CN104693811B - Functional gelatin food packaging film and preparation method thereof - Google Patents

Functional gelatin food packaging film and preparation method thereof Download PDF

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Publication number
CN104693811B
CN104693811B CN201510137884.XA CN201510137884A CN104693811B CN 104693811 B CN104693811 B CN 104693811B CN 201510137884 A CN201510137884 A CN 201510137884A CN 104693811 B CN104693811 B CN 104693811B
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beta
gelatin
schardinger dextrin
oil
solution
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CN104693811A (en
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李德富
叶友鑫
葛黎明
穆畅道
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Sichuan University
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Sichuan University
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Abstract

The invention provides a functional gelatin food packaging film and a preparation method thereof, and belongs to the field of food packaging. The method includes the steps that firstly, carboxylation beta-cyclodextrin is prepared through a hydrogen peroxide oxidation method, natural active matter dissolved in an ethanol solution is dripped into the carboxylation beta-cyclodextrin dissolved in the ethanol solution, the carboxylation beta-cyclodextrin stands still after ultrasonic operation, extracted, filtered, washed, frozen and dried, and then embedding carboxylation beta-cyclodextrin for embedding the natural active matter is obtained. The embedding carboxylation beta-cyclodextrin and a gelatin solution are blended, evenly stirred, taken out after being frozen, and completely dissolved, glycerinum and dialdehyde carboxymethylcellulose are sequentially added for reactions conducted for 10-40 minutes respectively, the materials are poured into a die after de-aeration and dried, and then the functional gelatin food packaging film is obtained. The prepared functional gelatin food packaging film has the advantages of resisting bacteria and oxidation and being good in mechanical performance and heat stability; products are safe, capable of achieving the healthcare effect and free of poisonous and side effects. The film can be degraded and beneficial to environmental protection, and has potential market application prospects.

Description

A kind of functional gelatin food package film and preparation method thereof
Technical field
The present invention relates to food packaging applications.In particular to one kind, there is antibacterial, anti-oxidant and good mechanical Functional gelatin food package film of energy and heat endurance and preparation method thereof.
Background technology
Resource, environment, population are three big principal elements of restriction China 21 century sustainable development.Environmental protection, resource Save the basic strategy having become as countries in the world the Implement of sustainable development.But, China human mortality sum is big, and economic growth is fast Speed, for the demand sharp increase of food package film, defines huge challenge to environment and resource.Therefore, research and development with Natural biologic material is that the food packaging items of raw material are increasingly becoming the study hotspot of packaging field.Wholefood packaging film be with Large biological molecule is main matrix, is aided with plasticizer, makes each flim forming molecule interphase interaction by certain treatment process, is formed A kind of dense film.It is mainly packaged by preventing the migration of the materials such as gas, steam, solute and fragrance ingredient from avoiding There is the change of the aspect such as local flavor and quality structure in food in storage and transportation, reach the quality ensureing food and prolongation is guaranteed the quality Phase etc. acts on.In recent years, common food package film has the wafer of packaged confectionary, the corn fire packaging that packaging ice river in Henan Province is insulted Cup, casing of the skin of soya-bean milk of packaging meat dish and packaging meat stuffing etc..It can be seen that packaging film purposes in life widely, has latent Market application foreground.
Due to having the advantages that good biocompatibility and degradability, protein-based packaging film was gradually subject in recent years To being widely recognized as.And attracted attention the most with gelatin film in numerous protein-based packaging films.Gelatin is a kind of by collagen three Stock helical structure is converted into the protein of random chain, mainly by the collagen egg in the connective tissues such as the skin of higher mammal, bone Plain boiled water solution obtains, rich in the necessary amino acid of human body, high in nutritive value.The hot water solubility of gelatin and colloidal sol are reversible with gel Property is that other film-forming colloids are incomparable.Additionally, gelatin wide material sources, preparing easy, cheap, it is extensively should of gelatin With providing necessary condition.But the range of application of simple gelatin film is limited by its active unification.Therefore, activate gelatin Research there is great significance.
Most of natural active matters have to air, daylight and temperature sensitivity, oxidizable rotten, volatile, in water The low shortcoming of solubility, as unstable in tea oil volatile, there is strong impulse smell, composition terpenes therein in light or Under oxygen effect, generate the p- cumene with skin irritation, property changes;Forulic acid is that one kind has anti-oxidant spy Property polyphenol derivatives, have significantly anti-oxidant, remove the pharmacological actions such as free radical, anti-infective and neuroprotective, but its It is easy to oxidized after being exposed to air, ultraviolet and heat, produce the change on function and sense organ, affect its use.Cause This, the application of such active material receives serious restriction.
Beta-schardinger dextrin is to be formed by connecting by α-Isosorbide-5-Nitrae-glycosidic bond by 7 d type glucopyranoses, and monomer is with annular form bundle It is tied together, forming an outside is to have hydrophilic surface, and the internal chiral hydrophobic cavity being to have certain size Closure tubular structure.But beta-schardinger dextrin is slightly soluble in the defect of water, limit its range of application, therefore, by hydrogen peroxide oxidation Beta-schardinger dextrin, makes carboxylated beta-schardinger dextrin, thus it is water-soluble to improve it.Hydrophobic property using carboxylated beta-schardinger dextrin inner chamber By natural active matter inclusion inside it, form Host-guest inclusion complex.After inclusion compound is formed, natural active products can be made Matter, from the impact of the environment such as ambient light, oxygen air and heat, improves its stability, reduces volatilization total amount, thus reaching slow release Effect;By carboxylated beta-schardinger dextrin hydrophobic interior cavities inclusion natural active matter, and the hydrophilic surface of outside carries indirectly The dissolubility of high natural active matter.Therefore, the use of carboxylated beta-schardinger dextrin provides for the application extending natural active matter One good approach.
The present invention makes inclusion compound using carboxylated beta-schardinger dextrin and natural active matter;By inclusion compound with gelatin solution altogether Mixed, make with functional gelatin food package film matrix solution;Mould is injected in this matrix solution deaeration, 20 ~ 60oUnder c, It is dried 1 ~ 5 day, be eventually fabricated a kind of functional gelatin food package film.The food package film of present invention preparation has antibacterial, anti- The characteristic such as oxidation and enhance immunity;Also there is special aromatic odor, food value can be improved.So far, not yet have Pertinent literature or invention carried out relevant report to this research.
Content of the invention
In order to improve beta-schardinger dextrin water solubility and play natural active matter effect, the present invention adopt carboxylated β- Cyclodextrin embedding natural active matter, thus improving stability and the dissolubility of natural active matter, with gelatin by a series of Process makes functional gelatin food package film.
The present invention is achieved through the following technical solutions, and unless otherwise indicated, involved number is parts by weight, percentage It is weight percentage than all.
The present invention provides a kind of functional gelatin food package film, and its preparation method is as follows:
(1) under stirring, hydrogen peroxide is sprayed in beta-schardinger dextrin, and to drip mass fraction be 0.01 ~ 1% Copper-bath, 40oC reacts 3 ~ 10 minutes, after 70oC reacts 5 ~ 30 minutes, then reactant is dissolved in 100oIn c boiling water And react 30 minutes, it is down to after room temperature after solution, centrifugation simultaneously precipitates, supernatant absolute ethyl alcohol with 10 ~ 40% ethanol solution After washing precipitation, pellet frozen is dried, obtains carboxylated beta-schardinger dextrin;
(2) 30~60oUnder c, by carboxylated beta-schardinger dextrin in 10 ~ 50% ethanol solution stirring and dissolving, simultaneously will be natural Active material stirring and dissolving in 0 ~ 30% ethanol solution, and dropping in above-mentioned carboxylated beta-schardinger dextrin solution, in 10 ~ 30oUltrasonic 2 ~ 6 hours of c, after 4oC stand 12 hours, then suction filtration and with 10 ~ 40% ethanol solution wash 3 times, by filter cake Freeze-drying, obtains embedding the embedding type carboxylated beta-schardinger dextrin of natural active matter;
(3) by embedding type carboxylated beta-schardinger dextrin with gelatin solution blending and stirring uniformly, in -20oC freezing 12 ~ 72 is little When, take out in 30 ~ 50oIt is completely dissolved under c, the glycerine reaction adding gelatin dry weight 5 ~ 30%, after 10 ~ 40 minutes, adds gelatin The dialdehyde carboxymethyl cellulose of dry weight 0.1 ~ 10% reacts 10 ~ 40 minutes, obtains functional gelatin food package film matrix solution;
(4) pour mould into by after above-mentioned matrix solution deaeration, 20 ~ 60oUnder c, it is 10 ~ 50% moving air in humidity Middle drying 1 ~ 5 day, obtains functional gelatin food package film.
Natural active matter described in above-mentioned technology case is grape seed extract, Rosmarinus officinalis extract, β-carrot Element, lycopene, alkannin, forulic acid, Tea Polyphenols, propolis flavone alcohol, menthol, black pepper resin, tea oil, bergamot In oil, oil of ginger, horse radish oil, curcuma oil, chive oil, oil of chamomile, fennel oil, onion oil and garlic oil any one or a few Mixture.
In above-mentioned technology case, described hydrogen peroxide is 1:(5 ~ 500 with the mass ratio of beta-schardinger dextrin).
In above-mentioned technology case, the ratio of described natural active matter and carboxylated beta-schardinger dextrin press dry weight be 1:(1 ~ 500).
In above-mentioned technology case, the ratio of described embedding type carboxylated beta-schardinger dextrin and gelatin press dry weight be 1:(1 ~ 1000).
Compared with the prior art the present invention, has many good effects and advantage, can inductive generalization as follows:
(1) the functional gelatin food package film that the present invention provides, its base stock is natural material, has no toxic side effect, It is a kind of edible packing membrane;
(2) the functional gelatin food package film that the present invention provides, with the beta-schardinger dextrin of hydrogen peroxide oxidation, obtains Carboxylated beta-schardinger dextrin, can improve the water solubility of beta-schardinger dextrin, widen its range of application;
(3) the functional gelatin food package film that the present invention provides, by the embedding effect of carboxylated beta-schardinger dextrin, no Natural active matter only can be made from the interference of external environment, improve its physical and chemical stability, give full play to its due characteristic, also The dissolubility of natural active matter can be improved, extend its range of application;
(4) the functional gelatin food package film that the present invention provides, can play controlled release to the natural active matter of embedding Effect, so as to slowly discharge for a long time, reaches long-acting effect;
(5) the functional gelatin food package film that the present invention provides, is combined carboxylated β-ring using gelatin as primary raw material Dextrin and natural active matter, add glycerine and dialdehyde carboxymethyl cellulose, and it is steady that the food package film obtaining has good heat Qualitative, barrier and mechanical performance;
(6) the functional gelatin food package film that the present invention provides, the natural active products of its carboxylated beta-schardinger dextrin embedding The effects such as matter has antibacterial, anti-oxidant and health care, packaging film can reduce food bacteria breed, it is to avoid the secondary pollution of food, Extend the shelf-life of food;
(7) the functional gelatin food package film that the present invention provides, has good biocompatibility and degradability, Can be good at substituting the plastic foil with oil as matrix, and discarded object does not result in environmental pollution;
(8) the functional gelatin food package film that the present invention provides, raw material sources are extensive, with low cost, the making work of film Skill is simple, has potential economic benefit, beneficial to widely using.
Specific implementation method
Three embodiments of the present invention are given below, by embodiment, the present invention are specifically described.It is necessary here It is noted that embodiment is served only for the present invention is further detailed it is impossible to be interpreted as the limit to the scope of the present invention System, the person skilled in the art in this field can make some nonessential improvement according to the content of the invention described above and adjust.
In the following example, unless otherwise indicated, involved number is parts by weight, and percentage is weight percent Than.
Embodiment 1
Under stirring, 4 parts of hydrogen peroxide are sprayed in 80 parts of beta-schardinger dextrins, and drip 1 part of mass fraction and be 0.02% copper-bath, 40oC reacts 5 minutes, after 70oC reacts 15 minutes, then reactant is dissolved in 100oC boiling water In and react 30 minutes, be down to after room temperature after solution, supernatant absolute ethyl alcohol is simultaneously precipitated by centrifugation, with 30% ethanol solution Washing precipitation, pellet frozen is dried, obtains carboxylated beta-schardinger dextrin;35oUnder c, by 50 parts of carboxylated beta-schardinger dextrins in 20% Ethanol solution in stirring and dissolving, simultaneously by 25 parts of natural active matter stirring and dissolving in 15% ethanol solution, and drop to Above-mentioned carboxylated beta-schardinger dextrin solution, in 15oUnder c, after ultrasonic 3 hours, 4oC stands 12 hours, and suction filtration is simultaneously molten with 20% ethanol Liquid washs 3 times, freeze-drying, obtains embedding the embedding type carboxylated beta-schardinger dextrin of natural active matter;By 10 parts of embedding type carboxylics Base beta-schardinger dextrin and gelatin solution blending and stirring that 1000 parts of mass fractions are 1% uniformly, in -20oFreeze 36 hours in c, take For 40oIt is completely dissolved under c, the glycerine reaction adding gelatin dry weight 15%, after 30 minutes, adds the dialdehyde carboxylic of gelatin dry weight 5% Methylcellulose reacts 30 minutes, obtains functional gelatin food package film matrix solution;To fall after above-mentioned matrix solution deaeration Enter mould, 50oUnder c, in humidity be 30% moving air in be dried 3 days, obtain functional gelatin food package film.
Embodiment 2
Under stirring, 1 part of hydrogen peroxide is sprayed in 50 parts of beta-schardinger dextrins, and drips 1 part of mass fraction and be 0.3% copper-bath, 40oC reacts 8 minutes, after 70oC reacts 30 minutes, then reactant is dissolved in 100oC boiling water In and react 30 minutes, be down to after room temperature after solution, supernatant absolute ethyl alcohol is simultaneously precipitated by centrifugation, with 20% ethanol solution Washing precipitation, pellet frozen is dried, obtains carboxylated beta-schardinger dextrin;45oUnder c, by 10 parts of carboxylated beta-schardinger dextrins in 10% Ethanol solution in stirring and dissolving, simultaneously by 1 part of natural active matter stirring and dissolving in 30% ethanol solution, and drop to Above-mentioned carboxylated beta-schardinger dextrin solution, in 10oUnder c, after ultrasonic 2 hours, 4oC stands 12 hours, then suction filtration with 10% second Alcoholic solution washs 3 times, freeze-drying, obtains embedding the embedding type carboxylated beta-schardinger dextrin of natural active matter;By 5 parts of embedding types Carboxylated beta-schardinger dextrin and gelatin solution blending and stirring that 2000 parts of mass fractions are 5% uniformly, in -20oFreeze 24 hours in c, Take out in 30oIt is completely dissolved under c, the glycerine reaction adding gelatin dry weight 20%, after 10 minutes, adds the double of gelatin dry weight 10% Aldehyde carboxymethylcellulose calcium reacts 20 minutes, obtains functional gelatin food package film matrix solution;By above-mentioned matrix solution deaeration After pour mould into, 60oUnder c, in humidity be 40% moving air in be dried 3 days, obtain functional gelatin food package film.
Embodiment 3
Under stirring, 5 parts of hydrogen peroxide are sprayed in 120 parts of beta-schardinger dextrins, and drip 1 part of mass fraction and be 0.5% copper-bath, 40oC reacts 5 minutes, after 70oC reacts 30 minutes, then reactant is dissolved in 100oC boiling water In and react 30 minutes, be down to after room temperature after solution, supernatant absolute ethyl alcohol is simultaneously precipitated by centrifugation, with 30% ethanol solution Washing precipitation, pellet frozen is dried, obtains carboxylated beta-schardinger dextrin;35oUnder c, by 25 parts of carboxylated beta-schardinger dextrins in 35% Ethanol solution in stirring and dissolving, simultaneously by 0.5 part of natural active matter stirring and dissolving in 25% ethanol solution, and drip To above-mentioned carboxylated beta-schardinger dextrin solution, in 20oUnder c, after ultrasonic 4 hours, 4oC stands 12 hours, then suction filtration with 25% Ethanol solution washs 3 times, freeze-drying, obtains embedding the embedding type carboxylated beta-schardinger dextrin of natural active matter;0.2 part is wrapped Bury type carboxylated beta-schardinger dextrin and gelatin solution blending and stirring that 1000 parts of mass fractions are 2% uniformly, in -20o48 are freezed in c Hour, take out in 45oIt is completely dissolved under c, the glycerine reaction adding gelatin dry weight 15%, after 30 minutes, adds gelatin dry weight 3% Dialdehyde carboxymethyl cellulose react 15 minutes, obtain functional gelatin food package film matrix solution;By above-mentioned matrix solution Mould is poured into, 40 after deaerationoUnder c, in humidity be 25% moving air in be dried 3 days, obtain functional gelatin packaging for foodstuff Film.

Claims (5)

1. a kind of functional gelatin food package film, is characterized in that preparation method is as follows:
(1) under stirring, hydrogen peroxide is sprayed in beta-schardinger dextrin, and drips the sulfuric acid that mass fraction is 0.01 ~ 1% Copper solution, 40oC reacts 3 ~ 10 minutes, after 70oC reacts 5 ~ 30 minutes, then reactant is dissolved in 100oIn c boiling water and anti- Answer 30 minutes, be down to after room temperature after solution, supernatant absolute ethyl alcohol is simultaneously precipitated, with 10 ~ 40% ethanol solution washing by centrifugation After precipitation, pellet frozen is dried, obtains carboxylated beta-schardinger dextrin;
(2) 30~60oUnder c, by carboxylated beta-schardinger dextrin in 10 ~ 50% ethanol solution stirring and dissolving, simultaneously by natural activity Material stirring and dissolving in 0 ~ 30% ethanol solution, and drop in above-mentioned carboxylated beta-schardinger dextrin solution, in 10 ~ 30oC surpasses Sound 2 ~ 6 hours, after 4oC stand 12 hours, then suction filtration and with 10 ~ 40% ethanol solution wash 3 times, filter cake is freezed It is dried, obtain embedding the embedding type carboxylated beta-schardinger dextrin of natural active matter;
(3) by embedding type carboxylated beta-schardinger dextrin with gelatin solution blending and stirring uniformly, in -20oC freezes 12 ~ 72 hours, takes out In 30 ~ 50oBe completely dissolved under c, add the glycerine reaction after 10 ~ 40 minutes of gelatin dry weight 5 ~ 30%, add gelatin dry weight 0.1 ~ 10% dialdehyde carboxymethyl cellulose reacts 10 ~ 40 minutes, obtains functional gelatin food package film matrix solution;
(4) pour mould into by after above-mentioned matrix solution deaeration, 20 ~ 60oUnder c, dry in the moving air for 10 ~ 50% for the humidity Dry 1 ~ 5 day, obtain functional gelatin food package film.
2. functional gelatin food package film according to claim 1, is characterized in that described natural active matter is grape Seed extract, Rosmarinus officinalis extract, beta carotene, lycopene, alkannin, forulic acid, Tea Polyphenols, propolis flavone alcohol, peppermint Alcohol, black pepper resin, tea oil, bergamot oil, oil of ginger, horse radish oil, curcuma oil, chive oil, oil of chamomile, fennel oil, ocean Any one or a few mixture in scallion oil and garlic oil.
3. functional gelatin food package film according to claim 1, is characterized in that the matter of hydrogen peroxide and beta-schardinger dextrin Amount ratio is 1:(5 ~ 500).
4. functional gelatin food package film according to claim 1, it is characterized in that natural active matter and carboxylated β- It is 1:(1 ~ 500 that the ratio of cyclodextrin presses dry weight).
5. functional gelatin food package film according to claim 1, it is characterized in that embedding type carboxylated beta-schardinger dextrin with It is 1:(1 ~ 1000 that the ratio of gelatin presses dry weight).
CN201510137884.XA 2015-03-27 2015-03-27 Functional gelatin food packaging film and preparation method thereof Expired - Fee Related CN104693811B (en)

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CN106751918B (en) * 2016-11-23 2019-05-03 宁波大学 A kind of preparation method of bamboo-leaves flavones fish scale gelatin edible freshness-keeping thin coat
CN107955195A (en) * 2017-11-09 2018-04-24 常州市雄图纺织有限公司 A kind of preparation method of modified gelatin film
IT201900013557A1 (en) * 2019-07-31 2021-01-31 Univ Degli Studi Di Sassari ANIMAL JELLIES MODIFIED WITH CYCLODEXTRINS, PROCEDURE FOR THEIR PREPARATION, FILMS OBTAINED FROM THE SAME AND THEIR USE IN THE PACKAGING FIELD
CN112279927A (en) * 2020-11-04 2021-01-29 暨南大学 Carboxyl nano-cellulose, preparation method and application thereof
CN112300425A (en) * 2020-11-17 2021-02-02 上海海洋大学 Gelatin/fiber composite antibacterial film and preparation method and application thereof
CN112705131B (en) * 2020-12-29 2023-01-24 广西中烟工业有限责任公司 Preparation method of eutectic solvent/hydroxypropyl-beta-cyclodextrin menthol microcapsule
CN114259052A (en) * 2021-12-29 2022-04-01 安徽省纽斯康生物工程有限公司 Lipid-lowering and blood-sugar-lowering linseed oil dietary powder and preparation method thereof
CN114605715A (en) * 2022-03-25 2022-06-10 成都大学 Propolis-cyclodextrin-graphene oxide film and preparation method and application thereof
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US8759279B2 (en) * 2008-06-30 2014-06-24 Kimberly-Clark Worldwide, Inc. Fragranced biodegradable film
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CN103865276A (en) * 2014-03-19 2014-06-18 李孟醒 Active antibacterial edible package with controlled release function and preparation method thereof
CN104140568B (en) * 2014-07-30 2016-12-07 江南大学 A kind of edible film with lasting anti-oxidation function and preparation method thereof and application

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