CN106508900A - Control of polyoxyethylene combined high molecular material on release of chlorine dioxide gas - Google Patents
Control of polyoxyethylene combined high molecular material on release of chlorine dioxide gas Download PDFInfo
- Publication number
- CN106508900A CN106508900A CN201610865721.8A CN201610865721A CN106508900A CN 106508900 A CN106508900 A CN 106508900A CN 201610865721 A CN201610865721 A CN 201610865721A CN 106508900 A CN106508900 A CN 106508900A
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- CN
- China
- Prior art keywords
- chlorine dioxide
- acid
- hypochlorite
- release
- polyethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
Abstract
The invention provides a monobasic combined packaged chlorine dioxide composition; a material polyoxyethylene (PEO) for controlling drug release in pharmacy and polyethylene glycol are used as high-molecular membrane materials and are used for coating tablet cores and small pill cores containing hypochlorite and an excitant, water is slowly blocked from entering, then reaction of chlorite and the excitant to generate chlorine dioxide and the release speed are controlled, the time for generation and release of chlorine dioxide is controlled to be as long as 6 months, and thus a sustained bactericidal effect is achieved.
Description
Technical field
The invention belongs to medicament slow release technology is applied to the release control of chlorine dioxide by field of household chemical.
Background technology
As the infection of the disease such as SARS virus and A type HINI influenza is popular, the living habit and life idea of people are received
Great impact is arrived, increasing people has received and begun to use sterile products.The action time of traditional disinfection agent is short, effect
It is really undesirable, stimulate skin, toxic and side effects are big, easily pollute environment.Increasingly serious health peace cannot be met in traditional disinfection agent
Under full conditions of demand, just started gradually to receive for common people by the green disinfectant products of representative with chlorine dioxide.
Chlorine dioxide (ClO2) used as a kind of antiseptic sterilization agent of efficient, safety, wide spectrum, fungicidal spectrum is shown in Table 1, at present
It is with a wide range of applications in all trades and professions.But chlorine dioxide is very active and unstable, readily volatilized,
General to be difficult to make compressed gas or concentrate solution, this is greatly lowered the commonly using property of chlorine dioxide.In order to overcome this
Limitation is planted, the stable, Chlorine dioxide production of slow release has developed the focus into people's research.
1 chlorine dioxide of table is to pathogenic bacterium and the sterilizing ability of microorganism.
The stable, Chlorine dioxide production of slow release this at present is divided into two class of solution-type and solid preparation.The chlorine dioxide of stability
Solution is a kind of liquid preparation, and wherein aqueous solution account for exhausted vast scale, and the content of chlorine dioxide is low, again necessary when in use
Use could be diluted after adding a certain amount of acidic activator, and this is to using bringing inconvenience;Activator species are different simultaneously,
The difference of consumption will also result in the very big difference of activation effect, cause different degrees of negative effect to dissipation effect.Relative to
ClO 2 solution preparation its solid preparation has simple to operate, ClO2 Content is high, stable in properties, transport and easy to use etc. excellent
Point.
Solid preparation of chlorine dioxide is that one kind can discharge chlorine dioxide under certain condition（ClO2）The solid of gas
Product.This kind of product is prepared by primary raw material of stable ClO 2 solution or sodium chlorite, can be colloid,
Mastic, powder, tablet, agglomerate and other variously-shaped solids.European patent, Japan Kokai JP58-161904;
United States Patent (USP) USP5399288 and the clear 60-161307 of Japan Kokai JP disclose solid preparation of chlorine dioxide product preparation side
Method.
Absorbent-type, response type can be generally divided into by preparation method and formulation principle solid preparation of chlorine dioxide type to ease up
Release three kinds of type.The preparation method of absorbent-type solid chlorine dioxide preparation is simple, prepares stable ClO first2Aqueous solution, then
Adsorbed using solid absorbent.Usually require that adsorbent there will be very big adsorption capacity, can at least absorb 50% water, compare table
Area is big, in 95m2/ g～200m2/ g or so, the pH values of adsorbent preferably between 8.5～9.0, to avoid what is adsorbed
Solution premature decomposition, discharges ClO2Gas.If during using acidic sorbent, it is necessary to first with NaOH, NaCO3And NaHCO3
PH is transferred to into 8.5～9.0 Deng alkaline solution.Used as the modified model of above first generation R type Solid Chlorine Dioxide Disinfection Powder agent, the country has
People proposes to add dry passivation agent (such as calcium chloride, lithium chloride, magnesium chloride etc.) to solve the steady of unitary packaging in above-mentioned formula
Qualitative question, such as Chinese patent 99109028.4.Although these chlorides reduce hypochlorite and solid to a certain extent
The contact of acidulant, but this kind of muriatic hygroscopicity is extremely strong, their moisture absorption point below 50%, and in conventional environment
Humidity often more than 60%.Accordingly, upon packaging air-tightness and watertightness it is poor, on the contrary can from environment a large amount of moisture absorptions and lead
Cause product that acidifying decomposition failure occurs.
The present invention is packed using the unitary of convenient use, will be applied to the material Polyethylene oxide of pharmacy Drug controlled release
（PEO）Coating is combined with other high molecular material compositions, is blocked the entrance of moisture, and then is controlled chlorite and SOLID ORGANIC
Acid reaction generates the speed of chlorine dioxide and release, most it is long can control to produce and discharge chlorine dioxide for up to 6 months.
The content of the invention
The present invention is to prepare the chlorine dioxide combination unitary packaging that a kind of slow release was up to 6 months, with use
Conveniently, the characteristics of release time is long.
In the present invention by the control to moisture realizing the release control to chlorine dioxide, specifically using height
Molecular material Polyethylene oxide and Polyethylene Glycol complexation form polymeric membrane to realize controlling the entrance of moisture.Moisture produce for
Chlorite and solid acid substance reaction production chlorine dioxide are particularly important, no moisture, what reaction did not almost occur, water
Content it is more, the speed of reaction is faster, and the chlorine dioxide of release is more, chlorine dioxide produce time it is shorter.This
It is bright effectively to extend the response time, control the release of chlorine dioxide.
Polyethylene oxide has the unshared electronics of ether oxygen to there is very strong adhesion to hydrogen bond, can be with many low molecule chemical combination
The material complexation such as thing, polyacrylic acid, polymethylacrylic acid and Polyethylene Glycol, forms the material with certain characteristic.In the present invention
The combination film forming of middle utilization Polyethylene oxide and Polyethylene Glycol, Polyethylene Glycol serve not only as the pliability that plasticizer changes coating membrane,
The component of film is also served as simultaneously, affects the entrance of hydrone.
In the present compositions, control moisture generation and depend primarily on Polyethylene oxide molecular weight, consumption and poly- second
The consumption of glycol, polyoxyethylated consumption are bigger, and moisture more is difficult to permeate, so as to generate the amount of chlorine dioxide with regard to little, poly- second two
Alcohol increases, and moisture penetration accelerates, and the intensity of reaction is big, and the amount of chlorine dioxide release is just more.
The compositionss of the present invention, the exciting agent are the conjugation salt of solid organic acid or solid organic acid, are with solid shape
Formula occurs, including one or more in citric acid, tartaric acid, malic acid, gluconic acid, hydroxyacetic acid.
The organic acid that the present invention is used its on the one hand have and hypochlorite reaction, the effect of slowly-releasing chlorine dioxide（Make
For exciting agent）, also can be collectively forming buffer system with its yoke alkali or pH buffer carrys out control composition to described organic acid simultaneously
PH, control chlorine dioxide generation reaction.
Present aspect unitary packaging containing produce chlorine dioxide hypochlorite, can be sodium hypochlorite, postassium hypochlorite or
Both arbitrary proportion mixture, these hypochlorites can be reacted in the state of with the presence of water and discharge two with acid material
Chlorine monoxid, it is generally the case that in the presence of having water, this reaction are carried out completely soon, and chlorine dioxide is unable to slow release.This
Polyethylene oxide and Polyethylene Glycol combination is employed in bright as the main material of polymer film forming, due to isolation and the bag of polymer
Hypochlorite and exciting agent solid acid material is wrapped up in, the presence reaction for not having water does not occur, and in the presence of having water, reaction is just sent out
Raw release chlorine dioxide.
On the one hand the present invention is had using solid organic acid and chlorine dioxide matrix reaction, the effect of slowly-releasing chlorine dioxide
（I.e. as exciting agent）, these solid organic acids can also be while also common with its yoke alkali or PH buffer agents using solid organic acid
Carry out the pH of control composition with formation buffer system, control the reaction of chlorine dioxide.
The present invention can by solid organic acid and hypochlorite according to certain ratio, according to adjuvant and technique known in pharmacy,
The tablet of different size, shape is pressed into, is adopted and is coated with the macromolecular material of Polyethylene oxide and Polyethylene Glycol.Containing
The surface of solid organic acid and hypochlorite covers a floor height molecular material to control the entrance of moisture, so as to reach control dioxy
Change the generation of chlorine.
In order to be combined into convenient use, and energy by hypochlorite and solid organic acid or with solid organic acid and its conjugate base
Control consumption, is compressed into tablet in the present invention, during compressed tablets, can also add the conventional filling in pharmacy
Agent, disintegrating agent, lubricant, stop-off gent, described filler can be starch, Icing Sugar, dextrin, Lactose, amylum pregelatinisatum, micro-
Crystalline cellulose（MCC）, Mannitol：Also inorganic salts such as calcium sulfate（Water of crystallization containing two molecules）, calcium hydrogen phosphate, medicinal charcoal
Sour calcium etc., disintegrating agent, comprising disintegrating agent.
The lubricant for being adopted is for magnesium stearate.One kind in Pulvis Talci, calcium stearate, sodium stearyl fumarate, stearic acid
Or it is various.
In the present invention, by the conjugation salt of hypochlorite and solid organic acid or solid organic acid and these filleies,
Disintegrating agent mixes, lubricant direct compression, or compositionss are mixed, or using dry granulation or the method system of wet granulation
Granulation.
Under such circumstances, the amount of the thickness of Polyethylene oxide component film, Polyethylene oxide and Polyethylene Glycol rising for moisture
Important effect.
Simultaneously in the filmogen that Polyethylene oxide film and Polyethylene Glycol are constituted, it is also possible to add other materials to carry out adjusting film
Transit dose to the water yield, such as different molecular weight, the ethyl cellulose of different amounts, hydroxypropylcellulose etc..By weight so
The weight ratio of the consumption and polyvinyl alcohol of material and Polyethylene Glycol gross weight is 3-10% or so,.
Can also contain irreducibility spice described in the compositionss of the present invention on carrier, these irreducibility spice be not with
The natural perfume material or synthetic spice of chlorine dioxide reaction.
The present invention's additionally provides preparation method of composition.
The preparation of label, according to prescription by hypochlorite, SOLID ORGANIC acidity material or solid organic acid and conjugate acid
Salt is constituted and mixture, is pulverized and mixed, and is added the mixing such as acceptable disintegrating agent, filler in pharmacy, is obtained pressed powder,
Carry out tabletting.
The preparation of piller capsule core is according to prescription is by hypochlorite, solid organic acid or solid organic acid and is conjugated hydrochlorate
Composition and mixture, it is pulverized and mixed, adds the mixing such as acceptable binding agent, filler in pharmacy, using extrusion spheronization
The method of method or centrifugal granulator, makes piller according to suitable technique.
Using Polyethylene oxide and Polyethylene Glycol as macromolecular material coating membrane, the thickness of its clothing film is according to coating process
Increase weight to control, in the present invention, the weightening of label is controlled in 2-10%, and further preferred weight is 3-6%.
The weightening of capsule core is controlled in 5-20%, and preferred weightening is 8-15%.
Take Polyethylene oxide, Polyethylene Glycol and add swelling, plasticizer known in addition pharmacy in solvent, antiplastering aid etc., stir
Mix, be suspended, sieve.It is sprayed onto on the label or piller capsule core by hypochlorite and solid acid material using spray gun, control temperature
Degree, is coated.
The coating solvent adopted in the present invention is ethanol or 70% ethanol water（V/V）.
The compositionss of the present invention need to be attached to closed plastic bottle or vial during storage, open bottle cap, change during use
On have the bottle cap in hole by use.
Polyvinyl alcohol is white solid, and Polyethylene oxide has the unshared electronics pair of ether oxygen, has very strong adhesion to hydrogen bond,
Complexation can be carried out with many low molecular compounds, Polyethylene Glycol, polyacrylic acid, polymethylacrylic acid etc..The present invention is using in
Etc. viscosity and high-viscosity polyvinyl alcohol, its molecular weight ranges is between 110000-200000.
Polyethylene Glycol is the normal adjuvant in pharmacy, according to molecular weight and the difference of consumption, as solvent, plasticizer, ointment
Substrate or lubricant etc., the Polyethylene Glycol for adopting Polyethylene Glycol in the present invention for molecular weight ranges more than more than 2000,
Specially business-like Macrogol 2000 and Macrogol 4000, Polyethylene Glycol and polyoxyethylated part by weight are 4:1-
1.5:1。
Control moisture is produced and depends primarily on the thickness of macromolecule clothing film, Polyethylene oxide molecular weight, the use of Polyethylene Glycol
Amount, polyoxyethylated amount are bigger, and moisture more is difficult to permeate, and so as to the amount for generating chlorine dioxide is just little, Polyethylene Glycol consumption increases,
Moisture penetration it is more, the amount of chlorine dioxide release is just more.
The ratio of the buffer agent of hypochlorite and solid organic acid or solid organic acid and its conjugate base is in the present invention
1:3,-5:1, preferred ratio is 1:2-4:1, further preferred ratio is 1:2-3:1.
Specific embodiment
Embodiment 1
Sodium hypochlorite 20g
Citric acid 10g
Sodium citrate 2g
Magnesium stearate 0.2g
Microcrystalline Cellulose 3g
Lactose 1g
Coating solution
Polyethylene oxide 5g
Macrogol 2000 3g
Pulvis Talci 3g
Dehydrated alcohol 50ml
Preparation method：According to prescription is by sodium hypochlorite, citric acid, sodium citrate composition and mixture, is pulverized and mixed, add micro-
Crystalline cellulose, magnesium stearate mixing, direct compression.
Coating solution：Polyethylene oxide and Macrogol 2000 are added in dehydrated alcohol, are stirred, it is swelling, Pulvis Talci is added,
Stirring, mixes.Label is preheated into 30-45 DEG C, spray gun is opened, spray speed is adjusted, coating, coating weight gain are controlled in 3-4%.
Embodiment 2
Postassium hypochlorite 20g
Tartaric acid 30g
Magnesium stearate 0.3g
Microcrystalline Cellulose 4g
Coating solution
Polyethylene oxide 5g
Macrogol 4000 2g
Titanium dioxide 4g
Dehydrated alcohol 50ml
Preparation method：Sodium hypochlorite, tartaric acid are constituted and mixture, are pulverized and mixed according to prescription, add Microcrystalline Cellulose,
Magnesium stearate mixes, direct compression.
Coating solution：Polyethylene oxide and Macrogol 4000 are added in dehydrated alcohol, are stirred, it is swelling, add titanium dioxide
Titanium, stirring are mixed.Label is preheated into 40-45 DEG C, spray gun is opened, spray speed is adjusted, coating, coating weight gain are controlled in 2-3%.
Embodiment 3
Postassium hypochlorite 40g
Tartaric acid 30g
Citric acid 10g
Microcrystalline Cellulose 4g
Polyvidone k30
Coating solution
Polyethylene oxide 10g
Macrogol 4000 4g
Pulvis Talci 10g
Dehydrated alcohol 100ml
Preparation method：Sodium hypochlorite, citric acid, tartaric acid are pulverized and mixed according to prescription, add Microcrystalline Cellulose, polyvidone
K30, extrusion spheronization prepare the capsule core of piller
Coating solution：Polyethylene oxide and Macrogol 4000 are added in dehydrated alcohol, are stirred, it is swelling, titanium dioxide is added, is stirred
Mix, mix.Label is preheated into 40-45 DEG C, spray gun is opened, spray speed is adjusted, coating, coating weight gain are controlled in 8-10%.
Claims (8)
1. a kind of compositionss that can slowly discharge chlorine dioxide, are characterized in that label and ball containing hypochlorite and exciting agent
Core, the generation for adopting Polyethylene oxide and Polyethylene Glycol to be coated for main coating material to control chlorine dioxide.
2. label and capsule core containing hypochlorite and exciting agent according to claim 1, is characterized in that hypochlorite is secondary
The mixture of sodium chlorate, postassium hypochlorite or both.
3. label and capsule core containing hypochlorite and exciting agent according to claim 2, its feature are solid in exciting agent
Organic acid substance.
4. according to claim 3 solid organic acid acids, including citric acid, tartaric acid, malic acid, gluconic acid, hydroxyacetic acid
In one or more mixing.
5. the ratio of acid according to claim 4, hypochlorite and acid is 1:3-5:1.
6. Polyethylene oxide according to claim 1 and Polyethylene Glycol, it is characterised in that：Both ratio Polyethylene oxide and poly-
The part by weight of ethylene glycol is 4:1-1.5:1.
7. Polyethylene Glycol according to claim 6, it is characterised in that：It is Macrogol 2000 or poly- second for Polyethylene Glycol
The mixing of glycol 4000 or both arbitrary proportion.
8. Polyethylene oxide according to claim 6, it is characterised in that：Its molecular weight ranges is 110000 to 180000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610865721.8A CN106508900A (en) | 2016-09-30 | 2016-09-30 | Control of polyoxyethylene combined high molecular material on release of chlorine dioxide gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610865721.8A CN106508900A (en) | 2016-09-30 | 2016-09-30 | Control of polyoxyethylene combined high molecular material on release of chlorine dioxide gas |
Publications (1)
| Publication Number | Publication Date |
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| CN106508900A true CN106508900A (en) | 2017-03-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN201610865721.8A Pending CN106508900A (en) | 2016-09-30 | 2016-09-30 | Control of polyoxyethylene combined high molecular material on release of chlorine dioxide gas |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102160552A (en) * | 2011-02-22 | 2011-08-24 | 天津市华阳新兴科技有限公司 | Controlled-release coated chlorine dioxide disinfectant |
| CN102791621A (en) * | 2010-02-02 | 2012-11-21 | 巴斯夫欧洲公司 | Encapsulated chlorine dioxide generator |
| CN104288809A (en) * | 2014-09-19 | 2015-01-21 | 明光瑞泰工业有限公司 | Novel air purifying preparation |
| CN104307017A (en) * | 2014-09-19 | 2015-01-28 | 明光瑞泰工业有限公司 | Air purifying agent with good purification effect |
| CN105079843A (en) * | 2015-08-28 | 2015-11-25 | 保护伞环保科技成都有限公司 | Air purifying agent |
| WO2016048413A1 (en) * | 2013-09-30 | 2016-03-31 | Kimberly-Clark Worldwide, Inc. | Thermoplastic article with active agent |
-
2016
- 2016-09-30 CN CN201610865721.8A patent/CN106508900A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791621A (en) * | 2010-02-02 | 2012-11-21 | 巴斯夫欧洲公司 | Encapsulated chlorine dioxide generator |
| CN102160552A (en) * | 2011-02-22 | 2011-08-24 | 天津市华阳新兴科技有限公司 | Controlled-release coated chlorine dioxide disinfectant |
| WO2016048413A1 (en) * | 2013-09-30 | 2016-03-31 | Kimberly-Clark Worldwide, Inc. | Thermoplastic article with active agent |
| CN104288809A (en) * | 2014-09-19 | 2015-01-21 | 明光瑞泰工业有限公司 | Novel air purifying preparation |
| CN104307017A (en) * | 2014-09-19 | 2015-01-28 | 明光瑞泰工业有限公司 | Air purifying agent with good purification effect |
| CN105079843A (en) * | 2015-08-28 | 2015-11-25 | 保护伞环保科技成都有限公司 | Air purifying agent |
Non-Patent Citations (1)
| Title |
|---|
| 张光杰等: "《药用辅料应用技术》", 31 December 1991, 中国医药科技出版社 * |
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Application publication date: 20170322 |