indicates parts by mass.

Production Example 1 Production of Adhesive (1) Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) had a solid content mass ratio of 100/40 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. Curing agent KW-75 (polyisocyanate, manufactured by DIC) was mixed with main agent A at a main agent / curing agent ratio = 10: 1.6 (5.2 converted to NCO / OH ratio (mol / mol)), and acetic acid was mixed. By diluting with ethyl, an adhesive (1) having a solid content of 35% was obtained as a blended solution.

(Production Example 2) Production of Adhesive (2) The solid mass ratio of Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) was 100/25 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. Curing agent KW-75 (polyisocyanate, manufactured by DIC) was mixed with main agent A at a main agent / curing agent ratio = 10: 1.6 (4.6 in terms of NCO / OH ratio (mol / mol)), and acetic acid was mixed. By diluting with ethyl, an adhesive (2) having a solid content of 35% was obtained as a blended solution.

(Production Example 3) Production of Adhesive (3) The solid mass ratio of Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) was 100/60 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. The main agent A was mixed with a curing agent KW-75 (polyisocyanate, manufactured by DIC) at a main agent / curing agent ratio = 10: 1.6 (5.9 converted to NCO / OH ratio (mol / mol)), and acetic acid was mixed. By diluting with ethyl, an adhesive (3) having a solid content of 35% was obtained as a blended solution.

(Production Example 4) Production of Adhesive (4) The solid mass ratio of Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) was 100/40 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. The main agent A is mixed with a curing agent KW-75 (polyisocyanate, manufactured by DIC) at a ratio of main agent / curing agent = 10: 1.4 (4.5 in terms of NCO / OH ratio (mol / mol)) and acetic acid. By diluting with ethyl, an adhesive (4) having a solid content of 35% was obtained as a blended solution.

(Production Example 5) Production of Adhesive (5) The solid mass ratio of Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) was 100/40 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. The main agent A is mixed with a curing agent KW-75 (polyisocyanate, manufactured by DIC) at a ratio of main agent / curing agent = 10: 1.8 (5.8 in terms of NCO / OH ratio (mol / mol)) and acetic acid. By diluting with ethyl, an adhesive (5) having a solid content of 35% was obtained as a blended solution.

(Production Example 6) Production of Adhesive (6) The solid mass ratio of Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) was 100/40 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. The main agent A was mixed with a curing agent KW-75 (polyisocyanate, manufactured by DIC) at a ratio of main agent / curing agent = 10: 2.0 (6.5 in terms of NCO / OH ratio (mol / mol)), and acetic acid. By diluting with ethyl, an adhesive (6) having a solid content of 35% was obtained as a blended solution.

(Production Example H1) Production of Adhesive (H1) The solid mass ratio of Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) was 100/10 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. The main agent A was mixed with a curing agent KW-75 (polyisocyanate, manufactured by DIC) at a main agent / curing agent ratio = 10: 1.6 (4.1 in terms of NCO / OH ratio (mol / mol)), and acetic acid. By diluting with ethyl, an adhesive (H1) having a solid content of 35% was obtained as a blended solution.

(Production Example H2) Production of Adhesive (H2) The solid mass ratio of Dick Dry LX-906 (polyester polyol, manufactured by DIC) and EPICLON-1050 (epoxy compound, manufactured by DIC) was 100/70 (polyol / epoxy). Compound A) and diluted with ethyl acetate to prepare main agent A having a solid content of 60%. The main agent A was mixed with a curing agent KW-75 (polyisocyanate, manufactured by DIC) at a ratio of main agent / curing agent = 10: 1.6 (6.3 converted to NCO / OH ratio (mol / mol)), and acetic acid was mixed. By diluting with ethyl, an adhesive (H2) having a solid content of 35% was obtained as a blended solution.

Example 1 Production of Blister Pack Laminate (1) Using Adhesive (1) Adhesive (1) was applied to a soft aluminum foil (thickness: 45 μm) with a dry laminator at a solid content of 3.0 g. After apply | coating and volatilizing a solvent, it bonded together with PVC (thickness 60 micrometers), and obtained the laminated body. Next, the adhesive (1) was applied to a biaxially stretched polyamide film (thickness 25 μm) with a dry laminator at a coating amount of solid content of 3.0 g, and the solvent was stripped, and then bonded to the aluminum surface of the laminate. The adhesive was cured by incubating at 40 ° C. for 96 hours to obtain a blister pack laminate (1).

(Examples 2 to 6)
Blister pack laminates (2) to (6) were obtained in the same manner as in Example 1 except that adhesives (2) to (6) were used in place of adhesive (1).

(Comparative Example 1) Production of Blister Pack Laminate (2) Using Adhesive (H1) Laminate (2) Other than using adhesive (H1) produced in Production Example 2 instead of adhesive (1) A blister pack laminate (H1) was prepared in the same manner as in 1).

(Comparative Example 2) Preparation of Blister Pack Laminate Using Adhesive (H2) Laminate (1) except for using adhesive (H2) produced in Production Example 3 instead of adhesive (1) In the same manner, a blister pack laminate (H2) was produced.

(Production of bottom material (1))
The blister pack laminate (1) obtained in Example (1) was cut into 60 mm length and width. This was press-molded to a depth of 6.0 mm in a vertical direction with respect to the laminate using a precision die machine with square molds of 30 mm in length and breadth to obtain a bottom material (1).
The punch shape of the mold used was a square with a side of 30 mm, a corner R2 mm, and a punch shoulder R1 mm. The die hole shape of the die used is a square of 34 mm per piece, a die hole corner R2 mm, a die hole shoulder R: 1 mm, and the clearance between the punch and the die hole is 0.3 mm on one side. An inclination corresponding to the molding height is generated by the clearance.

(Production of bottom materials (2) to (6), bottom materials (H1) to (H2))
Except for using the blister pack laminate (2) to (6), (H1) to (H2) instead of the blister pack laminate (1), Bottom materials (2) to (6) and bottom materials (H1) to (H2) were obtained.

<Evaluation of moldability>
For the bottom materials (1) to (6) and the bottom materials (H1) to (H2), the polyamide side is the convex side, and a molding is performed with a pressing machine of 3 cm square and a depth of 6 mm. ) And molded products (H1) to (H2) were obtained.

(Floating area)
About the corner | angular part of the obtained molding, the number and area of the location where polyamide floats from an aluminum surface were compared and evaluated.
Polyamide floating area of less than 5 mm: Small polyamide floating area of 5 mm or more and less than 10 mm: Medium polyamide floating area of 10 mm or more: Large.

(Number of metal breaks)
About the obtained molding, the number of the location where aluminum fractures was compared and evaluated.

The results are shown in Table 1.

<Evaluation of heat resistance>
(Production of blister pack)
Heating at 180 ° C. for 2 seconds using aluminum foil (thickness: 25 μm) filled with molded products (1) to (6) and molded products (H1) to (H2) filled with heat sealant. A blister pack was prepared by pasting together. After the heat sealing process for bonding the lid material, the number and area of the places where the polyamide at the corner of the molded product floats from the aluminum surface were compared and evaluated.

  As a result, the blister pack laminates using the adhesives of the examples were good with no float between the polyamide and the aluminum surface even after molding or after manufacture of the blister pack. On the other hand, in the blister pack laminate using the adhesive of the comparative example, floating occurred.

A: OP coat B: Ink C: Aluminum foil D: Heat-sealable resin layer E: Polyvinyl chloride (or unstretched polypropylene)
F: Adhesive G: Aluminum foil H: Adhesive I: Polyamide (or polyethylene terephthalate)
J: Contents K: Lid L: Bottom material

Claims (7)

It has a main agent containing a polyol and an epoxy compound, and a curing agent containing an isocyanate compound, and the solid content mass ratio of the polyol and the epoxy compound in the main agent is 100/20 to 100/60. Adhesive for blister pack laminates . The blister pack laminate adhesive according to claim 1, wherein a solid mass ratio of the isocyanate compound and the polyol is in the range of 1 to 30. The blister pack laminate adhesive according to claim 1 or 2, wherein the epoxy compound is a bisphenol A type epoxy compound. The laminated body for blister packs which the base material layer and metal foil were laminated | stacked through the adhesive bond layer in any one of Claims 1-3 . The blister pack laminate according to claim 4 , wherein the base material layer is polyamide. The laminated body for blister packs according to claim 4 or 5 , wherein the metal foil is an aluminum foil. The blister pack using the laminated body for blister packs in any one of Claims 4-6 .

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