CN105602261A - Method for improving thermal stability of fish skin gelatin film - Google Patents

Method for improving thermal stability of fish skin gelatin film Download PDF

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Publication number
CN105602261A
CN105602261A CN201610134320.5A CN201610134320A CN105602261A CN 105602261 A CN105602261 A CN 105602261A CN 201610134320 A CN201610134320 A CN 201610134320A CN 105602261 A CN105602261 A CN 105602261A
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gelatin
heat endurance
improves
film
gelatin film
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王稳航
高贵贤
张义
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/153—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of liquids or solids
    • A23B7/154—Organic compounds; Microorganisms; Enzymes
    • 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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • 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
    • C08J2389/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08J2389/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Microbiology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Dermatology (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention relates to a method for improving thermal stability of a fish skin gelatin film. The method includes the following steps that firstly, a cold fish skin gelatin solution, nano microcrystalline cellulose and glycerol are mixed to be prepared into a mixed solution; secondly, riboflavin is added in the mixed solution obtained in the first step; thirdly, the solution obtained in the second step is poured into an ultrasonic smasher to be subjected to ultrasonic smashing; fourthly, the solution obtained in the third step is poured on an acrylic flat plate and irradiated with an ultraviolet lamp; fifthly, the irradiated solution is dried and preserved at room temperature. The riboflavin is added, the thermal stability of the film is improved through an ultraviolet irradiation method, the method is easy and convenient and facilitates operation, the raw materials are non-toxic and free of pollution, and the thermal stability of the film can be well improved. The method is widely applied to the fields of food packaging and freshness retaining of casing for sausages and vegetables.

Description

A kind of method that improves fishskin gelatin film heat endurance
[technical field]
The invention belongs to food processing and packaging field, relate to fishskin gelatin film, especially a kind of raising fishskin gelatin film is thermally-stabilisedThe method of property.
[background technology]
Packaging industry goes from strength to strength in the development of China, and they have not only brought facility and benefit for people, due to these packagingsThe nondegradable characteristic of material, its discarded object causes increasing harm to human environment gradually. Therefore, exploitation environmental protectionGreen package becomes problem demanding prompt solution.
Edible film is a kind of environmentally friendly packing material, and it has edible characteristic, by preventing from affecting the material of food spoilageMigration ensures the quality of food, extends its shelf life. The edibility function that it is outstanding, can solve packaging waste effectivelyThe problem of polluting. Therefore, the Western European countries have abandoned plastics package once fashionable for a time gradually, the substitute is to degradePaper packaging bags and edible packaging bag. At the beginning of the nineties in last century, plastic packing bag has clearly been forbidden making in ItalyWith, Britain, the U.S. and Japan and other countries are all at exploitation edibility and degradable food product packing film, and oneself is through there being practical applicationAchievement. In recent years, along with China's expanding economy, China scientific worker is also to the edibility made from natural biologic materialPackaging material for food is studied.
The film of making as plasticizer taking glycerine etc. taking protein as matrix is as protein film. The gas barrier properties of albuminous membranae is more outstanding.Gelatin (Gelatin), structure and relative molecular weight are unfixing, by the collagen in the connective tissues such as animal skin, bone, sarolemma, flesh evil spiritPartial digestion and become white or faint yellow, micro-band gloss, translucent thin slice or powder; Be a kind of non-volatility, also colourlessTasteless, transparent hard AMAT, can be dissolved in hot water well, be not soluble in cold water, but slowly imbibition is softChange, gelatin can absorb and be equivalent to weight 5-10 water doubly. The most a kind of very important natural biological macromolecular material of gelatin,Be widely used in medicine, food and chemical industry. Herein according to these characteristics of gelatin using gelatin as making edible filmPrimary raw material. Isinglass film has caused a large amount of concerns with its unique advantage, and these advantages have following several: good one-tenthThe biologically active belongings that film ability, low water vapo(u)r transmission, good oxygen barrier, natural non-oxidizability are become reconciled. But,Compare fishskin gelatin film with animal gelatin film with other protein films and have very poor machinery, heat endurance and block-water performance. This may be withTheir amino acid composition, molecular weight distribution and rheological property are relevant. How to improve mechanical performance, heat endurance and water preventing ability,There is very large realistic meaning.
Cellulose nanocrystal (CNC), is also cellulose whiskers or nano microcrystalline fibre bundle (NCC), contains high crystal structure,Can from string, obtain. Acquisition that can be in many publications about the application of CNCs, for example, is receivingNano composite material field, CNCs be incorporated into bioabsorbable polymer material (as soybean protein, gelatin, shitosan, starch, fiberElement and cellulose derivative) in. In a research, bacteroidal nano micro crystal cellulose can improve the machinery of film significantlyPerformance. In another research, the nano micro crystal cellulose extracting from cotton thread is added in Tilapia mossambica gelatin film and can improve and drawStretch intensity and Young's modulus, but percentage elongation is impaired.
Photochemical crosslinking agent is the polymeric membrane method of a kind of effective improvement taking albumen as raw material. Since this object, sensitising agentAs b-carrotene, rose-bengal, ammoniated ruthenium oxychloride, Zn (II) N-alkylpyridylporpHyrins and ascorbate, these sensitising agentsCan be brought out by Uv and visible light. Riboflavin (riboflavin) is another kind of sensitising agent, and riboflavin is well-known water namelySoluble vitamin B2, is present in milk, egg and has the food of muscle or food and drink is mended as animals or humans exogenous nutritionFill in product. Riboflavin is the coenzyme of FMN flavin adenine dinucleotide, is the many redox reactions of catalysisMain component. Its main photoactivate structure is half heterocycle isoalloxazine, and maximum wavelength is 365 and 445nm, at visible ray or purpleUnder outer light radiation condition, riboflavin can play an active part in I type and the reaction of II type photosensitized oxidation, and in high molecular polymer, formation is expectedCrosslinked.
In photo-process, riboflavin absorption luminous energy is energized into the triplet state of very large activity, and then decline is to stable singlet.The riboflavin that is energized into triplet state produces active chalcogen, has the ability of the many large biological molecules of oxidation. By carrying electronics orCoupling proton translocation is in the amino acid side chain of tyrosine, histidine, tryptophan and cysteine in protein. Exist at oxygenSituation under, the oxygen that the triplet state of riboflavin can excited singlet1O2, then undertaken more by free radical and non-free radical reactionProfound oxidation reaction finally forms crosslinked that we expect in the network structure of polymer. Via1O2Free with otherThe mixture of base (as superoxide anion, riboflavin cation and radical anion), photoresponse is proceeded. Due to oxygenChange reaction, the formation of chemical bond that some are new, tyrosine forms dityrosine under OPK modification, this may be riboflavin withCollagen forms the reason of photochemical crosslinking.
By retrieval, not yet find that there is riboflavin and cellulose nanocrystal are joined and in isinglass film, improve its heat endurancePatent, open source literature report.
[summary of the invention]
The object of the invention is to overcome the weak point of current material, provide one to utilize light-sensitive material riboflavin to improve fish-skinThe method of the heat endurance of gelatin film.
The technical scheme that the present invention realizes object is as follows:
A method that improves fishskin gelatin film heat endurance, step is as follows:
(1) cold fishskin gelatin solution, nano micro crystal cellulose, glycerine are mixed and made into mixed liquor;
(2) in step (1) gained mixed liquor, add riboflavin;
(3) pour step (2) gained solution into ultrasonic disintegrator, Ultrasonic Pulverization;
(4) step (3) gained solution is poured on acrylic flat board, with ultra violet lamp;
(5) by room temperature dry, the preservation of postradiation solution.
And, described step (1) be by 10% cold fishskin gelatin solution mix 2% nano micro crystal cellulose disperse to make 10%,The new soln of w/w based on gelatin, then add 30%, the glycerine of w/w based on gelatin.
And the content of protein is 8% in described fishskin gelatin film.
And described nano micro crystal cellulose is plant cellulose, its addition is that 2%, w/w is based on gelatin.
And the addition of described step (2) riboflavin is that 0～0.5%, w/w is based on gelatin.
And the Ultrasonic Pulverization of described step (3) is to adopt pulse mode with power work 10～20s of 60～70%.
And, described step (4) ultra violet lamp be with uviol lamp at 350～370nm wavelength illumination, 20～30min, uviol lamp fromFilm 200～300mm.
And described step (5) is to be first at room temperature dried 24～48h, then film is taken off and is placed on drier from acrylic board,Regulate 20 ± 2 DEG C of dryer temperature, humidity 50 ± 5% to preserve 5～10d. Dry and the preservation of film will be under dark environment.
The invention still further relates to a kind of fishskin gelatin film of preparing according to said method in bowel lavage casing, packaging for foodstuff, fresh-keeping of vegetablesApplication.
The present invention utilizes ultraviolet irradiation to add the fishskin gelatin solution of riboflavin, and photosensitive material riboflavin and gelatin are handed overConnection reaction improves the heat endurance of film. Its principle is that riboflavin can play an active part in I type under visible ray or ultraviolet radiation conditionWith the reaction of II type photosensitized oxidation, in high molecular polymer, form expect crosslinked.
Advantage of the present invention and good effect are as follows:
1, the present invention utilizes and adds riboflavin and improve the heat endurance of film by ultraviolet irradiation, ultraviolet irradiation technology simply, easy behaviourDo, can popularize well.
2, the present invention's riboflavin used is a kind of natural complex, nontoxic and be the trace element useful to people.
3, the present invention can improve the heat endurance of edible film, and edible film is had to very large potential value in the application of packaging field heat sealability.
Brief description of the drawings
Fig. 1 is the curve map that melting temperature changes with riboflavin addition;
Fig. 2 is the curve map that maximum decomposition temperature changes with riboflavin addition.
[detailed description of the invention]
Below in conjunction with embodiment, technology contents of the present invention is described further; Following embodiment is illustrative, is not to limitProperty, can not limit protection scope of the present invention with following embodiment.
Embodiment 1:
10% cold fishskin gelatin solution is mixed to 2% nano micro crystal cellulose (NCC) (w/w, based on gelatin) to be disperseed to make 10%New soln, then add the glycerine of 30% (w/w, based on gelatin). Then, riboflavin adds with the concentration of 0% (w/w, based on gelatin)Enter solution. Mixture with aQ1375 ultrasonic disintegrator at pulse mode with 60% power (3s opens with 5s and closes) work 15s.Gelatin solution is poured acrylic flat board (13cm × 13cm) into, then uses uviol lamp (UVP, B-100AP, USA) at 365nm rippleThe long 30min that irradiates, uviol lamp is from film 250mm. With the at room temperature dry 24h of solution irradiating, film is taken off from acrylic boardBe placed in drier (20 ± 2 DEG C, RH50 ± 5%) and preserve, film will be put 7d before analysis in drier. Dry and the guarantor of filmDepositing will be under dark environment. Melting temperature is now 53.7 DEG C, and maximum decomposition temperature is 301 DEG C.
Embodiment 2:
Different from enforcement 1, riboflavin adds solution with the concentration of 0.05% (w/w, based on gelatin). Melting temperature is now55.4 DEG C, maximum decomposition temperature is 307 DEG C.
Embodiment 3:
Different from enforcement 1, riboflavin adds solution with the concentration of 0.1% (w/w, based on gelatin). Melting temperature is now55.9 DEG C, maximum decomposition temperature is 312 DEG C.
Embodiment 4:
Different from enforcement 1, riboflavin adds solution with the concentration of 0.2% (w/w, based on gelatin). Melting temperature is now56.4 DEG C, maximum decomposition temperature is 313 DEG C.
Embodiment 5:
Different from enforcement 1, riboflavin adds solution with the concentration of 0.5% (w/w, based on gelatin). Melting temperature is now67.8 DEG C, maximum decomposition temperature is 307 DEG C.

Claims (10)

1. a method that improves fishskin gelatin film heat endurance, is characterized in that: step is as follows:
(1) cold fishskin gelatin solution, nano micro crystal cellulose, glycerine are mixed and made into mixed liquor;
(2) in step (1) gained mixed liquor, add riboflavin;
(3) pour step (2) gained solution into ultrasonic disintegrator, Ultrasonic Pulverization;
(4) step (3) gained solution is poured on acrylic flat board, with ultra violet lamp;
(5) by room temperature dry, the preservation of postradiation solution.
2. the method for raising fishskin gelatin film heat endurance according to claim 1, is characterized in that: described step (1)Be by 10% cold fishskin gelatin solution and 2% nano micro crystal cellulose, w/w based on gelatin, be mixed and made into 10% new soln,Add again 30%, the glycerine of w/w based on gelatin.
3. a kind of method that improves fishskin gelatin film heat endurance according to claim 1, is characterized in that: described fish-skinIn gelatin film, the content of protein is 8%.
4. a kind of method that improves fishskin gelatin film heat endurance according to claim 1, is characterized in that: described receivesRice microcrystalline cellulose is plant cellulose, and its addition is that 2%, w/w is based on gelatin.
5. a kind of method that improves fishskin gelatin film heat endurance according to claim 1, is characterized in that: described step(2) addition of riboflavin is that 0～0.5%, w/w is based on gelatin.
6. a kind of method that improves fishskin gelatin film heat endurance according to claim 1, is characterized in that: described step(3) Ultrasonic Pulverization is to adopt pulse mode with power work 10～20s of 60～70%.
7. a kind of method that improves fishskin gelatin film heat endurance according to claim 1, is characterized in that: described step(4) ultra violet lamp is to use uviol lamp at 350～370nm wavelength illumination, 20～30min, and uviol lamp is from film 200～300mm.
8. a kind of method that improves fishskin gelatin film heat endurance according to claim 1, is characterized in that: described step(5) be to be first at room temperature dried 24～48h, then film taken off and is placed on drier from acrylic board, adjusting dryer temperature 20 ±2 DEG C, humidity 50 ± 5% preservation 5～10d.
9. a kind of method that improves fishskin gelatin film heat endurance according to claim 8, is characterized in that: film dryWith preserve will be under dark environment.
10. the fishskin gelatin film that according to claim 1 prepared by method is at bowel lavage casing, packaging for foodstuff, fresh-keeping of vegetablesIn application.
CN201610134320.5A 2016-03-08 2016-03-08 Method for improving thermal stability of fish skin gelatin film Pending CN105602261A (en)

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN106832366A (en) * 2017-01-24 2017-06-13 集美大学 The preparation method of food-grade albumen film
CN107691638A (en) * 2017-10-31 2018-02-16 广西浙缘农业科技有限公司 A kind of store method of blue or green jujube
CN108997760A (en) * 2018-09-04 2018-12-14 青海民族大学 A kind of microcrystalline cellulose synthesized thin film and preparation method thereof
CN109369961A (en) * 2018-10-16 2019-02-22 河南工程学院 A kind of nano-cellulose based film material and preparation method thereof of polypeptide enhancing
CN112679759A (en) * 2020-11-09 2021-04-20 康膝生物医疗(深圳)有限公司 In-situ crosslinking gel forming method for degradable protein
CN113150342A (en) * 2021-05-20 2021-07-23 南京工业大学 Photo-crosslinked chitosan-riboflavin edible film and preparation method thereof
US20220007692A1 (en) * 2020-07-13 2022-01-13 William Marsh Rice University Poly-albumen based green coating to enhance shelf life of perishable foods
CN114982917A (en) * 2022-06-13 2022-09-02 福建御味香冷冻食品有限公司 Preparation method for prolonging shelf life of roasted sausage
CN115286932A (en) * 2022-08-02 2022-11-04 浙江农林大学 Edible high-strength biomass material, preparation method thereof and biomass film

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106832366A (en) * 2017-01-24 2017-06-13 集美大学 The preparation method of food-grade albumen film
CN106832366B (en) * 2017-01-24 2020-05-12 集美大学 Preparation method of food-grade protein film
CN107691638A (en) * 2017-10-31 2018-02-16 广西浙缘农业科技有限公司 A kind of store method of blue or green jujube
CN108997760A (en) * 2018-09-04 2018-12-14 青海民族大学 A kind of microcrystalline cellulose synthesized thin film and preparation method thereof
CN109369961A (en) * 2018-10-16 2019-02-22 河南工程学院 A kind of nano-cellulose based film material and preparation method thereof of polypeptide enhancing
CN109369961B (en) * 2018-10-16 2020-11-20 河南工程学院 Polypeptide-enhanced nanocellulose-based thin film material and preparation method thereof
US20220007692A1 (en) * 2020-07-13 2022-01-13 William Marsh Rice University Poly-albumen based green coating to enhance shelf life of perishable foods
CN112679759A (en) * 2020-11-09 2021-04-20 康膝生物医疗(深圳)有限公司 In-situ crosslinking gel forming method for degradable protein
CN113150342A (en) * 2021-05-20 2021-07-23 南京工业大学 Photo-crosslinked chitosan-riboflavin edible film and preparation method thereof
CN114982917A (en) * 2022-06-13 2022-09-02 福建御味香冷冻食品有限公司 Preparation method for prolonging shelf life of roasted sausage
CN114982917B (en) * 2022-06-13 2023-07-18 福建御味香冷冻食品有限公司 Preparation method for prolonging shelf life of roast sausage
CN115286932A (en) * 2022-08-02 2022-11-04 浙江农林大学 Edible high-strength biomass material, preparation method thereof and biomass film

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Application publication date: 20160525