CN105176102A - Water-soluble casein membrane and preparing technology thereof - Google Patents
Water-soluble casein membrane and preparing technology thereof Download PDFInfo
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- CN105176102A CN105176102A CN201510614949.5A CN201510614949A CN105176102A CN 105176102 A CN105176102 A CN 105176102A CN 201510614949 A CN201510614949 A CN 201510614949A CN 105176102 A CN105176102 A CN 105176102A
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- 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
Abstract
The invention discloses a water-soluble casein membrane and a preparing technology thereof and aims at providing a novel water-soluble casein membrane and a preparing method thereof. The novel water-soluble casein membrane is prepared in the way that casein serves as a raw material, succinic anhydride serves as a modifier, and gelatin and glycerin serve as addition agents. The modifier succinic anhydride is small in toxic and side effect and remarkable in modifying effect, the carboxyl content of succinylation casein is remarkably increased, and the dissolving property and other processing characteristics of the casein are remarkably improved. The succinylation casein is used for preparing the casein membrane, sources of the raw materials are wide, safety performance is high, the technology is environmentally friendly, the prepared membrane can be easily dissolved in water, biological degradability is achieved, the environment-friendly performance of the casein membrane is remarkably improved, and the requirement of people for the degradable coating membrane is met. The novel water-soluble casein membrane is high in transparence, good in pull-up strength, high in water solubility, good in oil resistance and capable of meeting the coating requirement of the industry for the coating membrane. The novel water-soluble casein membrane is moderate in preparing condition and simple in technology, the preparing process is easy to control, and the novel water-soluble casein membrane is suitable for industrialized production and popularization.
Description
Technical field
The invention belongs to wrapping material field, is a kind of new type water-solubility casein coating film, be a kind of is specifically modified formulation with succinyl oxide, take casein as the new type water-solubility casein film of raw material production; The invention still further relates to a kind of preparation technology of water-soluble casein film.
Background technology
Along with the enhancing of socioeconomic development and people's environmental consciousness, the serious ecological problem that chemosynthesis wrapping material cause and food-safety problem are subject to people's attention day by day.Especially plastic wrapping usage quantity is huge, stable chemical nature, and be difficult to degraded, its waste pollution has become worldwide the difficult problem of environmental protection.In addition, the chemical composition in Plastic Packaging Materials also can be moved in Food storage process in food, brings secondary pollution to food, reduces the edible safety of food.Edible eggs tunica albuginea, because of the film homogeneous transparent formed, has good mechanical property, can degrade at occurring in nature, environmentally safe, have edible and digestibility, safety, and the advantage such as have no side effect.Therefore, to food and environmental nonpollution, and the protein film with property has become the study hotspot of packaging material for food.At present, domestic main direction of studying concentrates on vegetable protein is research and development and the property Quality Research that raw material (as zein, soybean protein, Phaseolus legume protein etc.) carries out associated protein membrane process.In recent years also occurred with albumen, whey-protein etc. for the correlative study of protein film prepared by material, and be aided with relevant treatment process and modification, optimization means, made this field development.
Casein is the natural protein that a kind of nutritive value is higher, its wide material sources, and processing mode is simple, is a kind of protein film starting material preferably.Because common casein film is crisp and frangible, the character such as stretchiness, ductility, water-soluble, saturating oiliness is not good, and modification casein film has the incomparable superiority of general proteins film.For different industrial requirements; to casein structures and characteristics in addition appropriateness improve and modify (as crosslinked in succinylation, acetylize, enzyme etc.); and prepared and develop become a kind of novel protein film make material; by certain technological process, prepare novel, there is property and the higher casein film of industrialization potential.There is no this type of industrialization, mass-producing product at present.
Summary of the invention
The object of the present invention is to provide a kind of novel water-soluble, degradable casein film, current protein film be crisp and frangible to solve, poorly water-soluble, thoroughly oiliness are high, the easy problem such as putrid and deteriorated.
Another object of the present invention is to provide a kind of above-mentioned water-soluble casein film production method.
For achieving the above object, the technical solution adopted in the present invention is: a kind of water-soluble casein film, and with acidylate casein for raw material, this Novel egg tunica albuginea is prepared from the steps below:
(1) milk casein is dissolved in deionized water by the feed liquid mass ratio of 1:50 ~ 1:150, stirs until casein dissolves completely at 35 ~ 45 DEG C, and pass through 1.0molL
-1sodium hydroxide solution adjust ph make it stabilize to 6.5 ~ 7.5, obtain casein solution, pass through 1.0molL
-1sodium hydroxide solution regulate the pH value of described casein solution to be 8.0 ~ 9.5; the ratio being 0.4 ~ 0.8:1 with succinyl oxide and caseic mass ratio several times adds solid succinyl oxide; stir under 40 ~ 50 DEG C of constant temperature and carry out acylation reaction; described succinyl oxide all adds rear continuation stirring 30 ~ 50min; it is made fully to react; obtain the casein solution after acidylate, adopt 1.0molL
-1hydrochloric acid soln adjustment acidylate after casein solution pH value to iso-electric point, make casein precipitate, in 3000 ~ 4000g centrifugal force, 20 ~ 40min; abandoning supernatant; be precipitated thing, this throw out to constant weight, obtains Powdered acidylate Casilan through lyophilize.
(2) by acidylate casein and water 7 ~ 9:100 mixing in mass ratio, and 1.0molL is passed through
-1sodium hydroxide solution adjust ph make it stabilize to 7.0 ~ 8.0, in 55 ~ 60 DEG C of water bath with thermostatic control, be constantly stirred to acidylate casein particle dissolve completely, obtain acidylate casein solution;
(3) by gelatin and water 11 ~ 9:100 mixing in mass ratio, in 55 ~ 60 DEG C of waters bath with thermostatic control, be constantly stirred to gelatin dissolve completely, obtain gelatin solution;
(4) ratio of described acidylate casein solution and gelatin solution 75:25 ~ 65:35 is in mass ratio mixed; drip 100 ~ 300 μ L glycerine; stir; raised temperature to 80 ~ 90 DEG C; concentrated 15 ~ 20min, stops heating, draws mixed solution and applies on masking plate; take off film after 6 ~ 8h, obtain protein film.
The present invention has following technique effect:
1, the present invention with casein and goods thereof for raw material; take succinyl oxide as modified formulation, preparation acidylate casein, overcomes the technical problem of the functional property differences such as natural caseiBl solvability, ductility; improve caseic processibility, expand its range of application.
2, the present invention with the casein of succinylation for protein film that raw material is obtained have transparency high, draw high the various features such as intensity is good, soluble in water, oil resistance is good, raw material sources are extensive, high safety, degradable, technique green is easy, the requirement of industry to coating film can be met.
3, preparation method's reaction conditions of a kind of water-soluble casein film of the present invention is gentle, and reaction process easily controls, and technique is simple, reduces energy consumption, has saved production cost.
Embodiment
Below in conjunction with specific embodiment to the detailed description of the invention.
embodiment 1
Take 5.0g casein, be dissolved in 500mL deionized water, at 40 DEG C, constant temperature stirs, and uses 1.0molL
-1sodium hydroxide solution constantly adjusts pH makes it be stabilized in 6.5.After stir about 1h, casein dissolves completely, both obtains casein solution, for subsequent use.Drip 1.0molL
-1sodium hydroxide solution regulates above-mentioned pH value of solution to be 8.0, and at 40 DEG C, constant temperature stirs, and divides and adds 2.0g succinyl oxide three times.1.0molL is used after adding
-1sodium hydroxide solution constantly regulates casein solution pH to make it be stabilized in 8.0 until acid anhydrides dissolves completely, continues to stir 50min, both obtains acidylate casein solution.Drip 1.0molL
-1hydrochloric acid soln also constantly stirs, until casein precipitate is separated out in a large number.Solution is placed in centrifuge tube, and in the centrifugal 40min of 3000g, abandoning supernatant, is placed in freeze drier teel pallet by precipitation, and in-50 DEG C, pressure is lyophilize under the condition of 500Pa, obtains Powdered acidylate Casilan after about 24h.
Take 3.5g acidylate casein, add the mixing of 50mL water, and pass through 1.0molL
-1sodium hydroxide solution adjust ph make it stabilize to 7.0, in 55 DEG C of water bath with thermostatic control, be constantly stirred to acidylate casein particle dissolve completely, obtain acidylate casein solution;
Take 5.5g gelatin, add the mixing of 50mL water, in 55 DEG C of waters bath with thermostatic control, be constantly stirred to gelatin dissolve completely, obtain gelatin solution;
Described acidylate casein solution mixed by 65:35 with gelatin solution, drip 100 μ L glycerine, stir, raised temperature to 80 DEG C, concentrated 15min, stops heating, draws mixed solution and applies on masking plate, take off film, obtain casein film finished product after 8h; Gained casein film is complete, bubble-free, smooth surface, and thickness is even, has gloss.
Get the rectangle square piece that the cutting of finished product casein film becomes 30mm × 30mm, surface is dripped appropriate vegetables oil or is measured its saturating oiliness and solvability after being immersed in the water 24h; Casein film is cut out the rectangle into 10cm × 2cm, utilizes tensiometer to measure film tensile strength and elongation; Vernier callipers is adopted to measure film thickness; The cutting of casein film is become the rectangle square piece of 1cm × 2.5cm, be affixed on cuvette inwall, under 480nm wavelength, adopt ultraviolet-visible spectrophotometer to measure its absorbancy;
After measured, oil penetrating rate=0% of this protein film; Water dissolution rate=100%; Tensile strength=6.16N; Stretching displacement=5.8mm; Average elongation=5.30%; Thickness≤1mm; Absorbance A=0.078.
embodiment 2
Take 5.0g casein, be dissolved in 500mL deionized water, at 40 DEG C, constant temperature stirs, and uses 1.0molL
-1sodium hydroxide solution constantly adjusts pH makes it be stabilized in 6.5.After stir about 1h, casein dissolves completely, both obtains casein solution, for subsequent use.Drip 1.0molL
-1sodium hydroxide solution regulates above-mentioned pH value of solution to be 8.0, and at 40 DEG C, constant temperature stirs, and divides and adds 2.0g succinyl oxide three times.1.0molL is used after adding
-1sodium hydroxide solution constantly regulates casein solution pH to make it be stabilized in 8.0 until acid anhydrides dissolves completely, continues to stir 50min, both obtains acidylate casein solution.Drip 1.0molL
-1hydrochloric acid soln also constantly stirs, until casein precipitate is separated out in a large number.Solution is placed in centrifuge tube, and in the centrifugal 30min of 3500g, abandoning supernatant, is placed in freeze drier teel pallet by precipitation, and in-50 DEG C, pressure is lyophilize under the condition of 500Pa, obtains Powdered acidylate Casilan after about 24h.
Take 4.0g acidylate casein, add the mixing of 50mL water, and pass through 1.0molL
-1sodium hydroxide solution adjust ph make it stabilize to 7.5, in 58 DEG C of water bath with thermostatic control, be constantly stirred to acidylate casein particle dissolve completely, obtain acidylate casein solution;
Take 5.0g gelatin, add the mixing of 50mL water, in 58 DEG C of waters bath with thermostatic control, be constantly stirred to gelatin dissolve completely, obtain gelatin solution;
Described acidylate casein solution mixed by 70:30 with gelatin solution, drip 200 μ L glycerine, stir, raised temperature to 85 DEG C, concentrated 18min, stops heating, draws mixed solution and applies on masking plate, take off film, obtain casein film finished product after 7h; Gained casein film is complete, bubble-free, smooth surface, and thickness is even, has gloss.
Get the rectangle square piece that the cutting of finished product casein film becomes 30mm × 30mm, surface is dripped appropriate vegetables oil or is measured its saturating oiliness and solvability after being immersed in the water 24h; Casein film is cut out the rectangle into 10cm × 2cm, utilizes tensiometer to measure film tensile strength and elongation; Vernier callipers is adopted to measure film thickness; The cutting of casein film is become the rectangle square piece of 1cm × 2.5cm, be affixed on cuvette inwall, under 480nm wavelength, adopt ultraviolet-visible spectrophotometer to measure its absorbancy;
After measured, oil penetrating rate=0% of this protein film; Water dissolution rate=100%; Tensile strength=6.22N; Stretching displacement=5.6mm; Average elongation=5.26%; Thickness≤1mm; Absorbancy is 0.072.
embodiment 3
Take 5.0g casein, be dissolved in 500mL deionized water, at 40 DEG C, constant temperature stirs, and uses 1.0molL
-1sodium hydroxide solution constantly adjusts pH makes it be stabilized in 6.5.After stir about 1h, casein dissolves completely, both obtains casein solution, for subsequent use.Drip 1.0molL
-1sodium hydroxide solution regulates above-mentioned pH value of solution to be 8.0, and at 40 DEG C, constant temperature stirs, and divides and adds 2.0g succinyl oxide three times.1.0molL is used after adding
-1sodium hydroxide solution constantly regulates casein solution pH to make it be stabilized in 8.0 until acid anhydrides dissolves completely, continues to stir 50min, both obtains acidylate casein solution.Drip 1.0molL
-1hydrochloric acid soln also constantly stirs, until casein precipitate is separated out in a large number.Solution is placed in centrifuge tube, and in the centrifugal 20min of 4000g, abandoning supernatant, is placed in freeze drier teel pallet by precipitation, and in-50 DEG C, pressure is lyophilize under the condition of 500Pa, obtains Powdered acidylate Casilan after about 24h.
Take 4.5g acidylate casein, add the mixing of 50mL water, and pass through 1.0molL
-1sodium hydroxide solution adjust ph make it stabilize to 8.0, in 60 DEG C of water bath with thermostatic control, be constantly stirred to acidylate casein particle dissolve completely, obtain acidylate casein solution;
Take 4.5g gelatin, add the mixing of 50mL water, in 60 DEG C of waters bath with thermostatic control, be constantly stirred to acidylate casein particle dissolve completely, obtain gelatin solution;
Described acidylate casein solution mixed by 75:25 with gelatin solution, drip 300 μ L glycerine, stir, raised temperature to 90 DEG C, concentrated 20min, stops heating, draws mixed solution and applies on masking plate, take off film, obtain protein film finished product after 6h; Gained casein film is complete, bubble-free, smooth surface, and thickness is even, has gloss.
Get the rectangle square piece that the cutting of finished product casein film becomes 30mm × 30mm, surface is dripped appropriate vegetables oil or is measured its saturating oiliness and solvability after being immersed in the water 24h; Casein film is cut out the rectangle into 10cm × 2cm, utilizes tensiometer to measure film tensile strength and elongation; Vernier callipers is adopted to measure film thickness; The cutting of casein film is become the rectangle square piece of 1cm × 2.5cm, be affixed on cuvette inwall, under 480nm wavelength, adopt ultraviolet-visible spectrophotometer to measure its absorbancy;
After measured, oil penetrating rate=0% of this protein film; Water dissolution rate=100%; Tensile strength=6.28N; Stretching displacement=5.2mm; Average elongation=5.18%; Thickness≤1mm; Absorbancy is 0.070.
Although carried out special description with reference to embodiment to the disclosed a kind of water-soluble casein film and preparation method thereof that relates to, embodiment described above is illustrative and not restrictive, without departing from the spirit and scope of the present invention, all changes and amendment are all within the scope of the present invention.
Claims (2)
1. water-soluble casein film and a preparation technology thereof, with acidylate casein for raw material, is characterized in that, this water-soluble casein film is prepared from according to following step:
Step 1: be dissolved in deionized water by the feed liquid mass ratio of 1:50 ~ 1:150 by milk casein, stirs until casein dissolves completely at 35 ~ 45 DEG C, and passes through 1.0molL
-1sodium hydroxide solution adjust ph make it stabilize to 6.5 ~ 7.5, obtain casein solution, pass through 1.0molL
-1sodium hydroxide solution regulate the pH value of described casein solution to be 8.0 ~ 9.5; the ratio being 0.4 ~ 0.8:1 with succinyl oxide and caseic mass ratio several times adds solid succinyl oxide; stir under 40 ~ 50 DEG C of constant temperature and carry out acylation reaction; and described succinyl oxide all adds rear continuation stirring 30 ~ 50min; it is made fully to react; obtain the casein solution after acidylate, adopt 1.0molL
-1hydrochloric acid soln adjustment acidylate after casein solution pH value to iso-electric point, make casein precipitate, in 3000 ~ 4000g centrifugal force, 20 ~ 40min, abandoning supernatant, be precipitated thing, this throw out to constant weight, obtains Powdered acidylate Casilan through lyophilize;
Step 2: by acidylate casein and water 7 ~ 9:100 mixing in mass ratio, and pass through 1.0molL
-1sodium hydroxide solution adjust ph make it stabilize to 7.0 ~ 8.0, in 55 ~ 60 DEG C of water bath with thermostatic control, be constantly stirred to acidylate casein particle dissolve completely, obtain acidylate casein solution;
Step 3: by gelatin and water 11 ~ 9:100 mixing in mass ratio, be constantly stirred to gelatin and dissolve completely in 55 ~ 60 DEG C of waters bath with thermostatic control, obtain gelatin solution;
Step 4: the ratio of described acidylate casein solution and gelatin solution 75:25 ~ 65:35 is in mass ratio mixed; drip 100 ~ 300 μ L glycerine; stir; raised temperature to 80 ~ 90 DEG C; concentrated 15 ~ 20min, stops heating, draws mixed solution and applies on masking plate; take off film after 6 ~ 8h, obtain casein film.
2. a kind of Novel egg tunica albuginea and preparation technology thereof according to claim 1, is characterized in that, in described step 1, milk casein can be commercially available casein food grade, self-control Acid precipitation casein, enzyme coagulate the Casilan such as casein, sodium-caseinate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105802253A (en) * | 2016-04-29 | 2016-07-27 | 江南大学 | Preparation method of edible enzyme modified egg white film |
| CN106174440A (en) * | 2016-07-05 | 2016-12-07 | 南昌大学 | A kind of preparation method of polymolecular layer controlled nutrient slow release nanometer curdling glue |
| WO2018035402A1 (en) * | 2016-08-19 | 2018-02-22 | The United States Of America, As Represented By The Secretary Of Agriculture | Alkaline ph-modified edible casein-based films and coatings, and method for the making thereof |
| CN109401339A (en) * | 2018-11-02 | 2019-03-01 | 南京财经大学 | A kind of preparation and application of the acylated rapeseed protein film of edibility |
| CN110878172A (en) * | 2018-09-05 | 2020-03-13 | 周维 | Edible gelatin sodium caseinate film and preparation method thereof |
| CN112194798A (en) * | 2020-10-21 | 2021-01-08 | 深圳大洲医学科技有限公司 | Modification method of gelatin |
| WO2022269196A1 (en) * | 2021-06-23 | 2022-12-29 | Lactips | Biodegradable thermoplastic film based on casein and/or caseinate and gelatin |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105802253A (en) * | 2016-04-29 | 2016-07-27 | 江南大学 | Preparation method of edible enzyme modified egg white film |
| CN106174440A (en) * | 2016-07-05 | 2016-12-07 | 南昌大学 | A kind of preparation method of polymolecular layer controlled nutrient slow release nanometer curdling glue |
| CN106174440B (en) * | 2016-07-05 | 2019-05-24 | 南昌大学 | A kind of preparation method of the controllable nutrients slow release nanometer curdling glue of polymolecular layer |
| WO2018035402A1 (en) * | 2016-08-19 | 2018-02-22 | The United States Of America, As Represented By The Secretary Of Agriculture | Alkaline ph-modified edible casein-based films and coatings, and method for the making thereof |
| US10906950B2 (en) | 2016-08-19 | 2021-02-02 | The United States Of America As Represented By The Secretary Of Agriculture | Alkaline pH-modified edible casein-based films and coatings, and method for the making thereof |
| CN110878172A (en) * | 2018-09-05 | 2020-03-13 | 周维 | Edible gelatin sodium caseinate film and preparation method thereof |
| CN109401339A (en) * | 2018-11-02 | 2019-03-01 | 南京财经大学 | A kind of preparation and application of the acylated rapeseed protein film of edibility |
| CN112194798A (en) * | 2020-10-21 | 2021-01-08 | 深圳大洲医学科技有限公司 | Modification method of gelatin |
| WO2022269196A1 (en) * | 2021-06-23 | 2022-12-29 | Lactips | Biodegradable thermoplastic film based on casein and/or caseinate and gelatin |
| FR3124511A1 (en) * | 2021-06-23 | 2022-12-30 | Lactips | Biodegradable thermoplastic film based on casein and/or caseinate and gelatin |
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Application publication date: 20151223 |