CN110803395A - Chlorine dioxide slow-release fresh-keeping packaging material and application thereof - Google Patents
Chlorine dioxide slow-release fresh-keeping packaging material and application thereof Download PDFInfo
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- CN110803395A CN110803395A CN201911088609.8A CN201911088609A CN110803395A CN 110803395 A CN110803395 A CN 110803395A CN 201911088609 A CN201911088609 A CN 201911088609A CN 110803395 A CN110803395 A CN 110803395A
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- film
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- chlorine dioxide
- keeping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
Abstract
The invention relates to a chlorine dioxide slow-release fresh-keeping packaging material which comprises a fresh-keeping A film and a fresh-keeping B film, wherein the fresh-keeping A film comprises an inner film layer, an activator layer and a first protective film layer, the activator layer comprises an activator and a viscous agent, the fresh-keeping B film comprises an outer film layer, a reactant layer and a second protective film layer, and the reactant layer comprises a reactant, a moisture-guiding agent and an adhesive; during application, the first protective film of the preservative A film and the second protective film of the preservative B film are respectively torn off, and the reactant layer of the preservative B film is attached to the activator layer of the preservative A film. The invention has the advantages of realizing slow release and fresh keeping and convenient use; the storage life and the service validity time of the product are prolonged; the production of by-products is reduced, and the use safety is improved.
Description
Technical Field
The invention relates to a fresh-keeping packaging material, in particular to a chlorine dioxide slow-release fresh-keeping packaging material and application thereof.
Background
The chlorine dioxide kills pathogenic bacteria by carrying out irreversible oxidative destruction on transport protein of living cells, is widely used for the fresh-keeping of fruits, vegetables and meat foods at home and abroad, and is an internationally recognized preservative and fresh-keeping agent which can be used for foods (meat, aquatic products, fruits and vegetables).
However, most of the applications of chlorine dioxide, whether in solid form or liquid form, can only be prepared at present, and can be used after long activation time and concentration preparation are needed, and the effective time is short, so that the application is difficult to maintain for more than 3 days. In addition to the inconvenience in use, chlorine dioxide is generated through reaction and harmful substances such as chlorate, chlorite and the like are generated, so that the chlorine dioxide is harmful to human bodies due to improper use and the application of the chlorine dioxide is limited.
The existing method for purifying chlorine dioxide is to introduce the high-concentration buffer salt chlorine dioxide liquid into a special absorption liquid in a gas mode to form an aqueous solution without chlorate and chlorite, but the solution has extremely poor stability, the concentration is rapidly reduced within 1 day, and the high-concentration chlorine dioxide can generate disproportionation reaction to generate chlorate and chlorite, so that the use effect of the chlorine dioxide is limited.
Disclosure of Invention
In order to solve the problems, the invention provides a chlorine dioxide slow-release fresh-keeping packaging material, which achieves the slow-release fresh-keeping effect by controlling the release speed of chlorine dioxide, has high oxygen transmission rate and high water vapor transmission rate, and can be directly used or prepared into a fresh-keeping bag.
The invention designs a chlorine dioxide slow-release fresh-keeping packaging material which comprises a fresh-keeping A film and a fresh-keeping B film, wherein the fresh-keeping A film comprises an inner film layer, an activator layer and a first protective film layer, the activator layer comprises an activator and a viscous agent, the fresh-keeping B film comprises an outer film layer, a reactant layer and a second protective film layer, and the reactant layer comprises a reactant, a moisture-guiding agent and an adhesive;
during application, the first protective film of the preservative A film and the second protective film of the preservative B film are respectively torn off, and the reactant layer of the preservative B film is attached to the activator layer of the preservative A film.
The chlorine dioxide is generated by mixing and reacting an activator and a reactant, and the active agent layer of the preservative A film and the reactant layer of the preservative B film are separately arranged, so that the effective period of a product is effectively prolonged; when the preservative film is used, after the first protective film of the preservative film A and the second protective film of the preservative film B are torn off, the reactant layer of the preservative film B is attached to the activator layer of the preservative film A, so that the reactant layer and the activator layer are in contact reaction to generate chlorine dioxide, the generated chlorine dioxide penetrates through the inner film to be in contact with foods such as preserved vegetables and fruits, and pathogenic bacteria on the surface of the chlorine dioxide are killed, so that the effect of preservation is achieved; the activation agent layer and the reaction agent layer are contacted with each other due to the wrapping effect of the adhesive and the bonding agent, so that the wrapped activation agent, the reaction agent and the moisture-inducing agent are slowly contacted and reacted, thereby achieving the slow release effect and prolonging the service life of the composite material.
Further, the activating agent accounts for 10-30% of the mass of the adhesive, the activating agent further comprises 75-85% of an acidic activating agent, 5-10% of a catalyst and 5-15% of a water absorbing agent according to the weight ratio, and the adhesive is acrylic resin. The adhesive is characterized in that acrylic resin is not easy to react with an acidic activator, a catalyst and a water absorbent in the activator, the acrylic resin, the acidic activator, the catalyst and the water absorbent are uniformly mixed according to a formula ratio during preparation of the activator layer, and then the mixed material is uniformly placed on an inner film on dry-process conforming equipment to obtain the activator layer, so that the preparation is simple.
Further, the acidic activator is one or more of sorbic acid, benzoic acid, citric acid, oxalic acid or sodium hypochlorite. The organic acid has good stability, is beneficial to prolonging the shelf life of the product, and is environment-friendly and harmless to human bodies.
Further, the catalyst is sodium tetrachloropalladate, and the water absorbent is sodium polyacrylate. The sodium tetrachloropalladate is used as a catalyst, so that the reaction is triggered to start when the activator layer is contacted with the reactant layer, the effect of quick reaction and fresh keeping is achieved, and the generated chlorine dioxide has high purity; the water absorbent sodium polyacrylate contains a strong hydrophilic group and has a certain degree of crosslinking, and the molecular structure of the water absorbent sodium polyacrylate contains carboxyl anions and carboxyl functional groups which can absorb chlorate and chlorite, so that the chlorate and the chlorite are effectively prevented from permeating food to influence the health of a human body.
Further, the reactant layer comprises 20-35 wt% of a reactant, 10-30 wt% of a moisture-inducing agent and 35-70 wt% of an adhesive. The moisture-inducing agent absorbs moisture in the ambient atmosphere to promote the reaction of generating chlorine dioxide by promoting the melting of the reactant. The preparation method comprises mixing the above materials at a certain proportion, and placing the mixture on inner membrane uniformly on dry process equipment to obtain reactant layer.
Further, the main reactant is any one of sodium chlorate or sodium chlorite, the moisture-inducing agent is one or more of magnesium sulfate, calcium chloride or calcium carbonate, and the adhesive is acrylic resin. The magnesium sulfate, the calcium oxide and the calcium carbonate have good moisture-guiding effect and are harmless to human bodies; the acrylic resin is not easy to react with other added substances, and the proportion of the added substances is ensured to meet the requirement of promoting the reaction.
Further, the inner film layer is obtained by tape casting of ethylene-vinyl acetate copolymer modified linear low-density polyethylene resin, the outer film layer is linear low-density polyethylene resin, and the first protective film layer and the second protective film layer are any one of polyethylene films, polypropylene films or polyvinyl chloride films. The inner film layer and the outer film layer both have certain water vapor transmission rate, and the water vapor is favorably permeated into the activating agent layer and the reactant layer to trigger the reaction to generate the chlorine dioxide.
Further, the inner membrane layer is a thin film with the thickness of 16-18 microns, the oxygen transmission rate of the inner membrane layer is 5 x 104-1 x 105ml/m2.day. atm, and the water vapor transmission rate is 20-200 g/m 2.day.
Further, the thickness of the outer film layer is 16-18 microns, the oxygen transmission rate of the outer film layer is 1 x 104-5 x 104ml/m2.day. atm, and the water vapor transmission rate is 10-100 g/m 2.day.
Further, the chlorine dioxide slow-release fresh-keeping packaging material is directly used as a fresh-keeping bag or a fresh-keeping film.
Compared with the prior art, the invention has the beneficial technical effects that:
firstly, realizing slow release preservation; according to the invention, the macromolecular structure of the acrylic resin is used for respectively coating the activating agent and the reactant, so that the prepared activating agent layer and the prepared reactant layer are contacted with each other and then have effective reaction speed, and chlorine dioxide is slowly released to achieve the effect of fresh keeping;
secondly, the use is convenient; when the preservative material is used, the activator layer and the reactant layer are bonded to obtain the preservative material capable of slowly releasing chlorine dioxide only by tearing off the first protective film layer and the second protective film layer, and the preservative material can be directly used;
thirdly, the storage life of the product is prolonged; according to the chemical reaction characteristics of the prepared chlorine dioxide, the preservative film is divided into a preservative film A containing an activating agent and a preservative film B containing a reactant, so that the direct contact reaction of the activating agent and the reactant is effectively avoided, and the storage life of the product is prolonged;
fourthly, prolonging the use validity time; according to the invention, the contact rate between the activator and the reactant is slowed down through the wrapping effect of the macromolecular structure of the acrylic resin, the release duration of chlorine dioxide is prolonged while the slow release is realized, and the use validity time is prolonged;
fifthly, the generation of byproducts is reduced, and the use safety is improved; the low-crosslinking sodium polyacrylate is added to adsorb toxic byproducts such as chlorate, chlorite and the like generated by reaction, so that the generation of the byproducts is reduced, and the use safety is improved.
Detailed Description
Example 1
A chlorine dioxide slow-release freshness-retaining packaging material comprises a freshness-retaining film A and a freshness-retaining film B, wherein the freshness-retaining film A comprises an inner film layer, an activator layer and a first protective film layer, the activator layer comprises an activator and a viscous agent, the freshness-retaining film B comprises an outer film layer, a reactant layer and a second protective film layer, and the reactant layer comprises a reactant, a moisture-guiding agent and an adhesive;
the activator accounts for 20% of the mass of the adhesive, the activator further comprises 75% of an acidic activator, 10% of a catalyst and 15% of a water absorbent according to the weight ratio, the adhesive is acrylic resin, and the acidic activator is sorbic acid; the catalyst is sodium tetrachloropalladate, and the water absorbent is sodium polyacrylate;
the reactant layer comprises 35% of reactant, 10% of moisture-inducing agent and 55% of adhesive according to weight ratio; the main reactant is sodium chlorate, the moisture-inducing agent is magnesium sulfate, and the adhesive is acrylic resin.
The inner film layer is a film which is obtained by casting ethylene-vinyl acetate copolymer modified linear low-density polyethylene resin, the thickness of the inner film layer is 16 microns, the oxygen transmission rate of the inner film layer is 5 multiplied by 104ml/m2.day.atm, and the water vapor transmission rate is 20g/m2. day; the outer film layer is made of linear low-density polyethylene resin, the thickness of the outer film layer is 16 microns, the oxygen transmission rate of the outer film layer is 2 x 104ml/m2.day. atm, and the water vapor transmission rate is 100g/m2. day; the first protective film layer and the second protective film layer are polyethylene films.
During application, the first protective film of the preservative A film and the second protective film of the preservative B film are respectively torn off, and the reactant layer of the preservative B film is attached to the activator layer of the preservative A film.
Example 2
A chlorine dioxide slow-release freshness-retaining packaging material comprises a freshness-retaining film A and a freshness-retaining film B, wherein the freshness-retaining film A comprises an inner film layer, an activator layer and a first protective film layer, the activator layer comprises an activator and a viscous agent, the freshness-retaining film B comprises an outer film layer, a reactant layer and a second protective film layer, and the reactant layer comprises a reactant, a moisture-guiding agent and an adhesive;
the activating agent accounts for 25% of the mass of the adhesive, the activating agent further comprises 85% of an acidic activating agent, 5% of a catalyst and 10% of a water absorbent according to the weight ratio, the adhesive is acrylic resin, and the acidic activating agent is benzoic acid; the catalyst is sodium tetrachloropalladate, and the water absorbent is sodium polyacrylate;
the reactant layer comprises 20% of reactant, 20% of moisture-inducing agent and 60% of adhesive by weight; the main reactant is sodium chlorite, the moisture-inducing agent is calcium chloride, and the adhesive is acrylic resin.
The inner film layer is a film which is obtained by casting ethylene-vinyl acetate copolymer modified linear low-density polyethylene resin, the thickness of the inner film layer is 17 micrometers, the oxygen transmission rate of the inner film layer is 1 multiplied by 105ml/m2.day.atm, and the water vapor transmission rate is 100g/m2. day; the outer film layer is made of linear low-density polyethylene resin, the thickness of the outer film layer is 17 micrometers, the oxygen transmission rate of the outer film layer is 4 x 104ml/m2.day. atm, and the water vapor transmission rate is 50g/m2. day; the first protective film layer and the second protective film layer are polyethylene films.
During application, the first protective film of the preservative A film and the second protective film of the preservative B film are respectively torn off, and the reactant layer of the preservative B film is attached to the activator layer of the preservative A film.
Example 3
A chlorine dioxide slow-release freshness-retaining packaging material comprises a freshness-retaining film A and a freshness-retaining film B, wherein the freshness-retaining film A comprises an inner film layer, an activator layer and a first protective film layer, the activator layer comprises an activator and a viscous agent, the freshness-retaining film B comprises an outer film layer, a reactant layer and a second protective film layer, and the reactant layer comprises a reactant, a moisture-guiding agent and an adhesive;
the activator accounts for 10% of the mass of the adhesive, the activator further comprises 80% of an acidic activator, 8% of a catalyst and 12% of a water absorbent according to the weight ratio, the adhesive is acrylic resin, and the acidic activator is citric acid; the catalyst is sodium tetrachloropalladate, and the water absorbent is sodium polyacrylate;
the reactant layer comprises 20% of reactant, 30% of moisture-inducing agent and 50% of adhesive in percentage by weight; the main reactant is sodium chlorite, the moisture-inducing agent is calcium chloride, and the adhesive is acrylic resin.
The inner film layer is a film which is obtained by casting ethylene-vinyl acetate copolymer modified linear low-density polyethylene resin, the thickness of the inner film layer is 18 microns, the oxygen transmission rate of the inner film layer is 1 multiplied by 105ml/m2.day.atm, and the water vapor transmission rate is 180 g/m2. day; the outer film layer is made of linear low-density polyethylene resin, the thickness of the outer film layer is 18 microns, the oxygen transmission rate of the outer film layer is 5 x 104ml/m2.day. atm, and the water vapor transmission rate is 75g/m2. day; the first protective film layer and the second protective film layer are polyethylene films.
During application, the first protective film of the preservative A film and the second protective film of the preservative B film are respectively torn off, and the reactant layer of the preservative B film is attached to the activator layer of the preservative A film.
Example 4
A chlorine dioxide slow-release freshness-retaining packaging material comprises a freshness-retaining film A and a freshness-retaining film B, wherein the freshness-retaining film A comprises an inner film layer, an activator layer and a first protective film layer, the activator layer comprises an activator and a viscous agent, the freshness-retaining film B comprises an outer film layer, a reactant layer and a second protective film layer, and the reactant layer comprises a reactant, a moisture-guiding agent and an adhesive;
the activator accounts for 28% of the mass of the adhesive, the activator further comprises 85% of an acidic activator, 6% of a catalyst and 8% of a water absorbent according to the weight ratio, the adhesive is acrylic resin, and the acidic activator is citric acid; the catalyst is sodium tetrachloropalladate, and the water absorbent is sodium polyacrylate;
the reactant layer comprises 24% of reactant, 18% of moisture-inducing agent and 58% of adhesive by weight; the main reactant is sodium chlorate, the moisture-inducing agent is calcium carbonate, and the adhesive is acrylic resin.
The inner film layer is a film which is obtained by casting ethylene-vinyl acetate copolymer modified linear low-density polyethylene resin, the thickness of the inner film layer is 16 microns, the oxygen transmission rate of the inner film layer is 6 multiplied by 104ml/m2.day.atm, and the water vapor transmission rate is 200 g/m2. day; the outer film layer is made of linear low-density polyethylene resin, the thickness of the outer film layer is 16 microns, the oxygen transmission rate of the outer film layer is 2 x 104ml/m2.day. atm, and the water vapor transmission rate is 35g/m2. day; the first protective film layer and the second protective film layer are polyethylene films.
During application, the first protective film of the preservative A film and the second protective film of the preservative B film are respectively torn off, and the reactant layer of the preservative B film is attached to the activator layer of the preservative A film.
And (3) respectively testing and comparing the fresh-keeping effects of the newly picked rapes in the embodiments 1 to 4 and the commercially available preservative film, taking 6 rapes which are just picked and have no mechanical damage, removing yellow leaves, putting the rapes into the preservative bags 1 to 4 and the control bag, taking out a bag of sample every 1 day, and testing the vitamins and the soluble solid content of the rapes.
The determination of the content of soluble solids (TSS) of the rape is carried out by adopting a PR-101 α type handheld refractometer for determination, repeating the determination three times and taking an average value.
Determination of vitamin C content (Vc): carrying out redox titration on the acid leachate containing the vitamin C by using a blue basic dye standard solution, reducing the dye to be colorless, displaying the excessive dye to be light red in an acid medium when the titration end point is reached, calculating the content of the reduced ascorbic acid in the sample according to the dye dosage, and obtaining the detection result shown in the following table.
The detection result shows that the fresh-keeping agent has good fresh-keeping effect and good fresh-keeping performance.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the scope of the present invention is defined by the claims.
Claims (10)
1. The chlorine dioxide slow-release fresh-keeping packaging material is characterized by comprising a fresh-keeping A film and a fresh-keeping B film, wherein the fresh-keeping A film comprises an inner film layer, an activator layer and a first protective film layer, the activator layer comprises an activator and a viscous agent, the fresh-keeping B film comprises an outer film layer, a reactant layer and a second protective film layer, and the reactant layer comprises a reactant, a moisture-guiding agent and an adhesive;
during application, the first protective film of the preservative A film and the second protective film of the preservative B film are respectively torn off, and the reactant layer of the preservative B film is attached to the activator layer of the preservative A film.
2. The chlorine dioxide slow-release fresh-keeping packaging material as claimed in claim 1, wherein the activating agent accounts for 10% -30% of the mass of the adhesive, the activating agent further comprises 75% -85% of an acidic activating agent, 5% -10% of a catalyst and 5% -15% of a water absorbent according to the weight ratio, and the adhesive is acrylic resin.
3. The chlorine dioxide slow-release fresh-keeping packaging material as claimed in claim 2, wherein the acidic activator is one or more of sorbic acid, benzoic acid, citric acid, oxalic acid or sodium hypochlorite.
4. The chlorine dioxide slow-release fresh-keeping packaging material as claimed in claim 3, wherein the catalyst is sodium tetrachloropalladate, and the water absorbent is sodium polyacrylate.
5. The chlorine dioxide slow-release fresh-keeping packaging material as claimed in claim 1, wherein the reactant layer comprises 20-35% of a reactant, 10-30% of a moisture-inducing agent and 35-70% of an adhesive by weight ratio.
6. The chlorine dioxide slow-release fresh-keeping packaging material as claimed in claim 5, wherein the main reactant is any one of sodium chlorate or sodium chlorite, the moisture-inducing agent is one or more of magnesium sulfate, calcium chloride or calcium carbonate, and the adhesive is acrylic resin.
7. The chlorine dioxide slow-release freshness-retaining packaging material according to any one of claims 1 to 6, wherein the inner film layer is obtained by casting ethylene-vinyl acetate copolymer modified linear low-density polyethylene resin, the outer film layer is linear low-density polyethylene resin, and the first protective film layer and the second protective film layer are any one of polyethylene film, polypropylene film or polyvinyl chloride film.
8. The chlorine dioxide slow-release freshness-retaining packaging material according to claim 7, wherein the thickness of the inner film layer is 16-18 microns, the oxygen transmission rate of the inner film layer is 5 x 104-1 x 105ml/m2.day.atm, and the water vapor transmission rate is 20-200 g/m 2.day.
9. The chlorine dioxide slow-release freshness-retaining packaging material according to claim 8, wherein the thickness of the outer film layer is 16 to 18 μm, the oxygen transmission rate of the outer film layer is 1 x 104 to 5 x 104ml/m2.day. atm, and the water vapor transmission rate is 10 to 100g/m 2.day.
10. A chlorine dioxide slow release freshness protection packaging material according to claims 1 to 9 for direct use as a freshness protection bag or a freshness protection film.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911088609.8A CN110803395A (en) | 2019-11-08 | 2019-11-08 | Chlorine dioxide slow-release fresh-keeping packaging material and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911088609.8A CN110803395A (en) | 2019-11-08 | 2019-11-08 | Chlorine dioxide slow-release fresh-keeping packaging material and application thereof |
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| CN1449991A (en) * | 2002-04-09 | 2003-10-22 | 新疆大学 | Chlorine dioxide gas generation agent |
| CN103300063A (en) * | 2013-07-04 | 2013-09-18 | 龚佳郎 | Solid chlorine dioxide release agent |
| CN104097849A (en) * | 2014-06-28 | 2014-10-15 | 北京印刷学院 | Fresh-keeping packaging material capable of slowly releasing chlorine dioxide disinfectant and preparation method of fresh-keeping packaging material |
| CN109645113A (en) * | 2019-03-01 | 2019-04-19 | 上海海洋大学 | A kind of fresh-keeping gel of chlorine dioxide slow-release and its preparation method and application |
| CN110150315A (en) * | 2019-05-17 | 2019-08-23 | 四川蓝洁绿源环保科技有限公司 | A kind of solid high-pure chlorinedioxide releasing agent |
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2019
- 2019-11-08 CN CN201911088609.8A patent/CN110803395A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449991A (en) * | 2002-04-09 | 2003-10-22 | 新疆大学 | Chlorine dioxide gas generation agent |
| CN103300063A (en) * | 2013-07-04 | 2013-09-18 | 龚佳郎 | Solid chlorine dioxide release agent |
| CN104097849A (en) * | 2014-06-28 | 2014-10-15 | 北京印刷学院 | Fresh-keeping packaging material capable of slowly releasing chlorine dioxide disinfectant and preparation method of fresh-keeping packaging material |
| CN109645113A (en) * | 2019-03-01 | 2019-04-19 | 上海海洋大学 | A kind of fresh-keeping gel of chlorine dioxide slow-release and its preparation method and application |
| CN110150315A (en) * | 2019-05-17 | 2019-08-23 | 四川蓝洁绿源环保科技有限公司 | A kind of solid high-pure chlorinedioxide releasing agent |
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Application publication date: 20200218 |
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