KR102011381B1

KR102011381B1 - Production method for outer tube for pre-filled syringe

Info

Publication number: KR102011381B1
Application number: KR1020147013273A
Authority: KR
Inventors: 타카테루 오노데라
Original assignee: 포리프라스틱 가부시키가이샤
Priority date: 2011-12-26
Filing date: 2012-11-07
Publication date: 2019-08-16
Also published as: TW201334823A; CN104039294A; WO2013099446A1; TWI621455B; KR20140106512A; JP2013132393A; JP6128731B2

Abstract

The present invention provides a technique for producing an outer cylinder for prefilled syringes, which is manufactured from cyclic olefin resin and has high transparency.
In the method of manufacturing the outer cylinder for prefilled syringes formed by injection molding a cyclic olefin resin composition, the surface roughness of the core of the injection molding die for shaping the outer cylinder for prefilled syringes is adjusted to a specific range, An outer cylinder for prefilled syringes having a light transmittance of 70% or more when light having a wavelength of 450 nm incident perpendicularly to the outer sidewall of the outer cylinder passes through the sidewall is produced.

Description

Manufacturing method of outer cylinder for prefilled syringes {PRODUCTION METHOD FOR OUTER TUBE FOR PRE-FILLED SYRINGE}

This invention relates to the outer cylinder for prefilled syringes manufactured using cyclic olefin resin.

The conventional general syringe is used by the method of sucking up a chemical at the time of use. However, such a use method tends to generate human errors such as poor operation efficiency and incorrect filling of medicines. Thus, in recent years, prefilled syringes filled with a predetermined amount of a predetermined drug in advance have been preferably used.

It is preferable that the material which comprises a prefilled syringe is resin from a viewpoint of the ease of handling, such as light weight and the point which cannot be easily broken. However, since prefilled syringes prepared using polypropylene used for general syringe production have low water vapor barrier properties, the water contained in the drug volatilizes during storage.

Moreover, depending on the kind of resin to be used, there arises a problem that components contained in the resin are eluted in the drug during prefilled syringe storage as a result of insufficient chemical resistance of the resin. In addition, since prefilled syringes are heat sterilized before the medicine is filled, they should be excellent in heat resistance.

For this reason, resin which can be used as a raw material of a prefilled syringe is limited, As an example of resin which can be used, the aromatic vinyl polymer as described in patent document 1 is mentioned.

Japanese Patent Laid-Open No. 11-164887

By the way, cyclic olefin resin is known as resin excellent in heat resistance, chemical-resistance, water vapor barrier property, etc. And since cyclic olefin resin is excellent also in transparency, when prefilled syringe is manufactured using cyclic olefin resin, the effect which a drug is easy to confirm visually can also be acquired.

MEANS TO SOLVE THE PROBLEM The present inventors tried to manufacture the outer cylinder for prefilled syringes which use cyclic olefin resin as a raw material for the purpose of improving the performance of the resin prefilled syringe, but the transparency of the manufactured outer cylinder for prefilled syringes was not favorable. .

This invention is made | formed in order to solve the said subject, The objective is providing the technique which manufactures the outer cylinder for prefilled syringes which is manufactured from cyclic olefin resin as a raw material and has high transparency.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors earnestly researched in order to manufacture the outer cylinder for prefilled syringes which are manufactured using cyclic olefin resin as a raw material, and have high transparency. As a result, when the surface roughness of the core (movable side) of the injection molding die for forming the outer cylinder for prefilled syringes is in a specific range, it has been found that the above problems can be solved and the present invention has been completed. More specifically, the present invention provides the following.

(1) A method for producing an outer cylinder for pre-filled syringes formed by injection molding a cyclic olefin resin composition, wherein the surface roughness (Rz) of the core constituting the injection-molding die is used in an injection molding die having a thickness of 50 µm or less. A method for producing a prefilled syringe outer cylinder having a light transmittance of 70% or more when light having a wavelength of 450 nm incident perpendicularly to the side wall of the syringe outer cylinder passes through the side wall.

(2) The manufacturing method of the outer cylinder for prefilled syringes as described in (1) whose said surface roughness is 30 micrometers or more.

(3) The manufacturing method of the outer cylinder for prefilled syringes as described in (1) or (2) whose draft angle of the core which comprises an injection molding metal mold | die is substantially 0 degree.

(4) The prefilled syringe according to any one of (1) to (3), wherein a lubricating hard film containing at least one element selected from Ti, Cr, Zr, C, Al, and Ni is formed on the core surface. Method for producing a paper outer barrel.

(5) The lubricating hard film is for prefilled syringes according to (4), which is composed of at least one selected from diamond-like carbon (DLC), CrN, TiN, TiC, TiCN, TiAlN, TiCrN, AlCrN, ZrN, or Ni. Manufacturing method of outer cylinder.

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

1: is a figure which shows a prefilled syringe typically, (a) is a perspective view, (b) is MM sectional drawing of (a).
Fig. 2 (a) is a diagram showing the dimensions of the outer cylinder for prefilled syringes produced in the example, and (b) is a diagram showing the positions of sprues, runners and gates in the mold.
3 is a schematic diagram for explaining a method for measuring light transmittance.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. However, the present invention is not limited to the following embodiment.

This invention is a method of manufacturing the outer cylinder for prefilled syringes. The shape of the outer cylinder for prefilled syringes manufactured by this invention is not specifically limited. First, a general prefilled syringe in which the outer cylinder for prefilled syringes of the present invention is used will be briefly described with reference to the drawings.

1: is a figure which shows a prefilled syringe typically, (a) is a perspective view, (b) is MM sectional drawing of (a). The pre-filled syringe 1 is a pre-filled syringe outer cylinder at the other end of the pre-filled syringe outer cylinder 10, the cannula 20 connected to one end of the pre-filled syringe outer cylinder 10, and the pre-filled syringe outer cylinder 10. And a plunger 30 removably inserted into the interior of 10.

At one end of the outer cylinder 10 for prefilled syringes, a luer 101 for connecting with the cannula 20 and a flange 102 at the other end are formed. In addition, the inner space of the outer cylinder 10 for prefilled syringes is a chemical | medical agent accommodation space in which a chemical | medical agent is accommodated. The plunger 30 is inserted into the opening of the outer cylinder 10 for prefilled syringes on the flange 102 side. In addition, as shown in FIG.1 (b), the gradient angle of the inner wall surface of the outer cylinder 10 for prefilled syringes was made into (theta).

The cannula 20 is provided with a stopper 201 at an end thereof, and the stopper 201 is fitted with the luer 101 so that the cannula 20 and the outer cylinder 10 for prefilled syringes are connected. do.

As described above, the plunger 30 is inserted into the chemical | medical agent accommodation space from the edge part of the outer cylinder 10 for prefilled syringes so that advance and retraction is possible. At the time of prefilled syringe storage, the end part of the plunger 30 is in contact with the chemical | medical agent in a chemical | medical agent accommodation space.

Next, the manufacturing method of the outer cylinder for prefilled syringes is demonstrated easily. After being stored for a certain period of time with the medicine filled in the prefilled syringe 1, the volume of the drug receiving space becomes smaller by further pushing the plunger 30 into the prefilled syringe barrel 10 during use. At the same time, the drug is pushed out of the luer 101, and the drug is pushed out of the cannula 20 and out of the prefilled syringe.

As described above, the prefilled syringe 1 is stored for a certain period of time in the state where the medicine is contained. For this reason, when the outer cylinder 10 for prefilled syringes is comprised from the material with high water vapor permeability, the problem that the water contained in a chemical | medical agent escapes to the outside arises.

In addition, if the drug is stored in the prefilled syringe 1 in a state where it is stored for a long time, the state in which the drug and the inner wall surface of the prefilled syringe outer cylinder 10 come into contact with each other continues for a long time. Therefore, when the chemical-resistance of the material which comprises the outer cylinder 10 for prefilled syringes is low, the problem that the decomposition product of the material melt | dissolves in a chemical agent arises.

The outer cylinder 10 for prefilled syringes obtained by the manufacturing method of this invention is comprised from the cyclic olefin resin composition mentioned later. Since the excellent chemical-resistance and water vapor barrier property of a cyclic olefin resin are revealed in a cyclic olefin resin composition, when the outer cylinder for prefilled syringes is manufactured using a cyclic olefin resin composition, the above problems do not arise.

However, when trying to manufacture the outer cylinder for prefilled syringes using a cyclic olefin resin composition, the problem that the outer cylinder for prefilled syringes does not have sufficient transparency arises.

In addition, when the outer cylinder for prefilled syringes is manufactured using a cyclic olefin resin composition as a raw material, it is difficult to take out the outer cylinder for prefilled syringes from a metal mold | die at the time of manufacture because of the rigidity inherent in cyclic olefin resin. The problem that it is difficult to take out the outer cylinder for prefilled syringes from a metal mold | die at the time of manufacture leads to a productivity fall.

In this invention, since the outer cylinder for prefilled syringes is manufactured by the following method, transparency of the outer cylinder for prefilled syringes manufactured using cyclic olefin resin can be improved.

In particular, when manufactured under the preferable conditions of this invention, the outer cylinder for prefilled syringes can be easily taken out from a metal mold | die at the time of manufacture, and the productivity of the outer cylinder for high quality prefilled syringes can be improved.

The manufacturing method of the outer cylinder for prefilled syringes of this invention is a manufacturing method of the outer cylinder for prefilled syringes formed by injection molding a cyclic olefin resin composition.

In the manufacturing method of this invention, the surface roughness Rz of a core is 50 micrometers or less as a metal mold | die for injection molding. By adjusting the surface roughness of a core to the said range, the outer cylinder for prefilled syringes with high transparency can be manufactured also when using a cyclic olefin resin composition as a raw material.

Although the method of adjusting the surface roughness Rz of a core to the said range is not specifically limited, The method of grind | polishing a core using the abrasive of 2000 to 10000 times of particle size number is mentioned. Here, the larger the particle number of the abrasive, the smaller the surface roughness Rz, and the smaller the particle size of the abrasive, the larger the surface roughness Rz. For this reason, the surface roughness Rz can be adjusted by appropriately adjusting the particle size number of the abrasive. In addition, the specific method at the time of grinding | polishing is not specifically limited, For example, the method of using a roughened abrasive body, such as sandpaper, or the abrasive body called the liquid abrasive (compound), and the buffing agent made from the cloth or sponge, The method to use, or the method of combining these methods, etc. are mentioned.

However, as the number of particle sizes increases, the surface roughness Rz decreases, making it difficult to take out the outer cylinder for prefilled syringes immediately after manufacture from the mold. For example, this problem starts to appear when the surface roughness Rz of the core becomes about 10 mu m or less. Therefore, it is also necessary to adjust the surface roughness of the core in consideration of the fact that the outer cylinder for prefilled syringes immediately after manufacture is easily taken out of the mold. For example, when the surface roughness Rz of a core is 20 micrometers or more and 50 micrometers or less, the outer cylinder for prefilled syringes is excellent in transparency, and the problem that it is difficult to take out the outer cylinder for prefilled syringes from a metal mold | die at the time of manufacture also does not arise. In order to adjust the surface roughness of a core to the said preferable range, it is preferable to use the abrasive of 2000-8000 times of particle size counts. The surface roughness Rz of especially preferable core is 30 micrometers or more and 50 micrometers or less.

Moreover, transparency of the outer cylinder for prefilled syringes can also be improved by providing a lubricating hard film in a core. The lubricity hard coat contains at least one element selected from Ti, Cr, Zr, C, Al, and Ni. In the present invention, the lubricity hard film is preferably composed of at least one selected from diamond-like carbon (DLC), CrN, TiN, TiC, TiCN, TiAlN, TiCrN, AlCrN, ZrN, or Ni.

Although the method of forming a lubricating hard film in a core is not specifically limited, For example, it forms by the deposition method. As the deposition method, a vapor phase method is suitable, for example, a CVD method such as a plasma vapor deposition (CVD) method using a direct current power source, an alternating current power source or a high frequency power source, or an arc ion plating (AIP) method. PVD (Physical Vapor Deposition) methods, such as a method, a magnetron sputtering method, sputtering methods, such as an ion beam sputtering method, ionization vapor deposition method, etc. are mentioned. Moreover, in the case of Ni etc., wet methods, such as electrolytic plating and electroless plating, are mentioned. These lubricity hard films may be a single layer or a multilayer.

The surface roughness Rz of the lubricity hard coat surface may not be 50 micrometers or less. Since the friction coefficient of the lubricity hard film surface is smaller than that of the core, the transparency of the outer cylinder for prefilled syringes is increased even if the surface roughness Rz is not 50 µm or less. However, the surface roughness of the surface of the mold for forming the lubricity hard film needs to be 50 µm or less for the reason of reducing the surface roughness of the outer cylinder inner surface.

The cyclic olefin resin composition which is a raw material of the outer cylinder for prefilled syringes is demonstrated. The cyclic olefin resin composition contains a cyclic olefin resin.

The cyclic olefin resin includes the cyclic olefin component as a copolymerization component, and is not particularly limited as long as it is a polyolefin resin containing the cyclic olefin component in the main chain. For example, the addition polymer of cyclic olefin or its hydrogenated substance, the addition copolymer of cyclic olefin and (alpha) -olefin, its hydrogenated substance, etc. are mentioned.

In addition, examples of the cyclic olefin resin include those obtained by grafting and / or copolymerizing an unsaturated compound having a polar group in the polymer.

Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, an ester group, a hydroxyl group, a sulfo group, a phosphono group, a phosphino group, and the like. , (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (C10 to C10) ester, alkyl maleic acid (C1-10), (Meth) acrylamide, (meth) acrylic acid 2-hydroxyethyl, etc. are mentioned, Preferably, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, ester group, a hydroxyl group, a sulfo group, A phosphono group and a phosphino group are mentioned.

As cyclic olefin resin, the addition copolymer of cyclic olefin and an alpha olefin or its hydrogenated substance is preferable.

Moreover, commercially available resin can also be used as cyclic olefin resin which contains a cyclic olefin component as a copolymerization component. Examples of commercially available cyclic olefin resins include TOPAS (registered trademark) (manufactured by Topas Advanced Polymers), Apel (registered trademark) (manufactured by Mitsui Chemicals), Zeones (registered trademark) (manufactured by Japan Zeon), Zeonoa (trademark) (made by Japan-Zeon Corporation), Aton (trademark) (made by JSR Corporation), etc. are mentioned.

Particularly preferred examples of the addition copolymer of the cyclic olefin and the α-olefin include a copolymer comprising the [1] alpha -olefin component having 2 to 20 carbon atoms and the cyclic olefin component represented by [2] the following general formula (I). Can be mentioned.

(Wherein, R ¹ to R ¹² may be the same or different, respectively, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group,

R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group,

R <^9> or R <^10> and R <^11> or R <^12> can form a ring mutually.

In addition, n represents 0 or a positive integer,

When N is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.)

[1] A C2-C20 α-olefin component will be described. The C2-C20 alpha olefin is not specifically limited. For example, the same thing as Unexamined-Japanese-Patent No. 2007-302722 is mentioned. In addition, these alpha-olefin components may be used individually by 1 type, and may use 2 or more types simultaneously. Of these, the single use of ethylene is most preferred.

[2] A cyclic olefin component represented by general formula (I) will be described. R ¹ to R ¹² in General Formula (I) may be the same or different, respectively, 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, for example, hydrogen atoms; Halogen atoms such as fluorine, chlorine and bromine; Lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, etc. are mentioned, These may differ, respectively, may differ partially, and all may be the same.

In addition, specific examples of R ⁹ to R ¹² include, for example, hydrogen atoms; Halogen atoms such as fluorine, chlorine and bromine; Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group and stearyl group; Cycloalkyl groups such as cyclohexyl group; Substituted or unsubstituted aromatic hydrocarbon groups, such as a phenyl group, a tril group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group, and an anthryl group; And aralkyl groups in which an aryl group is substituted with a benzyl group, a phenethyl group, and other alkyl groups, which may be different, partially different, or all the same.

As a specific example in the case of R <^9> and R <^10> or R <^11> and R <^12> being integrated and forming a bivalent hydrocarbon group, alkylidene groups, such as an ethylidene group, a propylidene group, an isopropylidene group, etc. are mentioned, for example. Can be.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the ring to be formed may be monocyclic or polycyclic, may be polycyclic having a crosslink, may be a ring having a double bond, It may also be a ring consisting of a combination of these rings. Moreover, these rings may have substituents, such as a methyl group.

As a specific example of the cyclic olefin component represented by general formula (I), the thing similar to Unexamined-Japanese-Patent No. 2007-302722 is mentioned.

These cyclic olefin components may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, bicyclo [2.2.1] hepta-2-ene (common name: norbornene) is preferably used alone.

[1] The polymerization method of the C2-C20 alpha olefin component and the cyclic olefin component represented by [2] General formula (I) and the hydrogenation method of the obtained polymer are not specifically limited, It carries out according to a well-known method. can do. It may be random copolymerization or block copolymerization, but it is preferable that it is random copolymerization.

Moreover, it does not specifically limit also about the polymerization catalyst used, A cyclic olefin resin can be obtained by a well-known method using conventionally well-known catalysts, such as a Ziegler-Natta type | mold, a metathesis type | system | group, and a metallocene type catalyst. .

Next, the other copolymerization component is demonstrated briefly. A cyclic olefin resin (A) is a range which does not inhibit the objective of this invention other than said [1] C2-C20 alpha-olefin component and [2] cyclic olefin component represented by General formula (I). If necessary, other copolymerizable unsaturated monomer components may be contained.

Although it does not specifically limit as an unsaturated monomer which may be copolymerized arbitrarily, For example, the hydrocarbon type monomer etc. which contain 2 or more of carbon-carbon double bonds in 1 molecule are mentioned. As a specific example of the hydrocarbon-type monomer containing two or more carbon-carbon double bonds in 1 molecule, the thing similar to Unexamined-Japanese-Patent No. 2007-302722 is mentioned.

When the above cyclic olefin resin is used, the outer cylinder for prefilled syringes becomes hard. Therefore, even when the draft angle (θ in FIG. 1 (b)) of the inner wall surface of the outer cylinder for prefilled syringes is small, if the draft angle is not substantially zero, the drug in the outer cylinder for prefilled syringes is pushed by the plunger during use. It will get in the way when pushing out. That the draft angle of the inner wall surface is 0 degrees means that the draft angle of the core constituting the injection molding die is substantially 0 degrees.

When manufacturing the outer cylinder for prefilled syringes using resin, it is preferable that the draft angle of the inner wall surface of the outer cylinder for prefilled syringes is not substantially zero, in order to make it easy to take out the outer cylinder for prefilled syringes immediately after manufacture. Do. However, when the injection molding die used in the present invention described above is used, even if the draft angle is substantially zero, the outer cylinder for prefilled syringes immediately after the manufacture is easily taken out of the mold.

Here, the said draft angle being substantially zero refers to the case where a draft angle is 0.5 degrees or less. And when the gradient angle is 0.5 degrees or less, the problem that it is difficult to take out arises.

Components other than cyclic olefin resin can be contained in cyclic olefin resin composition in the range which does not impair the effect of this invention. As another component, other resin, an inorganic filler, a nucleating agent, a pigment, antioxidant, a stabilizer, a plasticizer, a lubricating agent, a mold release agent, etc. are mentioned, for example.

The outer cylinder for prefilled syringes of this invention is manufactured by the injection molding method. The manufacturing conditions of injection molding are not specifically limited, It sets suitably according to the cyclic olefin resin composition to be used.

The prefilled syringe manufactured by the manufacturing method of this invention has high transparency. Specifically, the light transmittance is 70% or more when light having a wavelength of 450 nm incident perpendicularly to the side wall of the outer cylinder for prefilled syringes passes through the side wall.

Moreover, as the surface area of the outer cylinder for prefilled syringes increases, it becomes difficult to take out the outer cylinder for prefilled syringes immediately after manufacture from a metal mold | die. The length L of the outer cylinder for prefilled syringes is 30 mm or more and 150 mm or less normally, and the inner diameter R of the outer cylinder for prefilled syringes is 2 mm or more and 50 mm or less normally. If the outer cylinder for prefilled syringes of the above-mentioned normal size is set as mentioned above, the outer cylinder for prefilled syringes immediately after manufacture is set out by setting the unevenness | corrugation of the core of the injection molding die to 30 micrometers or more and 50 micrometers or less. Difficult problem also hardly occurs.

EXAMPLE

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

[Injection Mold]

In this embodiment, the outer cylinder for prefilled syringes of the shape shown in FIG. 1 is manufactured. The dimension of such an outer cylinder for prefilled syringes is shown to FIG. As shown in Fig. 2 (a), the draft angle of the inner wall surface of the outer cylinder for prefilled syringes produced in the example is 0 degrees.

The mold having the outer cylindrical cavity for the prefilled syringe includes a sprue, a runner, and a gate having a shape as shown in Fig. 2B. The position G of the gate is also shown in Fig. 2A. As shown in Fig. 2B, the sprue diameter, the length of the runner, and the gate diameter are 4.0 mm, 20 mm, and 3.0 mm, respectively. As shown in Fig. 2B, three ejector pins are provided at the connection point between the sprue and the runner and the connection point between the runner and the gate (PIN1 to 3). In addition, a pressure sensor ("9223 A", manufactured by Keesler Japan) for measuring mold release resistance is connected to the ejector pin indicated by PIN1. Data obtained from such a pressure sensor is converted using an industrial charge amplifier ("5073A", manufactured by Keesler Japan), and the converted data can be monitored by DATAFLOW Light II (manufactured by Keesler Japan).

And the metal mold | die with which the surface was processed on the conditions shown in Table 1 was prepared. In Table 1, "particle size number" shows the particle size number of the abrasive used for treating the surface of a core. Examples 1 to 5 are aerolab treatments performed using diamond abrasive grains, and Example 6 and Comparative Example 1 are polishing treatments performed by lathes using diamond paste. In addition, in Table 1, "coating" shows the kind of lubricious hard film formed in the surface of the core processed. In this embodiment, a lubricating hard film was formed by Ni electroless plating, CrN and TiN by PVD, and DLC by ionization deposition.

[Evaluation of Surface Roughness]

Method according to JIS B 0601-1994 for the surface roughness (Rz) of the core surface and the surface roughness (Rz) of the lubricity hard film surface using "Super Depth Color 3D Shape Measurement Microscope VK-9500" manufactured by Keyence Corporation. Measured by. The measurement results are shown in Table 1. In Table 1 the unit is μm.

[Manufacture of outer cylinder for prefilled syringe]

The outer cylinder for prefilled syringes of the Example and the comparative example was manufactured using the copolymer of norbornene and ethylene (TOPAS 6013S-04, the product made from Topas Advanced Polymers, glass transition temperature of 138 degreeC) as a cyclic olefin resin composition. As for manufacturing conditions, die temperature is 105 degreeC and cylinder temperature is 280 degreeC.

When taking out the outer cylinder for prefilled syringes immediately after manufacture from a metal mold | die, the pressure applied to PIN1 was measured with the said pressure sensor. The measurement result (maximum value in each measurement of Examples 1-6 and Comparative Example 1) was shown as Table 1 in the release resistance value. In Table 1, the unit is MPa.

[Evaluation of transparency]

The transparency of the outer cylinder for prefilled syringes of Examples 1 to 6 and Comparative Example 1 was obtained by setting "Integral sphere device ISN-470 type" in "UV-vis spectrophotometer V-570" manufactured by Japan Spectro. It measured using the apparatus. The sample was cut in half in the direction in which the outer cylinder for prefilled syringes was extended, and the cylindrical sample divided into two was cut out here (in this case, 17.5 mm from the connection position of the outer cylinder for luer and prefilled syringes). Cut out). As shown in FIG. 3, the cut-out sample was set in the sample holder, and the light transmittance with respect to 450 nm light was measured. The measurement results are shown in Table 1. In Table 1, the unit is%.

As shown in Table 1, when the surface roughness Rz of the core constituting the injection molding die is 50 µm or less, the transparency of the outer cylinder for prefilled syringes is increased. In addition, from Examples 1-5 and Example 6, when the surface roughness of the core was 30 micrometers or less, and a lubricous hard film was not formed in the metal mold core, it confirmed that the mold release resistance value became large. In addition, it is confirmed from Examples 1 and 2 to 5 that the release resistance value is lowered by forming a lubricating hard film, while Example 1 is excellent in transparency and release resistance even though no lubricating hard film is formed. It was confirmed that the value was also slightly higher than Examples 2-5.

1 pre-filled syringe
10 External cylinder for prefilled syringe
101 lures
102 flange
20 cannula
201 stopper
30 plunger

Claims

As a method of manufacturing the outer cylinder for prefilled syringes formed by injection molding a cyclic olefin resin composition,
Using the injection molding die whose surface roughness Rz of the core which comprises an injection molding die is 30 micrometers or more and 50 micrometers or less,
The light transmittance is 70% or more when light having a wavelength of 450 nm incident perpendicularly to the side wall of the outer cylinder for prefilled syringes passes through the side wall,
The core surface is a method for producing a pre-cylinder outer cylinder formed with a lubricating hard film containing at least one element selected from Ti, Cr, Zr, C, Al and Ni.

delete

The method of claim 1,
The manufacturing method of the outer cylinder for prefilled syringes whose gradient angle of the core which comprises an injection molding die is 0.5 degrees or less.

delete

The method of claim 1,
The lubricity hard film is a method for producing a pre-cylinder outer cylinder made of at least one selected from diamond-like carbon (DLC), CrN, TiN, TiC, TiCN, TiAlN, TiCrN, AlCrN, ZrN, or Ni.