CN106070569A - There is sterilization and the core-shell type cyclopropylene antistaling agent of fresh-keeping double effects and preparation method - Google Patents

There is sterilization and the core-shell type cyclopropylene antistaling agent of fresh-keeping double effects and preparation method Download PDF

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CN106070569A
CN106070569A CN201610415317.0A CN201610415317A CN106070569A CN 106070569 A CN106070569 A CN 106070569A CN 201610415317 A CN201610415317 A CN 201610415317A CN 106070569 A CN106070569 A CN 106070569A
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cyclopropylene
shell type
antistaling agent
mixture
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CN106070569B (en
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冯江涛
孙娜娜
徐浩
延卫
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Xian Jiaotong University
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154Organic compounds; Microorganisms; Enzymes
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/14Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/157Inorganic compounds

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Abstract

The present invention relates to a kind of there is sterilization and the core-shell type cyclopropylene antistaling agent of fresh-keeping double effects and preparation method, core-shell type cyclopropylene antistaling agent percentage, including the stratum nucleare of 45%~50%, 3%~5% can the sealing coat of deliquescence, and the shell of 45%~50%, and sealing coat and shell be coated on stratum nucleare the most successively;Wherein, stratum nucleare is counted by weight, including the 1 methyl cyclopropene stable inclusion compound of 1~70 part, the excipient of 10~50 parts, and the slow releasing agent of 1~20 part;Shell is counted by weight, including the chlorite of 20~50 parts, the villaumite of 5~50 parts, the acidulant of 25~45 parts, and the effervescent of 10~20 parts.The present invention is by mixing core layer material and Shell Materials respectively, carry out stratum nucleare tabletting the most successively, smear the step such as sealing coat and shell tabletting, make the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects, and nucleocapsid efficiently separates, and does not influences each other.

Description

There is sterilization and the core-shell type cyclopropylene antistaling agent of fresh-keeping double effects and preparation method
[technical field]
The invention belongs to agricultural product preserving fruit and vegetable utilizing field, be specifically related to a kind of nucleocapsid with sterilization and fresh-keeping double effects Formula cyclopropylene antistaling agent and preparation method.
[background technology]
Cyclopropene fruit and vegetable fresh-keeping agent, mainly 1-methyl cyclopropene, can effectively ethene suppressing be plucked by fruit and vegetable After dematuration, make the freshness date of picked fruits vegetable be greatly prolonged.There are some researches show at present, through 1-methyl cyclopropene Can keep the bright-coloured of cut-flower after process, extend the flower arrangement life-span, meanwhile, processing Fructus Mali pumilae, Fructus actinidiae chinensis, Fructus Kaki etc. with it can extend More than 1 times of time of its post-harvest fresh-keeping phase.But, 1-methyl cyclopropene is gas at normal temperatures and pressures, the guarantor to fruit and vegetable It is also required to during fresh use in a gaseous form, therefore, needs time fresh-keeping fruit and vegetable to seal fresh-keeping fruit and vegetable, and Preserve and transport.This just make fresh-keeping after fruit and vegetable be in airtight environment, easily make moist and mouldy.Although can reach Certain fresh-keeping effect, but substantial amounts of mouldy make fresh-keeping effect significantly weaken.
Chlorine dioxide is a kind of internationally recognized safe and nontoxic green sterilization antiseptic.Be highly soluble in water and not with water Reaction, hydrolyzes hardly.Domestic and international substantial amounts of experimentation shows, chlorine dioxide is safe and nontoxic disinfectant, nothing " three cause " effect (carcinogenic, teratogenesis, mutagenesis), does not generates " three with Organic substance generation chlorination in disinfecting process simultaneously Cause effect " organic chloride or other poisonous class material.But owing to chlorine dioxide has extremely strong oxidability, need low Use under concentration conditions.Human body will not be produced any impact, including Physiology and biochemistry aspect when concentration is at below 100ppm Impact, to skin also without any sensitization.Therefore, chlorine dioxide be widely used in drinking water, health care, On the sterilizing of food and fruit and vegetable.Typically all being fixed of chlorine dioxide is processed in order to easy to use, by system Piece agent, can release chlorine dioxide for sterilizing (specially as long as putting into during use in water or malaria Profit CN102246819B, CN104138390A).
During with 1-methyl cyclopropene fresh-keeping fruit and vegetable, need it is sealed.And fruit and vegetable adopts rear Repiration Relatively strong, sealing system can be made to become moist through and beneficially growth of microorganism, cause rotting of fruit and vegetable.This just requires fresh-keeping During carry out sterilizing process.It is typically all and first fruit and vegetable is carried out sterilizing, then carry out fresh-keeping research, whole Process is undertaken in two steps, and it is complicated that this allows for operating process, and higher to using process operation to require.Existing patent discloses Preparation anticorrosion and the cyclopropylene antistaling agent (publication number: CN1505992A) of fresh-keeping double effects, it is mainly antistaling agent and prevents Rotten agent processes and packs formation A agent and B agent respectively, it is used simultaneously, reach anticorrosion and fresh-keeping dual mesh when of use 's.But, it is the most active a kind of reducibility gas under 1-methyl cyclopropene normal temperature and pressure, it is easy to oxidized decomposition.And General sterilization antiseptic has oxidizing component, uses with 1-methyl cyclopropene simultaneously and is possible to weaken its fresh-keeping effect.
[summary of the invention]
It is an object of the invention to overcome problems of the prior art, it is provided that one has sterilization and fresh-keeping dual effect The core-shell type cyclopropylene antistaling agent of fruit and preparation method, be integrated in one antibacterial and antistaling agent, be independent of each other.
To achieve these goals, antistaling agent of the present invention adopts the following technical scheme that:
Described core-shell type cyclopropylene antistaling agent percentage, including the stratum nucleare of 45%~50%, 3%~5% Can the sealing coat of deliquescence, and the shell of 45%~50%, and sealing coat and shell be coated on stratum nucleare the most successively;
Wherein, stratum nucleare is counted by weight, including the 1-methyl cyclopropene stable inclusion compound of 1~70 part, 10~50 parts Excipient, and the slow releasing agent of 1~20 part;
Shell is counted by weight, including the chlorite of 20~50 parts, the villaumite of 5~50 parts, the acidifying of 25~45 parts Agent, and the effervescent of 10~20 parts.
Further, excipient includes glucose, maltose, alpha-cyclodextrin, beta-schardinger dextrin-, γ cyclodextrin, starch and carboxylic The mixture of one or more arbitrary proportions in base cellulose.
Further, during slow releasing agent includes calcium hydroxide, sodium carbonate, sodium bicarbonate and ammonium hydrogen carbonate one or both with The mixture of upper arbitrary proportion.
Further, sealing coat uses cyclodextrin derivative material;Cyclodextrin derivative material includes that hydroxy propyl-Beta-ring is stuck with paste Essence, methyl-B-cyclodextrin, amino-beta-cyclodextrin, mercapto group-beta-cyclodextrin, malt sugar group-beta-cyclodextrin, hydroxypropyl-α-ring is stuck with paste One or both in essence, methyl-alphacyclodextrin, amino-alpha-cyclodextrin, sulfydryl-alpha-cyclodextrin and malt-base-alpha-cyclodextrin The mixture of any of the above ratio.
Further, chlorite includes sodium chlorite;Villaumite includes anhydrous calcium chloride or sodium chloride;Acidulant includes Tartaric acid, citric acid or malic acid;Effervescent includes sodium bicarbonate, sodium carbonate or ammonium hydrogen carbonate.
Further, described core-shell type cyclopropylene antistaling agent is lamellar, and every weight is 0.8~1.2g.
The technical scheme of preparation method of the present invention is: comprise the following steps:
(1) take 1-methyl cyclopropene stable inclusion compound, excipient and slow releasing agent mix homogeneously and obtain mixture A, will mixing Stratum nucleare tablet made by thing A tabletting;Wherein, 1-methyl cyclopropene stable inclusion compound accounts for the 1%~60% of mixture A weight, figuration Agent accounts for the 10%~30% of mixture A weight, and slow releasing agent accounts for the 1%~20% of mixture A weight;
(2) cyclodextrin derivative solution is coated in stratum nucleare tablet surface drying and forming-film equably, in stratum nucleare tablet surface Form sealing coat;
(3) take chlorite, villaumite, acidulant and effervescent mix homogeneously and obtain mixture B, mixture B is wrapped in Insulation surface tabletting, make the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects;The most by weight hundred Mark meter, chlorite accounts for the 20%~50% of mixture B weight, and villaumite accounts for the 5%~45% of mixture B weight, acidulant Accounting for the 25%~45% of mixture B weight, effervescent accounts for the 10%~20% of mixture B weight;
Wherein, mixture A accounts for the 45%~50% of core-shell type cyclopropylene antistaling agent weight, and cyclodextrin derivative accounts for core-shell type The 3%~5% of cyclopropylene antistaling agent weight, mixture B accounts for the 45%~50% of core-shell type cyclopropylene antistaling agent weight.
Further, all temperature 5~35 DEG C in step (1) and step (3), enter in the environment of relative humidity 15~50% Row tabletting.
Further, the drying and forming-film of step (2) is to be dried 30~60min at 30~60 DEG C.
Further, cyclodextrin derivative is dissolved in solvent formation by the cyclodextrin derivative solution of step (2);Molten Agent includes the mixture of one or more arbitrary proportions of methanol, ethanol, ether, acetone, ethyl acetate, hexamethylene etc.; The concentration of cyclodextrin derivative solution is 0.3~0.6g/mL.
Compared with prior art, the present invention has a following useful technique effect:
Stratum nucleare that the cyclopropylene antistaling agent of nucleocapsid structure prepared by the present invention includes from inside to outside setting gradually, sealing coat and Shell, and sealing coat can deliquescence, have the advantage that
1, the fresh-keeping of fruit and vegetable and sterilization and anticorrosion are organically combined by the present invention, form stratum nucleare and shell, core simultaneously respectively Separating with sealing coat between shell two parts, sterilization is carried out successively with fresh-keeping, makes nucleocapsid not influence each other.Wherein, Shell Materials is Sterilization material layer, during use, is placed in antistaling agent of the present invention in a small amount of water or in malaria, shell and water or humidity Air contact first discharges rapidly chlorine dioxide bactericide, it is achieved the sterilization and anticorrosion of fruit and vegetable, after end to be sterilized, and sealing coat Easily being dissolved by water or humid air, ineffective, stratum nucleare contact water or humid air start slowly to discharge 1-methyl ring third afterwards Fruit and vegetable is carried out fresh-keeping by alkene antistaling agent gas.The chlorine dioxide (oxidant) that shell produces when fresh-keeping consumes the most substantially Complete, the 1-methyl cyclopropene (reducing agent) that will not produce stratum nucleare produces impact;
2, cyclodextrin material is used stratum nucleare and shell to be efficiently separated in the preparation process of antistaling agent so that it is sealing Will not contact with each other and react during storage and transport, it is ensured that this has the stability of antistaling agent of dual function;
3, the environment-friendly and green Chlorine Dioxide In Disinfectant using World Health Organization (WHO) to generally acknowledge, has broad-spectrum sterilization, and consumption is low, Speed of action is fast, bactericidal effect good, the advantages such as length, non-secondary pollution of holding time;
4, use 1-methyl cyclopropene antistaling agent, there is the advantages such as consumption low, good refreshing effect, green non-pollution.
1-methyl cyclopropene stable inclusion compound and certain excipient, slow releasing agent are first mixed all by preparation method of the present invention Even, then tabletting, form the core layer material with preservation, wrap up one layer of cyclodextrin derivative on stratum nucleare surface.Then exist The outer layer of the antistaling agent sheet after parcel again by the way of tabletting attached last layer can produce the Shell Materials of sterilization, be finally made Having the core-shell type cyclopropylene antistaling agent of sterilization and fresh-keeping double effects, preparation method is simple, by sterilization and anticorrosion and the guarantor of fruit and vegerable Fresh it is integrated in one, makes same material have fresh-keeping and sterilization dual function, and fresh-keeping part and sterilization part well intercept Will not influence each other.
[accompanying drawing explanation]
Fig. 1 is the structural representation of nucleocapsid antistaling agent of the present invention;
Fig. 2 is the sectional view of nucleocapsid antistaling agent of the present invention.
Wherein, 1-shell;2-sealing coat;3-stratum nucleare.
[specific implementation method]
Below in conjunction with the accompanying drawings the present invention is elaborated.
The present invention has the core-shell type cyclopropylene antistaling agent of sterilization and fresh-keeping dual function, and it is divided into stratum nucleare antistaling agent part Sterilize part with shell, and the material that can produce preservation as nucleome material, and must can produce bactericidal effect Material, as case material, needs between nucleome and housing to use certain material to intercept, the most direct to prevent Contact and react, it is ensured that fresh-keeping and sterilization and anticorrosion being organically combined, but does not influences each other.
Seeing Fig. 1 and Fig. 2, core-shell type cyclopropylene antistaling agent of the present invention is lamellar, and include being coated with the most successively Shell 1, sealing coat 2 and stratum nucleare 3, wherein the weight of stratum nucleare 3 and shell 1 accounts for the 45%~about 50% of full wafer weight respectively, And sealing coat 2 accounts for the 3%~5% of full wafer weight.
Core layer material predominantly can produce the material of 1-methyl cyclopropene fruit and vegetable fresh-keeping agent, counts by weight, including 1~ The cyclopropylene inclusion complex of 70 parts, the excipient of 10~50 parts and the slow releasing agent of 1~20 part.Cyclopropylene inclusion complex is 1-methyl ring third Alkene stable inclusion compound (i.e. the stable inclusion compound of patent 200610042683.2 preparation);Excipient is glucose, maltose, α-ring One or more of dextrin, beta-schardinger dextrin-, γ cyclodextrin, starch, carboxycellulose etc. coordinate;Slow releasing agent is calcium hydroxide, carbon One or more in acid sodium, sodium bicarbonate, ammonium hydrogen carbonate coordinate.
Isolated material between nucleocapsid is mainly deliquescent cyclodextrin derivative material, including HP-β-CD, Methyl-B-cyclodextrin, amino-beta-cyclodextrin, mercapto group-beta-cyclodextrin, malt sugar group-beta-cyclodextrin, Hydroxyproply-α-cyclodextrin, Mixing of one or more of methyl-alphacyclodextrin, amino-alpha-cyclodextrin, sulfydryl-alpha-cyclodextrin, malt-base-alpha-cyclodextrin etc. Close.
Shell Materials mainly produces the material of chlorine dioxide bactericide, counts by weight, including the Asia of 20~50 parts Chlorate, the villaumite of 5~50 parts, the acidulant of 25~45 parts, the effervescent etc. of 10~20 parts.Wherein chlorite predominantly Asia Sodium chlorate, villaumite is mainly anhydrous calcium chloride or sodium chloride, and it is organic that acidulant is mainly tartaric acid, citric acid and malic acid etc. Acid, effervescent is mainly sodium bicarbonate, sodium carbonate or ammonium hydrogen carbonate etc..
Preparation method of the present invention comprises the steps:
Stratum nucleare tabletting: first, by 1-methyl cyclopropene stable inclusion compound and certain excipient, slow releasing agent mix homogeneously, Temperature 5~35 DEG C, in the environment of relative humidity 15~50%, punch die is used to be pressed on tablet machine by the mixture of core layer material Make the tablet of weight about 0.5g, form the stratum nucleare tablet with preservation.
The coating of intermediate isolating layer: cyclodextrin derivative is dissolved in volatile solvent the height making 0.3~0.6g/mL Concentration viscous solution, is then coated in the stratum nucleare tablet surface suppressed also equably by the solution of the cyclodextrin derivative dissolved Being dried 30~60min at 30~60 DEG C, form one layer of film the thinnest in stratum nucleare tablet surface, protection core layer material will not be with shell Layer material contact and reaction;The easy volatile solvent used is methanol, ethanol, ether, acetone, ethyl acetate, hexamethylene etc. The mixing of one or more.
Shell tabletting: treat that intermediate isolating layer material coats and after drying, by the Shell Materials that is mixed in proportion (about 0.5g) temperature 5~35 DEG C, in the environment of relative humidity 15~50%, parcel stratum nucleare tablet is pressed into finally on tablet machine The tablet of weight 0.8~1.2g.
The present invention is by by the 1-methyl cyclopropene stable inclusion compound in patent (200610042683.2) and certain tax Shape agent, slow releasing agent mix homogeneously, be then pressed into small pieces, forms the core layer material with preservation, wraps up one on stratum nucleare surface Layer cyclodextrin derivative.Then the outer layer of the antistaling agent sheet after parcel again by the way of tabletting attached last layer can produce and kill The chlorine dioxide material of bacterium.It is finally made the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Below by specific embodiment, the present invention is described in further details.
Embodiment 1
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 10 weight portions and 5 weight portions of 1 dry weight portion are taken Slow releasing agent powder, mix after 30min in three-dimensional motion mixer and pour out, obtain mixture A, at temperature 5 DEG C, relative humidity In the environment of 15%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses glucose;Slow releasing agent Use sodium bicarbonate;
(2) HP-β-CD is dissolved in dehydrated alcohol makes the high concentration viscous solution of 0.5g/mL, with hair HP-β-CD solution is coated in stratum nucleare tablet surface by brush lightly, equably, and dries 60min in 50 DEG C of baking ovens Film forming, forms sealing coat in stratum nucleare tablet surface, obtains the tablet of band sealing coat;
(3) take the dry sodium chlorite of 20 weight portions, the anhydrous calcium chloride of 20 weight portions, the citric acid of 30 weight portions and The sodium bicarbonate of 10 weight portions is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, in temperature 5 DEG C, phase In the environment of humidity 15%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and at tablet machine Middle tabletting, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 1.0g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 47% of amount, cyclodextrin derivative accounts for the 3% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 50% of agent weight.
Embodiment 2
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 20 weight portions and 10 weight portions of 5 dry weight portions are taken Slow releasing agent powder, mix after 30min in three-dimensional motion mixer and pour out, obtain mixture A, temperature 10 DEG C, the wettest In the environment of degree 20%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses starch;Slow releasing agent Use sodium carbonate;
(2) methyl-B-cyclodextrin is dissolved in dehydrated alcohol makes the high concentration viscous solution of 0.4g/mL, with hairbrush Methyl-B-cyclodextrin solution is coated in lightly, equably stratum nucleare tablet surface, and in 40 DEG C of baking ovens, dries 50min film forming, Form sealing coat in stratum nucleare tablet surface, obtain the tablet of band sealing coat;
(3) the dry sodium chlorite of 30 weight portions, the sodium chloride of 15 weight portions, the tartaric acid of 40 weight portions and 11 weights are taken The sodium carbonate of amount part is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, at temperature 10 DEG C, relative humidity In the environment of 20%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and tabletting in tablet machine, Make the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 0.9g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 45% of amount, cyclodextrin derivative accounts for the 5% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 50% of agent weight.
The antistaling agent of nucleocapsid structure of the present invention is in use, it is only necessary to be directly added in a small amount of water, to being placed with water After processing 8-12h in the confined space of fruit vegetable, the container filling antistaling agent is taken out, use simple.Table 1 is this enforcement The antistaling agent that example prepares processes the effectiveness comparison of Fructus actinidiae chinensis with single 1-methyl cyclopropene antistaling agent and chlorine dioxide tablet.Knot Fruit display, what the present invention obtained has core-shell type antistaling agent and existing antistaling agent and the antibacterial of sterilization and fresh-keeping double effects Compare, effectively contained the mouldy of Fructus Kaki, Fructus Kaki fresh-keeping has been better achieved.
Table 1 has the core-shell type cyclopropylene antistaling agent of sterilization and fresh-keeping double effects to Fructus Kaki treatment effect (room temperature 32 My god)
Inorganic agent Fruit color Corrupt mouldy rate (%) The hardness of fruit (Kg/cm)
The present invention Yellow 0 12.7 (firmly)
1-methyl cyclopropene Yellow 13.8% 10.2 (firmly)
Chlorine dioxide Orange red 0 5.6 (the softest)
Comparison Peony 28.7% 2.1 (the softest)
Embodiment 3
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 30 weight portions and 1 weight portion of 10 dry weight portions are taken Slow releasing agent powder, mix after 30min in three-dimensional motion mixer and pour out, obtain mixture A, temperature 15 DEG C, the wettest In the environment of degree 50%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses maltose;Slow release Agent uses calcium hydroxide;
(2) amino-beta-cyclodextrin is made in methanol the high concentration viscous solution of 0.3g/mL, with hairbrush by ammonia Group-beta-cyclodextrin solution is coated in stratum nucleare tablet surface lightly, equably, and dries 40min film forming in 60 DEG C of baking ovens, at core Layer tablet surface forms sealing coat, obtains the tablet of band sealing coat;
(3) the dry sodium chlorite of 40 weight portions, the sodium chloride of 5 weight portions, the malic acid of 25 weight portions and 12 weights are taken The ammonium hydrogen carbonate of amount part is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, temperature 15 DEG C, the wettest In the environment of degree 50%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and presses in tablet machine Sheet, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 1.1g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 50% of amount, cyclodextrin derivative accounts for the 5% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 45% of agent weight.
Embodiment 4
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 40 weight portions and 15 weight of 20 dry weight portions are taken The slow releasing agent powder of part, pours out after mixing 30min, obtain mixture A, temperature 20 DEG C, relatively in three-dimensional motion mixer In the environment of humidity 45%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses alpha-cyclodextrin The mixture mixed with arbitrary proportion with beta-schardinger dextrin-;Slow releasing agent uses ammonium hydrogen carbonate;
(2) mercapto group-beta-cyclodextrin is dissolved in ether makes the high concentration viscous solution of 0.35g/mL, with hairbrush by mercapto Group-beta-cyclodextrin solution is coated in stratum nucleare tablet surface lightly, equably, and dries 55min film forming in 30 DEG C of baking ovens, at core Layer tablet surface forms sealing coat, obtains the tablet of band sealing coat;
(3) the dry sodium chlorite of 50 weight portions, the sodium chloride of 10 weight portions, the citric acid of 35 weight portions and 15 weights are taken The ammonium hydrogen carbonate of amount part is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, temperature 20 DEG C, the wettest In the environment of degree 45%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and presses in tablet machine Sheet, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 0.8g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 48% of amount, cyclodextrin derivative accounts for the 4% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 48% of agent weight.
Embodiment 5
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 50 weight portions and 20 weight of 30 dry weight portions are taken The slow releasing agent powder of part, pours out after mixing 30min, obtain mixture A, temperature 25 DEG C, relatively in three-dimensional motion mixer In the environment of humidity 35%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses carboxylated fiber Element;Slow releasing agent uses the mixture that calcium hydroxide and sodium carbonate mix with arbitrary proportion;
(2) cyclodextrin derivative is dissolved in ethyl acetate makes the high concentration viscous solution of 0.45g/mL, with hairbrush Cyclodextrin derivative solution is coated in lightly, equably stratum nucleare tablet surface, and in 35 DEG C of baking ovens, dries 45min film forming, Form sealing coat in stratum nucleare tablet surface, obtain the tablet of band sealing coat;Cyclodextrin derivative uses malt sugar group-beta-cyclodextrin The mixture mixed with arbitrary proportion with Hydroxyproply-α-cyclodextrin;
(3) the dry sodium chlorite of 25 weight portions, the sodium chloride of 30 weight portions, the tartaric acid of 45 weight portions and 20 weights are taken The sodium bicarbonate of amount part is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, temperature 25 DEG C, the wettest In the environment of degree 35%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and presses in tablet machine Sheet, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 1.2g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 46% of amount, cyclodextrin derivative accounts for the 4% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 50% of agent weight.
Embodiment 6
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 45 weight portions and 18 weight of 40 dry weight portions are taken The slow releasing agent powder of part, pours out after mixing 30min, obtain mixture A, temperature 30 DEG C, relatively in three-dimensional motion mixer In the environment of humidity 40%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient use glucose and The mixture that maltose mixes with arbitrary proportion;Slow releasing agent uses the mixing that sodium bicarbonate and ammonium hydrogen carbonate mix with arbitrary proportion Thing;
(2) cyclodextrin derivative dissolving is made in a solvent the high concentration viscous solution of 0.55g/mL, with hairbrush by ring Dextrin derivative solution is coated in stratum nucleare tablet surface lightly, equably, and dries 35min film forming in 45 DEG C of baking ovens, at core Layer tablet surface forms sealing coat, obtains the tablet of band sealing coat;Cyclodextrin derivative uses amino-alpha-cyclodextrin;Ethanol and The mixture that ethyl acetate mixes with arbitrary proportion;
(3) take the dry sodium chlorite of 35 weight portions, the anhydrous calcium chloride of 40 weight portions, the malic acid of 32 weight portions and The sodium carbonate of 18 weight portions is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, temperature 30 DEG C, relatively In the environment of humidity 40%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and in tablet machine Tabletting, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 0.8g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 49% of amount, cyclodextrin derivative accounts for the 3% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 48% of agent weight.
Embodiment 7
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 35 weight portions and 14 weight of 50 dry weight portions are taken The slow releasing agent powder of part, pours out after mixing 30min, obtain mixture A, temperature 35 DEG C, relatively in three-dimensional motion mixer In the environment of humidity 30%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses starch and carboxylic The mixture that base cellulose mixes with arbitrary proportion;Slow releasing agent uses sodium carbonate, sodium bicarbonate and ammonium hydrogen carbonate with arbitrary proportion The mixture of mixing;
(2) cyclodextrin derivative dissolving is made in a solvent the high concentration viscous solution of 0.6g/mL, with hairbrush, ring is stuck with paste Essence derivative solution is coated in stratum nucleare tablet surface lightly, equably, and dries 30min film forming in 55 DEG C of baking ovens, at stratum nucleare Tablet surface forms sealing coat, obtains the tablet of band sealing coat;Cyclodextrin derivative uses amino-alpha-cyclodextrin;Solvent uses The mixture that ethanol and ethyl acetate mix with arbitrary proportion;
(3) take the dry sodium chlorite of 45 weight portions, the anhydrous calcium chloride of 50 weight portions, the citric acid of 38 weight portions and The ammonium hydrogen carbonate of 16 weight portions is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, in temperature 35 DEG C, phase In the environment of humidity 30%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and at tablet machine Middle tabletting, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 0.9g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 48% of amount, cyclodextrin derivative accounts for the 3% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 49% of agent weight.
Embodiment 8
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 25 weight portions and 8 weight portions of 60 dry weight portions are taken Slow releasing agent powder, mix after 30min in three-dimensional motion mixer and pour out, obtain mixture A, temperature 20 DEG C, the wettest In the environment of degree 25%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses glucose, Fructus Hordei Germinatus The mixture that sugar and carboxylated fiber mix with arbitrary proportion;Slow releasing agent uses calcium hydroxide, sodium carbonate, sodium bicarbonate and bicarbonate The mixture that ammonium mixes with arbitrary proportion;
(2) cyclodextrin derivative dissolving is made in a solvent the high concentration viscous solution of 0.4g/mL, with hairbrush, ring is stuck with paste Essence derivative solution is coated in stratum nucleare tablet surface lightly, equably, and dries 40min film forming in 40 DEG C of baking ovens, at stratum nucleare Tablet surface forms sealing coat, obtains the tablet of band sealing coat;Cyclodextrin derivative uses methyl-B-cyclodextrin, amino-beta-ring The mixture that dextrin, Hydroxyproply-α-cyclodextrin and methyl-alphacyclodextrin mix with arbitrary proportion;Solvent use ethyl acetate and The mixture that hexamethylene mixes with arbitrary proportion;
(3) take the dry sodium chlorite of 35 weight portions, the anhydrous calcium chloride of 25 weight portions, the tartaric acid of 44 weight portions and The sodium bicarbonate of 15 weight portions is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, in temperature 20 DEG C, phase In the environment of humidity 25%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and at tablet machine Middle tabletting, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 1.0g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 50% of amount, cyclodextrin derivative accounts for the 4% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 46% of agent weight.
Embodiment 9
(1) 1-methyl cyclopropene stable inclusion compound, the excipient of 15 weight portions and 3 weight portions of 70 dry weight portions are taken Slow releasing agent powder, mix after 30min in three-dimensional motion mixer and pour out, obtain mixture A, temperature 25 DEG C, the wettest In the environment of degree 30%, mixture A tabletting in tablet machine is made stratum nucleare tablet;Wherein, excipient uses glucose, Fructus Hordei Germinatus The mixture that sugar, alpha-cyclodextrin, beta-schardinger dextrin-and γ cyclodextrin mix with arbitrary proportion;Slow releasing agent uses sodium bicarbonate;
(2) malt-base-alpha-cyclodextrin dissolving is made in a solvent the high concentration viscous solution of 0.3g/mL, with hairbrush Malt-base-alpha-cyclodextrin solution is coated in lightly, equably stratum nucleare tablet surface, and in 50 DEG C of baking ovens, dries 50min Film forming, forms sealing coat in stratum nucleare tablet surface, obtains the tablet of band sealing coat;Solvent uses methanol, ethanol and ether to appoint The mixture of meaning ratio mixing;
(3) take the dry sodium chlorite of 30 weight portions, the anhydrous calcium chloride of 35 weight portions, the malic acid of 26 weight portions and The sodium carbonate of 19 weight portions is poured out after mixing 30min in three-dimensional motion mixer, obtains mixture B, at warm 30 DEG C, the wettest In the environment of degree 25%, the tablet of band sealing coat step (2) prepared is positioned in mixture B, and presses in tablet machine Sheet, makes the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects.
Obtained core-shell type cyclopropylene antistaling agent weight is 1.2g/ sheet, and mixture A accounts for core-shell type cyclopropylene antistaling agent weight The 48% of amount, cyclodextrin derivative accounts for the 5% of core-shell type cyclopropylene antistaling agent weight, and it is fresh-keeping that mixture B accounts for core-shell type cyclopropylene The 47% of agent weight.
The method of antistaling agent of the present invention comprises the following steps: (1) drying materials;(2) core layer material and Shell Materials are respectively Mixing, (3) core layer material tabletting;(4) nucleocapsid isolated material is smeared;(5) Shell Materials tabletting.Prepared by the present invention has sterilization It is placed in water or malaria can quickly release (within 1~2min) with the core-shell type cyclopropylene antistaling agent of fresh-keeping dual function Release chlorine dioxide, play bactericidal action.1-methylcyclopropene gas fruit and vegetable fresh-keeping agent can be discharged again after 2-3h, rise Preservation to fruit and vegerable.Its advantage is to make the sterilization of fruit and vegerable and a fresh-keeping step carry out, easy to use, and will not to human body and Environment works the mischief.

Claims (10)

1. there is the core-shell type cyclopropylene antistaling agent of sterilization and fresh-keeping double effects, it is characterised in that: described core-shell type ring third Alkene antistaling agent percentage, including the stratum nucleare of 45%~50%, 3%~5% can the sealing coat of deliquescence, and 45% ~the shell of 50%, and sealing coat and shell be coated on stratum nucleare the most successively;
Wherein, stratum nucleare is counted by weight, including the 1-methyl cyclopropene stable inclusion compound of 1~70 part, the figuration of 10~50 parts Agent, and the slow releasing agent of 1~20 part;
Shell is counted by weight, including the chlorite of 20~50 parts, and the villaumite of 5~50 parts, the acidulant of 25~45 parts, with And the effervescent of 10~20 parts.
The core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 1, its feature exists In: excipient includes in glucose, maltose, alpha-cyclodextrin, beta-schardinger dextrin-, γ cyclodextrin, starch and carboxycellulose Plant or the mixture of two or more arbitrary proportion.
The core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 1, its feature exists In: slow releasing agent includes the mixed of one or more arbitrary proportions in calcium hydroxide, sodium carbonate, sodium bicarbonate and ammonium hydrogen carbonate Compound.
The core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 1, its feature exists In: sealing coat uses cyclodextrin derivative material;Cyclodextrin derivative material includes that HP-β-CD, methyl-β-ring is stuck with paste Essence, amino-beta-cyclodextrin, mercapto group-beta-cyclodextrin, malt sugar group-beta-cyclodextrin, Hydroxyproply-α-cyclodextrin, methyl-α-ring are stuck with paste One or more arbitrary proportions in essence, amino-alpha-cyclodextrin, sulfydryl-alpha-cyclodextrin and malt-base-alpha-cyclodextrin Mixture.
The core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 1, its feature exists In: chlorite includes sodium chlorite;Villaumite includes anhydrous calcium chloride or sodium chloride;Acidulant includes tartaric acid, citric acid Or malic acid;Effervescent includes sodium bicarbonate, sodium carbonate or ammonium hydrogen carbonate.
The core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 1, its feature exists In: described core-shell type cyclopropylene antistaling agent is lamellar, and every weight is 0.8~1.2g.
7. there is the preparation method of core-shell type cyclopropylene antistaling agent of sterilization and fresh-keeping double effects, it is characterised in that: include with Lower step:
(1) take 1-methyl cyclopropene stable inclusion compound, excipient and slow releasing agent mix homogeneously and obtain mixture A, mixture A is pressed Sheet makes stratum nucleare tablet;Wherein, 1-methyl cyclopropene stable inclusion compound accounts for the 1%~60% of mixture A weight, and excipient accounts for mixed The 10%~30% of compound A weight, slow releasing agent accounts for the 1%~20% of mixture A weight;
(2) cyclodextrin derivative solution is coated in stratum nucleare tablet surface drying and forming-film equably, is formed in stratum nucleare tablet surface Sealing coat;
(3) take chlorite, villaumite, acidulant and effervescent mix homogeneously and obtain mixture B, mixture B is wrapped in isolation Layer surface tabletting, make the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects;Wherein weight percent Meter, chlorite accounts for the 20%~50% of mixture B weight, and villaumite accounts for the 5%~45% of mixture B weight, and acidulant accounts for mixed The 25%~45% of compound B weight, effervescent accounts for the 10%~20% of mixture B weight;
Wherein, mixture A accounts for the 45%~50% of core-shell type cyclopropylene antistaling agent weight, and cyclodextrin derivative accounts for core-shell type ring third The 3%~5% of alkene antistaling agent weight, mixture B accounts for the 45%~50% of core-shell type cyclopropylene antistaling agent weight.
The preparation side of the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 7 Method, it is characterised in that: all temperature 5~35 DEG C in step (1) and step (3), carry out in the environment of relative humidity 15~50% Tabletting.
The preparation side of the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 7 Method, it is characterised in that: the drying and forming-film of step (2) is to be dried 30~60min at 30~60 DEG C.
The preparation side of the core-shell type cyclopropylene antistaling agent with sterilization and fresh-keeping double effects the most according to claim 7 Method, it is characterised in that: cyclodextrin derivative is dissolved in solvent formation by the cyclodextrin derivative solution of step (2);Solvent The mixture of one or more arbitrary proportions including methanol, ethanol, ether, acetone, ethyl acetate, hexamethylene etc.;Ring The concentration of dextrin derivative solution is 0.3~0.6g/mL.
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CN113367153A (en) * 2021-06-04 2021-09-10 湖南天为环保科技有限公司 Deodorant based on chlorine dioxide
CN113428950A (en) * 2021-07-06 2021-09-24 梅逸舟 Water purification sterilization precipitation tablet and preparation method thereof

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CN113367153A (en) * 2021-06-04 2021-09-10 湖南天为环保科技有限公司 Deodorant based on chlorine dioxide
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