Surface treatment process for high-isolation and high-cleanliness halogenated butyl rubber plug

By using a spray solution of fluorocarbon copolymer resin solution and a photoinitiator, the rubber plug surface is cured, and the problems of long curing time and poor coating adhesion in the rubber plug surface treatment process in the prior art are solved, and the rubber plug surface treatment effect with high isolation and biosafety is achieved.

CN119702400AInactive Publication Date: 2025-03-28HAIAN JIANMIN RUBBER PLASTIC CO LTD
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Patent Information

Application Number
CN202510000076.2
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-01-01
Publication Date
2025-03-28
Estimated Expiration
Not applicable · inactive patent

AI Technical Summary

Technical Problem

The existing rubber plug surface treatment process has problems such as long high-temperature curing time, poor coating adhesion, and easy silicone oil to fall off, which affects the isolation and stability of the drug.

Method used

The surface of the rubber plug is sprayed with a spray solution composed of a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon layer is closely combined with the surface of the rubber plug through ultraviolet light curing to form a graft polymer hydrophobic coating.

Benefits of technology

It improves the hydrophobicity and surface inertia of halogenated butyl rubber plugs, prevents direct contact between drugs and rubber, reduces particle contamination, protects drug stability, and has a short process time, low cost, and strong coating adhesion.

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Abstract

The invention discloses a surface treatment process for a high-isolation and high-cleanliness halogenated butyl rubber plug. The banana surface treatment process comprises the following steps: step S1, cleaning treatment; s2, carrying out plasma treatment; s3, spraying is conducted; and S4, performing ultraviolet light curing. The spraying liquid containing the fluorocarbon copolymer resin solution is adopted to spray the surface of the rubber plug, the surface of the rubber plug is modified, and the photoinitiator is added into the spraying liquid to enable the spraying liquid to initiate graft polymerization through ultraviolet curing to form a graft polymer hydrophobic coating, so that the hydrophobicity of the halogenated butyl rubber plug is improved, and the service life of the halogenated butyl rubber plug is prolonged. Therefore, the surface inertia of the rubber plug is further improved, a barrier is formed between the rubber plug and the water-containing solvent, direct contact between medicine and rubber is prevented, the rubber plug can be separated from the medicine and liquid medicine through the film layer formed on the surface of the treated rubber plug, mutual diffusion and permeation are avoided, and the adhesive force of the film on the surface of the treated rubber plug is good.
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Description

Technical Field

[0001] The invention relates to the technical field of rubber surface treatment, in particular to a surface treatment process for a high-isolation and high-cleanliness halogenated butyl rubber plug. Background Art

[0002] Halogenated butyl rubber plugs are widely used in the field of pharmaceutical packaging due to their high elasticity, excellent physical and chemical properties, stable sterilization at high temperatures, good compatibility with drugs, and unique air tightness. Medicinal halogenated butyl rubber plugs are usually used to make pharmaceutical bottles, syringes and other pharmaceutical packaging equipment, and are important sealing materials in pharmaceutical packaging materials.

[0003] Although butyl rubber has good chemical stability, there are still factors such as formula concentration gradient and raw materials that may cause the rubber plug to be immersed in drugs after drug encapsulation. The low-molecular substances in the rubber plug will slowly seep out, posing the risk of contaminating the drugs or reducing their efficacy.

[0004] The defects of existing rubber surface treatment are: 1. Patent document CN101560306B discloses a surface treatment method for medical rubber stoppers. However, after long-term use, the fluorine-containing substance filled on the surface of the rubber stopper may fall off, thereby affecting the inertness of the rubber stopper. The drug may also be adsorbed onto the rubber stopper material, reducing the actual concentration and efficacy of the drug. 2. Patent document CN104356418B discloses a method for significantly improving the hydrophobicity of the silicone rubber surface. The patent document discloses a surface treatment process for the rubber plug so that the rubber plug surface has a coating. However, the coating may have problems such as weak adhesion of the film material and easy detachment of the film. 3. In the prior art, in order to achieve high isolation, the rubber plug is usually fluorinated. However, the high-temperature curing time during the fluorination treatment is long, which makes the overall surface treatment process of the rubber plug take a long time. 4. The surface treatment process of butyl rubber bottle stoppers in the prior art is usually just conventional siliconization treatment. However, the silicone oil on the surface of the siliconized rubber stoppers will easily fall off over time, which may have an impact on the drugs. Summary of the invention

[0005] The purpose of the present invention is to provide a high-isolation and high-cleanliness halogenated butyl rubber plug surface treatment process to solve the problems raised in the above background technology.

[0006] To achieve the above object, the present invention provides the following technical solution: a surface treatment process for a high-isolation and high-cleanliness halogenated butyl rubber plug, the surface treatment process of the rubber specifically comprising the following steps: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV curing: The fluorocarbon layer is tightly bonded to the surface of the bottle stopper by UV curing; In step S3, the spraying liquid is a mixture of a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer.

[0007] Preferably, the components of the spraying liquid include 50 to 65 parts of fluorocarbon copolymer resin solution, 0.24 to 1.85 parts of coupling agent and 0.15 to 0.3 parts of photoinitiator in parts by weight.

[0008] Preferably, the coupling agent is an organic silane coupling agent, and preferably, the model of the organic silane coupling agent is A-174 or Si-69.

[0009] Preferably, the photoinitiator is a benzophenone ultraviolet light absorber, and preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone.

[0010] Preferably, in step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device with a transmission frequency of 13.5 MHz and an output power of 700 W to 1200 W.

[0011] Preferably, in step S2, the source gas capable of generating plasma in the plasma treatment is nitrogen or oxygen.

[0012] Preferably, the conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 2 minutes to 6 minutes.

[0013] Preferably, the device used for UV curing in step S4 is an ultraviolet high-pressure pump lamp, and the ultraviolet light intensity of the ultraviolet high-pressure pump lamp is 10mW / cm 2 ~40mW / cm 2 .

[0014] Preferably, in step S4, the sprayed rubber stopper is irradiated under an ultraviolet light source for 1 minute to 4 minutes.

[0015] Preferably, the surface of the rubber stopper is grafted and copolymerized through an ultraviolet light curing process to form a coating layer, and the thickness of the coating layer is 70nm to 85nm.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses a spraying liquid containing a fluorocarbon copolymer resin solution to spray the surface of the rubber stopper to modify the surface of the rubber stopper, and by adding a photoinitiator to the spraying liquid, it can initiate graft polymerization through ultraviolet light curing to form a grafted polymer hydrophobic coating, thereby improving the hydrophobicity of the halogenated butyl rubber stopper, thereby further improving the surface inertness of the rubber stopper, forming a barrier between the rubber stopper and the aqueous solvent, and preventing direct contact between the drug and the rubber.

[0017] 2. The coating layer formed on the surface of the rubber stopper after the surface treatment process of the present invention can isolate the rubber stopper from the drug and the drug solution, avoid mutual diffusion and penetration, reduce particulate contamination, protect the stability of the drug, and meet the compatibility requirements between the rubber stopper and the drug. The coating layer on the surface of the rubber stopper treated by the surface treatment process has good adhesion and can be stably attached to the surface of the rubber stopper, and has very reliable biosafety and biostability.

[0018] 3. The surface treatment process of the present invention adds a photoinitiator to the spraying liquid so that the spraying liquid on the surface of the rubber stopper can form a film under the action of ultraviolet light curing. The overall surface treatment process takes a short time and has a low process cost. The coating on the surface of the rubber stopper improves the surface smoothness of the rubber stopper, thereby reducing the friction coefficient between the rubber stopper and the drug packaging bottle, which is beneficial to the rapid production process of rubber stopper packaging and sealing drugs.

[0019] 4. The overall process flow of the surface treatment process of the present invention is simple. There is no need to perform siliconization on the rubber stopper to ensure high isolation between the rubber stopper and the drug, thereby avoiding the shedding of silicone oil on the surface of the rubber stopper after long-term use of the conventional siliconized rubber stopper, and further avoiding the shedding of silicone oil affecting the turbidity of the drug. DETAILED DESCRIPTION

[0020] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] The present invention provides a high-isolation and high-cleanliness halogenated butyl rubber plug surface treatment process, which specifically includes the following steps: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV light curing: UV light curing is used to tightly bond the fluorocarbon layer to the surface of the bottle stopper.

[0022] In step S3, the spraying liquid is a mixed liquid obtained by uniformly mixing a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer; The components of the spraying liquid include 50 to 65 parts of fluorocarbon copolymer resin solution, 0.24 to 1.85 parts of coupling agent and 0.15 to 0.3 parts of photoinitiator by weight, the coupling agent is an organic silane coupling agent, preferably, the model of the organic silane coupling agent is A-174 or Si-69, the photoinitiator is a benzophenone ultraviolet light absorber, preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone; In step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device, the emission frequency is 13.5 MHz, the output power is 700 W to 1200 W, the source gas capable of generating plasma in the plasma treatment is nitrogen or oxygen, and the conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 2 minutes to 6 minutes; The equipment used for UV curing in step S4 is a UV high-pressure pump lamp, and the UV light intensity of the UV high-pressure pump lamp is 10mW / cm 2 ~40mW / cm 2 In step S4, the sprayed rubber plug is irradiated under an ultraviolet light source for 1 minute to 4 minutes; After the UV curing process, the surface of the rubber stopper is grafted and copolymerized to form a coating layer with a thickness of 70nm to 85nm.

[0023] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0024] Embodiment 1: This embodiment provides a high-isolation and high-cleanliness halogenated butyl rubber plug surface treatment process, and the specific steps are as follows: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV light curing: UV light curing is used to tightly bond the fluorocarbon layer to the surface of the bottle stopper.

[0025] In step S3, the spraying liquid is a mixed liquid obtained by uniformly mixing a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer; The components of the spraying liquid include 60 parts of fluorocarbon copolymer resin solution, 1 part of coupling agent and 0.2 parts of photoinitiator by weight, the coupling agent is an organic silane coupling agent, preferably, the model of the organic silane coupling agent is A-174, the photoinitiator is a benzophenone ultraviolet light absorber, preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone; In step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device with a transmission frequency of 13.5 MHz and an output power of 700 W to 1200 W. The source gas capable of generating plasma in the plasma treatment is nitrogen or oxygen. The conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 4 minutes. The equipment used for UV curing in step S4 is a UV high-pressure pump lamp, and the UV light intensity of the UV high-pressure pump lamp is 10mW / cm 2 ~40mW / cm 2 In step S4, the sprayed rubber plug is irradiated under the ultraviolet light source for 3 minutes; After the UV curing process, the surface of the rubber stopper is grafted and copolymerized to form a coating layer with a thickness of 70nm to 85nm.

[0026] Embodiment 2: This embodiment provides a high-isolation and high-cleanliness halogenated butyl rubber plug surface treatment process, and the specific steps are as follows: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV light curing: UV light curing is used to tightly bond the fluorocarbon layer to the surface of the bottle stopper.

[0027] In step S3, the spraying liquid is a mixed liquid obtained by uniformly mixing a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer; The components of the spraying liquid include 55 parts of fluorocarbon copolymer resin solution, 1 part of coupling agent and 0.2 parts of photoinitiator by weight, the coupling agent is an organic silane coupling agent, preferably, the model of the organic silane coupling agent is A-174, the photoinitiator is a benzophenone ultraviolet light absorber, preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone; In step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device with a transmission frequency of 13.5 MHz and an output power of 700 W to 1200 W. The source gas capable of generating plasma in the plasma treatment is nitrogen or oxygen. The conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 4 minutes. The equipment used for UV curing in step S4 is a UV high-pressure pump lamp, and the UV light intensity of the UV high-pressure pump lamp is 10mW / cm 2 ~40mW / cm 2 In step S4, the sprayed rubber plug is irradiated under the ultraviolet light source for 3 minutes; After the UV curing process, the surface of the rubber stopper is grafted and copolymerized to form a coating layer with a thickness of 70nm to 85nm.

[0028] Embodiment three: This embodiment provides a high-isolation and high-cleanliness halogenated butyl rubber plug surface treatment process, and the specific steps are as follows: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV light curing: UV light curing is used to tightly bond the fluorocarbon layer to the surface of the bottle stopper.

[0029] In step S3, the spraying liquid is a mixed liquid obtained by uniformly mixing a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer; The components of the spraying liquid include 58 parts of fluorocarbon copolymer resin solution, 1 part of coupling agent and 0.2 parts of photoinitiator by weight, the coupling agent is an organic silane coupling agent, preferably, the model of the organic silane coupling agent is Si-69, the photoinitiator is a benzophenone ultraviolet light absorber, preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone; In step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device with a transmission frequency of 13.5 MHz and an output power of 700 W to 1200 W. The source gas capable of generating plasma in the plasma treatment is nitrogen or oxygen. The conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 4 minutes. The equipment used for UV curing in step S4 is a UV high-pressure pump lamp, and the UV light intensity of the UV high-pressure pump lamp is 10mW / cm 2 ~40mW / cm 2 In step S4, the sprayed rubber plug is irradiated under the ultraviolet light source for 3 minutes; After the UV curing process, the surface of the rubber stopper is grafted and copolymerized to form a coating layer with a thickness of 70nm to 85nm.

[0030] Embodiment 4: This embodiment provides a high-isolation and high-cleanliness halogenated butyl rubber plug surface treatment process, and the specific steps are as follows: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV light curing: UV light curing is used to tightly bond the fluorocarbon layer to the surface of the bottle stopper.

[0031] In step S3, the spraying liquid is a mixed liquid obtained by uniformly mixing a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer; The components of the spraying liquid include 65 parts of fluorocarbon copolymer resin solution, 1 part of coupling agent and 0.2 parts of photoinitiator by weight. The coupling agent is an organic silane coupling agent. Preferably, the model of the organic silane coupling agent is Si-69. The photoinitiator is a benzophenone ultraviolet light absorber. Preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone. In step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device with a transmission frequency of 13.5 MHz and an output power of 700 W to 1200 W. The source gas capable of generating plasma in the plasma treatment is nitrogen or oxygen. The conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 4 minutes. The equipment used for UV curing in step S4 is a UV high-pressure pump lamp, and the UV light intensity of the UV high-pressure pump lamp is 10mW / cm2 to 40mW / cm2. In step S4, the sprayed rubber plug is irradiated under the UV light source for 3 minutes; After the UV curing process, the surface of the rubber stopper is grafted and copolymerized to form a coating layer with a thickness of 70nm to 85nm.

[0032] Comparative Example 1: The surface treatment process of a rubber stopper provided in this comparative example is based on the specific steps of a method for significantly improving the hydrophobicity of the surface of silicone rubber in patent document CN104356418B: placing the rubber stopper in a closed reaction chamber, fluorinating the rubber stopper in a mixed gas composed of fluorine gas and inert gas in the reaction chamber, the fluorination temperature is 55°C to 75°C, the fluorination time is 55 minutes, the concentration of fluorine gas in the mixed gas is 20%, the pressure of the mixed gas in the reaction chamber is 0.6 bar, and the inert gas in the mixed gas is nitrogen; in a temperature-controlled furnace, the fluorinated rubber stopper is thermally cross-linked.

[0033] Comparative Example 2: The comparative example provides a rubber stopper surface treatment process, which uses a traditional siliconization method to treat the rubber stopper, that is, a dimethyl silicone oil spray liquid is prepared according to a dimethyl silicone oil content of 0.01-0.03 mg / cm2 per square centimeter of specific surface area, and before and after the rubber stopper is cleaned, the surface of the rubber stopper is sprayed with a spraying equipment so that the dimethyl silicone oil is adsorbed on the surface of the rubber stopper to play a lubricating role.

[0034] Comparative Example 3: The surface treatment process specifically includes the following steps: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV light curing: UV light curing is used to tightly bond the fluorocarbon layer to the surface of the bottle stopper.

[0035] In step S3, the spraying liquid is a mixed liquid obtained by uniformly mixing a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer; The components of the spraying liquid include 65 parts of fluorocarbon copolymer resin solution, 3 parts of coupling agent and 0.1 parts of photoinitiator by weight, the coupling agent is an organic silane coupling agent, preferably, the model of the organic silane coupling agent is A-174, the photoinitiator is a benzophenone ultraviolet light absorber, preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone; In step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device with a transmission frequency of 13.5 MHz and an output power of 700 W to 1200 W. The source gas capable of generating plasma in the plasma treatment is nitrogen or oxygen. The conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 4 minutes. The equipment used for UV curing in step S4 is a UV high-pressure pump lamp, and the UV light intensity of the UV high-pressure pump lamp is 10mW / cm 2 ~40mW / cm 2 In step S4, the sprayed rubber plug is irradiated under the ultraviolet light source for 3 minutes; After the UV curing process, the surface of the rubber stopper is grafted and copolymerized to form a coating layer with a thickness of 70nm to 85nm.

[0036] The difference between this comparative example and Example 1 is that the number of components of the spraying liquid in this comparative example is not within the range defined by the present invention, and the rest is the same as Example 1.

[0037] The components of the spraying liquid in Examples 1-4 and Comparative Examples 1-3 are as follows:

[0038] Performance test experiment: Coating adhesion test: The cross-hatch method is used to test the coating adhesion. The rubber plugs that have been surface treated are cross-hatched. If the cutting edge is completely smooth and there is no coating shedding on the squares, the cross-hatch result is set as Class A. If there is coating separation at the cutting intersection, the degree of impact on the cross-hatch area is obviously not more than 25%, and the cross-hatch result is set as Class B. If the coating falls off along the cutting edge and the coating on the squares falls off in large pieces, and the degree of impact on the cross-hatch area is obviously not more than 75%, it is set as Class C. The coating shedding situation that is more serious than Class C is set as Class D. Drug resistance test: The surface treated rubber stopper is packaged with chlorpromazine hydrochloride placed in an ampoule, inverted, and subjected to high temperature tests for 10 days and 30 days under constant temperature and humidity conditions (60°C, 75% RH), and the turbidity is compared (refer to Appendix IX of Part II of the Pharmacopoeia of the People's Republic of China 2000 edition). A turbidity of <0.5 indicates that the average turbidity is lower than the value of the No. 0.5 turbidity standard solution; a turbidity of 0.5-1 indicates that the average turbidity is between the values ​​of the No. 0.5 turbidity standard solution and the No. 1 turbidity standard solution. The surface treatment of the rubber described in Examples 1-4 and Comparative Examples 1-2 was subjected to relevant performance tests according to the above method, and the test results are as follows:

[0039] Combined with the above examples and comparative examples, and combined with the test results, analysis is performed: By comparing Examples 1-4 with Comparative Examples 1-3, it can be seen that the coating on the surface of the rubber stopper treated by the surface treatment process of the halogenated butyl rubber stopper of the present invention has strong adhesion and is not easy to fall off, and at the same time has the advantages of resistance.

[0040] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A surface treatment process for high-isolation and high-cleanliness halogenated butyl rubber plugs, characterized in that: The surface treatment process specifically includes the following steps: Step S1: cleaning: first cleaning with a sodium hydroxide solution having a mass percentage concentration of 0.2%, then cleaning with a hydrochloric acid solution having a mass percentage concentration of 1%, and finally cleaning with drinking water and drying; Step S2: plasma treatment: plasma treatment is performed on the surface of the halogenated butyl rubber stopper; Step S3: spraying: spraying the spraying liquid evenly on the surface of the rubber stopper after the plasma treatment; Step S4: UV curing: The fluorocarbon layer is tightly bonded to the surface of the bottle stopper by UV curing; In step S3, the spraying liquid is a mixture of a fluorocarbon copolymer resin solution, a coupling agent and a photoinitiator, and the fluorocarbon copolymer resin solution is produced by copolymerizing tetrafluoroethylene and a vinyl monomer.

2. A surface treatment process for a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1, characterized in that: The components of the spraying liquid include 50 to 65 parts of fluorocarbon copolymer resin solution, 0.24 to 1.85 parts of coupling agent and 0.15 to 0.3 parts of photoinitiator in parts by weight.

3. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1 is characterized in that: The coupling agent is an organic silane coupling agent. Preferably, the model of the organic silane coupling agent is A-174 or Si-69.

4. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1 is characterized in that: The photoinitiator is a benzophenone ultraviolet light absorber, and preferably, the benzophenone ultraviolet light absorber is 2,4-dihydroxybenzophenone.

5. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1 is characterized in that: In step S2, the equipment for plasma treatment of the rubber stopper is a radio frequency discharge plasma device with a transmission frequency of 13.5 MHz and an output power of 700 W to 1200 W.

6. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1 is characterized in that: In step S2, nitrogen or oxygen is selected as the source gas capable of generating plasma in the plasma treatment.

7. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1 is characterized in that: The conditions for the plasma treatment in step S2 are a discharge pressure of 150 Pa to 420 Pa and an irradiation time of 2 minutes to 6 minutes.

8. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1 is characterized in that: The equipment used for UV curing in step S4 is an ultraviolet high-pressure pump lamp, and the ultraviolet light intensity of the ultraviolet high-pressure pump lamp is 10mW / cm 2 ~40mW / cm 2 .

9. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1, characterized in that: In the step S4, the sprayed rubber plug is irradiated under the ultraviolet light source for 1 minute to 4 minutes.

10. The surface treatment process of a high-isolation and high-cleanliness halogenated butyl rubber plug according to claim 1, characterized in that: After the UV curing process, the surface of the rubber stopper is grafted and copolymerized to form a coating layer with a thickness of 70nm to 85nm.

Citation Information

Patent Citations

  • Surface processing method for medicinal rubber stopper

    CN101560306B

  • A method to significantly improve the hydrophobicity of silicone rubber surfaces

    CN104356418B