JP2022065796A - Syringe for prefill, method for storing contract agent in the syringe for prefill, and prefilled syringe and syringe barrel - Google Patents

Abstract

To provide a syringe for prefill which can store a hydrogen peroxide solution for a long period, a method for storing a contrast agent in the syringe for prefill, and a prefilled syringe and a syringe barrel.SOLUTION: A syringe for prefill contains an oxygen absorbing resin layer (A) containing an oxygen absorbing resin composition containing a polyester compound and a transition metal catalyst, and resin layers (B) containing a thermoplastic resin, and has a syringe barrel having a multilayer structure that the resin layers (B) are laminated on both sides of the oxygen absorbing resin layer (A), in which the polyester compound contains a structural unit represented by at least one selected from the group consisting of the following general formulae (1) to (3).SELECTED DRAWING: Figure 1

Description

The present invention relates to a prefilling syringe having excellent storage stability of an aqueous hydrogen peracid solution, a method for storing a contrast medium in the prefilling syringe, and a prefilled syringe and a syringe barrel.

Hydrogen peroxide solution is industrially used as a bleaching agent, an intermediate raw material for chemical products as an oxidizing agent, an industrial wastewater / sewage treatment agent, a bactericidal agent in the food field, a disinfectant in the medical field, and a cancer treatment method. Used in certain radiation therapies.

The hydrogen peroxide solution used in radiation therapy is used as a radiosensitizer as 0.1 to 10 W / V% sodium hyaluronate containing 0.01 to 3.5 W / V% of hydrogen peroxide. There is.

For example, when a hydrogen peroxide solution is used as a radiosensitizer as in Patent Document 1, it is required to weigh it from a storage container to a syringe when it is used because the hydrogen peroxide solution is easily decomposed. ..

Further, Patent Document 2 proposes a syringe in which the material of the syringe in the portion where the chemical solution comes into direct contact is resin and the decomposition rate of hydrogen peroxide in the hydrogen peroxide solution is lower than that of glass, instead of the glass syringe. ing.

International Publication WO2008 / 041514 Japanese Patent No. 6551857

When the hydrogen peroxide solution is used as a radiosensitizer, if the hydrogen peroxide solution is contained in a syringe and prefilled, there is a problem that oxygen is generated by the decomposition of the hydrogen peroxide solution during storage. For this reason, when a hydrogen peroxide solution is contained in a conventionally used glass syringe to be prefilled, there is a problem that the inside of the syringe expands and the gasket is pushed back, making long-term storage difficult.

On the other hand, the prefilling syringe described in Patent Document 2 using a resin instead of a glass syringe is a material constituting an outer cylinder by using a cycloolefin polymer (COP resin) or a cycloolefin copolymer (COC resin). The decomposition of hydrogen peroxide due to the above can be suppressed. However, the technique does not consider the decomposition of hydrogen peroxide by ultraviolet rays, and the decomposition of hydrogen peroxide under ultraviolet rays is not sufficiently suppressed. For this reason, when a syringe for prefilling is filled with a hydrogen peroxide solution and stored for a long period of time, the problem caused by ultraviolet rays cannot be said to be sufficiently solved, such as the decomposition product of hydrogen peroxide caused by ultraviolet rays causing the plunger to be pushed back. ..

The present invention provides a syringe for prefilling which can store a hydrogen peroxide solution for a long period of time, a method for storing a contrast medium in the syringe for prefilling, and a prefilled syringe and a syringe barrel in order to solve the above-mentioned problems. The purpose.

That is, the present invention is as follows.
As a result of diligent research on a medical prefill syringe that exhibits hydrogen peroxide storage and absorption of oxygen, which is a decomposition product of hydrogen peroxide, an oxygen-absorbing multi-layer container using an oxygen-absorbing resin for the intermediate layer was adopted. By doing so, it was found that the above-mentioned problems could be solved, and the present invention was completed.

＜２＞ 前記遷移金属触媒が、鉄、コバルト、ニッケル及び銅からなる群より選択される少なくとも１種の遷移金属を含む、前記＜１＞に記載のプレフィル用シリンジ。
＜３＞ 前記遷移金属触媒が、前記ポリエステル化合物１００質量部に対し、遷移金属量として０．０００１～１０質量部を含む、前記＜１＞又は前記＜２＞に記載のプレフィル用シリンジ。
＜４＞ 前記熱可塑性樹脂が、ポリオレフィンである、前記＜１＞～前記＜３＞のいずれかに記載のプレフィル用シリンジ。
＜５＞ 前記＜１＞～前記＜４＞のいずれかに記載のプレフィル用シリンジを用いた、過酸化水素溶液を含む、造影剤を保存する方法。
＜６＞ 前記＜１＞～前記＜４＞のいずれかに記載のプレフィル用シリンジに過酸化水素溶液を収容した、プレフィルドシリンジ。
＜７＞ プレフィル用シリンジに用いられるシリンジバレルであって、
ポリエステル化合物及び遷移金属触媒を含有する酸素吸収性樹脂組成物を含む酸素吸収性樹脂層（Ａ）と、熱可塑性樹脂を含む樹脂層（Ｂ）とを含み、且つ、少なくとも、前記樹脂層（Ｂ）が前記酸素吸収性樹脂層（Ａ）の両側に積層された、多層構造を有するシリンジバレルを備え、
前記ポリエステル化合物が、下記一般式（１）～（３）からなる群より選択される少なくとも１つで示される構成単位を含有する、シリンジバレル。

＜８＞ 前記遷移金属触媒が、鉄、コバルト、ニッケル及び銅からなる群より選択される少なくとも１種の遷移金属を含む、前記＜７＞に記載のシリンジバレル。
＜９＞ 前記遷移金属触媒が、前記ポリエステル化合物１００質量部に対し、遷移金属量として０．０００１～１０質量部を含む、前記＜７＞又は前記＜８＞に記載のシリンジバレル。
＜１０＞ 前記熱可塑性樹脂が、ポリオレフィンである、前記＜７＞～前記＜９＞のいずれかに記載のシリンジバレル。 <1> A syringe for prefilling,
An oxygen-absorbing resin layer (A) containing an oxygen-absorbing resin composition containing a polyester compound and a transition metal catalyst, and a resin layer (B) containing a thermoplastic resin, and at least the resin layer (B). ) Provided a syringe barrel having a multilayer structure laminated on both sides of the oxygen-absorbing resin layer (A).
A syringe for prefilling, wherein the polyester compound contains a structural unit represented by at least one selected from the group consisting of the following general formulas (1) to (3).

<2> The prefilling syringe according to <1>, wherein the transition metal catalyst contains at least one transition metal selected from the group consisting of iron, cobalt, nickel and copper.
<3> The prefilling syringe according to <1> or <2>, wherein the transition metal catalyst contains 0.0001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the polyester compound.
<4> The syringe for prefill according to any one of <1> to <3>, wherein the thermoplastic resin is polyolefin.
<5> A method for storing a contrast medium containing a hydrogen peroxide solution using the prefilling syringe according to any one of <1> to <4>.
<6> A prefilled syringe in which a hydrogen peroxide solution is contained in the prefill syringe according to any one of <1> to <4>.
<7> A syringe barrel used for a prefill syringe.
An oxygen-absorbing resin layer (A) containing an oxygen-absorbing resin composition containing a polyester compound and a transition metal catalyst, and a resin layer (B) containing a thermoplastic resin, and at least the resin layer (B). ) Provided a syringe barrel having a multi-layer structure in which the oxygen-absorbing resin layer (A) is laminated on both sides thereof.
A syringe barrel in which the polyester compound contains a structural unit represented by at least one selected from the group consisting of the following general formulas (1) to (3).

<8> The syringe barrel according to <7>, wherein the transition metal catalyst contains at least one transition metal selected from the group consisting of iron, cobalt, nickel and copper.
<9> The syringe barrel according to <7> or <8>, wherein the transition metal catalyst contains 0.0001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the polyester compound.
<10> The syringe barrel according to any one of <7> to <9>, wherein the thermoplastic resin is polyolefin.

According to the present invention, it is possible to provide a syringe for prefilling which can store a hydrogen peroxide solution for a long period of time, a method for storing a contrast medium in the syringe for prefilling, and a prefilled syringe and a syringe barrel.

It is a schematic diagram which shows the structure at the time of storage of the syringe of this embodiment. It is a schematic diagram for demonstrating the multi-layer structure of a syringe barrel (cylindrical body).

Hereinafter, embodiments of the present invention will be described. The following embodiments will explain the present invention. It should be noted that the following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments thereof.

<< Syringe for prefill >>
The prefilling syringe of the present embodiment (hereinafter, may be simply referred to as “syringe”) is a prefilling syringe.
An oxygen-absorbing resin layer (A) containing an oxygen-absorbing resin composition containing a polyester compound and a transition metal catalyst, and a resin layer (B) containing a thermoplastic resin, and at least the resin layer (B). ) Is provided on both sides of the oxygen-absorbing resin layer (A) to provide a syringe barrel having a multi-layer structure.
The polyester compound contains a structural unit represented by at least one selected from the group consisting of the following general formulas (1) to (3).

The syringe of this embodiment is particularly useful as a prefilling syringe for storing a hydrogen peroxide solution. In the syringe of the present embodiment, for example, since the innermost surface of the syringe barrel is the resin layer (B), the decomposition rate of hydrogen peroxide in the hydrogen peroxide solution is lower than that of glass, and further, ultraviolet rays and the like during storage are used. By absorbing oxygen, which is a decomposition product of hydrogen peroxide generated due to the influence of hydrogen peroxide, expansion in the syringe due to the oxygen can be suppressed. Therefore, the hydrogen peroxide solution can be stored (prefilled) for a long period of time (for example, 56 days or more).
The prefilled syringe used in the present embodiment is from the viewpoint of storing the hydrogen peroxide solution in a medical prefilled syringe which exhibits hydrogen peroxide storage stability and absorption of oxygen which is a hydrogen peroxide decomposition product. When the oxygen absorption rate of the oxygen-absorbing resin composition used for the oxygen-absorbing resin layer (A), which is the intermediate layer, was measured under the condition of 23 ° C. and 90% RH (relative humidity), 0.01 mL / g / 56 days. It is preferably 0.5 mL / g / 56 days or more, and more preferably 0.5 mL / g / 56 days or more.

<Syringe configuration>
The configuration of the syringe of this embodiment will be described. The following configuration is one aspect of the present invention, and the present invention is not limited to the following configurations.

FIG. 1 is a schematic view showing the configuration of the syringe of the present embodiment at the time of storage. As shown in FIG. 1, the syringe 100 includes a syringe barrel 10, a gasket 20, a plunger 30, and a cap 40. The syringe 100 is a syringe (prefill syringe) used for a so-called prefilled syringe that houses the drug solution 18 in a sealed state. Further, an embodiment in which a chemical solution (hydrogen peroxide solution) is contained in the syringe 100 is an example of the prefilled syringe of the present embodiment.

As shown in FIG. 1, the syringe barrel 10 has a tubular main body 12, and a chemical solution 18 is housed therein. In this embodiment, a hydrogen peroxide solution is contained. The tubular main body 12 is a tubular body having the same diameter along the same direction with the XX'straight line in FIG. 1 as the central axis. Further, the tip of the tubular main body 12 has a pouring portion 14 for pouring (discharging) the chemical solution 18, and the other end has an inserting portion 16 into which the gasket 20 is inserted.

As shown in FIG. 2, the cylindrical main body 12 has a multi-layer structure, and the syringe barrel in the present embodiment is an oxygen-absorbing multi-layer container. FIG. 2 is a schematic view for explaining the multi-layer structure of the tubular main body 12. The tubular main body 12 in the present embodiment has a three-layer structure in which the oxygen-absorbing resin layer A1 is laminated between the resin layers B1 and B2 (skin layer) so as to be an intermediate layer (core layer). .. The materials used for each resin layer and the oxygen-absorbing resin layer will be described later, but it is preferable that at least the resin layer B1 constituting the inner surface (innermost layer) of the tubular main body 12 contains a cycloolefin-based polymer. Since the syringe 100 of the present embodiment employs the resin layer (B) as the skin layer and the syringe barrel 10 has the oxygen-absorbing resin layer A1, it is peroxidized by contact with the inner surface of the syringe barrel 10. Decomposition of hydrogen is suppressed, and oxygen, which is a decomposition product of hydrogen peroxide due to ultraviolet rays, can be absorbed by the oxygen-absorbing resin layer, which is the core layer, so that expansion in the syringe during long-term storage is suppressed. be able to.

Next, as shown in FIG. 1, a cap 40 is fitted to the dispensing portion 14 of the tubular main body 12 when the syringe 100 is stored. When using the syringe 100, the cap 40 is removed and an injection needle is attached to the injection portion 14. The dispensing portion 14 is formed of a portion having a smaller diameter than the tubular main body 12, and can be formed in a tapered shape.

The gasket 20 is attached to one end of the plunger 30 and is installed so as to be slidable in the syringe barrel 10 along the XX'straight line in FIG. As described above, the gasket 20 is inserted from the insertion portion 16 of the syringe barrel 10, and when the syringe 100 is used, the gasket 20 is pushed and moved in the direction from the insertion portion 16 toward the ejection portion 14 (that is, the direction of the arrow P in FIG. 1). Is done. When the gasket 20 slides in the direction of the arrow P, the chemical solution 18 in the syringe barrel 10 receives pressure on the same direction. As described above, when the syringe 100 is used, an injection needle (not shown) is connected to the injection portion 14, and the chemical solution 18 pressured by the gasket 20 is sent from the injection needle via the injection portion 14. Be poured out.
Hereinafter, each member will be described.

<Syringe barrel>
The syringe of the present embodiment has an oxygen-absorbing resin layer (A) containing an oxygen-absorbing resin composition containing a polyester compound and a transition metal catalyst (hereinafter, may be simply referred to as “layer A”) and thermoplasticity. A resin layer (B) containing a resin (hereinafter, may be simply referred to as “layer B”) is included, and at least the resin layer (B) is laminated on both sides of the oxygen-absorbing resin layer (A). , Equipped with a syringe barrel having a multi-layer structure. Specifically, the tubular body constituting the syringe barrel described above has a multi-layer structure. In the multilayer structure of the tubular body, if a pair of layers B are laminated on both sides of the layer A and the layer B is located on the innermost surface of the syringe barrel (the portion in contact with the chemical solution), the layer A and the layer B may be formed. The number and type are not particularly limited. Further, the layer A may be referred to as a core layer and the layer B may be referred to as a skin layer. The minimum configuration of the multilayer structure is a three-layer structure including two resin layers (B) and an oxygen-absorbing resin layer (A) arranged between the two resin layers (B) (B / A /). B structure). Further, the multilayer structure of the syringe barrel in the present embodiment has a five-layer structure of B1 / B2 / A / B2 / B1 composed of one layer A and two types of four layers B of layers B1 and B2. May be good. Further, the multilayer structure of the syringe barrel in the present embodiment may include an arbitrary layer such as an adhesive layer (layer AD), if necessary, as described later, for example, B1 / AD / B2 / A / B2 /. It may have a 7-layer structure of AD / B1. The oxygen-absorbing resin layer (A) and the resin layer (B) may be laminated so as to be in direct contact with each other, or may be laminated via another layer.

[Oxygen absorbing resin layer A (layer A)]
The oxygen-absorbing resin layer (A) is a layer containing the oxygen-absorbing resin composition. The oxygen-absorbing resin composition comprises a polyester compound containing a structural unit represented by at least one selected from the group consisting of the above general formulas (1) to (3), and a transition metal catalyst. The structural unit contained in the polyester compound is a structural unit having a tetralin ring. The oxygen-absorbing resin layer (A) may contain a material other than the oxygen-absorbing resin composition, but may be formed only of the oxygen-absorbing resin composition.

(Tetralin ring-containing polyester compound)
The polyester compound in the present embodiment contains a structural unit having at least one tetralin ring selected from the group consisting of the general formulas (1) to (3). Here, "containing a structural unit" means having one or more of the structural units in the compound. It is preferable that such a structural unit is contained as a repeating unit in the tetralin ring-containing polyester compound. When the tetraline ring-containing polyester compound is a polymer, the polyester compound may be a homopolymer of the structural unit, a random copolymer of the structural unit and another structural unit, or the above-mentioned It may be either a block copolymer of a structural unit and another structural unit.

The polyester compound containing the structural units represented by the above general formulas (1) to (3) can be obtained by polycondensing a dicarboxylic acid having a tetralin ring or a derivative thereof, and a diol or a derivative thereof.

In the polyester compound of the present embodiment, a structural unit other than the structural units represented by the general formulas (1) to (3) may be incorporated as a copolymerization component as long as the performance is not affected. Specifically, a diol or a derivative thereof or a dicarboxylic acid or a derivative thereof can be used as a copolymerization component. When the polyester compound contains a structural unit other than the structural units represented by the general formulas (1) to (3), the content of the structural units represented by the general formulas (1) to (3) in the polyester compound. Is preferably 0.01 to 50 mol%, more preferably 0.01 to 20 mol%, from the viewpoint of reducing the cost of raw materials.

Examples of the diol or a derivative thereof include propylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, and 1,4-cyclohexanedim. Examples thereof include methanol and derivatives thereof. The diol or a derivative thereof may be used alone or in combination of two or more.

Examples of the dicarboxylic acid or a derivative thereof include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanedioic acid, and benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, 2. , 6-Naphthalenedicarboxylic acids such as naphthalenedicarboxylic acids, or derivatives thereof. The dicarboxylic acid or a derivative thereof may be used alone or in combination of two or more.

The ultimate viscosity of the polyester compound in the present embodiment (measured at 25 ° C. using a mixed solvent having a mass ratio of phenol and 1,1,2,2-tetrachloroethane of 6: 4) is not particularly limited, but the polyester compound. From the viewpoint of formability, 0.7 to 1.3 dL / g is preferable, and 0.9 to 1.1 dL / g is more preferable.

The method for producing the polyester compound used in the present embodiment is not particularly limited, and any conventionally known method for producing a polyester can be applied. For example, a melt polymerization method such as a transesterification method, a direct esterification method, or a solution polymerization method can be mentioned. Among the above-mentioned methods for producing a polyester compound, the transesterification method is preferably used from the viewpoint of easy availability of raw materials.

The weight average molecular weight (in terms of polystyrene) of the polyester compound in the present embodiment is not particularly limited, but 1.0 × 10 ³ or more is preferable, and 1.0 × 10 ³ to 8. 0 × 10 ⁶ is more preferable, and 5.0 × 10 ³ to 5.0 × 10 ⁶ is particularly preferable. Similarly, the number average molecular weight (in terms of polystyrene) is not particularly limited, but 1.0 × 10 ³ or more is preferable, and 1.0 × 10 ³ to 8.0 × 10 is also preferable from the viewpoint of desired performance and handleability. ⁶ is more preferable, and 5.0 × 10 ³ to 5.0 × 10 ⁶ is particularly preferable.

The glass transition temperature (Tg ¹ ) of the polyester compound in the present embodiment is preferably 50 ° C to 160 ° C, more preferably 55 ° C to 150 ° C, and more preferably 60 ° C to 140 ° C. More preferred. When the glass transition temperature (Tg ¹ ) of the polyester compound is in the temperature range, a syringe barrel having good heat resistance and moldability can be produced.

The content of the polyester compound in the oxygen-absorbing resin composition in the present embodiment is not particularly limited, but the content of the polyester compound with respect to the total mass of the resin components constituting the layer A is preferably 1 to 30% by mass. It can be further preferably set to 1.5 to 25% by mass, and particularly preferably 2 to 20% by mass.

(Transition metal catalyst)
The transition metal catalyst used in the oxygen-absorbing resin composition of the oxygen-absorbing resin layer (layer A) is known as long as it can function as a catalyst for the oxidation reaction of the above-mentioned tetralin ring-containing polyester compound. It can be appropriately selected and used, and is not particularly limited.

Specific examples of such a transition metal catalyst include organic salts of transition metals, halides, phosphates, phosphites, nitrates, sulfates, oxides, hydroxides and the like. Here, examples of the transition metal contained in the transition metal catalyst include, but are not limited to, titanium, vanadium, chromium, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium and the like. Among these, iron, cobalt, nickel and copper are preferable. Examples of organic acids include acetic acid, propionic acid, octainoic acid, lauric acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toll acid, and olein. Examples include, but are not limited to, acids, capric acid, naphthenic acid and the like. Among these, it is preferable that the transition metal catalyst contains at least one transition metal selected from the group consisting of iron, cobalt, nickel and copper. The transition metal catalyst is preferably a combination of these transition metals and an organic acid, the transition metal is iron, cobalt, nickel or copper, and the organic acids are acetic acid, stearic acid, 2-ethylhexanoic acid and oleic acid. Alternatively, a combination of naphthenic acids is more preferred. The transition metal catalyst may be used alone or in combination of two or more.

The content ratio of the tetralin ring-containing polyester compound and the transition metal catalyst in the oxygen-absorbing resin composition of the oxygen-absorbing resin layer (layer A) depends on the type of the tetralin ring-containing polyester compound and the transition metal used and the required performance. It can be set as appropriate 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 preferably 0.0001 to 10 parts by mass as the transition metal amount with respect to 100 parts by mass of the tetralin ring-containing polyester compound. More preferably, it is 0.0002 to 2 parts by mass.

(Preparation of oxygen-absorbing resin composition)
The tetralin ring-containing polyester compound and the transition metal catalyst can be mixed by a known method, but preferably, they can be used as an oxygen-absorbing resin composition having good dispersibility by kneading with an extruder. .. Further, the oxygen-absorbing resin composition includes additives such as desiccants, pigments, dyes, antioxidants, slip agents, antistatic agents and stabilizers, and calcium carbonate, as long as the effects of the present embodiment are not impaired. Fillers such as clay, mica, and silica, deodorants, and the like may be added, but various materials can be mixed without being limited to those shown above.

The oxygen-absorbing resin composition in the present embodiment may further contain other additives such as a radical generator and a photoinitiator, if necessary, in order to promote the oxygen absorption reaction. Specific examples of the radical generator include N-hydroxyimide compounds, for example, N-hydroxysucciimide, N-hydroxymaleimide, N, N'-dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyhexahydrophthalimide, and the like. N-Hydroxytetrachloroimide, 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-hydroxyhead acidimide, N-hydroxyhymic acidimide, N-hydroxytrimetateimide, N, N-dihydroxypyromellitic acid diimide, etc. However, the present invention is not particularly limited thereto. Specific examples of the photoinitiator include, but are not limited to, benzophenone and its derivatives, thiazine dyes, metal porphyrin derivatives, and anthraquinone derivatives. As these radical generators and photoinitiators, one type may be used alone or two or more types may be used in combination.

-Other thermoplastic resins-
Further, the oxygen-absorbing resin composition in the present embodiment can be kneaded with a thermoplastic resin other than the above-mentioned polyester compound by an extruder as long as the object of the present embodiment is not impaired.
Other thermoplastic resins that can be used for kneading include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, poly-1-butene, poly-4-methyl-1-pentene, or ethylene, propylene. Polypolymers such as random or block copolymers of α-olefins such as 1-butene and 4-methyl-1-pentene, acid-modified polyolefins such as maleic anhydride graph and polyethylene and maleic anhydride graft polypropylene, ethylene-vinyl acetate Copolymers, ethylene-vinyl alcohol copolymers, ethylene-vinyl chloride copolymers, ethylene- (meth) acrylic acid copolymers and their ion crossovers (ionomers), ethylene such as ethylene methyl methacrylate copolymers- Vinyl compound copolymers, polystyrenes, acrylonitrile-styrene copolymers, styrene resins such as α-methylstyrene-styrene copolymers, polyvinyl compounds such as methyl polyacrylate and polymethyl methacrylate, nylon (registered trademark), Nylon (registered trademark) 66, Nylon (registered trademark) 610, Nylon (registered trademark) 12, Polypolymer such as polymethoxylylene adipamide (MXD6), Polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), Polytrimethylene Ethylene terephthalate (PTT), polyethylene naphthalate (PEN), glycol-modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS), polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxy alkanoate. Such as polyester, polycarbonate, polyether such as polyethylenoxide, etc., or a mixture thereof and the like can be mentioned.

[Resin layer having a thermoplastic resin (layer B)]
The resin layer B (layer B) in the present embodiment is a layer containing a thermoplastic resin. The content of the thermoplastic resin in the layer B is not particularly limited, but the content of the thermoplastic resin with respect to the total mass of the layer B is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 90. ~ 100% by mass is particularly preferable.

As the thermoplastic resin contained in the layer B in the present embodiment, any thermoplastic resin can be used and is not particularly limited. For example, examples of the thermoplastic resin include polyolefins, polyesters, polyamides, ethylene-vinyl alcohol copolymers, plant-derived resins and chlorine-based resins, which are polyolefins from the viewpoint of preserving the hydrogen peroxide solution. Is preferable.

(Polyolefin)
Specific examples of the above-mentioned polymers include polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene), polypropylene, polybutene-1, poly-4-methylpentene-1, and the like. Ethylene and α-olefin copolymer, propylene and α-olefin copolymer, ethylene-α, β-unsaturated carboxylic acid copolymer, ethylene-α, β-unsaturated carboxylic acid copolymer, ethylene- Known resins such as α, β-unsaturated carboxylic acid ester copolymers can be mentioned. Examples of preferred polyolefins include cycloolefins ring-opening polymers such as norbornene or tetracyclododecene or derivatives thereof and hydrogenated products thereof; cycloolefins such as norbornene or tetracyclododecene or derivatives thereof and ethylene or propylene. Includes those in which cyclopentyl residues or substituted cyclopentyl residues are inserted into the molecular chain by the polymerization of. Moreover, as a specific example of a preferable polyolefin, a thermoplastic norbornene-based resin or a thermoplastic tetracyclododecene-based resin can be mentioned. Examples of the thermoplastic norbornene-based resin include a ring-opening polymer of a norbornene-based monomer, a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, and an addition-type polymer of a norbornene-based monomer and an olefin. Be done. Examples of the thermoplastic tetracyclododecene-based resin include a ring-opening polymer of a tetracyclododecene-based monomer, its hydrogen additive, an addition-type polymer of a tetracyclododecene-based monomer, and a tetracyclododecene-based single. Examples thereof include an addition polymer of a monomer and an olefin. The thermoplastic norbornene-based resin is described in, for example, JP-A-3-14882, JP-A-3-122137, JP-A-4-63807, and the like.

Particularly preferable polyolefins include a copolymer made of norbornene and an olefin such as ethylene, a cycloolefin copolymer (COC) which is a copolymer made of tetracyclododecene and an olefin such as ethylene, and a cycloolefin copolymer (COC). A cycloolefin polymer (COP), which is a polymer obtained by ring-opening and polymerizing norbornene and hydrogenating it, is also preferable. Such COC and COP are described in, for example, Japanese Patent Application Laid-Open No. 5-300939 or Japanese Patent Application Laid-Open No. 5-317411.

As the cycloolefin copolymer (COC), for example, one manufactured by Mitsui Chemicals, Inc. and commercially available as Apel (registered trademark) can be used. Further, the cycloolefin polymer (COP) is commercially available, for example, manufactured by Zeon Corporation, Zeonex (registered trademark) or Zeonoa (registered trademark), Daikyo Seiko Co., Ltd., and Daikyo Resin CZ (registered trademark). You can use what you have.

The above-mentioned COC and COP have chemical properties such as heat resistance and light resistance and chemical resistance as a polyolefin resin, and physical properties such as mechanical properties, melting, flow properties, and dimensional accuracy are amorphous resins. It is the most preferable material because it shows the characteristics of.

The weight average molecular weight (in terms of polystyrene) of the thermoplastic resin contained in the resin layer (B) is not particularly limited, but 1 × 10 ⁴ to 1 × 10 ⁵ is preferable, and 2.5 × 10 is preferable from the viewpoint of reducing raw material costs. ⁴ to 7.5 × 10 ⁴ is more preferable, and 5 × 10 ⁴ to 6 × 10 ⁴ is particularly preferable. Similarly, the number average molecular weight (in terms of polystyrene) is not particularly limited, but 1 × 10 ⁴ to 1 × 10 ⁵ is preferable, and 2.5 × 10 ⁴ to 7.5 × 10 ⁴ is preferable from the viewpoint of reducing raw material costs. More preferably, 5 × 10 ⁴ to 6 × 10 ⁴ are particularly preferable.

Further, the glass transition temperature (Tg ² ) of the thermoplastic resin contained in the resin layer (B) is relative to the glass transition temperature (Tg ¹ ) of the polyester compound in the present embodiment in the above-mentioned oxygen-absorbing resin composition. It is preferably −10 to + 20 ° C, more preferably −5 to + 15 ° C, and even more preferably ± 0 to + 10 ° C. When the glass transition temperature (Tg ² ) is in the above temperature range with respect to the glass transition temperature (Tg ¹ ), it is possible to produce a molded body having a good appearance in multi-layer molding with the oxygen-absorbing resin layer (A). can.

[Other layers]
In addition to the oxygen-absorbing resin layer (A) and the resin layer (B), the prefilling syringe of the present embodiment may include any other layer depending on the desired performance and the like. Such optional other layers include, for example, an adhesive layer.
For example, in the syringe barrel of the present embodiment, when practical interlayer adhesive strength cannot be obtained between two adjacent layers, an adhesive layer (layer AD) can be provided between the two layers. The adhesive layer preferably contains a thermoplastic resin having adhesiveness. As the plasticity having adhesiveness, for example, an acid-modified polyolefin resin 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, and itaconic acid. , Polyester-based thermoplastic elastomer containing a polyester-based block copolymer as a main component. As the adhesive layer, it is preferable to use a resin obtained by modifying the thermoplastic resin and the resin from the viewpoint of adhesiveness.

[Manufacturing method of prefilling syringe of this embodiment]
(Syringe for prefill)
The method for manufacturing the prefilling syringe and the syringe barrel and the layer structure of the present embodiment are not particularly limited, and can be manufactured by an ordinary injection molding method. For example, using a molding machine equipped with two or more injection machines and an injection mold, a material constituting the oxygen-absorbing resin layer A (layer A) and a material constituting the resin layer B (layer B) are used, respectively. It is possible to manufacture a syringe barrel having a multi-layer structure corresponding to the shape of the injection mold by injecting into the cavity from the injection cylinder of the above through a mold hot runner. Further, first, the material constituting the layer B is injected from the injection cylinder, then the material constituting the layer A is simultaneously injected from another injection cylinder at the same time as the resin constituting the layer B, and then the resin constituting the layer B is injected. A cylinder barrel having a multi-layer structure of a three-layer structure B / A / B can be manufactured by injecting a required amount of the cylinder to fill the cavity.
Further, first, the material constituting the layer B1 is injected from the injection cylinder, then the material constituting the layer A is independently injected, and finally the required amount of the material constituting the layer B2 is injected to fill the mold cavity. Thereby, a syringe barrel having a multi-layer structure of a 5-layer structure B1 / A / B2 / A / B1 can be manufactured.
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 at the same time as the resin constituting the layer B1, and then the layer A is formed. The resin is injected at the same time as the resin constituting the layer B1 and the layer B2, and then the required amount of the resin constituting the layer B1 is injected to fill the cavity, thereby forming a multilayer structure of the five-stage structure layer B1 / B2 / A / B2 / B1. A syringe barrel having a structure can be manufactured.
Further, it may be molded into a desired container shape by a molding means such as extrusion molding or compression molding (sheet molding, blow molding).

The configuration of the prefill syringe of the present embodiment is not different from that of a general prefill syringe container, and as described above, it has at least a syringe barrel for filling a hydrogen peroxide solution or the like, and other syringes. It can be configured to include a cap attached to a joining portion (extracting portion) for joining an injection needle to one end of the barrel, and a gasket and a plunger for extruding a hydrogen peroxide solution or the like during use. As described above, in the syringe for prefilling of the present embodiment, the syringe barrel is an oxygen-absorbing multilayer container, and the oxygen-absorbing resin layer containing the oxygen-absorbing resin composition in at least one layer of the intermediate layer (core layer). (A) becomes (layer A), and the innermost layer and the outer layer (skin layer) become resin layers (B) (layer B) containing a thermoplastic resin.

Further, the joint portion between the syringe barrel and the needle may be molded as an integral part, or may be molded separately.

The thickness of the syringe barrel may be about 0.5 mm to 10 mm depending on the purpose and size of use. Further, the thickness may be uniform or may be partially changed. Further, another gas absorbing film or a light-shielding film may be formed on the surface for the purpose of long-term storage stability of hydrogen peroxide. As such a film and a method for forming the film, the method described in JP-A-2004-323058 can be adopted.

In the prefilling syringe of the present embodiment, the thickness of the oxygen-absorbing resin layers (A) and (layer A) is not particularly limited, but is preferably 10 to 800 μm, more preferably 20 to 700 μm, and further preferably 20 to 700 μm. It is 30 to 500 μm. When the thickness of the oxygen absorption layer is within the above range, the oxygen absorption performance is further enhanced without excessively impairing workability and economy, and it is advantageous in that the hydrogen peroxide solution can be stored for a longer period of time. be.

The prefilling syringe of the present embodiment may have a plurality of resin layers (B) (layers B) as described above, and the configurations of the plurality of layers B may be the same or different from each other. The thickness of the layer B can be appropriately determined according to the intended use, and is preferably 100 to 5000 μm, more preferably 200 to 3000 μm, and further preferably 300, from the viewpoint of ensuring various physical characteristics required for the multilayer container. It is ~ 2000 μm.

Further, although not particularly limited, the mass of the oxygen-absorbing resin layer (A) with respect to the total mass of the syringe barrel in the present embodiment is 10 to 50% by mass from the viewpoint of sufficiently exhibiting the oxygen absorption performance. Is preferable, 20 to 40% by mass is preferable, and 25 to 35% by mass is more preferable.

As described above, when an adhesive layer (layer AD) is provided between any two layers, the thickness of the adhesive layer is preferably 2 from the viewpoint of ensuring molding processability while exhibiting practical adhesive strength. It is ~ 100 μm, more preferably 5 to 90 μm, and even more preferably 10 to 80 μm.

<Gasket>
The syringe barrel of the present embodiment exhibits good airtightness, liquidtightness and slidability by combining with a suitable gasket. A conventionally known gasket can be appropriately selected and combined with the syringe barrel of the present embodiment.

As a conventionally known gasket preferably used for the syringe barrel of the present embodiment, for example, a rubber gasket called a laminated gasket can be used. As the inert film, one having excellent slidability can be used, and the inert film can be laminated on the surface of the gasket. By using the laminated gasket, it is possible to suppress the transfer of the rubber component to the chemical solution and reduce the amount of the silicone compound while maintaining the slidability.

The rubber that is the raw material of the rubber composite that constitutes the main body of the gasket includes butyl rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, natural rubber, chloroprene rubber, nitrile rubber such as acrylonitrile butadiene rubber, and hydride nitrile. Series rubber, norbornene rubber, ethylene propylene rubber, ethylene-propylene-diene rubber, acrylic rubber, ethylene / acrylate rubber, fluororubber, chlorosulphonized polyethylene rubber, epichlorohydrin rubber, silicone rubber, urethane rubber, polysulfide rubber, phosfan Zen rubber or 1,2-polybutadiene or the like is used.
One of these may be used alone, or two or more thereof may be used in combination.

<Cap>
The cap in this embodiment is attached to the dispensing portion of the syringe barrel. As the material constituting the cap, it is preferable to use a material having an oxygen permeability coefficient of 300 mL · mm / (m ² · day · atm) or less. Further, the oxygen permeability coefficient of the material constituting the cap is preferably 200 mL · mm / (m ² · day · atm) or less, more preferably 150 mL · mm / (m ² · day · atm) or less, and more preferably 100 mL · mm / (m 2 · day · atm). m ² · day · atm) or less is particularly preferable. Examples thereof include butyl rubber composed of a copolymer of isobutylene and a small amount of isoprene, bromobutyl rubber obtained by halogenating butyl rubber, and chlorobutyl rubber, and bromobutyl rubber and chlorobutyl rubber are preferable. The thickness of the cap of the portion in contact with the injection portion of the syringe barrel is preferably 300 to 20000 μm, more preferably 500 to 10000 μm, and particularly preferably 1000 to 5000 μm from the viewpoint of oxygen barrier performance. The thickness of the cap of the portion covering the opening of the injection portion of the syringe barrel is preferably 500 to 30,000 μm, more preferably 1000 to 20000 μm, and particularly preferably 2000 to 10000 μm from the viewpoint of oxygen barrier performance.

<Plunger>
The plunger in the present embodiment is attached to the gasket, and the gasket is moved by pressing the plunger. As the plunger, a plunger used for a general syringe can be used, and the structure and material thereof are not limited.

<Prefilled syringe>
As one aspect of the prefilled syringe, the syringe provided with the syringe barrel, gasket, cap and plunger described above is configured to contain the drug solution and the like, and the tip side of the barrel is opened and the injection needle is attached at the time of use. Examples include a syringe.

<< How to store a contrast medium containing a hydrogen peroxide solution >>
As a method for storing the contrast medium containing the hydrogen peroxide solution of the present embodiment, the above-mentioned prefill syringe is used. The hydrogen peroxide solution stored in the prefill syringe has a hydrogen peroxide content of 0.01 to 3.5% by mass in the final preparation, and is a contrast agent (radiosensitizer) in radiation therapy, which is a cancer treatment method. Can be used as an agent).

The hydrogen peroxide solution used as a radiosensitizer is hyaluronic acid that can be injected into the human body, or a salt or gelatin thereof, for the purpose of relieving pain at the injection site and allowing hydrogen peroxide to stay locally for a long time. , Liposomal, glyceol, etc. are mixed. Further, any other substance may be used as long as it can be injected into the body.

The conditions for storing the prefilled syringe containing the hydrogen peroxide solution are not particularly limited, and the temperature conditions may be 25 ° C, 35 ° C, 45 ° C, or 60 ° C, and the storage period is 1 week or 2 It may be weekly, 3 weeks or 4 weeks, or 4 weeks or more.

(Sterilization)
In the storage method of the present embodiment, the medical multi-layer container (each member constituting the prefilling syringe) and the stored object can be sterilized in a form suitable for the stored object before filling the stored object. .. Sterilization methods include hot water treatment at 100 ° C or lower, heated hot water treatment at 100 ° C or higher, high temperature heat sterilization at 121 ° C or higher, electromagnetic wave sterilization such as ultraviolet rays, microwaves, gamma rays, and electrons, and gas treatment such as ethylene oxide. , Chemical solution sterilization such as hydrogen peroxide and hypochlorite.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, and treatment procedures shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 1]
<Example of Monomer Synthesis>
An autoclave having an internal volume of 18 L was charged with 350 g (50% by mass of water-containing product) of a catalyst in which 2.20 kg of dimethyl naphthalene-2,6-dicarboxylate, 11.0 kg of 2-propanol and 5% palladium were supported on activated carbon. Next, the air in the autoclave was replaced with nitrogen, the nitrogen was further replaced with hydrogen, and then hydrogen was supplied until the pressure in the autoclave became 0.8 mPa. Next, the stirrer was started, the rotation speed was adjusted to 500 rpm, the internal temperature was raised to 100 ° C. over 30 minutes, and then hydrogen was further supplied to set the pressure to 1 mPa. After that, the supply of hydrogen was continued so as to maintain 1 mPa in response to the pressure drop due to the progress of the reaction. Since the pressure drop disappeared after 7 hours, the autoclave was cooled, unreacted residual hydrogen was released, and then the reaction solution was taken out from the autoclave. After filtering the reaction solution and removing the catalyst, 2-propanol was evaporated from the separation filtrate by an evaporator. To the obtained crude product, 4.40 kg of 2-propanol was added and purified by recrystallization to obtain dimethyl tetralin-2,6-dicarboxylate in a yield of 80%. The purified tetralin-2,6-dicarboxylic acid dimethyl had a melting point of 77 ° C. The results of NMR analysis are as follows. 1H-NMR (400mhz cdcl3) δ7.76-7.96 (2H m), 7.15 (1H d), 3.89 (3H s), 3.70 (3H s), 2.70-3.09 (5H m), 2.19-2.26 (1H m), 1.80-1.95 (1H m)

<Polymer production example>
The tetralin-2,6-dicarboxylic acid obtained in the above-mentioned monomer synthesis example in a polyester resin manufacturing apparatus equipped with a filling tower type rectification column, a demultiplexer, a cold wrap, a stirrer, a heating device and a nitrogen introduction tube. 543 g of dimethyl, 217 g of ethylene glycol, 0.038 g of tetrabutyl titanate, and 0.15 g of zinc acetate were charged, and the mixture in the apparatus was heated to 230 ° C. in a nitrogen atmosphere to perform a transesterification reaction. After setting the reaction pass-through rate of the dicarboxylic acid component to 90% or more, the temperature was gradually raised and reduced over 90 minutes, and then polycondensation was carried out at 275 ° C. and 133 Pa or less for 1 hour to obtain a tetralin ring-containing polyester compound (a tetralin ring-containing polyester compound. Hereinafter, it is also simply referred to as “polyester compound”).

As a result of measuring the glass transition temperature and the melting point of the obtained polyester compound by DSC (differential scanning calorimetry), the glass transition temperature was 69 ° C., and the melting point was not recognized because it was amorphous. The ultimate viscosity was 0.98 dL / g. The polystyrene-equivalent weight average molecular weight of the obtained polyester compound was 2.8 × 10 ⁴ , and the number average molecular weight was 2.8 × 10 ⁴ . The ultimate viscosity was measured according to the following.
<Measurement of ultimate viscosity>
Measurements were carried out based on JIS K7367-5: 2000 "Plastic-How to determine the viscosity of a polymer diluted solution using a capillary viscometer-Part 5: Thermoplastic (TP) homopolymers and copolymers". Specifically, the flow time of a solvent (phenol / 1,1,2,2-tetrachloroethane) and a solution of 0.005 g / ml polymer at 25 ° C. was measured by the method described in JIS K7337-5: 2000, and these were measured. The viscosity number was calculated based on the measurement result of the above and the applied polymer concentration.

<Production example of oxygen-absorbing resin composition>
A mixture obtained by dry blending cobalt (II) stearate with a cobalt content of 0.025 parts by mass with respect to 100 parts by mass of the polyester compound obtained from the above, and having two screws having a diameter of 37 mm 2 Oxygen absorption having an oxygen absorption function is performed by supplying the shaft extractor at a rate of 15 kg / h, performing melt kneading under the condition of a cylinder temperature of 290 ° C., extruding the strands from the extruder head, cooling, and then pelletizing. A sex resin composition was obtained. The oxygen absorption rate of the obtained oxygen-absorbing resin composition was 1.2 mL / g / 56 days. The oxygen absorption rate was measured according to the following.

<Measurement of oxygen absorption rate of oxygen-absorbing resin>
An oxygen-absorbing resin film having a thickness of 200 μm and a 10 cm square was prepared using the oxygen-absorbing resin composition, and a gas barrier bag made of an aluminum foil laminated film was used to reduce the temperature inside the bag to 90% (RH: relative humidity). Three oxygen-absorbing resin films were sealed together with 200 ml of air and stored at 23 ° C. The amount of oxygen absorbed per 1 g of the film for 56 days from the start of storage was measured, and the amount of oxygen absorbed per 56 days was taken as the oxygen absorption rate.

<Manufacturing example of syringe barrel>
Under the following conditions, the material constituting the resin layer (B) (layer B) is injected from the injection cylinder, and then the material constituting the oxygen-absorbing resin layer (A) (layer A) is layered from another injection cylinder. By injecting at the same time as the resin constituting B and then injecting a required amount of the resin constituting layer B to fill the cavity in the injection mold, an injection molded product having a three-layer structure of B / A / B is manufactured. bottom. Then, the injection-molded article was cooled to a predetermined temperature, transferred to a blow mold, and then blow-molded to manufacture a syringe barrel. The mass of layer A was 30% by mass of the total mass of the syringe barrel. The thickness of the layer A was 45 μm, and the thickness of each layer B was 350 μm.
A cycloolefin polymer (manufactured by Nippon Zeon Corporation, product name: "ZEONEX (registered trademark) 5000" was used as the resin constituting the layer B. The resin constituting the layer A was the above-mentioned oxygen-absorbing resin composition. I used a thing.

(Shape of syringe barrel)
The content was 1 ml (Long) according to ISO11040-6. An injection blow integrated molding machine (manufactured by Nissei ASB Machinery Co., Ltd. Model: ASB12N / 10T) was used to manufacture the syringe barrel.

(Molding conditions for syringe barrel)
-Injection cylinder temperature for oxygen-absorbing resin layer (A) (layer A): 260 ° C.
-Injection cylinder temperature of resin layer (B) (layer B): 260 ° C.
・ Resin flow path temperature in injection molding: 260 ° C
・ Mold temperature: 18 ℃

<Preservation test of hydrogen peroxide solution>
Hydrogen peroxide using a syringe barrel (Example 1) having a three-layer structure having an oxygen-absorbing resin layer (A) and a resin layer (B) made of a cycloolefin polymer (COP) obtained from the above-mentioned production example. A storage test of the solution was carried out. The results are shown in Table 1.

(Contents of preservation test)
1 mL of a hydrogen peroxide solution having a hydrogen peroxide concentration of 2.5 to 3.5% was placed in a syringe barrel and sealed using a stopper. Then, the moving distance of the stopper was measured in a dark place and after storage at 60 ° C. for 30 days under light irradiation using two 27 W fluorescent lamps as a light source.

[Comparative Example 1]
The same test as in Example 1 was carried out except that the syringe barrel was a glass syringe containing silicon, oxygen, carbon, hydrogen and fluorine on the inner surface of the container. The results are shown in Table 1.

[Comparative Example 2]
The same test as in Example 1 was carried out except that the syringe barrel was a single-layer syringe made of cycloolefin polymer (COP: manufactured by Nippon Zeon Corporation, product name: "ZEONEX (registered trademark) 5000"). The results are shown in Table 1.

[Comparative Example 3]
The same test as in Example 1 was carried out except that the syringe barrel was a single-layer syringe made of a cycloolefin copolymer (COC: manufactured by Mitsui Chemicals, Inc., product name "Apel (registered trademark)"). The results are shown in Table 1.

As shown in Table 1, as a result of leaving the syringe in a dark place at 60 ° C. for 30 days, the glass syringe (Comparative Example 1) was 0.75 mm, the COP single-layer syringe was 0.45 mm (Comparative Example 2), and COC. 0.53 mm for a single-layer syringe (Comparative Example 3), 0 mm for a three-layer structure syringe (B) having an oxygen-absorbing resin layer (A) and a resin layer (B) made of a cycloolefin polymer (COP). The movement of the plunger was confirmed.

As a result of the above, the syringe of Example 1 was more decomposed by hydrogen peroxide than the syringes of Comparative Examples 1 to 3 (glass syringe, COP single layer syringe, COC single layer syringe) in the storage result in a dark place. It was found that the extrusion of the plunger was suppressed.

Further, as a result of light irradiation and leaving in an environment of 60 ° C. for 30 days, the glass syringe (Comparative Example 1) was 0.90 mm, the COP single-layer syringe (Comparative Example 2) was 0.54 mm, and the COC single-layer syringe (Comparative Example 2). In Comparative Example 3), it was confirmed that the plunger was pushed back by 0.63 mm, and in the oxygen-absorbing resin and the 3-layer syringe made of COP (Example 1), the plunger was pushed back by 0 mm.

In Comparative Examples 1 to 3, the moving distance of the storage result under light irradiation was larger than that of the storage result in a dark place. Therefore, hydrogen peroxide decomposition by ultraviolet rays is promoted in the syringes of these Comparative Examples. Was shown. On the other hand, in the syringe of Example 1, the extrusion distance was 0 mm even in the storage result under light irradiation.
As a result of the above, the syringe having a three-layer structure (Example 1) having the oxygen-absorbing resin layer (A) and the resin layer (B) made of the cycloolefin polymer (COP) is a syringe of the comparative example (glass syringe, COP). It was found that the decomposition of hydrogen peroxide by ultraviolet rays can be suppressed more than that of a single-layer syringe made of COC (single-layer syringe made of COC).

10 ... Syringe barrel, 12 ... Cylindrical body, 12A-12C ... Inner surface, 14 ... Dispensing part, 16
... Insert, 20 ... Gasket, 30 ... Plunger, 40 ... Cap, 100 ... Syringe

Claims (10)

A syringe for prefilling
An oxygen-absorbing resin layer (A) containing an oxygen-absorbing resin composition containing a polyester compound and a transition metal catalyst, and a resin layer (B) containing a thermoplastic resin, and at least the resin layer (B). ) Provided a syringe barrel having a multilayer structure laminated on both sides of the oxygen-absorbing resin layer (A).
A syringe for prefilling, wherein the polyester compound contains a structural unit represented by at least one selected from the group consisting of the following general formulas (1) to (3).

The prefilling syringe according to claim 1, wherein the transition metal catalyst comprises at least one transition metal selected from the group consisting of iron, cobalt, nickel and copper. The prefilling syringe according to claim 1 or 2, wherein the transition metal catalyst contains 0.0001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the polyester compound. The syringe for prefill according to any one of claims 1 to 3, wherein the thermoplastic resin is polyolefin. A method for storing a contrast medium containing a hydrogen peroxide solution using the prefilling syringe according to any one of claims 1 to 4. A prefilled syringe in which a hydrogen peroxide solution is contained in the prefill syringe according to any one of claims 1 to 4. A syringe barrel used for prefilling syringes.
An oxygen-absorbing resin layer (A) containing an oxygen-absorbing resin composition containing a polyester compound and a transition metal catalyst, and a resin layer (B) containing a thermoplastic resin, and at least the resin layer (B). ) Is provided on both sides of the oxygen-absorbing resin layer (A) to provide a syringe barrel having a multi-layer structure.
A syringe barrel in which the polyester compound contains a structural unit represented by at least one selected from the group consisting of the following general formulas (1) to (3).

The syringe barrel according to claim 7, wherein the transition metal catalyst contains at least one transition metal selected from the group consisting of iron, cobalt, nickel and copper. The syringe barrel according to claim 7, wherein the transition metal catalyst contains 0.0001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the polyester compound. The syringe barrel according to any one of claims 7 to 9, wherein the thermoplastic resin is polyolefin.

Images