JP2003111843A - Cap for syringe, syringe, and method of manufacturing for cap for syringe - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cap for a syringe, a syringe, and a method of manufacturing the cap, the cap being stable for a variety of medicines and having elasticity, ease of molding, and cost effectiveness as a cap. SOLUTION: Cap-shaped plunger packing 4 elastically mounted to a tip of a plunger rod 3 of the syringe 1 comprises composite materials including a hardened elastomer 41 forming a mounting recess 40 for mounting to the tip of the plunger rod 3, and a fluororesin seat 42 covering the outer surface of the hardened elastomer 41. The fluororesin seat 42 makes contact with a medicine in an outer cylinder 2, with a side face part 43 of the seat making sliding contact with the inner surface of the outer cylinder 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a syringe cap used at a portion in contact with a liquid medicine in a syringe for medical use or for discharging a resin or a medicine, and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, plastic syringes have become the mainstream in place of glass syringes.
This plastic syringe is generally composed of a plastic outer cylinder, a plastic plunger rod inserted into the outer cylinder, and a plunger packing (syringe cap) attached to the tip of the plunger rod. The plunger packing is in contact with the inner surface of the outer cylinder. As the plunger packing used for such a purpose, an elastomer cured body such as EPDM or IIR has been conventionally used.

[0003]

[Problems to be Solved by the Invention] However, EPD
Elastomer cured products such as M and IIR have chemical resistance to some extent, but elution of components from the elastomer cured product to the chemical liquid is unavoidable. Therefore, depending on the type of the chemical liquid, it was eluted from the elastomer cured product. There is a problem that it is inevitable that the components are injected into the human body. In addition, since the cured elastomers such as EPDM and IIR have strong adsorptivity, a new syringe has poor slidability of the syringe, and in a remarkable case, the tip end surface of the plunger packing is completely attached to the inner surface of the syringe. It may be adsorbed. For this reason, in the conventional plunger packing, it is necessary to apply silicone oil to the surface to enhance the slidability.

Furthermore, in recent years, for the purpose of eliminating the trouble of sucking a chemical solution, dealing with a high-viscosity chemical solution, preventing glass powder from being mixed when an ampoule is cut, and preventing an error in an injection amount, a predetermined amount of the injection liquid is injected into a syringe. It is considered that the drug solution is filled and supplied to a hospital or the like. In the case of such a prefill type syringe, the plunger packing attached to the tip of the plunger rod is in contact with the chemical liquid for a long period of time, which causes leakage of the chemical liquid due to deterioration of the cured elastomer body due to the chemical liquid. Becomes Further, since the plunger packing comes into contact with the chemical liquid for a long period of time that is not comparable to normal medical practice, depending on the type of the chemical liquid, elution of components from the cured elastomer to the chemical liquid may be a problem.

However, the above-mentioned syringe cap is
If a fluororesin that is stable in the chemical liquid is used, it is difficult to mold it into a cap shape, and it is not possible to obtain the elasticity required for the cap. Also,
There is also a problem that if the entire cap is made of a fluorine-based resin, it becomes considerably expensive.

In view of the above-mentioned problems, the present invention provides a syringe cap, a syringe cap, which is stable to various chemicals and has elasticity as a cap, easiness of molding and cost efficiency.
Another object of the present invention is to provide a method for manufacturing a syringe cap.

[0007]

In order to solve the above-mentioned problems, according to the present invention, a syringe cap mounted as a plunger packing on the tip portion of a plunger rod inserted into the outer cylinder of a syringe, and this syringe cap. In the syringe using, the syringe cap is
It is characterized in that it is composed of a composite material including an elastomer hardened body that constitutes a concave portion for mounting on the tip end portion of the plunger rod, and a fluororesin body that covers the outer surface of the elastomer hardened body.

In the syringe cap (plunger packing) according to the present invention, a fluorine-based resin having an excellent chemical resistance on the outer surface in contact with the chemical liquid with respect to the elastomer cured body forming the recess for mounting the tip of the plunger rod. Since it is covered with the body, there is no elution of components from the syringe cap into the drug solution when performing normal medical procedures or when filling the drug solution into the syringe and supplying it to hospitals, etc. No deterioration due to chemicals. Further, in the syringe cap, the fluororesin body that comes into contact with the outer cylinder has no adsorptivity unlike the elastomer cured body, so that even a new syringe has good slidability in the syringe, and
The tip surface of the syringe cap is not completely adsorbed on the inner surface of the syringe. Therefore, it is not necessary to apply silicone oil to the surface. Moreover, since the fluororesin body is a composite material with the elastomer cured body, it has elasticity enough to function as a cap, and at the same time, is easy to mold into a cap and cost effective.

Further, according to the present invention, there is provided a syringe cap mounted on a cylindrical needle mounting portion to which a base portion of a needle is mounted at a distal end portion of an outer cylinder of the syringe, and a syringe using the syringe cap, The syringe cap is characterized by being made of a composite material including an elastomer cured body that forms a mounting recess for the needle mounting portion, and a fluororesin body that covers the inner surface of the elastomer cured body.

In the syringe cap according to the present invention, the inner surface of the elastomer cured body, which constitutes the recess for mounting the needle mounting portion, in contact with the chemical, is covered with the fluororesin body having excellent chemical resistance. Therefore, even when a syringe is filled with a drug solution and supplied to a hospital or the like, there is no elution of components from the syringe cap into the drug solution, and there is no risk of leakage of the drug solution due to deterioration due to the drug solution. Moreover, since the fluororesin body is a composite material with the elastomer cured body, it has elasticity enough to function as a cap, and at the same time, is easy to mold into a cap and cost effective.

In the present invention, the fluororesin body is
For example, it is a fluororesin sheet. The elastomer cured product is, for example, silicone rubber or butyl rubber.

In the method for manufacturing a syringe cap according to the present invention, at least one surface of the fluororesin body is modified by low temperature plasma treatment under a gas atmosphere under a pressure of 0.1 to 1.1 kg / cm ^2. A first step of curing the fluororesin body, a second step of applying a silane coupling agent to the modified surface of the fluororesin body, and an unvulcanized elastomer composition containing a vulcanizing agent, the silane of the fluororesin body. A third step of obtaining a sheet-shaped composite material in which the fluororesin body and the elastomer cured body are joined and integrated by heating or heating and pressing while being in contact with the coupling agent application surface, and the sheet-like composite material And a fourth step of forming the syringe cap.

In the method for producing a syringe cap according to the present invention, at least one surface of the fluororesin body is subjected to a low temperature plasma treatment under a gas atmosphere under a pressure of 0.1 to 1.1 kg / cm ^2. The first step of modifying by the above, a second step of preparing an unvulcanized elastomer composition containing a vulcanizing agent and a silane coupling agent, and a modification of the fluororesin body with the unvulcanized elastomer composition. By heating or heating and pressing while in contact with the quality surface,
You may perform the 3rd process of obtaining the sheet-shaped composite material by which the said fluororesin body and the elastomer hardened | curing body were joined together, and the 4th process of forming the said cap for syringes from the said sheet-shaped composite material.

The inventors of the present application have conducted a series of studies on a method of modifying the surface of a resin material to form a stronger joint surface with an elastomer. A state in which a low-temperature plasma treatment is performed under a pressure of 1.1 kg / cm ^{2 which} is relatively close to atmospheric pressure, and a silane coupling agent is applied to the treated surface, or a silane coupling agent is contained in the elastomer in advance. It was found that when both are vulcanized and molded, an extremely high-strength joint surface, which cannot be obtained by the conventional method, can be obtained. Therefore, according to the present invention, with respect to the cured elastomer body that constitutes the mounting recess for mounting the tip end portion of the plunger rod or the needle mounting portion of the outer cylinder, the side in contact with the chemical liquid is covered with the fluororesin body. A syringe cap can be constructed.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described with reference to the drawings.

[First Embodiment] FIG. 1 is a perspective view showing the construction of a syringe to which the present invention is applied. 2A,
(B) is an exploded perspective view of a syringe to which the present invention is applied, and a cross-sectional view of a plunger packing (a syringe cap) attached to a tip end portion of a plunger rod. Figure 3
(A)-(D) is process sectional drawing which respectively shows the manufacturing method of the plunger packing shown in FIG.2 (B).

As shown in FIGS. 1 and 2 (A), a syringe 1 of the present embodiment has a circular outer cylinder 2 made of plastic, a cylindrical plunger rod 3 inserted into the outer cylinder 2, and a cylindrical plunger rod 3 A cylindrical needle mounting portion 21 to which the base of the needle 7 is mounted is formed at the tip of the outer cylinder 2 and is composed of a plunger packing 4 (a syringe cap) attached to the tip of the plunger rod 3. ing. In this syringe 1, the plunger rod 3 has a radial portion 4 extending from the central portion.
The plate-shaped portions 31 and the disc-shaped connecting portions 32 formed at the tips of the plate-shaped portions 31 and the four disc-shaped connecting portions 32 extending from the disc-shaped connecting portion 32 toward the tip side to form a constricted portion. A plate-shaped portion 33 and a disc-shaped cap mounting portion 34 formed on the tip end side of these plate-shaped portions 33 are configured, and the plunger packing 4 is configured to cover the disc-shaped cap mounting portion 34. It is elastically attached to the tip of the plunger rod 3.

The plunger packing 4 of this embodiment is shown in FIG.
As shown in (B), an elastomer cured body 41 that constitutes a mounting recess 40 on the tip of the plunger rod 3 and a fluorine resin sheet 42 (fluorine resin body) that covers the outer surface of the elastomer cured body 41 are provided. The fluororesin sheet 42 made of a composite material comes into contact with the chemical liquid in the outer cylinder 2, and the side surface portion 43 slides on the inner surface of the outer cylinder 2. In this embodiment, silicone rubber is used as the elastomer cured body 41. Here, the fluorine-based resin sheet 42 is the tip surface 41 of the elastomer cured body 41.
0 and the entire side surface portion 411 are covered. Further, in the plunger packing 4, a slight constricted portion is formed in the outer peripheral surface of the side surface portion 43 in the circumferential direction.
By collecting the chemical liquid for 30 minutes, liquid tightness is secured between the plunger packing 4 and the inner peripheral surface of the outer cylinder 2, and the slidability is improved.

On the inner surface of the plunger packing 4,
Small protrusions 46 are formed to prevent the plunger packings 4 from sticking to each other when handling them with a parts feeder or the like.

Thus, in the injector 1 of this embodiment,
In the plunger packing 4, the elastomer cured body 4 forming the mounting recess 40 in the tip end portion of the plunger rod 3
1, the outer surface in contact with the drug solution is covered with the fluorine-based resin sheet 42 having excellent chemical resistance, so that the drug solution is filled in the syringe 1 and supplied to a hospital or the like when performing a normal medical procedure. In either case, the components are not eluted from the plunger packing 4 into the chemical liquid, and the plunger packing 4 is not deteriorated by the chemical liquid.

For example, if 5 cc of toluene is filled in a 5 cc syringe and 6 hours have passed, a conventional plunger packing made of butyl rubber will swell, so that the initial stage required to move the plunger rod is increased. If the torque is set to 100, a torque of 270 is required to move the plunger rod after 6 hours. On the other hand, in the case of the plunger packing to which the present invention is applied, since the plunger packing does not swell, the initial torque required to move the plunger rod is 10
If 0, 100 torque is sufficient to move the plunger rod after 6 hours.

Further, in the plunger packing 4, the fluorine-based resin sheet 42 which is in contact with the outer cylinder 2 has no adsorptivity unlike the elastomer hardened body 41, so that even a new syringe has good slidability in the syringe 2. In addition, the tip end surface of the plunger packing 4 is not completely adsorbed to the inner surface of the syringe 2. Therefore, since it is not necessary to apply silicone oil to the surface, there is no risk that silicone oil will be mixed with the chemical liquid. Moreover, the fluorine-based resin sheet 42
Since it is a composite material with the elastomer cured body 41, it has elasticity enough to function as a cap, and also has easy molding into a cap shape and cost efficiency.

To manufacture the plunger packing 4 having such a structure, one surface of the fluororesin sheet 42 is
After being modified by low temperature plasma treatment under a pressure of 0.1 to 1.1 kg / cm ^{2 in} a gas atmosphere (first step), a silane coupling agent is applied to the modified surface of the fluororesin sheet 42 (first step). 2 step), and then, the unvulcanized elastomer composition containing the vulcanizing agent is heated or heated and pressed in a state of being in contact with the silane coupling agent application surface of the fluororesin sheet 42, so that the composition shown in FIG. As shown in (), a sheet-shaped composite material 45 in which the fluorine-based resin sheet 42 and the elastomer cured body 42 are joined and integrated is obtained (third step). The sheet-shaped composite material 45 includes a fluororesin sheet 42,
The sheet-shaped elastomer cured body 41 is joined and integrated with very high strength.

Next, as shown in FIG. 3B, a sheet-shaped composite material 45 is molded by using a predetermined mold material (not shown), and then, at a position indicated by an alternate long and short dash line L1 in FIG. 3B. It cuts and many plunger packings 4 are taken as shown in FIG.3 (C).

As a result, as shown in FIG. 3 (D), a cured elastomer body 41 and a cured elastomer body 4 which form a recess 40 for mounting the plunger rod 3 in the tip end portion.
It is possible to manufacture the plunger packing 4 made of the composite material including the fluorine-based resin sheet 42 that covers the outer surface of 1.

The sheet-like composite material 4 in which the fluorine-based resin sheet 42 and the cured elastomer body 41 are integrally joined together
In order to obtain No. 5, in addition to the above method, one surface of the sheet-shaped fluororesin sheet 42 is modified by low temperature plasma treatment under a gas atmosphere under a pressure of 0.1 to 1.1 kg / cm ^2. While vulcanizing (first step), an unvulcanized elastomer composition containing a vulcanizing agent and a silane coupling agent is prepared (second step), and the unvulcanized elastomer composition is treated with the fluororesin sheet 42. The sheet-shaped composite material 45 as shown in FIG. 3 (A) may be obtained by heating or pressurizing while being in contact with the modified surface (3) (third step). Also in this case, the plunger packing 4 can be formed from the sheet-shaped composite material 45 by the same method as described with reference to FIGS. 3B to 3D (fourth step).

In such a sheet-shaped composite material 45,
The sheet-shaped fluororesin sheet 42 is mainly composed of a fluororesin having excellent weather resistance, stain resistance, slidability, chemical resistance, heat resistance, and hot water resistance. Various fillers (graphite, short fibers such as carbon and glass, molybdenum disulfide, etc.) may be blended. In particular, when properties such as low gas permeability, folding resistance, high tear strength, etc. are required, it is preferable to select other compounding components with these in mind.

Specific fluororesins include tetrafluoroethylene (PTFE), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and trifluoroethylene. There are fluorinated ethylene chloride (PCTFE), propylene hexafluoride copolymer (FEP), etc.
ETFE is particularly preferable in terms of availability and price.

The uncured elastomer composition used for forming the sheet-like composite material 45 of the present invention comprises an uncured elastomer component, a vulcanizing agent, and an appropriate filler if necessary. Examples of the composition include: As the elastomer component, various types are used, but silicone rubber is suitable from the viewpoint of chemical resistance and the like.

Examples of the vulcanizing agent used in combination with the elastomer component include organic peroxides, metal oxides and polyols. As the organic peroxide, various kinds are used, but among them, a dialkyl peroxide is preferable.

Specific examples of the dialkyl peroxide include di-t-butyl peroxide, di-t-amyl peroxide, t-butylcumyl peroxide, dicumyl peroxide and 2,5-dimethyl-2. , 5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-
(3), α, α′-bis (t-butylperoxy) diisopropylbenzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,
3-bis (t-butylperoxyisopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) ) Propane, 2,2-bis-
(T-Butylperoxy) butane, 1,1-di- (t-
Butyl peroxy) cyclohexane and the like. Among them, dicumyl peroxide, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane is particularly preferable because it is relatively easy to handle and generally available.

Further, as the metal oxide, ZnO, Mg
Examples thereof include O, PbO, Pb ₃ O _{4 and the} like.

The low-temperature plasma treatment used in the present invention is a treatment carried out by utilizing plasma (also called non-equilibrium plasma) generated in a region where the electron temperature is high but the gas temperature is low. It is a technique of activating the surface by causing ions, electrons, radicals, vacuum ultraviolet rays and the like to act on the surface of the material to perform surface modification such as etching, implantation and radical generation. During the implantation, functional groups such as a hydroxyl group, a carbonyl group, and a carboxyl group are introduced on the surface of the material to improve the adhesiveness and the wettability. These act on the silane coupling agent and the vulcanizing agent of the unvulcanized elastomer composition to not only significantly improve the adhesion, but also to form a strong composite interface that can withstand various stresses.

As the gas used for this low temperature plasma treatment, an inert gas such as He, Ar, Ne, Kr, Xe, or C
Carbon oxide gas such as O ₂ and CO, oxidizing gas such as O ₂ and C
Examples of the reaction gas include F _{4 and the} like, polymerizable unsaturated compound gas such as ethylene and propylene, and air. These are appropriately selected according to the purpose and used alone or in combination. However, in the present invention, the low temperature plasma treatment is performed under a pressure of 0.1 to 1.1 kg / cm ² , and therefore, among them, an inert gas, a carbon oxide gas, and a polymerizable unsaturated compound gas are used. It is preferable to use a mixed gas in which the above are combined, and in particular, it is particularly preferable to use a mixed gas of Ar, CO _2, and ethylene.

When a mixed gas is used, 1 to 1 of the polymerizable unsaturated compound gas is added to 100 mol of the inert gas.
5 mol, 1 to 20 mol of carbon oxide gas is preferably blended, and most preferably, 3 to 10 mol of the polymerizable unsaturated compound gas and 1 to 10 mol of the carbon oxide gas are added to 100 mol of the inert gas. It is to mix 12 mol. This is because when the mixing ratio of the polymerizable unsaturated compound gas and the carbon oxide gas increases, the initial discharge voltage increases and the discharge treatment becomes difficult.

The discharge treatment method is performed by exposing the surface of the fluorine-based resin sheet 42 to be treated in a predetermined gas atmosphere and applying a high frequency voltage of, for example, 3 to 40 kHz between the electrodes. The temperature during the discharge treatment is not particularly limited, but is usually preferably in the range of 10 to 80 ° C, and particularly preferably in the range of 25 to 60 ° C.

In the present invention, the low temperature plasma treatment is
The reason why the pressure is 0.1 to 1.1 kg / cm ² is as follows. That is, if it is attempted to carry out under a pressure of less than 0.1 kg / cm ² , it is necessary to maintain a vacuum in the system, so a special device is required, which increases the equipment cost and lowers the gas density. This is because such a modified surface cannot be obtained. On the other hand, if it exceeds 1.1 kg / cm ² , no further treatment effect can be obtained although the gas consumption increases, which is not economical.

In the present invention, it is particularly preferable to use the apparatus shown in FIG. 4 because the low temperature plasma treatment of the fluororesin sheet 42 can be continuously performed.

FIG. 4 is an explanatory diagram of a low temperature plasma processing apparatus that can be used for implementing the present invention. In this figure, since the low temperature plasma processing apparatus 100 performs the low temperature plasma processing under a pressure close to atmospheric pressure, the plasma furnace 113 is provided with slits 114 and 115.
The belt-shaped fluororesin sheet 42 fed from the supply roll 116 is introduced into the furnace through the slit 114, passed between the upper and lower electrodes 117 and 118 to perform low temperature plasma treatment, and discharged from the slit 115 to the outside of the furnace. By winding on the winding roll 119, the fluororesin sheet 4
In contrast to No. 2, the low temperature plasma treatment is continuously performed. A gas such as an inert gas is continuously supplied into the furnace from the gas supply port 120, and the slit 11
It comes out from 4, 115. Also, 12
Reference numeral 1 is a dielectric coating attached to the upper and lower electrodes 117 and 118.

Next, examples of the silane coupling agent applied to the modified surface of the fluororesin sheet 42 obtained by the low temperature plasma treatment include the silane coupling agent represented by the following chemical formula (1). These may be used alone or in combination of two or more.

[0041]

[Chemical 1]

Specific examples of this silane coupling agent include γ-methacryloxypropyltriethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropyl methyl dietoxylan,
γ-methacryloxypropyl methoxysilane, N-β-
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, γ-
Glycidoxypropylpropylmethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) Examples thereof include silane and γ-isocyanatopropyltriethoxysilane. However, among these silane coupling agents, amino-functional silane compounds are effective adhesion promoters, but when used in a large amount, they cause remarkable discoloration when continuously exposed to a high temperature of about 100 ° C. Or, since the curing deterioration progresses and the adhesive force decreases, it is preferable not to use it alone if possible. In addition, by using an isocyanate-based silane coupling, the material to be joined,
Since a high-strength joint surface having a certain level or more can be obtained regardless of the joint form, it has a wide range of application and is suitable.

These silane coupling agents may be used as they are, or if they are difficult to use as they are, they may be diluted with water, a solvent or the like from the viewpoint of coating workability. In that case, although the dilution ratio depends on the type of the silane coupling agent and the type of the elastomer component to be bonded, it is usually preferable to set it to 1.1 to 20 times in terms of workability.

The coating amount of the silane coupling agent (including the diluting liquid) on the modified surface of the fluororesin sheet 42 is not particularly limited, but is usually set to 10 to 40 g / m ^2. Is preferred. That is, the coating amount is 10 g
If it is less than / m ² , the adhesive strength is difficult to stabilize, and conversely it is 40
If it exceeds g / m ² , pressure may exude in the direction parallel to the coating surface during injection molding or compression molding, and the molding die may be contaminated, which may hinder removal of the molded product.

The coating method of the silane coupling agent is not particularly limited, and any coating method may be used, but spray coating is preferable in terms of uniform coating.

Usually, when a silane coupling agent is used to reinforce the joint between two materials, one surface of the material is coated with the silane coupling agent, the coated surface is dried, and then the other material is used. However, in the present invention, the silane coupling agent applied to the modified surface of the fluororesin sheet 42 is undried, and this surface is immediately treated with the unvulcanized elastomer composition. When the two are integrally molded by heating or heating and pressing so as to be in contact with each other, a higher-strength bonding interface can be obtained, which is preferable.

That is, in order to bond the fluororesin sheet 42 and the cured elastomer 41 with high strength, it is considered that the wettability of the unvulcanized elastomer composition with the fluororesin sheet 42 has a great influence. When the ring agent is brought into contact with the vulcanized elastomer composition in an undried wet state and molded and integrated in one step by heating or heating and pressing, the fluororesin receives the contact pressure of the unvulcanized elastomer composition. Wetting of the silane coupling agent to the modified surface of the sheet 42 and wetting of the silane coupling agent to the unvulcanized elastomer composition are simultaneously realized, and at this time, the silane coupling agent and the unvulcanized elastomer composition are They are mixed and diffused by the contact pressure of each other and the flow of the unvulcanized elastomer composition. As a result, the interface of the low-temperature plasma treated surface / silane coupling agent / unvulcanized elastomer composition is crosslinked by the action of the vulcanizing agent in a state in which the three components are mixed, and a bonding interface of unprecedented strength is obtained. it is conceivable that.

The "undried state" of the silane coupling agent means the state immediately after the completion of the coating operation without leaving the surface coated with the silane coupling agent for drying or leaving it to be air-dried.

Of the above-mentioned silane coupling agents, in particular, the methacryloxy-based silane coupling agent in which Y is a methacryloxy group in the above general formula (1) is generally prepared by preparing an aqueous solution thereof. The solution is sprayed onto the target surface and dried to develop the coupling effect. However, in the present invention, the methacryloxy silane coupling agent is applied as it is to the modified surface of the fluororesin sheet 42 as the undiluted solution. Just by applying, to the fluororesin sheet 42 and the unvulcanized elastomer composition,
A strong bonding interface can be formed. Further, with the methacryloxy-based silane coupling agent, it is possible to obtain a product in which the steps can be greatly simplified and the bonding strength is extremely excellent. It is considered that this is because the methacryloxy group of the methacryloxy silane coupling agent is directly supplied to the modified surface without being hydrolyzed and directly participates in the crosslinking via the vulcanizing agent.

In the present invention, the heating or heating / pressurizing conditions for curing the unvulcanized elastomer composition depend on the type of the elastomer composition and the size and thickness of the desired cured product. Heating temperature is 120-18
It is preferable that the temperature is 0 ° C. and the heating time is 1 to 60 minutes. The pressurizing condition is appropriately set according to the type of molding apparatus and the like.

The molding apparatus is not particularly limited, but a general injection molding machine, a pressure molding machine or the like can be used.

The sheet composite material 45 thus obtained
Is a dense and uniform surface treatment on the fluorocarbon resin sheet 42 by low temperature plasma treatment performed in a special pressure range,
Combined with the silane coupling agent and the complex crosslinking effect of the vulcanizing agent contained in the unvulcanized elastomer composition,
The joining surface of the fluorine-based resin sheet 42 and the cured elastomer 41 is integrated with a high strength that has never been seen before.

In the method of manufacturing the sheet-shaped composite material 45, when the method of incorporating the silane coupling agent into the unvulcanized elastomer composition is performed, the same silane coupling agent as described above can be used. However, in the case of the method of applying the silane coupling agent, in consideration of the coating workability, there was a case where the solvent diluted as well as the silane coupling agent was used as it was. When contained in the sulfurized elastomer composition, the silane coupling agent may be blended as it is without being diluted.

Here, the mixing ratio of the silane coupling agent is not particularly limited, but is particularly 0.1 per 100 parts by weight of the unvulcanized elastomer composition (hereinafter abbreviated as "part"). It is preferable to set to 2.0 parts. That is, if the compounding ratio is less than 0.1 part, the bonding interface strength of the obtained composite material 10 may be unstable, and conversely, if it exceeds 2.0 parts, in the obtained composite material 10, the elastomer cured body 12 is obtained. This is because there is a risk of impairing the mechanical properties of.

[Second Embodiment] FIGS. 5A and 5B show
FIG. 3 is an exploded perspective view of a syringe to which the present invention is applied and a cross-sectional view of a plunger packing (a syringe cap) attached to a tip end portion of a plunger rod. FIG. 6 (A)-
5D is a process cross-sectional view showing the method for manufacturing the plunger packing shown in FIG. 5B. Since the plunger packing and the syringe of the present embodiment have the same basic configuration as that of the first embodiment, the parts having the common functions are designated by the same reference numerals and shown in the drawings. Is omitted.

As shown in FIGS. 5 (A) and 5 (B), the syringe 1 of the present embodiment also has a plastic outer cylinder 2 and a cylinder inserted into the outer cylinder 2, as in the first embodiment. -Shaped plunger rod 3 and a plunger packing 4 (a syringe cap) attached to the tip of the plunger rod 3, and a cylindrical base to which the base of the needle is attached at the tip of the outer cylinder 2. The needle mounting portion 21 is formed, and the plunger packing 4 is elastically mounted on the tip end portion of the plunger rod 3 so as to cover the disk-shaped cap mounting portion 34.

The plunger packing 4 of this embodiment is shown in FIG.
As shown in (B), an elastomer cured body 41 that constitutes a mounting recess 40 on the tip of the plunger rod 3 and a fluorine resin sheet 42 (fluorine resin body) that covers the outer surface of the elastomer cured body 41 are provided. The fluororesin sheet 42 made of a composite material comes into contact with the chemical liquid in the outer cylinder 2, and the side surface portion 43 slides on the inner surface of the outer cylinder 2. In this embodiment, silicone rubber is used as the elastomer cured body 41. Here, the fluorine-based resin sheet 42 is the tip surface 41 of the elastomer cured body 41.
0, and most of the side surface portion 411 is covered, but the elastomer cured body 41 is exposed near the opening edge of the side surface portion 43.

As described above, in the plunger packing 4 of the present embodiment and the syringe 1 using the plunger packing 4, the plunger packing 4 is different from the hardened elastomer body 41 which constitutes the mounting recess 40 at the tip of the plunger rod 3. Since the outer surface in contact with the chemical solution is covered with the fluororesin sheet 42 having excellent chemical resistance, when performing a normal medical procedure,
Alternatively, in any case where the syringe 1 is filled with a drug solution and supplied to a hospital or the like, there is no elution of components from the plunger packing 4 to the drug solution, and there is no deterioration of the plunger packing 4 due to the drug solution. It has the same effect as 1.

In order to manufacture the plunger packing 4 having such a structure, for example, as in the first embodiment, as shown in FIG.
As shown in FIG. 6A, after the sheet-shaped composite material 45 in which the fluororesin sheet 42 and the elastomer cured body 41 are joined and integrated is obtained, as shown in FIG. (Not shown) is used to form the sheet-like composite material 45, and thereafter the sheet-shaped composite material 45 is cut at the position indicated by the alternate long and short dash line L2 in FIG. 6 (B), and as shown in FIG. 6 (C), a large number of plunger packings 4 are taken. To do. As a result, as shown in FIG. 6 (D), a composite including an elastomer cured body 41 that constitutes the mounting recess 40 on the tip end portion of the plunger rod 3 and a fluorine resin sheet 42 that covers the outer surface of the elastomer cured body 41. The plunger packing 4 made of material can be manufactured.

[Third Embodiment] In recent years, it has been considered to fill a syringe with a drug solution and supply it to a hospital or the like as a prefill type syringe, which is formed at the tip of the outer cylinder. Since a cap is attached to the tubular needle attachment portion in place of the needle, the present invention may be applied to such a syringe cap.

That is, as shown in FIG. 7, the syringe cap 5 is elastically mounted on the cylindrical needle mounting portion 21 to which the base of the needle is mounted at the tip of the outer cylinder 2 of the syringe 1. However, the syringe cap 5 according to the present embodiment is configured such that the elastomer cured body 41 such as the silicone rubber forming the mounting recess 50 in the needle mounting portion 21 and the fluorine-based resin sheet 42 (fluorine coated on the inner surface of the elastomer cured body 41). It is composed of a composite material including a resin material).

Therefore, in this syringe cap 5, the inside of the elastomer cured body 41 forming the mounting recess 20 in the needle mounting portion 21 is a fluororesin sheet 42 having excellent chemical resistance on the inner surface in contact with the chemical solution. Since it is covered, even when the drug solution is filled in the syringe and supplied to a hospital or the like, there is no elution of components from the syringe cap 5 to the drug solution, and there is no leakage of the drug solution due to deterioration due to the drug solution. . Moreover, since the fluorine-based resin sheet 42 is a composite material with the elastomer cured body 41, it has elasticity enough to function as a cap, and also has ease of molding into a cap shape and cost efficiency.

The method of manufacturing such a syringe cap 5 is basically the same as that of the first embodiment, and therefore its explanation is omitted.

[Other Embodiments] In all of the above-mentioned embodiments, an example in which silicone rubber is used as the elastomer cured product has been described, but butyl rubber may be used as the elastomer cured product.

In each of the above-mentioned embodiments, the cap for a syringe used in a syringe used in a medical field has been described as an example. However, the syringe can be used as a dispenser in various manufacturing sites or laboratories in an organic solvent, grease, or the like. The present invention may be applied to a syringe cap used in a syringe for such an application, since it is also used in the case of quantitatively discharging an industrial oil, an adhesive such as an instant adhesive, a resin, and a chemical. .

Furthermore, a cap for a syringe according to the present invention may be attached to an apparatus for attaching a membrane filter to the tip of the syringe to filter a drug solution or the like.

[0067]

As described above, according to the present invention, a fluororesin sheet such as a fluororesin sheet is subjected to low-temperature plasma treatment in a special pressure range to obtain a silane coupling agent and an unvulcanized elastomer composition. By carrying out complex cross-linking with the vulcanizing agent contained in the product, the joining surface of the fluororesin sheet and the elastomer cured product can be integrated with unprecedented high strength. Therefore, when a syringe cap is manufactured using such a composite material, since the fluorocarbon resin sheet is in contact with the drug solution, there is no elution of components into the drug solution, and the elastomer cured body is sufficient as a cap. Elasticity can be obtained. Moreover, with such a composite material, molding into a cap shape is easy.

[Brief description of drawings]

FIG. 1 is a perspective view showing a configuration of a syringe to which the present invention is applied.

2 (A) and 2 (B) are an exploded perspective view of the syringe according to the first embodiment of the present invention and a cross-sectional view of a syringe cap mounted as a plunger packing on the tip end portion of the plunger rod.

3 (A) to (D) are process cross-sectional views showing a method for manufacturing the syringe cap shown in FIG. 2 (B).

FIG. 4 is an explanatory diagram of a low temperature plasma processing apparatus that can be used to manufacture the sheet-shaped composite material according to the present invention.

5 (A) and 5 (B) are an exploded perspective view of a syringe according to a second embodiment of the present invention and a cross-sectional view of a syringe cap mounted as a plunger packing on a tip end portion of a plunger rod.

6A to 6D are process cross-sectional views showing the method for manufacturing the syringe cap shown in FIG. 5B.

FIG. 7 is a syringe according to a third embodiment of the present invention,
It is sectional drawing of the cap for syringes with which the needle mounting part was mounted | worn.

[Explanation of symbols]

1 syringe 2 outer cylinder 3 Plunger rod 4 Plunger packing (cap for syringe) 5 Syringe cap 7 needles 21 Needle mount 34 Cap mounting part 40, 50 mounting recess 41 Elastomer cured product 42 Fluorine resin sheet (Fluorine resin sheet) 45 composite

Continued front page    (72) Inventor Toshihiro Nakata             Nagasaki Prefecture Minami Azumi-gun Azusagawa-mura             AW I Mach Co., Ltd.             Within F-term (reference) 4C066 AA09 BB01 CC01 DD08 EE14                       FF05 GG07 GG18 HH12 NN01                       PP02 PP04

Claims (7)

[Claims] 1. A syringe cap to be mounted as a plunger packing on the tip of a plunger rod inserted into the outer cylinder of a syringe, wherein the elastomer hardened body constitutes a recess for mounting on the tip of the plunger rod. And a composite material including a fluorine-based resin body that covers the outer surface of the cured elastomer, and a cap for a syringe. 2. A syringe cap, which is mounted on a cylindrical needle mounting portion to which a base of a needle is mounted at a tip portion of an outer cylinder of a syringe, and which prevents leakage of a drug solution filled in the syringe. A cap for a syringe, which is composed of a composite material including an elastomer cured body that forms a recess for mounting on a needle mounting portion, and a fluororesin body that covers an inner surface of the elastomer cured body. 3. The cap for a syringe according to claim 1, wherein the fluororesin body is a fluororesin sheet. 4. The method according to any one of claims 1 to 3,
The syringe cap is characterized in that the cured elastomer is silicone rubber or butyl rubber. 5. A syringe comprising the syringe cap defined in any one of claims 1 to 4. 6. The method for manufacturing a cap for a syringe according to claim 1, wherein at least one surface of the fluororesin body is 0.1 to 1.
A first step of modifying by a low temperature plasma treatment under a pressure of 1 kg / cm ² , a second step of applying a silane coupling agent to the modified surface of the fluororesin body, and a vulcanizing agent-free step. A sheet-like composite in which the fluorinated resin body and the cured elastomer are joined and integrated by heating or heating and pressing the vulcanized elastomer composition in a state of being in contact with the silane coupling agent-coated surface of the fluorinated resin body. A method for manufacturing a syringe cap, comprising a third step of obtaining a material and a fourth step of forming the syringe cap from the sheet-shaped composite material. 7. The method for manufacturing a syringe cap according to any one of claims 1 to 4, wherein at least one surface of the fluororesin body is 0.1 to 1.
First step of modifying by low temperature plasma treatment under a pressure of 1 kg / cm ² , and ^second step of preparing an unvulcanized elastomer composition containing a vulcanizing agent and a silane coupling agent
A step in which the unvulcanized elastomer composition is heated or heated and pressed in a state of being in contact with the modified surface of the fluororesin body, whereby the fluororesin body and the cured elastomer body are joined and integrated. And a fourth step of forming the syringe cap from the sheet-shaped composite material.