JP2014172219A - Oxygen-absorbing medical multilayer container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxygen-absorbing medical multilayer containers which has excellent oxygen barrier properties, keeps strength through long-term storage, reduces the elution amount of impurities and is excellent in interlayer adhesion.SOLUTION: An oxygen-absorbing medical multilayer container comprises, in order, a first resin layer containing a polyester, an oxygen-absorbing layer containing an oxygen-absorbing composition and a second resin layer containing a polyester, and the oxygen-absorbing composition comprises at least one compound having a tetralin ring of a specified structure, a transition metal catalyst and a thermoplastic resin.

Description

  The present invention relates to an oxygen-absorbing medical multilayer container.

  Prevents oxygen oxidation of various products that are easily altered or deteriorated by the influence of oxygen, such as food, beverages, pharmaceuticals, and cosmetics, and removes oxygen in the package that contains them for the purpose of long-term storage. The oxygen absorber to be used is used.

  As the oxygen absorbent, an oxygen absorbent containing iron powder as a main reaction agent is generally used from the viewpoint of oxygen absorption capacity, ease of handling, and safety. However, since this iron-based oxygen absorbent is sensitive to a metal detector, it has been difficult to use the metal detector for foreign object inspection. Moreover, since the package which enclosed the iron-type oxygen absorber has a possibility of ignition, it cannot be heated with a microwave oven. Furthermore, since water is essential for the oxidation reaction of iron powder, the effect of oxygen absorption could only be exhibited if the material to be preserved was a high moisture type.

  In addition, the container is made of a multilayer material in which an oxygen absorbing layer made of an oxygen absorbing resin composition in which an iron-based oxygen absorber is blended with a thermoplastic resin, thereby improving the gas barrier property of the container and improving the container itself. Development of packaging containers having an oxygen absorbing function has been carried out (see Patent Document 1). Specifically, in an oxygen-absorbing multilayer film, an oxygen absorbent is dispersed between a conventional gas-barrier multilayer film formed by laminating a heat seal layer and a gas barrier layer, optionally with an intermediate layer made of a thermoplastic resin. It has been used as an oxygen absorbing layer that is a thermoplastic resin layer that has been added to provide a function to absorb oxygen in the container in addition to the function of preventing oxygen permeation from the outside, such as extrusion lamination, co-extrusion lamination, and dry lamination. It is manufactured using a known manufacturing method. However, this is also a problem that it can not be detected by metal detectors used for detecting foreign substances such as food, it can not be heated with a microwave oven, and the object to be stored only exhibits high moisture content have. Furthermore, there is a problem that the internal visibility is insufficient due to the problem of opacity. Those using oxygen absorbers such as iron powder are detected by metal detectors used to detect foreign objects such as food, when internal visibility is insufficient due to opacity problems, and the contents are alcoholic drinks There has been a problem that an aldehyde is generated by an oxidation reaction of alcohol using iron as a catalyst, and the flavor is lowered.

  In view of the above circumstances, an oxygen absorbent using an organic substance as a reaction main agent is desired. As an oxygen absorbent containing an organic substance as a main reaction agent, an oxygen absorbent containing ascorbic acid as a main agent is known (see Patent Document 2).

  On the other hand, an oxygen-absorbing resin composition comprising a resin and a transition metal catalyst is known. For example, a resin composition comprising a polyamide, particularly a xylylene group-containing polyamide and a transition metal catalyst as an oxidizable organic component is known (see Patent Documents 3 and 4). Further, Patent Documents 3 and 4 also exemplify an oxygen absorbent, a packaging material, and a multilayer laminated film for packaging obtained by molding this resin composition.

  As an oxygen-absorbing resin composition that does not require moisture for oxygen absorption, an oxygen-absorbing resin composition comprising a resin having a carbon-carbon unsaturated bond and a transition metal catalyst is known (see Patent Document 5). .

  Furthermore, as a composition for collecting oxygen, a composition comprising a polymer containing a substituted cyclohexene functional group or a low molecular weight substance to which the cyclohexene functional group is bonded and a transition metal is known (see Patent Document 6). .

  On the other hand, injection molding (injection molding) is widely used in machine parts, automobile parts, electrical / electronic parts, food / medicine containers, etc. because it can produce molded bodies having complicated shapes and has high productivity. . In recent years, various plastic containers have been widely used as packaging containers because they have advantages such as light weight, transparency and easy moldability. As a typical plastic container, for example, in a container such as a beverage, an injection molded body in which a screw shape is formed on a cap so that a lid can be sufficiently tightened is frequently used.

  Examples of the material used for the injection molded article include general-purpose thermoplastic resins such as polyolefin (polyethylene, polypropylene, etc.), polyester, polystyrene, and the like. In particular, injection molded articles mainly composed of polyester such as polyethylene terephthalate (PET) are widely used as plastic containers for beverages such as tea, fruit juice beverages, carbonated beverages and alcoholic beverages. However, although the injection-molded body mainly composed of thermoplastic resin is excellent as a packaging material, unlike glass bottles and metal containers, it tends to allow oxygen to permeate from the outside. There remains a problem with sex. Therefore, in order to impart gas barrier properties to such an injection-molded body made of a general-purpose resin, an injection-molded body having a gas barrier layer as an intermediate layer has been put into practical use.

  Conventionally, glass ampules, vials, prefilled syringes, and the like have been used as medical packaging containers for filling and storing chemical solutions in a sealed state. However, these glass containers are colored when a light-shielding glass container colored with metal is used, in which sodium ions and the like are eluted in the liquid in the container during storage, and a fine substance called flakes is generated. There is a problem that the metal for use is mixed into the contents, and is easily broken by an impact such as dropping. Further, since the specific gravity is relatively large, there is a problem that the medical packaging container is heavy. Therefore, development of alternative materials is expected. Specifically, plastics that are lighter than glass, such as polyester, polycarbonate, polypropylene, and cycloolefin polymers, are being considered as glass substitutes.

  For example, a medical container made of a polyester resin material has been proposed (see Patent Document 7).

  On the other hand, in order to provide a gas barrier property to a container made of plastic, a multilayer container having a gas barrier layer as an intermediate layer has been studied. Specifically, a prefilled syringe with an improved oxygen barrier property, which has an innermost layer and an outermost layer made of a polyolefin-based resin, and an intermediate layer made of a resin composition having an excellent oxygen barrier property, is presented (Patent Literature). 8). In addition, polyamide obtained from metaxylylenediamine and adipic acid (hereinafter sometimes referred to as “nylon MXD6”), ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinylidene chloride, aluminum foil, carbon Multi-layer containers in which a gas barrier layer such as a coat or inorganic oxide deposition is laminated on a resin layer are also being studied.

  On the other hand, in recent years, it has been proposed that a small amount of transition metal compound is added to and mixed with nylon MXD6 to give an oxygen absorbing function, and this is used as an oxygen barrier material constituting containers and packaging materials ( (See Patent Document 9).

  In addition to ampoules, vials, and syringes, examples of medical containers include artificial kidney hemodialyzers (dialyzers). For the housing of the dialyzer, polystyrene or polycarbonate is used as a transparent plastic that allows the contents to be clearly seen. However, in order to avoid damage due to dropping or other impact, polycarbonate having good impact resistance is more preferred ( (See Patent Document 10).

Japanese Patent Application Laid-Open No. 09-234832 JP-A-51-136845 JP 2001-252560 A JP 2009-108153 A Japanese Patent Laid-Open No. 05-115776 Special table 2003-521552 gazette JP 08-127641 A JP 2004-229750 A Japanese Patent Laid-Open No. 02-500846 Japanese Patent Laid-Open No. 01-259870

  However, the oxygen absorbent of Patent Document 2 has a problem that oxygen absorption performance is low in the first place, and only a high-moisture material is effective and is relatively expensive.

  Moreover, since the resin composition of patent document 3 expresses an oxygen absorption function by containing a transition metal catalyst and oxidizing a xylylene group-containing polyamide resin, the polymer chain due to oxidative degradation of the resin after oxygen absorption. There is a problem that cutting occurs and the strength of the packaging container itself is reduced. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture. Further, Patent Document 4 describes a method for improving delamination, but the effect is limited. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture.

  Furthermore, the oxygen-absorbing resin composition of Patent Document 5 generates a low molecular weight organic compound that becomes an odor component by breaking the polymer chain accompanying the oxidation of the resin in the same manner as described above, and generates odor after oxygen absorption. There's a problem.

  On the other hand, the composition of Patent Document 6 needs to use a special material containing a cyclohexene functional group, and this material still has a problem that it is relatively easy to generate an odor.

  On the other hand, the above-mentioned conventional gas barrier multilayer containers and medical multilayer containers have insufficient basic performance such as oxygen barrier property, water vapor barrier property, chemical solution adsorption property, container durability, etc. Improvement is required from the viewpoint of storage stability.

  In particular, when foods, chemicals, etc. are stored using a conventional gas barrier multilayer container, it is difficult or extremely uneconomical to completely remove oxygen in the packaging container no matter how the gas replacement operation is performed. There is a fact that. That is, it is difficult to completely eliminate oxygen dissolved in the liquid of the contents, oxygen contained in bubbles generated and mixed when the contents are mixed, water added thereto, and the like. Although it is possible to remove oxygen as much as possible by performing advanced management in the selection / preparation conditions and manufacturing conditions of raw materials, such handling that ignores economic efficiency is not realistic. In addition, since the oxygen barrier property of the gas barrier multilayer container is not sufficient as described above, it is not possible to completely eliminate the trace amount of oxygen that permeates through the wall of the container and enters from the outside.

  For example, although the medical container made of polyester resin of Patent Document 7 has relatively excellent oxygen barrier property, the oxygen barrier property is insufficient to completely block oxygen, and the polyolefin resin Compared to a container made of, the water vapor barrier property is also inferior. Moreover, this polyester resin does not have oxygen absorption performance. Therefore, when oxygen enters the container from the outside, or oxygen remains in the head space existing above the contents of the container, there is a problem that the chemical solution in the container cannot be prevented from deteriorating. there were.

  Moreover, although the prefilled syringe of patent document 8 has relatively excellent oxygen barrier property and water vapor barrier property, the oxygen barrier property is insufficient to completely block oxygen. And the oxygen barrier resin composition of an intermediate | middle layer does not have oxygen absorption performance. Therefore, when oxygen enters the container from the outside, or oxygen remains in the head space existing above the contents of the container, there is a problem that the chemical solution in the container cannot be prevented from deteriorating. there were.

  On the other hand, the resin composition of Patent Document 9 has a problem that, as in Patent Documents 3 and 4 described above, a decrease in strength occurs due to oxidative degradation of the resin after oxidative absorption, and the strength of the packaging container itself decreases. Yes. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture.

  The housing of the dialyzer disclosed in Patent Document 10 has excellent transparency and impact resistance, but polycarbonate is insufficient in oxygen barrier property and water vapor barrier property to be applied to a container for storing and storing a chemical solution. There is a problem in terms of long-term storage of the contents.

  The present invention has been made in view of the above circumstances, and the object thereof is oxygen having excellent oxygen barrier properties, maintaining strength even during long-term storage, having a small amount of impurity elution, and excellent interlayer adhesion. It is to provide an absorbent medical multilayer container.

  As a result of diligent investigations, the present inventors have found that a first resin layer containing polyester, an oxygen-absorbing layer containing a predetermined oxygen-absorbing composition, a second resin layer containing polyester, The present inventors have found that an oxygen-absorbing medical multilayer container having at least three layers in this order can solve the above-mentioned problems.

That is, the present invention is as follows.
[1]
An oxygen-absorbing medical multilayer having at least three layers of a first resin layer containing polyester, an oxygen-absorbing layer containing an oxygen-absorbing composition, and a second resin layer containing polyester in this order. A container,
The oxygen-absorbing composition includes at least one compound having a tetralin ring represented by the following general formula (1), a transition metal catalyst, and a thermoplastic resin.
(Wherein R _{1 to} R ₁₂ each independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio group, imide And at least one selected from the group consisting of a substituent represented by the following general formula (1a) and a substituent represented by the following general formula (1b), and these further have a substituent. Alternatively, two substituents out of R _{1 to} R ₁₂ may be bonded to form a ring, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring.
(In the general formula (1a) and the general formula (1b), R each independently represents a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio These are at least one selected from the group consisting of a group and an imide group, which may further have a substituent, and two substituents of R may be bonded to form a ring. W is a bond or a divalent organic group, and the divalent organic group is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. Saturated fat Group hydrocarbon group and heterocyclic group, at least selected from the group consisting of —C (═O) —, —OC (═O) —, —N (H) C (═O) —, and any combination thereof. (M represents an integer of 0 to 4, n represents an integer of 0 to 7, p represents an integer of 0 to 8, and q represents an integer of 0 to 3.)
Oxygen-absorbing medical multilayer container.
[2]
The oxygen-absorbing medical multilayer container according to [1], wherein the compound having a tetralin ring represented by the general formula (1) has two or more carbonyl groups.
[3]
In the general formula (1), at least two of R _{1 to} R ₁₂ are monovalent substituents represented by the following general formula (2).

-C (= O) -X (2)

(Wherein X is one selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, a monoalkylamino group, and a dialkylamino group, and a plurality of Xs may be the same. And may be different.)
[2] The oxygen-absorbing medical multilayer container according to [2].
[4]
The oxygen-absorbing medical multilayer container according to any one of [1] to [3], wherein the compound having a tetralin ring represented by the general formula (1) has two or more tetralin rings.
[5]
Of the compound having the tetralin ring represented by the general formula (1) with respect to the total amount of the compound having the tetralin ring represented by the general formula (1) and the thermoplastic resin in the oxygen-absorbing composition. The oxygen-absorbing medical multilayer container according to any one of [1] to [4], wherein the ratio is 1 to 30% by mass.
[6]
The oxygen-absorbing medicine according to any one of [1] to [5], wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper. Multi-layer container.
[7]
In the oxygen-absorbing composition, the transition metal catalyst has a transition metal amount of 0 with respect to 100 parts by mass of the total amount of the compound having a tetralin ring represented by the general formula (1) and the thermoplastic resin. The oxygen-absorbing medical multilayer container according to any one of [1] to [6], which is contained in an amount of 0.001 to 10 parts by mass.
[8]
More than 70 mol% in the dicarboxylic acid unit of the polyester is terephthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. [1] to [7], which is a unit derived from one or more dicarboxylic acids selected from the group consisting of acids, 2,7-naphthalenedicarboxylic acids, and ester-forming derivatives thereof. Oxygen-absorbing medical multilayer molded container.
[9]
The oxygen-absorbing medical multilayer molded container according to any one of [1] to [7], wherein 70 mol% or more in the dicarboxylic acid unit of the polyester is a unit derived from terephthalic acid.
[10]
The oxygen-absorbing medical multilayer molded container according to any one of [1] to [7], wherein 90 mol% or more in the dicarboxylic acid unit of the polyester is a unit derived from terephthalic acid.
[11]
The oxygen-absorbing medical multilayer molding according to any one of [1] to [7], wherein 70 mol% or more in the dicarboxylic acid unit of the polyester is a unit derived from 2,6-naphthalenedicarboxylic acid. container.
[12]
The oxygen-absorbing medical multilayer molding according to any one of [1] to [7], wherein 90 mol% or more in the dicarboxylic acid unit of the polyester is a unit derived from 2,6-naphthalenedicarboxylic acid. container.

  According to the present invention, an oxygen-absorbing medical device having excellent oxygen-absorbing performance, having excellent oxygen-barrier performance, maintaining strength even during long-term storage, reducing the amount of impurities eluted, and having excellent interlayer adhesion Multi-layer containers can be provided. Moreover, according to the preferred embodiment of the present invention, an oxygen-absorbing multilayer injection molded article that is excellent in visibility inside the container and is insensitive to a metal detector can be realized.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[Oxygen-absorbing medical multilayer container]
The oxygen-absorbing medical multilayer container of the present embodiment includes at least a first resin layer containing polyester, an oxygen-absorbing layer containing an oxygen-absorbing composition, and a second resin layer containing polyester. An oxygen-absorbing medical multilayer container having three layers in this order, wherein the oxygen-absorbing composition includes at least one compound having a tetralin ring represented by the following general formula (1), a transition metal catalyst, And thermoplastic resin,
(Wherein R _{1 to} R ₁₂ each independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio group, imide And at least one selected from the group consisting of a substituent represented by the following general formula (1a) and a substituent represented by the following general formula (1b), and these further have a substituent. Alternatively, two substituents out of R _{1 to} R ₁₂ may be bonded to form a ring, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring.
(In the general formula (1a) and the general formula (1b), R each independently represents a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio These are at least one selected from the group consisting of a group and an imide group, which may further have a substituent, and two substituents of R may be bonded to form a ring. W is a bond or a divalent organic group, and the divalent organic group is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. Saturated fat Group hydrocarbon group and heterocyclic group, at least selected from the group consisting of —C (═O) —, —OC (═O) —, —N (H) C (═O) —, and any combination thereof. (M represents an integer of 0 to 4, n represents an integer of 0 to 7, p represents an integer of 0 to 8, and q represents an integer of 0 to 3.)
This is an oxygen-absorbing medical multilayer container.

  The oxygen-absorbing medical multilayer container of the present embodiment can be used as, for example, a medical container for storing a content article (a storage object). In this case, the oxygen in the container is absorbed, and if there is a small amount of oxygen that permeates or penetrates from the outside of the container, the permeated or invading oxygen is also absorbed and stored. Can be prevented from being deteriorated by oxygen. This oxygen-absorbing medical multilayer container can absorb oxygen regardless of the presence or absence of moisture in the object to be stored, and the production of low molecular weight compounds after oxygen absorption is remarkably suppressed, so it can be used for various pharmaceuticals and medical products. can do. Moreover, since the strength decrease due to oxidation or the like is extremely small even after oxygen absorption and the strength of the oxygen absorption layer is maintained even during long-term use, it is possible to realize an oxygen-absorbing medical multilayer container that hardly causes delamination. Therefore, the oxygen-absorbing medical multilayer container of the present invention is particularly useful for storing pharmaceuticals, biopharmaceuticals, medical products and the like that are required to be stored under a low oxygen concentration.

  The oxygen-absorbing medical multilayer molded container of this embodiment contains at least a first resin layer (layer B) containing at least polyester, an oxygen-absorbing layer (layer A) made of an oxygen-absorbing composition, and at least polyester. It has at least three layers in this order with the second resin layer (layer B).

  The oxygen-absorbing medical multilayer molded container of the present embodiment absorbs oxygen in the container, and if there is little oxygen that permeates or penetrates the container wall surface from outside the container, the oxygen-absorbing medical multilayer molded container also has this permeated or infiltrated oxygen. It is possible to prevent alteration or the like due to oxygen of the content article (preservation object) to be absorbed and stored.

  As long as these layers are arranged in the order of B / A / B, the layer structure in the oxygen-absorbing medical multilayer molded container of this embodiment is a resin layer (layer) containing an oxygen-absorbing layer (layer A) and polyester. The number and type of B) are not particularly limited. For example, a five-layer configuration of B1 / B2 / A / B2 / B1 including one layer A, two layers B1, and two layers B2 may be used, and one layer A and two layers B1 and B2 A three-layer structure of B1 / A / B2 composed of two seed layers may be used. Moreover, the oxygen-absorbing medical multilayer molded container of the present 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 configuration of B1 may be used.

[Oxygen absorbing layer (layer A)]
The oxygen-absorbing layer (layer A) of the oxygen-absorbing medical multilayer container of the present embodiment includes at least a compound having a tetralin ring represented by the general formula (1) (hereinafter also simply referred to as “tetralin compound”). It is a layer containing an oxygen-absorbing composition containing one type, a transition metal catalyst, and a thermoplastic resin.

<Compound with tetralin ring>
In the general formula (1), examples of the monovalent substituent represented by R _{1 to} R ₁₂ include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably having 1 to 15 carbon atoms, More preferably, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-octyl group, or 2-ethylhexyl. Group, cyclopropyl group, cyclopentyl group), alkenyl group (preferably a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, for example, vinyl group, allyl group ), An alkynyl group (preferably an alkynyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, such as an ethynyl group or a propargyl group), an aryl group (preferably carbon Is an aryl group having 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). Monovalent groups obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound, for example, 1-pyrazolyl group, 1-imidazolyl group, 2-furyl Group), cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group (preferably linear or branched having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) A cyclic alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms such as a phenoxy group), (Including a formyl group, preferably an alkylcarbonyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, preferably 7 to 12 carbon atoms, more preferably 7 to 9 carbon atoms. An arylcarbonyl group such as an acetyl group, a pivaloyl group or a benzoyl group), an amino group (preferably an alkylamino group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, preferably 6 to 12 carbon atoms). , More preferably an anilino group having 6 to 8 carbon atoms, preferably a heterocyclic amino group having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, such as an amino group, a methylamino group, and an anilino group) , A thiol group, an alkylthio group (preferably an alkylthio group having 1 to 10 carbon atoms, more preferably an alkylthio group having 1 to 6 carbon atoms, such as a methylthio group or an ethylthio group), an arylthio group (Preferably an arylthio group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 2 to 10 carbon atoms, more preferably 1 carbon number) To 6 heterocyclic thio groups such as 2-benzothiazolylthio group), imide groups (preferably having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, such as N-succinimide group). , N-phthalimido group) and the like, but not limited thereto.

In the compound represented by the general formula (1), at least one hydrogen atom is bonded to the benzyl position of the tetralin ring. As will be described later, an excellent oxygen absorption ability and the like can be expressed by the action of a hydrogen atom bonded to the benzyl position of the tetralin ring and a transition metal catalyst described later. Examples of the compound in which at least one hydrogen atom is bonded to the benzyl position of the tetralin ring include, for example, any one of R ₁ , R ₄ , R ₉ and R _{12 in} the general formula (1) is a hydrogen atom. The compound etc. which are are mentioned.

In addition, when the above monovalent substituents R _{1 to} R ₁₂ have a hydrogen atom, the hydrogen atom is a substituent T (wherein the substituent T is the same as that described for the monovalent substituent R above). It may be further substituted with the same meaning. Specific examples thereof include an alkyl group substituted with a hydroxy group (eg, hydroxyethyl group), an alkyl group substituted with an alkoxy group (eg, methoxyethyl group), and an alkyl group substituted with an aryl group (eg, benzyl). Group), an alkyl group substituted with a primary or secondary amino group (eg, aminoethyl group), an aryl group substituted with an alkyl group (eg, p-tolyl group), an aryl substituted with an alkyl group Examples thereof include, but are not particularly limited to, an oxy group (for example, 2-methylphenoxy group) and the like. When the monovalent substituent R has a monovalent substituent T, the carbon number described above does not include the carbon number of the substituent T. For example, a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group. When the monovalent substituent R has a substituent T, there may be a plurality of the substituents T.

Two of the monovalent substituents R _{1 to} R ₁₂ may be bonded to form a ring. Specific examples thereof include compounds in which two of R _{1 to} R ₁₂ are condensed to form a 5- to 8-membered ring. The ring herein may be any known ring structure and is not particularly limited, but is preferably an aromatic ring, aliphatic ring or heterocycle having 4 to 7 carbon atoms (more preferably , Cyclohexane ring, cycloheptane ring, acid anhydride ring (for example, succinic anhydride ring, glutaric anhydride ring, adipic anhydride ring, etc.), benzene ring, bicyclo ring, etc.). ).

From the viewpoint of suppressing loss due to volatilization during use and increasing the amount of oxygen absorbed per unit mass of the compound, the compound having a tetralin ring represented by the general formula (1) is at least _one of R _{1 to} R ₁₂ . One is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a hydroxy group, a carboxyl group, a substituted or unsubstituted ester group, an alkoxy group, an acyl group, a substituted or unsubstituted amide group, and a substituted or unsubstituted group. One selected from the group consisting of substituted imide groups (hereinafter also simply referred to as “substituent group S”); preferably one in which two or more Rs are condensed to form a 5- to 6-membered ring. . Among these substituent groups S, there are substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, hydroxy groups, carboxyl groups, alkoxy groups, substituted or unsubstituted ester groups, and substituted or unsubstituted amide groups. More preferred.

As a preferred first embodiment of the compound having a tetralin ring represented by the above general formula (1), there may be mentioned those having the structures shown below.
(In the general formula (1c), R _{1 to} R ₈ each independently represents a monovalent substituent, and the monovalent substituent has the same meaning as R _{1 to} R ₁₂ described above, provided that Two or more of R _{1 to} R ₈ are not bonded to form a ring.)

In the first aspect, at least two of R _{1 to} R ₈ are one selected from the substituent group S described above, and the other R _{1 to} R ₈ are hydrogen atoms. It is preferable that two of R _{1 to} R ₈ are one selected from the substituent group S, and 6 of R _{1 to} R ₈ is more preferably a hydrogen atom.

In the first aspect, various isomers are included. For example, when two substituents are introduced into tetralin represented by the following general formula (1-1), the structural isomers are represented by the following general formulas. Although tetralin derivatives represented by (1-2) to (1-15) may be generated, the introduction position (substitution position) of the substituent is not particularly limited.

Hereinafter, examples included in the first aspect are listed, but not limited thereto.
(In each formula, n is an integer of 0 to 3, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is an aromatic hydrocarbon group, saturated or It is at least one selected from the group consisting of an unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and an acyl group.)

  Here, examples of the aromatic hydrocarbon group include, but are not particularly limited to, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a fluorenyl group. Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, and a cycloalkenyl group, but are not particularly limited thereto. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group, and n-octyl group. Group, 2-ethylhexyl group, n-decyl group, lauryl group, stearyl group, palmityl group and other linear and branched alkyl groups, ethenyl group, propenyl group, butenyl group, octenyl group, nonadecenyl group, pentacosenyl group Examples include alkenyl groups such as groups, but are not limited thereto. Examples of the acyl group include, but are not limited to, an acetyl group, a pivaloyl group, and a benzoyl group. These may further have a substituent, and specific examples thereof include, for example, halogen, alkoxy group, hydroxy group, carboxyl group, carboalkoxy group, amino group, acyl group, thio group (for example, alkylthio group). , Phenylthio group, tolylthio group, pyridylthio group, etc.), amino group (for example, unsubstituted amino group, methylamino group, dimethylamino group, phenylamino group, etc.), cyano group, nitro group and the like.

  Moreover, as a preferable 2nd aspect of the compound which has a tetralin ring represented by said general formula (1), the thing of the structure represented by the following general formula (2-1)-(2-5) is mentioned. It is done.

_(Wherein, R 1 to R ₈ each independently represent a hydrogen atom or a monovalent substituent, _{R 1} a monovalent substituent _R 1 to R ₈ are as described in the general formula (1) to R ₁₂ in the above formula, arc a is the number of carbon atoms of the substituted or unsubstituted is an aromatic ring, heterocyclic or acid anhydride ring of 4-7.)

  In said 2nd aspect, it is preferable that the circular arc A is a C4-C7 aromatic ring, an aliphatic ring, or a heterocyclic ring. Specific examples thereof include benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, acid anhydride ring (succinic acid anhydride ring, glutaric acid anhydride ring, adipic acid anhydride ring) and the like.

  Furthermore, a preferred third embodiment of the compound having a tetralin ring represented by the general formula (1) includes those having two or more carbonyl groups.

As an example of the third embodiment having two or more carbonyl groups, monovalent substitution in which two or more of R _{1 to} R ₁₂ of the general formula (1) are represented by the following general formula (2) It is preferably a group.
(In Formula (1), R < ₁ > -R < ₁₂ > shows a hydrogen atom or a monovalent substituent each independently, and monovalent substituent R < ₁ > -R < ₁₂ > is synonymous with what was demonstrated above. However, two or more of R _{1 to} R ₁₂ are not bonded to form a ring.)

-C (= O) X (2)

(In Formula (2), X is one selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, a monoalkylamino group, and a dialkylamino group, and the plurality of Xs are the same. May be different or different.)

Further, in the third embodiment of the _above, R 1 _{to R 12} are the following requirements (A) ~ (C);
(A) One or more monovalent substituents represented by the above general formula (2) are bonded to the aromatic ring of the tetralin ring, and the aliphatic ring of the tetralin ring is represented by the above general formula (2). One or more monovalent substituents are bonded.
(B) Two or more monovalent substituents represented by the general formula (2) are bonded to the aromatic ring of the tetralin ring.
(C) Two or more monovalent substituents represented by the general formula (2) are bonded to the aliphatic ring of the tetralin ring.
Those satisfying any of these are more preferable.

  In the monovalent substituent represented by the general formula (2), X is preferably an alkoxy group represented by an —O—Z group or a monoalkylamino group represented by an NH—Z group. -Z represents an aromatic hydrocarbon group having 1 to 10 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group, or a linear or branched saturated or unsaturated aliphatic hydrocarbon group. It is more preferable that In addition, since these specific examples overlap with what was demonstrated by the substituent R mentioned above, description here is abbreviate | omitted.

Hereinafter, although the example of the 3rd aspect which satisfy | fills said requirements (A)-(C) is enumerated, it does not specifically limit to these.
(In each formula, Z has the same meaning as described in the general formula (2).)

Among the above third embodiments, compounds represented by the following general formulas (3-10) to (3-20) are more preferable.

Specific examples of the compound having a tetralin ring represented by the general formula (1) are shown below, but are not particularly limited thereto.
(In the formula, n is an integer of 0 to 3.)

  Furthermore, as a preferable fourth aspect of the compound having a tetralin ring represented by the general formula (1), those having two or more tetralin rings can be mentioned. The upper limit of the tetralin ring is preferably 12 or less, and preferably 3 or less from the viewpoint of availability. In particular, the number of tetralin rings is more preferably 2 from the viewpoint of the balance between oxygen absorption performance and heat resistance and availability.

As an example of the fourth embodiment having two or more tetralin rings, at least one compound selected from the group consisting of the following general formulas (4-1) to (4-6) is preferable.
(In the formula, each R independently represents a monovalent substituent, and the monovalent substituent R has the same meaning as R _{1 to} R ₁₂ described above. M represents 0 to 7, and n represents 0. -3, p represents an integer of 0-4, q represents an integer of 0-6, and one or more hydrogen atoms are bonded to the benzylic position of the tetralin ring, and X represents an aromatic hydrocarbon group, saturated or Represents a divalent group containing at least one group selected from the group consisting of an unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group. Y represents an ester group or an amide group, and t represents an integer of 0 to 6.)

Examples of the substituent represented by R in the general formulas (4-1) to (4-6) include those exemplified as R _{1 to} R ₁₂ above. Among these, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a hydroxy group, a carboxyl group, an ester group, an alkoxy group, an acyl group, an amide group, and an imide group are preferable, a hydrogen atom, a substituted group Or an unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, an ester group and an acyl group are more preferred, and a hydrogen atom, an unsubstituted alkyl group, an alkoxy group and an ester group are particularly preferred.

  The molecular weight of the compounds represented by the general formulas (4-1) to (4-6) is preferably 276 to 1000, more preferably 300 to 800, and particularly preferably 350 to 600. A molecular weight of 276 or more is preferable because loss due to volatilization during use can be suppressed as compared with a molecular weight of less than 276. Further, when the molecular weight is 1000 or less, the proportion of the tetralin ring moiety in the compound is higher than that when the molecular weight exceeds 1000, and this is preferable because the amount of oxygen absorbed per unit mass of the compound is increased.

  In addition, the compounds represented by the general formulas (4-1) to (4-6) preferably have a high boiling point and a low vapor pressure at the temperature at the time of use because loss due to volatilization at the time of use can be suppressed. Further, when the compound is an oxygen-absorbing composition to be described later, the vapor pressure at the kneading temperature with the thermoplastic resin is lower, and the higher the 3% weight loss temperature, the more loss due to volatilization during the production of the oxygen-absorbing composition. Since it can suppress, it is preferable. The 3% weight loss temperature is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher.

  Among the above functional groups, those having a hydrogen atom may be further substituted with the above group, for example, an alkyl group substituted with a hydroxy group (for example, a hydroxyethyl group), an alkyl substituted with an alkoxy group A group (eg, methoxyethyl group), an alkyl group substituted with an aryl group (eg, benzyl group), an aryl group substituted with alkyl (eg, p-tolyl group), an aryloxy group substituted with an alkyl group ( Examples thereof include, but are not limited to, 2-methylphenoxy group. In addition, when a functional group is further substituted, the carbon number mentioned above shall not include the carbon number of the further substituent. For example, a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group. The substituent of tetralin having a substituent may have a plurality of substituents. Moreover, it is not always necessary to use a single substance, and two or more kinds may be mixed and used.

  As the compounds represented by the general formulas (4-1) to (4-6), the compounds represented by the following general formulas (4-7) to (4-16) are more preferable. 7), (4-10), (4-13) or (4-16) is particularly preferred.

(In the formula, X represents an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group.)

Although the preferable specific example of the said General formula (4-7) is shown below, this embodiment is not limited to these.

Although the preferable specific example of the said General formula (4-10) is shown below, this embodiment is not limited to these.

Although the preferable specific example of the said General formula (4-13) is shown below, this embodiment is not limited to these.

Although the preferable specific example of the said General formula (4-16) is shown below, this embodiment is not limited to these.

  As a compound having two tetralin rings in one molecule, the above general formulas (4-1) to (4-16) and formulas (4-17) to (4-33) were shown. In the present embodiment, a compound having three or more tetralin rings is also preferably used.

  The manufacturing method of the compound represented by General Formula (4-1)-(4-6) is not limited at all, and can be manufactured by a known method. For example, a transesterification reaction between an ester of a polycarboxylic acid having two or more carboxyl groups and a compound having a hydroxy group and a tetralin ring, a polyol having two or more hydroxy groups, and a compound having a carboxyl group and a tetralin ring And the reaction of an aldehyde with a compound having a tetralin ring are preferably exemplified.

  In another preferred example of the fourth aspect having two or more tetralin rings, the tetralin ring has two or more tetralin rings, and at least one of the tetralin rings has a hydrogen atom bonded to its benzylic position. And compounds having two or more imide bonds.

By having two or more tetralin rings, many reaction points with oxygen can be included, and furthermore, by having two or more imide bonds, heat resistance can be further improved. As such a compound, for example, at least one selected from the group consisting of the following general formulas (4-34) to (4-37) is preferable.
(In the general formulas (4-34) to (4-37), R each independently represents a monovalent substituent, and the monovalent substituent R has the same meaning as R _{1 to} R ₁₂ described above. M is an integer from 0 to 6, n is an integer from 0 to 3, p is an integer from 0 to 7, q is an integer from 0 to 2, r is an integer from 0 to 4, and s is an integer from 0 to 5. In at least one tetralin ring, one or more hydrogen atoms are bonded to the benzyl position, X represents a divalent substituent, and the divalent substituent is aromatic. It is at least one selected from the group consisting of a hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. )

  The molecular weight of the compounds represented by the general formulas (4-34) to (4-37) is not particularly limited, but is preferably 414 to 1000, more preferably 430 to 800, and further preferably 450 to 600. When the molecular weight is 414 or more, loss due to volatilization during use can be further suppressed. When the molecular weight is 1000 or less, the oxygen absorption capacity is further improved.

  As the compounds represented by the general formulas (4-34) to (4-37), those having a high boiling point and a low vapor pressure at the temperature during use are preferable because loss due to volatilization during use can be further suppressed. Further, these compounds preferably have a low vapor pressure at the kneading temperature with the thermoplastic resin. Moreover, as these compounds, 3% weight loss temperature is so preferable that it is high. Although it does not specifically limit as 3% weight reduction | decrease temperature, 150 degreeC or more is preferable, 200 degreeC or more is more preferable, 250 degreeC or more is further more preferable, 270 degreeC or more is more preferable.

  It does not specifically limit as a manufacturing method of the compound represented by General formula (4-34)-(4-37), For example, it can manufacture by a well-known method. For example, it can be obtained by reacting a diamine compound and an acid anhydride compound.

  All of the compounds having a tetralin ring represented by the general formula (1) described above have hydrogen at the benzyl position of the tetralin ring, and when used in combination with a transition metal catalyst described later, the hydrogen at the benzyl position is pulled. By pulling out, it exhibits excellent oxygen absorption ability.

  In addition, the oxygen-absorbing composition of the present embodiment is one in which the generation of low molecular weight compounds after oxygen absorption is remarkably suppressed. Although the reason is not clear, for example, the following oxidation reaction mechanism is assumed. That is, in the compound having a tetralin ring represented by the general formula (1), hydrogen at the benzyl position of the tetralin ring is first extracted to generate a radical, and then the benzyl position is obtained by the reaction between the radical and oxygen. It is considered that the carbon of this is oxidized to form a hydroxy group or a ketone group. Therefore, as the oxygen-absorbing composition, the molecular chain of the oxygen-absorbing main agent is not broken by the oxidation reaction as in the prior art, and the structure of the oxygen-absorbing main agent (compound) is maintained. It is presumed that the production of low molecular weight compounds is remarkably suppressed.

The molecular weight of the compound having a tetralin ring represented by the general formula (1) described above can be appropriately adjusted according to desired properties and substituents R _{1 to} R ₈ to be introduced, and is not particularly limited. From the viewpoint of suppressing loss due to volatilization during use and increasing the amount of oxygen absorbed per unit mass of the compound, the molecular weight is preferably in the range of 190 to 1500, more preferably 210 to 1200, and even more preferably 250 to 1000. In addition, the compound which has a tetralin ring represented by General formula (1) mentioned above can be used individually by 1 type or in combination of 2 or more types.

  Among the compounds having a tetralin ring represented by the general formula (1), those having a high boiling point, that is, a low vapor pressure at the temperature during use, are preferably used from the viewpoint of suppressing loss due to volatilization during use. . For example, as the compound, a compound having a lower vapor pressure at a kneading temperature with a thermoplastic resin is preferable because loss due to volatilization during production of the oxygen-absorbing composition can be suppressed. As an index of loss due to volatilization, for example, a 3% weight loss temperature can be adopted. That is, the compound preferably has a 3% weight loss temperature of 100 ° C or higher, more preferably 150 ° C or higher, and further preferably 200 ° C or higher. The upper limit value of the 3% weight reduction temperature is not particularly limited.

  The ratio of the compound having the tetralin ring represented by the general formula (1) to the total amount of the compound having the tetralin ring represented by the general formula (1) and the thermoplastic resin described later in the oxygen-absorbing composition is: 1 to 30% by mass, more preferably 1.5 to 25% by mass, and still more preferably 2 to 20% by mass. By making the ratio of the compound having a tetralin ring represented by the general formula (1) equal to or higher than the above lower limit value, the oxygen absorption performance can be further increased, and by setting the ratio below the upper limit value, the moldability is further improved. Can be increased.

<Transition metal catalyst>
The transition metal catalyst used in the oxygen-absorbing composition of the present embodiment is appropriately selected from known ones as long as it can function as a catalyst for the oxidation reaction of the compound having a tetralin ring. There is no particular limitation.

  Specific examples of the transition metal catalyst include, for example, organic acid salts, halides, phosphates, phosphites, hypophosphites, nitrates, sulfates, oxides and hydroxides of transition metals. Here, 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, manganese, iron, cobalt, nickel, and copper are preferable. 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, toluic acid, oleic acid, Although capric acid and naphthenic acid are mentioned, it is not limited to these. The transition metal catalyst is preferably a combination of these transition metals and an organic acid, the transition metal is manganese, iron, cobalt, nickel or copper, and the organic acid is acetic acid, stearic acid, 2-ethylhexanoic acid, olein. A combination that is an acid or naphthenic acid is more preferred. In addition, a transition metal catalyst can be used individually by 1 type or in combination of 2 or more types.

  The blending amount of the transition metal catalyst can be appropriately set according to the type of the compound having the tetralin ring used, the thermoplastic resin, the transition metal catalyst, and the desired performance, and is not particularly limited. From the viewpoint of the amount of oxygen absorbed by the oxygen-absorbing composition, the blending amount of the transition metal catalyst is based on 100 parts by mass of the total amount of the compound having a tetralin ring represented by the general formula (1) and the thermoplastic resin. The amount of transition metal is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 2 parts by mass, and still more preferably 0.01 to 1 part by mass.

  The compound, the transition metal catalyst and the thermoplastic resin can be mixed by a known method, but can be used as an oxygen-absorbing composition having a good dispersion state, preferably by kneading with an extruder. Further, for example, the mixture of the compound and the transition metal catalyst is processed into a powder, granule, pellet or other small piece by applying a known granulation method or molding method, and a thermoplastic resin. It can also mix | blend with and can also be set as the layer A.

  Here, the oxygen-absorbing composition used in the present embodiment may further contain a carrier substance as necessary. At this time, the oxygen-absorbing composition containing the carrier material can be used as an oxygen absorbent as it is as a mixture of the compound, the thermoplastic resin, the transition metal catalyst, and the carrier material. In addition, a carrier having the tetralin ring represented by the general formula (1) described above supported on or impregnated on a carrier material by supporting or impregnating the compound with a transition metal catalyst on a carrier material as necessary. (Hereinafter also referred to as “oxygen absorbent carrier”), and this carrier can also be used as an oxygen absorbent. Thus, by carrying or impregnating the above-mentioned compound on a carrier substance, the contact area with oxygen can be increased, the oxygen absorption rate or oxygen absorption amount can be increased, and handling can be simplified.

  The carrier material can be appropriately selected from those known in the art. Specific examples thereof include, for example, synthetic calcium silicate, slaked lime, activated carbon, zeolite, pearlite, diatomaceous earth, activated clay, silica, kaolin, talc, bentonite, activated alumina, gypsum, silica alumina, calcium silicate, magnesium oxide, graphite. , Powders of carbon black, aluminum hydroxide, iron oxide and the like are mentioned, but not limited thereto. Among these, synthetic calcium silicate, diatomaceous earth, silica, and activated carbon are preferably used. In addition, a carrier substance can be used individually by 1 type or in combination of 2 or more types.

  The amount of the carrier substance can be set as appropriate according to the type of the compound used, the thermoplastic resin or the transition metal catalyst and the desired performance, and is not particularly limited, but has a tetralin ring represented by the general formula (1). It is preferable that it is 10-1000 mass parts with respect to 100 mass parts of compounds, More preferably, it is 20-800 mass parts.

  The loading of the compound on the carrier material can be carried out according to a conventional method and is not particularly limited. For example, a mixed solution containing a compound having a tetralin ring represented by the above general formula (1) or a mixed solution containing this compound and a transition metal catalyst is prepared, and this mixed solution is applied to a support material. Alternatively, it is possible to obtain an oxygen absorbent carrier in which the above-mentioned compound (and a transition metal catalyst if necessary) is carried (impregnated) on the carrier material by immersing the carrier material in this mixed solution. In addition, a solvent can be further contained during the preparation of the mixed solution. When the compound or the transition metal catalyst is a solid, it can be efficiently supported on a support material by using a solvent. The solvent used here can be appropriately selected from known ones in consideration of the solubility of the compound and transition metal catalyst, and is not particularly limited. For example, methanol, 2-propanol, ethylene glycol , Toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, diisopropyl ether, tetrahydrofuran, methyl ethyl ketone, dichloromethane, chloroform, and other organic solvents are preferred, and methanol, 2-propanol, ethyl acetate, and methyl ethyl ketone are more preferred. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

<Thermoplastic resin>
The oxygen-absorbing composition of the present embodiment contains a thermoplastic resin. At this time, the content of the compound and the transition metal catalyst in the oxygen-absorbing composition is not particularly limited. For example, the compound and the transition metal catalyst may be contained in the thermoplastic resin as they are, or the compound and the transition metal catalyst may be contained in the thermoplastic resin in a state of being supported on the above-described carrier material.

  The method for preparing the oxygen-absorbing composition can be performed according to a conventional method and is not particularly limited. For example, an oxygen-absorbing composition can be obtained by mixing or kneading the compound, the transition metal catalyst, and a carrier material blended as necessary in a thermoplastic resin.

  As the above thermoplastic resin, known ones can be used as appropriate, and are not particularly limited. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, Polyolefin such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or a random or block copolymer of α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene ; Acid-modified polyolefin such as maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene; ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene- (meth) acrylic acid copolymer Polymers and their ion cross-linked products (ionomers) , Ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymer; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer; polymethyl acrylate, polymethacryl Polyvinyl compounds such as methyl acid; polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, polymetaxylylene adipamide (MXD6); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate ( PTT), polyethylene naphthalate (PEN), glycol-modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS), polylactic acid, polyglycolic acid, Polycarbonates; Li caprolactone, polyesters such as polyhydroxyalkanoates polyethers such as polyethylene oxide or mixtures thereof. In addition, a thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  Among these, the thermoplastic resin is preferably at least one selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, plant-derived resin, and chlorine-based resin. Hereinafter, these preferable thermoplastic resins will be described in detail.

<Polyolefin>
Examples of the polyolefin used in the oxygen-absorbing composition of the present embodiment include, for example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylene, and polybutene- 1, olefin homopolymers such as poly-4-methylpentene-1; ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, ethylene-cycloolefin copolymer Copolymers of ethylene and α-olefins such as ethylene; ethylene-α, β-unsaturated carboxylic acid copolymers such as ethylene- (meth) acrylic acid copolymers, ethylene-ethyl (meth) acrylate copolymer Ethylene-α, β-unsaturated carboxylic acid ester copolymer, ethylene, etc. -Other ethylene copolymers such as ionic cross-linked products of α, β-unsaturated carboxylic acid copolymers, ethylene-vinyl acetate copolymers; ring-opening polymers of cyclic olefins and hydrogenated products thereof; cyclic olefins- And ethylene copolymers; and graft-modified polyolefins obtained by graft-modifying these polyolefins with acid anhydrides such as maleic anhydride.

<Polyester>
Examples of the polyester used in the oxygen-absorbing composition of the present embodiment include a polyhydric alcohol containing one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof and glycols. The thing consisting of 1 type or 2 or more types chosen, what consists of hydroxycarboxylic acid and these ester-forming derivatives, what consists of cyclic ester, etc. are mentioned. The ethylene terephthalate-based thermoplastic polyester is composed of an ethylene terephthalate unit in the majority of 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. Those in the range of ° C. are preferred. Polyethylene terephthalate is particularly excellent as an ethylene terephthalate-based thermoplastic polyester in terms of pressure resistance, heat resistance, heat resistance and pressure resistance. Copolyesters containing a small amount of ester units can also be used.

  Specific examples of the dicarboxylic acid 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-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid Saturated aliphatic dicarboxylic acids exemplified in the above, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified in fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid Terephthalic acid, 1 Naphthalenedicarboxylic acids such as 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid Aromatics exemplified by acids, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, anthracene dicarboxylic acid and the like Dicarboxylic acids or their ester-forming derivatives, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid Metals exemplified by acids Honeto group-containing aromatic dicarboxylic acid or lower alkyl ester derivatives thereof, and the like.

  Among the above dicarboxylic acids, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acids are particularly preferable from the viewpoint of physical properties of the resulting polyester. In addition, you may copolymerize another dicarboxylic acid as needed.

  Specific examples of polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyl. Examples thereof include tetracarboxylic acid and ester-forming derivatives thereof.

  Specific examples of glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 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-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol Aliphatic glycols exemplified by polytrimethylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis ( β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A , Bisphenol C, 2,5-naphthalenediol, and aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols.

  Among the above glycols, it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main component.

  Specific examples of polyhydric alcohols other than these glycols include trimethylol methane, trimethylol ethane, trimethylol propane, pentaerythritol, glycerol, hexanetriol, and the like.

  Specific examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. Or ester-forming derivatives thereof.

  Specific examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide and the like.

  Specific examples of ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides and the like.

  Among those described above, a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol is preferable.

  The polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing terephthalic acid or an ester-forming derivative thereof in total of 70 mol% or more based on the total acid components, More preferred is a polyester containing 80 mol% or more, and even more preferred is a polyester containing 90 mol% or more. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acids or an ester-forming derivative thereof, more preferably It is a polyester containing 80 mol% or more, more preferably a polyester containing 90 mol% or more.

  Among the above-mentioned naphthalenedicarboxylic acids or ester-forming derivatives thereof, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid exemplified in dicarboxylic acids 2,7-naphthalenedicarboxylic acid or their ester-forming derivatives are preferred.

  Further, the polyester in which the main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, and more preferably polyester containing 80 mol% or more. More preferably, it is a polyester containing 90 mol% or more. In addition, the alkylene glycol here may contain a substituent or an alicyclic structure in the molecular chain.

  The copolymer components other than the terephthalic acid / ethylene glycol are isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, from the viewpoint of achieving both transparency and moldability. It is preferably at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propanediol. Isophthalic acid, diethylene glycol, neopentyl glycol and 1 More preferred is at least one selected from the group consisting of 1,4-cyclohexanedimethanol.

  A preferred example of the polyester used in the oxygen-absorbing composition of the present embodiment is a polyester whose main repeating unit is composed of ethylene terephthalate. More preferred is a linear polyester containing 70 mol% or more of ethylene terephthalate units, still more preferred is a linear polyester containing 80 mol% or more of ethylene terephthalate units, and particularly preferred is a line containing 90 mol% or more of ethylene terephthalate units. Polyester.

  Another preferred example of the polyester used in the oxygen-absorbing composition of the present embodiment is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate. More preferably, it is a linear polyester containing 70 mol% or more of ethylene-2,6-naphthalate units, more preferably a linear polyester containing 80 mol% or more of ethylene-2,6-naphthalate units, and particularly preferred is , A linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units.

  Other preferable examples of the polyester used in the oxygen-absorbing composition of the present 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, A linear polyester containing 70 mol% or more of 1,4-cyclohexanedimethylene terephthalate units, a linear polyester containing 70 mol% or more of butylene naphthalate units, or a linear polyester containing 70 mol% or more of butylene terephthalate units.

  From the viewpoint of coexistence of transparency and moldability, particularly suitable polyesters include a combination of terephthalic acid / isophthalic acid / ethylene glycol, terephthalic acid / ethylene glycol / 1,4-cyclohexanedimethanol as a combination of the whole polyester. Combination, terephthalic acid / ethylene glycol / neopentyl glycol combination. Needless to say, the above polyester may contain a small amount (5 mol% or less) of diethylene glycol produced by dimerization of ethylene glycol during esterification (transesterification) reaction or polycondensation reaction. Nor.

  Other preferable examples of the polyester used in the oxygen-absorbing composition of the present embodiment include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide. The polyglycolic acid may be one in which other components such as lactide are copolymerized.

<Polyamide>
As the polyamide used in the oxygen-absorbing composition of the present embodiment, for example, a polyamide having a unit derived from lactam or aminocarboxylic acid as a main constituent unit, or derived from an aliphatic diamine and an aliphatic dicarboxylic acid. Units derived from aliphatic polyamides whose units are main constituent units, partially aromatic polyamides whose main constituent units are units derived from aliphatic diamines and aromatic dicarboxylic acids, and aromatic diamines and aliphatic dicarboxylic acids And partially aromatic polyamides having a main structural unit. In addition, the polyamide here may be copolymerized with monomer units other than the main structural unit, if necessary.

  Specific examples of the lactam or aminocarboxylic acid include lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, and aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid. Can be mentioned.

  Specific examples of the aliphatic diamine include an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof, an alicyclic diamine, and the like. The aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine. Specific examples of such linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples thereof include aliphatic diamines such as nonamethylene diamine, decamethylene diamine, undecamethylene diamine and dodecamethylene diamine. Specific examples of the alicyclic diamine include cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like.

  Specific examples of the aliphatic dicarboxylic acid include linear aliphatic dicarboxylic acid and alicyclic dicarboxylic acid. In particular, a linear aliphatic dicarboxylic acid having an alkylene group having 4 to 12 carbon atoms is preferable. As the linear aliphatic dicarboxylic acid, adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid, dimer acid and their functions And the like. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like.

  Specific examples of aromatic diamines include metaxylylenediamine, paraxylylenediamine, para-bis (2-aminoethyl) benzene, and the like.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and functional derivatives thereof. Is mentioned.

  Specific 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, polymetaxylylene azide. Pamide (Polyamide MXD6), Isophthalic acid copolymer polymetaxylylene adipamide (Polyamide MXD6I), Polymetaxylylene sebamide (Polyamide MXD10), Polymetaxylylene decanamide (Polyamide MXD12), Poly 1,3-bis Examples include aminocyclohexane adipamide (polyamide BAC6) and polyparaxylylene sebacamide (polyamide PXD10). More preferable polyamides include polyamide 6, polyamide MXD6, and polyamide MXD6I.

  The copolymer component that may be copolymerized with the polyamide includes a polyether having at least one terminal amino group or a terminal carboxyl group and a number average molecular weight of 2000 to 20000, or a polymer having the terminal amino group. An organic carboxylate of ether or an amino salt of a polyether having a terminal carboxyl group can also be used. Specific examples thereof include bis (aminopropyl) poly (ethylene oxide) (polyethylene glycol having a number average molecular weight of 2000 to 20000).

  The partially aromatic polyamide may contain a structural unit derived from a polybasic carboxylic acid having 3 or more bases such as trimellitic acid and pyromellitic acid within a substantially linear range.

<Ethylene-vinyl alcohol copolymer>
As the ethylene vinyl alcohol copolymer used in the oxygen-absorbing composition of the present embodiment, those having an ethylene content of 15 to 60 mol% and a saponification degree of the vinyl acetate component of 90 mol% or more are suitable. It is. The ethylene content is preferably 20 to 55 mol%, more preferably 29 to 44 mol%. The saponification degree of the vinyl acetate component is preferably 95 mol% or more. The ethylene vinyl alcohol copolymer is composed of α-olefin such as propylene, isobutene, α-octene, α-dodecene, α-octadecene, unsaturated carboxylic acid or salt thereof, partial alkyl ester, complete alkyl ester, nitrile, amide. Further, a small amount of a comonomer such as anhydride, unsaturated sulfonic acid or a salt thereof may be further contained.

<Plant-derived resin>
The plant-derived resin used in the oxygen-absorbing composition of the present embodiment is not particularly limited as long as it is a resin containing a plant-derived substance as a raw material. Specific examples of plant-derived resins include aliphatic polyester-based biodegradable resins. Examples of the aliphatic polyester biodegradable resin include poly (α-hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLA); polybutylene succinate (PBS), polyethylene succinate (PES). And polyalkylene alkanoates.

<Chlorine-based resin>
As the chlorine-based resin used in the oxygen-absorbing composition of the present embodiment, a resin containing chlorine in the structural unit may be used, and a known resin can be used. Specific examples of the chlorine-based resin include polyvinyl chloride, polyvinylidene chloride, and copolymers of these with vinyl acetate, maleic acid derivatives, higher alkyl vinyl ethers, and the like.

  Among the thermoplastic resins exemplified above, linear low density polyethylene (LLDPE), ethylene-vinyl alcohol copolymer (EVOH), nylon 6 (PA6), polyethylene terephthalate (PET), polyvinyl chloride (PVC), It is preferably used as a food packaging material.

  Note that the oxygen-absorbing composition of the present embodiment may further contain a radical generator and a photoinitiator as necessary in order to promote the oxygen absorption reaction. Specific examples of the radical generator 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-hydroxyhexahydrophthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide , N, N-dihydroxypyromellitic acid diimide and the like, but are not particularly limited thereto. Specific examples of the photoinitiator include, but are not limited to, benzophenone and its derivatives, thiazine dyes, metal porphyrin derivatives, anthraquinone derivatives, and the like. In addition, these radical generators and photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  Moreover, said oxygen absorptive composition may contain various well-known additives in this industry in the range which does not impair the effect of this embodiment. Examples of such optional components include fillers such as calcium carbonate, clay, mica and silica, drying agents, pigments, dyes, antioxidants, slip agents, antistatic agents, stabilizers, plasticizers, deodorants and the like. Although it is mentioned, it is not specifically limited to these.

[Resin layer containing polyester (layer B)]
In the oxygen-absorbing medical multilayer container of the present embodiment, the resin layer (layer B) is a layer containing polyester.

  Specific examples of the polyester used in the layer B of the oxygen-absorbing multilayer body of the present embodiment include one or two or more selected from polycarboxylic acids including dicarboxylic acids and ester-forming derivatives thereof, and polymers including glycols. What consists of 1 type, or 2 or more types chosen from a monohydric alcohol; What consists of hydroxycarboxylic acid and these ester-forming derivatives; What consists of cyclic ester etc. are mentioned.

  Specific examples of the dicarboxylic acid 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-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid Saturated aliphatic dicarboxylic acids exemplified in the above, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified in fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid Terephthalic acid, 1 Naphthalenedicarboxylic acids such as 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid Aromatics exemplified by acids, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, anthracene dicarboxylic acid and the like Dicarboxylic acids or their ester-forming derivatives, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid Metals exemplified by acids Honeto group-containing aromatic dicarboxylic acid or lower alkyl ester derivatives thereof, and the like.

  Among the above dicarboxylic acids, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids, and ester-forming derivatives thereof are particularly preferable from the viewpoint of physical properties of the resulting polyester. Specifically, as polyester, terephthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7 -It is more preferable to have a unit derived from one or more dicarboxylic acids selected from the group consisting of naphthalenedicarboxylic acid and these ester-forming derivatives. In addition, you may copolymerize another dicarboxylic acid as needed. The total amount of the above repeating units is preferably 70 mol%, more preferably 90 mol% or more of the dicarboxylic acid unit of the polyester.

  Specific examples of polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyl. Examples thereof include tetracarboxylic acid and ester-forming derivatives thereof.

  Specific examples of glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 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-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol Aliphatic glycols exemplified by polytrimethylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis ( β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A , Bisphenol C, 2,5-naphthalenediol, and aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols.

  Among the above glycols, it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main component.

  Specific examples of polyhydric alcohols other than these glycols include trimethylol methane, trimethylol ethane, trimethylol propane, pentaerythritol, glycerol, hexanetriol, and the like.

  Specific examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. Or ester-forming derivatives thereof.

  Specific examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide and the like.

  Specific examples of the above ester-forming derivatives include these alkyl esters, acid chlorides, acid anhydrides and the like.

  Among those described above, a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol is preferable.

  Of the dicarboxylic acid units of the polyester, preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more are units derived from terephthalic acid. Such a polyester is preferably a linear polyester.

  Of the dicarboxylic acid units of the polyester, preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more are units derived from 2,6-naphthalenedicarboxylic acid. Such a polyester is preferably a linear polyester.

  Further, the polyester in which the main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, and more preferably polyester containing 80 mol% or more. More preferably, it is a polyester containing 90 mol% or more. In addition, the alkylene glycol said here may contain the substituent and the alicyclic structure in the molecular chain.

  Other preferred examples of the polyester used for layer B of the oxygen-absorbing multilayer body of the present embodiment include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide. It is done. The polyglycolic acid may be one in which other components such as lactide are copolymerized.

  Furthermore, the resin layer (layer B) containing polyester may further contain a thermoplastic resin other than polyester. As another thermoplastic resin, for example, a thermoplastic resin other than polyester used in the layer A described above can be used. The other thermoplastic resin is preferably at least one selected from the group consisting of polyolefin, polyamide, ethylene-vinyl alcohol copolymer, plant-derived resin, and chlorine-based resin. In addition, the thermoplastic resin used in the layer B of the present embodiment preferably contains 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount of the layer B. is there.

  The layers B of the oxygen-absorbing medical multilayer container of the present embodiment may be the same as or different from each other. Further, in the oxygen-absorbing medical multilayer container of the present embodiment, the thickness of the layer B can be appropriately determined according to the application and desired performance, and is not particularly limited, but is a drop required for the medical multilayer container. From the viewpoint of securing various physical properties such as strength such as resistance and flexibility, the thickness is preferably 50 to 10,000 μm, more preferably 100 to 7000 μm, and still more preferably 300 to 5000 μm.

  Moreover, the layer B of the oxygen-absorbing medical multilayer container of the present embodiment may contain various additives known in the art in addition to the polyester and the thermoplastic resin. Examples of such optional components include desiccants, coloring pigments such as titanium oxide, dyes, antioxidants, slip agents, antistatic agents, plasticizers, stabilizers, additives such as lubricants, calcium carbonate, clay, mica, Examples thereof include fillers such as silica, deodorants and the like, but are not particularly limited thereto. In particular, it is preferable to add an antioxidant to the layer B from the viewpoint of recycling and reworking offcuts generated during production.

[Other layers]
The oxygen-absorbing medical multilayer body of the present embodiment further includes an optional layer in addition to the above-described oxygen-absorbing layer (layer A) and polyester-containing resin layer (layer B) depending on the desired performance and the like. May be included. Examples of such an arbitrary layer include an adhesive layer, a metal vapor deposition layer, and an organic-inorganic film.

  For example, from the viewpoint of further increasing the interlayer adhesive strength between two adjacent layers, it is preferable to provide an adhesive layer (layer AD) between the two layers. The adhesive layer preferably contains a thermoplastic resin having adhesiveness. As the thermoplastic resin having adhesiveness, for example, an acid modification in which a polyolefin resin such as polyethylene or polypropylene is modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Polyolefin resin; polyester-based thermoplastic elastomer mainly composed of a polyester-based block copolymer. Further, from the viewpoint of enhancing the adhesiveness with the above-described polyester-containing resin layer (layer B), it is preferable to modify the same type of resin as the thermoplastic resin used in the layer B. The thickness of the adhesive layer is not particularly limited, but is preferably 2 to 100 μm, more preferably 5 to 90 μm, and still more preferably from the viewpoint of ensuring molding processability while exhibiting practical adhesive strength. Is 10-80 μm.

  Further, from the viewpoint of further improving the gas barrier property, it is preferable to provide a metal vapor deposition layer or an organic-inorganic film on one surface of the layer B described above. Although it does not specifically limit as a metal vapor deposition layer, In order to ensure the content visibility, transparent vapor deposition films, such as a silica and an alumina, are preferable. Examples of the method for forming a vapor deposition film include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition methods such as PECVD, but are not particularly limited and are publicly known. This method is applicable. Moreover, 5-500 nm is preferable from a gas barrier viewpoint, and, as for the thickness of a vapor deposition film, More preferably, it is 5-200 nm. On the other hand, the organic-inorganic film layer is not particularly limited, but a silica-polyvinyl alcohol hybrid film prepared from a sol-gel method or the like is preferable. The thickness of the coating film is preferably 100 nm to 50 μm, more preferably 1 to 15 μm, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like.

[Manufacturing method]

  The manufacturing method of the oxygen-absorbing medical multilayer container of the present embodiment can be applied with known methods depending on the properties of various materials, the target shape, and the like, and is not particularly limited. Various injection molding methods can be applied to produce an oxygen-absorbing medical multilayer container.

  Multi-layer injection molding methods and bodies can be manufactured. Further, first, the material constituting the layer B is injected, then the material constituting the layer A is injected alone, and finally the necessary amount of the material constituting the layer B is injected to fill the cavity. A multilayer injection molded article having the structure B / A / B / A / B can be produced. Still further, first, the material constituting the layer B1 is injected from the injection cylinder, then the material constituting the layer B2 is injected from another injection cylinder simultaneously with the resin constituting the layer B1, and then the layer A is constituted. By injecting the resin simultaneously with the resins constituting the layers B1 and B2, and then injecting a necessary amount of the resin constituting the layer B1 to fill the cavity, the five-layer structure B1 / B2 / A / B2 / B1 A multilayer injection molded article can be produced.

  The thickness of the oxygen-absorbing medical multilayer container of the present embodiment is not particularly limited, but is preferably 500 to 5000 μm from the viewpoint of enhancing oxygen absorption performance and ensuring various physical properties required for the medical container. Preferably it is 700-4000 micrometers, More preferably, it is 800-3000 micrometers.

  By using the oxygen-absorbing medical multilayer container of the present embodiment as a part of the components of the sealing container, the oxygen in the container is absorbed and little oxygen permeates or penetrates the container wall from the outside of the container. However, in some cases, this permeating or penetrating oxygen can also be absorbed to prevent alteration of the stored content item (stored object) due to oxygen. At this time, the injection molded body of this embodiment may itself be molded into a container shape. Moreover, it can also shape | mold into a desired container shape by giving secondary processing to the obtained injection molded object. As the secondary processing, blow molding or the like can be applied. Considering that the oxygen-absorbing medical multilayer container of the present embodiment exhibits oxygen absorption performance, it is preferably a storage container such as an ampoule, a vial, or a prefilled syringe.

  As a method other than the injection molding method, for example, a multilayer molded body can be obtained by a compression molding method. For example, an oxygen-absorbing composition is provided in a thermoplastic resin melt, and the molten mass is made into a male mold. While supplying, it compresses with a female type | mold, and a multilayer molded object can be obtained by cooling and solidifying a compression molding.

  Further, as a method other than the injection molding method and the compression molding method, a multilayer molded body can be obtained by an extrusion blow molding method. For example, a cylindrical parison using an extrusion blow device comprising a plurality of extruders and a cylindrical die. The parison is extruded into a tube shape, the parison is sandwiched between molds, the parison lower part is pinched off and fused, and blown by high-pressure air or the like before being cooled, to expand the parison A multilayer molded body can be obtained.

  The usage mode of the oxygen-absorbing medical multilayer container of the present embodiment is not particularly limited, and can be used in various applications and forms. Preferred examples of usage include, but are not particularly limited to, vials, ampoules, prefilled syringes, vacuum blood collection tubes, and the like. Hereinafter, preferred usage modes will be described in detail.

[Vial]
The oxygen-absorbing medical multilayer molded container of this embodiment can be used as a vial. In general, a vial is composed of a bottle, a rubber stopper, and a cap. After filling the bottle with a chemical solution, the vial is sealed with a rubber stopper, and the cap is tightened from above to seal the inside of the bottle. The oxygen-absorbing medical multilayer molded container of this embodiment can be used for the bottle portion of this vial.

  As a method for molding the oxygen-absorbing medical multilayer molded container of the present embodiment into the bottle portion of the vial, for example, injection blow molding, extrusion blow molding and the like are suitable. As a specific example, an injection blow molding method is shown below. For example, using a molding machine equipped with two or more injection machines and an injection mold, the material constituting layer A and the material constituting layer B are passed through the mold hot runners from the respective injection cylinders, and the injection mold. By injecting into the cavity of the mold, a multilayer injection molded body having a three-layer structure B / A / B having a shape corresponding to the cavity shape of the injection mold can be manufactured. First, the material constituting the layer B is injected from the injection cylinder, then the material constituting the layer A is injected from another injection cylinder simultaneously with the resin constituting the layer B, and then the resin constituting the layer B By injecting a necessary amount of the solution to fill the cavity, a multilayer injection molded body having a three-layer structure B / A / B can be manufactured. Furthermore, by first injecting the material constituting the layer B, then injecting the material constituting the layer A alone, and finally injecting the necessary amount of the material constituting the layer B to fill the mold cavity, A multilayer injection molded article having a five-layer structure B / A / B / A / B can be produced. Still further, first, the material constituting the layer B1 is injected from the injection cylinder, then the material constituting the layer B2 is injected from another injection cylinder simultaneously with the resin constituting the layer B1, and then the layer A is constituted. By injecting the resin simultaneously with the resins constituting the layers B1 and B2, and then injecting a necessary amount of the resin constituting the layer B1 to fill the cavity, the five-layer structure B1 / B2 / A / B2 / B1 A multilayer injection molded article can be produced. In this injection blow molding, the multilayer injection molded body obtained by the above method is fitted in a final shape mold (blow mold) while being heated to some extent, and air is blown and inflated into the mold. It can be formed into a bottle shape by closely contacting and solidifying by cooling.

〔ampoule〕
Moreover, the oxygen-absorbing medical multilayer molded container of the present embodiment can be used as an ampoule. In general, an ampoule is composed of a small container having a narrow neck, and the container is hermetically sealed by filling the container with a chemical solution and then sealing the tip of the neck. The oxygen-absorbing medical multilayer molded container of this embodiment can be used for this ampoule (small container). As a method of forming the oxygen-absorbing medical multilayer molded container of this embodiment into an ampoule, for example, injection blow molding, extrusion blow molding and the like are suitable.

[Prefilled syringe]
Furthermore, the oxygen-absorbing medical multilayer molded container of the present embodiment can be used as a barrel of a prefilled syringe. The shape of a general prefilled syringe barrel is a male luer taper nozzle to which an injection needle can be connected, a shoulder portion is formed from the nozzle base end to the cylindrical portion, and a flange is formed at the base end of the cylindrical portion. . When the medicine is accommodated, the nozzle is sealed with a cap, and a gasket connected with a plunger is inserted into the cylindrical portion. The oxygen-absorbing medical multilayer molded container of this embodiment can be used for this barrel.

  As a method of molding the oxygen-absorbing medical multilayer molded container of the present embodiment into the barrel of a prefilled syringe, for example, an injection molding method is suitable. Specifically, a certain amount of resin constituting the layer B is injected into the cavity from a gate provided at the nozzle tip of the barrel barrel, and then a certain amount of the resin constituting the layer A is injected. The resin constituting the layer B injected earlier is cooled by the cavity and the wall surface of the core mold to form a skin layer, and the resin constituting the layer A becomes the core layer and is formed between the skin layers. Thereafter, by injecting a certain amount of the resin constituting the layer B again, a barrel can be manufactured as a multilayer injection molded article. Here, the injection amount of the resin constituting the layer B to be injected first is preferably adjusted so that the layer A is formed closer to the base end of the cylindrical portion than the planned insertion position of the gasket to be inserted into the barrel. . By forming the oxygen absorbing layer (layer A) up to the position where the gasket is to be inserted, the barrier property of the barrel is further ensured. Further, it is preferable that the injection amount of the resin constituting the layer A is adjusted so as to be formed closer to the nozzle tip than the cap sealing planned position. By forming the oxygen absorbing layer (layer A) up to the cap sealing planned position, the barrier property of the barrel is further ensured.

  The thickness of the container of the barrel of the prefilled syringe can be appropriately set according to the purpose of use and size, and is not particularly limited. In general, from the viewpoint of long-term storage stability of a chemical solution, moldability, and operability of a syringe, about 0.5 to 20 mm is preferable, and about 0.5 to 5 mm is more preferable. Moreover, even if thickness is uniform, what changed thickness may be sufficient. Further, another gas barrier film or a light shielding film may be further formed on the barrel surface for the purpose of long-term storage stability. These arbitrary films and methods for forming them are described in, for example, Japanese Patent Application Laid-Open No. 2004-323058.

[Vacuum blood collection tube]
In addition, the oxygen-absorbing medical multilayer container of the present embodiment can be used as a vacuum blood collection tube. In general, the vacuum blood collection tube is composed of a tubular body and a stopper. The oxygen-absorbing medical multilayer container of this embodiment can be used for this tubular body.

  As a method for forming the oxygen-absorbing medical multilayer container of the present embodiment into a tubular body of a vacuum blood collection tube, for example, an injection molding method is suitable. Specifically, first, a certain amount of resin constituting the layer B is injected into the cavity of the injection mold, then a certain amount of resin constituting the layer A is injected, and a certain amount of resin constituting the layer B is again injected. By injecting, a tubular body can be produced as a multilayer injection molded body.

[Contained items]
The material to be stored (filled material) filled in the oxygen-absorbing medical multilayer molded container of the present embodiment is not particularly limited. For example, vitamins such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin D, vitamin E and vitamin K, alkaloids such as atropine, hormones such as adrenaline and insulin, sugars such as glucose and maltose, ceftriaxone Any natural product or compound such as antibiotics such as cephalosporin and cyclosporine, and benzodiazepines such as oxazolam, flunitrazepam, clothiazepam and clobazam can be filled. When filled with these natural products and compounds, the oxygen-absorbing medical multilayer molded container of the present embodiment has a small amount of adsorption of these natural products and compounds, and can suppress alteration due to oxidation.

  The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, NMR measurements were performed at room temperature.

Synthesis Example 1 Diester Compound A Having a Tetralin Ring
In a reactor equipped with a thermometer, a partial condenser, a total condenser, and a stirrer, 248 g (1.0 mol) of dimethyl 1,2,3,4-tetrahydronaphthalene-2,6-dicarboxylate, 409 g of n-hexyl alcohol (4.0 mol) and 0.34 g of tetrabutyl titanate were charged, the temperature was raised to 150 ° C. under a nitrogen atmosphere, and the reaction was carried out while removing the produced methanol out of the system. After the formation of methanol stopped, the mixture was cooled to room temperature, and unreacted n-hexyl alcohol was removed under reduced pressure to obtain diester compound A. Using a differential heat / thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, trade name “DTG-60”), the 3% weight reduction temperature of the obtained compound was measured. Table 1 shows the structural formula, molecular weight, and 3% weight loss temperature of the obtained compound. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.73-7.79 (2H m), 7.16 (1H d), 4.29 (2H t), 4.10 (2H t), 3.01-3 .08 (2H m), 2.82-2.97 (2H m), 2.70-2.78 (1H m), 2.18-2.24 (1H m), 1.84-1.94 (1H m), 1.71-1.79 (2H m), 1.58-1.68 (2H m), 1.25-1.48 (12H m), 0.90 (6H t).

(Synthesis example 2) Diester compound B having a tetralin ring
The same procedure as in Synthesis Example 1 was performed except that n-octyl alcohol was used instead of n-hexyl alcohol, the blending amount was 521 g (4.0 mol), and the reaction temperature was 190 ° C. Diester compound B Got. Using a differential heat / thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, trade name “DTG-60”), the 3% weight reduction temperature of the obtained compound was measured. Table 1 shows the structural formula, molecular weight, and 3% weight loss temperature of the obtained compound. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.68-7.74 (2H m), 7.10 (1H d), 4.23 (2H t), 4.04 (2H t), 2.92-3 0.00 (2H m), 2.72-2.89 (2H m), 2.63-2.70 (1H m), 2.10-2.18 (1H m), 1.76-1.85 (1H m), 1.63-1.72 (2H m), 1.50-1.59 (2H m), 1.9-1.40 (20H m), 0.90 (6H t).

Synthesis Example 3 Diester Compound C Having a Tetralin Ring
The same as Synthesis 2 except that dimethyl 1,2,3,4-tetrahydronaphthalene-1,8-dicarboxylate was used instead of dimethyl 1,2,3,4-tetrahydronaphthalene-2,6-dicarboxylate. Operation was performed to obtain a diester compound C. Using a differential heat / thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, trade name “DTG-60”), the 3% weight reduction temperature of the obtained compound was measured. Table 1 shows the structural formula, molecular weight, and 3% weight loss temperature of the obtained compound. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.78 (1H d), 7.17-7.29 (2H m), 4.50 (1H t), 4.22 (2H t), 3.98-4 .12 (2H m), 2.76-2.93 (2H m), 2.21-2.30 (1H m), 1.89-1.99 (1H m), 1.67-1.83 (4H m), 1.50-1.63 (3H m), 1.18-1.44 (19H m), 0.89 (6H t).

Synthesis Example 4 Diester Compound D Having a Tetralin Ring
The reactor used in Synthesis Example 1 was charged with 108 g (0.62 mmol) of dimethyl adipate and 300 g (1.85 mmol) of 6-hydroxymethyl-1,2,3,4-tetrahydronaphthalene, and the temperature was raised to 130 ° C. . After adding 0.58 g of titanium tetrabutoxide, the temperature was raised to 200 ° C., and the reaction was carried out while removing the produced methanol out of the system. After the production of methanol ceased, the reaction mixture was cooled to room temperature, unreacted 6-hydroxymethyl-1,2,3,4-tetrahydronaphthalene was removed under reduced pressure, and then diester compound D was obtained by recrystallization. Using a differential heat / thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, trade name “DTG-60”), the 3% weight reduction temperature of the obtained compound was measured. Table 1 shows the structural formula, molecular weight, and 3% weight loss temperature of the obtained compound. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.00 (6H m), 5.02 (4H s), 2.70-2.79 (8H m), 2.34 (4H t), 1.74-1 .83 (8H m), 1.64-1.70 (4H m).

Synthesis Example 5 Diamide Compound E Having a Tetralin Ring
A 2000 mL autoclave equipped with a thermometer and a stirrer was charged with 248 g (1.0 mol) of dimethyl 1,2,3,4-tetrahydronaphthalene-2,6-dicarboxylate and 607 g (6.0 mol) of n-hexylamine, and then nitrogen. After the replacement, the temperature was raised to 220 ° C. and stirred for 5 hours. After cooling to room temperature, filtration was performed, and diamide compound E was obtained by recrystallization. Using a differential heat / thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, trade name “DTG-60”), the 3% weight reduction temperature of the obtained compound was measured. Table 1 shows the structural formula, molecular weight, and 3% weight loss temperature of the obtained compound. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.42 (1H s), 7.37 (1H d), 7.04 (1H d), 5.99 (1H m), 5.53 (1H m), 3 .32-3.41 (2H m), 3.15-3.24 (2H m), 2.68-3.03 (4H m), 2.35-2.43 (1H m), 1.97 -2.05 (1Hm), 1.76-1.87 (1Hm), 1.17-1.58 (12Hm), 0.83 (6Ht).

Synthesis Example 6 Acid anhydride F having a tetralin ring
Into an 18 L autoclave, 1.8 g of 1,8-naphthalic anhydride and 300 g of a catalyst (dry product) in which 5 wt% palladium was supported on activated carbon and 7.5 kg of ethyl acetate were charged. At room temperature, the inside of the autoclave was replaced twice with 1 MPa of nitrogen, and then replaced twice with 1 MPa of hydrogen. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 80 ° C., the pressure was increased to 5 MPa with hydrogen, and the mixture was stirred at 500 rpm at the same temperature and the same pressure for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, released hydrogen, and replaced with 1 MPa of nitrogen twice. Then, the catalyst was filtered off, and the catalyst was washed with 1.0 kg of acetone three times. The solvent was removed from the obtained mother liquor under reduced pressure by an evaporator to obtain a crude product. The acid anhydride F was obtained by recrystallizing the obtained composition organism. Using a differential heat / thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, trade name “DTG-60”), the 3% weight reduction temperature of the obtained compound was measured. Table 1 shows the structural formula, molecular weight, and 3% weight loss temperature of the obtained compound. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.98 (1H d), 7.47 (1H d), 7.38 (1H dd), 3.93 (1H t), 2.80-3.00 (2H m), 2.55-2.64 (1H m), 2.14-2.24 (1H m), 1.77-1.94 (2H m).

Example 1
Using a twin screw extruder having two 37 mm diameter screws, 95 parts by mass of an ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., trade name “EVAL L171B”, hereinafter also abbreviated as “EVOH”). On the other hand, 5 parts by mass of the diester compound A and cobalt (II) stearate are melt-kneaded at 220 ° C. so that the amount of cobalt is 0.05 parts by mass, the strand is extruded from the extruder head, cooled, and pelletized. An oxygen-absorbing composition (1) was obtained. Next, as shown below, a vial, which is an oxygen-absorbing medical multilayer molded body, was produced using this oxygen-absorbing composition (1). Then, the performance evaluation of the obtained vial was performed as shown below. The evaluation results are shown in Table 2.

[Manufacture of vials]
Under the following conditions, polyester constituting the polyester-containing resin layer (layer B) is injected from the injection cylinder, and then the oxygen-absorbing composition (1) constituting the oxygen-absorbing layer (layer A) is injected into another injection cylinder. Injection of the polyester constituting the layer B, and then injecting a necessary amount of the polyester constituting the layer B to fill the cavity in the injection mold. Got the body. Thereafter, the obtained injection-molded product was cooled to a predetermined temperature, transferred to a blow mold, and blow-molded to produce a vial (bottle part). Here, the total mass of the vial was 24 g, and the mass of the layer A was 30% by mass of the total mass of the vial. Further, as the polyester constituting the layer B, polyethylene terephthalate resin (manufactured by Nippon Unipet Co., Ltd., trade name “RT-553C”, hereinafter also abbreviated as “PET”) was used.

(Vial shape)
The total length was 89 mm, the outer diameter was 40 mmφ, and the wall thickness was 1.8 mm. For the manufacture of the vial, an injection blow integrated molding machine (manufactured by UNILOY, model: IBS 85, 4 pieces) was used.
(Vial molding conditions)
Injection cylinder temperature for layer A: 220 ° C
Injection cylinder temperature for layer B: 280 ° C
Resin channel temperature in injection mold: 280 ° C
Blow temperature: 150 ° C
Blow mold cooling water temperature: 15 ° C

[Performance evaluation of vials]
The measurement of the oxygen permeability of the obtained vial, the appearance evaluation after molding, the drop test, and the dissolution test were measured and evaluated according to the following methods and standards.

(1) Vials oxygen permeability (OTR)
The oxygen permeability on the 30th day from the start of measurement was measured in an atmosphere of 23 ° C., 50% relative humidity outside the molded body, and 100% relative humidity inside the molded body. For the measurement, an oxygen permeability measuring device (manufactured by MOCON, trade name “OX-TRAN 2-21 ML”) was used. It shows that oxygen barrier property is so favorable that a measured value is low. The lower limit of detection of the measurement is oxygen permeability 5 × 10 ⁻⁵ mL / (0.21 atm · day · package).

(2) Appearance after molding Visibility of the contents of the vial was visually observed. Those with no problem in visibility were accepted.

(3) Drop test After the vial was stored at 40 ° C. and 90% RH for one month, it was filled with 50 mL of pure water, and then sealed with a rubber stopper and an aluminum cap. The sealed container thus obtained was dropped from a height of 2 m, and the appearance of the container at that time was examined. In the drop test, 20 containers were prepared and tested under the same conditions.

(4) Dissolution test After the vial was stored at 40 ° C. and 90% RH for 1 month, it was filled with 50 mL of pure water, and then sealed with a rubber stopper and an aluminum cap. The sealed container thus obtained was stored at 40 ° C. and 60% RH for 4 months, and then the total carbon content (hereinafter referred to as TOC) in pure water was measured.
(TOC measurement)
Device: TOC-V _CPH manufactured by Shimadzu Corporation
Combustion furnace temperature: 720 ° C
Gas and flow rate: High-purity air, TOC meter section 150 mL / min
Injection volume: 150 μL
Detection limit: 1 μg / mL

(Example 2)
A multilayer vial was prepared in the same manner as in Example 1 except that the diester compound A was replaced with the diester compound B, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 3)
A multilayer vial was prepared in the same manner as in Example 1 except that the diester compound A was replaced with the diester compound C, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

Example 4
A multilayer vial was prepared in the same manner as in Example 1 except that the diester compound A was replaced with the diester compound D, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 5)
A multilayer vial was prepared in the same manner as in Example 1 except that the diester compound A was replaced with the diamide compound E, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 6)
A multilayer vial was prepared in the same manner as in Example 1 except that the diester compound A was replaced with the acid anhydride F, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 7)
EVOH is replaced with amorphous polyamide (trade name “NOVAMID X21-F07”, hereinafter also abbreviated as “6IT”, manufactured by Mitsubishi Engineering Plastics Co., Ltd.), except that the injection cylinder temperature for layer A is 260 ° C. A multilayer vial was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 8)
A multilayer vial was prepared in the same manner as in Example 7 except that the diester compound A was replaced with the diester compound B, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

Example 9
A multilayer vial was prepared in the same manner as in Example 7 except that the diester compound A was replaced with the diester compound C, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 10)
A multilayer vial was prepared in the same manner as in Example 7 except that the diester compound A was replaced with the diester compound D, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 11)
A multilayer vial was prepared in the same manner as in Example 7 except that the diester compound A was replaced with the diamide compound E, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 12)
A multilayer vial was prepared in the same manner as in Example 7 except that the diester compound A was replaced with the acid anhydride F, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Comparative Example 1)
A multilayer vial was prepared in the same manner as in Example 1 except that the diester compound A and cobalt stearate were not used, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 2)
A multilayer vial was prepared in the same manner as in Example 7 except that the diester compound A and cobalt stearate were not used, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 3)
A mixture obtained by dry blending cobalt stearate (II) so that the amount of cobalt is 0.04 parts by mass with respect to 100 parts by mass of nylon MXD6 (trade name “S7007” manufactured by Mitsubishi Gas Chemical Co., Ltd.) By feeding a twin-screw extruder having two 37 mm diameter screws at a speed of 15 kg / h, performing melt kneading at a cylinder temperature of 280 ° C., extruding strands from the extruder head, cooling, and pelletizing An oxygen-absorbing composition (M) was obtained. A vial was produced in the same manner as in Example 1 except that this oxygen-absorbing composition (M) was used instead of the oxygen-absorbing composition (1), and the injection cylinder temperature for layer B was 260 ° C. . The performance evaluation of the obtained vial was performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

  As is clear from Table 2, the vials of Examples 1 to 12 can reduce the oxygen transmission rate relative to Comparative Examples 1 to 3, and the visibility inside the container is ensured, which is good even after long-term storage. It was confirmed that the strength was maintained and the amount of elution from the container to the contents was low. Furthermore, it was confirmed that the vials of Examples 1 to 6, 11, and 12 were excellent in transparency and the contents visibility was very good.

  Since the oxygen-absorbing medical multilayer container of the present invention has an excellent oxygen-absorbing property, it can absorb oxygen regardless of the presence or absence of moisture in the object to be stored. Since production is suppressed, it can be used particularly effectively in, for example, pharmaceuticals and health foods. Moreover, since it is not sensitive to metal detectors, foreign objects such as metals and metal pieces can be inspected from the outside with a metal detector, and can be used widely and effectively.

Claims (12)

An oxygen-absorbing medical multilayer having at least three layers of a first resin layer containing polyester, an oxygen-absorbing layer containing an oxygen-absorbing composition, and a second resin layer containing polyester in this order. A container,
The oxygen-absorbing composition includes at least one compound having a tetralin ring represented by the following general formula (1), a transition metal catalyst, and a thermoplastic resin.
(Wherein R _{1 to} R ₁₂ each independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio group, imide And at least one selected from the group consisting of a substituent represented by the following general formula (1a) and a substituent represented by the following general formula (1b), and these further have a substituent. Alternatively, two substituents out of R _{1 to} R ₁₂ may be bonded to form a ring, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring.
(In the general formula (1a) and the general formula (1b), R each independently represents a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio These are at least one selected from the group consisting of a group and an imide group, which may further have a substituent, and two substituents of R may be bonded to form a ring. W is a bond or a divalent organic group, and the divalent organic group is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. Saturated fat Group hydrocarbon group and heterocyclic group, at least selected from the group consisting of —C (═O) —, —OC (═O) —, —N (H) C (═O) —, and any combination thereof. (M represents an integer of 0 to 4, n represents an integer of 0 to 7, p represents an integer of 0 to 8, and q represents an integer of 0 to 3.)
Oxygen-absorbing medical multilayer container.   The oxygen-absorbing medical multilayer container according to claim 1, wherein the compound having a tetralin ring represented by the general formula (1) has two or more carbonyl groups. In the general formula (1), at least two of R _{1 to} R ₁₂ are monovalent substituents represented by the following general formula (2).

-C (= O) -X (2)

(Wherein X is one selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, a monoalkylamino group, and a dialkylamino group, and a plurality of Xs may be the same. And may be different.)
The oxygen-absorbing medical multilayer container according to claim 2.   The oxygen-absorbing medical multilayer container according to any one of claims 1 to 3, wherein the compound having a tetralin ring represented by the general formula (1) has two or more tetralin rings.   Of the compound having the tetralin ring represented by the general formula (1) with respect to the total amount of the compound having the tetralin ring represented by the general formula (1) and the thermoplastic resin in the oxygen-absorbing composition. The oxygen-absorbing medical multilayer container according to any one of claims 1 to 4, wherein the ratio is 1 to 30% by mass.   The oxygen-absorbing medical multilayer according to any one of claims 1 to 5, wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper. container.   In the oxygen-absorbing composition, the transition metal catalyst has a transition metal amount of 0 with respect to 100 parts by mass of the total amount of the compound having a tetralin ring represented by the general formula (1) and the thermoplastic resin. The oxygen-absorbing medical multilayer container according to any one of claims 1 to 6, which is contained in an amount of 0.001 to 10 parts by mass.   More than 70 mol% in the dicarboxylic acid unit of the polyester is terephthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. The oxygen according to any one of claims 1 to 7, which is a unit derived from one or more dicarboxylic acids selected from the group consisting of acids, 2,7-naphthalenedicarboxylic acids, and ester-forming derivatives thereof. Absorbent medical multi-layer molded container.   The oxygen-absorbing medical multilayer molded container according to any one of claims 1 to 7, wherein 70 mol% or more in the dicarboxylic acid unit of the polyester is a unit derived from terephthalic acid.   The oxygen-absorbing medical multilayer molded container according to any one of claims 1 to 7, wherein 90 mol% or more in the dicarboxylic acid unit of the polyester is a unit derived from terephthalic acid.   The oxygen-absorbing medical multilayer molded container according to any one of claims 1 to 7, wherein 70 mol% or more of the dicarboxylic acid unit of the polyester is a unit derived from 2,6-naphthalenedicarboxylic acid.   The oxygen-absorbing medical multilayer molded container according to any one of claims 1 to 7, wherein 90 mol% or more in the dicarboxylic acid unit of the polyester is a unit derived from 2,6-naphthalenedicarboxylic acid.