CN103405335A - Surface-modified rubber plug and preparation method thereof - Google Patents
Surface-modified rubber plug and preparation method thereof Download PDFInfo
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- CN103405335A CN103405335A CN2013103319298A CN201310331929A CN103405335A CN 103405335 A CN103405335 A CN 103405335A CN 2013103319298 A CN2013103319298 A CN 2013103319298A CN 201310331929 A CN201310331929 A CN 201310331929A CN 103405335 A CN103405335 A CN 103405335A
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Abstract
The invention discloses a surface-modified rubber plug and a preparation method thereof. The rubber plug comprises a rubber plug body and a modification layer on the surface of the rubber plug body. The modification layer is modified through PVDC (polyvinyl dichloride) emulsion. Chemical modification is performed on the surface of the rubber plug by the aid of the corona-aided high polymer material surface modification technology, oxygen-blocking and dampness-blocking features of the PVDC is utilized to increase negative pressure maintaining capacity of a vacuum container, block the contact of the rubber plug body and medicines and blood, and increase safety and biocompatibility of the rubber plug. The method is suitable for the existing rubber plugs available on the market, thermoplastic elastomer rubber plugs and surface modification of sealing parts with complex shapes.
Description
Technical field
The present invention relates to the medical rubber stopper technical field, particularly plug of a kind of finishing and preparation method thereof.
Background technology
Pharmaceutical packing material and packaged form, the packaging material that especially directly contact with medicine, have important function to the stability that guarantees medicine.Unfavorable packaging material can cause the absorption of active constituents of medicine on packaging material, perhaps the composition in packaging material is adsorbed in medical surfaces, even packaging material and medicine generation chemical reaction, and cause loss of drug potency, sometimes even can produce serious toxic and side effects.Although it is all fine that the butyl rubber that tradition is commonly used and halogenated butyl rubber plug are compared natural rubber at aspects such as cleanliness factor, chemical stability, air-tightness, biological safeties, but because of its formula is complicated and add the relation of material concentration gradient, after encapsulation, easily by medicine and blood absorption, absorption, leaching, infiltration, can produce the consistency problem of plug and inclusions.
Teflon film plug and other film capsules arise at the historic moment, but its cost is very high, and its sealing property and anti-exfoliation poor performance.The practice of Japan is at plug surface spraying fluorine silicon materials, has namely solved the adhesion problems of plug, has solved again the upper machine problem of plug when the medicine fill, but with high costs.Chinese patent CN200720087033.X, medicinal coating film rubber plug, adopt chemical vapor deposition (CVD) technique and for the xylol film, solve plug precipitate problem in the uniform polychlorostyrene of plug surface deposition coating one deck.Chinese patent CN 200520068811.1, exempt from the silication medical rubber stopper, reaches and exempt from the silication purpose by surperficial PET overlay film.
In addition, prepare at present almost whole dependence on import of butyl rubber that plug adopts, for breaking away from the dependence to butyl rubber, also can adopt the technique of thermoplastic elastomer injection mo(u)lding to prepare plug, yet the thermoplastic elastomer (TPE) plug can't compare favourably with butyl rubber all the time aspect air-tightness.
In sum, the subject matter that in prior art, all kinds of medical rubber stoppers exist is:
1. the sealing property of plug and security performance are unreliable.
2. the difficulty of plug coating technique is large, and cost is high.
3. the medical rubber stopper material mainly is confined to butyl rubber, halogenated butyl rubber plug, has increased production cost.
PVDC, formal name used at school " polyvinylidene chloride ", because its intermolecular cohesive force is strong, degree of crystallinity is high, chlorine atom in the PVDC molecule has hydrophobicity, can not form hydrogen bond, and oxygen molecule and hydrone are difficult to move in the PVDC molecule, thereby it is moist with resistance to make it have good oxygen barrier, and its oxygen barrier is not subjected to the impact of ambient humidity.That is to say, under any temperature or damp condition, have concurrently remarkable block water, the choke ability, be the best plastic package material of combination property aspect barrier of generally acknowledging at present.Utilize the gas barrier property of PVDC, can delay the generation of medicine oxidation deterioration phenomenon, greatly extend the product shelf phase, the while can be avoided the fragrance of content to scatter and disappear and prevent the intrusion of outside bad smell; Utilize its resistance moist, can prevent the phenomenon of product generation dehydration exsiccation, mouthfeel variation, can, because the product water suction damages the packing prototype, not prevent quantitative goods generation natural wastage (weightlessness).Gas barrier properties does not change with the variation of humidity, rotten even high humidity environment can not cause product yet; Utilize its hypotonicity, can prevent loss of aroma, and not absorption of residual residual air flavor and off-taste, have excellent weather resistance, even long term exposure, outdoor, directly is subjected to solar radiation, also can not occur that packing material fades and catabiosis.And safety and environmental protection, by FDA(FDA (Food and Drug Adminstration)) authentication.
The characteristic of PVDC is: high molecular, and density is large, compound with regular structure, the wet ability of excellent resistance, good oil resistant, drug-resistant and solvent resistance, especially have excellent barrier property to airborne oxygen, water vapour, carbon dioxide.In the situation that thickness is identical, PVDC is 1500 times of PE to the barrier property of oxygen, is 100 times of PP, is 100 times of PET, and block water steam and oxygen all are better than PVC.In addition, the sealing property of PVDC material, the indices such as impact strength, tensile strength all can meet the specific (special) requirements of drug packaging.It both had been different from polyvinyl alcohol increases along with moisture absorption and gas barrier properties is sharply descended, also be different from nylon membrane because water absorption makes the moisture barrier property variation, but a kind ofly hinder high barrier material wet, that choke is all excellent, environment is very little on the impact of its barrier, is the development priority of drug packing material from now on.
Therefore, the method that adopts the PVDC emulsion to modify is carried out surface modification to medical rubber stopper, can meet the requirement of medical rubber stopper at aspects such as chemical stability, air-tightness, resistance to ag(e)ing and the low property separated out.
Summary of the invention
The object of the present invention is to provide a kind of plug of finishing, comprise the decorative layer on rubber plug body and surface thereof, can greatly improve safety and the biocompatibility of plug.
Another object of the present invention is to provide a kind of plug preparation method of finishing, utilize corona assistant high molecular material surface modification technology, low and the efficient chemical modification of cost is carried out in the plug surface, improve the negative pressure hold facility blocking-up rubber plug body of Dewar vessel and contacting of medicine and blood.
For achieving the above object, the invention provides a kind of plug of finishing, comprise the decorative layer of rubber plug body and body surface, described decorative layer is modified and is formed by the PVDC emulsion, and plug can be in type or commercially available medical rubber stopper.
The present invention also provides a kind of preparation method of plug of above-mentioned finishing, comprises the following steps:
Step 1, provide rubber plug body;
Step 2, cleaning, dry rubber plug body;
Step 3, drop into sided corona treatment 20-120 minute in closed corona stirred tank by the plug after cleaning-drying;
Step 4, the plug after processing are put under condition of nitrogen gas in the middle of the PVDC emulsion of 60-120 ℃, stir 6-24 hour;
Step 5, from emulsion, taking out, water, ethanol, chloroform clean and are dry successively by plug, obtain the medical rubber stopper of finishing.
The raw materials of described rubber plug body is halogenated butyl rubber or conventional butyl rubbers or other synthetic rubber or thermoplastic elastomer (TPE).
Described closed corona stirred tank is normal pressure or low tension corona plasma stirred tank.
Described corona plasma stirred tank is gases used comprises a kind of in air, oxygen, nitrogen, helium, argon or two or more mixture.
Described PVDC emulsion is PVDC oligomer emulsion, and PVDC content is 75-90%, in described emulsion, contains at least a kind of acrylic polymer of acrylate soft monomer, and its consumption is the 8-20% of polymer total amount, and unsaturated fatty acid content is 1-5%.
Beneficial effect of the present invention:
1. the present invention has promoted sealing property and the security performance of medical rubber stopper.
2. the present invention can realize applying at the plug to complex-shaped, as the surface-coated of lyophilizing class plug.
3. the present invention has widened plug film coating technique field, has reduced difficulty and the cost of plug surface coating technique, easy to implement, successful.
4. the present invention has widened existing medical rubber stopper field, and by single halogenated butyl rubber plug, being expanded is natural rubber, isoprene rubber, other synthetic rubber plugs, thermoplastic elastomer (TPE) plug.
The specific embodiment
The preparation method of the medical rubber stopper that PVDC of the present invention modifies comprises the following steps:
Step 1, provide rubber plug body, and rubber plug body can adopt in type or commercially available medical rubber stopper;
Step 2, cleaning, dry rubber plug body;
Step 3, drop into sided corona treatment 20-120 minute in closed corona stirred tank by the plug after cleaning-drying;
Step 4, the plug after sided corona treatment are put under condition of nitrogen gas in the middle of the PVDC emulsion of 60-120 ℃, stir 6-24 hour;
Step 5, from emulsion, taking out, water, ethanol, chloroform clean and are dry successively by plug, obtain the medical rubber stopper of finishing.
Embodiment 1
Commercially available halogenated butyl rubber plug is cleaned also and puts into the corona stirred tank after drying, regulate current intensity to 9A, under normal pressure, the corona in air Cement Composite Treated by Plasma is 20 minutes, close corona, in two hours, plug is transferred in the PVDC emulsion of lower 70 ℃ of condition of nitrogen gas, stirred 6 hours, by plug from emulsion, taking out, water, ethanol, chloroform clean and are dry successively, obtain the plug of finishing.
Embodiment 2
Adopt the natural rubber plug, current intensity 12A, normal pressure nitrogen plasma treatment 60 minutes, 80 ℃ of PVDC emulsions, stirred 16 hours, and all the other are with embodiment 1.
Embodiment 3
Adopt the isoprene rubber plug, current intensity 9A, the atmospheric air corona plasma was processed 120 minutes, and 90 ℃ of PVDC emulsions, stirred 24 hours, and all the other are with embodiment 1.
Embodiment 4
Adopt the thermoplastic elastomer (TPE) plug, current intensity 14A, atmospheric air corona ion body was processed 90 minutes, and 100 ℃ of PVDC emulsions, stirred 10 hours, and all the other are with embodiment 1.
Embodiment 5
Commercially available halogenated butyl rubber plug is cleaned also and puts into the corona stirred tank after drying, regulate current intensity to 16A, under normal pressure, the corona in air Cement Composite Treated by Plasma is 20 minutes, close corona, under stirring, blowing air is 60 minutes, in two hours, plug is transferred in the PVDC emulsion of lower 100 ℃ of condition of nitrogen gas, stirred 6 hours, from emulsion, taking out, water, ethanol, chloroform clean and are dry successively by plug, obtain the plug of finishing.
Embodiment 6
Adopt the natural rubber plug, current intensity is 16A, and under low pressure, the nitrogen corona plasma was processed 60 minutes, and 60 ℃ of PVDC emulsions, stirred 10 hours, and all the other are with embodiment 5.
Embodiment 7
Adopt the thermoplastic elastomer (TPE) plug, current intensity is 18A, and under low pressure, the helium corona plasma was processed 80 minutes, and 120 ℃ of PVDC emulsions, stirred 12 hours, and all the other are with embodiment 5.
Embodiment 8
Adopt the thermoplastic elastomer (TPE) plug, current intensity is 16A, and the atmospheric air corona plasma was processed 100 minutes, and 100 ℃ of PVDC emulsions, stirred 24 hours, and all the other are with embodiment 5.
According to related request, each embodiment is tested, wherein the testing standard of test event puncture exfoliation is YBB00042005, and the testing standard of other test events is YBB00302004, and test result is as shown in table 1.
Table 1
Although the inventor has done comparatively detailed elaboration and has enumerated technical scheme of the present invention; be to be understood that; for one of ordinary skill in the art; according to disclosed content; embodiment is made modification and/or changes or adopt the replacement scheme be equal to is apparent, and it all can not break away from the scope of protection of present invention.
Claims (7)
1. the plug of a finishing comprises and it is characterized in that the decorative layer of rubber plug body and body surface that described decorative layer is modified and formed by the PVDC emulsion.
2. plug as claimed in claim 1, it is characterized in that, described PVDC emulsion is PVDC oligomer emulsion, PVDC content is 75-90%, in described emulsion, contain at least a kind of acrylic polymer of acrylate soft monomer, its consumption be the polymer total amount 8-20%, unsaturated fatty acid content is 1-5%.
3. plug as claimed in claim 1, is characterized in that, the main material of described rubber plug body is halogenated butyl rubber or conventional butyl rubbers or other synthetic rubber or thermoplastic elastomer (TPE).
4. as the preparation method of the plug of the described finishing of claim 1-3 any one, it is characterized in that, comprise the following steps:
Step 1, provide rubber plug body;
Step 2, cleaning, dry rubber plug body;
Step 3, drop into sided corona treatment 20-120 minute in closed corona stirred tank by the plug after cleaning-drying;
Step 4, put into the plug after sided corona treatment under condition of nitrogen gas in the middle of the PVDC emulsion of 60-120 ℃, stirs 6-24 hour;
Step 5, from emulsion, taking out, water, ethanol, chloroform clean and are dry successively by plug, obtain the plug of finishing.
5. the preparation method of the plug of finishing as claimed in claim 4, is characterized in that, described closed corona stirred tank is normal pressure or low tension corona plasma stirred tank.
6. the preparation method of the plug of finishing as claimed in claim 5, is characterized in that, described corona plasma stirred tank is gases used comprises a kind of in air, oxygen, nitrogen, helium, argon or two or more mixture.
7. the preparation method of the plug of described finishing as claimed in claim 4, it is characterized in that, described PVDC emulsion is PVDC oligomer emulsion, PVDC content is 75-90%, in described emulsion, contain at least a kind of acrylic polymer of acrylate soft monomer, its consumption be the polymer total amount 8-20%, unsaturated fatty acid content is 1-5%.
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| CN2013103319298A CN103405335A (en) | 2013-08-02 | 2013-08-02 | Surface-modified rubber plug and preparation method thereof |
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| CN2013103319298A CN103405335A (en) | 2013-08-02 | 2013-08-02 | Surface-modified rubber plug and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079953A (en) * | 2019-06-14 | 2020-12-15 | 北京诺维新材科技有限公司 | Medical rubber and preparation method and application thereof |
| CN113969100A (en) * | 2020-07-21 | 2022-01-25 | 中国石油化工股份有限公司 | Coating composition containing molecular sieve catalyst, coating liquid for non-silicification rubber plug, preparation method of coating liquid and preparation method of non-silicification rubber plug |
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| WO2013016153A1 (en) * | 2011-07-22 | 2013-01-31 | Meadwestvaco Corporation | Product container having moisture barrier feature |
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2013
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| CN1160775A (en) * | 1996-01-30 | 1997-10-01 | 贝克顿迪金森公司 | Non-ideal barrier coating sequence composition |
| CN1676119A (en) * | 2004-03-29 | 2005-10-05 | 中本包装株式会社 | Infusion solution bag and laminated film therefor |
| EP1941910A1 (en) * | 2005-09-29 | 2008-07-09 | ESPINOZA ABDALA, Leopoldo de Jesús | Pharmaceutical form for the treatment of patients with acute cases and exacerbations of rheumatoid arthritis and related acute disorders |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079953A (en) * | 2019-06-14 | 2020-12-15 | 北京诺维新材科技有限公司 | Medical rubber and preparation method and application thereof |
| CN112079953B (en) * | 2019-06-14 | 2022-07-08 | 北京诺维新材科技有限公司 | Medical rubber and preparation method and application thereof |
| CN113969100A (en) * | 2020-07-21 | 2022-01-25 | 中国石油化工股份有限公司 | Coating composition containing molecular sieve catalyst, coating liquid for non-silicification rubber plug, preparation method of coating liquid and preparation method of non-silicification rubber plug |
| CN113969100B (en) * | 2020-07-21 | 2023-02-24 | 中国石油化工股份有限公司 | Coating composition containing molecular sieve catalyst, coating liquid for non-silicified rubber plug, preparation method of coating liquid and preparation method of non-silicified rubber plug |
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Application publication date: 20131127 |