CN109438776A - A kind of high-barrier zeins chitosan edible film and preparation method thereof - Google Patents

A kind of high-barrier zeins chitosan edible film and preparation method thereof Download PDF

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Publication number
CN109438776A
CN109438776A CN201811309603.4A CN201811309603A CN109438776A CN 109438776 A CN109438776 A CN 109438776A CN 201811309603 A CN201811309603 A CN 201811309603A CN 109438776 A CN109438776 A CN 109438776A
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zeins
chitosan
film
barrier
preparation
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CN201811309603.4A
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Chinese (zh)
Inventor
刘战丽
张利铭
韩祥波
孙阳
王楠
王延林
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Shandong University of Technology
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Shandong University of Technology
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Priority to CN201811309603.4A priority Critical patent/CN109438776A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/463—Edible packaging materials
    • 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
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00—Characterised by the use of proteins; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Wrappers (AREA)

Abstract

The present invention relates to a kind of high-barrier zeins chitosan edible films and preparation method thereof, belong to food, drug packing technical field.It is dissolved, is mixed, pour mask, being finally dried using zeins and chitosan as substrate, and high-barrier zeins chitosan edible film is prepared into.The method of the present invention simple process, the edible film of preparation uniformly, bubble-free, and there is good degradability and mechanical performance and barrier property, can effectively extend Food Shelf-life, meet the requirement of food, Key works Drug packing.

Description

A kind of high-barrier zeins chitosan edible film and preparation method thereof
Technical field
The present invention relates to a kind of high-barrier zeins chitosan edible films and preparation method thereof, and belonging to food can drop Solve packaging material field.
Background technique
It is greatly paid close attention to currently, environmental problem and food safety have caused people, to meet more and more consumption Demand of the person to the wholefood of high quality and safety, edible film is novel as one kind, and pollution-free, degradation material is sent out rapidly Exhibition, is increasingly becoming the research hotspot of food packaging applications.Edible film is the macromolecular polysaccharide for selecting Pure natural nontoxic harmless, egg White matter and lipid material etc. are coated on food surface as film agent, using the methods of dipping, smearing, sprinkling, to reach Good physical state and quality are kept during food storage, transport and sale and extend the effect of effective period of food quality. Field of food industry is generally used for as the degradable package material for replacing plastics.
Chitosan is derivative of the chitin after deacetylated, is a kind of with D- Glucosamine and N-acetylamino The linear glycosaminoglycan of glucose unit.Because containing free amine group in chitosan molecule, in an acidic solution easily at salt, in sun Ionic nature.Its distinctive structure determines that it has a variety of unique physicochemical properties, such as has very high viscosity, good guarantor Moist, film forming, thickening property, gelation, biocompatibility and biological degradability.
Zeins is the main component of corn protein, accounts for about the 68%~72% of zein content, is by putting down The mixture that the protein that equal relative molecular mass is 25000~45000 forms, what molecule was bar-like, with axial ratio for 6: 1 The asymmetric molecular structure that elongates exist, be natural degradable resource.Due to containing a large amount of nonpolar amino acid, lack alkalinity With acid amino acid with unique dissolubility.It is not soluble in water, but dissolve in alcoholic solution, high concentration urea liquid, The alkali (pH >=11) or anion active agent of high concentration, wherein ethanol solution is most common solvent.Zeins can It is made under conditions of being not necessarily to additive, tanning agent with good moist and oxygen barrier the film of resistance.
All haves the defects that certain, such as corn alcohol since zeins or chitosan is used alone as agent is film-made Film mechanical strength obtained by molten albumen is low, and flexibility is poor, and stability is poor, crisp and frangible, thus limits its practical application. Single chitosan film hygroscopicity and gas permeability are poor.Zeins combines with chitosan to can to play advantage mutual Benefit effect, to prepare the edible composite film with good physical mechanical performance and barrier property.Due to the molten egg of corn alcohol It is white be dissolved in 60%~95% ethyl alcohol, different concentration of alcohol is affected to zeins/chitosan complex film performance. Therefore optimization zeins/chitosan complex film processing conditions is very necessary.
Summary of the invention
Invention aim to overcome that the deficiencies in the prior art in place of, providing a kind of can overcome drawbacks described above and operation letter It is single, at low cost, the preparation method of the high-barrier zeins chitosan edible film of good application effect.
Its technical solution are as follows: weigh the ethanol solution that a certain amount of zeins is dissolved in 90%, 95% respectively, be prepared into The film liquid that zeins mass percentage concentration is 2%.The acetic acid solution that a certain amount of chitosan is dissolved in 1% is weighed, is prepared into The film liquid that chitosan mass percentage concentration is 2%.By the maize alcohol-soluble protein film liquid prepared and chitosan film liquid by volume 1: 1,1:3,1:5 are mixed, and are added the plasticizer that mass percentage concentration is 1% after mixing, are heated 80 DEG C of magnetic agitation, 20min is obtained To mixing film liquid, the total mixed solution of the 90~110mL prepared is poured on the saturating benzene PS modeling of the dry tack free cleaning of 25cm × 25cm Expect in culture dish, casting film-forming, being subsequently placed in temperature is dry 5~6h in 50~60 DEG C of drying box, taken off after cooling film to get To high-barrier zeins chitosan edible film.
Its fresh keeping principle are as follows: chitosan contains a large amount of basic amine group, in an acidic solution, chitosan segment amide proton Change formation-NH3 +, solution total electrical charge quantity can be significantly improved；Zeins molecular side chain amino acid energy both sexes dissociation, cruelly Exposing-COO-With-NH3+；Under certain condition, reciprocation occurs between albumen and polysaccharide group, crosslinking is generated and is uniformly distributed Reticular structure, have the characteristics that preferable composite membrane, not only have the good barrier property of maize alcohol-soluble protein film, but also have shell The advantages of glycan film good mechanical performance.
Beneficial effects of the present invention:
(1) composite membrane that this method is prepared on the basis of selecting optimal concentration of alcohol has more excellent performance.
(2) this method does not generate bubble in composite membrane liquid preparation process, and the composite film thickness of preparation is uniform, eliminates This cumbersome process flow of bubble removing.
(3) it uses zeins and chitosan for compound film raw material, there is reducing blood lipid, the effect of blood pressure lowering makes film With nutritive value abundant.
(4) present invention makes full use of the property of zeins and chitosan, and the composite membrane of preparation can with excellent Degradability, good mechanical performance and barrier property, and natural pollution-free, effective Shelf-life, be widely used in fruits and vegetables, The food such as meat it is fresh-keeping.
(5) the method for the present invention is simple, easily operated, low production cost, high production efficiency, is suitble to industrialization promotion production Using.
Detailed description of the invention
Fig. 1 composite membrane scanning electron microscope (SEM) photograph prepared by the present invention (A, 90% ethyl alcohol 1:1 composite membrane scanning electron microscope (SEM) photograph；B, 90% Ethyl alcohol 1:3 composite membrane scanning electron microscope (SEM) photograph；C, 90% ethyl alcohol 1:5 composite membrane scanning electron microscope (SEM) photograph；D, the scanning of 95% ethyl alcohol 1:1 composite membrane Electron microscope).
Fig. 2 90% ethyl alcohol 1:1 composite membrane DSC thermal property scanning figure prepared by the present invention.
Fig. 3 90% ethyl alcohol 1:3 composite membrane DSC thermal property scanning figure prepared by the present invention.
Fig. 4 90% ethyl alcohol 1:5 composite membrane DSC thermal property scanning figure prepared by the present invention.
Fig. 5 95% ethyl alcohol 1:1 composite membrane DSC thermal property scanning figure prepared by the present invention.
Specific embodiment
To keep technical solution of the present invention more apparent, the present invention is further described below by specific embodiment It is bright.
Embodiment 1
2g zeins is dissolved in 90% ethanol solution of 100ml, heating stirring 20min in 80 DEG C of water-baths is prepared into The film liquid that zeins mass percentage concentration is 2%.
2g chitosan is dissolved in 1% acetic acid solution of 100ml, heating stirring 20min in 80 DEG C of water-baths, prepares shelling The film liquid that glycan mass percentage concentration is 2%.
By the maize alcohol-soluble protein film liquid prepared, 1:1 is uniformly mixed by volume with the chitosan film liquid for preparing, is added Enter the plasticizer that mass percentage concentration is 1%, heating stirring 20min in 80 DEG C of water-baths is prepared into composite membrane liquid.
The total mixed solution of the 90~110mL prepared is poured on to the saturating benzene PS plastic of the dry tack free cleaning of 25cm × 25cm In culture dish, casting film-forming is subsequently placed in dry 5~6h in the drying box that temperature is 50~60 DEG C, takes off film after cooling to get arriving High-barrier zeins chitosan edible film, Figure 1A are the scanning electricity of high-barrier zeins chitosan edible film Mirror figure.
Gained edible film is analyzed, at this time its performance are as follows: film thickness 0.039mm, tensile strength 19.087MPa, fracture Elongation is 72.814%, vapor transmission coefficient 36.367mgcm-2·d-1, oxygen permeability 8.554mgcm-2·d-1, DSC heat Performance evaluation is as shown in Figure 2.
Embodiment 2
2g zeins is dissolved in 90% ethanol solution of 100ml, heating stirring 20min in 80 DEG C of water-baths is prepared into The film liquid that zeins mass percentage concentration is 2%.
2g chitosan is dissolved in 1% acetic acid solution of 100ml, heating stirring 20min in 80 DEG C of water-baths, prepares shelling The film liquid that glycan mass percentage concentration is 2%.
By the maize alcohol-soluble protein film liquid prepared, 1:3 is uniformly mixed by volume with the chitosan film liquid for preparing, is added Enter the glycerol that mass percentage concentration is 1%, heating stirring 20min in 80 DEG C of water-baths is prepared into composite membrane liquid.
The total mixed solution of the 90~110mL prepared is poured on to the saturating benzene PS plastic of the dry tack free cleaning of 25cm × 25cm In culture dish, casting film-forming is subsequently placed in dry 5~6h in the drying box that temperature is 50~60 DEG C, takes off film after cooling to get arriving High-barrier zeins chitosan edible film, Figure 1B are the scanning electricity of high-barrier zeins chitosan edible film Mirror figure.
Gained edible film is analyzed, at this time its performance are as follows: film thickness 0.037mm, tensile strength 14.137MPa, fracture Elongation is 60.157%, vapor transmission coefficient 40.866mgcm-2·d-1, oxygen permeability 9.294mgcm-2·d-1, DSC Thermal performance analysis is as shown in Figure 3.
Embodiment 3
2g zeins is dissolved in 90% ethanol solution of 100ml, heating stirring 20min in 80 DEG C of water-baths is prepared into The film liquid that zeins mass percentage concentration is 2%.
2g chitosan is dissolved in 1% acetic acid solution of 100ml, heating stirring 20min in 80 DEG C of water-baths, prepares shelling The film liquid that glycan mass percentage concentration is 2%.
By the maize alcohol-soluble protein film liquid prepared, 1:5 is uniformly mixed by volume with the chitosan film liquid for preparing, is added Enter the glycerol that mass percentage concentration is 1%, heating stirring 20min in 80 DEG C of water-baths is prepared into composite membrane liquid.
The total mixed solution of the 90~110mL prepared is poured on to the saturating benzene PS plastic of the dry tack free cleaning of 25cm × 25cm In culture dish, casting film-forming is subsequently placed in dry 5~6h in the drying box that temperature is 50~60 DEG C, takes off film after cooling to get arriving High-barrier zeins chitosan edible film, Fig. 1 C are the scanning of high-barrier zeins chitosan edible film Electron microscope.
Gained edible film is analyzed, at this time its performance are as follows: film thickness 0.067mm, tensile strength 14.241MPa, fracture Elongation is 64.888%, vapor transmission coefficient 43.536mgcm-2·d-1, oxygen permeability 9.787mgcm-2·d-1, DSC Thermal performance analysis is as shown in Figure 4.
Embodiment 4
2g zeins is dissolved in 95% ethanol solution of 100ml, heating stirring 20min in 80 DEG C of water-baths is prepared into The film liquid that zeins mass percentage concentration is 2%.
By the maize alcohol-soluble protein film liquid prepared, 1:1 is uniformly mixed by volume with the chitosan film liquid for preparing, is added Enter the glycerol that mass percentage concentration is 1%, heating stirring 20min in 80 DEG C of water-baths is prepared into composite membrane liquid.
The total mixed solution of the 90~110mL prepared is poured on to the saturating benzene PS modeling of the dry tack free cleaning of 25cm × 25cm Expect in culture dish, casting film-forming, being subsequently placed in temperature is dry 5~6h in 50~60 DEG C of drying box, taken off after cooling film to get To high-barrier zeins chitosan edible film, Fig. 1 D is sweeping for high-barrier zeins chitosan edible film Retouch electron microscope.
Gained edible film is analyzed, at this time its performance: film thickness 0.038mm, tensile strength 19.087MPa, fracture are stretched Long rate is 60.157%, vapor transmission coefficient 37.357mgcm-2·d-1, oxygen permeability 8.894mgcm-2·d-1, DSC heat Performance evaluation is as shown in Figure 5.

Claims (4)

1. a kind of high-barrier zeins chitosan edible film and preparation method thereof, specific implementation step are as follows:
(1) 2g zeins is dissolved in 90%~95% ethanol solution of 100ml, mixing, 80 DEG C of water-baths is sufficiently stirred Middle heating stirring 20min is prepared into the film liquid that zeins mass percentage concentration is 2%；
(2) 2g chitosan is dissolved in 1% acetic acid solution of 100ml, heating stirring 20min in 80 DEG C of water-baths, preparation shelling is poly- The film liquid that sugared mass percentage concentration is 2%；
(3) by maize alcohol-soluble protein film liquid that step (1), (2) prepare and the chitosan film liquid for preparing by volume 1:1, 1:3,1:5 are uniformly mixed, and the plasticizer that mass percentage concentration is 1%, the uniform 20min of heating stirring in 80 DEG C of water-baths, system is added For at composite membrane liquid；
(4) the total mixed solution of 90~110mL that (3) prepare is poured on to the saturating benzene PS modeling of the dry tack free cleaning of 25cm × 25cm Expect in culture dish, casting film-forming, being subsequently placed in temperature is dry 5~6h in 50~60 DEG C of drying box, taken off after cooling film to get To high-barrier zeins chitosan edible film.
2. the preparation method of high-barrier zeins chitosan edible film according to claim 1, it is characterised in that: The product with a thickness of 0.04~0.07mm.
3. the preparation method of high-barrier zeins chitosan edible film according to claim 1, it is characterised in that: The plasticizer is glycerol.
4. the preparation method of high-barrier zeins chitosan edible film according to claim 1, it is characterised in that: Above-mentioned raw materials are food-grade.
CN201811309603.4A 2018-11-06 2018-11-06 A kind of high-barrier zeins chitosan edible film and preparation method thereof Pending CN109438776A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102964847A (en) * 2012-12-20 2013-03-13 青岛海尔软件有限公司 Protein/chitosan composite edible film and preparation method thereof
JP2014122184A (en) * 2012-12-21 2014-07-03 Nisshin Pharma Inc Chitosan-containing composition and chitosan coating composition
CN106957458A (en) * 2017-03-27 2017-07-18 广西大学 A kind of preparation method of natural complex fresh-keeping film or coating using chitosan zeins as raw material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102964847A (en) * 2012-12-20 2013-03-13 青岛海尔软件有限公司 Protein/chitosan composite edible film and preparation method thereof
JP2014122184A (en) * 2012-12-21 2014-07-03 Nisshin Pharma Inc Chitosan-containing composition and chitosan coating composition
CN106957458A (en) * 2017-03-27 2017-07-18 广西大学 A kind of preparation method of natural complex fresh-keeping film or coating using chitosan zeins as raw material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LIMING ZHANG等: ""Effect of ethanol content on rheology of film-forming solutions andproperties of zein/chitosan film"", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 *
LIMING ZHANG等: ""The properties of chitosan/zein blend film and effect of film on quality of mushroom (Agaricus bisporus)"", 《POSTHARVEST BIOLOGY AND TECHNOLOGY》 *
李梦琴等: ""玉米醇溶蛋白壳聚糖复合膜的制备"", 《中国食品学报》 *

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