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WO2019151532A1 - Stratifié et récipient en plastique - Google Patents

Stratifié et récipient en plastique Download PDF

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Publication number
WO2019151532A1
WO2019151532A1 PCT/JP2019/004018 JP2019004018W WO2019151532A1 WO 2019151532 A1 WO2019151532 A1 WO 2019151532A1 JP 2019004018 W JP2019004018 W JP 2019004018W WO 2019151532 A1 WO2019151532 A1 WO 2019151532A1
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WO
WIPO (PCT)
Prior art keywords
resin layer
resin
laminate
elastomer
olefin
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
Application number
PCT/JP2019/004018
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English (en)
Japanese (ja)
Inventor
篤 美尾
豊明 鈴木
純平 野村
果穂 鳥屋部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zacros Corp
Original Assignee
Fujimori Kogyo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujimori Kogyo Co Ltd filed Critical Fujimori Kogyo Co Ltd
Priority to JP2019569643A priority Critical patent/JP7216027B2/ja
Publication of WO2019151532A1 publication Critical patent/WO2019151532A1/fr
Anticipated expiration legal-status Critical
Priority to JP2023005979A priority patent/JP7585562B2/ja
Priority to JP2024175736A priority patent/JP2024177492A/ja
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/10—Bag-type containers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents

Definitions

  • the present invention relates to a laminate and a container.
  • PO resin polyolefin resins
  • PE polyethylene
  • PP polypropylene
  • a film formed from a resin generally used as a material for pharmaceutical containers such as vinyl chloride adsorbs or permeates some chemicals including radical scavenging preparations.
  • the active ingredient of the chemical solution is adsorbed to the plastic container, or the chemical solution interacts with the additives and low-molecular components contained in the resin film constituting the plastic container. It was an issue above.
  • a cyclic olefin-based resin as a resin having a barrier (shielding) property by suppressing the adsorption and permeation of chemicals and the like to the plastic container. Since the cyclic olefin-based resin has an alicyclic hydrocarbon structure in the molecular skeleton, the movement of the molecular chain is restricted due to its bulk, and therefore, absorption and permeation of molecules are difficult to occur. It is known that it exhibits excellent storage stability due to its small interaction.
  • an infusion bag having a configuration in which an outer layer (surface layer) is PP, an innermost layer is a cyclic olefin-based resin, and an intermediate layer between both layers is PP is a container for storing “Edaravone”. It is described as suitable.
  • the container having such a configuration has sufficient storage stability of the preparation, since the cyclic olefin resin has a hard and brittle nature, the seal part is not removed when an impact such as accidental dropping of the container is applied. There is a problem in impact resistance, such as partial peeling or destruction of pinholes, leading to liquid leakage.
  • Cyclic olefin-based resins have a problem that they tend to cause gels or fish eyes due to aggregation of components contained in the resin or defects caused by oxidation or carbonization (in the sense of kneaded foreign substances) during film formation or molding. .
  • Patent Document 2 and Patent Document 3 describe a method of blending polyethylene, polypropylene, and an ethylene / ⁇ -olefin copolymer (olefin resin) at a constant ratio with the cyclic olefin resin. Proposed.
  • the ratio of the olefin resin to be blended must be increased, and the molecular mobility of the barrier layer is increased.
  • the storage stability performance that should function as a container such as a decrease in the component concentration of the contents, may be insufficient.
  • plastic containers that have sufficient transparency and physical properties but have excellent storage stability of chemical components have not been completed. Is desired.
  • the present invention has been made in view of the above circumstances, and it is difficult for a decrease in transparency to occur due to sterilization treatment, damage due to an impact such as a drop is difficult to occur, and has an appropriate strength as a storage container, and further contains It is an object of the present invention to provide a laminate and a plastic container excellent in storage stability of components such as pharmaceuticals.
  • the present invention provides a first resin layer containing an amorphous cyclic olefin resin composed of an olefin monomer component having a cyclic hydrocarbon skeleton, and polyethylene, polypropylene, or ethylene / ⁇ -olefin.
  • a laminate comprising at least two or more layers including a second resin layer containing a copolymer as a main component, wherein the first resin layer contains an elastomer in a proportion of 10% by mass or less.
  • a laminate is provided.
  • the elastomer may be a thermoplastic elastomer.
  • the thermoplastic elastomer may be selected from one or more of an olefin-based thermoplastic elastomer and a styrene-based thermoplastic elastomer.
  • the elastomer may be contained in the first resin layer in a proportion of 0.05 to 10% by mass.
  • the present invention is characterized by comprising an accommodating portion for storing the contents and a mouth portion for discharging the contents, which are arranged so as to overlap each other so that the above-described laminates are opposed to each other.
  • a plastic container is provided.
  • the content may be a pharmaceutical product.
  • the pharmaceutical product may be an aqueous solution containing edaravone, which is a pyrazolone derivative, or a pharmaceutically acceptable salt thereof.
  • the plastic container may be an infusion bag or a blow molded container.
  • the adhesive strength between layers and heat seal strength are excellent, transparency is not easily lowered even in high-temperature sterilization treatment, etc., and damage due to impact such as dropping is less likely to occur.
  • the laminate of this embodiment includes a first resin layer containing an amorphous cyclic olefin resin composed of an olefin monomer component having a cyclic hydrocarbon skeleton, and polyethylene, polypropylene, or an ethylene / ⁇ -olefin copolymer. And a second resin layer containing at least two layers as a main component, wherein the first resin layer contains an elastomer in a proportion of 10% by mass or less.
  • a laminated body 20 shown in FIG. 2 has a three-layer structure in which the second resin layer 12 is disposed on both sides of the first resin layer 11.
  • the innermost layer that contacts the contents may be the first resin layer 11, and the second resin layer 12 may be disposed on the outer side.
  • the innermost layer that contacts the contents may be one second resin layer 12 and the outer side may be the other second resin layer 12.
  • the second resin layer 12 is mainly composed of polyethylene, polypropylene, or ethylene / ⁇ -olefin copolymer.
  • the second resin layer 12 preferably contains a total of, for example, 50 to 100% by weight of at least one of polyethylene, polypropylene, or ethylene / ⁇ -olefin copolymer if it is two or more.
  • the thickness, composition, etc. of each second resin layer 12 may be the same, and at least one of thickness, resin grade, blend ratio, etc. The above may be different.
  • a polypropylene resin having a high melting point may be disposed in the second resin layer 12 instead of the polyethylene resin.
  • the second resin layer 12 includes a polypropylene resin
  • an adhesive resin layer that adheres well to both layers between the first resin layer 11 and the second resin layer 12 as shown in FIGS. A structure provided with 13 is appropriate.
  • the laminated body 30 shown in FIG. 3 has a three-layer structure in which the second resin layer 12 is disposed on one side of the first resin layer 11 with the adhesive resin layer 13 interposed therebetween.
  • the fourth resin layer 4 has a five-layer structure in which the second resin layer 12 is disposed on both sides of the first resin layer 11 with the adhesive resin layer 13 interposed therebetween.
  • the thickness, composition, etc. of each adhesive resin layer 13 may be the same, and at least one of thickness, resin grade, blend ratio, etc. The above may be different.
  • the second resin layer 12 is disposed on both sides of the first resin layer 11, only the second resin layer 12 on one side may contain a polypropylene resin, and the first resin layer 11 and the second resin layer 12 on one side It is good also as a 4 layer structure which provided the adhesive resin layer 13 only between.
  • the second resin layer 12 and the adhesive resin layer 13 are used by mixing two or more kinds of resins having different physical properties in order to impart physical properties such as flexibility and transparency suitable as a plastic container. Or it is good also as arrangement
  • two or more second resin layers 12 mainly composed of polyethylene, polypropylene, or ethylene / ⁇ -olefin copolymer may be adjacent to each other.
  • two or more adhesive resin layers 13 may be disposed between the first resin layer 11 and the second resin layer 12.
  • LLDPE linear low density polyethylene
  • LLDPE usually has a linear molecular structure with few long-chain branches by copolymerizing ⁇ -olefins having 4 or more carbon atoms and introducing short-chain branches.
  • Examples of the ⁇ -olefin copolymerized with LLDPE include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.
  • LLDPE polymerized using a single-site catalyst is preferable because of its narrow molecular weight distribution and excellent mechanical properties.
  • the single site catalyst include metallocene catalysts.
  • the metallocene catalyst include a catalyst containing a metallocene compound that contains a ligand having a cyclopentadienyl skeleton and whose metal is zirconium, hafnium, or the like.
  • the polypropylene resin layer used for the second resin layer 12 is a layer mainly containing a polypropylene (PP) resin.
  • the polypropylene resin used for the polypropylene resin layer may be a propylene homopolymer or a copolymer with at least one of ethylene or an ⁇ -olefin having 4 to 8 carbon atoms. Also good.
  • the copolymer may be a random copolymer or a block copolymer.
  • the polypropylene resin layer may contain one type of polypropylene resin or may contain two or more types of polypropylene resin layers.
  • a grade of soft polypropylene (R-TPO) may be selected, and rubber or a thermoplastic elastomer component may be added as necessary.
  • the adhesive resin layer 13 includes, for example, a resin component composed of a linear low density polyethylene, a styrene elastomer, and a polypropylene resin when the cyclic olefin resin layer and the polypropylene resin layer are bonded.
  • Modic registered trademark
  • Zelas registered trademark
  • the resin etc. which have a cyclic hydrocarbon frame
  • the resin constituting the first resin layer 11 is a polymer composed of one or more olefin monomers or a polymer in which double bonds thereof are hydrogenated, and at least one of the olefin monomers is a cyclic hydrocarbon skeleton. It is a cyclic olefin monomer having Examples of the cyclic olefin monomer include a norbornene compound.
  • amorphous polymer is referred to herein as a cyclic olefin resin.
  • the cyclic olefin resin may be a copolymer in which at least one of the two or more olefin monomers is an acyclic olefin monomer having no cyclic hydrocarbon skeleton.
  • Examples of the acyclic olefin monomer that can be used for the cyclic olefin resin include ethylene and ⁇ -olefins having 4 to 8 carbon atoms.
  • Cyclic olefin resins are polymers obtained by ring-opening metathesis polymerization of norbornene compounds, hydrogenated remaining double bonds, addition polymers composed of two or more cyclic olefin monomers, cyclic olefin monomers and acyclic olefin monomers. The addition polymer etc. which copolymerized these are included.
  • the production method of the cyclic olefin resin includes a method of hydrogenating a ring-opening metathesis polymer of a norbornene compound, a method of copolymerization of two or more types of cyclic olefin monomers, and a copolymerization reaction of a cyclic olefin monomer and an ⁇ -olefin. A method is mentioned.
  • Examples of the basic structure of a polymer obtained by hydrogenating a ring-opening metathesis polymer of a norbornene compound include the following formula (I). That is, the formula (I) is described as a polymer in which a cyclic skeleton and an ethylene skeleton are alternately arranged.
  • the cyclic skeleton of the formula (1) is a 1,3-cyclopentylene skeleton.
  • the ring-opening metathesis polymer of the norbornene compound itself does not need to be a copolymer.
  • n is an integer of 1 or more, and R 1 and R 2 represent a hydrogen atom or an alkyl group. R 1 and R 2 may be the same as or different from each other. R 1 and R 2 may be bonded to each other to form a ring.
  • the structure shown in the formula (I) is such that the substituents R 1 and R 2 of n 1,3-cyclopentylene skeletons are the same as each other, and the ring-opening metathesis polymer of a norbornene compound is a homopolymer. It is not limited to the case.
  • the structure shown in Formula (I) may be a polymer obtained by hydrogenating a ring-opening metathesis polymer of two or more norbornene compounds.
  • the following formula (II) is mentioned as the example.
  • m and n are integers of 1 or more, and R 1 and R 2 represent a hydrogen atom or an alkyl group. m and n may be the same as or different from each other. R 1 and R 2 may be the same as or different from each other. R 1 and R 2 may be bonded to each other to form a ring.
  • a polymer obtained by hydrogenating a ring-opening metathesis polymer of a norbornene compound include “ZEONEX (registered trademark)” and “ZEONOR (registered trademark)” manufactured by Zeon Corporation.
  • the copolymer of formula (III) is described as a polymer in which a cyclic skeleton and an ethylene skeleton are randomly arranged.
  • the cyclic skeleton of the formula (I1I) is a 2,3-norbornanylene skeleton.
  • m and n are integers of 1 or more, and R 1 , R 2 and R 3 represent a hydrogen atom or an alkyl group. m and n may be the same as or different from each other. R 1 , R 2 and R 3 may be the same or different from each other. R 1 and R 2 may be bonded to each other to form a ring.
  • examples of the polymer in which R 1 , R 2 and R 3 are all hydrogen atoms include “TOPAS (registered trademark)” manufactured by Polyplastics Co., Ltd.
  • examples of the polymer in which R 1 and R 2 are alkyl groups and R 3 is a hydrogen atom include “Apel (registered trademark)” manufactured by Mitsui Chemicals, Inc.
  • the first resin layer preferably contains at least one cyclic olefin-based resin in a total amount of, for example, 50 wt% or more and less than 100 wt% if there are two or more types.
  • the first resin layer may contain one type of cyclic olefin resin or may contain two or more types of cyclic olefin resins.
  • the two or more cyclic olefin resins may be two or more cyclic olefin resins corresponding to any one of the formulas (I) to (III).
  • the first resin layer may be the innermost layer (sealant layer) in the laminate.
  • the first resin layer contains an elastomer in addition to the cyclic olefin resin.
  • the elastomer used for the first resin layer include rubber and thermoplastic elastomer.
  • the proportion of the elastomer contained in the first resin layer is preferably 10% by mass or less, and preferably between 0.05 and 10% by mass.
  • the proportion of the cyclic olefin-based resin contained in the first resin layer is preferably 90% by mass or more, and preferably between 90 and 99.95% by mass.
  • the first resin layer may not contain an acyclic polyolefin resin such as PE or PP, and the polymer component contained in the first resin layer may be only a cyclic olefin resin and an elastomer.
  • the elastomer used for the first resin layer is a styrene elastomer.
  • the styrene elastomer used for the first resin layer include a copolymer of styrene and an aliphatic olefin.
  • a block containing styrene constitutes a hard block, and a block containing aliphatic olefin constitutes a soft block.
  • styrene elastomer examples include styrene-ethylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-butylene.
  • SEBS Styrene-butadiene-styrene block copolymer
  • SBS Styrene-isoprene-styrene block copolymer
  • SIBS Styrene-isoprene-butadiene-styrene block copolymer
  • SEBC Styrene-ethylene-butylene-olefin crystal block copolymer
  • HSBR hydrogenated styrene-butadiene rubber
  • the elastomer used for the first resin layer may be an olefin-based thermoplastic elastomer.
  • an olefinic thermoplastic elastomer may be referred to as “TPO”
  • TPO olefinic thermoplastic elastomer
  • PE polyethylene
  • PP polypropylene
  • the flexible component soft segment
  • rubber elasticity include a copolymer having an olefinic rubber component such as ethylene-propylene-diene terpolymer (EPDM) and ethylenepropylene rubber (EPR).
  • Each layer constituting the laminate of the present embodiment that is, the material constituting the first resin layer, the adhesive resin layer, the second resin layer, etc. has improved container appearance, stabilized quality, and other required performance. Therefore, various additives such as an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, and an antiblocking agent may be contained within a range that does not impair safety and health.
  • each layer (film) used for the laminate (sheet) of the present embodiment is not particularly limited, and examples thereof include T-die molding and inflation molding. You may quench a film, a sheet, etc. with a cooling roll after T-die shaping
  • the laminated body is exemplified by a structure in which a base material, a sealant layer, and other layers are laminated as necessary. That is, an adhesive layer or an anchor agent layer may be interposed between the layers, or the layers may be laminated so that the layers are in direct contact with each other.
  • an adhesive layer or an anchor agent layer may be interposed between the layers, or the layers may be laminated so that the layers are in direct contact with each other.
  • one layer or a plurality of layers can be selected as appropriate, such as a reinforcing layer, a gas barrier layer, a light shielding layer, and a printing layer.
  • the sealant layer is a layer used for heat sealing, and is disposed in the innermost layer in contact with the contents as a packaging material.
  • the heat seal is a method of bonding by melting the sealant layer, but the seal method is not particularly limited, and examples thereof include a hot plate seal, an ultrasonic seal, a high frequency seal, and an impulse seal.
  • the base material may be the outermost surface of the other side of the laminate that is opposite to the sealant layer, or may be laminated inside the outermost surface of the other.
  • the thickness of the sealant layer depends on the use of the packaging material and is not particularly limited, but is usually about 5 to 150 ⁇ m, preferably 15 to 100 ⁇ m.
  • the thickness of the adhesive resin layer is not particularly limited, but is, for example, 10 to 100 ⁇ m.
  • the total thickness of the laminate is preferably 150 to 300 ⁇ m, especially 190 to 250 ⁇ m, in view of the balance between required performance (transparency and flexibility) and cost (productivity and material costs). Is common.
  • the interlayer strength between the first resin layer and the second resin layer or the interlayer strength between the first resin layer, the adhesive resin layer, and the second resin layer is significantly improved. be able to.
  • a 2nd resin layer contains polypropylene resin
  • it has high heat resistance compared with the laminated body comprised from a polyethylene-type resin layer and a cyclic olefin-type resin layer. . For this reason, it has heat resistance even at a high temperature exceeding 120 ° C., and high-pressure steam sterilization is possible.
  • the laminate of this embodiment has higher heat resistance compared to a laminate composed of a polypropylene-based resin layer and a cyclic olefin-based resin layer, and has a peel strength even when high-pressure steam sterilization is performed. The decrease is suppressed, and the impact resistance of the container can be improved.
  • the container of this embodiment can be formed using the laminate of this embodiment.
  • the container include a packaging bag (pouch) and tube packaging.
  • the spout can be suitably used as long as it can be sealed with a sealant layer of a laminate constituting the packaging bag to ensure sealing performance.
  • the spout When heat-sealing the laminate and the spout, the spout may be inserted and heat sealed while the laminate is overlapped with the sealant layer on the inside, and a flange or boat-shaped melt may be attached to one end of the spout.
  • An attachment base portion may be provided, and the flange portion or the fusion base portion may be heat-sealed with the peripheral edge of the hole provided in the laminate or the inner surface of the opening portion of the packaging bag.
  • the container of the present embodiment can be suitably used as a container for storing drugs such as pharmaceuticals, food and drink, and cosmetics.
  • the drug may be a substance having high adsorptivity or permeability to general resins, such as nitroglycerin, albumin, vitamins, trace elements, radical scavengers, and the like.
  • preferable drugs such as pharmaceuticals include aqueous solutions containing edaravone, which is a pyrazolone derivative, or a pharmaceutically acceptable salt thereof.
  • the pyrazolone derivative may have one or more substituents such as an alkyl group, an aromatic group, and a halogen atom on the carbon atom or nitrogen atom of pyrazolone.
  • the pyrazolone derivative may form a salt with an organic acid, an inorganic acid or the like.
  • the form of the packaging bag includes three-sided bags, four-sided bags, joint-attached bags, gusset bags, and small packaging bags (pouches) such as self-standing bags, as well as large bags such as inner bags for bag-in-boxes and drum can interior bags, etc. It can be applied without any particular limitation.
  • a plastic container 50 having an accommodating part 51 for storing the contents and a mouth part 52 for discharging the contents is preferable.
  • the accommodating part 51 can be arrange
  • Laminate manufacturing method Using a T-die type multilayer film forming machine, a laminate was produced by a coextrusion method so that the thickness of the surface layer / intermediate layer / innermost layer was 180 ⁇ m / 50 ⁇ m / 30 ⁇ m, respectively.
  • a polypropylene-based thermoplastic elastomer “ZELATH (registered trademark)” manufactured by Mitsubishi Chemical Corporation, density 0.89 g / cm 3 , melting peak temperature 162 ° C.
  • pellets obtained by dry blending three components composed of LLDPE, polypropylene (PP), and a compatibilizer at a predetermined ratio were used.
  • LLDPE vapor phase metallocene polyethylene “Harmolex (registered trademark)” (manufactured by Nippon Polyethylene Co., Ltd., density 0.908 g / cm 3 , melting peak temperature 120 ° C.) was used.
  • PP metallocene polypropylene “Wintech (registered trademark)” (manufactured by Nippon Polypro Co., Ltd., density 0.90 g / cm 3 , melting peak temperature 125 ° C.) was used.
  • SEBS “Tuftec (registered trademark)” manufactured by Asahi Kasei Corporation having a styrene content of 12% by weight was used.
  • a cyclic olefin resin “TOPAS (registered trademark)” (density 1.02 g / cm 3 , glass transition temperature 138 ° C.) is used, and various elastomer components shown in Table 1 are predetermined. It mix
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • Teftec registered trademark
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • Septon registered trademark
  • SEBC Styrene-Ethylene-Butylene-Olefin Crystal Block Copolymer
  • HSBR Hydrophilic Styrene-Butadiene Rubber
  • CEBC Olefin Crystal-Ethylene-Butylene-Olefin Crystal Block Copolymer
  • Example 1 A laminate having the innermost layer having the composition shown in Table 2 was produced using the laminate production method described above. Using the film-formed laminate, the innermost layers were overlapped, the outer periphery of the laminate was heat-sealed except for the filling port, and an infusion bag-shaped pouch container having an outer dimension of 172 mm ⁇ 115 mm was produced. Trimming was performed so that the outer peripheral seal width was 5 mm, and the interior of the pouch was filled with 105 mL of water, and then the filling port was heat sealed to seal the pouch.
  • the high-pressure sterilization treatment of the pouch after sealing was performed using a high-pressure steam sterilizer at 121 ° C. for 20 minutes. After the high pressure sterilization treatment, the temperature of the pouch was quickly lowered with cooling water, and then the heat seal strength, transparency, and impact resistance of the pouch were measured. Moreover, the stability when stored for a long time was evaluated by using a sample filled with a model preparation described later as a sample instead of water.
  • the heat seal strength was measured by the following procedure. First, a test piece having a width of 15.0 mm in a direction perpendicular to the heat seal portion of the pouch and a development length of 100 mm or more is collected, and the sheet portions on both sides of the heat seal portion are 180 ° with the heat seal portion of the test piece as the center. The sheet portions on both sides were attached to the grip portion of the tensile tester with a grip interval of 50 mm. Next, the tensile load was measured until the heat seal part broke at a constant speed of 300 mm / min, and the maximum load (N / 15 mm) until breakage was defined as the heat seal strength.
  • Transparency was evaluated by the following procedure.
  • JP17 Japanese Pharmacopoeia
  • the transparency test method 1 described in the 7.02 plastic drug container test method the specimen of the laminate was measured to a size of 0.9cm x 4cm from the pouch.
  • the sample was cut out, immersed in an ultraviolet absorption spectrum measurement cell filled with water, and the light transmittance at a wavelength of 450 nm was measured and recorded with an ultraviolet-visible spectrophotometer using a cell filled with only water as a control.
  • the average of the measured values of the light transmittance of 5 samples is 65. % Or higher was determined as “good”, and those lower than that were determined as “bad”.
  • the impact resistance by the drop test was evaluated by the following procedure.
  • the bag filled with water and sterilized was cooled in a refrigerator at 5 ° C. for 12 hours or more. While maintaining a cold temperature state, a test of freely dropping the pouch belly downward from a height of 2 m was carried out 50 times continuously for one bag. When cracking of the bag was observed, the test was stopped at that number of times, the number of drops when the bag broke out was recorded, and a score represented by the following formula was assigned.
  • the test was conducted in units of 10 bags for each level, and the drop test total score of 10 specimens was taken as the drop test total score.
  • the drop test total points at each level were compared with each other to determine whether the performance was superior or inferior.
  • a drop test total score of 80 or more was designated as “good”, and a drop test score of less than 80 was designated as “bad”.
  • the storage stability of the model preparation was evaluated by the following procedure. As described above, an infusion bag-shaped pouch container was formed from the laminate formed according to the above-described laminate production method. In the container, an edaravone-containing aqueous solution adjusted to pH 3.85 with the composition shown in Table 3 below (composition of edaravone model preparation) was used as a model preparation, and the container was filled with 105 mL and sealed. The container containing the model preparation was sterilized at 121 ° C. for 20 minutes using a high-pressure steam sterilizer, and after cooling was completed, the outside of the container was dried to obtain a back preparation.
  • Table 3 composition of edaravone model preparation
  • the bag preparation that has been subjected to the sterilization operation is placed in a dry laminate outer bag having a three-layer structure of biaxially stretched polyester / aluminum foil / linear low density polyethylene, and an oxygen scavenger (“AGELESS” manufactured by Mitsubishi Gas Chemical Co., Ltd.). Registered))) and heat sealed the opening of the outer bag to complete the preparation of the bag sample containing the model preparation.
  • a dry laminate outer bag having a three-layer structure of biaxially stretched polyester / aluminum foil / linear low density polyethylene, and an oxygen scavenger (“AGELESS” manufactured by Mitsubishi Gas Chemical Co., Ltd.). Registered))
  • the produced sample bag containing the model preparation was stored in an environment of temperature: 70 ° C. and relative humidity: 90% for 15 days.
  • the residual ratio of edaravone after storage was measured by a liquid chromatographic method under the following conditions.
  • Detector UV absorptiometer (measurement wavelength: 243 nm)
  • Column A column for liquid chromatography, in which a stainless steel tube having an inner diameter of 4.6 mm and a length of 150 mm is packed with octadecylsilylated silica gel having a particle diameter of 5 ⁇ m.
  • Column temperature constant temperature around 40 ° C.
  • Flow rate 1.0 mL / min.
  • Injection volume 20 ⁇ L
  • Edaravone remaining rate (%) (peak area of edaravone after completion of storage test) / (peak area of edaravone of initial value) ⁇ 100 (%)
  • Table 4 shows the results of a series of evaluations. It was shown that when the innermost layer (first resin layer) contains an elastomer component and an amorphous polymer, the heat seal strength does not decrease and the impact resistance is greatly improved. However, if the amount of elastomer component added is excessive, it is clear that the transparency after sterilization and the storage stability of the model formulation will approach an inadequate level. Was suggested to be appropriate.
  • Example 2 In order to verify whether or not the same performance improvement effect appears when an elastomer component other than that used in Experiment 1 was added, a laminate having the innermost layer of the elastomer addition amount shown in Table 5 was manufactured. Other procedures (pouch preparation, sterilization treatment, heat seal strength and transparency measurement, drop test, storage stability of model preparation) were the same as in Experiment 1.
  • Example 3 In place of the elastomer added to the innermost layer in Experiment 1 and Experiment 2, when the polyolefin resin presented in Patent Document 2 or Patent Document 3 is added, whether or not the performance improvement effect is expressed, and the performance improvement effect is expressed In order to verify the amount of addition required for this, a laminate was produced with the additive resin shown in Table 7 and the innermost layer composition of the blending amount. Other procedures (pouch preparation, sterilization treatment, heat seal strength and transparency measurement, drop test, storage stability of model preparation) were the same as in Experiment 1 and Experiment 2. Among the polyolefin species in Table 7, LLDPE and random PP used the same brand as the resin constituting the intermediate layer (adhesive resin layer).
  • Table 8 shows a series of evaluation results in Experiment 3 together with the evaluation results of Experiments 1 and 0 and 1-1.
  • LLDPE polyethylene
  • the required performance cannot be obtained with the same level of addition as the elastomer, and there is a tendency to require a large amount of blending as shown in No. 3-4 to increase the impact resistance. It was. In the blend of polypropylene (random PP), even when added up to 20%, the impact resistance was insufficient. On the other hand, when the blending amount was increased, the residual rate of edaravone in the model preparation decreased, suggesting that the performance required as a storage container for pharmaceuticals could not be satisfied.
  • the adhesive strength between layers and heat seal strength are excellent, transparency is not easily lowered even in high-temperature sterilization treatment, etc., and damage due to impact such as dropping is less likely to occur.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Hematology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Veterinary Medicine (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Medicinal Preparation (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Un stratifié composé d'au moins deux couches, les couches comprenant une première couche de résine (11) qui comprend une résine à base d'oléfine cyclique amorphe configurée à partir d'un composant monomère d'oléfine ayant un squelette hydrocarboné cyclique, et une seconde couche de résine (12) qui a un copolymère de polypropylène ou d'éthylène-alpha-oléfine en tant que composant principal, la première couche de résine (11) contenant un élastomère dans une proportion de 10 % en masse ou moins.
PCT/JP2019/004018 2018-02-05 2019-02-05 Stratifié et récipient en plastique Ceased WO2019151532A1 (fr)

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JP2024175736A JP2024177492A (ja) 2018-02-05 2024-10-07 積層体およびプラスチック容器

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JP2021177839A (ja) * 2020-05-12 2021-11-18 藤森工業株式会社 点眼剤容器
JPWO2022177025A1 (fr) * 2021-02-22 2022-08-25
WO2023006565A1 (fr) 2021-07-26 2023-02-02 Medichem, S.A. Procédé de préparation de formulations d'édaravone
JP2023066723A (ja) * 2021-10-29 2023-05-16 藤森工業株式会社 積層体及びプラスチック容器

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JP2011062529A (ja) * 2007-11-22 2011-03-31 Mitsubishi Tanabe Pharma Corp 環状ポリオレフィン層を含むプラスチック容器
JP2010162344A (ja) * 2008-12-19 2010-07-29 Fujimori Kogyo Co Ltd 包装体
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JP2021177839A (ja) * 2020-05-12 2021-11-18 藤森工業株式会社 点眼剤容器
JPWO2022177025A1 (fr) * 2021-02-22 2022-08-25
WO2022177025A1 (fr) * 2021-02-22 2022-08-25 株式会社細川洋行 Corps multicouche de récipient, récipient, récipient médical et récipient médical contenant un médicament
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WO2023006565A1 (fr) 2021-07-26 2023-02-02 Medichem, S.A. Procédé de préparation de formulations d'édaravone
JP2023066723A (ja) * 2021-10-29 2023-05-16 藤森工業株式会社 積層体及びプラスチック容器
JP7753055B2 (ja) 2021-10-29 2025-10-14 Ｚａｃｒｏｓ株式会社 積層体及びプラスチック容器

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