JP5657361B2 - Syringe member, medical syringe using the syringe member, and method for manufacturing the syringe member - Google Patents

Description

  The present invention relates to a member having excellent slidability that is preferably used as a member of a medical syringe, and a method for producing the member.

  2. Description of the Related Art Pre-filled syringes that are pre-filled with a medical solution filled in a syringe and sealed in a medical field are known. Such prefilled syringes have been widely used in recent years for the purpose of reducing the work process of medical staff to increase work efficiency and preventing the occurrence of medical errors due to transfer from a container. In such a prefilled syringe, the liquid medicine is sealed and stored by filling the liquid medicine into the syringe outer cylinder that is sealed with the cap member fitted into the cylinder tip, and inserting the plunger having the gasket into the syringe external cylinder. The

  When using the prefilled syringe, a medical worker removes the cap fitted to the tip of the syringe outer cylinder. Then, the plunger inserted into the syringe outer cylinder is moved under a very low speed condition by a syringe pump so that the chemical solution is discharged. Specifically, for example, when discharging at 1 mL / hour, in a syringe having a diameter of about 24 mm, the moving speed of the plunger is about 2 mm / hour. In such a case, high slidability is required for the gasket in order to stably discharge the chemical solution.

  2. Description of the Related Art Conventionally, in medical syringes, a method of applying a lubricant such as silicone oil to the inner wall of a syringe outer cylinder or a gasket has been widely used as a technique for improving the slidability of the gasket. For example, Patent Document 1 below discloses that a reactive silicone oil is applied to the outer surface of a gasket body and heated under water vapor to form a multilayer having excellent sliding properties.

  Patent Document 2 below discloses a thermoplastic elastomer molded article whose surface is treated with a silicone aqueous solution containing a silicone emulsion and / or a water-soluble silicone having a silicone concentration of 1 to 30% by weight. Such a thermoplastic elastomer molded article is excellent in working environment without greatly detracting from the general physical properties of the thermoplastic elastomer molded article, and is excellent in thermoplasticity such as a medical tube having improved sliding property and sliding wear property. It is described that an elastomer molded article can be provided.

Utility Model Registration No. 3134991 JP 2006-161020 A

  Even if the surface treatment disclosed in Patent Document 1 and Patent Document 2 is applied to the surface of the gasket used for the prefilled syringe, it still has high slidability to such an extent that the chemical solution can be discharged completely stably. A gasket for prefilled syringes was not obtained.

  Moreover, in the manufacturing process of a prefilled syringe, there existed the following problems. Since the cap that seals the tube tip of the syringe outer cylinder of the prefilled syringe is required to have a hermetic sealing property, an elastic body similar to that used for the gasket is used. Such an elastic body usually has low slipperiness. Since the lubricant is usually applied to the inner wall of the syringe outer cylinder, it is relatively easy to insert the plunger provided with the gasket into the syringe outer cylinder. On the other hand, the lubricant is not applied to the tube tip of the syringe outer tube. Therefore, when a cap is fitted to the tube tip of the syringe outer tube to which the lubricant is not applied in the manufacturing process of the prefilled syringe, it is difficult to fit because the slip of the tube tip is low, which causes a decrease in productivity. In addition to this, when the cap was not securely fitted into the syringe outer cylinder, there was a problem that it was unintentionally removed relatively easily.

  The present invention relates to a syringe member having high slidability when a slidable coating is formed on a syringe gasket in order to solve the above-described problems.

（式中、ｍは５〜１００、Ｒ ₁ は、少なくとも一方が、−C ₃ H ₆ NH ₂ ，−C ₃ H ₆ NHC ₂ H ₄ NH ₂ ，−C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ NH ₂ ，−CH ₂ CH（CH ₃ ）CH ₂ NHC ₂ H ₄ NH ₂ ，−C ₃ H ₆ N（CH ₂ CH（OH）CH ₂ OH）C ₂ H ₄ NH（CH ₂ CH（OH）CH ₂ OH）からなる群から選ばれる少なくとも１種であり、他方は水素原子または他の炭化水素基であってもよい）で示される、側鎖にアミノ基を有する両末端水酸基封鎖変性シリコーンオイル（以下単に、変性シリコーンオイルとも呼ぶ）であるシリンジ用部材である。このようなシリンジ用部材をガスケットに用いた場合にはシリンジ用外筒の内壁面との安定した摺動性を確保することができる。また、シリンジの筒先のキャップに用いた場合には、筒先に容易且つ確実に嵌め込むことができる。
In one aspect of the present invention, at least a sliding region of an elastic molded body having a sliding region is surface-treated with a treatment liquid containing silicone oil, and the silicone oil is represented by the following general formula (1):

(In the formula, m is 5 to 100, and R ₁ is at least one of —C ₃ H ₆ NH ₂ , —C ₃ H ₆ NHC ₂ H ₄ NH ₂ , —C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ NH ₂ , -CH ₂ CH (CH ₃ ) CH ₂ NHC ₂ H ₄ NH ₂ , -C ₃ H ₆ N (CH ₂ CH (OH) CH ₂ OH) C ₂ H ₄ NH (CH ₂ CH (OH) CH ₂ OH), at least one selected from the group consisting of ( CH ₂ OH), and the other may be a hydrogen atom or other hydrocarbon group). It is a member for syringes (hereinafter simply referred to as modified silicone oil). When such a syringe member is used as a gasket, stable slidability with the inner wall surface of the syringe outer cylinder can be ensured. Moreover, when it uses for the cylinder tip cap of a syringe, it can be easily and reliably fitted in the tube tip.

  Another aspect of the present invention includes a syringe outer cylinder and a plunger slidably inserted into the syringe outer cylinder, and a syringe gasket is attached to the distal end of the plunger. A cap is fitted on the tube tip of the tube, and a gasket or cap is formed from the syringe member. The gasket using the above-described syringe member exhibits excellent slidability with little variation in the presence of a lubricant. Moreover, the cap using the syringe member described above has sufficient slidability to fit into the tube tip of the syringe outer tube, and can be securely fitted into the tube tip.

  Another aspect of the present invention is a method for producing the above-described member for a syringe, which is brought into contact with an aqueous liquid containing a modified silicone oil for at least a sliding region of at least a sliding region of the elastic molded body and then washed with water. It is a manufacturing method of the member for syringes. By providing the step of washing with water, no white droplet marks remain on the appearance of the syringe member having high slidability.

  The syringe member of the present invention exhibits excellent slidability with little variation when used as a gasket attached to the tip of a plunger inserted into the inner wall of the syringe outer cylinder. In addition, when used as a cap that is fitted to the cylinder tip of the syringe outer cylinder and removed during use, it can be easily and reliably fitted into the cylinder tip.

FIG. 1 is a schematic sectional view of a prefilled syringe 25 of the present embodiment. FIG. 2 is a schematic front view of the gasket 1 in the present embodiment. FIG. 3 is a schematic cross-sectional view of the gasket 1 in the present embodiment. FIG. 4 is a schematic cross-sectional view of the cap 2 in the present embodiment.

  The prefilled syringe 25 provided with the gasket 1 and the cap 2 which are one Embodiment of the member for syringes which concerns on this invention is demonstrated in detail with reference to drawings.

  FIG. 1 is a cross-sectional view of the prefilled syringe 25. In FIG. 1, 1 is a gasket, 2 is a cap, 3 is a plunger, 4 is an outer cylinder for a syringe, 5 is a flange provided on the outer cylinder 4, 6 is a chemical solution, and 7 is a cylinder tip portion of the outer cylinder 4 with an open end. , 8 are injection needle mounting portions provided on the tube tip portion 7. A chemical solution 6 is accommodated in the outer cylinder 4. The gasket 1 attached to the tip of the plunger 3 slidably inserted into the outer cylinder 4 seals the chemical liquid 6 at one end of the outer cylinder 4 in a liquid-tight manner. A removable cap 2 is fitted to the tube tip portion 7 of the syringe outer tube, and the chemical solution 6 is sealed in a liquid-tight manner.

  The outer cylinder 4 is made of a transparent or translucent material. Preferably, it is made of a material having low oxygen permeability and water vapor permeability. Specific examples of the material for forming the outer cylinder 4 include polyolefins such as polypropylene, polyethylene, poly (4-methylpentene-1), and cyclic polyolefin; polyesters such as polyethylene terephthalate, polyethylene naphthalate, and amorphous polyarylate; Examples thereof include polystyrene, polyamide, polycarbonate, polyvinyl chloride, acrylic resin, acrylonitrile-butadiene-styrene copolymer, and amorphous polyetherimide. Among these, polypropylene, poly (4-methylpentene-1), cyclic polyolefin, polyethylene naphthalate, and amorphous polyetherimide are preferable in terms of transparency and vapor pressure sterilization.

  The plunger 3 includes a plunger main body portion 3a extending in the axial direction, a male screw portion 3b provided at the tip portion, and a pressing disk portion 3c provided at the rear end of the plunger main body portion 3a. The male screw portion 3b is provided to be screwed with a female screw-like plunger mounting portion provided in the gasket 1.

  FIG. 2 is a schematic front view of the gasket 1, and FIG. 3 is a schematic cross-sectional view of the gasket 1. As shown in FIG. 2, the gasket 1 includes an annular outer wall 1 a extending to substantially the same outer diameter, an annular rib 1 b provided on the front end side along the outer periphery of the annular outer wall 1 a, and a rear end provided on the rear end side. It is a molded body of an elastic material provided with an end-side annular rib 1c. Each of the annular ribs 1b and 1c is made slightly larger than the inner diameter of the outer cylinder 4, and is compressed and deformed in the outer cylinder 4 so as to be in contact with the inner wall while maintaining a close contact state. In the prefilled syringe 25, the inner wall surface of the outer cylinder 4 and the annular ribs 1 b and 1 c provided on the gasket 1 come into contact with each other to seal the drug solution 6 in the outer cylinder 4 in a liquid-tight manner. The number of annular ribs is not limited to two, and may be one or three or more.

  As shown in FIG. 3, the gasket 1 includes a plunger mounting portion 1d provided as a recess from the bottom surface. The plunger mounting portion 1d is formed as a substantially cylindrical recess extending from the bottom surface of the rear end of the gasket 1 to the vicinity of the tip portion inside the annular outer wall 1a, and a female screw is provided on the side surface of the recess.

  FIG. 4 is a schematic cross-sectional view of the cap 2.

  The cap 2 is a cap-shaped molded body of an elastic material that is fitted into the cylinder tip portion 7 in which the outer cylinder 4 is opened as shown in FIG. 1 in the manufacturing process of the prefilled syringe. The cap 2 fitted in the tube tip portion 7 has an inner diameter slightly smaller than the outer diameter of the tube tip portion 7 in order to prevent the chemical liquid 6 accommodated in the outer tube 4 from leaking from the tube tip portion 7 before use. The chemical solution 6 is sealed in a liquid-tight manner while being expanded by elasticity. Further, when using the prefilled syringe, a medical worker removes the cap 2 from the outer cylinder 4 and attaches an unillustrated injection needle to the injection needle mounting portion 8 at the tip thereof. Normally, the surface of the tube tip portion 7 is not coated with a lubricant in order to prevent unintentional removal.

The manufacturing method of the gasket 1 and the cap 2 will be described in detail.
The gasket 1 and the cap 2 are molded bodies of an elastic material obtained by surface-treating the surface of the molded body with an aqueous liquid containing, for example, a both-end hydroxyl group-blocked modified silicone oil having an amino group in the side chain.

  Specific examples of the elastic material include various rubber materials such as natural rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, nitrile-butadiene rubber, styrene-butadiene rubber, butadiene rubber, and silicone rubber; Various elastomer materials such as hydrogenated styrene-based elastomer, polyvinyl chloride-based elastomer, olefin-based elastomer, polyester-based elastomer, polyamide-based elastomer, and polyurethane-based elastomer can be used. These elastic materials may be blended with oil such as liquid paraffin and process oil and inorganic fillers such as talc and mica as necessary to adjust slidability and mechanical properties. Good. These elastic materials may be used alone or in combination of two or more.

  The molding method of the molded body of the gasket or cap is not particularly limited, and for example, a conventionally known molding method of a rubber molding or a molding method of a thermoplastic elastomer is used. Moreover, the obtained molded object is heat-processed for a vulcanization process or a crosslinking process as needed.

  The molded body for the gasket or cap is treated with an aqueous liquid containing a hydroxyl group-modified silicone oil having both ends having amino groups in the side chains. The both-end hydroxyl-blocked modified silicone oil having an amino group in the side chain is preferably treated with an aqueous solution that does not use an organic solvent or the like from the viewpoint of the environment in order not to cause condensation in the solution. Examples of the method for treating the molded body with an aqueous liquid include a method in which the aqueous liquid is brought into contact with the sliding region of the molded body for a predetermined time and then dried.

Hydroxyl groups at both ends capped modified silicone for oil having an amino group in the side chain, under following general formula (1):

（式中、ｍは５〜１００、Ｒ ₁ は、少なくとも一方が、−C ₃ H ₆ NH ₂ ，−C ₃ H ₆ NHC ₂ H ₄ NH ₂ ，−C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ NH ₂ ，−CH ₂ CH（CH ₃ ）CH ₂ NHC ₂ H ₄ NH ₂ ，−C ₃ H ₆ N（CH ₂ CH（OH）CH ₂ OH）C ₂ H ₄ NH（CH ₂ CH（OH）CH ₂ OH）からなる群から選ばれる少なくとも１種であり、他方は水素原子または他の炭化水素基であってもよい）、
に示される、化合物である。

(In the formula, m is 5 to 100, and R ₁ is at least one of —C ₃ H ₆ NH ₂ , —C ₃ H ₆ NHC ₂ H ₄ NH ₂ , —C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ NH ₂ , -CH ₂ CH (CH ₃ ) CH ₂ NHC ₂ H ₄ NH ₂ , -C ₃ H ₆ N (CH ₂ CH (OH) CH ₂ OH) C ₂ H ₄ NH (CH ₂ CH (OH) At least one selected from the group consisting of ( CH ₂ OH), and the other may be a hydrogen atom or another hydrocarbon group),
It is shown in a reduction compounds.

  The aqueous liquid containing the modified silicone oil is used in the form of an emulsion or solution containing the modified silicone oil at a predetermined concentration. Although the density | concentration of the modified silicone oil in an aqueous liquid is not specifically limited, Specifically, it is preferable that it is 0.0002 to 0.5 mass%, for example, and also 0.01 to 0.3 mass%. If the concentration of the modified silicone oil in the aqueous liquid is too low, the effect of improving the slidability tends to be insufficient, and if it is too high, the further improvement of the effect of improving the slidability is small and economically unsatisfactory. Tend to be profitable.

  As the aqueous liquid, an emulsion of a modified silicone oil is particularly preferable because of its excellent stability. The type of surfactant for emulsifying the modified silicone oil is not particularly limited. Specific examples thereof include anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, and alkyl phosphates; Nonionic surfactants such as oxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; alkyl betaines, Examples include amphoteric surfactants such as alkylimidazolines.

  Such an emulsion is commercially available as a silicone oil emulsion having a concentration of about 20 to 80% by mass. The aqueous liquid used in the present embodiment is preferably used by diluting such a silicone oil emulsion with water, for example, to a modified silicone oil concentration of about 0.0002 to 0.5 mass%.

  The aqueous liquid may further contain other additive components. Specific examples of such additives include low molecular weight silane compounds, silane coupling agents, titanate coupling agents, aluminate coupling agents, etc. for improving the adhesion between the coating film to be formed and the substrate. Coupling agents, fluororesin powder, silicone rubber powder, silicone resin powder, and inorganic fillers such as talc and clay, which are components that can improve slidability and pulsation. Among these, in particular, when 0.5 to 20 parts by mass of a low molecular siloxane compound such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane is included with respect to 100 parts by mass of the modified silicone oil, the solution stability ( From the viewpoint of (dispersibility).

  The liquidity of the aqueous liquid is not particularly limited, but in order to improve the solution stability (dispersibility) and form a uniform film, the pH is in the range of 4.5 to 7.5, and further the pH is 4.5 to 7.0. It is preferable to adjust to the range. The pH is adjusted by, for example, dissolving a pH adjusting agent such as acetic acid or formic acid in a solution or emulsion.

  Examples of the method of bringing the molded body main body into contact with the aqueous liquid include a method of immersing the molded body main body in the aqueous liquid, and a method of bringing the aqueous liquid into contact with only a predetermined sliding region of the molded body main body by spray coating. The surface treatment does not necessarily have to be performed on the entire surface, and it is sufficient that the surface treatment is performed at least on the sliding region. The contact time is not particularly limited, but specifically, for example, it is preferably about 5 minutes to 6 hours, more preferably about 10 minutes to 1 hour. If the immersion time is too long, further improvement of the slidability improvement effect is small and economically disadvantageous. If the immersion time is too short, the improvement effect of the slidability tends to be insufficient. .

  The temperature of the aqueous liquid is preferably in the range of 20 to 80 ° C, more preferably about 30 to 50 ° C. When the temperature of the aqueous liquid is too low, the modified silicone oil does not adhere sufficiently to the surface of the molded article body, and it tends to take too much time to adhere sufficiently, and when it is too high Has a tendency that the stability of the aqueous liquid is lowered, and a film is deposited on the surface of the aqueous liquid or the emulsion is broken.

  It is preferable that the molded article main body immersed or brought into contact with the aqueous liquid for a predetermined time is washed with water. By washing the molded body that has been treated with the aqueous liquid with water and washing away the aqueous liquid that has not adhered to the surface, no stains remain on the surface of the treated molded body. In addition, when it dries without performing such water washing, there exists a tendency for a white droplet trace to remain as a spot. And after washing with water in this way, it dries. The drying conditions are not particularly limited, but it is preferable to dry at a temperature of 120 ° C. or lower from the viewpoint of preventing thermal deterioration of the molded product body. For example, air drying may be performed by blowing high-pressure air to the molded product body after washing. . By such a surface treatment, a member for a syringe in which a film having excellent slidability is formed on the surface of the elastic molded body is obtained.

  The elastic member such as the gasket 1 and the cap 2 of the present embodiment is preferably used as an elastic member used for a sliding portion of a medical prefilled syringe or a disposable syringe, for example.

  For example, the prefilled syringe 25 is manufactured as follows. First, the cap 2 is fitted into a tube tip portion where the tip of the tip portion of the syringe outer tube 4 is opened. And the chemical | medical solution 6 is filled into the inside of the outer cylinder 4 by which the front-end | tip was sealed with the cap 2. As shown in FIG. And the gasket 1 is arrange | positioned in the opening part of the outer cylinder 4 in a pressure-reduced atmosphere, and after that, the gasket 1 is inserted so that it may contact | abut to the inner wall face of the outer cylinder 4 by making it a normal pressure state. And by attaching the plunger 3 to the gasket 1, the prefilled syringe 25 in which the chemical | medical solution 6 was accommodated is obtained.

  Such a prefilled syringe 25 has a coating with excellent slidability formed on the surface of the gasket 1, so there is little variation in slidability, and the plunger is moved under extremely low speed conditions using a syringe pump. In such a case, it is possible to suppress a trouble such that the plunger stops moving due to frictional resistance and the syringe pump stops. In addition, the cap that is fitted to the cylinder tip of the outer cylinder and removed during use is not easily dropped because the cap is properly fitted to the cylinder tip.

  The present invention will be described more specifically with reference to examples. The scope of the present invention is not limited to the examples.

[Example 1]
Using a butyl rubber composition mainly composed of chlorobutyl rubber, a gasket body having a shape as shown in FIGS. 2 and 3 and a cap body having a shape as shown in FIG. 4 were produced. Specifically, the butyl rubber composition was press-molded and vulcanized in a gasket-shaped or cap-shaped mold. The shape of the molded product main body of the obtained gasket is as follows: the outer diameter of the annular outer wall is 19.6 mm, the height of the annular outer wall is 10.5 mm, the height from the upper end of the annular outer wall to the gasket tip is 3.5 mm, the rib on the front end and the rear end The outer diameter of the side annular rib was 20.5 mm, and the length from the center of the front end side annular rib to the center of the rear end side annular rib was 7 mm. Moreover, the shape of the obtained cap was a cylindrical shape with an outer diameter of 10 mm and a height of 14 mm, and a bottomed cylindrical shape with an inner diameter of 4 mm and a height of 8 mm.

  Then, a hydroxyl-terminated dimethyl (aminoethylaminopropyl) methylsiloxane emulsion containing a nonionic surfactant (X52-2265 manufactured by Shin-Etsu Chemical Co., Ltd. having a modified silicone oil concentration of 40 mass%) is diluted with ion-exchanged water. Furthermore, a modified silicone oil concentration of 0.05% by mass by mixing a low molecular weight silane compound (octamethylcyclotetrasiloxane, SH244 manufactured by Toray Dow Corning Co., Ltd.) and acetic acid according to the composition shown in Table 1. An aqueous liquid was prepared. The pH of the obtained aqueous liquid was 5.0.

  And three gasket main bodies and a cap main body were immersed in 100 mL of aqueous liquid heated to 40 degreeC for 30 minutes. Then, the immersed gasket main body and cap main body were taken out and further immersed in water and washed with water three times. Washing with water was performed by exchanging water each time, and each immersion was performed for 1 minute. And the gasket and cap by which surface treatment was carried out were performed by applying compressed air to the gasket main body and cap main body after water washing, and removing water sufficiently. And the sliding resistance of the obtained gasket was evaluated by the following method. In addition, the ease of fitting the cap and the detachability were evaluated by the following methods.

(Evaluation of sliding resistance of gasket)
A ready-made gasket at the tip of the plunger of a commercially available syringe (manufactured by Terumo Corp.) having a syringe outer cylinder with a length of 93 mm, an inner diameter of 19.7 mm, an outer diameter of the tip of 4.1 mm, and a length of the tip of 10 mm, It was replaced with the produced gasket. And silicone oil SH200 12,500cs (Toray Dow Corning Co., Ltd.) was apply | coated to the inner wall surface of the outer cylinder for syringes. Then, the plunger is inserted up to a predetermined marked line of the outer cylinder for syringe, and the load when the plunger is pushed 10 mm from the predetermined marked line at a pushing speed of 0.5 mm / min is a strograph (V1-C, Toyo Seiki Seisakusho The maximum load at that time was defined as sliding resistance. Three tests were performed, and the average value was calculated.

(Ease of fitting the cap)
The caps obtained at the tip of the syringe outer cylinder were attached to and removed from 10 randomly selected monitors, and the ease of fitting and removal were determined according to the following criteria.
A: Fits up to the base of the tube.
B: The resistance is remarkably increased in the middle of the tube tip and is not fitted to the base of the tube tip.

(Evaluation of cap removal)
After lightly fitting the cap obtained at the tip of the syringe outer cylinder, it was fitted using a strograph at a speed of 10 mm / min until a load of 5.6 kgf was reached, and the fitting situation was confirmed. Then, the plunger was pushed in at a speed of 50 mm / min using a strograph, and the load at which the cap was removed from the cylinder tip was measured. Three tests were performed, and the average value was calculated.
The results are shown in Table 1.

[Example 2]
An aqueous liquid was prepared in the same manner as in Example 1 except that the low molecular weight silane compound was not added. The pH of the obtained aqueous liquid was 5.1. Then, the gasket main body and the cap main body were subjected to surface treatment in the same manner as in Example 1 except that the surface treatment was performed by immersing in this aqueous liquid, and a gasket and a cap were obtained and evaluated in the same manner. The results are shown in Table 1.

[Example 3]
An aqueous liquid was prepared in the same manner as in Example 1 except that acetic acid was not added. The pH of the obtained aqueous liquid was 7.5. Then, the gasket main body and the cap main body were subjected to surface treatment in the same manner as in Example 1 except that the surface treatment was performed by immersing in this aqueous liquid, and a gasket and a cap were obtained and evaluated in the same manner. The results are shown in Table 1.

[Example 4]
In the treatment with the aqueous liquid, the molded product main body was immersed in an aqueous liquid at 40 ° C. for 30 minutes, and instead of drying with compressed air, the molded product main body was immersed in an aqueous liquid at 20 ° C. for 1 minute, and then 50 ° C. Except for drying in the oven for 3 hours, the gasket main body and the cap main body were subjected to surface treatment in the same manner as in Example 1 to obtain a gasket and a cap, which were similarly evaluated. The results are shown in Table 1.

[Comparative Example 1]
Evaluation was performed in the same manner as in Example 1 except that the gasket body and the cap body were used as they were without performing the surface treatment immersed in the aqueous liquid instead of the gasket and the cap surface-treated by immersion in the aqueous liquid. The results are shown in Table 1.

[Comparative Example 2]
Silicone prepared using a silicone oil emulsion containing 28% by mass of dimethyl silicone oil (KM-742T, Shin-Etsu Chemical Co., Ltd.) instead of an emulsion containing hydroxyl-terminated dimethyl (aminoethylaminopropyl) methylsiloxane Except for using an aqueous liquid having an oil concentration of 2% by mass, the gasket main body and the cap main body were subjected to surface treatment in the same manner as in Example 4 to obtain a gasket and a cap, which were similarly evaluated. The results are shown in Table 1.

[Comparative Example 3]
Gasket and cap were subjected to surface treatment of the gasket body and cap body in the same manner as in Comparative Example 2, except that an aqueous liquid having a silicone oil concentration of 9% by mass was used instead of the aqueous liquid having a silicone oil concentration of 2% by mass. And evaluated similarly. The results are shown in Table 1.

[Comparative Example 4]
Instead of an emulsion containing a hydroxyl-terminated dimethyl (aminoethylaminopropyl) methylsiloxane, a 100% silicone oil solution containing a polyether-modified organopolysiloxane (KM-244F from Shin-Etsu Chemical Co., Ltd.) was used. The gasket main body and the cap main body were subjected to surface treatment in the same manner as in Example 4 except that an aqueous solution having a silicone oil concentration of 2% by mass was used. The results are shown in Table 1.

[Comparative Example 5]
A gasket and a cap were obtained by performing a surface treatment on the gasket body and the cap body in the same manner as in Comparative Example 4 except that an aqueous solution with a silicone oil concentration of 9 mass% was used instead of the aqueous solution with a silicone oil concentration of 2 mass%. , Evaluated in the same way. The results are shown in Table 1.

From the results in Table 1, it can be seen that the gaskets obtained in Examples 1 to 4 all show a lower sliding resistance than the gasket of the comparative example. In addition, it can be seen that the caps obtained in Examples 1 to 4 are easier to fit than the caps of the comparative examples, and when fitted, they are not easily removed.
Moreover, when it processes with the aqueous liquid of Example 2 which does not contain octamethylsiloxane, it turns out that sliding property falls a little. This seems to be because the adhesion of the coating on the surface is slightly inferior. It can also be seen that the slidability is slightly lowered when the aqueous solution of Example 3 which was not adjusted for pH with acetic acid. This seems to be because the stability of the solution was lowered and the homogeneity of the surface treatment of the molded body was lowered.

DESCRIPTION OF SYMBOLS 1 Gasket for syringes 2 Cap 3 Plunger 4 Outer cylinder for syringes 5 Flange 6 Chemical solution 7 Tube tip 8 Injection needle mounting part 25 Prefilled syringe

Claims (9)

At least the sliding region of the elastic molded body having a sliding region is surface-treated with a treatment liquid containing silicone oil,
The silicone oil has the following general formula (1):

(In the formula, m is 5 to 100, and R ₁ is at least one of —C ₃ H ₆ NH ₂ , —C ₃ H ₆ NHC ₂ H ₄ NH ₂ , —C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ NH ₂ , -CH ₂ CH (CH ₃ ) CH ₂ NHC ₂ H ₄ NH ₂ , -C ₃ H ₆ N (CH ₂ CH (OH) CH ₂ OH) C ₂ H ₄ NH (CH ₂ CH (OH) At least one selected from the group consisting of ( CH ₂ OH), and the other may be a hydrogen atom or other hydrocarbon group)
A member for a syringe, which is a silicone oil having both ends hydroxyl-blocked and modified with an amino group in the side chain , as shown in FIG .   2. The syringe member according to claim 1, wherein the both-end hydroxyl group-blocked modified silicone oil having an amino group in the side chain is hydroxyl-terminated dimethyl (aminoethylaminopropyl) methylsiloxane.   The syringe member according to claim 1 or 2, wherein the treatment liquid further contains a low molecular weight silane compound.   The syringe member according to any one of claims 1 to 3, wherein the elastic molded body is a molded body of a composition containing halogenated butyl rubber as a main component.   It is a gasket for syringes, The member for syringes of any one of Claims 1-4.   It is a cap attached to the cylinder tip part of the outer cylinder for syringes, The member for syringes of any one of Claims 1-4. A syringe outer cylinder and a plunger slidably inserted into the syringe outer cylinder;
A syringe gasket is attached to the tip of the plunger,
A cap is fitted to the tube tip of the syringe outer tube,
A medical syringe, wherein the syringe gasket is the syringe gasket according to claim 5 and / or the cap is the cap according to claim 6. A method for producing the syringe member according to claim 1,
A method for producing a member for a syringe, comprising: contacting at least the sliding region of the elastic molded body with an aqueous liquid containing the silicone oil for a certain period of time, followed by washing with water. The method for producing a member for a syringe according to claim 8, wherein the liquidity of the aqueous liquid is in a range of pH 4.5 to 7.5.

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