TW201334824A - Production method for pre-filled syringe outer tube and production method for injection molding mold - Google Patents

Abstract

Provided is a technology for the production of an outer tube for a pre-filled syringe having high transparency and produced by using a cyclic olefin resin as a raw material therefor. In a method for producing an outer tube for a pre-filled syringe formed by injection molding of a cyclic olefin resin composition, an injection molding mold is used, as a mold for injection molding, that has: a surface roughness (Rz) (ten-point average roughness) of a core configuring the injection molding mode of no more than 50 [mu]m; a lubricating hard film formed that includes at least one type of element selected from Ti, Cr, Zr, C, Al, and Ni; and a polished surface on the lubricating hard film.

Description

Method for producing outer cylinder for prefilled syringe and method for manufacturing injection molding die

The present invention relates to a method for producing an outer cylinder for a prefilled syringe, and a method for producing an injection molding mold which can be used in the production method.

A conventional syringe has been used by a method of sucking up a drug at the time of use. However, this method of use is prone to human error in the efficiency of the operation or the filling failure of the drug. Thus, recently, it has been preferred to use a prefilled syringe that is prefilled with a prescribed amount of prescribed medicament.

The material constituting the prefilled syringe is preferably a resin from the viewpoints of ease of handling such as being lightweight, not easily broken, and the like. However, the heat resistance of the prefilled syringe-based polypropylene which is produced by using polypropylene which is produced by a general syringe is low, and therefore, there is a problem that deformation occurs due to sterilization of water vapor before filling the chemical.

Further, the chemical resistance of the resin is insufficient due to the type of the resin to be used. As a result, in the storage of the prefilled syringe, the component contained in the resin is dissolved in the drug. Further, when the water vapor barrier property of the prefilled syringe is lowered, the moisture contained in the drug is volatilized during storage.

For this reason, it is limited to the resin which can be used as a raw material of a prefilled syringe, and the series of the resin which can be used, for example, the aromatic vinyl type polymer of the patent document 1 is mentioned.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-164887

However, the cyclic olefin resin is known to be a resin which is excellent in heat resistance, chemical resistance, and water vapor barrier properties. Further, since the cyclic olefin resin also has good transparency, when a prefilled syringe is produced by using a cyclic olefin resin, the effect of easily identifying the drug is also obtained.

The inventors of the present invention have attempted to manufacture an outer cylinder for a prefilled syringe using a cyclic olefin resin as a raw material for the purpose of improving the performance of a prefilled syringe made of a resin, and the transparency of the outer cylinder for prefilled syringe manufactured is changed. It is not good, and there is a problem in formability.

The present invention has been made to solve the above problems, and an object of the invention is to provide a technique for producing an outer cylinder for a prefilled syringe having high transparency by efficiently producing a cyclic olefin resin as a raw material.

In order to solve the above-mentioned problems, the inventors of the present invention have studied the use of a cyclic olefin resin as a raw material and manufactured an outer cylinder for a prefilled syringe having high transparency. turn out: The surface roughness of the core portion (movable side) constituting the injection molding die for forming the outer cylinder for pre-filling the syringe is within a specific range and a specific lubricious hard film is formed on the surface of the core portion and ground. In the case of the surface of the lubricious hard film, an outer cylinder for prefilled syringes having a very high transparency is obtained, so that the present invention has been completed. More specifically, the present invention provides the following.

(1) A method for producing a pre-filled syringe outer cylinder, which is a method for producing an outer cylinder for pre-filling a syringe which is formed by injection molding a cyclic olefin resin composition, and which constitutes a core portion of an injection molding die The surface roughness Rz (ten-point average roughness) is 50 μm or less, and a lubricative hard film containing at least one element selected from the group consisting of Ti, Cr, Zr, C, Al, and Ni is formed and the surface of the lubricious hard film is polished. The injection molding die is used, and the light transmittance of the light beam having a wavelength of 450 nm which is vertically incident on the side wall of the outer cylinder for prefilling the syringe passes through the side wall is 70% or more.

(2) The method for producing a pre-filled syringe outer cylinder according to the first aspect of the invention, wherein the lubricative hard film is made of diamond-like carbon (DLC), CrN, TiN, TiC, TiCN, TiAlN, TiCrN It is composed of AlCrN, ZrN or Ni.

(3) The method for producing a pre-filled syringe outer cylinder according to the first or second aspect of the invention, wherein the core of the injection molding die has a mold release slope of substantially 0 degrees.

(4) A method for producing an injection molding die for producing an injection molding die for producing an injection molding die for prefilling a syringe, comprising: forming a surface of a core portion of the injection molding die Roughness Rz becomes a core surface roughness adjustment process of 50 μm or less; for the core portion after the adjustment process, a lubricative hard film containing a lubricative hard film of at least one element selected from Ti, Cr, Zr, C, Al, and Ni is formed Forming a process; and grinding a surface of the surface of the aforementioned lubricious hard film.

According to the present invention, a cyclic olefin resin can be used as a raw material, and an outer cylinder for a prefilled syringe having high transparency can be efficiently produced.

1‧‧‧Prefilled syringe

10‧‧‧Prefilled syringe outer cylinder

20‧‧‧Intubation

30‧‧‧Plunger

101‧‧‧Attraction

102‧‧‧Flange

201‧‧ ‧block

Fig. 1 is a view schematically showing a prefilled syringe, Fig. 1(a) is a perspective view, and Fig. 1(b) is a MM sectional view of Fig. 1(a).

Fig. 2(a) is a view showing the dimensions of the outer cylinder for the prefilled syringe manufactured in the embodiment, and Fig. 2(b) is a view showing the positions of the gate, the runner, and the gate in the mold.

Fig. 3 is a schematic view for explaining a method of measuring light transmittance.

Hereinafter, embodiments of the present invention will be described. Further, the present invention is not limited to the following embodiments.

The present invention is a method of manufacturing an outer cylinder for prefilling a syringe. The shape of the outer cylinder for the prefilled syringe manufactured by the present invention is not particularly limited. First, a general prefilled syringe using the outer cylinder for prefilled syringe of the present invention will be briefly described using the drawings.

<Prefilled syringe>

Figure 1 is a diagram schematically showing a prefilled syringe. The prefilled syringe 1 includes an outer cylinder 10 for prefilling the syringe, a cannula 20 coupled to one end of the outer cylinder 10 for prefilling the syringe, and a freely retractable insertion from the other end of the outer cylinder 10 for prefilling the syringe. The plunger 30 inside the outer cylinder 10 for pre-filling the syringe is pre-filled.

At one end of the prefilled syringe outer cylinder 10, a suction portion 101 for connecting to the cannula 20 is formed, and at the other end, a flange 102 is formed. Further, the internal space of the outer cylinder 10 for prefilling the syringe is a space for storing the medicine for the medicine. Starting from the opening of the outer cylinder 10 for the prefilled syringe on the side of the flange 102, the plunger 30 is inserted. Further, as shown in Fig. 1(b), the mold release slope of the inner wall surface of the prefilled syringe outer cylinder 10 is made θ.

The cannula 20 is a stopper 201 having an end portion, and the stopper 201 is coupled to the cannula portion 20 and the prefilled syringe outer cylinder 10 by being fitted to the suction portion 101 described above.

The plunger 30 is inserted into the drug storage space so as to be freely retractable from the end of the outer cylinder 10 for prefilling the syringe, as described above. At the time of storage of the prefilled syringe, the end portion of the plunger 30 is in a state of being in contact with the medicine in the drug storage space.

Next, the method of manufacturing the outer cylinder for prefilling the syringe will be briefly described. After being stored in the prefilled syringe 1 for a predetermined period of time, the plunger 30 is pushed into the outer cylinder 10 for pre-filling the syringe to reduce the volume of the drug storage space. At the same time, the medicament is squeezed out by the suction portion 101, and the extruded medicine is passed through the cannula 20. Leave inside to the outside of the prefilled syringe.

As described above, the prefilled syringe 1 is stored in a state in which the drug is stored inside for a predetermined period of time. Therefore, in the state in which the outer cylinder 10 for pre-filling the syringe is made of a material having a low water vapor permeability, the problem of moisture contained in the medicine and leaving to the outside occurs.

In addition, when the drug is stored in the inside of the prefilled syringe 1 for a long period of time, the drug continues to be in contact with the inner wall surface of the prefilled syringe outer tube 10 for a long period of time. Therefore, in a state in which the chemical resistance of the material constituting the outer cylinder 10 for prefilling the syringe is lowered, a problem that the decomposition product of the material or the like is dissolved in the medicine occurs.

The pre-filled syringe outer cylinder 10 obtained by the production method of the present invention is composed of a cyclic olefin resin composition described later. In the cyclic olefin resin composition, the chemical resistance of the cyclic olefin resin and the water vapor barrier property are exhibited. Therefore, in the state in which the outer cylinder for the prefilled syringe is produced by using the cyclic olefin resin composition, it does not occur. The aforementioned problem.

However, in an attempt to manufacture a pre-filled outer cylinder for a syringe by using a cyclic olefin resin composition, there is a problem that the outer cylinder for the prefilled syringe does not have sufficient transparency.

In addition, when the outer cylinder for prefilled syringe is manufactured using the cyclic olefin resin composition as a raw material, since the hardness of the cyclic olefin resin is inherent, it is not easy to take out the prefilled syringe by the mold at the time of manufacture. Use the outer tube. At the time of manufacture, the problem that the outer cylinder for prefilling the syringe is not easily taken out by the mold is attached to the inner surface of the outer cylinder, and scratches occur, which is also related to a decrease in transparency and a decrease in productivity.

According to the present invention, since the outer cylinder for prefilling the syringe is manufactured by the following method, the transparency of the outer cylinder for the prefilled syringe which is produced by using the cyclic olefin resin can be improved.

In particular, if the production is carried out under the ideal conditions of the present invention, the outer cylinder for prefilling the syringe can be easily taken out by the mold at the time of manufacture, and the productivity of the outer cylinder for the high-quality prefilled syringe can be improved.

<Method of Manufacturing Outer Tube for Prefilled Syringe>

The method for producing an outer cylinder for a prefilled syringe according to the present invention is a method for producing an outer cylinder for a prefilled syringe which is formed by injection molding a cyclic olefin resin composition.

In the production method of the present invention, the surface roughness Rz of the core portion constituting the injection molding die is 50 μm or less, and a lubricative hard material containing at least one element selected from Ti, Cr, Zr, C, Al, and Ni is formed. A core portion formed by a film for injection molding on the surface of a film and a lubricated hard film. The core portion constituting the injection molding die can be produced in any manner. For example, a core portion of the injection molding die manufactured by the following method can be used.

[Method of Manufacturing the Core of the Mold for Injection Molding]

An example of a method for producing a core portion of a mold for injection molding is a series of manufacturing methods having the following processes (i) to (iii).

(i) A core surface roughness adjustment process in which the surface roughness Rz of the core portion constituting the injection molding die is 50 μm or less.

(ii) forming, for the surface of the core after the adjustment process, at least one element selected from the group consisting of Ti, Cr, Zr, C, Al, and Ni A lubricious hard film forming process for a slippery hard film.

(iii) a grinding process for grinding the surface of the aforementioned lubricious hard film.

The core surface roughness adjustment process of (i) is, for example, a process of grinding a core surface using an abrasive material of 2000 or more in JISR6010 of a particle size count. Here, the larger the particle size count of the abrasive material and the smaller the surface roughness Rz, the smaller the particle size count and the larger the surface roughness Rz. Therefore, the surface roughness Rz can be adjusted by appropriately adjusting the particle size count of the abrasive. Further, the specific method at the time of polishing is not particularly limited, and examples thereof include a method of using a polishing body such as diamond paper, or a polishing material (mixture) using a liquid material and a polishing body called a polishing wheel made of a cloth or sponge. Method, air grinding, lathe, or a method of combining these methods, and the like.

In the lubricative hard film forming process of (ii), a lubricative hard film containing at least one element selected from the group consisting of Ti, Cr, Zr, C, Al, and Ni is formed on the surface after the process of (i). In the present invention, a lubricative hard film composed of pseudo diamond carbon (DLC), CrN, TiN, TiC, TiCN, TiAlN, TiCrN, AlCrN, ZrN or Ni is preferred.

As a series of methods for forming a lubricative hard film on the surface of the core, for example, a deposition method is used. The gas phase method is preferably a CVD method such as a plasma CVD (Chemical Vapor Deposition) method using a DC power source, an AC power source, or a high-frequency power source as a power source, and AIP (Arc Ion Plating). : PVD (Physical Vapor Deposition) method such as PVD method, sputtering method such as magnetron sputtering method, ion beam sputtering method, and ionization vapor deposition method. In addition, in Ni, etc. In the state, a wet method such as electrolytic plating or electroless plating is listed. These lubricious hard film systems may be a single layer or a plurality of layers.

The film surface roughness adjustment process in (iii) is a process for polishing the surface of the lubricious hard film. Next, the surface roughness Rz of the surface of the lubricative hard film after polishing is preferably 40 μm or less. The polishing method is not particularly limited, and a method of using a polishing body such as diamond paper or a method of using a liquid-like abrasive (mixture) and a cloth or sponge called a polishing body for a polishing wheel, air grinding, or a lathe can be used. Or a method of combining these methods or the like. Further, in order to prevent the lubricating hard film from being peeled off during polishing, it is preferable to use diamond paper.

[The core part of the mold for injection molding]

As described above, in the present invention, a lubricative hard film containing at least one element selected from the group consisting of Ti, Cr, Zr, C, Al, and Ni is formed on the surface having a surface roughness Rz of 50 μm or less, and the lubricity is polished. The surface of the hard film.

In order to obtain a pre-filled syringe outer cylinder which has high transparency and is easily taken out by a mold immediately after the production, the reason for reducing the surface roughness of the inner surface of the outer cylinder is that the surface roughness Rz must be A surface of 50 μm or less forms a lubricious hard film.

Further, since the friction coefficient of the surface of the lubricative hard coating film is smaller than the surface of the core portion, the lubricative hard film is formed on the surface of the core portion, and it is easy to take out the prefilled syringe by the mold immediately after the manufacture. cylinder. However, if the surface of the hard lubricious hard film is not provided, the fine protrusions on the surface which is formed when the lubricative hard film is formed are taken out by the mold. When the outer cylinder for the syringe is prefilled, there is a state in which the inner wall of the outer cylinder for the prefilled syringe is damaged. Therefore, in order to produce an outer cylinder for a prefilled syringe having a very high transparency, it is necessary to polish the surface of the lubricious hard film even in a state where the surface roughness Rz of the lubricative hard film is small.

However, when the surface roughness Rz of the lubricative hard film after polishing is excessively large, the transparency of the outer cylinder for the prefilled syringe is lowered. Therefore, the surface roughness of the lubricious hard film after polishing is preferably 40 μm or less.

<Ring olefin resin composition>

This will be described as a cyclic olefin resin composition for pre-filling the outer tube raw material for a syringe. The cyclic olefin resin composition contains a cyclic olefin resin.

The cyclic olefin resin is a cyclic olefin component and is not particularly limited as long as it is a polyolefin resin containing a cyclic olefin component in the main chain. For example, an addition polymer of a cyclic olefin or a hydrogen additive thereof, an addition copolymer of a cyclic olefin and an α-olefin, or a hydrogen additive thereof may be mentioned.

Further, the cyclic olefin resin is a polymer comprising the above-mentioned polymer, and further includes grafting and/or copolymerization of an unsaturated compound having a polar group.

Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amine group, a decylamino group, an ester group, a hydroxyl group, a sulfo group, a phosphorus group, a phosphino group, and the like. Examples of the unsaturated compound having a polar group include ( Methyl)acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1 to 10), cis Alkylene dialkyl (Carbon number 1 to 10) ester, (meth) acrylamide, (meth) acrylate 2-hydroxyethyl, etc., preferably a carboxyl group, an acid anhydride group, an epoxy group, an amine group, a decylamino group, Ester group, hydroxyl group, sulfo group, phosphorus group, phosphino group.

The cyclic olefin resin is preferably an addition copolymer of a cyclic olefin and an α-olefin or a hydrogen additive thereof.

Further, as the cyclic olefin resin which is a copolymer component and which contains a cyclic olefin component, a commercially available resin can also be used. The cyclic olefin resin which is commercially available, for example, TOPAS (registered trademark) (manufactured by Topas Advanced Polymers Co., Ltd.), apel (registered trademark) (manufactured by Mitsui Chemicals, Inc.), ZEONEX (registered trademark) (manufactured by Japan ZEON Co., Ltd.), ZEONOR (registered trademark) (manufactured by Japan ZEON Co., Ltd.), ARTON (registered trademark) (manufactured by JSR Corporation), and the like.

Examples of the addition copolymer of a cyclic olefin and an α-olefin include [1] an α-olefin component having 2 to 20 carbon atoms and [2] a cyclic olefin component represented by the following general formula (I). The copolymer is a particularly desirable example.

(In the chemical formula, R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be integrated. A divalent hydrocarbon group is formed, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. Further, n represents 0 or a positive integer, and in the state where n is 2 or more, R ⁵ to R ⁸ are It can be the same or different in each repeating unit.)

The [1] α-olefin component having 2 to 20 carbon atoms will be described. The α-olefin having 2 to 20 carbon atoms is not particularly limited. For example, the same as the same as Japanese Patent Laid-Open No. 2007-302722 can be cited. Further, these α-olefin components may be used alone or in combination of two or more. Among these, the best ideal is to use ethylene alone.

The cyclic olefin component represented by the general formula (I) will be described in [2]. The R ¹ to R ¹² groups of the formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.

Specific examples of R ¹ to R ⁸ include a hydrogen atom; a halogen atom such as fluorine, chlorine or bromine; and a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; these may be different. They may also be partially different, or they may all be the same.

Further, specific examples of R ⁹ to R ¹² include a hydrogen atom; a halogen atom such as fluorine, chlorine or bromine; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, and the like. An alkyl group such as a stearyl group; a cycloalkyl group such as a cyclohexyl group; a substituted or unsubstituted aromatic hydrocarbon group such as a phenyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group or a fluorenyl group; The group, the phenethyl group, the aralkyl group which substitutes the aryl group in other alkyl groups, etc. may be different, may be partially different, or may be all the same.

Specific examples of the state in which R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrally formed to form a divalent hydrocarbon group include an alkylidene group such as an ethylidene group, a propylidene group or an isopropylidene group.

In a state in which R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the ring system formed may be a single ring, a polycyclic ring, or a polycyclic ring having cross-linking, or may have The ring of double bonds, and may also be a ring composed of a combination of these rings. Further, these ring systems may have a substituent such as a methyl group.

Specific examples of the cyclic olefin component represented by the general formula (I) include the same ones as those disclosed in JP-A-2007-302722.

These cyclic olefin components may be used alone or in combination of two or more. Among these, it is preferred to use a bicyclo[2.2.1]hepta-2-olefin (common name: raw spinane) alone.

[1] The α-olefin component having 2 to 20 carbon atoms and [2] the polymerization method of the cyclic olefin component represented by the formula (I) and the hydrogen addition method of the obtained polymer are not particularly limited, and may be Follow the conventional method. It may be a random copolymerization or a block copolymerization, but it is preferably a random copolymerization.

In addition, the polymerization catalyst to be used is not particularly limited, and it is possible to use a Ziegler-Natta system, a metathesis system, an aromatic cycloolefin metal derivative catalyst, and the like. A conventional olefin-based resin is obtained by a conventional method.

Next, the other copolymerization components will be briefly described. The cyclic olefin-based resin (A) may be in addition to the above-mentioned [1] α-olefin component having 2 to 20 carbon atoms and [2] a cyclic olefin component represented by the general formula (I). Other copolymerizable unsaturated monomer components are contained as needed in the range which does not impair the object of the present invention.

The unsaturated single system which can be arbitrarily copolymerized is not particularly limited, and examples thereof include a hydrocarbon-based monomer containing two or more carbon-carbon double bonds in one molecule. Specific examples of the hydrocarbon-based monomer containing two or more carbon-carbon double bonds in one molecule are the same as those in JP-A-2007-302722.

In the state in which the above-mentioned cyclic olefin resin is used, the outer cylinder for prefilling the syringe is hardened. Therefore, even in the state where the mold release slope (the θ in Fig. 1(b)) becomes smaller in the inner wall surface of the outer cylinder for the prefilled syringe, if the mold release slope becomes substantially zero, it is also used. It is a hindrance when the plunger is pressed and the drug in the outer cylinder for the syringe is pre-filled. Further, the mold release slope of the inner wall surface is 0 degree, and the mold release slope of the core portion constituting the injection molding die is substantially 0 degree.

In the state in which the outer cylinder for the prefilled syringe is manufactured by using the resin, in order to easily take out the outer cylinder for the prefilled syringe immediately after the manufacture, the mold release slope of the inner wall of the outer cylinder for prefilling the syringe is the most The good thing is that it does not become zero in substance. However, if the above-described mold is used, even in the state where the above-described mold release slope is substantially zero, it is easy to take out the outer cylinder for prefilled syringe immediately after the manufacture by the mold.

Here, the above-described mold release slope is substantially zero and the mold release slope is in a state of 0.5 degrees or less. Then, in a state where the mold release slope is 0.5 degrees or less, the above-described problem that it is not easy to take out occurs.

In addition, the cyclic olefin resin composition can be used without damaging the present The range of the effects of the invention includes components other than the cyclic olefin resin. Examples of other components include other resins, inorganic fillers, nucleating agents, pigments, oxidation inhibitors, stabilizers, plasticizers, slip agents, release agents, and the like.

<Method of Manufacturing Outer Tube for Prefilled Syringe>

The outer cylinder for a prefilled syringe of the present invention is produced by an injection molding method. The production conditions for the injection molding are not particularly limited, and are appropriately set in accordance with the cyclic olefin resin composition to be used.

<For outer cylinder for prefilled syringe>

The outer cylinder for a prefilled syringe manufactured by the production method of the present invention has a high degree of transparency. Specifically, the light transmittance at the wavelength of 450 nm which is perpendicularly incident on the side wall of the outer cylinder for prefilled syringe is 70% or more.

Further, the larger the surface area of the outer cylinder for prefilling the syringe, the more difficult it is to take out the outer cylinder for the prefilled syringe immediately after manufacture by the mold. The length L of the outer cylinder for the prefilled syringe is usually 30 mm or more and 150 mm or less, and the inner diameter R of the outer cylinder for the prefilled syringe is usually 2 mm or more and 50 mm or less.

[Examples]

In the following, the present invention will be more specifically described based on the examples, but the present invention is not limited by these examples.

[Mold for injection molding]

In the present embodiment, an outer cylinder for a prefilled syringe of the shape shown in Fig. 1 was produced. The size of the outer cylinder for the prefilled syringe is shown in Fig. 2(a). Further, as shown in Fig. 2(a), the mold release slope of the inner wall surface of the outer cylinder for the prefilled syringe manufactured in the example was 0 degree.

The mold having the cavity of the shape of the outer cylinder for prefilling the syringe described above includes a gate, a runner and a gate of the shape shown in Fig. 2(b). The position G of the gate is also shown in Figure 2(a). Further, as shown in Fig. 2(b), the diameter of the gate, the length of the runner, and the diameter of the gate are 4.0 mm, 20 mm, and 3.0 mm, respectively. Next, as shown in Fig. 2(b), three injection turbines (PINs 1 to 3) are provided at the connection point of the gate and the runner, and the connection point between the runner and the gate. Further, a pressure sensor ("9223A", manufactured by Kistler Co., Ltd., Japan) for measuring the mold release resistance is connected to the injection turbine indicated by PIN1. The data obtained by the pressure sensor was converted using an industrial load amplifier ("5073A", manufactured by Kistler, Japan), and the converted data can be monitored by DATAFLOW Light II (manufactured by Kistler Co., Ltd., Japan).

Next, the mold of the surface was prepared by the conditions shown in Table 1. The "number of particles" in Table 1 indicates the particle size count of the abrasive material used to treat the surface of the core. Examples 1 to 3 and Comparative Examples 1 to 5 were air-polished by using diamond abrasive grains, and Example 4 and Comparative Examples 6 to 8 were polished by a lathe using a diamond paste. In addition, the "coating" of Table 1 shows the kind of the lubricious hard film formed in the surface of the surface-treated core part. In the present embodiment, a lubricative hard film is formed by electroless plating in the state of Ni, and a lubricative hard film is formed by the PVD method in the state of CrN and TiN, and in the state of DLC, A lubricative hard film is formed by ionization vapor deposition. Further, in Example 1, the surface of the lubricious hard film was polished by diamond paper No. 2000, and in the second and fourth embodiments, the surface of the lubricious hard film was ground by diamond paper of No. 4000. In Example 3, the surface of the lubricious hard film was ground by diamond paper of 8000 surface. Further, the steel material used in the core portion of the present embodiment was HPM-38 (quenched) manufactured by Hitachi Metals Co., Ltd.

[Evaluation of surface roughness]

The surface roughness Rz of the surface of the core and the surface roughness of the surface of the lubricious hard film were measured by the method of JIS B 0601-1994 using the "Ultra Deep Color 3D Shape Measuring Microscope VK-9500" manufactured by KEYENCE Co., Ltd. Rz and the surface roughness Rz of the surface of the lubricious hard film after polishing. The results of the measurement are shown in Table 1. Further, the unit in Table 1 is μm.

[Manufacture of outer cylinder for prefilled syringes]

As a cyclic olefin resin composition, a copolymer of raw spinel and ethylene (TOPAS 6013S-04, manufactured by Topas Advanced Polymers Co., Ltd., glass transition temperature: 138 ° C) was used, and an outer cylinder for prefilled syringes of Examples and Comparative Examples was produced. Further, the production conditions were a mold temperature of 105 ° C and a cylinder temperature of 280 ° C.

The pressure applied to the PIN 1 was measured by the aforementioned pressure sensor while the outer cylinder for pre-filling the syringe immediately after the manufacture was taken out by the mold. The results of the measurement (the maximum values of the respective measurements of Examples 1 to 4 and Comparative Examples 1 to 8) were shown in Table 1 as the mold release resistance values. In addition, when the mold resistance value is less than 10.0 MPa, the continuous formability is "○", and the continuous formability of "10.0 MPa or more" is "X".

[Evaluation of transparency]

The transparency of the outer cylinder for the prefilled syringes of Examples 1 to 4 and Comparative Examples 1 to 8 was carried out by using an "ultraviolet-visible spectrophotometer, V-570" manufactured by JASCO Corporation. -470 type" The device was measured. The sample is in the direction in which the outer cylinder for prefilling the syringe is extended, and the syringe is cut into half, and a cylindrical sample divided into two is cut out therefrom (here, the suction tube and the outer cylinder for the prefilled syringe) The connection position was cut out in the vicinity of 17.5 mm.) As shown in Fig. 3, the cut sample was attached to the sample holder, and the light transmittance with respect to 450 nm light was measured. The results of the measurement are shown in Table 1. The unit in Table 1 is %.

[Evaluation of scars]

The surface flaws of the outer cylinders for the prefilled syringes of Examples 1 to 4 and Comparative Examples 1 to 8 were confirmed by visual observation. In the case of no scars, the following two stages of evaluation are performed. The results of the evaluation are shown in Table 1.

"○": The state of the scar is 3 or less

"X": The state of the scar is more than 4

It is confirmed from the results of Table 1 that the outer cylinder for prefilled syringes can be formed by injection molding for the formation of a cyclic olefin resin composition. A method of forming a lubricative hard film containing at least one element selected from Ti, Cr, Zr, C, Al, and Ni and grinding the surface of the lubricious hard film in a core having a surface roughness Rz of 50 μm or less The injection molding die is used as an injection molding die, and a high-productivity is produced to produce a pre-filled syringe outer cylinder which is free from scratches and has good transparency.

1‧‧‧Prefilled syringe

10‧‧‧Prefilled syringe outer cylinder

20‧‧‧Intubation

30‧‧‧Plunger

101‧‧‧Attraction

102‧‧‧Flange

201‧‧ ‧block

Claims (4)

A method for producing a pre-filled syringe outer cylinder for producing a pre-filled syringe outer cylinder which is formed by injection molding of a cyclic olefin resin composition, wherein a surface roughness Rz of a core portion constituting the injection molding die is formed ( The ten-point average roughness is 50 μm or less, and a mold for injection molding in which a lubricative hard film containing at least one element selected from the group consisting of Ti, Cr, Zr, C, Al, and Ni is formed and the surface of the lubricative hard film is polished is used. The light transmittance of the light source having a wavelength of 450 nm incident perpendicularly to the side wall of the outer cylinder for prefilling the syringe is 70% or more. The method for producing a pre-filled syringe outer cylinder according to the first aspect of the invention, wherein the lubricative hard film is made of diamond-like carbon (DLC), CrN, TiN, TiC, TiCN, TiAlN, TiCrN, AlCrN, ZrN. Or Ni. The method for producing an outer cylinder for a prefilled syringe according to the first or second aspect of the invention, wherein the mold release slope of the core portion constituting the injection molding die is substantially 0 degree. A method for producing an injection molding die, comprising: an injection molding die for producing an injection molding die for pre-filling an outer cylinder for a syringe, comprising: a surface roughness Rz of a core portion constituting the injection molding die of 50 μm or less The surface roughness adjustment process of the core portion; forming a lubricative hard film forming a lubricative hard film containing at least one element selected from the group consisting of Ti, Cr, Zr, C, Al, and Ni for the surface of the core after the adjustment process a process; and a grinding process for grinding the surface of the aforementioned lubricious hard film.