CN102120514B - Marine polysaccharide multilayer composite packaging film with antibacterial function - Google Patents
Marine polysaccharide multilayer composite packaging film with antibacterial function Download PDFInfo
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- CN102120514B CN102120514B CN 201010577744 CN201010577744A CN102120514B CN 102120514 B CN102120514 B CN 102120514B CN 201010577744 CN201010577744 CN 201010577744 CN 201010577744 A CN201010577744 A CN 201010577744A CN 102120514 B CN102120514 B CN 102120514B
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Abstract
The invention relates to a marine polysaccharide multilayer composite packaging film with an antibacterial function and a preparation method thereof, belonging to the fields of high polymer materials and food package. The marine polysaccharide multiplayer composite packaging film is prepared by forming a three-layer polyelectrolyte composite film by utilizing the static function of polycation electrolyte chitosan and polyanion electrolyte sodium alginate, and adding natural germicide, i.e. clove oil, to a middle film layer. The preparation method of the packaging film is simple; and the obtained packaging film has favorable mechanical performance, is superior to a low-density polyethylene film, can meet common requirements of food package, has favorable antibacterial controlled-release performance, can effectively prolong the shelf life of foods and can be used for fresh-keeping packaging of various foods, such as meat, cut fruits and vegetables, and the like.
Description
Technical field
The present invention relates to a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions and preparation method thereof, belong to High molecular material and packaging for foodstuff field.
Background technology
Traditional food package film mainly is the synthetic plasticss such as polyethylene, polypropylene, and these materials have increased the weight of the world energy sources crisis take oil industry as the basis, do not meet development tendency and the requirement of low-carbon economy; Simultaneously, because it can not be biodegradable, caused serious environmental pollution.Therefore, utilize the abundant natural polymer biologicals of reserves to prepare biodegradable packaging film, have important practical significance.Shitosan and sodium alginate all belong to marine polysaccharide, and wide material sources are cheap, and filming performance is good, utilize these two kinds of natural high molecular substances to prepare biodegradable composite package film, and report is not also arranged both at home and abroad.
Germ not only causes food apoilage, and more seriously, the food that some pathogenic bacteria polluted can cause food poisoning, harm people's health.Thereby antimicrobial packaging is by adding the breeding of antiseptic control germ in packing.The speed that antiseptic discharges from packing has material impact to antibacterial effect.Traditional method is directly antimicrobial component to be added in the polymeric material, and antiseptic discharges very fast, and out of reach delays the purpose of food apoilage for a long time.Therefore, need to take more rational technology to delay the rate of release of antiseptic from packing, finally to reach the purpose that prolongs Food Shelf-life.
Summary of the invention
The present invention provides a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions and preparation method thereof for above-mentioned two aspect problems.This packaging film utilizes the good filming performance of marine polysaccharide sodium alginate and shitosan and advantage with low cost, choose the natural antibacterial agent clove oil, in conjunction with compound polyelectrolyte and two kinds of actv. slow release methods of multilayer film, the packaging film mechanical strength of preparation is good, and can delay the putrid and deteriorated of food, can effectively prolong Food Shelf-life.
Technical scheme provided by the invention is: a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions, and its preparation technology comprises following two parts:
(1) film-forming process, basic composition and the percentage by weight thereof of packaging film are respectively: antiseptic 1～10%, plasticizer 25～30%, sodium alginate 10～40%, shitosan 30～60%;
(2) solidification process, basic composition is of curing agent: the aqueous system of sodium citrate and calcium chloride, its mass concentration is respectively 3～15%, 1～7%.
Described antiseptic is clove oil, and its eugenol content is not less than 85%.
Described plasticizer is glycerine.
Described sodium alginate is that viscosity is any between 200～800.
Described shitosan is that deacetylation is 65～95%, mol wt is any between 50,000～500,000.
The invention provides a kind of preparation method with marine polysaccharide multilayer composite packaging film of antibacterial functions, specifically comprise following flow process:
(1) described shitosan is dissolved in the glacial acetic acid aqueous system, adds described plasticizer, the rear hold over night that stirs is dissolved it fully, obtains the glacial acetic acid aqueous system (note A liquid) of shitosan-plasticizer;
(2) described antiseptic is dissolved in the edible alcohol, stirring is dissolved it fully, obtains antiseptic-edible alcohol solution;
(3) with in the described sodium alginate soln water, add described plasticizer, magnetic agitation is dissolved it fully, then adds antiseptic-edible alcohol solution, magnetic agitation obtains sodium alginate-plasticizer-antimicrobial (note B liquid) to mixing;
(4) described curing agent is water-soluble, obtain curing agent solution;
(5) A liquid is watered cast from the mould, dry evaporation remove portion solvent forms chitosan film; Then at this chitosan film top casting one deck B liquid, the A liquid of casting again behind the dry evaporation remove portion solvent has namely formed sandwich diaphragm after the drying; Mould is put into the tank that fills above-mentioned curing agent solution to be solidified; Mould is taken out, and the curing agent that water flushing membrane surface is unnecessary after drying is complete is taken complex film off, namely obtains having the marine polysaccharide multilayer composite packaging film of antibacterial functions.
Advantage of the present invention is:
(1) shitosan, sodium alginate are the marine source polysaccharide, and filming performance is good, and wide material sources, and cost is low, and is biodegradable at occurring in nature, can not produce problem of environmental pollution;
(2) clove oil is a kind of natural antibacterial agent, with synthetic antibacterial agents, compares such as potassium sorbate, Sodium Benzoate, n-propyl gallate etc., has the high advantage of edible safety;
(3) this packaging film has slow release effect;
(4) preparation method is simple, and the packaging film of preparation is colourless or be cream-yellow, and transparent, mechanical strength and elasticity are good, can satisfy the general packing requirements of food.
The specific embodiment
Example 1: a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions, it basic composition is: 6.7% clove oil, 26.7% glycerine, 22.2% sodium alginate, 44.4% shitosan.
The preparation method of this packaging film is as follows:
Get the 0.5mL glacial acetic acid, join in the 100mL water, stir, obtain the glacial acetic acid aqueous system; Get 1g shitosan, 0.4g glycerine, it is joined in the above-mentioned glacial acetic acid aqueous system, the rear hold over night that stirs is dissolved it fully, vacuumizes the removal bubble, obtains the glacial acetic acid aqueous system (note A liquid) of shitosan-glycerine; Get the 0.3g clove oil, join in the 10mL edible alcohol, stir, obtain clove oil-edible alcohol solution; Get 1g sodium alginate, 0.4g glycerine, it is joined the 100mL aqueous system, magnetic agitation adds above-mentioned clove oil-edible alcohol solution after it is dissolved fully again, and magnetic agitation obtains sodium alginate-glycerine-clove oil solution (note B liquid) to mixing; Get 10g sodium citrate and 5g calcium chloride, be dissolved in the 100mL water, obtain curing agent solution; At mould top casting 50mL A liquid, place 40 ℃ of dry 1h of baking oven first, evaporation remove portion solvent forms chitosan film; Then at this chitosan film top casting 50mL B liquid, place 40 ℃ of dry 1.5h of baking oven, the 50mL A liquid of casting again behind the evaporation remove portion solvent places 40 ℃ of dry 8h of baking oven to make the film all dry, namely forms sandwich diaphragm; Mould is put into the tank that contains above-mentioned curing agent solution to be solidified; Mould is taken out, and water flushing complex film surface places 40 ℃ of baking ovens fully dry to remove unnecessary curing agent solution, takes off film, namely prepares a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions.
Example 2: a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions, it basic composition is: 1.2% clove oil, 28.2% glycerine, 23.5% sodium alginate, 47.1% shitosan.
The preparation method of this packaging film is as follows:
Being to get the 0.05g clove oil when preparing except clove oil-edible alcohol solution, is to get 5g sodium citrate and 3g calcium chloride when curing agent solution prepares, and all the other are identical with example 1.
Example 3: a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions, it basic composition is: 4.1% clove oil, 27.4% glycerine, 13.7% sodium alginate, 54.8% shitosan.
The preparation method of this packaging film is as follows:
Be to get 15g sodium citrate and 1g calcium chloride when preparing except curing agent solution, the casting amount of B liquid is 25mL, and all the other are identical with example 1.
Example 4: a kind of marine polysaccharide multilayer composite packaging film with antibacterial functions, it basic composition is: 9.7% clove oil, 25.7% glycerine, 32.3% sodium alginate, 32.3% shitosan.
The preparation method of this packaging film is as follows:
Be to get 3g sodium citrate and 7g calcium chloride when preparing except curing agent solution, the casting amount of B liquid is outside the 100mL, and all the other are identical with example 1.
Claims (6)
1. marine polysaccharide multilayer composite packaging film with antimicrobial sustained-release function, it is characterized in that, this packaging film utilizes marine polysaccharide shitosan, sodium alginate and shitosan to interact and forms sandwich diaphragm, add clove oil at middle one deck sodium alginate film simultaneously, the curing cross-linked technique by curing agent is prepared from last.
2. the marine polysaccharide multilayer composite packaging film with antimicrobial sustained-release function as claimed in claim 1, it basic composition is: clove oil 1～10%, plasticizer glycerine 25～30%, sodium alginate 10～40%, shitosan 30～60%.
3. the marine polysaccharide multilayer composite packaging film with antimicrobial sustained-release function as claimed in claim 1, basic composition is of its curing agent: 3～15% sodium citrates and 1～7% calcium chloride.
4. the marine polysaccharide multilayer composite packaging film with antimicrobial sustained-release function as claimed in claim 1, the viscosity of its sodium alginate is between 200～800.
5. the marine polysaccharide multilayer composite packaging film with antimicrobial sustained-release function as claimed in claim 1, its deacetylating degree of chitosan are 65～95%, mol wt is 50,000～500,000.
6. one kind prepares the method with marine polysaccharide multilayer composite packaging film of antimicrobial sustained-release function claimed in claim 1, and step is as follows:
(1) shitosan is dissolved in the glacial acetic acid aqueous system, adds glycerine, the rear hold over night that stirs is dissolved it fully, vacuumizes the removal bubble;
(2) clove oil is dissolved in the edible alcohol, stirring is dissolved it fully;
(3) sodium alginate is soluble in water, add glycerine, magnetic agitation is dissolved it fully, then adds the prepared clove oil-edible alcohol solution of step (2), and magnetic agitation vacuumizes the removal bubble to mixing;
(4) curing agent is mixed in proportion rear water-soluble;
(5) with step (1) gained solution-cast in mould, place the dry certain hour of baking oven, evaporation remove portion solvent forms chitosan film; Then at this chitosan film top casting one deck step (3) gained solution, place the dry certain hour of baking oven, evaporation remove portion solvent, formation contains the interlayer of the sodium alginate film of clove oil; At this film top casting one deck step (1) gained solution, place baking oven to make its all dry again, form sandwich diaphragm; Mould is put into the tank that fills step (4) gained solution solidify, take out, the curing agent that the water flush away is unnecessary places baking oven fully dry; At last complex film is taken off, placed under the environment of uniform temperature and relative humidity and preserve, obtain having the marine polysaccharide multilayer composite packaging film of antimicrobial sustained-release function.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010577744 CN102120514B (en) | 2010-04-28 | 2010-11-16 | Marine polysaccharide multilayer composite packaging film with antibacterial function |
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| CN201010168360 | 2010-04-28 | ||
| CN201010168360.4 | 2010-04-28 | ||
| CN 201010577744 CN102120514B (en) | 2010-04-28 | 2010-11-16 | Marine polysaccharide multilayer composite packaging film with antibacterial function |
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| CN102120514A CN102120514A (en) | 2011-07-13 |
| CN102120514B true CN102120514B (en) | 2013-04-10 |
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| JP2015509530A (en) * | 2012-03-05 | 2015-03-30 | セラディス ベー．フェー． | Polyelectrolyte complex containing natamycin and / or phosphite for biocide enhancement |
| US20160213051A1 (en) | 2013-09-04 | 2016-07-28 | Ceradis B.V. | Processed edible product comprising a polyelectrolyte complex and an antimicrobial compound |
| CN104530495A (en) * | 2014-12-11 | 2015-04-22 | 青岛佰众化工技术有限公司 | Edible biological membrane |
| WO2018038669A1 (en) | 2016-08-24 | 2018-03-01 | Organoclick Ab | Bio-based polyelectrolyte complex compositions comprising non-water soluble particles |
| JP7145514B2 (en) * | 2016-08-24 | 2022-10-03 | オルガノクリック アーベー | Bio-based polyelectrolyte complex compositions with increased hydrophobicity containing fatty compounds |
| SE1651136A1 (en) | 2016-08-24 | 2018-02-25 | Organoclick Ab | Bio-based pec compositions as binders for fiber based materials, textiles, woven and nonwoven materials |
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| CN107840981A (en) * | 2017-11-08 | 2018-03-27 | 海南师范大学 | A kind of sodium alginate chitosan bilayer edible film, its preparation method and its application |
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| CN108639564B (en) * | 2018-05-24 | 2020-06-12 | 青岛农业大学 | Edible composite film and preparation method and application thereof |
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| US20220289999A1 (en) * | 2019-07-11 | 2022-09-15 | StenCo, LLC | Biodegradable material |
| CN110746658B (en) * | 2019-11-05 | 2020-09-08 | 江南大学 | Chitosan/kojic acid/chlorinated kojic acid composite bacteriostatic preservative film and preparation method thereof |
| CN113174071B (en) * | 2021-04-26 | 2022-07-01 | 东北林业大学 | Press sealing method of anionic polysaccharide film |
| CN113292383B (en) * | 2021-07-02 | 2023-05-09 | 江西中科高博科技服务有限公司 | Preparation technology of fertilizer special for high yield of phyllostachys praecox shoots |
| CN114698691A (en) * | 2022-04-20 | 2022-07-05 | 浙江工商大学 | Preservation method of fresh blueberry fruits |
| CN115339168B (en) * | 2022-04-22 | 2023-06-06 | 浙江省农业科学院 | High-ductility multilayer edible antibacterial packaging film and preparation method thereof |
| CN114957811A (en) * | 2022-06-11 | 2022-08-30 | 李远超 | Preparation method of food-grade antibacterial plastic |
| CN115530222B (en) * | 2022-09-19 | 2024-01-26 | 福建农林大学 | Food fresh-keeping pad with slow-release antibacterial and antioxidant functions and preparation method thereof |
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| CN1589776A (en) * | 2003-09-01 | 2005-03-09 | 中国科学院大连化学物理研究所 | Microencapsulated saccharomyces and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1589776A (en) * | 2003-09-01 | 2005-03-09 | 中国科学院大连化学物理研究所 | Microencapsulated saccharomyces and its application |
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Effective date of registration: 20160414 Address after: 362700, Fujian, Quanzhou Province, Shishi, Hong Shan, East Village, one side of the main thoroughfare Patentee after: Fujian Wanhong Marine Biotechnology Co., Ltd. Address before: 266003 Shandong province Qingdao City fish Road No. 5 Patentee before: Ocean University of China |