CN101376730B - Thermoplastic elastomer material, preparation thereof and method for manufacturing medicinal bottle stopper by using the same - Google Patents
Thermoplastic elastomer material, preparation thereof and method for manufacturing medicinal bottle stopper by using the same Download PDFInfo
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- CN101376730B CN101376730B CN200710076843XA CN200710076843A CN101376730B CN 101376730 B CN101376730 B CN 101376730B CN 200710076843X A CN200710076843X A CN 200710076843XA CN 200710076843 A CN200710076843 A CN 200710076843A CN 101376730 B CN101376730 B CN 101376730B
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Abstract
The invention provides thermoplastic elastomer materials used for a bottle cork for manufacturing medicines, a preparation method thereof and a method for applying the bottle cork for manufacturing medicines thereof. The materials are prepared by the following components: styrene copolymer or rubber materials as well as polyolefine matters. The styrene copolymer is PP or PE; besides, the materials also contain a plasticizer and a loading agent, contain or do not contain a compatibilizer, contain or do not contain an antioxidant, contain or do not contain an antistatic agent, contain or do notcontain adhesion preventives. The preparation method thereof includes the steps of drying the materials, fusing a reaction kettle, using a plastic extruding machine to extrude the materials, using a cooling water slot to cool and shape the materials, using a hauling machine to haul and cut off the materials, and the like. The thermoplastic elastomer materials provided by the invention have the advantages of stable chemical property, no poison, low polarity and good rebound resilience.
Description
Technical field
The present invention relates to thermoplastic elastic material (TPE), its preparation method that a kind of pharmaceutical purpose bottle stopper uses and use the method that it makes medicinal bottle stopper.
Background technology
Medicine is to have certain biological activity and chemically reactive, is the mankind's be used to prevent, treat, keep healthy and live particular matters of procreation.Ensure drug quality, guarantee that drug safety is to cause to close important major issue.For this reason; Container and material for drug packaging; Particularly directly be used for the intravital injection pharmaceutical packing of people medicinal bottle stopper, must adopt chemical property stable, good airproof performance; Can directly contact medicine, and the elastomer material that can ensure drug quality stable is made the medicinal bottle stopper of injection drug packaging.
In the past, people adopt tree elastomer to make medicinal bottle stopper.Tree elastomer derives from the glue juice (latex) of rubber tree; Contain: natural gum, resin, vegeto-alkali, enzyme, materials such as toxin and assorted bacterium; Use it for injection drug packaging bottle stopper; Directly the contact medicine is prone to pollute to medicine, has been prohibited by country to be used to make injection pharmaceutical packing bottle stopper at present.
At present, injection drug packaging both at home and abroad adopts generally that resistance to air loss is good, the purified synthetic halogenated butyl rubber of composition is made medicinal bottle stopper, is referred to as medicinal halogenated butyl rubber bottle stopper.Its manufacturing process flow generally comprises batching, banburying successively, opens refining, calendering, molded vulcanization, die-cut, clean, dry, silication and packaging and other steps.
Medicinal halogenated butyl rubber belongs to thermoset rubber; The straight-chain molecular structure that contains unsaturated link(age); The cooperation and the vulcanization of rubber under certain temperature, pressure, time conditions through rubber; Make the straight-chain molecule of halogenated butyl rubber change into the irreversible network molecular structure of three dimensional hinge, process the medicinal bottle stopper of all size.Outside surface at medicinal halogenated butyl rubber bottle stopper; Form the very fragile and incomplete molecular state rubber diaphragm of one deck; The inside is wrapped in the various auxiliary materials (rubber compounding) of the necessary cooperation system of halogenated butyl rubber bottle stopper, as has the materials such as reinforcing filler of anti-aging agent, softening agent and the rubber of certain chemically active vulcanizer and vulcanization aid thereof, rubber.
The technological process of the prescription of medicinal halogenated butyl rubber and manufacturing medicinal bottle stopper has determined medicinal halogenated butyl rubber bottle stopper to have following shortcoming:
(1) directly contacts with medicine owing to medicinal bottle stopper, if do not have consistency, with the steady quality that directly influences medicine with medicine.Therefore, must through with the compatibility test of medicine, select to be applicable to the prescription of the halogenated butyl rubber bottle stopper of certain medicine.Yet because medicine is various in style, physico-chemical property is different; Present medicinal halogenated butyl rubber bottle stopper prescription is comparatively single, is difficult to adapt to the requirement of various drug qualities to medicinal halogenated butyl rubber bottle stopper.
(2) because medicinal halogenated butyl rubber bottle stopper surface is to form fragile, the incomplete molecular state rubber diaphragm of one deck ten minutes; Materials such as packing strengthening agent in the parcel rubber cooperation system that can not be complete; And insoluble substance such as lime carbonate, white bole, white titanium pigment easy to wear, that it is prone to discharge reinforcing filler causes the injection medicine; Particularly the visible foreign matters in the infusion medicine, particulate matter exceed standard, thereby influence drug quality and drug safety.
(3) be employed in medicinal halogenated butyl rubber bottle stopper surface and coat ZX 21 polymer inert materials such as (TEFULO); Process overlay film (plated film) plug; Solve the problem of above (1) and (2), can increase the manufacturing cost of medicinal bottle stopper, simultaneously because polymeric membrane material ground is hard; Not tight with container sealing, be prone to cause problems such as packing soup seepage and microbiological contamination.
(4) be the rubber diaphragm on the medicinal halogenated butyl rubber bottle stopper of protection surface, simultaneously for increasing medicinal bottle stopper lubricating on the pharmaceutical equipment delivery track, must be at the quantitative silicone oil of medicinal halogenated butyl rubber bottle stopper surface coated.And the repellency material in the inherent Synergist S-421 95 of the silicone oil of medicinal halogenated butyl rubber bottle stopper surface coated and rubber influences the steady quality of indivedual medicines to external diffusion; Simultaneously, form " repellency oil film ", cause the injection liquid medicine, particularly " hanging pearl " (extension water) phenomenon of infusion medicine glass containers internal surface at the drug container internal surface.
(5) medicinal halogenated butyl rubber bottle stopper is prone to the acupuncture exfoliation takes place in the clinical application process, causes the drug safety problem.
(6) because halogenated butyl rubber is to have the polar polymkeric substance, and has tackiness, cause medicinal halogenated butyl rubber bottle stopper very easily to adsorb dust, fiber, influence drug quality.Very difficulty is dispeled in cleaning, becomes pharmaceutical industry and pays close attention to a quality difficult problem that solves.
(7) medicinal halogenated butyl rubber belongs to thermosetting elastomer, and leftover bits and the imperfections of manufacturing process can't recyclings; Medicinal halogenated butyl rubber medicinal bottle stopper is again disposable running stores, causes the waste of resource and to the pollution of environment.China will produce nearly 16,000,000,000 powder ampoule agent for injection (comprising lyophilized injectable powder) medicine every year, ton surplus 6,000,000,000 bottles of (bag) infusion solutions medicines, annual depleted medicine halogenated butyl rubber bottle stopper 6,000,000, only consume halogenated butyl rubber reach 2,880,000 surplus ton.
(8) make medicinal halogenated butyl rubber medicinal bottle stopper, production process is long, and production environment is strict, and the expense of founding the factory is big, and production energy consumption is high.
Summary of the invention
The technical problem that the embodiment of the invention will solve is, provides that a kind of chemical property is stable, non-toxic and safe, polarity is low and rebound resilience is good thermoplastic elastic material.
Another technical problem that the embodiment of the invention will solve is, a kind of preparation method of above-mentioned thermoplastic elastic material is provided.
The technical problem again that the embodiment of the invention will solve is, a kind of method that above-mentioned thermoplastic elastic material prepares medicinal bottle stopper of using is provided.
The thermoplastic elastic material that the embodiment of the invention provides is used to prepare medicinal bottle stopper, is prepared from having following components in part by weight:
350～500 parts of styrene copolymers, said styrene copolymer are selected from polystyrene-poly ethene-polybutylenes-poly styrene polymer (SEBS) and the PS-butadiene-styrene polymkeric substance (SBS) any;
100～450 parts of polyolefins materials, said polyolefins material be in Vestolen PP 7052 (PP) or the Vilaterm (PE) any;
200～500 parts of softening agent;
50～150 parts of weighting agents;
0～3 part of expanding material;
0～1 part of oxidation inhibitor;
0～1 part of static inhibitor; And
0～3 part of release agent.
The preparation method of the thermoplastic elastic material that the embodiment of the invention provides comprises the steps:
(1) material is under 80～100 ℃ of temperature, and through 1～3 hour, being dried to water content was to be no more than 0.1% of its gross weight; Wherein material comprises said styrene copolymer; Said polyolefins material, softening agent and weighting agent contain or do not contain expanding material, contain or do not contain oxidation inhibitor; Contain or do not contain static inhibitor, contain or do not contain release agent;
(2) dry back material in the step (1) is added reaction kettle; Under 160～220 ℃, stir after 1～1.5 hour, under 220～230 ℃, extrude through plastics extruder; After tractor traction severing is a particulate state, promptly get said thermoplastic elastic material at the cooling trough cooling and shaping.
The embodiment of the invention provides, and uses the method that above-mentioned thermoplastic elastic material prepares medicinal bottle stopper, comprises the steps:
(1) under 80～100 ℃ of temperature, through 1～3 hour, dry said thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is processed medicinal bottle stopper through injection moulding or extrusion equipment, injection temperature is 190 ℃～250 ℃, and injection pressure is 40～60MPa; Extrusion temperature is 170 ℃～230 ℃, port mould forming section＜1mm, filter screen >=100 orders.
The medicinal bottle stopper that adopts technique scheme to make, the halogenated butyl rubber bottle stopper of producing with prior art compares, and has following advantage:
1, the inherent main chain copolymerization of the thermoplastic elastic material (TPE) that provides of the embodiment of the invention or the special construction of component blend determine that its chemical property is stable, safety non-toxic, polarity is low, rebound resilience good.Have consistency widely with various medicines, can be made into the medicinal bottle stopper of all size, be applicable to various drug packagings.The compsn that using the embodiment of the invention provides is made medicinal bottle stopper, need not to remake overlay film on the medicinal bottle stopper surface and handles, and can not discharge visible foreign matters and particulate matter, can not pollute medicine.
2, because the composition material toughness that the embodiment of the invention provides is strong, process the injection medicinal bottle stopper, acupuncture exfoliation and particulate matter can not take place, guarantee drug safety in clinical application.
3, because the medical rubber plug that the composition material that the embodiment of the invention provides is processed can not adsorb dust, fiber, can not pollute medicine.
4, the composition material that provides of the embodiment of the invention belongs to environment-friendly materials, economizes on resources at the leftover bits of medicinal bottle stopper manufacturing processed with the finished product medicinal bottle stopper is recyclable utilizes again.
5, the composition material that provides of the embodiment of the invention can be through injection moulding, extrude or mode such as mold pressing, one-step moulding is made medicinal bottle stopper, Device-General, mold temperature is low relatively, the time is short, technology is easy.Than the production of existing halogenated butyl rubber bottle stopper, technical process has shortened 4/5, and energy efficient >=90% has improved production efficiency greatly, cut down the consumption of energy.
6, use the composition material manufacturing medicinal bottle stopper that the embodiment of the invention provides, technical process is short, and production unit is few, and the factory area is little, and construction investment is few.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The thermoplastic elastic material (TPE) that the pharmaceutical purpose bottle stopper that the embodiment of the invention provides is used is prepared from having following components in part by weight:
350～500 parts of styrene copolymers or rubber type of material; Said styrene copolymer is selected from polystyrene-poly ethene-polybutylenes-poly styrene polymer (SEBS) and the PS-butadiene-styrene polymkeric substance (SBS) any, and said rubber type of material is selected from terpolymer EP rubber (EPDM), paracril (NBR), butyl rubber (IIR), Chlorobutyl (CI-IIR) and gathers in the 1.4-synthetic polyisoprene (NR) any;
100～450 parts of polyolefins materials, said polyolefins material be in Vestolen PP 7052 (PP) or the Vilaterm (PE) any;
200～500 parts of softening agent;
50～150 parts of weighting agents;
0～3 part of expanding material;
0～1 part of oxidation inhibitor;
0～1 part of static inhibitor; And
0～3 part of release agent.
Said softening agent is white oil or paraffin.
Said weighting agent is a calcium powder.
Said expanding material is selected from NSC 446, Triethylenetetramine (TETA) and the Vestolen PP 7052 maleic anhydride any.
Said oxidation inhibitor is selected from four [β-(3,5-di-t-butyl 4-hydroxyl-phenyl) propionic acid] pentaerythritol esters and β-(3,5-di-t-butyl 4-hydroxyl-phenyl) propionic acid octadecyl ester any.
Said static inhibitor is selected from dodecyl-2 alcohol radicals-Propylamino-ethanol and the undecyl-formamido--propyl group-Trimethylamine 99-methylsulfonic acid any.
Said release agent is the food grade release agent, is selected from erucicamide, mountain Yu acid acid amides, the two stearic acid acid amides of ethylene, the two amine hydroxybenzenes of ethylene, silicon-dioxide and the silica gel any.
The preparation method of the thermoplastic elastic material that the embodiment of the invention provides comprises the steps:
(1) under 80～100 ℃ of temperature, through 1～3 hour, dried material to water content was to be no more than 0.1% of its gross weight; Wherein, material comprises 350～500 parts of said styrene copolymer or rubber type of material, 100～450 parts, 200～500 parts softening agent of said polyolefins material and 50～150 parts of weighting agents; 0～3 part of expanding material; 0～1 part of oxidation inhibitor, 0～1 part of static inhibitor, and 0～3 part of release agent.
(2) dry back material in the step (1) is added reaction kettle; Under 160～220 ℃, stir after 1～1.5 hour, under 220～230 ℃, extrude through plastics extruder; After tractor traction severing is a particulate state, promptly get said thermoplastic elastic material at the cooling trough cooling and shaping.
Barrel among this preparation method cleans, and adopts Vestolen PP 7052 or Vilaterm; Use is based on Vestolen PP 7052 or poly look female.
The preparation method of thermoplastic elastic material can be divided into chemical polymerization and mechanical blending two major types.Thermoplastic elastomer is that raw material merges the structures that form polymer chain down at 160～220 ℃ with the polystyrene-poly ethene-polybutylenes-poly styrene polymer (SEBS) of styrenic material or the Vestolen PP 7052 (PP) or the Vilaterm (PE) of PS-butadiene-styrene polymkeric substance (SBS) and polyolefins material, is called for short the main chain copolymerization.
Wherein the styrenic material is the rubber segments (soft section) in the copolymerization chain, and the polyolefins material is the resin section (hard section) in the copolymerization chain.
Thermoplastic elastomer is with rubber type of material terpolymer EP rubber (EPDM), paracril (NBR), butyl rubber (IIR), Chlorobutyl (CI-IIR) or gather 1.4-synthetic polyisoprene (NR) wherein the Vestolen PP 7052 (PP) or the Vilaterm (PE) of any and polyolefins material are that raw material is at 160～220 ℃ of following mechanical blendings; Terpolymer EP rubber class elastomeric material is realized dynamic vulcanization; Rubber with particulate form is dispersed in the resin; Form the disperse phase (island phase) of thermoplastic elastic material; The polyolefins material of Vestolen PP 7052 (PP) or Vilaterm (PE) forms the blending structure of the external phase (marine facies) of thermoplastic elastic material, is called for short the blend of island structure.
The special construction of above-mentioned thermoplastic elastomer makes it possess characteristics:
1, at high temperature presents plasticity, can soften or melt, present plastic flow adding to depress, manifest the processing characteristics of thermoplastics.
2, the physical and mechanical propertiess such as elasticity, intensity and deformation behavior that show vulcanized rubber at normal temperatures.
3, thermoplastic elastomer is a Stability Analysis of Structures ground inert body material; The present invention prepares former that thermoplastic elastomer adopts, auxiliary material, and it is stable, nontoxic, harmless to be chemical property.
The embodiment of the invention provides, and uses the method that above-mentioned thermoplastic elastic material prepares medicinal bottle stopper, comprises the steps:
(1) under 80～100 ℃ of temperature, through 1～3 hour, dry said thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is processed medicinal bottle stopper through injection moulding or extrusion equipment, injection temperature is 190 ℃～250 ℃, and injection pressure is 40～60MPa; Extrusion temperature is 170 ℃～230 ℃, port mould forming section＜1mm, filter screen >=100 orders;
Barrel among this preparation method cleans, and adopts Vestolen PP 7052 or Vilaterm; Use is based on Vestolen PP 7052 or poly look female.
Following embodiment explains thermoplastic elastic material of the present invention and preparation method thereof.
Embodiment 1
By weight, select 500 parts of polystyrene-poly ethene-polybutylenes-poly styrene polymers (SEBS) for use, 100 parts of Vestolen PP 7052 (PP); 500 parts of white oils, 3 parts of Triethylenetetramine (TETA)s, 150 parts of calcium powders; 1 part of four [β-(3,5-di-t-butyl 4-hydroxyl-phenyl) propionic acid] pentaerythritol ester, 3 parts of erucicamides are as the material for preparing thermoplastic elastic material; Under 90 ℃ of temperature, through 2 hours, dried material to water content was to be no more than 0.1% of its gross weight; Material after the drying is added reaction kettle, under 200 ℃, stir and made its fusion in 1 hour, under 225 ℃, extrude, after tractor traction severing is a particulate state, promptly get said thermoplastic elastic material at the cooling trough cooling and shaping through plastics extruder;
Barrel among this preparation method cleans, and adopts Vestolen PP 7052 or Vilaterm; Use is based on Vestolen PP 7052 or poly look female.
Embodiment 2
By weight, select 400 parts of polystyrene-poly ethene-polybutylenes-poly styrene polymers (SEBS) for use, 200 parts of Vestolen PP 7052 (PP), 300 parts of white oils, 100 parts of calcium powders, 3 parts of erucicamides, 1 part of dodecyl-2 alcohol radicals-Propylamino-ethanol.
The preparation method is with embodiment 1.
Embodiment 3
By weight, select 350 parts of terpolymer EP rubbers (EPDM) for use, 450 parts of Vestolen PP 7052 (PP), 200 parts of paraffin, 3 parts of Triethylenetetramine (TETA)s, 50 parts of calcium powders, 3 parts of erucicamides, 1 part of dodecyl-2 alcohol radicals-Propylamino-ethanol.
The preparation method is with embodiment 1.
Embodiment 4
By weight, select 300 parts of terpolymer EP rubbers (EPDM) for use, 450 parts of Vestolen PP 7052 (PP), 200 parts of paraffin, 100 parts of white oils, 3 parts of diethylene tetramines, 3 parts of mountain Yu acid acid amides, 1 part of undecyl-formamido--propyl group-Trimethylamine 99-methylsulfonic acid.
The preparation method is with embodiment 1.
Embodiment 5
By weight, select for use 300 parts to gather 1.4-isoprene (NR), 450 parts of Vestolen PP 7052 (PP), 100 parts of paraffin, 100 parts of white oils, 50 parts of calcium powders, 3 parts of Triethylenetetramine (TETA)s, 50 parts of calcium powders, 3 parts of erucicamides, 1 part of dodecyl-2 alcohol radicals-Propylamino-ethanol.
The preparation method is with embodiment 1.
Embodiment 6
By weight, select 350 parts of butyl rubbers (IIR) for use, 450 parts of Vilaterm (PP), 100 parts of paraffin, 100 parts of white oils, 3 parts of Vestolen PP 7052 maleic anhydrides, 3 parts of two amine hydroxybenzenes of ethylene, 1 part of dodecyl-2 alcohol radicals-Propylamino-ethanol.
The preparation method is with embodiment 1.
Application implementation example 1-6 gained thermoplastic elastic material prepares medicinal bottle stopper respectively, and the preparation method is following:
(1) under 80～100 ℃ of temperature, through 1 hour, dry said thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is processed medicinal bottle stopper through injection moulding or extrusion equipment, injection temperature is 190 ℃～250 ℃, and injection pressure is 40～60MPa; Extrusion temperature is 170 ℃～230 ℃, port mould forming section＜1mm, filter screen >=100 orders;
Barrel among this preparation method cleans, and adopts Vestolen PP 7052 or Vilaterm; Use is based on Vestolen PP 7052 or poly look female.
Performance test:
Get the foregoing description 1～6 gained thermoplastic elastic material (TPE) and carry out performance test, detection method in testing method such as the following table, test result all can meet the listed quality standard of following table.
CP refers to Chinese Pharmacopoeia in the last table, and YBB refers to " the immediate packaging materials and containers standard " of State Food and Drug Administration (SFDA) promulgation cartridge bag material standard.GB refers to national standard, and GB/T refers to country's (recommendation) standard.
Referring to last table, can find out that the thermoplastic elastic material chemical property that the embodiment of the invention provides is stable, have consistency widely with various medicines, and polarity is low, nontoxic, harmless, rebound resilience is good, be the ideal material of preparation injection medicinal bottle stopper.
As previously mentioned, specific embodiment of the present invention only is used for explanation of the present invention and explanation are not limited the present invention.All any modifications of within spirit of the present invention and principle, being done, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.
[0105]
Claims (5)
1. a thermoplastic elastic material is used to prepare medicinal bottle stopper, is prepared from having following components in part by weight:
350～500 parts of styrene copolymers, said styrene copolymer are selected from polystyrene-poly ethene-polybutylenes-poly styrene polymer and the PS-butadiene-styrene polymkeric substance any;
100～450 parts of polyolefins materials, said polyolefins material be in Vestolen PP 7052 or the Vilaterm any;
200～500 parts of softening agent;
50～150 parts of weighting agents;
0～3 part of expanding material;
0～1 part of oxidation inhibitor;
0～1 part of static inhibitor; And
0～3 part of release agent;
Wherein softening agent is white oil or paraffin; Weighting agent is a calcium powder; Oxidation inhibitor is selected from any in four [β-(3,5-di-t-butyl 4-hydroxyl-phenyl) propionic acid] pentaerythritol esters or β-(3,5-di-t-butyl 4-hydroxyl-phenyl) propionic acid octadecyl ester; Static inhibitor is selected from any in dodecyl-2 alcohol radicals-Propylamino-ethanol or the undecyl-formamido--propyl group-Trimethylamine 99-methylsulfonic acid, and release agent is selected from the food grade release agent.
2. thermoplastic elastic material according to claim 1, wherein expanding material is selected from any in NSC 446, Triethylenetetramine (TETA) or the Vestolen PP 7052 maleic anhydride.
3. thermoplastic elastic material according to claim 1, wherein release agent is selected from any in food grade release agent erucicamide, mountain Yu acid acid amides, the two stearic acid acid amides of ethylene, the two amine hydroxybenzenes of ethylene, silicon-dioxide or the silica gel.
4. the preparation method of thermoplastic elastic material according to claim 1 comprises the steps:
(1) material is under 80～100 ℃ of temperature; Through 1～3 hour; Being dried to water content is to be no more than 0.1% of its gross weight; Wherein, material comprises said styrene copolymer, said polyolefins material, softening agent and weighting agent, contains or does not contain expanding material, contains or do not contain oxidation inhibitor, contain or do not contain static inhibitor, contain or do not contain release agent;
(2) dry back material in the step (1) is added reaction kettle; Under 160～220 ℃, stir after 1～1.5 hour, under 220～230 ℃, extrude through plastics extruder; After tractor traction severing is a particulate state, promptly get said thermoplastic elastic material at the cooling trough cooling and shaping.
5. use the method for material prepn medicinal bottle stopper according to claim 1 for one kind, comprise the steps:
(1) under 80～100 ℃ of temperature, through 1～3 hour, dry said thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is processed medicinal bottle stopper through injection moulding or extrusion equipment, injection temperature is 190 ℃～250 ℃, and injection pressure is 40～60MPa; Extrusion temperature is 170 ℃～230 ℃, port mould forming section＜1mm, filter screen >=100 orders.
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| CN200710076843XA CN101376730B (en) | 2007-08-31 | 2007-08-31 | Thermoplastic elastomer material, preparation thereof and method for manufacturing medicinal bottle stopper by using the same |
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| CN105367978A (en) * | 2015-11-18 | 2016-03-02 | 安徽雄亚塑胶科技有限公司 | TPE composition and liquor bottle stopper prepared from TPE composition |
| CN106589757A (en) * | 2016-12-06 | 2017-04-26 | 佛山市高明区生产力促进中心 | Insulating TPE material |
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| CN110791030A (en) * | 2019-12-04 | 2020-02-14 | 北京橡胶工业研究设计院有限公司 | Zinc-free halogenated butyl rubber/polypropylene thermoplastic elastomer and preparation method thereof |
| CN111269473A (en) * | 2020-03-05 | 2020-06-12 | 武汉鼎塑实业有限公司 | Medical sealing gasket and preparation method thereof |
| 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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| US4444330A (en) * | 1981-10-02 | 1984-04-24 | Terumo Kabushiki Kaisha | Medical container stopper |
| CN1312322A (en) * | 2000-02-09 | 2001-09-12 | 三井化学株式会社 | Low-atomizing thermoplastic elastic composition and production process and use of said composition |
| CN1353658A (en) * | 1999-05-28 | 2002-06-12 | 诺沃挪第克公司 | Injection-molder stopper for medical containers |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4444330A (en) * | 1981-10-02 | 1984-04-24 | Terumo Kabushiki Kaisha | Medical container stopper |
| CN1353658A (en) * | 1999-05-28 | 2002-06-12 | 诺沃挪第克公司 | Injection-molder stopper for medical containers |
| CN1312322A (en) * | 2000-02-09 | 2001-09-12 | 三井化学株式会社 | Low-atomizing thermoplastic elastic composition and production process and use of said composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751050A (en) * | 2016-12-16 | 2017-05-31 | 吴中区穹窿山师匠新材料技术咨询服务部 | A kind of antistatic macromolecule material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101376730A (en) | 2009-03-04 |
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