JP6060711B2 - Prefilled syringe - Google Patents

Description

  The present invention relates to a prefilled syringe having oxygen barrier performance and oxygen absorption function.

  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. In addition, since the package containing the iron-based oxygen absorbent requires water for the oxidation reaction of the iron powder, it can exhibit the effect of oxygen absorption only if the object to be preserved is a high-water content. could not.

  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 this multilayer material, an oxygen absorption layer made of a thermoplastic resin in which an iron-based oxygen absorbent is dispersed is provided between layers of a gas barrier multilayer film having a conventional structure in which a heat seal layer and a gas barrier layer are laminated. This is an oxygen-absorbing multilayer film, which has a function of absorbing oxygen in the container in addition to the function of preventing oxygen permeation from the outside, and is conventionally known as extrusion lamination, co-extrusion lamination, dry lamination, etc. It is manufactured using the manufacturing method. However, this also has the problem that the object to be preserved is only effective when detected by a metal detector used for detecting foreign substances such as foods. Furthermore, there is a problem that the internal visibility is insufficient due to the problem of opacity.

  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 ring is bonded and a transition metal is known (see Patent Document 6).

  On the other hand, glass ampules, vials, prefilled syringes, and the like have been conventionally 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 improved oxygen barrier properties, which has an innermost layer and an outermost layer made of a polyolefin-based resin, and an intermediate layer made of a resin composition excellent in oxygen barrier properties, has been 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 medical multi-layer container has insufficient basic performance such as oxygen barrier property, water vapor barrier property, chemical solution adsorption property, and container durability, and is therefore improved from the viewpoint of storage stability of contents such as chemical solution. Is required.

  In particular, when storing a chemical solution using a conventional gas barrier multi-layer 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. 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 in 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 in 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 problems, and its purpose is to remarkably suppress the generation of low molecular weight compounds after oxygen absorption, and to have excellent oxygen absorption performance, preferably excellent water vapor barrier performance. It is also intended to provide a novel oxygen-absorbing prefilled syringe that maintains its strength even during long-term storage, has a very low impurity elution amount, and has low chemical solution adsorption. Another object of the present invention is to provide an oxygen-absorbing prefilled syringe having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity.

  As a result of intensive studies on the oxygen-absorbing prefilled syringe, the present inventors have developed an oxygen-absorbing layer using a copolymerized polyolefin compound having a predetermined tetralin ring and a transition metal catalyst, and a resin layer using a polyester. It was found that the above-mentioned problems can be solved by laminating, and the present invention was completed.

That is, the present invention provides the following <1> to <10>.
<1> A prefilled syringe in which a medicine is previously stored in a sealed state, and the sealed state is released upon use so that the medicine can be dispensed, wherein the prefilled syringe contains at least a polyester. A multilayer structure having at least three layers in this order: a resin layer, an oxygen-absorbing layer comprising an oxygen-absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, and a second resin layer containing at least a polyester Become
The copolymer polyolefin compound is a structural unit (a) represented by the following general formula (1);

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a first monovalent substituent, wherein the first monovalent substituent is a halogen atom, an alkyl Group, alkenyl group, 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, mercapto group, alkylthio And at least one selected from the group consisting of a group, an arylthio group, a heterocyclic thio group, and an imide group, which may further have a substituent.)
At least one structural unit (a) selected from the group consisting of:
Structural units represented by the following general formulas (2) and (3);

(Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently 3 monovalent substituents, wherein the second monovalent substituent and the third monovalent substituent are each independently 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, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and It is at least one selected from the group consisting of imide groups, and these may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , R ₈ , R ₉ , R ₁₀ or R ₁₁ may be the same or different from each other, m is 0 to 3, n is 0 to 7, p is 0 to 6, and q is 0 to 4. Each represents an integer, and at least one hydrogen atom is bonded to the benzylic position of the tetralin ring, where X is — (C═O) O—, — (C═O) NH—, —O (C═O). A divalent group selected from the group consisting of-, -NH (C = O)-and-(CHR) s-, wherein s represents an integer of 0 to 12. Y is-(CHR) t-. T represents an integer of 0 to 12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.
An oxygen-absorbing prefilled syringe which is a copolymerized polyolefin compound containing a structural unit (b) having at least one tetralin ring selected from the group consisting of:
<2> The oxygen-absorbing prefilled syringe according to <1>, wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.
<3> The oxygen-absorbing prefilled syringe according to <1> or <2>, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the copolymerized polyolefin compound. .
<4> The above <1>, wherein the content ratio of the structural unit (a) to the content ratio of the structural unit (b) contained in the copolymerized polyolefin compound is 1/99 to 99/1 in molar ratio. The oxygen-absorbing prefilled syringe according to any one of to <3>.
<5> Structural units in which the structural unit (a) is represented by the following formulas (4) and (5);

At least one structural unit selected from the group consisting of:
The structural unit (b) is represented by the following formulas (6) and (7);

The oxygen-absorbing prefilled syringe according to any one of the above <1> to <4>, which is at least one type of structural unit selected from the group consisting of:
<6> 70 mol% or more 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 -The oxygen-absorbing prefilled syringe according to any one of <1> to <5>, which is derived from one or more dicarboxylic acids selected from the group consisting of naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid.
<7> The oxygen-absorbing prefilled syringe according to any one of <1> to <5>, in which 70% by mole or more of the polyester in the dicarboxylic acid unit is derived from terephthalic acid.
<8> The oxygen-absorbing prefilled syringe according to any one of <1> to <5>, wherein 90% by mole or more of the polyester in the dicarboxylic acid unit is derived from terephthalic acid.
<9> The oxygen-absorbing prefilled syringe according to any one of <1> to <5>, wherein 70% by mole or more of the polyester in the dicarboxylic acid unit is derived from 2,6-naphthalenedicarboxylic acid.
<10> The oxygen-absorbing prefilled syringe according to any one of <1> to <5>, wherein 90% by mole or more of the polyester in the dicarboxylic acid unit is a 2,6-naphthalenedicarboxylic acid skeleton.

  According to the present invention, it has excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, has a good oxygen barrier property, and is further excellent in a water vapor barrier property and a low chemical solution adsorption property in a preferred embodiment. An oxygen-absorbing prefilled syringe can be realized. And this oxygen absorptive prefilled syringe can absorb oxygen irrespective of the presence or absence of moisture in the object to be stored. In addition, the oxygen-absorbing prefilled material is less susceptible to delamination because the decrease in strength of the copolymerized polyolefin compound having a tetralin ring due to oxidation is extremely small after oxygen absorption and the strength of the oxygen-absorbing layer is maintained even in long-term use. A syringe can also be realized. Furthermore, since the production | generation of the low molecular weight organic compound after oxygen absorption is suppressed remarkably, the oxygen absorptive prefilled syringe with very few mixing into the content of this low molecular weight organic compound can also be implement | achieved. Therefore, the oxygen-absorbing prefilled syringe 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.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

[Prefilled syringe]
The oxygen-absorbing prefilled syringe of this embodiment includes a first resin layer (layer B) containing at least polyester, an oxygen absorbing layer (layer A) made of an oxygen-absorbing resin composition, and a first resin containing at least polyester. It has at least three layers in this order with two resin layers (layer B).

  The oxygen-absorbing prefilled syringe of the present embodiment absorbs oxygen in the container, and also absorbs this permeating or penetrating oxygen when there is little oxygen that permeates or penetrates the container wall from the outside of the container. Further, it is possible to prevent alteration of the stored content item (stored object) due to oxygen.

  As long as these layers are arranged in the order of B / A / B, the layer configuration in the oxygen-absorbing prefilled syringe of the present embodiment is the number of oxygen-absorbing layers (layer A) and polyester-containing layers (layer B). The type is 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. In addition, the oxygen-absorbing prefilled syringe of the present embodiment may include an arbitrary layer such as an adhesive layer (layer AD) as necessary. For example, B1 / B2 / AD / A / AD / B2 / B1 7 A layer structure may be used.

[Oxygen absorbing layer (layer A)]
The oxygen absorption layer (A) of the oxygen-absorbing prefilled syringe of the present embodiment is a structural unit that is at least one ethylene or substituted ethylene structural unit selected from the group consisting of structural units represented by the general formula (1). And (a) and a structural unit (b) that is a substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural units represented by the general formula (2) or (3) And an oxygen-absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst.

  The content ratio of the tetralin ring-containing copolymer polyolefin compound in layer A is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass with respect to the total amount of layer A. That's it. When the content ratio of the tetralin ring-containing copolymer polyolefin compound is equal to or more than the preferable value, the oxygen absorption performance can be further improved as compared to the case where the content is not so.

<Tetralin ring-containing copolymer polyolefin compound>
The tetralin ring-containing copolymer polyolefin compound of this embodiment is a structural unit (a) that is at least one ethylene or substituted ethylene structural unit selected from the group consisting of structural units represented by the general formula (1), And a structural unit (b) which is a substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural units represented by the general formula (2) or (3).

  The structural unit (a) represented by the general formula (1) is preferably at least one selected from the group consisting of structural units represented by the above formulas (4) and (5). The structural unit (b) represented by the general formula (2) is preferably at least one selected from the group consisting of structural units represented by the above formulas (6) and (7). Here, “containing a structural unit” means that the compound has one or more of the structural unit. Such a structural unit is preferably contained as a repeating unit in the tetralin ring-containing copolymer polyolefin compound. The tetralin ring-containing copolymer polyolefin compound may be either a random copolymer of the structural unit (a) and the structural unit (b) or a block copolymer of the structural unit (a) and the structural unit (b). . Alternatively, the form of copolymerization of these structural units may be, for example, alternating copolymerization or graft copolymerization.

  Further, the tetralin ring-containing copolymer polyolefin compound may contain other structural units other than the structural unit (a) and the structural unit (b), and the structural unit (a), the structural unit (b), and the other structural units. Any of a random copolymer with a structural unit and the block copolymer of the said structural unit (a), a structural unit (b), and another structural unit may be sufficient. Alternatively, the form of copolymerization of these structural units may be, for example, alternating copolymerization or graft copolymerization.

In the structural units represented by the general formulas (1) to (3), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ (Denoted as “R _{1 to} R ₁₁ ”, the same applies hereinafter) (first monovalent substituent, second monovalent substituent, and third monovalent substitution) As the group, a halogen atom (for example, chlorine atom, bromine atom, iodine atom), an alkyl group (preferably having a carbon number of 1 to 15, more preferably a straight chain, branched or cyclic having 1 to 6 carbon atoms) Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group), alkenyl group (preferably having carbon number) 2 to 10, more preferably a straight chain having 2 to 6 carbon atoms , Branched or cyclic alkenyl groups such as vinyl and allyl groups, alkynyl groups (preferably alkynyl groups having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms such as ethynyl groups and propargyl groups). ), An aryl group (preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 12 carbon atoms, Preferably, a monovalent group obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound having 2 to 6 carbon atoms, such as a 1-pyrazolyl group 1-imidazolyl group, 2-furyl group), cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group (preferably having 1 to 10 carbon atoms, Preferably, it is a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, such as a methoxy group or an ethoxy group, and an aryloxy group (preferably having 6 to 12 carbon atoms, more preferably 6 carbon atoms). An aryloxy group having ˜8, for example, a phenoxy group, an acyl group (including a formyl group, preferably an alkylcarbonyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, preferably 7 carbon atoms. To 12, more preferably an arylcarbonyl group having 7 to 9 carbon atoms, such as an acetyl group, a pivaloyl group or a benzoyl group, an amino group (preferably having a carbon number of 1 to 10, more preferably 1 to 6 carbon atoms). Alkylamino group, preferably 6-12 carbon atoms, more preferably an anilino group having 6-8 carbon atoms, preferably 1-12 carbon atoms, more preferably 2-6 carbon atoms. Heterocyclic amino group, for example, amino group, methylamino group, anilino group), mercapto group, alkylthio group (preferably an alkylthio group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, for example, methylthio group) , Ethylthio group), arylthio group (preferably having 6 to 12 carbon atoms, more preferably arylthio group having 6 to 8 carbon atoms, for example, phenylthio group), heterocyclic thio group (preferably having 2 to 10 carbon atoms, More preferably, the heterocyclic thio group having 1 to 6 carbon atoms, such as a 2-benzothiazolylthio group, or an imide group (preferably having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms). Examples thereof include, but are not particularly limited to, N-succinimide group and N-phthalimide group).

In the case where the substituents _R 1 _{to R 11} of the above monovalent have a hydrogen atom, with the hydrogen atoms substituent T (wherein the substituents T is a substituent _R 1 _{to R 11} of the above monovalent It may be further substituted with the same meaning as described. 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 substituents R _{1 to} R ₁₁ have a monovalent substituent T, the number of carbons described above does not include the number of carbons 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. Further, if the substituents R ₁ to R ₁₁ of the above monovalent has a substituent T, the substituent T can be a plurality.

In the structural unit represented by the general formula (2) or (3), X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH. The divalent group selected from the group which consists of (C = O)-and-(CHR) s- is shown, and s shows the integer of 0-12. Y is-(CHR) t-, and t represents an integer of 0 to 12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom (—H), a methyl group (—CH ₃ ), and an -ethyl group (C ₂ H ₅ ).

  The tetralin ring-containing copolymer polyolefin compound of the present embodiment can be obtained by copolymerizing a vinyl compound (I) having a tetralin ring and another vinyl compound (II).

As vinyl compound (I) which has a tetralin ring used by this embodiment, the vinyl compound selected from the group which consists of a compound represented by the following general formula (8) or (9) is mentioned, for example. The vinyl compound (I) having a tetralin ring can be used singly or in combination of two or more.

(Wherein R _{5 to} R ₇ each independently represents a hydrogen atom or a second monovalent substituent, and R _{8 to} R ₁₁ each independently represents a third monovalent substituent. , The second monovalent substituent and the third monovalent substituent are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, At least one selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group a seed, it may further have a _{substituent, and} when R _8, R _{9, R 10} or _{R 11} there are a plurality, the plurality of _{R 8,} R _{9, R 10} or _{R 11} are each M is 0 to 3, n is 0 to 7, p is 0 to 6, q is an integer of 0 to 4, and at least one is present at the benzyl position of the tetralin ring. Hydrogen atoms are bonded, X is — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O) — and — (CHR) a divalent group selected from the group consisting of s-, wherein s represents an integer of 0 to 12. Y represents-(CHR) t-, t represents an integer of 0 to 12, R represents -H, it shows a -CH _3, and _-C 2 _H species monovalent selected from the group consisting of _5.)

As vinyl compound (II) used by this embodiment, the vinyl compound selected from the group which consists of a compound represented by following General formula (10) is mentioned, for example. Vinyl compound (II) can be used individually by 1 type or in combination of 2 or more types.

(Wherein R _{1 to} R ₄ each independently represent a hydrogen atom or a first monovalent substituent, and the first monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, or 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, mercapto group, alkylthio group, arylthio group, heterocyclic ring It is at least one selected from the group consisting of a thio group and an imide group, and these may further have a substituent.)

  Examples of the vinyl compound represented by the general formula (10) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene Ethylene or α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohex Cycloolefins such as cene and cyclooctene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; butadiene, isoprene, Conjugated dienes such as 2,3-dimethylbutadiene, pentadiene, hexadiene; styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4 -Styrenes such as dodecylstyrene, 2-ethyl-4-benzylstyrene, 2,4,6-trimethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl ( (Meth) acrylate, n-butyl (meth) Acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, (meth) acrylic acid, crotonic acid , Cinnamic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, (meth) acrylonitrile, α-chloroacrylonitrile, ethacryl Ronitrile, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, (meth) acrylamide, α-chloro (meth) acrylamide, ethacrylamide, N-methyl (meth) acrylamide, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-nitroethyl (meth) acrylate, 3-nitropropyl (meth) acrylate and the like can be mentioned. These can be used alone or in combination of two or more. In addition, (meth) acrylate means an acrylate and its corresponding methacrylate, and (meth) acrylic acid means acrylic acid and its corresponding methacrylic acid.

The tetralin ring-containing copolymer polyolefin compound of this embodiment is a substituent having at least one naphthalene ring selected from the group consisting of the structural unit (a) and a structural unit represented by the following general formula (11). It can also be obtained by reacting a copolymerized polyolefin compound containing a structural unit (c) that is a substituted ethylene structural unit containing hydrogen with hydrogen.

(Wherein R _{5 to} R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ and R ₉ each independently represent a third monovalent substituent. , The second monovalent substituent and the third monovalent substituent are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, At least one selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group a seed, it may further have a substituent, and when R ₈ or R ₉ there are a plurality, the plurality of R ₈ or R ₉ is optionally being the same or different .m 0 to 3, n represents an integer of 0 to 4, and X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O )-And-(CHR) s- represents a divalent group selected from the group consisting of-and s represents an integer of 0 to 12. Y is-(CHR) t-, where t is 0-12. R represents a monovalent chemical species selected from the group consisting of —H, —CH ₃ , and —C ₂ H _5. )

  As another production method of the tetralin ring-containing copolymer polyolefin compound of the present embodiment, there is a method of reacting a polyolefin (III) having a reactive functional group in the side chain with a compound (IV) having a tetralin ring. It is done.

  Examples of the polyolefin (III) having a reactive functional group in the side chain include unsaturated carboxylic acid polymers such as poly (meth) acrylic acid; unsaturated carboxylic acid ester polymers such as poly (meth) acrylic acid methyl Polyvinyl acetate and polyvinyl acetate derivatives such as polyvinyl acetate; ethylene-unsaturated carboxylic acid copolymer; ethylene-unsaturated carboxylic acid ester copolymer; ethylene-vinyl alcohol copolymer; maleic anhydride-modified polyethylene, maleic anhydride Examples include maleic anhydride-modified polyolefin such as acid-modified polypropylene. These can be used alone or in combination of two or more.

  As the compound (IV) having a tetralin ring, a compound having a functional group that easily binds to the polyolefin (III) having a reactive functional group in the side chain is preferable, and an alcohol compound, an amine compound, a carboxyl having a tetralin ring is preferable. Examples thereof include acid compounds, acid anhydride compounds, and epoxide compounds. These can be used alone or in combination of two or more.

  In particular, a tetralin ring as the compound (IV) having the tetralin ring is added to a solution obtained by dissolving a polyolefin having an ester group in the side chain as a polyolefin (III) having a reactive functional group in the side chain in an organic solvent. A method of adding an alcohol compound having a transesterification catalyst and a transesterification reaction is preferable.

  The transesterification reaction can be performed by a known method. The reaction temperature and reaction time are not particularly limited as long as transesterification is possible, but the reaction temperature is preferably 50 to 300 ° C. and the reaction time is preferably 10 minutes to 24 hours. The organic solvent used for the transesterification reaction can be used without particular limitation as long as it is an organic solvent capable of dissolving the polymer. Examples of such an organic solvent include benzene, toluene, xylene, decalin and the like.

  As another method of transesterification, for example, a polyolefin (III) having a reactive functional group in the side chain as a polyolefin (III) having an ester group in the side chain and a tetralin ring as the compound (IV) having the tetralin ring are used. Examples thereof include a method of melt-kneading the alcohol compound having and the transesterification catalyst with a single screw extruder, a twin screw extruder, a kneader, or the like.

  As the transesterification catalyst used in the transesterification reaction, a known substance can be used. For example, sodium tert-butoxide, sodium propoxide, sodium ethoxide, sodium hydroxide, tetraisopropyl titanate, tetrabutyl titanate , Titanium oxide, titanium chloride, zirconium chloride, hafnium chloride, tin chloride, and metallocene complex catalysts of titanium, zirconium, and tin. These can be used alone or in combination of two.

  The content ratio ((a) / (b)) of the structural unit (a) to the content ratio of the structural unit (b) contained in the tetralin ring-containing copolymer polyolefin compound of the present embodiment is 1/99 in molar ratio. To 99/1, more preferably 1/19 to 19/1, and particularly preferably 1/9 to 9/1.

  The MFR (measured in accordance with JIS K7210 at 190 ° C. and a load of 2.16 kg) of the tetralin ring-containing copolymer polyolefin compound of the present embodiment is not particularly limited. ˜500 g / 10 min is preferable, and 0.2 to 100 g / 10 min is more preferable.

  Preferable specific examples of the structural unit (a) include, but are not limited to, the structural unit represented by the above formula (4) or (5).

Preferred specific examples of the structural unit (b) include structural units represented by the above formula (6) or (7) and structural units represented by the following formula (12) or (13). It is not limited.

The molecular weight of the tetralin ring-containing copolymer polyolefin compound can be appropriately set in consideration of desired performance and handling properties, and is not particularly limited. In general, the weight average molecular weight (Mw) is preferably 1.0 × 10 ^{3 to} 8.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁵ . Similarly, the number average molecular weight (Mn) is preferably 1.0 × 10 ^{3 to} 1.0 × 10 ⁶ , and more preferably 5.0 × 10 ^{3 to} 1.0 × 10 ⁵ . In addition, all the molecular weights here mean the value of polystyrene conversion. In addition, said tetralin ring containing copolymer polyolefin compound can be used individually by 1 type or in combination of 2 or more types.

  All of the tetralin ring-containing copolymer polyolefin compounds described above have hydrogen at the benzylic position of the tetralin ring, and when used in combination with the transition metal catalyst described in detail later, the hydrogen at the benzylic position is extracted, which is excellent. Expresses oxygen absorption ability.

  Moreover, the oxygen-absorbing resin composition of the present embodiment is one in which odor generation 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 above-described tetralin ring-containing copolymer polyolefin compound, hydrogen at the benzylic position of the tetralin ring is first extracted to generate a radical, and then the carbon at the benzylic position is oxidized by the reaction between the radical and oxygen, Group or ketone group is considered to be formed. Therefore, in the oxygen-absorbing resin composition of the present embodiment, the molecular chain of the oxygen-absorbing main agent is not broken by the oxidation reaction as in the prior art, the structure of the tetralin ring-containing copolymer polyolefin compound is maintained, and the odor is reduced. This is presumably because the low molecular weight organic compound that is the cause is difficult to be formed after oxygen absorption.

<Transition metal catalyst>
The transition metal catalyst used in the oxygen-absorbing resin 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 tetralin ring-containing copolymer polyolefin compound. It can be used and is not particularly limited.

  Specific examples of such transition metal catalysts include 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, Examples include capric acid and naphthenic acid, but are not limited thereto. The transition metal catalyst is preferably a combination of the above-mentioned transition metal and an organic acid, more preferably the transition metal is manganese, iron, cobalt, nickel or copper, still more preferably manganese, iron or cobalt, organic More preferably, the acid is acetic acid, stearic acid, 2-ethylhexanoic acid, oleic acid or naphthenic acid, even more preferably acetic acid or stearic acid, and the combination of any of these transition metals with any of organic acids is particularly preferred preferable. In addition, a transition metal catalyst can be used individually by 1 type or in combination of 2 or more types.

  The content ratio of the tetralin ring-containing copolymer polyolefin compound and the transition metal catalyst in the oxygen-absorbing resin composition of the present embodiment is appropriately determined according to the type and desired performance of the tetralin ring-containing copolymer polyolefin compound and the transition metal catalyst used. It can be set and is not particularly limited. From the viewpoint of the oxygen absorption amount of the oxygen-absorbing resin composition, the content of the transition metal catalyst is 0.001 to 10 parts by mass as the transition metal amount with respect to 100 parts by mass of the tetralin ring-containing copolymer polyolefin compound. Preferably, more preferably 0.002 to 2 parts by mass, still more preferably 0.005 to 1 part by mass, still more preferably 0.008 to 0.5 parts by mass, particularly preferably 0.01 to 0.2 parts by mass. Part.

<Other thermoplastic resins>
Moreover, the oxygen-absorbing resin composition of the present embodiment may further contain other thermoplastic resin other than the tetralin ring-containing copolymer polyolefin compound as necessary. By using another thermoplastic resin in combination, moldability and handleability can be improved.

  As other thermoplastic resins, known ones can be used as appropriate. Low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, various polyethylenes such as polyethylene by metallocene catalyst, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random Random or block copolymer of α-olefins such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc. Polyolefins such as polymers; acid-modified polyolefins such as maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene; ethylene-vinyl acetate copolymers, ethylene-vinyl chloride copolymers, ethylene- (meth) acrylic acid copolymers, Ion-crosslinked products (ionomers), ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymer; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer; Polyvinyl compounds such as polymethyl acrylate and polymethyl methacrylate, 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) Polyesters such as polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate; polycarbonates; polyethers such as polyethylene oxide; cyclic polyolefins such as cycloolefin polymers and cycloolefin copolymers using cyclic olefins or mixtures thereof For example, but not limited to. These thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.

  The tetralin ring-containing copolymer polyolefin compound, the transition metal catalyst, and other thermoplastic resins contained as necessary can be mixed by a known method. Moreover, the oxygen-absorbing resin composition which has higher dispersibility can also be obtained by kneading | mixing these using an extruder.

<Various additives>
Here, the oxygen-absorbing resin composition of the present embodiment may contain various additives known in the art as long as the effects of the present embodiment are not excessively impaired in addition to the components described above. . Examples of such optional additives include additives such as desiccants, pigments such as titanium oxide, dyes, antioxidants, slip agents, antistatic agents, stabilizers, calcium carbonate, clay, mica, silica, and the like. An agent, a deodorant, etc. are mentioned, However, It does not specifically limit to these.

  Furthermore, the oxygen-absorbing resin 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. Specifically, N-hydroxysuccinimide, N-hydroxymaleimide, N, N′-dihydroxycyclohexanetetracarboxylic diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxy Hexahydrophthalimide, 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-hydroxyhexahydride Examples include phthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide, N, N-dihydroxypyromellitic acid diimide and the like. However, it is not particularly limited to these. 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. These radical generators and photoinitiators can be used singly or in combination of two or more.

  In the oxygen-absorbing prefilled syringe of this embodiment, the thickness of the oxygen-absorbing layer (layer A) can be appropriately set according to the use and desired performance, and is not particularly limited. From the viewpoint of securing required physical properties, the thickness is preferably 1 to 1000 μm, more preferably 50 to 900 μm, and still more preferably 100 to 800 μm.

[Resin layer containing polyester (layer B)]
In the oxygen-absorbing prefilled syringe of this embodiment, the resin layer (layer B) is a layer containing polyester. The content of the polyester in the layer B can be appropriately set and is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, further based on the total amount of the layer B. Preferably it is 90-100 mass%. By setting the content of the polyester to 70% by mass or more, the chemical solution storage stability and the low chemical solution adsorption property can be enhanced.

  The oxygen-absorbing prefilled syringe of this embodiment may have a plurality of layers B, and the configurations of the plurality of layers B may be the same as or different from each other. The thickness of the layer B can be appropriately determined according to the use and is not particularly limited, but is preferably 50 to 10,000 μm, more preferably 100 to 7000 μm, from the viewpoint of ensuring various physical properties required for the prefilled syringe. More preferably, it is 300-5000 micrometers.

<Polyester>
Specific examples of the polyester used in the layer B of this embodiment are selected from polyhydric carboxylic acids containing dicarboxylic acids and one or more selected from these ester-forming derivatives and polyhydric alcohols containing glycols. The thing which consists of 1 type, or 2 or more types, or what consists of hydroxycarboxylic acid and these ester-forming derivatives, or 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 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid such as 2,7-naphthalenedicarboxylic acid, 4,4′- Examples include biphenyl dicarboxylic acid, 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. Aromatic 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 Exemplified by sulfoterephthalic acid Genus sulfonate 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.

  In addition, the polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof in total with respect to the total acid component, 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 naphthalenedicarboxylic acid or an ester-forming derivative in total of 70 mol% or more, 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.

  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.

  In particular, the polyester used in the layer B of the present embodiment is 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 preferred. Moreover, it is preferable that 70 mol% or more of alkylene glycol is included at points, such as a physical characteristic, and it is more preferable that 90 mol% or more is included. Among the dicarboxylic acids described above, terephthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, The use of 2,7-naphthalenedicarboxylic acid is preferred in terms of the physical properties of the resulting polyester, and preferably contains 70 mol% or more. Among these dicarboxylic acids, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid are particularly preferable. Further, it is preferable that 70 mol% or more of terephthalic acid and / or 2,6-naphthalenedicarboxylic acid is included in terms of physical properties, and more preferably 90 mol% or more. You may copolymerize other dicarboxylic acid as needed. And at least selected from the group consisting of isophthalic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol and 2-methyl-1,3-propanediol. The use of one or more copolymerization components is preferable for achieving both transparency and moldability, and in particular, at least one selected from the group consisting of isophthalic acid, diethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol. The above is more preferable.

  The oxygen-absorbing prefilled syringe of this embodiment includes an arbitrary 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. Also good. Examples of such an arbitrary layer include an adhesive layer.

  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 obtained by modifying a polyolefin resin such as polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid Polyolefin resin; polyester-based thermoplastic elastomer mainly composed of a polyester-based block copolymer. 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.

  The manufacturing method of the oxygen-absorbing prefilled syringe of this embodiment can apply a well-known method according to the property of various materials, the target shape, etc., and is not specifically limited. For example, it can be manufactured by applying various injection molding methods.

  The thickness of the oxygen-absorbing prefilled syringe of the present embodiment is not particularly limited, but is preferably 3 to 5000 μm, more preferably 5 to 5% from the viewpoint of enhancing oxygen absorption performance and ensuring various physical properties required for the prefilled syringe. It is 4500 micrometers, More preferably, it is 10-4000 micrometers.

  Moreover, as a method other than the injection molding method, for example, a multilayer molded body can be obtained by a compression molding method, and the obtained multilayer molded body is molded into a desired shape by performing the above-described secondary processing. You can also. For example, a multilayer molded article can be obtained by providing an oxygen-absorbing resin composition in a polyester melt, supplying the molten mass to a male mold, compressing with a female mold, and cooling and solidifying the compression molded article. . Further, as the secondary processing, for example, extrusion molding, compression molding (sheet molding, blow molding) or the like can be applied.

[Prefilled syringe]
The oxygen-absorbing prefilled syringe of this embodiment is not different from a general prefilled syringe. At least a barrel for filling a chemical, a joint for joining an injection needle to one end of the barrel, and a chemical at the time of use are used. It is a syringe that is composed of a plunger for extruding, is configured to store a medicine in a sealed state in a barrel in advance, and to open the front end side of the barrel and attach an injection needle during use. Widely used for convenience. The oxygen-absorbing resin composition of this embodiment can be used for this barrel.

  As a method for molding the oxygen-absorbing prefilled syringe of the present embodiment, 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 barrel can be manufactured as a multilayer injection molded article. The oxygen absorbing layer (layer A) is preferably formed up to the vicinity of the nozzle tip surface. By forming the oxygen absorbing layer (layer A) up to the vicinity of the front end face, the barrier property of the barrel can be ensured more reliably. Moreover, it is preferable that the oxygen absorption layer (layer A) is formed up to the 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. It should be noted that the barrel and the joint may be molded as an integral part, or may be joined separately. Moreover, after filling the chemical solution, it is necessary to seal the tip of the joint, but the method is not particularly limited, and a known method can be adopted. For example, the resin at the tip of the joint may be heated to a molten state and sandwiched with pliers or the like to be fused.

  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 the chemical solution, moldability, and operability of the 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. The barrel has a male luer taper nozzle that can connect the injection needle in a liquid-tight manner at the tip, and a shoulder is formed from the base end of the nozzle to the cylindrical wall. A cylindrical shape having a finger hook flange at the end is preferably employed. Note that 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 the formation method thereof are described in, for example, Japanese Patent Application Laid-Open No. 2004-323058.

[Contained items]
The material to be stored (filled material) filled in the oxygen-absorbing prefilled syringe 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 products and compounds such as antibiotics such as cephalosporin and cyclosporine, and benzodiazepines such as oxazolam, flunitrazepam, clothiazepam and clobazam can be filled. The oxygen-absorbing prefilled syringe of this embodiment, when filled with these natural products and compounds, has a small amount of adsorption of these natural products and compounds, can suppress alteration due to oxidation, It is also possible to suppress transpiration (for example, moisture).

  In addition, before and after the filling of these objects to be stored, the medical multilayer container and the objects to be stored can be sterilized in a form suitable for the objects to be stored. As sterilization methods, for example, hot water treatment at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, high temperature heat treatment at 121 ° C. or higher, etc., electromagnetic wave sterilization of ultraviolet rays, microwaves, gamma rays, etc., ethylene Examples include gas treatment of oxide and the like, and chemical sterilization such as hydrogen peroxide and hypochlorous acid.

  Although the prefilled syringe of this invention is demonstrated in more detail below using an Example and a comparative example, this invention is not limited by this.

(Synthesis Example 1)
In a four-necked separable flask with an internal volume of 1000 mL, 100 g of ethylene-methyl methacrylate copolymer (product name: “Acrylift WK402” manufactured by Sumitomo Chemical Co., Ltd.) having a methyl methacrylate content of 25 mass%, 6-hydroxylmethyl -1,2,3,4-tetrahydronaphthalene 81g, decalin 160g, tetrabutyl titanate 0.2g as a transesterification catalyst were charged, and the temperature of the reaction solution was raised to 210 ° C in a nitrogen atmosphere while stirring, and methanol was distilled. The reaction was carried out for 3 hours while leaving. After methanol was not distilled off, the pressure was gradually reduced to distill off unreacted 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene and decalin. Then, it returned to normal pressure and cooled and the solid reaction crude product was obtained. Next, toluene is added to the obtained reaction crude product so that the concentration thereof becomes 3 to 4% by mass, and the solution is heated to 80 ° C. to dissolve, then the solution is cooled to about 40 ° C., methanol is added, The precipitated tetralin ring-containing copolymer polyolefin compound (1) was recovered by filtration.

As a result of measuring the weight average molecular weight and number average molecular weight of the obtained tetralin ring-containing copolymer polyolefin compound (1) by GPC (gel permeation chromatography), the weight average molecular weight in terms of polystyrene was 9.5 × 10 ⁴ , number. The average molecular weight was 3.1 × 10 ⁴ . As a result of measuring the melting point by DSC, the melting point was 71 ° C.

(Synthesis Example 2)
Instead of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene in Synthesis Example 1, 1,5-dimethyl-8-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was used, and the mass was 95. A tetralin ring-containing copolymer polyolefin compound (2) was synthesized in the same manner as in Synthesis Example 1 except that the amount was 0.0 g. This tetralin ring-containing copolymer polyolefin compound (2) had a polystyrene equivalent weight average molecular weight of 9.1 × 10 ⁴ , a number average molecular weight of 3.0 × 10 ⁴ , and a melting point of 71 ° C.

(Synthesis Example 3)
Instead of the ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 25% by mass in Synthesis Example 1, an ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 5% by mass (product name: Sumitomo Chemical Co., Ltd.) Tetralin ring in the same manner as in Synthesis Example 1 except that the amount of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was changed from 81 g to 16.2 g. The containing copolymer polyolefin compound (3) was synthesized. This tetralin ring-containing copolymer polyolefin compound (3) had a polystyrene equivalent weight average molecular weight of 9.6 × 10 ⁴ , a number average molecular weight of 3.0 × 10 ⁴ , and a melting point of 98 ° C.

(Synthesis Example 4)
Instead of the ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 25% by mass in Synthesis Example 1, an ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 10% by mass (product name: Sumitomo Chemical Co., Ltd.) Tetralin ring in the same manner as in Synthesis Example 1 except that the amount of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was changed from 81 g to 32.4 g. A copolymerized polyolefin compound (4) was synthesized. This tetralin ring-containing copolymer polyolefin compound (4) had a polystyrene-equivalent weight average molecular weight of 9.3 × 10 ⁴ , a number average molecular weight of 3.1 × 10 ⁴ , and a melting point of 92 ° C.

Example 1
A mixture obtained by dry blending cobalt stearate (II) so that the amount of cobalt is 0.05 parts by mass with respect to 100 parts by mass of the copolymerized polyolefin compound (1) 2 having two screws having a diameter of 37 mm Oxygen-absorbing resin composition (1) is supplied to a shaft extruder at a rate of 30 kg / h, melt kneaded at a cylinder temperature of 220 ° C., extruding strands from the extruder head, cooling, and pelletizing. ) Next, as shown below, a syringe was produced using this oxygen-absorbing resin composition (1). Then, performance evaluation of the obtained syringe was performed as shown below. The evaluation results are shown in Table 1.

[Manufacture of syringes]
Under the following conditions, the polyester constituting the resin layer (layer B) is injected from the injection cylinder, and then the oxygen-absorbing resin composition constituting the oxygen absorption layer (layer A) is formed from another injection cylinder to form layer B. A syringe having a B / A / B three-layer structure was manufactured by injecting a necessary amount of the thermoplastic resin constituting the layer B and filling the cavity in the injection mold. Here, the total mass of the syringe was 1.95 g, and the mass of the layer A was 30% by mass of the total mass of the syringe. As the thermoplastic resin constituting the layer B, polyethylene terephthalate (manufactured by Nippon Unipet Co., Ltd., trade name: RT-553C, hereinafter abbreviated as PET) was used.

(Syringe shape)
The internal capacity is 1 cc (standard) in accordance with ISO11040-6. An injection molding machine (manufactured by Nissei ASB Machine Co., Ltd., model: ASB-12N / 10) was used for manufacturing the syringe.
(Syringe 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
Mold temperature: 18 ℃

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

(1) An oxygen concentration vial in a syringe was filled with 1 mL of pure water and sealed with a plunger equipped with a top cap and a gasket. It preserve | saved at 23 degreeC60% RH, and measured the oxygen concentration of the head space 3 days and 1 month later with the oxygen concentration measuring apparatus (LC-750F by Toray Engineering Co., Ltd.).

(2) Contents visibility of syringe The contents visibility of the syringe was observed visually. Those with no problem in visibility were accepted.

(3) Impact resistance test After storing the syringe at 40 ° C. and 90% RH for 1 month, 50 g of a metal ball was dropped from a height of 2 m onto the syringe barrel, and the presence or absence of destruction at this time was determined by 20 samples. Investigated against.

(4) Dissolution test After the syringe was stored at 40 ° C. and 90% RH for 1 month, it was filled with 1 cc of pure water and sealed with a plunger equipped with a top cap and a gasket. The syringe thus obtained was stored at 40 ° C. and 60% RH for 4 months, and then the total amount of carbon (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

(Examples 2 to 4)
An oxygen-absorbing resin composition and a syringe were produced in the same manner as in Example 1 except that the copolymerized polyolefin compound shown in Table 2 was used instead of the copolymerized polyolefin compound (1). The performance evaluation of the obtained syringe was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 1)
In place of the oxygen-absorbing resin composition (1), 100 parts by mass of polyethylene terephthalate resin (trade name: RT-553C, hereinafter abbreviated as PET) manufactured by Nippon Unipet Co., Ltd. was used, and the cylinder temperature for layer A was A single-layer syringe having the same shape as in Example 1 was produced in the same manner as in Example 1 except that the temperature was 280 ° C. The performance evaluation of the obtained syringe was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 2)
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 (S7007 manufactured by Mitsubishi Gas Chemical Co., Ltd.), a screw having a diameter of 37 mm Oxygen-absorbing resin is supplied to a twin screw extruder having two at a rate of 30 kg / h, melt kneaded at a cylinder temperature of 280 ° C., extruding a strand from the extruder head, cooling, and pelletizing. A composition (M) was obtained. A syringe is manufactured in the same manner as in Example 1 except that this oxygen-absorbing resin composition (M) is used in place of the oxygen-absorbing resin composition (1) and the cylinder temperature for the layer A is 280 ° C. did. The performance evaluation of the obtained syringe was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

  As is clear from Table 1, the syringes of Examples 1 to 4 have good oxygen absorption, maintain good strength even after long-term storage, and confirm that the amount of elution from the container to the contents is low. It was done. Furthermore, it was confirmed that the syringes of Examples 1 to 4 have excellent visibility inside the container and are excellent in transparency.

Claims (10)

A prefilled syringe that contains a medicine in a sealed state in advance and can release the sealed state when the medicine is used, wherein the prefilled syringe contains at least a polyester. And a multilayer structure having in this order at least three layers of an oxygen absorbing layer comprising an oxygen absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, and a second resin layer containing at least a polyester,
The copolymer polyolefin compound is a structural unit represented by the following general formula (1);

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a first monovalent substituent, wherein the first monovalent substituent is a halogen atom, an alkyl Group, alkenyl group, 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, mercapto group, alkylthio And at least one selected from the group consisting of a group, an arylthio group, a heterocyclic thio group, and an imide group, which may further have a substituent.)
At least one structural unit (a) selected from the group consisting of:
Structural units represented by the following general formulas (2) and (3);

(Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently 3 monovalent substituents, wherein the second monovalent substituent and the third monovalent substituent are each independently 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, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and It is at least one selected from the group consisting of imide groups, and these may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , R ₈ , R ₉ , R ₁₀ or R ₁₁ may be the same or different from each other, m is 0 to 3, n is 0 to 7, p is 0 to 6, and q is 0 to 4. Each represents an integer, and at least one hydrogen atom is bonded to the benzylic position of the tetralin ring, where X is — (C═O) O—, — (C═O) NH—, —O (C═O). A divalent group selected from the group consisting of-, -NH (C = O)-and-(CHR) s-, wherein s represents an integer of 0 to 12. Y is-(CHR) t-. T represents an integer of 0 to 12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.
An oxygen-absorbing prefilled syringe which is a copolymerized polyolefin compound containing a structural unit (b) having at least one tetralin ring selected from the group consisting of:   The oxygen-absorbing prefilled syringe according to claim 1, wherein the transition metal catalyst contains at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.   The oxygen-absorbing prefilled syringe according to claim 1 or 2, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the copolymer polyolefin compound.   The content rate of the said structural unit (a) with respect to the content rate of the said structural unit (b) contained in the said copolymerization polyolefin compound is 1 / 99-99 / 1 in molar ratio, Any of Claims 1-3 The oxygen-absorbing prefilled syringe according to claim 1. The structural unit (a) is represented by the following formulas (4) and (5);

At least one structural unit selected from the group consisting of:
The structural unit (b) is represented by the following formulas (6) and (7);

The oxygen-absorbing prefilled syringe according to any one of claims 1 to 4, wherein the oxygen-absorbing prefilled syringe is at least one structural unit selected from the group consisting of:   70% by mole or more of the polyester in the dicarboxylic acid unit is terephthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. The oxygen-absorbing prefilled syringe according to any one of claims 1 to 5, which is derived from at least one dicarboxylic acid selected from the group consisting of an acid and 2,7-naphthalenedicarboxylic acid.   The oxygen-absorbing prefilled syringe according to any one of claims 1 to 5, wherein 70% by mole or more of the polyester in the dicarboxylic acid unit is derived from terephthalic acid.   The oxygen-absorbing prefilled syringe according to any one of claims 1 to 5, wherein 90% by mole or more of the polyester in the dicarboxylic acid unit is derived from terephthalic acid.   The oxygen-absorbing prefilled syringe according to any one of claims 1 to 5, wherein 70% by mole or more of the polyester in the dicarboxylic acid unit is derived from 2,6-naphthalenedicarboxylic acid.   The oxygen-absorbing prefilled syringe according to any one of claims 1 to 5, wherein 90% by mole or more of the polyester in the dicarboxylic acid unit is a 2,6-naphthalenedicarboxylic acid skeleton.