WO2023233984A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2023233984A1
WO2023233984A1 PCT/JP2023/018075 JP2023018075W WO2023233984A1 WO 2023233984 A1 WO2023233984 A1 WO 2023233984A1 JP 2023018075 W JP2023018075 W JP 2023018075W WO 2023233984 A1 WO2023233984 A1 WO 2023233984A1
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WO
WIPO (PCT)
Prior art keywords
layer
container
polyester compound
resin composition
oxygen
Prior art date
Application number
PCT/JP2023/018075
Other languages
English (en)
Japanese (ja)
Inventor
俊 小川
康明 吉村
弘毅 長谷川
翔太 荒川
喜子 佐久間
Original Assignee
三菱瓦斯化学株式会社
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
Priority claimed from JP2022090859A external-priority patent/JP2023177899A/ja
Priority claimed from JP2022090857A external-priority patent/JP2023177897A/ja
Priority claimed from JP2022090833A external-priority patent/JP2023177878A/ja
Priority claimed from JP2022090852A external-priority patent/JP2023177894A/ja
Priority claimed from JP2022090836A external-priority patent/JP2023177881A/ja
Priority claimed from JP2022090877A external-priority patent/JP2023177910A/ja
Priority claimed from JP2022090856A external-priority patent/JP2023177896A/ja
Priority claimed from JP2022090838A external-priority patent/JP2023177883A/ja
Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Publication of WO2023233984A1 publication Critical patent/WO2023233984A1/fr

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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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00—Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178—Syringes
    • A61M5/28—Syringe ampoules or carpules, i.e. ampoules or carpules provided with a needle
    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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—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, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • 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
    • 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
    • B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
    • 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
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • 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
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • a first embodiment of the present invention relates to a resin composition, and particularly to a resin composition containing at least a polyester compound having a predetermined structure and a transition metal catalyst.
  • a second embodiment of the present invention relates to a multilayer injection molded article and a container containing the multilayer injection molded article.
  • a third embodiment of the invention relates to a multilayer body and a container containing the multilayer body.
  • a fourth embodiment of the present invention relates to a multilayer medical container.
  • a fifth embodiment of the present invention relates to a prefill syringe.
  • the sixth embodiment of the present invention relates to a method for preserving a biopharmaceutical in which the biopharmaceutical is stored in a multilayer container having oxygen barrier performance and oxygen absorption performance.
  • a seventh embodiment of the present invention relates to a method for preserving an adrenaline-containing drug solution.
  • the eighth embodiment of the present invention relates to a modified polyester, and particularly to a modified polyester obtained by subjecting a polyester compound having a predetermined structure to radiation irradiation treatment.
  • Oxygen absorbers are used.
  • an oxygen absorbent containing iron powder as the main reaction agent is generally used from the viewpoint of oxygen absorption capacity, ease of handling, and safety.
  • this iron-based oxygen absorbent is sensitive to metal detectors, it has been difficult to use metal detectors for foreign object inspection.
  • a package enclosing an iron-based oxygen absorber cannot be heated in a microwave oven due to the risk of ignition.
  • moisture is essential for the oxidation reaction of iron powder, the oxygen absorption effect could only be achieved if the object to be preserved had a high moisture content.
  • an oxygen absorbent that uses an organic substance as the main reaction agent is desired.
  • an oxygen absorbent using an organic substance as a main reaction agent an oxygen absorbent using ascorbic acid as a main agent is known (see Patent Document 2).
  • oxygen-absorbing resin compositions that are composed of a resin and a transition metal catalyst and have oxygen-scavenging properties are known.
  • a resin composition comprising polyamide, particularly xylylene group-containing polyamide, and a transition metal catalyst as an oxidizing organic component is known (see Patent Document 3).
  • this Patent Document 3 also exemplifies oxygen absorbers, packaging materials, and multilayer laminated films for packaging obtained by molding this resin composition.
  • an oxygen-absorbing resin composition that does not require moisture for oxygen absorption
  • an oxygen-absorbing resin composition consisting of a resin having a carbon-carbon unsaturated bond and a transition metal catalyst is known (see Patent Document 4). .
  • composition for scavenging oxygen a composition consisting of a transition metal and a polymer containing a substituted cyclohexene functional group or a low molecular weight substance to which the cyclohexene ring is bonded is known (see Patent Document 5).
  • the applicant has proposed an oxygen-absorbing resin composition having a tetralin ring (see Patent Document 6).
  • injection molding can produce molded bodies with complex shapes and has high productivity, so it is widely used in the production of mechanical parts, automobile parts, electrical/electronic parts, food/medicine containers, etc.
  • various plastic containers have been used as packaging containers because they have advantages such as being lightweight, transparent, and easily moldable.
  • Typical plastic containers include, for example, containers for beverages, etc., which are injection-molded bodies (hereinafter also referred to as "injection-molded bodies") with a screw-shaped spout formed to allow the lid to be sufficiently tightened. is frequently used.
  • Materials used for the injection molded article include general-purpose thermoplastic resins such as polyolefins (polyethylene, polypropylene, etc.), polyester, and polystyrene.
  • general-purpose thermoplastic resins such as polyolefins (polyethylene, polypropylene, etc.), polyester, and polystyrene.
  • injection molded products mainly made of polyester such as polyethylene terephthalate (PET) are widely used as plastic containers for beverages such as tea, fruit juice drinks, carbonated drinks, and alcoholic drinks.
  • PET polyethylene terephthalate
  • injection molded products made mainly of thermoplastic resin are excellent as packaging materials, but unlike glass bottles and metal containers, they have the property of allowing oxygen to pass through from the outside, and the contents filled and sealed are There are still problems with storage.
  • multilayer injection molded products having a gas barrier layer as an intermediate layer have been put into practical use.
  • glass ampoules, vials, prefilled syringes, etc. have traditionally been used as medical packaging containers for filling and storing drug solutions in a sealed state (note that a prefilled syringe is a container in which the drug is prefilled in the barrel).
  • This syringe is a syringe that can be sealed in a sealed state and released from the sealed state to dispense the drug, and is widely used because of its ease of use.
  • sodium ions, etc. may be eluted into the liquid inside the container, minute substances called flakes may be generated, and colored light-shielding glass containers may not be used.
  • Plastics are lighter than glass, and polycarbonate, polypropylene, and cycloolefin polymers, for example, are being considered as plastic substitutes for glass, but their oxygen barrier properties, water vapor barrier properties, and chemical adsorption properties do not meet the requirements. The current situation is that no progress has been made in replacing them. Unlike glass and metal containers, plastic has the property of permeating oxygen, which poses a problem in the storage stability of chemical solutions. In order to impart gas barrier properties to containers made of such plastics, multilayer containers having a gas barrier layer as an intermediate layer have been proposed.
  • Patent Document 7 proposes a prefilled syringe with improved oxygen barrier properties, in which the innermost and outermost layers of the barrel are made of polyolefin resin, and the intermediate layer is made of a resin with excellent oxygen barrier properties. .
  • gas barrier layers include polyamide obtained from metaxylylene diamine and adipic acid (hereinafter sometimes referred to as "nylon MXD6”), ethylene-vinyl alcohol copolymer, polyacrylonitrile, and polyamide.
  • Methods of laminating gas barrier layers such as vinylidene chloride, aluminum foil, carbon coat, and inorganic oxide vapor deposition as constituent materials have been used, but the gas in the head space that exists above the contents after filling the molded body is It is not possible to remove residual oxygen.
  • oxygen-absorbing resin compositions that are composed of a resin and a transition metal catalyst and have oxygen-scavenging properties are known.
  • resin compositions having an oxygen-trapping function oxygen absorbers obtained by molding the resin compositions, packaging materials, multilayer laminated films for packaging, and multilayer containers (see Patent Document 9 below).
  • adrenaline also known as “epinephrine”
  • Adrenaline is released into the blood when the action of the sympathetic nervous system increases, causing increases in blood pressure and blood sugar levels, increased heart rate, and bronchodilation. Utilizing this effect, it is used as a cardiotonic agent and a blood pressure increasing agent, as well as a vasoconstrictor and a bronchodilator during bronchial asthma attacks.
  • Epinephrine is available in a variety of formulations suitable for routes of administration by injection, inhalation, or topical use.
  • prefilled syringe preparations a preparation in which a "prefill syringe" is prefilled with epinephrine
  • epinephrine is easily oxidized when exposed to air, when used as a prefilled syringe preparation, a glass prefilled syringe is used.
  • Japanese Patent Application Publication No. 09-234832 Japanese Unexamined Patent Publication No. 51-136845 Japanese Patent Application Publication No. 2001-252560 Japanese Patent Application Publication No. 05-115776 Special Publication No. 2003-521552 Patent No. 6124114 Japanese Patent Application Publication No. 2004-229750 Japanese Patent Application Publication No. 2-500846 Japanese Patent Application Publication No. 2009-108153
  • Patent Document 2 has the problems that its oxygen absorption performance is low to begin with, that it is effective only when the object to be preserved is a high moisture type, and that it is relatively expensive.
  • Patent Documents 3 and 8 express oxygen absorption function by containing a transition metal catalyst and oxidizing the xylylene group-containing polyamide resin, so that after oxygen absorption, polymers due to oxidative deterioration of the resin There is a problem in that chain breakage occurs and the strength of the packaging container itself decreases.
  • Patent Document 9 describes a method for improving delamination, but the effect is limited. Furthermore, this resin composition has the problem that its oxygen absorption performance is still insufficient, and the effect is only exhibited when the preserved material is of high moisture content.
  • Patent Document 5 still has the problem that it is necessary to use a special material containing a cyclohexene functional group, and this material is relatively likely to generate odor.
  • the oxygen-absorbing resin composition having a tetralin ring disclosed in Patent Document 6 does not generate any odor after absorbing oxygen and has excellent oxygen-absorbing performance under a wide range of humidity conditions from low humidity to high humidity. There is a problem that it turns yellow and its appearance deteriorates when used as a packaging material.
  • Patent Document 7 has insufficient oxygen barrier properties to completely block out oxygen, and is also unable to remove residual oxygen in the gas in the head space above the contents of the container. The problem was that it was possible
  • a first embodiment of the present invention aims to provide a resin composition that exhibits good oxygen barrier performance, has a good color tone after oxygen absorption, has excellent strength and shape retention, and has excellent moldability.
  • a second embodiment of the present invention provides a multilayer injection molded article and a container that exhibit good oxygen barrier performance, have a good color tone after oxygen absorption, have excellent strength and shape retention, and have a good appearance.
  • the task is to
  • a third embodiment of the present invention aims to provide a multilayer body and a container that exhibit good oxygen barrier performance, have a good color tone after oxygen absorption, have excellent strength and shape retention, and have a good appearance. shall be.
  • the fourth embodiment of the present invention provides a medical multilayer container that has excellent oxygen barrier properties, water vapor barrier properties, moldability, drop strength, strength and shape retention, and has a good color tone after storage (after oxygen absorption). The challenge is to provide.
  • the fifth embodiment of the present invention has excellent oxygen barrier properties, water vapor barrier properties, moldability, strength and shape maintenance properties, has little elution from the container, and has little change in color of the container after storage.
  • An object of the present invention is to provide a prefill syringe with good visibility.
  • the sixth embodiment of the present invention prevents biopharmaceuticals from deterioration, decrease in efficacy, and contamination with impurities, and also uses containers that have little color change after storage and good visibility of contents.
  • the challenge is to provide a preservation method.
  • the seventh embodiment of the present invention can prevent adrenaline from being oxidized, reduce components eluted from the container, and reduce color change of the container after storage when storing an adrenaline-containing drug solution.
  • An object of the present invention is to provide a method for preserving an adrenaline-containing drug solution.
  • the eighth embodiment of the present invention aims to provide a modified polyester that exhibits good oxygen barrier performance, has a good color tone after oxygen absorption, has excellent strength and shape retention, and has excellent moldability.
  • a layer (A) containing a resin composition containing a polyester compound (a) having a predetermined structure and a transition metal catalyst and a layer (A) containing a resin composition containing a polyester compound (a) having a predetermined structure and a transition metal catalyst;
  • the problem of the third embodiment is solved by a multilayer body containing at least three layers, in which a layer (B) containing a thermoplastic resin (b) different from a) is laminated on both sides of the layer (A). They discovered this and completed the present invention.
  • polyester compound (a) a transition metal catalyst; A resin composition containing,
  • the polyester compound (a) is based on a total of 100 mol% of the structural units represented by the following formulas (1), (2), and (3) in the polyester compound (a), 30 to 55 mol% of the structural unit represented by the following formula (1), 15 to 40 mol% of the structural unit represented by the following formula (2), 20 to 40 mol% of the structural unit represented by the following formula (3), A resin composition containing.
  • n represents the amount of repeating unit, and the structural unit represented by the above formula (1), the structural unit shown by the above formula (2), and the above formula ( Corresponds to the composition ratio of the constituent units expressed in 3).)
  • the polyester compound (a) is based on a total of 100 mol% of the structural units represented by the following formulas (1), (2), and (3) in the polyester compound (a), 40 to 50 mol% of the structural unit represented by the above formula (1), 20 to 35 mol% of the structural unit represented by the formula (2), 25 to 35 mol% of the structural unit represented by the formula (3), Contains The resin composition according to [1], wherein the total of the structural units represented by formulas (1) to (3) is 95 mol% or more with respect to 100 mol% of the total structural units of the polyester compound (a).
  • a container comprising the multilayer body according to [9].
  • a method for storing biopharmaceuticals in containers comprising:
  • the container includes an oxygen absorbing layer (layer A) made of the resin composition according to any one of [1] to [4], and a resin layer (layer A) containing polyolefin (b) laminated on both sides of the layer A.
  • B) A method for preserving a biopharmaceutical, the container having a multilayer structure containing at least three layers.
  • the polyolefin (b) is a cycloolefin copolymer or a cycloolefin polymer.
  • a multilayer injection molded article and a container that exhibit good oxygen barrier performance, have a good color tone after oxygen absorption, have excellent strength and shape retention, and have a good appearance. can do.
  • a multilayer body and a container that exhibit good oxygen barrier performance, have a good color tone after oxygen absorption, have excellent strength and shape retention, and have a good appearance. I can do it.
  • the medical multilayer has excellent oxygen barrier properties, water vapor barrier properties, moldability, drop strength, strength and shape maintenance properties, and has a good color tone after storage (after oxygen absorption).
  • a container can be provided.
  • the fifth embodiment of the present invention has excellent oxygen barrier properties, water vapor barrier properties, moldability, strength and shape maintenance properties, has little elution from the container, and has little change in color tone of the container after storage. It is possible to provide a prefill syringe with good visibility of contents.
  • a method for preserving biopharmaceuticals which prevents deterioration of biopharmaceuticals, decreases in efficacy, and contamination with impurities, and also allows for minimal change in color of containers after storage and good visibility of contents. can be provided.
  • this embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content.
  • ⁇ is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • the resin composition of the first embodiment contains at least a polyester compound (a) and a transition metal catalyst, and the polyester compound (a) is represented by the following formula (1), formula (2), and formula (3).
  • the polyester compound (a) is represented by the following formula (1), formula (2), and formula (3).
  • the total 100 mol% of the structural units represented 30 to 55 mol% of the structural unit represented by the following formula (1), 15 to 40 mol% of the structural unit represented by the following formula (2), Contains 20 to 40 mol% of the structural unit represented by the following formula (3).
  • n represents the amount of repeating unit
  • the structural unit represented by the above formula (1), the structural unit shown by the above formula (2), and the above formula Corresponds to the composition ratio of the constituent units expressed in 3).
  • the resin composition according to the first embodiment exhibits good oxygen barrier performance, has a good color tone after oxygen absorption, has excellent strength and shape retention, and has excellent moldability.
  • the resin composition according to the first embodiment preferably has excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, and absorbs oxygen regardless of the presence or absence of moisture in the object to be preserved. It can be used in a wide range of applications, such as foods, cooked foods, beverages, medicines, and health foods, as it can absorb oxygen and does not cause odor or yellowing after absorbing oxygen. can.
  • this resin composition it is possible to realize an oxygen-absorbing film or the like in which the decrease in strength after oxygen absorption is extremely small and the deterioration of strength over time is suppressed.
  • the polyester compound (a) contained in the resin composition of the first embodiment contains structural units represented by the above formulas (1) to (3).
  • "containing a structural unit” means having one or more such structural units in the compound.
  • the above-mentioned structural unit may be either a random copolymer of the above-mentioned structural unit and other structural units, or a block copolymer of the above-mentioned structural unit.
  • the polyester compound (a) contains a structural unit represented by the above formula (1) based on a total of 100 mol% of the structural units represented by the above formula (1), the above formula (2), and the above formula (3). 15 to 40 mol% of the structural unit represented by the above formula (2), and 20 to 40 mol% of the structural unit represented by the above formula (3).
  • the structural unit represented by the above formula (1) is It is preferable that the amount of the structural unit represented by the above formula (2) is 20 to 35 mol%, and the amount of the structural unit represented by the above formula (3) is 25 to 35 mol%.
  • the total of the structural units represented by the above formulas (1) to (3) is 95 mol% or more based on 100 mol% of all the structural units of the polyester compound (a).
  • the content of the structural units represented by formulas (1) to (3) can be measured by 1H-NMR in deuterated chloroform.
  • the content of the structural unit of the above formula (1) is less than 30 mol%, the oxygen barrier properties of the polyester compound (a) will decrease. Moreover, when the structural unit of the above formula (1) exceeds 55 mol%, the oxygen absorption performance of the polyester compound (a) decreases.
  • the content of the structural unit of formula (2) is less than 15 mol%, the oxygen absorption performance of the polyester compound (a) decreases. Furthermore, if the content of the structural unit of the above formula (2) exceeds 40 mol %, deterioration of appearance due to yellowing will be accelerated.
  • the content of the structural unit of the above formula (3) is less than 20 mol%, the oxygen barrier properties of the polyester compound (a) will decrease. Moreover, if the structural unit of the above formula (3) exceeds 40 mol %, the low molecular weight component will increase, causing bleeding during molding and occurrence of mold deposits.
  • the method for producing the polyester compound (a) containing the structural units represented by the above formulas (1) to (3) in the first embodiment is not particularly limited, and any conventionally known method for producing polyester may be applied. be able to.
  • methods for producing polyester include melt polymerization methods such as transesterification and direct esterification, and solution polymerization.
  • the transesterification method or the direct esterification method is preferred from the viewpoint of easy availability of raw materials, in which 2,6-naphthalene dicarboxylic acid or its derivative (I) and 2,6-tetraline dicarboxylic acid or It can be obtained by polycondensing its derivative (II), isophthalic acid or its derivative (III), and ethylene glycol or its derivative (IV).
  • Various catalysts such as transesterification catalysts, esterification catalysts, and polycondensation catalysts, various stabilizers such as etherification inhibitors, heat stabilizers, and light stabilizers, and polymerization modifiers used in the production of polyester compound (a) are also conventionally known. Any of these can be used, and these are appropriately selected depending on the reaction rate, color tone of the polyester compound (a), safety, thermal stability, weather resistance, dissolution properties of the polyester compound (a), and the like.
  • the various catalysts mentioned above include compounds of metals such as zinc, lead, cerium, cadmium, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, tin (e.g. fatty acid salts, carbonates, Examples include phosphates, hydroxides, chlorides, oxides, alkoxides) and metal magnesium, and these can be used alone or in combination.
  • the intrinsic viscosity (value measured at 25°C using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a mass ratio of 6:4) of the polyester compound (a) of the first embodiment is particularly limited. However, in terms of moldability of the polyester compound (a), it is preferably 0.5 to 1.5 dL/g, more preferably 0.8 to 1.2 dL/g.
  • the polyester resin in the first embodiment may contain any structural units other than the structural units represented by formulas (1) to (3) above, as long as it does not affect its performance.
  • Specific examples of such arbitrary structural units include, but are not limited to, units derived from dicarboxylic acids or derivatives thereof and diols or derivatives thereof other than the units described above.
  • the content of arbitrary structural units in the polyester resin is not particularly limited, it is preferably less than 5 mol% with respect to 100 mol% of all structural units of the polyester resin.
  • Diols or derivatives thereof as arbitrary structural units include, but are not limited to, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane.
  • Diols aliphatic diols such as neopentyl glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalene dimethanol, 1,3-decahydronaphthalene dimethanol, 1, Alicyclic diols such as 4-decahydronaphthalene dimethanol, 1,5-decahydronaphthalene dimethanol, 1,6-decahydronaphthalene dimethanol, 2,7-decahydronaphthalene dimethanol, tetralin dimethanol, or These derivatives can be mentioned.
  • the above diols or derivatives thereof can be used alone or in combination of two or more.
  • dicarboxylic acids or derivatives thereof as arbitrary structural units include, but are not limited to, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedioic acid, phthalic acid, Examples include benzenedicarboxylic acids such as terephthalic acid, naphthalene dicarboxylic acids such as 1,5-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid, and derivatives thereof.
  • One kind of dicarboxylic acid or its derivative can be used alone or two or more kinds can be used in combination.
  • the transition metal catalyst used in the resin composition of the first embodiment may be appropriately selected from known catalysts as long as it can function as a catalyst for the oxidation reaction of the polyester compound (a). can. Oxygen barrier properties can be improved through oxygen absorption by the oxidation reaction of the polyester compound (a).
  • the transition metal contained in the transition metal catalyst is preferably a metal from groups 4 and 8 to 11 of the periodic table. In order to exhibit the effect with a small amount, metals from groups 8 to 11 of the periodic table are more preferable.
  • transition metal catalysts include organic acid salts, halides, phosphates, phosphites, hypophosphites, nitrates, sulfates, oxides, and hydroxides of transition metals.
  • examples of the transition metal contained in the transition metal catalyst include, but are not limited to, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, and rhodium. Among these, cobalt, nickel, and copper are preferred.
  • Examples of organic acids include acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, tolic acid, oleic acid, Examples include, but are not limited to, capric acid and naphthenic acid.
  • the transition metal catalyst is preferably a combination of these transition metals and an organic acid, where the transition metal is cobalt, nickel or copper, and the organic acid is acetic acid, stearic acid, 2-ethylhexanoic acid, oleic acid or naphthenic acid. More preferred is a combination. Note that the transition metal catalyst can be used alone or in combination of two or more.
  • the blending amount of the transition metal catalyst can be appropriately set depending on the type of the polyester compound (a) and transition metal catalyst used and the desired performance, and is not particularly limited.
  • the amount of transition metal preferably a metal from Groups 8 to 11 of the periodic table, more preferably cobalt, nickel or copper
  • total amount thereof is preferably 0.5 to 10 ppm, more preferably 1 to 5 ppm, and most preferably 1.5 to 3 ppm, based on the mass of the polyester compound (a).
  • the amount of the transition metal contained in the remaining catalyst is also included in the above numerical range.
  • the amount and type of transition metal can be determined by inductively coupled plasma mass spectrometry.
  • the amount of transition metal is 0.5 ppm or more, oxygen absorption performance tends to be further improved.
  • the amount of transition metal is 10 ppm or less, yellowing tends to be further suppressed.
  • the polyester compound (a) and the transition metal catalyst can be mixed by a known method, but preferably by kneading with an extruder, it can be used as a resin composition with good dispersibility.
  • the resin composition may contain additives such as desiccants, pigments, dyes, antioxidants, slip agents, antistatic agents, stabilizers, calcium carbonate, clay, etc., to the extent that the effects of the first embodiment are not impaired.
  • fillers such as mica and silica, deodorants, etc. may be added, but the material is not limited to those shown above, and various materials can be mixed.
  • the resin composition of the first embodiment may further contain a radical generator or a photoinitiator, if necessary, in order to promote the oxygen absorption reaction.
  • radical generators include various N-hydroxyimide compounds, such as N-hydroxysuccinimide, N-hydroxymaleimide, N,N'-dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxyhexahydrophthalimide, 3-sulfonyl-N-hydroxyphthalimide, 3-methoxycarbonyl-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 3 -Hydroxy-N-hydroxyphthalimide, 4-nitro-N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide, 4-methoxy-N-hydroxyphthalimide, 4-dimethylamino-N-hydroxyphthalimide, 4-carboxy-N -
  • photoinitiators examples include, but are not particularly limited to.
  • specific examples of photoinitiators include benzophenone and its derivatives, thiazine dyes, metal porphyrin derivatives, anthraquinone derivatives, etc., but are not particularly limited thereto.
  • these radical generators and photoinitiators can be used individually or in combination of two or more types.
  • thermoplastic resins used for kneading include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear very low density polyethylene, polypropylene, poly-1-butene, and poly-4-methyl.
  • thermoplastic resins used for kneading include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear very low density polyethylene, polypropylene, poly-1-butene, and poly-4-methyl.
  • - Polyolefins such as random or block copolymers of ⁇ -olefins such as -1-pentene or ethylene, propylene, 1-butene, 4-methyl-1-pentene, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, etc.
  • ethylene-Ethylene-vinyl compound copolymers such as methyl methacrylate copolymer, styrene resins such as polystyrene, acrylonitrile-styrene copolymer, ⁇ -methylstyrene-styrene copolymer, polymethyl acrylate, polymethyl methacrylate, etc.
  • polyvinyl compounds nylon 6, nylon 66, nylon 610, nylon 12, polyamides such as polymethaxylylene adipamide (MXD6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), Polyesters such as polyethylene naphthalate (PEN), glycol-modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS), polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate, polycarbonate, Examples include polyethers such as polyethylene oxide, and mixtures thereof.
  • MXD6 polymethaxylylene adipamide
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PTT polytrimethylene terephthalate
  • Polyesters such as polyethylene naphthalate (PEN), glycol-modified polyethylene terephthalate (PETG), poly
  • the resin composition of the first embodiment is used in the form of a powder, granules, pellets, film, or other small pieces, which is then filled into an air-permeable packaging material to form an oxygen absorbent bag.
  • it can be formed into a film and used as an oxygen absorber in the form of labels, cards, packing, etc.
  • the resin composition of the first embodiment can of course be used as a packaging material and packaging container in the form of a single layer, and can also be used as a laminate of at least one layer made of the resin composition and at least one layer made of another resin. It can be used as multi-layer packaging material and multi-layer packaging containers.
  • the resin composition of the first embodiment is preferably provided inside the outer surface of the container, etc. so as not to be exposed to the outer surface of the container, etc., and for the purpose of avoiding direct contact with the contents. , it is preferable to provide it outside the inner surface of the container or the like.
  • a resin composition as at least one intermediate layer of the multilayer.
  • the multilayer injection molded article according to the second embodiment includes a layer (A) containing the resin composition according to the first embodiment (hereinafter also referred to as "layer A”), and a layer (A) containing the resin composition according to the first embodiment, and a layer (hereinafter also referred to as "layer A") that is heated to a temperature different from that of the polyester compound (a). It contains at least a layer (B) (hereinafter also referred to as "layer B”) containing a plastic resin (b). Note that in the second embodiment, descriptions of other embodiments can be cited as appropriate.
  • the multilayer injection molded article and container according to the second embodiment exhibit good oxygen barrier performance, have a good color tone after oxygen absorption, have excellent strength and shape retention, and have a good appearance.
  • the multilayer injection molded article and the container according to the second embodiment preferably have excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, and can be used regardless of the presence or absence of moisture in the stored material. Because it can absorb oxygen without causing any odor or yellowing after absorbing oxygen, it can be used for a wide range of purposes, such as food, cooked foods, beverages, pharmaceuticals, health foods, etc. can do.
  • the second embodiment that does not contain iron powder or the like, it is also possible to realize a multilayer injection molded body and a container that are not sensitive to metal detectors. Further, according to a preferred aspect of the second embodiment, it is possible to realize a multilayer injection molded article and a container that have extremely low strength loss after oxygen absorption, maintain strength even during long-term use, and are less likely to cause delamination. You can also do it.
  • the layer structure in the multilayer injection molded article and container of the second embodiment is not particularly limited, and the number and type of layers A and B are not particularly limited.
  • it may be an A/B configuration consisting of one layer A and one layer B, or a three-layer configuration of B1/A/B2 consisting of one layer A and two layers B1 and B2. It may be.
  • layer B1 and layer B2 may be the same layer or different layers.
  • it may have a five-layer structure of B1/B2/A/B2/B1, which is composed of one layer A and two types of four layers B1 and B2.
  • both layers B1 may have the same composition or different compositions
  • both layer B2 may have the same composition or different compositions.
  • the multilayer injection molded article and container of the second embodiment may include an arbitrary layer such as an adhesive layer (layer AD) as necessary, for example, B1/AD/B2/A/B2/AD/ A seven-layer structure of B1 may be used.
  • layer AD adhesive layer
  • both layers B1 may have the same composition or different compositions
  • both layers B2 may have the same composition or different compositions
  • both layers AD may have the same composition. may be different.
  • the multilayer injection molded article and container of 2nd Embodiment when it has multiple layers B, it may have layer A between the layers B.
  • the thickness of layer A is not particularly limited, but is preferably 10 to 1000 ⁇ m, more preferably 50 to 700 ⁇ m, and even more preferably 100 to 500 ⁇ m. By setting it as this range, it tends to be possible to further improve the oxygen barrier performance of layer A and to prevent economic efficiency from being impaired.
  • the ⁇ polyester compound> of the second embodiment is as described in the section of the ⁇ polyester compound> of the first embodiment.
  • ⁇ Transition metal catalyst> of the second embodiment is as described in the section of ⁇ transition metal catalyst> of the first embodiment.
  • the resin composition and layer A of the second embodiment may contain thermoplastic resins other than the polyester compound (a) within a range that does not impede the purpose of the second embodiment.
  • thermoplastic resins are as described as "thermoplastic resin" in the first embodiment.
  • resins with high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymers are more preferred.
  • the layer (A) contains a polyolefin, it can be distinguished from the layer (B) described below depending on whether or not it contains the polyester compound (a).
  • Layer B of the second embodiment contains thermoplastic resin (b).
  • the thermoplastic resin (b) is not particularly limited as long as it is different from the polyester compound (a).
  • the content of the thermoplastic resin (b) in layer B is not particularly limited, but the content of the thermoplastic resin (b) with respect to the total amount of layer B is preferably 70 to 100% by mass, and 80 to 100% by mass. is more preferable, and even more preferably 90 to 100% by mass. By setting it as the said range, the transparency and moldability of layer B can be improved.
  • the thermoplastic resin (b) can be used alone or in combination of two or more.
  • the multilayer injection molded article and container of the second embodiment may have a plurality of layers B together with the layer A, and the configurations of the plurality of layers B may be the same or different from each other.
  • the thickness of layer B can be determined as appropriate depending on the application, and from the viewpoint of ensuring various physical properties such as strength such as drop resistance and flexibility required for multilayer injection molded bodies and containers, it is preferably 30 mm. -1000 ⁇ m, more preferably 50-800 ⁇ m, still more preferably 100-600 ⁇ m. In addition, it shows better oxygen barrier performance, has a better color tone after oxygen absorption, has better strength and shape retention, and has a better appearance. is preferably 100 to 300 ⁇ m, the thickness of the intermediate layer (layer A) is preferably 200 to 400 ⁇ m, and the thickness of the outer container layer (layer B) is preferably 400 to 600 ⁇ m.
  • thermoplastic resin can be used as the thermoplastic resin (b) in the second embodiment, and is not particularly limited. Examples include polyolefins, polyesters, polyamides, ethylene-vinyl alcohol copolymers, plant-derived resins, and chlorine-based resins.
  • the thermoplastic resin (b) preferably contains at least one selected from the group consisting of these resins. These resins can be used alone or in combination of two or more.
  • polyolefins include polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene), polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene and Known copolymers such as copolymers with ⁇ -olefins, propylene and ⁇ -olefin copolymers, ethylene- ⁇ , ⁇ -unsaturated carboxylic acid copolymers, ethylene- ⁇ , ⁇ -unsaturated carboxylic acid ester copolymers, etc.
  • the resins are preferably ring-opening polymers of cycloolefins such as norbornene or tetracyclododecene or derivatives thereof, hydrogenated products thereof, cycloolefins such as norbornene or tetracyclododecene or derivatives thereof, and ethylene or propylene. It is a copolymer resin in which a cyclopentyl residue or a substituted cyclopentyl residue is inserted into the molecular chain by polymerization with
  • cycloolefins include monocyclic and polycyclic ones.
  • Preferred are thermoplastic norbornene resins or thermoplastic tetracyclododecene resins.
  • thermoplastic norbornene resins include ring-opening polymers of norbornene monomers, hydrogenated products thereof, addition polymers of norbornene monomers, and addition polymers of norbornene monomers and olefins. It will be done.
  • Thermoplastic tetracyclododecene resins include ring-opening polymers of tetracyclododecene monomers, hydrogenated products thereof, addition polymers of tetracyclododecene monomers, and tetracyclododecene monomers. Examples include addition polymers of polymers and olefins.
  • Thermoplastic norbornene resins are described in, for example, JP-A-3-14882, JP-A-3-122137, and JP-A-4-63807.
  • One kind of polyolefin can be used alone or two or more kinds can be used in combination.
  • norbornene and Copolymers made from olefins such as ethylene, cycloolefin copolymers (COC), which are copolymers made from tetracyclododecene and olefins such as ethylene, and ring-opening polymerization of norbornene and hydrogenation.
  • COC cycloolefin copolymers
  • COCs and COPs are described in, for example, Japanese Patent Laid-Open No. 5-300939 or Japanese Patent Laid-Open No. 5-317411.
  • COC is, for example, manufactured by Mitsui Chemicals Co., Ltd. and is commercially available as APEL (registered trademark)
  • COP is, for example, manufactured by Nippon Zeon Co., Ltd., as ZEONEX (registered trademark) or ZEONOR (registered trademark), or Daikyo Co., Ltd. It is manufactured by Seiko and is commercially available as Daikyo Resin CZ (registered trademark).
  • ZEONEX (registered trademark) manufactured by Zeon Corporation include ZEONEX (registered trademark) 690R (trade name).
  • COC and COP exhibit better oxygen barrier performance, have better color tone after oxygen absorption, have better strength and shape retention, and can provide multilayer injection molded products and containers with better appearance. Therefore, chemical properties such as heat resistance and light resistance and chemical resistance exhibit the characteristics of a polyolefin resin, while physical properties such as mechanical properties, melting, flow characteristics, and dimensional accuracy exhibit characteristics of an amorphous resin. Therefore, it is particularly preferable.
  • the polyester described here is a polyester that can be used as the thermoplastic resin (b), and is different from the polyester compound (a) of the second embodiment.
  • the polyester is one or more selected from polyhydric carboxylic acids including dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols including glycol. or hydroxycarboxylic acids and their ester-forming derivatives, or cyclic esters.
  • Ethylene terephthalate thermoplastic polyester has ethylene terephthalate units occupying most of the ester repeating units, generally 70 mol% or more, and has a glass transition point (Tg) of 50 to 90°C and a melting point (Tm) of 200 to 275. C.
  • polyethylene terephthalate-based thermoplastic polyester polyethylene terephthalate is particularly excellent in terms of pressure resistance, heat resistance, heat pressure resistance, etc., but in addition to ethylene terephthalate units, dibasic acids such as isophthalic acid and naphthalene dicarboxylic acid and diols such as propylene glycol Copolymerized polyesters containing small amounts of ester units consisting of can also be used.
  • dibasic acids such as isophthalic acid and naphthalene dicarboxylic acid and diols such as propylene glycol Copolymerized polyesters containing small amounts of ester units consisting of can also be used.
  • One kind of polyester can be used alone or two or more kinds can be used in combination.
  • dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3- Examples include cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc.
  • saturated aliphatic dicarboxylic acids or their ester-forming derivatives unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, or their ester-forming derivatives, orthophthalic acid, isophthalic acid, terephthalic acid , 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, Aromatic dicarboxylic acids exemplified by 4,4'-biphenylsulfone dicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, anthracene dicarboxylic acid,
  • terephthalic acid terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid are particularly preferred in terms of the physical properties of the resulting polyester, and other dicarboxylic acids may be copolymerized as necessary. .
  • Polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3',4'-biphenyltetracarboxylic acid, and ester-forming derivatives thereof.
  • Glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4 -Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol , 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polytrimethylene glycol, polytetramethylene Aliphatic glycols such as glycols, hydroquinon
  • glycols it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main components.
  • Polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like.
  • hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these. Examples include ester-forming derivatives of.
  • cyclic ester examples include ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, glycolide, and lactide.
  • ester-forming derivatives of polyhydric carboxylic acids and hydroxycarboxylic acids include their alkyl esters, acid chlorides, and acid anhydrides.
  • the polyester used in the second embodiment is preferably a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative, and whose main glycol component is alkylene glycol.
  • the polyester whose main acid component is terephthalic acid or its ester-forming derivative is preferably a polyester containing 70 mol% or more of terephthalic acid or its ester-forming derivative based on the total acid component, and more preferably Preferably it is a polyester containing 80 mol% or more, and more preferably a polyester containing 90 mol% or more.
  • the polyester whose main acid component is naphthalene dicarboxylic acid or its ester-forming derivative preferably contains 70 mol% or more in total of naphthalene dicarboxylic acid or its ester-forming derivative, more preferably 80 mol% or more. It is a polyester containing mol% or more, more preferably 90 mol% or more.
  • Naphthalene dicarboxylic acid or its ester-forming derivative used in the second embodiment includes 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, and 1,5-naphthalene dicarboxylic acid, which are exemplified in the dicarboxylic acids mentioned above. , 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, or ester-forming derivatives thereof are preferred.
  • the polyester whose main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more, more preferably 80 mol% or more of alkylene glycol based on all glycol components, More preferably, it is a polyester containing 90 mol% or more.
  • the alkylene glycol mentioned here may contain a substituent or an alicyclic structure in its molecular chain.
  • Copolymerization components other than the above terephthalic acid/ethylene glycol include isophthalic acid, 2,6-naphthalene dicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propane. At least one selected from the group consisting of diol and 2-methyl-1,3-propanediol is preferable in order to achieve both transparency and moldability, and in particular, isophthalic acid, diethylene glycol, neopentyl glycol, More preferably, it is at least one selected from the group consisting of 1,4-cyclohexanedimethanol.
  • a preferable example of the polyester used in the second embodiment is a polyester whose main repeating unit is composed of ethylene terephthalate, more preferably a linear polyester containing 70 mol% or more of ethylene terephthalate units, and even more preferably a linear polyester containing ethylene terephthalate units in an amount of 70 mol% or more.
  • a linear polyester containing 80 mol% or more of terephthalate units is particularly preferred, and a linear polyester containing 90 mol% or more of ethylene terephthalate units is particularly preferred.
  • polyester used in the second embodiment is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate, more preferably 70 moles of ethylene-2,6-naphthalate units. % or more, more preferably linear polyesters containing 80 mol% or more of ethylene-2,6-naphthalate units, particularly preferably 90 mol% or more of ethylene-2,6-naphthalate units. It is a linear polyester containing
  • polyester used in the second embodiment include a linear polyester containing 70 mol% or more of propylene terephthalate units, a linear polyester containing 70 mol% or more of propylene naphthalate units, and 1,4-cyclohexane.
  • the combination of terephthalic acid/isophthalic acid//ethylene glycol, the combination of terephthalic acid//ethylene glycol/1,4-cyclohexanedimethanol, and the combination of terephthalic acid//ethylene glycol/neopentyl glycol are transparent. This is preferable in terms of achieving both properties and moldability. It goes without saying that a small amount (5 mol % or less) of diethylene glycol produced by dimerization of ethylene glycol may be included during the esterification (transesterification) reaction and polycondensation reaction.
  • polyester used in the second embodiment include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate, or ring-opening polycondensation of glycolide.
  • This polyglycolic acid may be copolymerized with other components such as lactide.
  • the polyamide used in the second embodiment is a polyamide whose main constitutional unit is a unit derived from a lactam or an aminocarboxylic acid, or a polyamide whose main constitutional unit is a unit derived from an aliphatic diamine and an aliphatic dicarboxylic acid.
  • One kind of polyamide can be used alone or two or more kinds can be used in combination.
  • lactams such as ⁇ -caprolactam and laurolactam
  • aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid
  • aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid, etc.
  • an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof can be used.
  • an alicyclic diamine may be used.
  • the aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine.
  • linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples include aliphatic diamines such as nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine.
  • alicyclic diamine include cyclohexane diamine, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane.
  • linear aliphatic dicarboxylic acids and alicyclic dicarboxylic acids are preferable, and linear aliphatic dicarboxylic acids having an alkylene group having 4 to 12 carbon atoms are particularly preferable.
  • linear aliphatic dicarboxylic acids include adipic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadionic acid, dodecanedioic acid, dimer acid and their functional Derivatives etc. can be mentioned.
  • alicyclic dicarboxylic acid examples include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.
  • aromatic diamine examples include metaxylylene diamine, para-xylylene diamine, para-bis(2-aminoethyl)benzene, and the like.
  • aromatic dicarboxylic acids examples include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and functional derivatives thereof. It will be done.
  • polyamides include polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 4,6, polyamide 6,6, polyamide 6,10, polyamide 6T, polyamide 9T, polyamide 6IT, and polymethaxylylene azide.
  • a copolymerization component of the polyamide a polyether having a number average molecular weight of 2,000 to 20,000 and having at least one terminal amino group or a terminal carboxyl group, or an organic carboxylate of the polyether having the terminal amino group, or Amino salts of polyethers having the aforementioned terminal carboxyl groups can also be used.
  • a specific example is bis(aminopropyl)poly(ethylene oxide) (polyethylene glycol having a number average molecular weight of 2,000 to 20,000).
  • the partially aromatic polyamide may contain a substantially linear structural unit derived from a polyhydric carboxylic acid having three or more bases, such as trimellitic acid and pyromellitic acid.
  • the ethylene-vinyl alcohol copolymer used in the second embodiment is not particularly limited, but preferably has an ethylene content of 15 to 60 mol%, more preferably 20 to 55 mol%, and more preferably 29 to 44 mol%. %, and the degree of saponification of the vinyl acetate component is preferably 90 mol% or more, more preferably 95 mol% or more.
  • the ethylene-vinyl alcohol copolymer may further include a small amount of ⁇ -olefin such as propylene, isobutene, ⁇ -octene, ⁇ -dodecene, ⁇ -octadecene, etc., within a range that does not adversely affect the effects of the second embodiment. It may contain comonomers such as unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides, anhydrides, unsaturated sulfonic acids or salts thereof.
  • the ethylene-vinyl alcohol copolymer can be used alone or in combination of two or more.
  • the plant-derived resin used in the second embodiment may be any resin that contains a plant-derived substance as a raw material, and the plant-derived substance used as a raw material is not particularly limited. Specific examples include aliphatic polyester biodegradable resins. Examples of aliphatic polyester biodegradable resins include poly( ⁇ -hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLA); polybutylene succinate (PBS), polyethylene succinate (PES), etc. Examples include polyalkylene alkanoate. One type of plant-derived resin can be used alone or two or more types can be used in combination.
  • the chlorine-based resin used in the second embodiment may be any resin containing chlorine in its structural unit, and any known resin may be used. Specific examples include polyvinyl chloride, polyvinylidene chloride, and copolymers of these with vinyl acetate, maleic acid derivatives, higher alkyl vinyl ethers, and the like. One type of chlorine-based resin can be used alone or two or more types can be used in combination.
  • the multilayer injection molded article and container of the second embodiment may include other layers depending on desired performance and the like.
  • the other layers may have the same composition as or different from the compositions of layers A and B, as long as they are laminated so that they can be distinguished from layers A and B in the multilayer injection molded article and container.
  • Examples of other layers include an adhesive layer and the like.
  • an adhesive layer is provided between the two layers. It is preferable.
  • the adhesive layer preferably contains a thermoplastic resin having adhesive properties.
  • adhesive thermoplastic resins include acid-modified polyolefins obtained by modifying polyolefin resins such as polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid.
  • polyester thermoplastic elastomers whose main components are resins and polyester block copolymers.
  • the adhesive layer from the viewpoint of adhesiveness, it is preferable to use a modified resin of the same type as the thermoplastic resin (b) used as layer B.
  • the thickness of the adhesive layer is preferably 2 to 100 ⁇ m, more preferably 5 to 90 ⁇ m, and still more preferably 10 to 80 ⁇ m, from the viewpoint of ensuring moldability while exhibiting practical adhesive strength.
  • the manufacturing method and layer structure of the multilayer injection molded article of the second embodiment are not particularly limited, and the multilayer injection molded article can be manufactured by a normal injection molding method. For example, using a molding machine and an injection mold equipped with two or more injection machines, the material constituting layer A and the material constituting layer B are passed from the respective injection cylinders through the mold hot runner and into the cavity. A multilayer injection molded article corresponding to the shape of the injection mold can be manufactured by injecting the resin into a mold.
  • the material constituting layer B is injected from an injection cylinder, then the material constituting layer A is injected from another injection cylinder simultaneously with the resin constituting layer B, and then the resin constituting layer B is injected.
  • the material constituting layer B is injected from an injection cylinder, then the material constituting layer A is injected from another injection cylinder simultaneously with the resin constituting layer B, and then the resin constituting layer B is injected.
  • a multilayer injection molded article having a five-layer configuration B/A/B/A/B can be produced.
  • the material constituting layer B1 is injected from an injection cylinder, then the material constituting layer B2 is injected from another injection cylinder simultaneously with the resin constituting layer B1, and then the resin constituting layer A is injected. is injected simultaneously with the resins constituting layers B1 and B2, and then the required amount of resin constituting layer B1 is injected to fill the cavity, resulting in multilayer injection of a five-layer configuration B1/B2/A/B2/B1. Molded objects can be produced.
  • the mouth and neck portion may be crystallized by heat treatment at this stage.
  • the degree of crystallinity is preferably 30-50%, more preferably 35-45%. Note that crystallization may be performed after performing secondary processing, which will be described later.
  • the container of the second embodiment includes the multilayer injection molded body of the second embodiment.
  • the container has good oxygen barrier properties, good color tone after oxygen absorption, excellent strength and shape retention, and has a good appearance.
  • the multilayer injection molded article of the second embodiment itself is a container, it has good oxygen barrier properties, good color tone after oxygen absorption, excellent strength and shape retention, and has a good appearance. Furthermore, in addition to the slight amount of oxygen that enters from outside the container, it can also absorb oxygen within the container to prevent the stored contents from deteriorating due to oxygen.
  • the shapes of the multilayer injection molded body and container of the second embodiment are not particularly limited, and can be made into any shape depending on the mold. Considering that the multilayer injection molded article of the second embodiment can exhibit oxygen barrier performance, the multilayer injection molded article of the second embodiment and the container can be used as storage containers such as cup-shaped containers and bottle-shaped containers. It is preferable that there be. Further, for secondary processing such as blow molding, which will be described later, such as a PET bottle, the multilayer injection molded article of the second embodiment is preferably a test tube-shaped preform (parison).
  • the container of the second embodiment can also be obtained by further processing (that is, secondary processing) the multilayer injection molded product of the second embodiment.
  • the container has good oxygen barrier properties, good color tone after oxygen absorption, excellent strength and shape retention, and has a good appearance. Furthermore, in addition to the slight amount of oxygen that enters from outside the container, it can also absorb oxygen within the container to prevent the stored contents from deteriorating due to oxygen. Examples of secondary processing methods include injection blow molding and stretch blow molding. Containers obtained through secondary processing include bottles and vials.
  • a test tube-shaped preform (parison) is first molded as the multilayer injection molded article of the second embodiment, and then the mouth of the heated preform is fixed with a jig, and the preform is shaped into the final shape.
  • the preform can be molded into a bottle by fitting it into a mold, blowing air through the mouth, inflating the preform, bringing it into close contact with the mold, and cooling and solidifying it.
  • injection stretch blow molding the mouth of a heated preform is fixed with a jig, the preform is fitted into a final shape mold, and air is blown into the preform while stretching it with a stretching rod from the mouth. It can be molded into a bottle by blow-stretching it, bringing it into close contact with a mold, and cooling and solidifying it.
  • Injection stretch blow molding methods can be broadly classified into hot parison methods and cold parison methods. In the former method, the preform is blow molded in a softened state without being completely cooled.
  • the preform is formed as a supercooled bottomed preform that is considerably smaller than the dimensions of the final shape and the resin is amorphous, and this preform is preheated to the drawing temperature to form the final shape. It is suitable for mass production because it is stretched in the axial direction in a mold and blow-stretched in the circumferential direction.
  • this multilayer preform is heated to a stretching temperature higher than the glass transition point (Tg), and then stretched by stretch blow molding in a final shape mold heated to a heat setting temperature. It is stretched in the machine direction and also stretched in the cross direction with blow air.
  • the stretching ratio of the final blow molded product is preferably 1.2 to 6 times in the machine direction and 1.2 to 4.5 times in the transverse direction.
  • the final shape mold described above is heated to a temperature that promotes crystallization of the resin, for example, 120 to 230 °C for PET resin, preferably 130 to 210 °C, and during blowing, the outside of the vessel wall of the molded body is heated to a temperature that promotes crystallization of the resin.
  • Heat treatment is performed by contacting the inner surface for a predetermined period of time. After heat treatment for a predetermined time, the blowing fluid is switched to an internal cooling fluid to cool the inner layer.
  • the heat treatment time varies depending on the thickness and temperature of the blow molded product, but is generally 1.5 to 30 seconds, preferably 2 to 20 seconds in the case of PET resin.
  • the cooling time also varies depending on the heat treatment temperature and the type of cooling fluid, but is generally 0.1 to 30 seconds, preferably 0.2 to 20 seconds. Through this heat treatment, each part of the molded body is crystallized.
  • Cooling fluids include air at room temperature, various cooled gases such as -40°C to +10°C nitrogen, air, and carbon dioxide, as well as chemically inert liquefied gases such as liquefied nitrogen gas and liquefied gas.
  • Carbon dioxide gas, liquefied trichlorofluoromethane gas, liquefied dichlorodifluoromethane gas, other liquefied aliphatic hydrocarbon gases, etc. can be used.
  • This cooling fluid may also contain a liquid mist having a large heat of vaporization, such as water.
  • two molds are used for stretch blow molding, and the first mold is heat-treated within a predetermined temperature and time range, and then the blow molded product is transferred to the second mold for cooling, and then again.
  • the blow molded article may be cooled at the same time as blowing.
  • the outer layer of the blow-molded product taken out from the mold is cooled by standing to cool or by blowing cold air.
  • the multilayer preform is made into a primary blow molded body with a size larger than the final blow molded body using a primary stretch blow mold, and then this primary blow molded body is heated and shrunk, and then a second blow molded body is formed.
  • One example is two-stage blow molding in which stretch blow molding is performed using a subsequent mold to obtain a final blow molded product. According to this method for producing a blow molded body, the bottom of the blow molded body is sufficiently thinned by stretching, and a blow molded body with excellent resistance to deformation and impact at the bottom during hot filling and heat sterilization can be obtained. .
  • the multilayer injection molded product of the second embodiment, the container obtained from the multilayer injection molded product, and the container obtained by secondary processing the multilayer injection molded product may be coated with a vapor-deposited film of an inorganic substance or inorganic oxide, or an amorphous carbon film.
  • Examples of the inorganic substance or inorganic oxide include aluminum, alumina, silicon oxide, and the like.
  • a vapor-deposited film of an inorganic substance or an inorganic oxide can shield eluted substances such as acetaldehyde and formaldehyde from a multilayer injection molded article, a container, and the like.
  • the method for forming the deposited film is not particularly limited, and examples thereof include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition methods such as PECVD.
  • the thickness of the deposited film is preferably 5 to 500 nm, more preferably 5 to 200 nm, from the viewpoint of gas barrier properties, light shielding properties, bending resistance, etc.
  • the amorphous carbon film is a diamond-like carbon film, and is a hard carbon film also called an i-carbon film or a hydrogenated amorphous carbon film.
  • a method for forming the film a method is exemplified in which the inside of the hollow molded body is evacuated by evacuation, a carbon source gas is supplied thereto, and the carbon source gas is turned into plasma by supplying energy for plasma generation. Thereby, an amorphous carbon film can be formed on the inner surface of a multilayer injection molded body, a container, etc.
  • the amorphous carbon film can not only significantly reduce the permeability of low-molecular-weight inorganic gases such as oxygen and carbon dioxide, but also suppress the sorption of various low-molecular-weight organic compounds that have odors.
  • the thickness of the amorphous carbon film is preferably 50 to 5000 nm from the viewpoints of suppressing the sorption of low-molecular-weight organic compounds, improving gas barrier properties, adhesion to plastics, durability, transparency, and the like.
  • Multilayer injection molded products, containers, etc. exhibit good oxygen barrier performance, have a good color tone after oxygen absorption, have excellent strength and shape retention, and have a good appearance.
  • multilayer injection molded products and containers do not require moisture to absorb oxygen, so they have excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, and they also have excellent flavor retention of the contents. . Therefore, multilayer injection molded bodies, containers, etc. are suitable for packaging various articles.
  • beverages such as milk, juice, coffee, tea, and alcoholic beverages
  • liquid seasonings such as sauces, soy sauce, and dressings
  • prepared foods such as soups, stews, and curries; and jams, mayonnaise, etc.
  • Paste-like foods Marine products such as tuna and fish and shellfish; Processed milk products such as cheese and butter; Processed meat products such as meat, salami, sausage, and ham; Vegetables such as carrots and potatoes; Eggs; Noodles; Before cooking Processed rice products such as rice, cooked rice, and rice porridge; powdered seasonings, powdered coffee, powdered milk for infants, cooked foods for infants, powdered diet foods, nursing care foods, dried vegetables, dried foods such as rice crackers, etc. Chemicals such as pesticides and insecticides; Pharmaceutical products; Pet food; Detergents, and various other products can be mentioned, but are not particularly limited thereto.
  • contents that are susceptible to deterioration in the presence of oxygen such as beverages such as beer, wine, fruit juice, carbonated soft drinks, etc., and foods such as fruits, nuts, vegetables, meat products, infant foods, coffee, jam, mayonnaise, and ketchup.
  • beverages such as beer, wine, fruit juice, carbonated soft drinks, etc.
  • foods such as fruits, nuts, vegetables, meat products, infant foods, coffee, jam, mayonnaise, and ketchup.
  • packaging materials such as edible oils, dressings, sauces, tsukudani foods, dairy products, and other products such as pharmaceuticals and cosmetics.
  • the multilayer injection molded body, container, etc., and the objects to be preserved can be sterilized in a form suitable for the objects to be preserved.
  • Sterilization methods include heat sterilization such as hot water treatment at 100°C or lower, pressurized hot water treatment at 100°C or higher, ultra-high temperature heat treatment at 130°C or higher, electromagnetic wave sterilization such as ultraviolet rays, microwaves, and gamma rays, and ethylene oxide.
  • gas treatment such as sterilization, chemical sterilization using hydrogen peroxide and hypochlorous acid, etc.
  • the multilayer body of the third embodiment includes a layer (A) containing the resin composition according to the first embodiment (hereinafter also referred to as "layer A”) and a thermoplastic resin different from the polyester compound (a). It contains at least three layers in which layer (B) containing (b) (hereinafter also referred to as "layer B") is laminated on both sides of layer A. Note that in the third embodiment, descriptions of other embodiments can be cited as appropriate.
  • the multilayer body and container according to the third embodiment exhibit good oxygen barrier performance, have a good color tone after oxygen absorption, have excellent strength and shape retention, and have a good appearance.
  • the multilayer body and container according to the third embodiment preferably have excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, and can absorb oxygen regardless of the presence or absence of moisture in the stored material. Moreover, it does not generate odor or deteriorate appearance due to yellowing after absorbing oxygen, so it can be used in a wide range of applications regardless of the target, such as food, cooked foods, beverages, medicines, health foods, etc. I can do it.
  • the third embodiment that does not contain iron powder or the like, it is also possible to realize a multilayer body and a container that are not sensitive to metal detectors. Further, according to a preferred aspect of the third embodiment, it is possible to realize a multilayer body and a container that have extremely low strength loss after oxygen absorption, maintain strength even during long-term use, and are less likely to cause delamination. .
  • the multilayer body and container of the third embodiment has at least three layers: layer A and layer B laminated on both sides of layer A.
  • the multilayer body and container of the third embodiment only need to have a layer B/layer A/layer B configuration, and any other layer may be provided.
  • the layers B stacked on both sides of the layer A may be the same layer or different layers.
  • the number and type of the multilayer body and container are not particularly limited as long as they include one or more layers of layer A and two or more layers of layer B. For example, it may have a five-layer structure of B1/B2/A/B2/B1, which includes one layer A and four layers B of two types, layer B1 and layer B2.
  • both layers B1 may have the same composition or different compositions, and both layer B2 may have the same composition or different compositions.
  • the multilayer body and container of the third embodiment may include an arbitrary layer such as an adhesive layer (layer AD) between layer A and layer B, for example, B1/AD/B2.
  • layer AD adhesive layer
  • a seven-layer structure of /A/B2/AD/B1 may be used.
  • both layers B1 may have the same composition or different compositions
  • both layers B2 may have the same composition or different compositions
  • both layers AD may have the same composition. may be different.
  • the multilayer body and container of 3rd Embodiment when it has multiple layers B, it may have layer A between the layers B.
  • Layer B is laminated on both sides of layer A and layer A because it is easier to mold, has a better color tone after oxygen absorption, and can provide a multilayer injection molded article and container with a better appearance.
  • a three-layer structure of B/A/B is preferable.
  • the multilayer injection molded body and container are suitable for medical use because the multilayer injection molded body and container have a better color tone after oxygen absorption and a better appearance.
  • the thickness of layer A is not particularly limited, but is preferably 10 to 1000 ⁇ m, more preferably 50 to 700 ⁇ m, and even more preferably 100 to 500 ⁇ m. By setting it as this range, it tends to be possible to further improve the oxygen barrier performance of layer A and to prevent economic efficiency from being impaired.
  • the ⁇ polyester compound> of the third embodiment is as described in the section of the ⁇ polyester compound> of the first embodiment.
  • ⁇ Transition metal catalyst> of the third embodiment is as described in the section of ⁇ transition metal catalyst> of the first embodiment.
  • the resin composition and layer A of the third embodiment may contain thermoplastic resins other than the polyester compound (a) within a range that does not impede the purpose of the third embodiment.
  • thermoplastic resins are as described as "thermoplastic resin" in the first embodiment.
  • resins with high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymers are more preferred.
  • the layer (A) contains a polyolefin, it can be distinguished from the layer (B) described below depending on whether or not it contains the polyester compound (a).
  • [Method for manufacturing multilayer body] [Method for manufacturing a multilayer body] in the third embodiment is the same as described in the section [Method for manufacturing a multilayer injection molded body] in the second embodiment.
  • [container] [Container] in the third embodiment is as described in the [Container] section of the second embodiment.
  • ⁇ Injection blow molding> of the third embodiment is as described in the ⁇ injection blow molding> section of the second embodiment.
  • the medical multilayer container according to the fourth embodiment includes a layer A containing the resin composition according to the first embodiment and a layer B containing the polyolefin (b), and the layer A includes the layer A containing the polyolefin (b).
  • Layer B has a laminated multilayer structure including at least three layers. Note that in the fourth embodiment, descriptions of other embodiments can be cited as appropriate.
  • the fourth embodiment it is possible to realize an oxygen-absorbing medical multilayer container that has excellent oxygen-absorbing performance under a wide range of humidity conditions, preferably from low humidity to high humidity. Furthermore, the present invention has excellent oxygen barrier performance, excellent water vapor barrier performance, excellent drop strength, maintains strength even during long-term storage, and has low odor generation and elution of impurities after oxygen absorption. It is also possible to realize an oxygen-absorbing multilayer medical container that does not deteriorate in appearance due to yellowing. Furthermore, since the medical multilayer container of the fourth embodiment uses an oxygen-absorbing resin composition containing a polyester compound (A) and a fiber metal catalyst, continuous molding may be performed when layer A is formed by injection molding.
  • A polyester compound
  • mold deposits It is difficult for deposits (hereinafter sometimes referred to as “mold deposits") to remain on the mold. As described above, since the medical multilayer container of the fourth embodiment has excellent moldability, there is no need to frequently clean the mold even when molding is performed continuously, resulting in excellent productivity.
  • the medical multilayer container of the fourth embodiment is a multilayer structure having at least three layers, including layer A and layer B laminated on both sides of layer A.
  • the medical multilayer container of the fourth embodiment only needs to have a layer B/layer A/layer B configuration, and any other layers may be provided.
  • the layers B stacked on both sides of the layer A may be the same layer or different layers.
  • the number and type of the medical multilayer container are not particularly limited as long as it includes one or more layers A and two or more layers B. For example, it may have a five-layer structure of layer B1/layer B2/layer A/layer B2/layer B1, which includes one layer A and two types of four layers B1 and B2.
  • both layers B1 may have the same composition or different compositions, and both layer B2 may have the same composition or different compositions.
  • the medical multilayer container of the fourth embodiment may include an arbitrary layer such as an adhesive layer (layer AD) between layer A and layer B as necessary.
  • layer AD adhesive layer
  • layer B1/layer AD It may have a seven-layer structure: /layer B2/layer A/layer B2/layer AD/layer B1.
  • both layers B1 may have the same composition or different compositions
  • both layers B2 may have the same composition or different compositions
  • both layers AD may have the same composition. may be different.
  • the medical multilayer container of 4th Embodiment when it has multiple layers B, it may have layer A between the layers B.
  • the thickness of the oxygen absorbing layer (layer A) is not particularly limited, but is preferably 10 to 1000 ⁇ m, more preferably 50 to 700 ⁇ m, and particularly preferably 100 to 500 ⁇ m. By setting it as this range, it becomes possible to further improve the ability of the oxygen absorbing layer (layer A) to absorb oxygen, and to prevent economic efficiency from being impaired.
  • ⁇ Polyester compound (a)> The ⁇ polyester compound (a)> of the fourth embodiment is as described in the section of ⁇ polyester compound> of the first embodiment.
  • ⁇ Transition metal catalyst> of the fourth embodiment is as described in the section of ⁇ transition metal catalyst> of the first embodiment.
  • layer A in the fourth embodiment may contain other thermoplastic resins within a range that does not impede the purpose of the fourth embodiment.
  • These thermoplastic resins are as described as "thermoplastic resin" in the first embodiment.
  • resins with high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymers are more preferred.
  • Layer B in the fourth embodiment is a resin layer containing polyolefin (b).
  • the content of polyolefin (b) in layer B is not particularly limited, but the content of polyolefin (b) relative to the total amount of layer B is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, Particularly preferred is 90 to 100% by weight. By setting it as the said range, the transparency, moldability, and water vapor barrier property of layer B can be improved.
  • the thermoplastic resin (b) can be used alone or in combination of two or more.
  • the medical multilayer container of the fourth embodiment may have a plurality of layers B, and the configurations of the plurality of layers B may be the same or different.
  • the thickness of layer B can be determined as appropriate depending on the application, and is preferably 30 to 1500 ⁇ m from the viewpoint of ensuring various physical properties such as strength and flexibility such as drop resistance required for medical multilayer containers. , more preferably 50 to 1000 ⁇ m, still more preferably 100 to 700 ⁇ m. In addition, it shows better oxygen barrier performance, has a better color tone after oxygen absorption, has better strength and shape retention, and has a better appearance. is preferably 100 to 300 ⁇ m, the thickness of the intermediate layer (layer A) is preferably 200 to 400 ⁇ m, and the thickness of the outer container layer (layer B) is preferably 400 to 600 ⁇ m.
  • ⁇ Polyolefin> of the fourth embodiment is as described in the ⁇ polyolefin> column of the second embodiment.
  • [Method for manufacturing multilayer medical containers] [Method for manufacturing multilayer medical container] of the fourth embodiment is the same as described in the section [Method for manufacturing multilayer injection molded product] of the second embodiment.
  • the shape of the medical multilayer container of the fourth embodiment is not particularly limited, examples thereof include a vial, an ampoule, a prefill syringe, and a vacuum blood collection tube.
  • the structure of the vial of the fourth embodiment is no different from a general vial, and is composed of a bottle, a rubber stopper, and a cap. After filling a bottle with a medicinal solution, a rubber stopper is placed on the bottle, and then a cap is wrapped over the top to seal the bottle.
  • the bottle portion is a medical multilayer molded container according to the fourth embodiment, wherein at least one of the intermediate layers is an oxygen absorption layer (layer A) that can be formed using an oxygen absorption resin composition, and the innermost layer is an oxygen absorption layer (layer A) that can be formed using an oxygen absorption resin composition. and the outermost layer is a resin layer (layer B) containing polyolefin.
  • the bottle portion of the vial of the fourth embodiment is manufactured, for example, by injection blow molding or extrusion blow molding.
  • an injection blow molding method for a multilayer molded body constituting a vial is shown below.
  • the material constituting layer A and the material constituting layer B are passed from the respective injection cylinders through the mold hot runner and into the cavity.
  • a multilayer molded body corresponding to the shape of the injection mold can be manufactured by injection.
  • the material constituting layer B is injected from an injection cylinder, then the material constituting layer A is injected from another injection cylinder simultaneously with the resin constituting layer B, and then the resin constituting layer B is injected.
  • a multilayer molded product having a three-layer structure can be manufactured by injecting the required amount of the mixture to fill the cavity. Also, by first injecting the material constituting layer B, then injecting the material constituting layer A alone, and finally injecting the required amount of material constituting layer B to fill the mold cavity, A multilayer molded body having a five-layer structure (layer B/layer A/layer B/layer A/layer B) can be produced. In addition, first, the material constituting layer B1 is injected from an injection cylinder, then the material constituting layer B2 is injected from another injection cylinder simultaneously with the material constituting layer B1, and then the material constituting layer A is injected.
  • the multilayer molded product obtained by the above method is fitted into a final shape mold (blow mold) while keeping it heated to a certain extent, air is blown into it, it is inflated and brought into close contact with the mold, and then cooled and solidified. By doing so, it can be formed into a bottle shape.
  • the configuration of the ampoule of the fourth embodiment is similar to that of a general ampoule, and may be a small container with a narrow neck. After filling the ampoule with a medicinal solution, the end of the neck is sealed to seal it.
  • the above-mentioned ampoule is a medical multilayer molded container according to the fourth embodiment, in which at least one layer of the intermediate layer is an oxygen absorbing layer (layer A) that can be formed from an oxygen absorbing resin composition, and the innermost layer and the outermost layer is a resin layer (layer B) containing polyolefin.
  • the ampoule of the fourth embodiment is manufactured, for example, by injection blow molding or extrusion blow molding.
  • the configuration of the prefill syringe of the fourth embodiment is the same as that of a general prefill syringe, and includes at least a barrel for filling a drug solution, a joint for joining a syringe needle to one end of the barrel, and a joint for connecting a drug solution during use. Consists of a plunger for extrusion.
  • the above-mentioned barrel is a medical multilayer molded container according to the fourth embodiment, in which at least one layer of the intermediate layer is an oxygen absorbing layer (layer A) that can be formed using an oxygen absorbing resin composition, and the innermost layer, The outermost layer is a resin layer (layer B) containing polyolefin.
  • the prefill syringe of the fourth embodiment is manufactured, for example, by an injection molding method.
  • a certain amount of material forming layer B is injected into the cavity, then a certain amount of material forming layer A is injected, and a certain amount of material forming layer B is injected again.
  • the barrel and the joint may be molded as one piece, or they may be molded separately and then joined. It is necessary to seal the tip of the joint, which can be done by heating the resin at the tip of the joint to a molten state, and then pinching it with pliers or the like to fuse it.
  • the thickness of the barrel may be about 0.5 to 5 mm, depending on the purpose of use and size. Furthermore, the thickness may be uniform or may vary. Further, another gas barrier film or light shielding film may be formed on the surface (untreated) for the purpose of long-term storage stability. As such a film and its formation method, the method described in Japanese Patent Application Laid-open No. 2004-323058, etc. can be adopted.
  • the configuration of the vacuum blood collection tube of the fourth embodiment is similar to that of a general vacuum blood collection tube, and is composed of a tubular body and a stopper.
  • the tubular body is a medical multilayer molded container according to the fourth embodiment, wherein at least one layer of the intermediate layer is an oxygen absorbing layer (layer A) that can be formed from an oxygen absorbing resin composition, and the innermost layer and the outermost layer is a resin layer (layer B) containing polyolefin.
  • the vacuum blood collection tube of the fourth embodiment is manufactured, for example, by an injection molding method. To make a tubular body that will become a multilayer molded container for medical use, first a certain amount of the material forming layer B is injected into the cavity, then a certain amount of material forming layer A is injected, and then a certain amount of material forming layer B is injected again. Manufactured by mass injection.
  • the medical multilayer container of the fourth embodiment does not require moisture for oxygen absorption, so it has excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity (relative humidity 0% to 100%). Suitable for packaging various items.
  • a typical example of something to be preserved is biopharmaceuticals, which tend to deteriorate in the presence of oxygen.
  • the biopharmaceutical is not particularly defined as long as it contains a protein-derived medicinal ingredient, and a wide variety of biopharmaceuticals known to those skilled in the art can be used. Specifically, it is preferably a biopharmaceutical selected from the group consisting of antibodies, hormones, enzymes, and complexes containing these.
  • biopharmaceuticals include adrenergic antagonists, analgesics, anesthetics, angiotensin antagonists, anti-inflammatory drugs, anxiolytics, antiarrhythmics, anticholinergics, anticoagulants, antiepileptics, antidiarrheals, and antidiarrheals.
  • Drugs hormones, hematopoietic growth factors, interferons, interleukin products, vaccines, monoclonal antibodies, tumor necrosis factors, therapeutic enzymes, antibody-drug conjugates, biosimilars, erythropoietin, immunoglobulins, somatic cells, gene therapy, tissue, and therapeutic recombinant proteins.
  • medical multilayer containers and objects to be preserved can be sterilized in a form suitable for the objects to be preserved.
  • Sterilization methods include heat sterilization such as hot water treatment at 100°C or lower, pressurized hot water treatment at 100°C or higher, high-temperature heat treatment at 121°C or higher, electromagnetic wave sterilization such as ultraviolet rays, microwaves, and gamma rays, ethylene oxide, etc. gas treatment, and chemical sterilization using hydrogen peroxide, hypochlorous acid, etc.
  • the prefill syringe of the fifth embodiment is a prefill syringe that can accommodate a drug in a sealed state and that can release the sealed state and pour out the drug when used, A layer A containing the resin composition according to the first embodiment; and a layer B containing polyolefin (b), and the layer B is laminated on both sides of the layer A, and has a multilayer structure including at least three layers. Note that in the fifth embodiment, descriptions of other embodiments can be cited as appropriate.
  • an oxygen-absorbing prefill syringe that preferably has excellent oxygen absorption performance and water vapor barrier performance.
  • the prefill syringe since the generation of low molecular weight compounds after oxygen absorption is suppressed, it is possible to prevent the low molecular weight compounds from being mixed into the contents. Further, even after oxygen absorption, the strength of the polyester compound decreases very little, and the strength of the oxygen-absorbing layer is maintained even during long-term use, so it is possible to provide a prefill syringe that is less prone to delamination. Furthermore, it is also possible to realize a prefill syringe that does not deteriorate in appearance due to yellowing.
  • the prefill syringe of the fifth embodiment uses an oxygen-absorbing resin composition containing a polyester compound (A) and a fiber metal catalyst, even when continuous molding is performed when layer A is formed by injection molding, there is no metallurgy. It is difficult for deposits (hereinafter sometimes referred to as "mold deposits") to remain on the mold. As described above, since the prefill syringe of the fifth embodiment has excellent moldability, there is no need to frequently clean the mold even when molding is performed continuously, resulting in excellent productivity.
  • the prefill syringe of the fifth embodiment is a multilayer structure having at least three layers, in which layer A and layer B are laminated on both sides of layer A.
  • the prefill syringe of the fifth embodiment only needs to have a layer B/layer A/layer B structure as its layer structure, and any other layers may be provided.
  • the layers B stacked on both sides of the layer A may be the same layer or different layers.
  • the number and type of prefill syringes are not particularly limited as long as they include one or more layers of layer A and two or more layers of layer B.
  • it may have a five-layer structure of layer B1/layer B2/layer A/layer B2/layer B1, which includes one layer A and two types of four layers B1 and B2.
  • both layers B1 may have the same composition or different compositions, and both layer B2 may have the same composition or different compositions.
  • the prefill syringe of the fifth embodiment may include an arbitrary layer such as an adhesive layer (layer AD) between layer A and layer B as necessary.
  • layer AD adhesive layer
  • layer B1/layer AD/ It may have a seven-layer structure of layer B2/layer A/layer B2/layer AD/layer B1.
  • both layers B1 may have the same composition or different compositions
  • both layers B2 may have the same composition or different compositions
  • both layers AD may have the same composition. may be different.
  • the prefill syringe of the fifth embodiment when it has a plurality of layers B, it may have a layer A between the layers B.
  • the thickness of the oxygen absorbing layer (layer A) is not particularly limited, but is preferably 10 to 1000 ⁇ m, more preferably 50 to 700 ⁇ m, and particularly preferably 100 to 500 ⁇ m. By setting it as this range, it becomes possible to further improve the ability of the oxygen absorbing layer (layer A) to absorb oxygen, and to prevent economic efficiency from being impaired.
  • ⁇ Polyester compound (a)> The ⁇ polyester compound (a)> of the fifth embodiment is as described in the section of the ⁇ polyester compound> of the first embodiment.
  • ⁇ Transition metal catalyst> of the fifth embodiment is as described in the section of ⁇ transition metal catalyst> of the first embodiment.
  • layer A in the fifth embodiment may contain other thermoplastic resins within a range that does not impede the purpose of the fifth embodiment.
  • thermoplastic resins are as described as "thermoplastic resin" in the first embodiment.
  • resins with high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymers are more preferred.
  • ⁇ Polyolefin> of the fifth embodiment is as described in the ⁇ polyolefin> column of the second embodiment.
  • Method for manufacturing prefill syringe [Method for manufacturing a prefill syringe] of the fifth embodiment is the same as described in the section [Method for manufacturing a multilayer injection molded body] of the second embodiment.
  • [Drug] [Drug] in the fifth embodiment is as described in the [Medicine] column of the fourth embodiment.
  • the method for producing a biopharmaceutical according to the sixth embodiment includes: A method for storing biopharmaceuticals in containers, the method comprising: The container includes an oxygen absorbing layer (layer A) made of the resin composition according to the first embodiment, and a resin layer (layer B) containing polyolefin (b) laminated on both sides of the layer A. , a multi-layered container containing at least three layers. Note that in the sixth embodiment, descriptions of other embodiments can be cited as appropriate.
  • biopharmaceuticals can be stored under low oxygen concentrations, so deterioration of biopharmaceuticals and decrease in efficacy can be suppressed. Furthermore, in the container used in the sixth embodiment, the generation of low-molecular organic substances after oxygen absorption is suppressed, so that it is possible to prevent impurities from being mixed into the contents. Further, in the container according to the sixth embodiment, the polyester compound undergoes extremely little deterioration due to oxidation even after oxygen absorption, and the strength of the container is maintained even during long-term use, so biopharmaceuticals can be stored for a long period of time. Furthermore, since the color change of the container after storage is small, visibility of the contents is also good.
  • the thickness of the oxygen absorbing layer (layer A) is not particularly limited, but is preferably 10 to 1000 ⁇ m, more preferably 50 to 700 ⁇ m, and particularly preferably 100 to 500 ⁇ m. By setting the thickness of layer A within the above range, it tends to be possible to further improve the oxygen absorbing performance and to prevent economic efficiency from being impaired.
  • ⁇ Polyester compound> The ⁇ polyester compound> of the sixth embodiment is as described in the section of ⁇ polyester compound> of the first embodiment.
  • ⁇ Transition metal catalyst> of the sixth embodiment is as described in the section of ⁇ transition metal catalyst> of the first embodiment.
  • the resin composition constituting layer A of the sixth embodiment may contain thermoplastic resins other than the polyester compound (a) within a range that does not impede the purpose of the sixth embodiment.
  • thermoplastic resins are as described as "thermoplastic resin" in the first embodiment. From the viewpoint of effectively exhibiting the oxygen absorption effect, resins with high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymer are more preferable.
  • layer A contains a polyolefin, it can be distinguished from layer B, which will be described later, depending on whether or not it contains the polyester compound (a).
  • ⁇ Polyolefin (b)> ⁇ Polyolefin (b)> in the sixth embodiment is as described in the column of ⁇ polyolefin> in the second embodiment.
  • [Container manufacturing method] [Method for manufacturing a container] in the sixth embodiment is the same as described in the section "Method for manufacturing a multilayer injection molded body" in the second embodiment.
  • [Container shape] of the sixth embodiment is as described in the section of [Medical multilayer container type] of the fourth embodiment.
  • a method for storing an adrenaline-containing drug solution according to a seventh embodiment is a method for storing an adrenaline-containing drug solution in a container, wherein the container includes an oxygen-absorbing layer A (containing the resin composition according to the first embodiment). (hereinafter also referred to as "layer A”); and a resin layer B (hereinafter also referred to as "layer B") disposed on both sides of the oxygen absorbing layer A and containing polyolefin (b). , is the method. Note that in the seventh embodiment, descriptions of other embodiments can be cited as appropriate.
  • the method for storing an adrenaline-containing drug solution according to the seventh embodiment is configured as described above, when storing the adrenaline-containing drug solution, oxidation of adrenaline can be prevented and components eluted from the container can be reduced. In addition, it is possible to reduce the color change of the container after storage. As described above, the method for preserving an adrenaline-containing drug solution according to the seventh embodiment allows the adrenaline-containing drug solution to be stored under a low oxygen concentration. Therefore, deterioration of adrenaline and decrease in drug efficacy are suppressed. Furthermore, when carrying or using adrenaline-containing medicinal solutions, there is less risk of breakage compared to glass, and it is also lightweight, making it highly convenient.
  • the thickness of layer A is not particularly limited, but is preferably 10 to 1000 ⁇ m, more preferably 50 to 700 ⁇ m, and particularly preferably 100 to 500 ⁇ m. By setting it as this range, the oxygen absorption performance of layer A tends to be further improved, and it becomes possible to prevent economic efficiency from being impaired.
  • ⁇ Polyester compound> of the seventh embodiment is as described in the section of ⁇ polyester compound> of the first embodiment.
  • ⁇ Transition metal catalyst> of the seventh embodiment is as described in the section of ⁇ transition metal catalyst> of the first embodiment.
  • the layer (A) may contain a thermoplastic resin other than the polyester compound (a).
  • thermoplastic resins are as described as "thermoplastic resin" in the first embodiment.
  • resins with high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymers are more preferred.
  • the layer (A) contains a polyolefin, it can be distinguished from the layer (B) described below depending on whether or not it contains the polyester compound (a).
  • [Layer B] of the seventh embodiment is as described in the section of [Layer B (resin layer containing polyolefin (b))] of the fourth embodiment.
  • ⁇ Polyolefin (b)> ⁇ Polyolefin (b)> in the seventh embodiment is as described in the column of ⁇ polyolefin> in the second embodiment.
  • [Container manufacturing method] [Method for manufacturing a container] in the seventh embodiment is the same as described in the section "Method for manufacturing a multilayer injection molded body" in the second embodiment.
  • [Container shape] in the seventh embodiment is as described in the section [Type of medical multilayer container] in the fourth embodiment.
  • the adrenaline concentration of the adrenaline-containing drug solution in the seventh embodiment is not particularly limited and can be appropriately determined depending on the application, and is preferably 0.01 to 10 mg/mL, more preferably 0.02 to 9 mg/mL. mL, more preferably 0.05 to 8 mg/mL. Additionally, the adrenaline-containing drug solution may contain additives such as sodium pyrosulfite, sodium hydrogensulfite, chlorobutanol, hydrochloric acid, sodium hydroxide, and sodium chloride.
  • the storage conditions for the adrenaline-containing drug solution in the seventh embodiment are not particularly limited, and may be the same as the storage conditions for general adrenaline-containing drug solutions.
  • the adrenaline-containing drug solution in the seventh embodiment is preferably stored at a temperature of 1 to 30° C. and a humidity of 75% RH or less.
  • the modified polyester according to the eighth embodiment exhibits good oxygen barrier performance, has a good color tone after oxygen absorption, has excellent strength and shape retention, and has excellent moldability.
  • the modified polyester according to the eighth embodiment preferably has excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, and absorbs oxygen regardless of the presence or absence of moisture in the preserved material. It can be used in a wide range of applications, such as foods, cooked foods, beverages, medicines, and health foods, as it can absorb oxygen and does not cause odor or yellowing after absorbing oxygen. can.
  • this modified polyester it is possible to realize an oxygen-absorbing film or the like in which the decrease in strength after oxygen absorption is extremely small and the deterioration of strength over time is suppressed.
  • ⁇ Polyester compound> The ⁇ polyester compound> of the eighth embodiment is as described in the section of ⁇ polyester compound> of the first embodiment.
  • the radiation treatment examples include ultraviolet ray treatment, X-ray treatment, ⁇ -ray treatment, and electron beam treatment. More preferred are gamma ray treatment and electron beam treatment.
  • the mechanism by which oxygen barrier performance is developed by these treatments is not clear, it is speculated that the oxidation reaction mechanism is caused by the extraction of hydrogen at the benzylic position of the tetralin ring to generate radicals. It is not easy to identify the structure of modified polyester obtained by radiation treatment.
  • the radiation dose in the radiation treatment is preferably 5 kGy or more and less than 60 kGy, more preferably 10 kGy or more and less than 50 kGy.
  • ⁇ Usage mode> of the eighth embodiment is as described in the ⁇ Usage mode> column of the first embodiment.
  • Oxygen barrier property was evaluated by the oxygen permeability of the vial obtained by the method described below.
  • the oxygen permeability was measured using OX-TRAN2/21 manufactured by MOCON under measurement conditions of 23° C. and 65% RH. A sample whose oxygen permeability was less than 0.0005 cc/package/day, which is the lower detection limit of the device, was judged to have good oxygen barrier properties.
  • the color change ( ⁇ YI) of the container was determined by using a vial obtained by the method described below, filled with 10 cc of distilled water, and sealed with a rubber stopper and an aluminum seal. It was calculated from the difference between the initial yellowness (YI) measured using a color measuring device COH-300A and the yellowness (YI) after storage for 3 months at 40° C. and 20% RH. When ⁇ YI did not exceed 2, it was judged that the color tone change was small.
  • Moldability Moldability was confirmed by visually observing the mold after 1000 shot molding of the vial obtained by the method described below. Those with no adhesion of mold deposits were judged to have passed.
  • a vial having a three-layer structure of layer B/layer A/layer B from the outside was obtained, having an inner volume of 10 cc, an overall height of 45 mm, an outer diameter of 24 mm ⁇ , and a wall thickness of 1 mm, and having a shape according to ISO 8362-1.
  • layer B a cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd., product name: "ZEONEX (registered trademark) 690R") was used, and for layer A, the resin compositions of Examples and Comparative Examples were used.
  • ZEONEX registered trademark
  • polyester compound (Manufacturing example 1) 8,668.9 g of dimethyl 2,6-naphthalene dicarboxylate was placed in a 30 L polyester resin manufacturing equipment equipped with a packed column type rectification column, partial condenser, total condenser, cold trap, stirrer, heating device, and nitrogen introduction tube. , 4895.5 g of dimethyl tetralin-2,6-dicarboxylate, 4594.6 g of dimethyl isophthalate, 8811.8 g of ethylene glycol, 0.559 g of potassium titanium oxalate dihydrate, and 1.519 g of zinc acetate were charged, and the mixture was heated in a nitrogen atmosphere.
  • the temperature was raised to 230°C to carry out the transesterification reaction.
  • the reaction conversion rate of the dicarboxylic acid component was 95% or more, 1039.6 g of germanium oxide 0.5 wt% ethylene glycol solution and 154.6 g of phosphoric acid ethylene glycol solution were added, and the temperature was gradually increased and the pressure was reduced to 270%.
  • Polycondensation was carried out at 133 Pa or less at a temperature of 133 Pa or less, and after reaching a predetermined torque, the product was taken out in the form of a strand from the bottom of the production apparatus and cut with a pelletizer to obtain a polyester compound (1) in the form of pellets.
  • the mol% of the structural units represented by formulas (1) to (3) shown in Table 1 is a value calculated from the amount of the corresponding monomer charged.
  • a polyester compound (6) was prepared in the same manner as in Production Example 1, except that dimethyl 2,6-naphthalenedicarboxylate and dimethyl isophthalate were not used, and dimethyl tetralin-2,6-dicarboxylate was 18147.3 g and ethylene glycol was 8166.1 g. I got it.
  • Example 1 Cobalt (II) stearate was blended with the polyester compound (1) to give a cobalt content of 2.5 ppm, and the resulting resin composition was passed through a twin-screw extruder having two screws with a diameter of 20 mm.
  • a resin composition (1) in the form of pellets was obtained by extrusion in the form of a strand at an extrusion temperature of 280° C. and a screw rotation speed of 50 rpm, and cut with a pelletizer.
  • the resulting resin composition was evaluated for oxygen barrier properties, change in container color, moldability, and shape/strength retention using the methods described above. The evaluation results are shown in Table 1.
  • Example 2 A resin composition (2) was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1).
  • the resulting resin composition was evaluated for oxygen barrier properties, change in container color, moldability, and shape/strength retention using the methods described above. The evaluation results are shown in Table 1.
  • Example 3 A resin composition (3) was obtained in the same manner as in Example 1, except that cobalt (II) stearate was blended to have a cobalt content of 20 ppm. The resulting resin composition was evaluated for oxygen barrier properties, change in container color, moldability, and shape/strength retention using the methods described above. The evaluation results are shown in Table 1.
  • Example 1 A resin composition (4) was obtained in the same manner as in Example 1 except that polyester compound (3) was used instead of polyester compound (1).
  • the resulting resin composition was evaluated for oxygen barrier properties, change in container color, moldability, and shape/strength retention using the methods described above. The evaluation results are shown in Table 1.
  • Example 2 A resin composition (5) was obtained in the same manner as in Example 1 except that polyester compound (4) was used instead of polyester compound (1).
  • the resulting resin composition was evaluated for oxygen barrier properties, change in container color, moldability, and shape/strength retention using the methods described above. The evaluation results are shown in Table 1.
  • Example 3 A resin composition (6) was obtained in the same manner as in Example 1 except that polyester compound (5) was used instead of polyester compound (1).
  • the resulting resin composition was evaluated for oxygen barrier properties, change in container color, moldability, and shape/strength retention using the methods described above. The evaluation results are shown in Table 1.
  • Example 4 A resin composition (7) was obtained in the same manner as in Example 1 except that polyester compound (6) was used instead of polyester compound (1).
  • the resulting resin composition was evaluated for oxygen barrier properties, change in container color, moldability, and shape/strength retention using the methods described above. The evaluation results are shown in Table 1.
  • the resin composition of the first embodiment exhibits good oxygen barrier performance, good color tone after oxygen absorption, excellent strength and shape retention, and excellent moldability. This was confirmed.
  • Shape/strength retention was determined by storing samples at 40°C, 100% RH, using a vial obtained by the method described below, filled with 10 cc of distilled water, and sealed with a rubber stopper and an aluminum seal. It was stored for 3 months. Thereafter, the vial was disassembled, the intermediate layer (A) was taken out, and the condition of the intermediate layer (A) was visually confirmed. Those in which the shape and strength of the intermediate layer (A) were maintained were considered to be passed.
  • a vial having a three-layer structure of layer B/layer A/layer B from the outside was obtained, having an inner volume of 10 cc, an overall height of 45 mm, an outer diameter of 24 mm ⁇ , and a wall thickness of 1 mm, and having a shape according to ISO 8362-1.
  • the material constituting layer B is injected from the injection cylinders, and then the layer The material constituting A is injected simultaneously with the resin constituting layer B from another injection cylinder, and then the required amount of resin constituting layer B is injected to fill the cavity in the injection mold, thereby forming the inner layer of the container.
  • a multilayer injection molded product with a three-layer structure of B/A/B was obtained, in which the thickness of (layer B) was 200 ⁇ m, the thickness of the intermediate layer (layer A) was 300 ⁇ m, and the thickness of the outer layer of the container (layer B) was 500 ⁇ m.
  • the obtained multilayer injection molded product was cooled to a predetermined temperature, transferred to a blow mold, and then blow molded to produce a vial (bottle part).
  • a cycloolefin polymer manufactured by Nippon Zeon Co., Ltd., product name: "ZEONEX (registered trademark) 690R" was used as layer B, and layer A of the example and comparative example.
  • a resin composition was used. (Injection and blow conditions) Injection cylinder temperature for layer B: 325°C Injection cylinder temperature for layer A: 220°C Temperature of resin flow path in injection mold: 285°C Injection mold temperature: 80°C Blow mold temperature: 20°C Primary blow pressure: 1.0MPa Secondary blow pressure: 3.0MPa
  • Polyester compounds (1) to (6) were obtained according to (Production Example 1) to (Production Example 6) of the first embodiment.
  • Example 1 Cobalt (II) stearate was blended with the polyester compound (1) to give a cobalt content of 2.5 ppm, and the resulting resin composition was passed through a twin-screw extruder having two screws with a diameter of 20 mm.
  • a resin composition (1) in the form of pellets was obtained by extrusion in the form of a strand at an extrusion temperature of 280° C. and a screw rotation speed of 50 rpm, and cut with a pelletizer.
  • a multilayer injection molded product (1) (vial) is molded by the method described above, and the multilayer injection molded product (1) is tested by the method described above to improve oxygen barrier properties, color change of the container, Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in.
  • Example 2 A resin composition (2) was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer injection molded product (2) (vial) is molded by the method described above, and the multilayer injection molded product (2) is tested by the method described above to improve oxygen barrier properties, color change of the container, Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in Table 2.
  • Example 3 A resin composition (3) was obtained in the same manner as in Example 1, except that cobalt (II) stearate was blended to have a cobalt content of 20 ppm. Using the obtained resin composition, a multilayer injection molded product (3) (vial) is molded by the method described above, and the multilayer injection molded product (3) is tested for oxygen barrier properties, color change of the container, and color change by the method described above. Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in Table 2.
  • Example 1 A resin composition (4) was obtained in the same manner as in Example 1 except that polyester compound (3) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer injection molded product (4) (vial) is molded by the method described above, and the multilayer injection molded product (4) is tested by the method described above to improve oxygen barrier properties, color change of the container, Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in Table 2.
  • Example 2 A resin composition (5) was obtained in the same manner as in Example 1 except that polyester compound (4) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer injection molded product (5) (vial) is molded by the method described above, and the multilayer injection molded product (5) is tested for oxygen barrier properties, color change of the container, and color change by the method described above. Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in Table 2.
  • Example 3 A resin composition (6) was obtained in the same manner as in Example 1 except that polyester compound (5) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer injection molded product (6) (vial) is molded by the method described above, and the multilayer injection molded product (6) is tested by the method described above to improve oxygen barrier properties, color change of the container, Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in Table 2.
  • Example 4 A resin composition (7) was obtained in the same manner as in Example 1 except that polyester compound (6) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer injection molded product (7) (vial) is molded by the method described above, and the multilayer injection molded product (7) is tested for oxygen barrier properties, color change of the container, and color change by the method described above. Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in Table 2.
  • Nylon MXD6 manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: MX Nylon S7007
  • cobalt (II) stearate was blended to a cobalt content of 20 ppm
  • a vial was prepared.
  • a resin composition (8) was obtained in the same manner as in Example 1, except that the temperature of the injection cylinder for layer A during production was 260°C.
  • a multilayer injection molded product (8) (vial) is molded by the method described above, and the multilayer injection molded product (8) is tested by the method described above to improve oxygen barrier properties, color change of the container, Evaluations of moldability, shape and strength retention were conducted. The evaluation results are shown in Table 2.
  • the multilayer injection molded article of the second embodiment exhibited good oxygen barrier performance, good color tone after oxygen absorption, excellent strength and shape retention, and good moldability. It was confirmed that it is excellent.
  • Polyester compounds (1) to (6) were obtained according to (Production Example 1) to (Production Example 6) of the first embodiment.
  • Example 1 Cobalt (II) stearate was blended with the polyester compound (1) to give a cobalt content of 2.5 ppm, and the resulting resin composition was passed through a twin-screw extruder having two screws with a diameter of 20 mm.
  • a resin composition (1) in the form of pellets was obtained by extrusion in the form of a strand at an extrusion temperature of 280° C. and a screw rotation speed of 50 rpm, and cut with a pelletizer.
  • a multilayer body (1) (vial) is molded by the method described above, and the multilayer body (1) is tested by the method described above for oxygen barrier properties, color change of the container, moldability, and shape. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • Example 2 A resin composition (2) was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer body (2) (vial) is molded by the method described above, and the multilayer body (2) is evaluated for oxygen barrier properties, color change of the container, moldability, and shape by the method described above. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • Example 3 A resin composition (3) was obtained in the same manner as in Example 1, except that cobalt (II) stearate was blended to have a cobalt content of 20 ppm. Using the obtained resin composition, a multilayer body (3) (vial) is molded by the method described above, and the multilayer body (3) is evaluated for oxygen barrier properties, color change of the container, moldability, and shape by the method described above. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • Example 1 A resin composition (4) was obtained in the same manner as in Example 1 except that polyester compound (3) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer body (4) (vial) is molded by the method described above, and the multilayer body (4) is evaluated for oxygen barrier properties, color change of the container, moldability, and shape by the method described above. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • Example 2 A resin composition (5) was obtained in the same manner as in Example 1 except that polyester compound (4) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer body (5) (vial) is molded by the method described above, and the multilayer body (5) is evaluated for oxygen barrier properties, color change of the container, moldability, and shape by the method described above. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • Example 3 A resin composition (6) was obtained in the same manner as in Example 1 except that polyester compound (5) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer body (6) (vial) is molded by the method described above, and the multilayer body (6) is tested for oxygen barrier properties, color change of the container, moldability, and shape by the method described above. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • Example 4 A resin composition (7) was obtained in the same manner as in Example 1 except that polyester compound (6) was used instead of polyester compound (1). Using the obtained resin composition, a multilayer body (7) (vial) is molded by the method described above, and the multilayer body (7) is tested for oxygen barrier properties, color change of the container, moldability, and shape by the method described above. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • Nylon MXD6 manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: MX Nylon S7007
  • cobalt (II) stearate was blended to a cobalt content of 20 ppm
  • a vial was prepared.
  • a resin composition (8) was obtained in the same manner as in Example 1, except that the temperature of the injection cylinder for layer A during production was 260°C.
  • a multilayer body (8) (vial) is molded by the method described above, and the multilayer body (8) is tested for oxygen barrier properties, color change of the container, moldability, and shape by the method described above. ⁇ Evaluation of strength maintenance was conducted. The evaluation results are shown in Table 3.
  • the multilayer body of the third embodiment exhibits good oxygen barrier performance, has a good color tone after oxygen absorption, has excellent strength and shape retention, and has excellent moldability. was confirmed.
  • Drop test A sample obtained by the method described below was filled with 10 cc of distilled water and sealed with a rubber stopper and an aluminum seal, and was used as a measurement sample. After being stored for 1 day at 23°C and 65% RH, it was dropped to 150 cm. The product was dropped from a height of If there was no damage in all 20 samples, it was judged as "passed".
  • Polyester compounds (1) to (6) were obtained according to (Production Example 1) to (Production Example 6) of the first embodiment.
  • Example 1 Cobalt (II) stearate was blended with the polyester compound (1) to give a cobalt content of 2.5 ppm, and the resulting resin composition was passed through a twin-screw extruder having two screws with a diameter of 20 mm.
  • a resin composition (1) in the form of pellets was obtained by extrusion in the form of a strand at an extrusion temperature of 280° C. and a screw rotation speed of 50 rpm, and cut with a pelletizer.
  • the obtained resin composition was molded into a vial using the method described above, and the oxygen barrier property, water vapor barrier property, color change of the container, moldability, drop strength, and shape/strength maintenance were evaluated. The evaluation results are shown in Table 4.
  • Example 2 A vial was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • Example 3 A vial was obtained in the same manner as in Example 1, except that cobalt (II) stearate was blended to give a cobalt content of 20 ppm.
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • Example 1 A vial was obtained in the same manner as in Example 1 except that polyester compound (3) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • Example 2 A vial was obtained in the same manner as in Example 1 except that polyester compound (4) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • Example 3 A vial was obtained in the same manner as in Example 1, except that polyester compound (5) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • Example 4 A vial was obtained in the same manner as in Example 1 except that polyester compound (6) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • Example 5 A vial was obtained in the same manner as in Example 1, except that the resin for layer B was polycarbonate (Lexan 144R manufactured by Sabic) and the injection cylinder temperature for layer B was 280°C.
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • Example 6 Comparative example 6 Examples except that nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon S7007) was used instead of polyester compound (1), and cobalt (II) stearate was blended to give a cobalt content of 20 ppm.
  • a resin composition was obtained in the same manner as in Example 1.
  • a vial was obtained in the same manner as in Example 1, except that the temperature of the injection cylinder for the intermediate layer (layer A) was 260° C. for the obtained resin composition.
  • the obtained vials were evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, drop strength, and shape/strength retention using the methods described above. The evaluation results are shown in Table 4.
  • the medical multilayer container of the fourth embodiment has excellent oxygen barrier properties, water vapor barrier properties, moldability, drop strength, strength and shape retention, and has excellent It was confirmed that the color tone of (after) was good.
  • Oxygen barrier property was evaluated by the oxygen permeability of the syringe obtained by the method described below. The oxygen permeability was measured using OX-TRAN2/21 manufactured by MOCON under measurement conditions of 23° C. and 65% RH. A sample whose oxygen permeability was less than 0.0005 cc/package/day, which is the lower detection limit of the device, was judged to have good oxygen barrier properties.
  • the water vapor barrier property was measured by using a syringe obtained by the method described below filled with 5 cc of distilled water and sealed with a top cap and a stopper as a measurement sample, and comparing the initial mass and 40°C 20%. It was calculated from the difference from the mass after being stored for 3 months under RH storage conditions. The water vapor barrier property was judged to be good if it was less than 0.03 cc/package/3 months.
  • Container color change ( ⁇ YI) color change after oxygen absorption
  • ⁇ YI color change after oxygen absorption
  • the color tone change ( ⁇ YI) of the container was measured by using a syringe obtained by the method described below filled with 5 cc of distilled water and sealed with a top cap and a stopper as a measurement sample. It was calculated from the difference between the initial yellowness index (YI) measured using a temperature measuring device COH-300A and the yellowness index (YI) after storage for 3 months in an air atmosphere at 40° C. and 20% RH. A sample whose ⁇ YI did not exceed 1 was judged to have a small change in color tone.
  • Shape/strength retention was determined by storing the sample at 40°C, 100% RH, using a syringe obtained by the method described below, filled with 5 cc of distilled water, and sealed with a top cap and stopper. Stored for months. Thereafter, the syringe was disassembled and the state of the intermediate layer (layer A) taken out was visually confirmed. If the intermediate layer (layer A) did not collapse or the like and maintained its shape, it was considered that the shape and strength were maintained and it was judged as "passed”.
  • a syringe having a three-layer structure of layer B/layer A/layer B from the outside and having an internal volume of 5 mL in accordance with ISO 11040-6 was obtained.
  • an injection molding machine manufactured by Sodick Corporation, model: GL-150
  • the material constituting layer B is injected from the injection cylinder, and then the material constituting layer A is injected into another injection molding machine.
  • the material constituting layer B is simultaneously injected, and then the required amount of material constituting layer B is injected to fill the cavity in the injection mold, thereby forming the three layers of layer B/layer A/layer B.
  • a syringe with a layered structure was obtained. Note that, for layer B, a cycloolefin polymer (manufactured by Nippon Zeon Co., Ltd., product name: "ZEONEX (registered trademark) 5000”) was used, and for layer A, the resin compositions of Examples and Comparative Examples were used.
  • Injection cylinder temperature for layer B 315°C Injection cylinder temperature for layer A: 265°C Injection mold inner layer B resin flow path temperature: 320°C Injection mold inner layer A resin flow path temperature: 280°C Injection mold temperature: 30°C
  • Polyester compounds (1) to (6) were obtained according to (Production Example 1) to (Production Example 6) of the first embodiment.
  • Example 1 Cobalt (II) stearate was blended with the polyester compound (1) to give a cobalt content of 2.5 ppm, and the resulting resin composition was passed through a twin-screw extruder having two screws with a diameter of 20 mm.
  • a resin composition (1) in the form of pellets was obtained by extrusion in the form of a strand at an extrusion temperature of 280° C. and a screw rotation speed of 50 rpm, and cut with a pelletizer.
  • the resulting resin composition was molded into a syringe using the method described above, and evaluated for oxygen barrier properties, water vapor barrier properties, color change in the container, moldability, shape/strength maintenance, and elution test. The evaluation results are shown in Table 5.
  • Example 2 A syringe was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1).
  • the obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength maintenance, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • Example 3 A syringe was obtained in the same manner as in Example 1, except that cobalt (II) stearate was blended to have a cobalt content of 20 ppm.
  • the obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength maintenance, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • Example 1 A syringe was obtained in the same manner as in Example 1 except that polyester compound (3) was used instead of polyester compound (1).
  • the obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength maintenance, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • Example 2 A syringe was obtained in the same manner as in Example 1 except that polyester compound (4) was used instead of polyester compound (1). The obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength maintenance, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • Example 3 A syringe was obtained in the same manner as in Example 1 except that polyester compound (5) was used instead of polyester compound (1).
  • the obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength maintenance, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • Example 4 A syringe was obtained in the same manner as in Example 1 except that polyester compound (6) was used instead of polyester compound (1). The obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength retention, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • Example 5 A syringe was obtained in the same manner as in Example 1, except that the resin for layer B was polycarbonate (Lexan 144R manufactured by Sabic) and the injection cylinder temperature for layer B was 280°C. The obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength retention, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • Example 6 Comparative example 6 Examples except that nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon S7007) was used instead of polyester compound (1), and cobalt (II) stearate was blended to give a cobalt content of 20 ppm.
  • a resin composition was obtained in the same manner as in Example 1.
  • a syringe was obtained using the obtained resin composition in the same manner as in Example 1.
  • the obtained syringe was evaluated for oxygen barrier properties, water vapor barrier properties, color change of the container, moldability, shape/strength retention, and elution test using the methods described above. The evaluation results are shown in Table 5.
  • the prefill syringe of the fifth embodiment has excellent oxygen barrier properties, water vapor barrier properties, moldability, strength and shape retention, and has little elution from the container. It was confirmed that the visibility of the contents was good because the color change of the container after storage was small.
  • TOC measurement Equipment: TOC-VCPH manufactured by Shimadzu Corporation Combustion furnace temperature: 720°C Gas/Flow rate: High purity air, TOC meter 150ml/min Injection volume: 150 ⁇ L Detection limit: 1 ⁇ g/mL
  • Polyester compounds (1) to (6) were obtained according to (Production Example 1) to (Production Example 6) of the first embodiment.
  • Example 1 Cobalt (II) stearate was blended with the polyester compound (1) so that the amount of cobalt was 2.5 ppm, and the resulting oxygen-absorbing resin composition was transferred to a twin-screw machine with two screws each having a diameter of 20 mm.
  • the oxygen-absorbing resin composition (1) was extruded in the form of a strand at an extrusion temperature of 280° C. and a screw rotation speed of 50 rpm, and cut with a pelletizer to obtain an oxygen-absorbing resin composition (1) in the form of pellets.
  • the obtained oxygen-absorbing resin composition was molded into a vial using the method described above, and the antibody activity retention rate, elution test, and container color change were evaluated. The evaluation results are shown in Table 6.
  • Example 2 A vial was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1).
  • the obtained vials were evaluated for antibody activity retention, elution test, and color change of the container using the methods described above. The evaluation results are shown in Table 6.
  • Example 3 An oxygen-absorbing resin composition (3) was obtained in the same manner as in Example 1, except that cobalt (II) stearate was blended to have a cobalt content of 20 ppm.
  • the obtained oxygen-absorbing resin composition was molded into a vial using the method described above, and the obtained vial was evaluated for antibody activity retention, elution test, and color change of the container using the method described above. The evaluation results are shown in Table 6.
  • Example 1 A vial was obtained in the same manner as in Example 1, except that polyester compound (3) was used instead of polyester compound (1).
  • the obtained vials were evaluated for antibody activity retention, elution test, and color change of the container using the methods described above. The evaluation results are shown in Table 6.
  • Example 2 A vial was obtained in the same manner as in Example 1 except that polyester compound (4) was used instead of polyester compound (1).
  • the obtained vials were evaluated for antibody activity retention, elution test, and color change of the container using the methods described above. The evaluation results are shown in Table 6.
  • Example 3 A vial was obtained in the same manner as in Example 1 except that polyester compound (5) was used instead of polyester compound (1).
  • the obtained vials were evaluated for antibody activity retention, elution test, and color change of the container using the methods described above. The evaluation results are shown in Table 6.
  • Example 4 A vial was obtained in the same manner as in Example 1, except that polyester compound (6) was used instead of polyester compound (1).
  • the obtained vials were evaluated for antibody activity retention, elution test, and color change of the container using the methods described above. The evaluation results are shown in Table 6.
  • Example 5 Comparative example 5 Examples except that nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon S7007) was used instead of polyester compound (1), and cobalt (II) stearate was blended to give a cobalt content of 20 ppm.
  • An oxygen-absorbing resin composition (6) was obtained in the same manner as in Example 1.
  • a vial was obtained in the same manner as in Example 1, except that the temperature of the injection cylinder for layer (A) was 260° C. for the obtained oxygen-absorbing resin composition.
  • the obtained vials were evaluated for antibody activity retention, elution test, and color change of the container using the methods described above. The evaluation results are shown in Table 6.
  • the biopharmaceuticals preserved by the preservation method of the sixth embodiment have a high activity retention rate, little elution from the container, and little change in color of the container after storage. Therefore, it was confirmed that the visibility of the contents was also good.
  • a prefill syringe (inner capacity 1 mL (long)) having a three-layer structure of layer B/layer A/layer B from the outside was obtained as follows.
  • an injection molding machine manufactured by Sodick Corporation, model: GL-150
  • the material constituting layer B is injected from the injection cylinder, and then the material constituting layer A is injected into another injection molding machine.
  • the resin constituting layer B is simultaneously injected, and then the required amount of resin constituting layer B is injected to fill the cavity in the injection mold, thereby forming three layers: layer B/layer A/layer B.
  • Injection and blow conditions Injection cylinder temperature for layer (B): 315°C Injection cylinder temperature for layer (A): 265°C Injection mold inner layer (B) resin flow path temperature: 320°C Injection mold inner layer (A) resin flow path temperature: 280°C Injection mold temperature: 30°C
  • Polyester compounds (1) to (6) were obtained according to (Production Example 1) to (Production Example 6) of the first embodiment.
  • Example 1 Cobalt (II) stearate was blended with the polyester compound (1) so that the amount of cobalt was 2.5 ppm, and the resulting oxygen-absorbing resin composition was passed through a twin-screw machine with two screws each having a diameter of 20 mm. Using an extruder, the oxygen-absorbing resin composition (1) was extruded in the form of a strand at an extrusion temperature of 280° C. and a screw rotation speed of 50 rpm, and cut with a pelletizer to obtain an oxygen-absorbing resin composition (1) in the form of pellets.
  • the obtained oxygen-absorbing resin composition was molded into a prefill syringe using the method described above, and a storage test for an adrenaline-containing drug solution, an elution test, and an evaluation of color tone change of the container were performed.
  • the evaluation results are shown in Table 7.
  • Example 2 A prefill syringe was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1).
  • the obtained prefill syringe was subjected to a storage test for an adrenaline-containing drug solution, an elution test, and an evaluation of color change of the container using the methods described above. The evaluation results are shown in Table 7.
  • Example 3 An oxygen-absorbing resin composition (3) was obtained in the same manner as in Example 1, except that cobalt (II) stearate was blended to have a cobalt content of 20 ppm.
  • the obtained oxygen-absorbing resin composition was molded into a prefill syringe using the method described above, and the obtained prefill syringe was subjected to a storage test, an elution test, and an evaluation of color tone change of the container for the adrenaline-containing drug solution using the method described above. did.
  • the evaluation results are shown in Table 7.
  • Example 1 A prefill syringe was obtained in the same manner as in Example 1, except that polyester compound (3) was used instead of polyester compound (1).
  • the obtained prefill syringe was subjected to a storage test for an adrenaline-containing drug solution, an elution test, and an evaluation of color change of the container using the methods described above. The evaluation results are shown in Table 7.
  • Example 2 A prefill syringe was obtained in the same manner as in Example 1 except that polyester compound (4) was used instead of polyester compound (1).
  • the obtained prefill syringe was subjected to a storage test for an adrenaline-containing drug solution, an elution test, and an evaluation of color change of the container using the methods described above. The evaluation results are shown in Table 7.
  • Example 3 A prefill syringe was obtained in the same manner as in Example 1 except that polyester compound (5) was used instead of polyester compound (1).
  • the obtained prefill syringe was subjected to a storage test for an adrenaline-containing drug solution, an elution test, and an evaluation of color change of the container using the methods described above. The evaluation results are shown in Table 7.
  • Example 4 A prefill syringe was obtained in the same manner as in Example 1 except that polyester compound (6) was used instead of polyester compound (1).
  • the obtained prefill syringe was subjected to a storage test for an adrenaline-containing drug solution, an elution test, and an evaluation of color change of the container using the methods described above. The evaluation results are shown in Table 7.
  • Example 5 Example except that nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon S7007) was used instead of polyester compound (1), and cobalt (II) stearate was blended to give a cobalt content of 20 ppm.
  • An oxygen-absorbing resin composition (6) was obtained in the same manner as in Example 1.
  • a prefill syringe was obtained in the same manner as in Example 1, except that the temperature of the injection cylinder for layer (A) was 260° C. for the obtained oxygen-absorbing resin composition.
  • the obtained prefill syringe was subjected to a storage test for an adrenaline-containing drug solution, an elution test, and an evaluation of color change of the container using the methods described above. The evaluation results are shown in Table 7.
  • the adrenaline-containing drug solution stored by the method for preserving an adrenaline-containing drug solution according to the seventh embodiment did not undergo yellowing (that is, did not undergo oxidation). ), it was confirmed that there was little elution from the container, and the color change of the container after storage was small, so the visibility of the contents was also good.
  • Polyester compounds (1) to (6) were obtained according to (Production Example 1) to (Production Example 6) of the first embodiment.
  • Example 1 After molding a vial using the polyester compound (1) by the method described above, the vial was irradiated with 20 kGy of gamma rays to obtain a vial in which the modified polyester was the intermediate layer. The obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using the polyester compound (1), the film obtained by the above method was irradiated with 20 kGy of gamma rays to evaluate its shape and strength retention. The evaluation results are shown in Table 8.
  • Example 2 A vial having a modified polyester as an intermediate layer was obtained in the same manner as in Example 1 except that polyester compound (2) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using the polyester compound (2), the film obtained by the above method was irradiated with 20 kGy of gamma rays to evaluate its shape and strength retention. The evaluation results are shown in Table 8.
  • Example 3 A vial in which the intermediate layer was made of modified polyester was obtained in the same manner as in Example 1 except that the ⁇ -ray irradiation amount was 40 kGy. The obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using the polyester compound (1), the film obtained by the above method was irradiated with 40 kGy of gamma rays to evaluate its shape and strength retention. The evaluation results are shown in Table 8.
  • Example 1 A vial containing the modified polyester as an intermediate layer was obtained in the same manner as in Example 1, except that polyester compound (3) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using the polyester compound (3), the film obtained by the above method was irradiated with 20 kGy of gamma rays to evaluate its shape and strength retention. The evaluation results are shown in Table 8.
  • Example 2 A vial containing the modified polyester as an intermediate layer was obtained in the same manner as in Example 1, except that polyester compound (4) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using the polyester compound (4), the film obtained by the above method was irradiated with 20 kGy of gamma rays to evaluate the shape and strength retention properties. The evaluation results are shown in Table 8.
  • Example 3 A vial in which the modified polyester was used as an intermediate layer was obtained in the same manner as in Example 1, except that polyester compound (5) was used instead of polyester compound (1).
  • the obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using the polyester compound (5), the film obtained by the above method was irradiated with 20 kGy of gamma rays to evaluate the shape and strength retention properties. The evaluation results are shown in Table 8.
  • Example 4 A vial containing the modified polyester as an intermediate layer was obtained in the same manner as in Example 1, except that polyester compound (6) was used instead of polyester compound (1). The obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using the polyester compound (6), the film obtained by the above method was irradiated with 20 kGy of gamma rays to evaluate its shape and strength retention. The evaluation results are shown in Table 8.
  • Example 5 A vial was obtained in the same manner as in Example 1, except that nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon S7007) was used instead of the polyester compound (1), with the nylon MXD6 modified product serving as the intermediate layer. Ta.
  • the obtained vials were evaluated for oxygen barrier properties, color change of the container, and moldability. Further, using nylon MXD6, the film obtained by the above method was irradiated with 20 kGy of gamma rays to evaluate its shape and strength retention. The evaluation results are shown in Table 8.
  • the vial has an intermediate layer made of unmodified polyester that does not irradiate the vial with gamma rays. Oxygen barrier properties, color change of the container, and formability An evaluation was conducted. Further, using polyester compound (1), the shape and strength maintenance properties of unmodified polyester, which was not irradiated with gamma rays, were evaluated for the film obtained by the method described above. The evaluation results are shown in Table 8.
  • the modified polyester of the eighth embodiment exhibits good oxygen barrier performance, has a good color tone after oxygen absorption, has excellent strength and shape retention, and has excellent moldability. This was confirmed.

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Abstract

La présente invention aborde le problème de la fourniture d'une composition de résine ou similaire qui présente des performances de barrière à l'oxygène favorables et un ton de couleur favorable après absorption de l'oxygène, et qui présente une excellente résistance et une excellente rétention de forme ainsi qu'une excellente aptitude au moulage. Le problème peut être résolu par une composition de résine contenant un catalyseur de métal de transition et un composé de polyester ayant une structure prescrite.
PCT/JP2023/018075 2022-06-03 2023-05-15 Composition de résine WO2023233984A1 (fr)

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JP2022090859A JP2023177899A (ja) 2022-06-03 2022-06-03 プレフィル用シリンジ
JP2022-090852 2022-06-03
JP2022-090856 2022-06-03
JP2022090857A JP2023177897A (ja) 2022-06-03 2022-06-03 多層体及び容器
JP2022090833A JP2023177878A (ja) 2022-06-03 2022-06-03 アドレナリン含有薬液の保存方法
JP2022-090833 2022-06-03
JP2022-090838 2022-06-03
JP2022090852A JP2023177894A (ja) 2022-06-03 2022-06-03 多層射出成形体及び容器
JP2022090836A JP2023177881A (ja) 2022-06-03 2022-06-03 樹脂組成物
JP2022-090859 2022-06-03
JP2022-090857 2022-06-03
JP2022090877A JP2023177910A (ja) 2022-06-03 2022-06-03 バイオ医薬品の保存方法
JP2022-090877 2022-06-03
JP2022090856A JP2023177896A (ja) 2022-06-03 2022-06-03 医療用多層容器
JP2022090838A JP2023177883A (ja) 2022-06-03 2022-06-03 改質ポリエステル
JP2022-090836 2022-06-03

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134194A (ja) * 1994-11-02 1996-05-28 Teijin Ltd 共重合ポリエチレンナフタレートフイルム
WO2014057991A1 (fr) * 2012-10-10 2014-04-17 三菱瓦斯化学株式会社 Composition de résine absorbant l'oxygène
WO2014136811A1 (fr) * 2013-03-05 2014-09-12 三菱瓦斯化学株式会社 Composition de résine absorbant l'oxygène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134194A (ja) * 1994-11-02 1996-05-28 Teijin Ltd 共重合ポリエチレンナフタレートフイルム
WO2014057991A1 (fr) * 2012-10-10 2014-04-17 三菱瓦斯化学株式会社 Composition de résine absorbant l'oxygène
WO2014136811A1 (fr) * 2013-03-05 2014-09-12 三菱瓦斯化学株式会社 Composition de résine absorbant l'oxygène

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