CN101376730A - 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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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 not contain 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 be directly used in 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 natural rubber to make medicinal bottle stopper.Natural rubber derives from the glue juice (latex) of rubber tree, contain: natural gum, resin, alkaloid, enzyme, materials such as toxin and assorted bacterium, use it for injection drug packaging bottle stopper, directly the contact medicine easily pollutes medicine, has now been prohibited by country to be used to make injection pharmaceutical packing bottle stopper.
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, make 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) because medicinal bottle stopper directly contacts with medicine,, the steady quality of medicine will be influenced directly if do not have consistency with medicine.Therefore, must by 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 very fragile, the incomplete molecular state rubber diaphragm of one deck, materials such as packing strengthening agent in the parcel rubber cooperation system that can not be complete, and it is easy to wear, it easily discharges the insoluble substance such as lime carbonate, white bole, titanium dioxide of reinforcing filler, cause the injection medicine, particularly the visible foreign matters in the infusion medicine, particulate matter exceed standard, thereby influence drug quality and drug safety.
(3) adopt at medicinal halogenated butyl rubber bottle stopper surface coating teflon polymer inert materials such as (TEFULO), make 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, easily cause problems such as packing soup seepage and microbiological contamination.
(4) for the rubber diaphragm on the medicinal halogenated butyl rubber bottle stopper of protection surface, be increase medicinal bottle stopper lubricating on the pharmaceutical equipment delivery track simultaneously, 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) the acupuncture exfoliation easily takes place in the clinical application process in medicinal halogenated butyl rubber bottle stopper, 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.Cleaning is dispeled very difficult, becomes the quality difficult problem of solution that pharmaceutical industry is paid close attention to.
(7) medicinal halogenated butyl rubber belongs to thermosetting elastomer, and manufacturing the leftover bits of process and defect ware can't recycling; 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, the production energy consumption height.
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 prepared from by having following components in part by weight:
350～500 parts of styrene copolymers or rubber type of material, described styrene copolymer is selected from polystyrene-polyethylene-polybutene-poly styrene polymer (SEBS) and the polystyrene-polybutene-poly styrene polymer (SBS) any, and described rubber type of material is selected from terpolymer EP rubber (EPDM), paracril (NBR), isoprene-isobutylene rubber (IIR), chlorinated butyl rubber (CI-IIR) and the poly-1.4-synthetic polyisoprene (NR) any;
100～450 parts of polyolefins materials, described polyolefins material be in polypropylene (PP) or the polyethylene (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, through 1～3 hour, being dried to water content is to be no more than 0.1% of its gross weight, wherein material comprises described styrene copolymer or rubber type of material, described 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 reactor, 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 described 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 described thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is made 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 composition 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, make 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 made 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 by 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
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with embodiment.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 by having following components in part by weight:
350～500 parts of styrene copolymers or rubber type of material, described styrene copolymer is selected from polystyrene-polyethylene-polybutene-poly styrene polymer (SEBS) and the polystyrene-polybutene-poly styrene polymer (SBS) any, and described rubber type of material is selected from terpolymer EP rubber (EPDM), paracril (NBR), isoprene-isobutylene rubber (IIR), chlorinated butyl rubber (CI-IIR) and the poly-1.4-synthetic polyisoprene (NR) any;
100～450 parts of polyolefins materials, described polyolefins material be in polypropylene (PP) or the polyethylene (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.
Described softening agent is white oil or paraffin.
Described weighting agent is a calcium powder.
Described expanding material is selected from diethylenetriamine, Triethylenetetramine (TETA) and the polypropylene maleic anhydride any.
Described 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.
Described static inhibitor is selected from dodecyl-2 alcohol radicals-Propylamino-ethanol and the undecyl-formamido--propyl group-Trimethylamine 99-methylsulfonic acid any.
Described 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 is to be no more than 0.1% of its gross weight, wherein, material comprises 350～500 parts of described styrene copolymer or rubber type of material, 100～450 parts, 200～500 parts softening agent of described 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 reactor, 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 described thermoplastic elastic material at the cooling trough cooling and shaping.
Barrel among this preparation method cleans, and adopts polypropylene or polyethylene; Use is based on polypropylene or poly look mother.
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-polyethylene-polybutene-poly styrene polymer (SEBS) of styrenic material or the polypropylene (PP) or the polyethylene (PE) of polystyrene-polybutene-polystyrene (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), isoprene-isobutylene rubber (IIR), chlorinated butyl rubber (CI-IIR) or poly-1.4-synthetic polyisoprene (NR) the wherein polypropylene (PP) or the polyethylene (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 polypropylene (PP) or polyethylene (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 described thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is made 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 polypropylene or polyethylene; Use is based on polypropylene or poly look mother.
The following examples illustrate thermoplastic elastic material of the present invention and preparation method thereof.
Embodiment 1
By weight, select 500 parts of polystyrene-polyethylene-polybutene-poly styrene polymers (SEBS) for use, 100 parts of polypropylene (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 reactor, under 200 ℃, stir and made its fusion in 1 hour, under 225 ℃, extrude, after tractor traction severing is a particulate state, promptly get described thermoplastic elastic material at the cooling trough cooling and shaping through plastics extruder;
Barrel among this preparation method cleans, and adopts polypropylene or polyethylene; Use is based on polypropylene or poly look mother.
Embodiment 2
By weight, select 400 parts of polystyrene-polyethylene-polybutene-poly styrene polymers (SEBS) for use, 200 parts of polypropylene (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 polypropylene (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 polypropylene (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 300 parts of poly-1.4-isoprene (NR) for use, 450 parts of polypropylene (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 isoprene-isobutylene rubbers (IIR) for use, 450 parts of polyethylene (PP), 100 parts of paraffin, 100 parts of white oils, 3 parts of polypropylene 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 Example 1-6 gained thermoplastic elastic material prepares medicinal bottle stopper respectively, and the preparation method is as follows:
(1) under 80～100 ℃ of temperature, through 1 hour, dry described thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is made 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 polypropylene or polyethylene; Use is based on polypropylene or poly look mother.
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.
| N0 | Test item | Detection method | Standard | Foundation |
| 01 | [outward appearance] | Range estimation: particle is clean and tidy, color even, inclusion-free. | ||
| 02 | [discriminating] | |||
| 2-1 | Infrared spectra | Detect by infrared spectrophotometry. | With contrast collection of illustrative plates basically identical | Two appendix IV of CP2005 C |
| 2-2 | Hardness | International rubber hardness degrees (the pocket sclerometer penetration hardness of the pocket sclerometer method of 30～90IRHD) mensuration rubber test method | Shore-A30～60 | GB 11204-1989 GB/T531-199 9 |
| 2-3 | Density | Plastic density and relative density test method densitometry | 0.90～1.10 g/cm 3 | GB 1033-86 YBB0013200 3 |
| 2-4 | Tensile strength | The mensuration tensile property assay method of vulcanized rubber high temperature tensile strength and tensile yield | 3.0～7.0MPa | GB/T 528-1998 YBB0011200 3 |
| 2-5 | Elongation at break | The mensuration tensile property assay method of vulcanized rubber high temperature tensile strength and tensile yield | 300～720% | GB/T 528-1998 YBB0011200 3 |
| 2-6 | Compression set | Vulcanized rubber and thermoplastic rubber are at the 23 ℃/22h of mensuration of normal temperature, high temperature and low temperature lower compression tension set | 12～22% | GB 7759-1996 |
| 2-7 | Shrinking percentage | The mensuration of thermoplastics injection molding shrinking percentage | 2.2～2.6% | GB/T15585-1 995 |
| 2-8 | Stretching strength retentivity | 150 ℃/the 168h of mensuration of vulcanized rubber high temperature tensile strength and tensile yield | 106～115% | GB/T 6073-1985 |
| 2-9 | Rebound resilience | The vulcanized rubber rebound resilience is measured | 42～90% | GB/T1681-19 91 |
| 03 | [residue on ignition] | The 5.0g that draws materials, dry 100 ℃/1h, 800 ℃ of calcinations are to constant weight. | AHS≤0.22% | YBB0004～52 005 |
| 04 | [compatibility test] | |||
| Thermal adaptability | Moist heat sterilization adaptability (standard sterilization value F 0〉=8) 124 ℃/50min | Moltenly contract, adhesion, test piece three-dimensional dimension no change | ||
| 05 | [particulate matter] | Press the particulate matter test procedure, the particle dia inspection is: | 〉=5 μ m≤100/ml 〉=10 μ m≤10/ml 〉=25 μ m≤1/ml | Two appendix IX of CP2005 C |
| 06 | [additive] | By the tlc test | Test liquid does not show the impurity spot; Contrast liquid shows two spots. | YBB0001～two appendix V of 22 002 CP2005 B |
| 07 | [drug release test] | |||
| 7-1 | Clarity | Measure by the clarity test procedure | The solution clarification. | YBB0001～two appendix IX of 22 002 CP2005 B |
| 7-2 | Color | Pressing the solution colour test procedure measures | Solution is colourless | YBB0001～22 002 |
| Two appendix IX of CP2005 A | ||||
| 7-3 | PH value | Get test liquid 20ml, add Klorvess Liquid (1 → 1000) ml, press the pH value test procedure and measure. | PH:5.0～7.0。 | YBB0001～two appendix VIH of 22 002 CP2005 |
| 7-4 | Ultraviolet absorptivity | Get test liquid and be contrast, press ultraviolet visible spectrophotometry and measure, in wavelength 220～350nm scope, scan with the blank solution. | 220～240nm maximum absorption degree≤0.08; 241～350nm maximum absorption degree≤0.05. | YBB0001～two appendix IV of 22 002 CP2005 A |
| 7-5 | Non-volatile matter | Measure each 250ml of test liquid and blank solution, place the furnace pot of constant weight respectively, water bath method is dried to constant weight in 105 ℃. | Poor≤the 12.5mg of test liquid non-volatile matter residue and its blank solution residue | YBB0001200 2 YBB0002200 2 |
| 7-6 | Readily oxidizable substance | 10ml and sulfuric acid (2mol/ L) 10ml is heated to little 3min of boiling, and is cooled to room temperature.Add potassiumiodide 0.1g, to light brown, add 5 of starch indicating liquids with Sulfothiorine (0.01mol/L) titration again, back titration is to colourless.Do blank test with method. | Test liquid and titrating solution that blank solution consumes, the poor≤1.5ml of the two. | YBB0001200 2 YBB0002200 2 |
| 7-7 | Ammonium ion | The preparation of contrast liquid: precision is measured blank solution 46ml, (getting ammonium chloride 31.5mg, to add no ammoniacal liquor an amount of to add ammonium chloride solution, make its dissolving and be diluted to 1000ml) 4.0ml, add alkaline test solution of mercuric potassium iodide 2ml; Precision is measured test liquid 50ml, adds alkaline test solution of mercuric potassium iodide 2ml, places 15min, as colour developing, with the contrast liquor ratio, must not be darker.(0.00008%) | NH4≤0.8ppm | YBB00012002 YBB00022002 |
| 7-8 | Zine ion | Adopt hydrochloric acid, the yellow prussiate of potash method detects | Do not develop the color | YBB00042005 |
| 7-9 | Barium ion | It is an amount of to get test liquid, and evaporation concentration improves it and detects model | ≤ 1ppm. | YBB0001200 2 |
| Enclose, press under the metal element entry and detect, | YBB0002200 2 | |||
| 7-10 | Cupric ion | It is an amount of to get test liquid, and evaporation concentration makes it improve sensing range, presses under the metal element entry and detects | ≤ 1ppm. | YBB00012002 YBB00022002 |
| 7-11 | Cadmium ion | It is an amount of to get test liquid, and evaporation concentration makes it improve sensing range, and press under the metal element entry and detect, | ≤ 0.1ppm. | YBB00012002 YBB0002200 2 |
| 7-12 | Lead ion | It is an amount of to get test liquid, and evaporation concentration makes it improve sensing range, presses under the metal element entry and detects | ≤ 1ppm. | YBB00012002 YBB0002200 2 |
| 7-13 | Tin ion | It is an amount of to get test liquid, and evaporation concentration makes it improve sensing range, presses under the metal element entry and detects | ≤ 0.1ppm. | YBB00012002 YBB0002200 2 |
| 7-14 | Chromium ion | It is an amount of to get test liquid, and evaporation concentration makes it improve sensing range, presses under the metal element entry and detects | ≤ 1ppm. | YBB00012002 YBB0002200 2 |
| 7-15 | Aluminum ion | It is an amount of to get test liquid, and evaporation concentration makes it improve sensing range, by atomic absorption spectrophotometry, measure at the wavelength place of 309.3nm, | ≤ 0.05ppm. | Two appendix IV of YBB00012002 CP2005 D |
| 7-16 | Heavy metal | Precision is measured test liquid 20ml, adds acetate buffer (PH3.5) 2ml, presses the heavy metal test procedure and measures. | Content≤1ppm | Two appendix VIII of CP2005 H, first method |
| 7-17 | Specific conductivity | Measure the test liquid of existing configuration, the specific conductivity of contrast liquid at 20 ± 1 ℃ respectively with conductivitimeter. | Contrast liquid≤3.0 μ S/cm test liquids≤40. μ S/cm | YBB0004200 5 |
| 08 | [metallic element] | Residue on ignition adds HCl (1 → 2) 25ml according to atomic absorption spectroscopy determination | Should meet following provisions: | Two appendix IV of CP2005 D |
| 8-1 | Copper (Cu) | Wavelength place at 324.8mm measures | ≤ 3ppm | YBB0001～2,200 2 |
| 8-2 | Cadmium (Cd) | Wavelength place at 228.8mm measures | ≤ 3ppm | YBB0001～22 002 |
| 8-3 | Chromium (Cr) | Wavelength place at 357.9mm measures | ≤3ppm | YBB0001～22 002 |
| 8-4 | Plumbous (Pb) | Wavelength place at 217.0mm measures | ≤3ppm | YBB0001～22 002 |
| 8-5 | Tin (Sn) | Wavelength place at 286.3mm measures | ≤3ppm | YBB0001～22 002 |
| 8-6 | Barium (Ba) | Wavelength place at 553.6mm measures | ≤3ppm | YBB0001～22 002 |
| 09 | [easy volatile sulfide] | Press the volatile sulfur compounds assay method | ≤2.5μg Na 2S cm 2 | YBB0030200 4 |
| 10 | [biological test] | |||
| 10-1 | Thermal source | Press the heat source check method | No thermal source effect | YBB0002200 3 GB /T14233.2-93 |
| 10-2 | Cytotoxicity | By the cytotoxicity detection method | Relative increment degree≤2 grades | YBB0001200 3 GB /T14233.2-93 |
| 10-3 | Haemolysis | Press the haemolysis test procedure | Hemolysis rate≤5% | YBB0003200 3 GB /T14233.2-93 |
| 10-4 | Acute general toxicity test | According to acute general toxicity test procedure | There is not acute general toxicity | YBB0004200 3 GB /T14233.2-93 |
| 10-5 | The intracutaneous irritant test | Press intracutaneous and stimulate test procedure | Have no stimulation | YBB0006200 3 GB /T14233.2-93 |
| 11 | [gas permeation amount] | Vulcanized rubber, thermoplastic rubber's gas permeability test are pressed plastic film sheet material gas permeability test assay method | ≤0.5cm 3/ (m 2.24h.atm) | GB/T1038-20 00 YBB0008200 3 |
| 12 | [steam penetrating capacity] | Press 38 ± 0.6 ℃ of plastic film, the cup type methods of sheet material water vapor transmission test method determination, relative humidity 90 ± 2% steam penetrating capacity assay methods | ≤0.01g/(m 2，24h) | GB/T1037-19 87 YBB0009200 3 |
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's promulgation, and SFDA refers to " cartridge bag material standard ".GB refers to national standard, and GB/T refers to country's (recommendation) standard.
Ginseng sees the above table, and as can be seen, 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, is the ideal material of preparation injection medicinal bottle stopper.
As previously mentioned, specific embodiments of the invention only are used for explanation of the invention and explanation, do not limit the present invention.All any modifications of being done within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1, a kind of thermoplastic elastic material is prepared from by having following components in part by weight:
350～500 parts of styrene copolymers or rubber type of material, described styrene copolymer is selected from polystyrene-polyethylene-polybutene-poly styrene polymer and the polystyrene-polybutene-poly styrene polymer any, and described rubber type of material is selected from terpolymer EP rubber, paracril, isoprene-isobutylene rubber, chlorinated butyl rubber and the poly-1.4-synthetic polyisoprene any;
100～450 parts of polyolefins materials, described polyolefins material be in polypropylene or the polyethylene 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.
2, thermoplastic elastic material according to claim 1, wherein softening agent is white oil or paraffin.
3, thermoplastic elastic material according to claim 1, wherein weighting agent is a calcium powder.
4, thermoplastic elastic material according to claim 1, wherein expanding material is selected from any in diethylenetriamine, Triethylenetetramine (TETA) or the polypropylene maleic anhydride.
5, thermoplastic elastic material according to claim 1, wherein 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.
6, thermoplastic elastic material according to claim 1, wherein static inhibitor is selected from any in dodecyl-2 alcohol radicals-Propylamino-ethanol or the undecyl-formamido--propyl group-Trimethylamine 99-methylsulfonic acid.
7, 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.
8, 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 described styrene copolymer or rubber type of material, described 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 reactor, 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 described thermoplastic elastic material at the cooling trough cooling and shaping.
9, a kind of application method of material preparation medicinal bottle stopper according to claim 1 comprises the steps:
(1) under 80～100 ℃ of temperature, through 1～3 hour, dry described thermoplastic elastic material to water content was to be no more than 0.1% of its gross weight;
(2) thermoplastic elastic material is made 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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