CN101427980A - Chlorinated butyl rubber bung for injection and method of producing the same - Google Patents
Chlorinated butyl rubber bung for injection and method of producing the same Download PDFInfo
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Abstract
The invention discloses a chlorinated butyl rubber plug used for injections and a preparation method thereof. 100 parts of chlorinated butyl rubbers are dosed for the chlorinated butyl rubber plug used for the injections; all components have the mixture ratios as follows: 100 parts of the chlorinated butyl rubbers, 10 to 100 parts of reinforcing fillers, 3 to 5 parts of curing ingredients, 3 to 5 parts of promoting agents, 1 to 5 parts of accessory ingredients, and 0 to 5 parts of colorants; and the preparation method comprises the following steps sequentially: (1) proportioning, (2) compounding, (3) vulcanizing, (4) die cutting, (5) cleaning and (6) packing. The performance of the chlorinated butyl rubber plug completely accords with the requirements of the national standard YBB00042005, and corresponds to the technical targets for producing similar products in foreign countries.
Description
Technical field
The present invention relates to a kind of medical rubber plug and preparation method thereof, specifically a kind of chlorinated butyl rubber bung for injection and preparation method thereof.
Background technology
" state food medicine prison is annotated [2000] No. 13 " files specify of State Food and Drug Administration was ended to December in 2005 on the 31st, and the natural rubber bottle stopper that all drug packaging bottles use must be finished replacement work, use butyl rubber bottle stopper instead or be coated with, the overlay film plug.Why natural plug is thoroughly eliminated, just because of there is following shortcoming in it: 1, biological safety is relatively poor, and the moisture absorption is mouldy easily; 2, the foreign preteins of stripping is one of key factor that causes people's body heat source from natural plug; 3, easily carcinogenic, the teratogenesis of the steep compounds of the arsenic of stripping, mutagenesis; 4, chemical property is more active, and easy and medicine reacts to each other; 5, air-tightness is relatively poor; Has higher diffusibility for all gases; 6, in when sterilization, materials such as the heavy metal in a large amount of harmful residual chemical promoters, vulcanizing agent, the adjuvant, protein are concentrated in the space of moving to plug footpath and pad film top, and direct intravasation vein through puncturing after endangers patient unawares.The simple butyl rubber that uses but has following shortcoming: 1, have the microgranule obscission, influence medicinal liquid clarity; 2, character is not absolute stability, reacts with some medicines, influences drug quality.Overlay film plug system employing polymer composite is sprayed on the plug surface and reaches the purpose of comforting from plug.But spraying easily causes non-uniform film thickness even, and in spraying process, composite liquefaction back easily reacts with plug, causes the control of plug difficult quality.Chinese patent CN1751973 (application number 200510021897.7) discloses a kind of surface coating one deck and molten point of rubber at rubber stopper and has differed less than 10 ℃ of macromolecule member materials, described membrane material is a polyethylene, polypropylene, poly-vinegar, polyphenyl alkene, politef or their composite.But there is following defective in this improvement: 1, the overlay film layer easily comes off, and directly influences stability of drug.2, cross thick coating and cause sealing property to reduce, influence the long-term stability of medicine.3, at the bottom of the overlay film plug product percent of pass, the manufacturing cost height is unfavorable for the large-scale popularization application.
Summary of the invention
Purpose of the present invention just provides a kind of chlorinated butyl rubber bung for injection and preparation method thereof
The present invention realizes by following technical proposals: chlorinated butyl rubber bung for injection and preparation method thereof, and described chlorinated butyl rubber bung for injection is in 100 parts of chlorinated scolines, and the proportioning of each component is:
100 parts of chlorinated scolines,
Reinforcing filler 10-100 part,
Vulcanizing agent 3-5 part,
Activating agent 3-5 part,
Auxiliary agent 1-5 part,
Coloring agent 0-5 part.
The preparation method of described chlorinated butyl rubber bung for injection comprises the following steps: successively
1. prepare burden: component is strict with the prescription weighing;
2. mixing: it is mixing to adopt banbury to carry out in order load weighted raw material, and feed temperature 64-66 ℃, drop temperature 78-80 ℃, the restriction dump temperature is not higher than 115 ℃;
3. sulfuration: after supercooling, adopt the vacuum molding vulcanizing press carry out sulfurization the raw stock behind the mixing removing from mould;
4. die-cut: as will to vulcanize refrigerative film and be put in and carry out after the die cavity driving fit die-cutly, and guarantee the plug apparent size;
5. clean: with die-cut good plug under the condition of vacuum cycle, clean, rinsing, silication, drying, sterilization, oven dry;
6. the packing: with cleaned plug carry out aseptic inside and outside pack finished product.
Described chlorinated scoline is a medical grade chlorinated scoline 1066, described reinforcing filler is Kaolin (960 ℃ of calcinated argils) XT-0, described vulcanizing agent be bromination right-Te Xinji phenolic aldehyde sulfuration resin HY-2055I, described activating agent is zinc oxide BA01-05 (an I type), described auxiliary agent is a stearic acid 200, and described coloring agent is white carbon black or titanium dioxide (titanium dioxide) BA01-01.
Described mixing, its charging sequence is divided into three times: chlorinated scoline and coloring agent → reinforcing filler, activating agent and auxiliary agent → vulcanizing agent; Each reinforced once mixing, mixing time is respectively 3min, 1min20s, 1min.
Described rinse water water quality reaches state-promulgated pharmacopoeia water for injection standard.
Described conditions of vulcanization is the negative 800Pa of the negative 700-of vacuum, 170-175 ℃ of patrix temperature, 170-175 ℃ of counterdie temperature, sulfuration first pressing 95-105kN, sulfuration final pressure 195-205kN, rising timing 2-4s, first pressing stops 2-4s, aerofluxus length 3-9s, aerofluxus stops 5-11s, vacuum release 9-12s, cure time 240-260s, aerofluxus number of times 1 time.
Described cleaning condition is the adding abluent, previous cleaning 900 seconds, and towards clear 600 seconds, rinsing 600 seconds was washed 600 seconds, and fine purifiation is 600 seconds again, 1 rev/min of fine purifiation rotating speed; Described silication is carried out silication for adding silicone oil; Described sterilising conditions is 100-120 ℃ of a steam sterilization temperature, 0.2 rev/min of sterilization rotating speed, steam sterilizing time 400 seconds; Described drying is a vacuum drying under the sterilizing state, 500 seconds time; Described drying condition is 120 ℃ of bake out temperatures, 400 seconds hot blast time.
The vulcanizing system that chlorinated scoline is commonly used has organic accelerator vulcanizing system and resin cure system, two kinds of systems respectively have characteristics, be easy to relative with consumption of organic accelerator vulcanizing system vulcanizing agent kind adjusted, calendering process is better, the easy demoulding of vulcanizate, mold fouling is little, but recipe design or calendering process grasp are bad, the plug leachable is more, and the ejection phenomenon easily takes place; Resin cure system leachable is less, and it is less influenced by filler, and scorch safety is good, but the compounding ingredient difficulties in dispersion, demoulding difficulty, it is serious to pollute mould.According to the characteristics of concrete production technology, adopting the resin cure system is vulcanizing agent of the present invention.
During for main body rubber design medical product prescription, inorganic mineral filler is best selection with the chlorinated scoline, and kind commonly used has Kaolin, barium sulfate, Pulvis Talci, precipitated silica, calcium silicates etc.Result of the test shows, the kind of filler and consumption have tangible influence to the curingprocess rate of sizing material, processing performance, acupuncture exfoliation, physical and mechanical properties etc.White carbon, talcous use can make curingprocess rate obviously delay; The Kaolin of low pH value can make rubber vulcanization speed up; The use of the low and Pulvis Talci of amount of filler, barium sulfate can make plug obtain excellent acupuncture exfoliation performance, but Pulvis Talci, needle-like barium sulfate can ejection under some process conditions.According to the raw material sources situation, adopt reinforcing filler based on Kaolin.
Using the purpose of processing aid is to improve the processing performance of sizing material, kind commonly used has oil, vaseline, stearic acid, low molecular polyethylene, low molecular weight polycaprolactone butylene etc., the application of this class material, can improve the flowability of sizing material, mixing and drawability, improve the demolding performace of vulcanizate, but recipe design is improper or technological fluctuation easily makes the low molecule leachable of plug increase, with medicine compatibility variation, the plug surface easily produces the bloom phenomenon, we are in the formula development process, and having selected the stearic acid with the fabulous difficult ejection of rubber compatibility is processing aid of the present invention.
The effect of activating agent is the activity that increases promoter, reduces the consumption of promoter or shortens cure time, improves cured properties, and selecting inorganic active agent zinc oxide is activating agent of the present invention.
The purpose of using coloring agent is in order to change the painted of goods, and selecting inorganic colourant white carbon black, titanium dioxide for use is coloring agent of the present invention.
Advantage of the present invention is: technology is simple, non-environmental-pollution, easy to control, the good product quality of working condition; Simultaneously because chlorinated scoline is the modification kind of butyl rubber, in its molecular structure, introduce the chlorine element and increased reactivity, thereby improved the rate of cure of sizing material greatly, and can obviously reduce the consumption of vulcanizing agent and vulcanization accelerator, leachable is less, scorch safety is good, and the performance of product meets the requirement of national standard YBB00042005 fully, and is suitable with external production like product technical specification.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
Below in conjunction with drawings and Examples, the utility model is described in further detail, but do not constitute any restriction of the present utility model.
Embodiment one
A kind of chlorinated butyl rubber bung for injection, described chlorinated butyl rubber bung for injection is in 100 parts of chlorinated scolines, and the proportioning of each component is:
100 parts of chlorinated scolines (medical grade chlorinated scoline 1066)
45 parts of reinforcing fillers (Kaolin XT-0)
3 parts of vulcanizing agents (resin HY-2055I)
5 parts of activating agents (zinc oxide BA01-05)
2.5 parts of auxiliary agents (stearic acid 200)
1.5 parts of coloring agent (white carbon black)
3 parts of coloring agent (titanium dioxide BA01-01)
Preparation method:
1. prepare burden: raw material is strict with above-mentioned prescription weighing;
2. mixing: with the raw material of weighing by charging sequence be divided into three times reinforced: medical grade chlorinated scoline 1066 and titanium dioxide BA01-01 → Kaolin XT-0, zinc oxide BA01-05 and stearic acid 200 → resin HY-2055I, adopt the tipping bucket type banbury to carry out mixing, 65 ℃ of feed temperatures, 79 ℃ of drop temperatures, the restriction dump temperature is not higher than 115 ℃; Each reinforced once mixing, mixing time is respectively 3min, 1min20s, 1min.
3. sulfuration: after supercooling, adopt the vacuum molding vulcanizing press to vulcanize the raw stock behind the mixing removing from mould, vacuum-750Pa, 170 ℃ of patrix temperature, 170 ℃ of counterdie temperature, sulfuration first pressing 100kN, sulfuration final pressure 200kN, rising timing 3s, first pressing stops 3s, aerofluxus length 6s, aerofluxus stops 8s, vacuum release 10s, cure time 250s, aerofluxus 1 time;
4. die-cut: as will to vulcanize refrigerative film and be put in and carry out after the die cavity driving fit die-cutly, and guarantee the plug apparent size;
5. clean: with die-cut good plug under the condition of vacuum cycle, clean, rinsing, silication, drying, sterilization, oven dry; Adopt secondary reverse osmosis water blood processor, and equipped hollow-fibre ultrafiltration device, can filter out the thermal source macromole, make device outlet water quality reach state-promulgated pharmacopoeia water for injection standard, guarantee the clean level that plug cleans; Cleaning equipment has ultrasonic cleaning equipment, has further guaranteed the cleaning quality of plug; Discharging opening is located at cleanliness factor to be between ten thousand grades inner packing and to be positioned under hundred grades the laminar flow hood, guarantees that the clean level of plug meets the requirement in pharmaceutical factory; Add abluent 200ml, previous cleaning 900 seconds, towards clear 600 seconds, rinsing 600 seconds was washed 600 seconds, and fine purifiation is 600 seconds again, 1 rev/min of fine purifiation rotating speed; Add dimethicone and carry out silication; 120 ℃ of steam sterilization temperature, 0.2 rev/min of sterilization rotating speed, steam sterilizing time 400 seconds; Vacuum drying under the sterilizing state, 500 seconds time; 120 ℃ of bake out temperatures, 400 seconds hot blast time.
6. the packing: with cleaned plug carry out aseptic inside and outside pack finished product.
Embodiment two
A kind of chlorinated butyl rubber bung for injection, described chlorinated butyl rubber bung for injection is in 100 parts of chlorinated scolines, and the proportioning of each component is:
100 parts of chlorinated scolines (medical grade chlorinated scoline 1066)
50 parts of reinforcing fillers (Kaolin XT-0)
3.5 parts of vulcanizing agents (resin HY-2055I)
4.5 parts of activating agents (zinc oxide BA01-05)
3 parts of auxiliary agents (stearic acid 200)
1.5 parts of coloring agent (white carbon black)
3 parts of coloring agent (titanium dioxide BA01-01)
Preparation method:
1. prepare burden: raw material is strict with above-mentioned prescription weighing;
2. mixing: with the raw material of weighing by charging sequence be divided into three times reinforced: medical grade chlorinated scoline 1066 and titanium dioxide BA01-01 → Kaolin XT-0, zinc oxide BA01-05 and stearic acid 200 → resin HY-2055I, adopt the tipping bucket type banbury to carry out mixing, 64 ℃ of feed temperatures, 80 ℃ of drop temperatures, the restriction dump temperature is not higher than 115 ℃; Each reinforced once mixing, mixing time is respectively 3min, 1min20s, 1min.
3. sulfuration: after supercooling, adopt the vacuum molding vulcanizing press to vulcanize the raw stock behind the mixing removing from mould, vacuum-780Pa, 175 ℃ of patrix temperature, 175 ℃ of counterdie temperature, sulfuration first pressing 105kN, sulfuration final pressure 205kN, rising timing 4s, first pressing stops 4s, aerofluxus length 8s, aerofluxus stops 10s, vacuum release 11s, cure time 250s, aerofluxus 1 time;
4. die-cut: as will to vulcanize refrigerative film and be put in and carry out after the die cavity driving fit die-cutly, and guarantee the plug apparent size;
5. clean: with die-cut good plug under the condition of vacuum cycle, clean, rinsing, silication, drying, sterilization, oven dry; Adopt secondary reverse osmosis water blood processor, and equipped hollow-fibre ultrafiltration device, can filter out the thermal source macromole, make device outlet water quality reach state-promulgated pharmacopoeia water for injection standard, guarantee the clean level that plug cleans; Cleaning equipment has ultrasonic cleaning equipment, has further guaranteed the cleaning quality of plug; Discharging opening is located at cleanliness factor to be between ten thousand grades inner packing and to be positioned under hundred grades the laminar flow hood, guarantees that the clean level of plug meets the requirement in pharmaceutical factory; Add abluent 200ml, previous cleaning 900 seconds, towards clear 600 seconds, rinsing 600 seconds was washed 600 seconds, and fine purifiation is 600 seconds again, 1 rev/min of fine purifiation rotating speed; Add dimethicone and carry out silication; 110 ℃ of steam sterilization temperature, 0.2 rev/min of sterilization rotating speed, steam sterilizing time 400 seconds; Vacuum drying under the sterilizing state, 500 seconds time; 120 ℃ of bake out temperatures, 400 seconds hot blast time.
6. the packing: with cleaned plug carry out aseptic inside and outside pack finished product.
Claims (7)
1, chlorinated butyl rubber bung for injection and preparation method thereof is characterized in that: described chlorinated butyl rubber bung for injection is in 100 parts of chlorinated scolines, and the proportioning of each component is:
100 parts of chlorinated scolines,
Reinforcing filler 10-100 part,
Vulcanizing agent 3-5 part,
Activating agent 3-5 part,
Auxiliary agent 1-5 part,
Coloring agent 0-5 part.
2, chlorinated butyl rubber bung for injection according to claim 1 and preparation method thereof is characterized in that: its preparation method comprises the following steps: successively
1. prepare burden: component is strict with the prescription weighing;
2. mixing: it is mixing to adopt banbury to carry out in order load weighted raw material, and feed temperature 64-66 ℃, drop temperature 78-80 ℃, the restriction dump temperature is not higher than 115 ℃;
3. sulfuration: after supercooling, adopt the vacuum molding vulcanizing press carry out sulfurization the raw stock behind the mixing removing from mould;
4. die-cut: as will to vulcanize refrigerative film and be put in and carry out after the die cavity driving fit die-cutly, and guarantee the plug apparent size;
5. clean: with die-cut good plug under the condition of vacuum cycle, clean, rinsing, silication, drying, sterilization, oven dry;
6. the packing: with cleaned plug carry out aseptic inside and outside pack finished product.
3, chlorinated butyl rubber bung for injection according to claim 1 and preparation method thereof, it is characterized in that: described chlorinated scoline is a medical grade chlorinated scoline 1066, described reinforcing filler is Kaolin (960 ℃ of calcinated argils) XT-0, described vulcanizing agent be bromination right-Te Xinji phenolic aldehyde sulfuration resin HY-2055I, described activating agent is zinc oxide BA01-05 (an I type), described auxiliary agent is a stearic acid 200, and described coloring agent is white carbon black or titanium dioxide (titanium dioxide) BA01-01.
4, chlorinated butyl rubber bung for injection according to claim 2 and preparation method thereof is characterized in that: described mixing, its charging sequence is divided into three times: chlorinated scoline and coloring agent → reinforcing filler, activating agent and auxiliary agent → vulcanizing agent; Each reinforced once mixing, mixing time is respectively 3min, 1min20s, 1min.
5, chlorinated butyl rubber bung for injection according to claim 2 and preparation method thereof is characterized in that: described rinse water water quality reaches state-promulgated pharmacopoeia water for injection standard.
6, chlorinated butyl rubber bung for injection according to claim 2 and preparation method thereof is characterized in that: described conditions of vulcanization is the negative 800Pa of the negative 700-of vacuum, 170-175 ℃ of patrix temperature, 170-175 ℃ of counterdie temperature, sulfuration first pressing 95-105kN, sulfuration final pressure 195-205kN, rising timing 2-4s, first pressing stops 2-4s, aerofluxus length 3-9s, aerofluxus stops 5-11s, vacuum release 9-12s, cure time 240-260s, aerofluxus number of times 1 time.
7, chlorinated butyl rubber bung for injection according to claim 2 and preparation method thereof is characterized in that: described cleaning condition is for adding abluent, previous cleaning 900 seconds, towards clear 600 seconds, rinsing 600 seconds was washed 600 seconds, fine purifiation is 600 seconds again, 1 rev/min of fine purifiation rotating speed; Described silication is carried out silication for adding silicone oil; Described sterilising conditions is 100-120 ℃ of a steam sterilization temperature, 0.2 rev/min of sterilization rotating speed, steam sterilizing time 400 seconds; Described drying is a vacuum drying under the sterilizing state, 500 seconds time; Described drying condition is 120 ℃ of bake out temperatures, 400 seconds hot blast time.
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| CNA2007101352671A CN101427980A (en) | 2007-11-06 | 2007-11-06 | Chlorinated butyl rubber bung for injection and method of producing the same |
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| CNA2007101352671A CN101427980A (en) | 2007-11-06 | 2007-11-06 | Chlorinated butyl rubber bung for injection and method of producing the same |
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| CN102702574A (en) * | 2012-06-04 | 2012-10-03 | 郑州市翱翔医药包装有限公司 | Vulcanizing system and medical chlorinated butyl rubber plug |
| CN102993493A (en) * | 2012-08-22 | 2013-03-27 | 安徽中马橡塑制品有限公司 | Medicinal synthetic polyisoprene gasket composition |
| CN101851377B (en) * | 2009-12-31 | 2013-05-08 | 山东省药用玻璃股份有限公司 | Novel medical powder injection rubber plug and manufacturing method thereof |
| CN103112168A (en) * | 2012-12-31 | 2013-05-22 | 山东省药用玻璃股份有限公司 | Method for manufacturing piston for refilling injection syringe |
| CN104448589A (en) * | 2013-09-18 | 2015-03-25 | 湖北航天化学技术研究所 | Transparent chlorinated butyl rubber material and a preparation method thereof |
| CN105153560A (en) * | 2015-10-20 | 2015-12-16 | 河北橡一医药科技股份有限公司 | Halogenated butyl rubber gasket for medicinal aerosol valve systems |
| CN106009341A (en) * | 2016-07-06 | 2016-10-12 | 湖北华强科技有限责任公司 | Formula of halogenated butyl rubber plug capable of achieving low-temperature vulcanization |
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| CN106147055A (en) * | 2016-08-24 | 2016-11-23 | 湖北华强科技有限责任公司 | A kind of sterilized powder halogenated butyl rubber plug formula and preparation method |
| CN106366470A (en) * | 2016-08-29 | 2017-02-01 | 湖北华强科技有限责任公司 | High-purity rubber plug formula |
| CN108169123A (en) * | 2017-12-25 | 2018-06-15 | 湖北华强科技有限责任公司 | A kind of membrane material and rubber adhesion intensity evaluation method |
| CN109575390A (en) * | 2018-11-26 | 2019-04-05 | 盛州医药包装材料科技（中国）有限公司 | It is a kind of can cryogenic vulcanization rubber stopper formula and preparation method thereof |
| CN109679240A (en) * | 2018-12-28 | 2019-04-26 | 江阴市海华橡塑有限公司 | A kind of medicinal chlorinated butyl rubber plug and its production technology |
| CN109705483A (en) * | 2018-12-28 | 2019-05-03 | 江阴市海华橡塑有限公司 | A kind of transfusion chlorinated butyl rubber plug and preparation method thereof |
| CN110016169A (en) * | 2019-06-04 | 2019-07-16 | 应城市恒天药业包装有限公司 | A kind of overlay film chlorinated butyl rubber bung and preparation method thereof |
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| CN114181472A (en) * | 2021-12-27 | 2022-03-15 | 湖北华强科技股份有限公司 | Self-film-forming butyl rubber plug |
| CN115785583A (en) * | 2023-01-31 | 2023-03-14 | 烟台华胜医药包装有限公司 | Zinc-free and sulfur-free vulcanization system medicinal chlorinated butyl rubber plug and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101851377B (en) * | 2009-12-31 | 2013-05-08 | 山东省药用玻璃股份有限公司 | Novel medical powder injection rubber plug and manufacturing method thereof |
| CN102702574A (en) * | 2012-06-04 | 2012-10-03 | 郑州市翱翔医药包装有限公司 | Vulcanizing system and medical chlorinated butyl rubber plug |
| CN102993493A (en) * | 2012-08-22 | 2013-03-27 | 安徽中马橡塑制品有限公司 | Medicinal synthetic polyisoprene gasket composition |
| CN103112168A (en) * | 2012-12-31 | 2013-05-22 | 山东省药用玻璃股份有限公司 | Method for manufacturing piston for refilling injection syringe |
| CN104448589A (en) * | 2013-09-18 | 2015-03-25 | 湖北航天化学技术研究所 | Transparent chlorinated butyl rubber material and a preparation method thereof |
| CN105153560A (en) * | 2015-10-20 | 2015-12-16 | 河北橡一医药科技股份有限公司 | Halogenated butyl rubber gasket for medicinal aerosol valve systems |
| CN106009341B (en) * | 2016-07-06 | 2018-06-19 | 湖北华强科技有限责任公司 | It is a kind of can cryogenic vulcanization halogenated butyl rubber plug formula |
| CN106009341A (en) * | 2016-07-06 | 2016-10-12 | 湖北华强科技有限责任公司 | Formula of halogenated butyl rubber plug capable of achieving low-temperature vulcanization |
| CN106084515A (en) * | 2016-07-06 | 2016-11-09 | 湖北华强科技有限责任公司 | One has puncture plug and preparation method |
| CN106147055A (en) * | 2016-08-24 | 2016-11-23 | 湖北华强科技有限责任公司 | A kind of sterilized powder halogenated butyl rubber plug formula and preparation method |
| CN106366470A (en) * | 2016-08-29 | 2017-02-01 | 湖北华强科技有限责任公司 | High-purity rubber plug formula |
| CN108169123A (en) * | 2017-12-25 | 2018-06-15 | 湖北华强科技有限责任公司 | A kind of membrane material and rubber adhesion intensity evaluation method |
| CN109575390A (en) * | 2018-11-26 | 2019-04-05 | 盛州医药包装材料科技（中国）有限公司 | It is a kind of can cryogenic vulcanization rubber stopper formula and preparation method thereof |
| CN109679240A (en) * | 2018-12-28 | 2019-04-26 | 江阴市海华橡塑有限公司 | A kind of medicinal chlorinated butyl rubber plug and its production technology |
| CN109705483A (en) * | 2018-12-28 | 2019-05-03 | 江阴市海华橡塑有限公司 | A kind of transfusion chlorinated butyl rubber plug and preparation method thereof |
| CN109705483B (en) * | 2018-12-28 | 2021-10-22 | 江阴市海华橡塑有限公司 | Transfusion chlorinated butyl rubber plug and preparation method thereof |
| CN110016169A (en) * | 2019-06-04 | 2019-07-16 | 应城市恒天药业包装有限公司 | A kind of overlay film chlorinated butyl rubber bung and preparation method thereof |
| CN111171422A (en) * | 2020-02-21 | 2020-05-19 | 郑州华净新材料科技有限公司 | Piston for pre-filling and sealing injector and manufacturing method thereof |
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| CN114181472A (en) * | 2021-12-27 | 2022-03-15 | 湖北华强科技股份有限公司 | Self-film-forming butyl rubber plug |
| CN114181472B (en) * | 2021-12-27 | 2024-03-12 | 湖北华强科技股份有限公司 | Butyl rubber plug capable of forming film automatically |
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