JP7047260B2 - Composite rubber molded body for pharmaceuticals - Google Patents

Description

The present invention relates to a composite rubber molded body, and more particularly to a pharmaceutical composite rubber molded body having a fluorine-based resin film laminated on the surface.

Since fluororesin films are generally extremely inert, they are used to improve chemical resistance, slipperiness, and adhesion prevention properties for various pharmaceutical rubber products such as rubber stoppers for pharmaceutical containers and gaskets for syringes. , It is often used as a film for laminating the surface (legs and top) of a rubber base material.

However, since the fluororesin film is extremely inactive, its adhesiveness and compatibility with other members such as rubber are poor. Conventionally, the surface of the fluororesin film is previously modified and then rubber is used. It has adhered to other members such as. Examples of such reforming treatment include chemical treatment, sputter etching treatment, plasma treatment and the like. However, such a modification treatment has a technical problem that the fluororesin film is colored and the appearance of the rubber molded body laminated with the fluororesin film is impaired. For example, when the color of the rubber molded body is from achromatic to bluish, if a fluororesin film discolored to yellow or brown is used, the appearance is greatly impaired. As a result, even though a fluororesin film is used to improve chemical resistance, slipperiness, and adhesion prevention property, its physical properties may be suspected.

Further, in addition to the above-mentioned technical problems, the fluororesin film has a technical problem that it is inferior in processability as a rubber stopper laminating film because it has poor elasticity and flexibility. In response to such technical problems, Patent Document 1 proposes using a fluororesin-containing resin composition in which polyvinylidene fluoride is mixed with a specific fluororesin for a laminated film of a rubber stopper.

Further, in Patent Document 2, in order to improve the adhesiveness between the fluororesin film and the thermoplastic resin, the fluororesin film is irradiated with an ion beam to roughen the surface, and then the surface-modified fluorine obtained by roughening the surface. It has been proposed that the resin film and the thermoplastic resin are pressure-bonded in a state where the thermoplastic resin exhibits a fluid state.

Japanese Unexamined Patent Publication No. 2-136139 Japanese Unexamined Patent Publication No. 2013-139809

However, even if the technique described in Patent Document 1 improves the processability and adhesiveness of the fluororesin film, there is no control over the suitable color of the surface of the rubber molded body laminated with the fluororesin film. It has not been examined and may spoil the appearance of the rubber molded body. Further, in the technique described in Patent Document 2, the discoloration of the fluorine-based resin film itself due to the ion beam is described, but up to the control of the suitable color of the surface of the rubber molded body laminated with the fluorine-based resin film. Not considered.

The present invention has been made in view of the above background art, and an object thereof is to provide a composite rubber molded body having controlled color and excellent chemical resistance, solvent resistance, slipperiness, and adhesion prevention property. To provide.

As a result of diligent studies to solve the above problems, the present inventors have adjusted the composition ratios of carbon and fluorine within a specific range on the surface of the composite rubber molded body, and controlled the color tones. It has been found that it is possible to provide a composite rubber molded body having excellent chemical resistance, solvent resistance, slipperiness, and adhesion prevention property without spoiling the appearance. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention.
A composite rubber molded body for pharmaceuticals with a fluorine-based resin film laminated on the surface.
On the surface of the composite rubber molded body, the ratio of fluorine is 40% or more with respect to the total of 100% of the three elements of carbon, oxygen, and fluorine, and b * in the L * a * b * color system is 2.0. The following composite rubber molded body is provided.

Further, according to another aspect of the present invention.
A composite rubber molded body for pharmaceuticals with a fluorine-based resin film laminated on the surface.
On the surface of the composite rubber molded body, the fluorine / carbon element ratio (F / C) is 0.8 or more, and b * in the L * a * b * color system is 2.0 or less. The body is provided.

In the aspect of the present invention, it is preferable that b * in the L * a * b * color system is −5.0 or more and 0.0 or less on the surface of the composite rubber molded body.

In the aspect of the present invention, it is preferable that a * in the L * a * b * color system is 2.0 or less on the surface of the composite rubber molded body.

In the aspect of the present invention, it is preferable that a * in the L * a * b * color system is −3.0 or more and 0.0 or less on the surface of the composite rubber molded body.

In the aspect of the present invention, it is preferable that the fluororesin film contains a copolymer resin of ethylene and tetrafluoroethylene.

In the aspect of the present invention, it is preferable that the fluororesin film contains a copolymer resin of ethylene and chlorotrifluoroethylene.

In the aspect of the present invention, it is preferable that the composite rubber molded body is a rubber stopper or a gasket.

According to the present invention, by adjusting the composition ratio of carbon and fluorine within a specific range and controlling the color on the surface of the composite rubber molded body, chemical resistance and solvent resistance are not impaired without spoiling the appearance. It is possible to provide a composite rubber molded body having excellent properties, slipperiness, and adhesion prevention properties.

It is sectional drawing which showed one Embodiment of the composite rubber molded body (laminated rubber stopper) of this invention. It is an external perspective view which showed one Embodiment of the composite rubber molded body (laminated rubber stopper) of this invention. It is sectional drawing which showed one Embodiment of the composite rubber molded body (laminated rubber stopper) of this invention. It is a schematic block diagram which shows the plasma processing apparatus which performs plasma processing of the fluororesin film used for the composite rubber molded body of this invention.

<Composite rubber molded body>
The composite rubber molded body of the present invention has a fluorine-based resin film laminated on the surface thereof, and has excellent chemical resistance, solvent resistance, slipperiness, adhesion prevention, etc., and therefore has a rubber stopper for a pharmaceutical container. It can be used for various pharmaceutical rubber products such as gaskets for syringes and syringes.

In the composite rubber molded body, the surface modification side of the following fluororesin film is laminated so as to face the rubber, thereby achieving good adhesiveness between the two and having excellent chemical resistance on the rubber surface. It is possible to impart property, solvent resistance, slipperiness, adhesion prevention property and the like.
In the case of the rubber stopper, the fluorine-based resin film may be laminated only on the top surface portion or the leg portion, or the fluorine-based resin film may be laminated on both the top surface portion and the leg portion.

As one form of the composite rubber molded body of the present invention, for example, a laminated rubber stopper in which a fluororesin film is laminated on the legs of the rubber stopper can be mentioned. FIG. 1 shows a schematic cross-sectional view of the laminated rubber stopper, and FIG. 2 shows an external perspective view of an embodiment of the laminated rubber stopper 4 of the present invention. The laminated rubber stopper 1 shown in FIG. 1 is obtained by laminating the surface-modified side of the surface-modified fluororesin film 2 to the legs of the rubber stopper 3. With such a configuration, for example, when used as a stopper for a container containing a liquid, it is effective to prevent the components contained in the rubber from elution into the liquid and to leak the liquid contained in the container. Can be prevented. Further, the laminated rubber stopper according to the present invention is excellent in that it does not cause coloring of the fluororesin, unlike the one obtained by the treatment with the conventional metallic sodium complex.

Another form of the composite rubber molded body of the present invention includes a laminated rubber stopper obtained by laminating the above-mentioned fluorine-based resin film on the top surface of the rubber stopper. FIG. 3 shows a schematic cross-sectional view of the laminated rubber stopper. The laminated rubber stopper 5 shown in FIG. 3 is obtained by laminating the surface-modified side of the surface-modified fluororesin film 6 onto the top surface of the rubber stopper 7. With such a configuration, it can be used as a rubber stopper for a vial for freeze-drying. The method of using this rubber stopper is to half-plug the rubber stopper into the mouth of a vial filled with the chemical solution and then put it in a freeze-drying chamber to freeze-dry the chemical solution. Then, all the rubber stoppers are plugged in the same chamber. At this time, since the fluorine-based resin film is laminated, it is possible to prevent the rubber stopper from adhering to the pressing plate for tapping.

The unmodified surface of the fluororesin film is exposed on the surface of the composite rubber molded body on which the surface-modified fluororesin film is laminated. The fluororesin film has a large number of CF bonds having a higher binding energy than the CH bond, and the binding energy of the CH bond increases due to the electron-withdrawing property of the adjacent F. It exhibits chemical resistance, solvent resistance, slipperiness, adhesion prevention, etc. In order to exhibit such physical properties, the ratio of fluorine to 100% of the total of the three elements of carbon, oxygen and fluorine on the surface of the composite rubber molded body is 40% or more, preferably 40% or more. It is 75% or less, more preferably 45% or more and 70% or less, further preferably 48% or more and 67% or less, further preferably 50% or more and 65% or less, and the carbon ratio is preferably 30. % Or more and 60% or less, more preferably 35% or more and 55% or less, and the oxygen ratio is preferably 0% or more and 10% or less, and more preferably 0.1% or more and 5% or less. The fluorine / carbon element ratio (F / C) is 0.8 or more, preferably 0.8 or more and 1.8 or less, more preferably 1.0 or more and 1.7 or less, and further preferably. It is 1.1 or more and 1.6 or less, and even more preferably 1.2 or more and 1.5 or less. The ratio of each element can be adjusted by controlling the type and composition of the fluororesin film.

Since the color of the composite rubber molded body is measured at the portion where the surface-modified fluororesin film is laminated, the color of the rubber and the surface-modified fluororesin film combined is measured.
The difference in color that can be discerned by the human eye differs depending on the color, but the difference in color is easy to discriminate in a color having low saturation, and the color difference (ΔE * ab) can be discriminated by about 2.0. When an achromatic color or an achromatic color to a bluish color is used in a rubber molded body, discoloration to yellow or brown is disliked, so b * is preferably +2.0 or less, preferably -5.0 or more and 0. It is 0.0 or less, more preferably -4.0 or more and -0.5 or less. Since discoloration to red is also disliked, a * is preferably +2.0 or less, preferably -3.0 or more and 0.0 or less, and more preferably -2.0 or more and -0.5 or less. be.

(Rubber material)
The rubber material used for the composite rubber molded body of the present invention is not particularly limited, but is butyl rubber, chlorinated butyl rubber, brominated butyl rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, silicone rubber, and fluororubber. And so on. Among them, butyl rubber is preferable, and chlorinated butyl rubber is particularly preferable, from the viewpoint of gas impermeableness.

As the rubber material, various compounding agents such as an inorganic reinforcing agent, a vulcanizing agent, a vulcanization activity aid, and a coloring agent are used, if necessary. Examples of the inorganic reinforcing agent include clay, barium sulfate, talc, silica and the like. The blending amount of the inorganic reinforcing agent is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the rubber material. Examples of the vulcanizing agent include triazine thiol-based, organic sulfur-based, amine-based, and silane coupling agents. The blending amount of the vulcanizing agent is preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the rubber material. Examples of the vulcanization active aid include zinc oxide, magnesium oxide, zinc steering acid, synthetic hydrotalcite and the like. The blending amount of the vulcanization active aid is preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the rubber material. Examples of the colorant include titanium oxide, carbon black, organic pigments and the like. The blending amount of the colorant is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the rubber material.

(Fluorine resin film)
The fluororesin film used in the present invention is inert and has excellent chemical resistance, solvent resistance, slipperiness, and adhesion prevention property. Therefore, by laminating it on a rubber material, the surface of the rubber molded body (legs and legs) It is possible to impart excellent chemical resistance, solvent resistance, slipperiness, and adhesion prevention property to the top surface).

The fluororesin film is not particularly limited, and is, for example, a copolymer resin of ethylene and tetrafluoroethylene (ETFE), a copolymer resin of ethylene and chlorotrifluoroethylene (ECTFE), and polytetrafluoroethylene. Resin (PTFE), perfluoroalkoxy resin (PFA) composed of a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, copolymer resin (FEP) of tetrafluoroethylene and hexafluoropropylene, tetrafluoroethylene and per. Examples thereof include a copolymer resin (EPE) of fluoroalkyl vinyl ether and hexafluoropropylene, polychlorotrifluoroethylene resin (PCTFE), vinylidene fluoride resin (PVDF), and polyvinyl fluoride resin (PVF). Among these, a copolymer resin (ETFE) of ethylene and tetrafluoroethylene is preferable because it is easy to modify the surface by plasma treatment and has chemical resistance, solvent resistance and slipperiness. Further, a modified type ethylene and tetrafluoroethylene copolymer resin (ETFE) can be used. The modified type ethylene / tetrafluoroethylene copolymer resin (ETFE) is preferably obtained by ternary copolymerizing ethylene, tetrafluoroethylene, and a fluorovinyl monomer copolymerizable with them.

The fluorine-based resin film can be improved in adhesiveness to rubber by performing the following modification treatment. In the present invention, it is preferable that only one surface of the fluororesin film is modified and the modified region surface is laminated with rubber. By not modifying the other surface, the original performance of the fluororesin film is not impaired, and the surface of the composite rubber molded body is provided with chemical resistance, solvent resistance, slipperiness, and adhesion prevention. can do.

In the modified region of the fluorine-based resin film subjected to the following plasma treatment as the modification treatment, the ratio of carbon is 45% or more and 70% or less with respect to the total of 100% of the four elements of carbon, nitrogen, oxygen and fluorine. Yes, preferably 50% or more and 68% or less, more preferably 55% or more and 65% or less, and the nitrogen ratio is 0.1% or more and 5% or less, preferably 0.5% or more and 4% or less. It is more preferably 1.0% or more and 3.0% or less, the oxygen ratio is 13% or more, preferably 14% or more and 30% or less, and more preferably 15% or more and 25% or less. Yes, the proportion of fluorine is 35% or less, preferably 10% or more and 33% or less, and more preferably 15% or more and 30% or less. When the ratios of the four elements of carbon, nitrogen, oxygen, and fluorine are within the above range in the modified region of the fluorine-based resin film, a fluorine-based resin film having excellent adhesion to rubber and reduced coloring can be obtained. be able to. The ratio of each element can be adjusted by controlling the following conditions of the reforming treatment.

(Modification process)
The surface modification treatment of the fluororesin film is not particularly limited, and examples thereof include treatment with a chemical solution, treatment with an electron beam, corona treatment, atmospheric pressure plasma treatment, and low pressure plasma treatment. From the viewpoint of productivity, corona treatment, atmospheric pressure plasma treatment, low pressure plasma treatment and the like are preferable. Low pressure plasma treatment is particularly preferred because the proportion of gas species for the introduction of functional groups can be used in a wide range.

(Plasma processing)
When the surface layer portion of the fluorine-based resin is activated by low-pressure plasma treatment or the like, fluorine atoms are detached from the skeleton of the fluorine-based resin, and carbon radicals are generated. After that, a functional group such as a hydroxyl group, a carboxyl group, an aldehyde group, or a ketone group is formed by a hydrogen atom which is bonded to oxygen in the atmosphere and is further supplied from the atmosphere. Further, when a hydrogen atom is bonded to the skeleton of the fluororesin, the hydrogen atom is similarly separated from the skeleton of the fluororesin to generate a carbon radical. After that, a functional group such as a hydroxyl group, a carboxyl group, an aldehyde group, or a ketone group is formed by a hydrogen atom bonded to oxygen in the atmosphere and further separated from the hydrogen atom or a hydrogen atom supplied from the atmosphere.
Alternatively, oxygen radicals generated in the atmosphere by low-pressure plasma treatment cause extraction of fluorine atoms from the skeleton of the fluorine-based resin and addition reaction of oxygen to the fluorine-based resin, and hydrogen atoms supplied from the atmosphere cause hydroxyl groups. , Oxygen-containing functional groups such as carboxyl group, aldehyde group and ketone group are formed. Further, when a hydrogen atom is bonded to the skeleton of the fluororesin, the hydrogen atom is similarly extracted from the skeleton of the fluororesin and the addition reaction of oxygen to the fluororesin occurs, and the extracted hydrogen atom is further generated. And hydrogen atoms supplied from the atmosphere form functional groups such as hydroxyl groups, carboxyl groups, aldehyde groups, and ketone groups.
When the surface activated by low-pressure plasma treatment is returned to atmospheric pressure, functional groups derived from oxygen and nitrogen in the air are formed. Therefore, oxygen and nitrogen are detected on the surface even under the treatment conditions where there is no oxygen or nitrogen in the plasma atmosphere.
It is considered that the surface layer in which these functional groups are present has a remarkably improved affinity and reactivity with other resins, and the adhesiveness of the fluororesin is exhibited.

On the other hand, when the carbon concentration of the surface layer is increased by the plasma treatment, coloring becomes easy. In the present invention, by optimizing the plasma treatment conditions, the carbon concentration of the surface layer is controlled, the oxygen concentration is increased, nitrogen is introduced, and fluorine is reduced to improve the adhesiveness and reduce the coloring. can do.

(Plasma processing equipment)
A device capable of low-pressure plasma processing is preferable because of the ease of controlling the plasma atmosphere and the degree of freedom of the gas that can be used. As the low-pressure plasma processing device, an ICP type plasma processing device, a parallel plate type plasma processing device, a roll-to-roll type plasma processing device, or the like can be used. From the viewpoint of productivity, a roll-to-roll type plasma processing device is preferable.
As the power source used for plasma generation, a conventionally known power source such as a high frequency power source and a pulse wave power source can be used. If the frequency of the power supply is in the range of 100 kHz or less, the degree of freedom of the gas is high, and a large proportion of the gas type for actively introducing the functional group can be used. Examples of such a gas include O ₂ , CO, CO ₂ , NH ₃ , N ₂ O, SO ₂ , H ₂ S and the like.

As an example of the roll-to-roll type plasma processing apparatus, FIG. 4 shows a schematic configuration diagram. The plasma treatment apparatus shown in FIG. 4 is an apparatus for producing a surface-modified fluororesin film 50 by subjecting the fluororesin film 51 to surface modification treatment by performing plasma treatment on the fluororesin film 51. Is. Such a plasma processing apparatus includes a chamber 11, a film supply unit 12 and a film winding unit 13 arranged in the chamber 11, a mask 52 and a magnetic field generating unit 60 in the chamber 11, and plasma processing in the chamber 11. It is provided with a processing gas supply unit 40 for supplying the processing gas for the purpose.

Of these, the film supply unit 12 includes a supply roller 12a around which the fluorine-based resin film 51 is wound and supplies the fluorine-based resin film 51. Further, the film winding unit 13 includes a winding roller 13a around which the surface-modified fluororesin film 50 is wound and the surface-modified fluororesin film 50 is wound. Further, a rotary main roll 14 is arranged between the film supply unit 12 and the film winding unit 13. A fluorine-based resin film 51 is wound around the main roll 14 along the surface thereof, and plasma treatment is applied to the fluorine-based resin film 51 on the main roll 14. Further, between the film supply unit 12 and the main roll 14, and between the main roll 14 and the film winding unit 13, a plurality of fluororesin films 51 are guided from the film supply unit 12 to the film winding unit 13. The guide roll 16 is provided. The film supply unit 12, the film winding unit 13, the main roll 14, and the guide roll 16 constitute a roll-to-roll type film transfer device 15. Further, an exhaust pump 17 for evacuating the inside of the chamber 11 is connected to the chamber 11 via a connecting pipe 18. Further, the connecting pipe 18 is provided with a valve 19 for adjusting the degree of vacuum (pressure) in the chamber 11.

Further, the processing gas supply unit 40 includes a gas nozzle 34 for ejecting the processing gas into the chamber 11, gas supply pipes 44, 45, 46 for supplying the processing gas, and processing gas storage units 41, 42 for storing the processing gas. It has 43 and. The gas supply pipes 44, 45, and 46 are provided with mass flow controllers (MFCs) 47, 48, and 49, respectively, that control the flow rate of the gas. As the supply gas, for example, argon, helium, and oxygen can be used.

Furthermore, a magnetic field generation unit 60 including a magnet 61 as used in a sputtering device is provided at a position in the chamber 11 facing the opening of the mask 52. A 40 kHz high frequency power supply is connected to the main roll. Plasma P is generated by the introduction of the processing gas, the adjustment of the pressure in the chamber 11, and the introduction of the high frequency power. By installing the magnetic field generating unit 60 and introducing high-frequency power to the main roll, a region having a high plasma density is formed in the vicinity of the fluororesin film 51, and plasma treatment can be efficiently performed. A partition wall 65 is provided in the chamber 11. The partition wall 65 plays a role of suppressing the generated plasma P from spreading to the film supply unit 12 and the film winding unit 13 side, and depositing the generated product due to the plasma treatment on the film supply unit 12 and the film winding unit 13 side. Fulfill.

<Manufacturing of surface-modified fluororesin film>
[Example 1]
An ETFE film ^{* 1} (Neophron EF-0050, manufactured by Daikin Corporation) having a width of 300 mm was passed through the roll-to-roll plasma processing apparatus described above as a fluororesin film, the chamber was closed, and the pressure was reduced to 0.01 Pa or less. After that, Ar was introduced by 200 sccm and oxygen was introduced by 1500 sccm. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 8 Pa, the electric power was set to 370 W and plasma treatment was performed. The transport speed of the fluororesin film was 4.2 m / min, and the plasma treatment was repeated three times. After the plasma treatment was completed, the discharge and the supply of gas were stopped, the pressure was reduced to 0.01 Pa or less, and the film was vented and returned to atmospheric pressure to obtain a surface-modified fluororesin film.

[Examples 2 to 10] [Comparative Examples 1 to 8]
Plasma treatment was carried out in the same manner as in Example 1 except that the plasma treatment conditions shown in Table 1 were changed to obtain a surface-modified fluororesin film. In Example 5 and Comparative Example 5, an ECTFE film (TEFKA, manufactured by Denka Co., Ltd.) was used as the fluororesin film. Further, in Examples 6 to 9 and Comparative Examples 7 to 8, ETFE film ^{* 2} (manufactured by Asahi Glass Co., Ltd., Aflex) was used as the fluororesin film. However, in Comparative Example 1 and Comparative Example 6, a rubber stopper was molded without using a fluororesin film in the production of the following composite rubber molded body.

<Manufacturing of composite rubber molded body>
An unvulcanized chlorinated butyl rubber sheet was prepared as a rubber material for the composite rubber molded body. For the chlorinated butyl rubber, a material consisting of a silica-based reinforcing agent, magnesium oxide, titanium oxide, carbon black, and a vulcanizing agent was used as the main additive.

(Laminate on the top surface)
The plasma-treated surface of the surface-modified fluororesin film produced in the above Examples and Comparative Examples and the above-mentioned unvulcanized chlorinated butyl rubber sheet are overlapped so as to face each other, and the leg length is 10 mm and the leg diameter is 13 mm. Vulcanization molding with a vacuum press with the surface-modified fluororesin film in contact with the top surface side of the rubber stopper with the upper and lower dies that match the dimensions of the rubber stopper with a top surface thickness of 3 mm and an outer diameter of the top surface of 19 mm. Then, a laminated rubber stopper was obtained. The mold temperature at the time of molding was 170 ± 3 ° C., the vulcanization time was 420 seconds, and the preheating time of the film was 30 seconds.

(Laminate on legs)
The plasma-treated surface of the surface-modified fluororesin film produced in the above Examples and Comparative Examples and the above-mentioned unvulcanized chlorinated butyl rubber sheet are overlapped so as to face each other, and the leg length is 10 mm and the leg diameter is 13 mm. Vulcanization molding with a vacuum press with the surface-modified fluororesin film in contact with the leg side of the rubber stopper with the upper and lower dies that match the dimensions of the rubber stopper with a top surface thickness of 3 mm and an outer diameter of the top surface of 19 mm. Then, a laminated rubber stopper was obtained. The mold temperature at the time of molding was 170 ± 3 ° C., the vulcanization time was 420 seconds, and the preheating time of the film was 30 seconds.

With respect to the rubber stoppers (2 each) obtained above, the adhesiveness (peeling property) at the burr portion was visually confirmed and evaluated according to the following criteria. The measurement results are shown in Table 2.
(Evaluation criteria)
◯: The surface-modified fluororesin film did not peel off at the burr portion of the rubber stopper.
X: The surface-modified fluororesin film was peeled off at the burr portion of the rubber stopper.

<Measurement of surface color>
On the surface of the laminated rubber stopper manufactured above, the color represented by the L * a * b * color system was measured with reflected light using a spectrocolorimeter CM-600d manufactured by Comicaminolta. The measurement conditions were SCE (specular reflection removal), 10 ° field of view, and D65 light source.
When measuring the top surface of the rubber stopper, the measurement was performed with the sample surface opening of the spectrocolorimeter facing the top surface and the measuring instrument in contact with a part of the top surface. When measuring the legs of the rubber stopper, the measurement was performed with the sample surface opening of the spectrocolorimeter facing the legs and the measuring instrument in contact with the cap and a part of the legs.

<Measurement of surface composition>
Regarding the surface composition of the laminated rubber stopper manufactured above, C1s, O1s, and F1s are shown in Table 3 as X-ray guns: MgKα, 20mA, 10kV using an X-ray photoelectron spectroscopy analyzer (ESCA-3400 manufactured by KRATOS). It was measured under the conditions described. With the analysis software, the background was drawn from the peak of each element obtained by the measurement by the Schilley method, and the element concentration on the surface of the laminated rubber stopper was calculated from the integrated strength (area) of the peak of each element. The required element ratio was calculated from the obtained element concentration. The measurement results are as shown in Table 2.

＜評価結果＞

<Evaluation result>

Explanation of the sign

1: Laminated rubber stopper 2: Surface-modified fluororesin film 3: Rubber stopper 4: Laminated rubber stopper 5: Laminated rubber stopper 6: Surface-modified fluorine-based resin film 7: Rubber stopper P: Plasma 11: Chamber 12: Film Supply part 12a: Film roller 13: Film winding part 13a: Winding roller 14: Main roll 15: Film transfer device 16: Guide roll 17: Exhaust pump 18: Connecting pipe 19: Valve 34: Gas nozzle
40: Processed gas supply unit 41, 42, 43: Gas cylinder 44, 45, 46: Gas supply pipe 47, 48, 49: Mass flow controller 50: Surface-modified fluorine-based resin film 51: Fluorine-based resin film 52: Mask 60: Magnetic field generator 61: Magnet 65: Bulkhead

Claims (8)

A composite rubber molded body for pharmaceuticals with a fluorine-based resin film laminated on the surface.
The rubber and the fluororesin film laminated on the rubber are provided.
The fluororesin film includes one surface laminated on the rubber and the other surface exposed on the surface of the composite rubber molded body.
On the surface of the composite rubber molded body, the ratio of fluorine is 50 % or more with respect to the total of 100% of the three elements of carbon, oxygen, and fluorine, and b * in the L * a * b * color system is +2.0. Is below
On one side of the fluorine-based resin film, the ratio of carbon is 45% or more and 70% or less with respect to the total of 100% of the four elements of carbon, nitrogen, oxygen, and fluorine, and the ratio of nitrogen is 0.1. A composite rubber molded body comprising a region containing% or more and 5% or less, an oxygen ratio of 13% or more, and a fluorine ratio of 35% or less . A composite rubber molded body for pharmaceuticals with a fluorine-based resin film laminated on the surface.
The rubber and the fluororesin film laminated on the rubber are provided.
The fluororesin film includes one surface laminated on the rubber and the other surface exposed on the surface of the composite rubber molded body.
On the surface of the composite rubber molded body, the fluorine / carbon element ratio (F / C) is 1.2 or more, and b * in the L * a * b * color system is +2.0 or less .
On one side of the fluorine-based resin film, the ratio of carbon is 45% or more and 70% or less with respect to the total of 100% of the four elements of carbon, nitrogen, oxygen, and fluorine, and the ratio of nitrogen is 0.1. A composite rubber molded body comprising a region containing% or more and 5% or less, an oxygen ratio of 13% or more, and a fluorine ratio of 35% or less . The composite rubber molded body according to claim 1 or 2, wherein b * in the L * a * b * color system is −5.0 or more and 0.0 or less on the surface of the composite rubber molded body. The composite rubber molded body according to any one of claims 1 to 3, wherein a * in the L * a * b * color system is +2.0 or less on the surface of the composite rubber molded body. The composite rubber molding according to any one of claims 1 to 4, wherein a * in the L * a * b * color system is −3.0 or more and 0.0 or less on the surface of the composite rubber molded body. body. The composite rubber molded product according to any one of claims 1 to 5, wherein the fluororesin film contains a copolymer resin of ethylene and tetrafluoroethylene. The composite rubber molded product according to any one of claims 1 to 5, wherein the fluororesin film contains a copolymer resin of ethylene and chlorotrifluoroethylene. The composite rubber molded body according to any one of claims 1 to 7, which is a rubber stopper or a gasket.

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