CN109957130A - Edible Unidirectional water permeable polymeric membrane and preparation method thereof - Google Patents
Edible Unidirectional water permeable polymeric membrane and preparation method thereof Download PDFInfo
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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
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- C08J5/18—Manufacture of films or sheets
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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Abstract
The invention discloses a kind of edible Unidirectional water permeable polymeric membranes and preparation method thereof, belong to high molecular material and food packaging applications.Solves the problems such as existing packaging film non-degradable, shelf-life is short, it is made of hydrophobic outer film and internal layer hydrophilic film, and internal layer hydrophilic film is by 1-4 parts of gelatin, 1.2-3.6 parts of Kappa-Carraginan, 0.08-0.2 parts of curcumin, 0.6-3.8 parts of glycerol and ethyl alcohol and deionized water form.Specific steps: water swelling in deionized water is added in gelatin, Kappa-Carraginan is added to stir to obtain solution A；Curcumin is dissolved in after ethyl alcohol, simultaneously glycerol adding stirring in solution A is added, adjusted pH value of solution to neutrality, this solution is poured on obtained by drying to hydrophilic film on tetrafluoroethene plate；Stirring and dissolving in ethyl alcohol is added in zeins, glycerol is added and stirs to obtain hydrophobic coating solution；Hydrophobic coating solution is uniformly coated in hydrophilic film and is drying to obtain the product.The present invention can be used for preparing the packaging film of aquatic products.
Description
Technical field
The present invention relates to a kind of edible Unidirectional water permeable polymeric membranes and preparation method thereof, belong to high molecular material and food packet
Dress field.
Background technique
In recent years, as consumer more and more pays close attention to health problem relevant to meat products, to Aquatic products consumption
Amount increased.Aquatic products are the good source of plain boiled pork, due to its high protein, low fat, especially low cholesterol and by disappearing
The person of expense welcomes.But due to aquatic products not storage endurance and the shelf-life it is short, and cold chain transportation expense is high.It is generally only to have very much
It is commercialized in the market bounds of limit as raw material.
Polyethylene is a kind of material based on petroleum, has been widely used for food packaging, but since it biological can not be dropped
The characteristic of solution has caused serious environmental problem.Since packaging material is directly contacted with food, it is necessary to meet non-toxicity requirements；Cause
This, develops a kind of new aquatic products packaging, can biology using natural polymer and the industry byproduct manufacture of renewable resource
It is imperative to substitute traditional plastics package for the packaging material of degradation.
Summary of the invention
The purpose of the present invention is to provide a kind of edible Unidirectional water permeable polymeric membrane, there is Unidirectional water permeable, moisture-proof, degradable
The features such as.
The present invention additionally provides a kind of preparation method of edible Unidirectional water permeable polymeric membrane simultaneously.
The edible Unidirectional water permeable polymeric membrane, is made of hydrophobic outer film and internal layer hydrophilic film, the internal layer parent
Moisture film is made of the raw material of following parts by weight: 1-4 parts of gelatin, 1.2-3.6 parts of Kappa-Carraginan, and 0.08-0.2 parts of curcumin, glycerol
0.6-3.8 parts, mass fraction is 20 parts of ethanol solution, 165-180 parts of deionized water of 95%.
Further speaking, the hydrophobic outer film is made of the raw material of following parts by weight: 8-20 parts of zeins,
Mass fraction is 20 parts of ethanol solution, 3.2-8 parts of glycerol of 85%.
Further speaking, the molecular weight of the gelatin is greater than 300kd, and the molecular weight of Kappa-Carraginan is greater than 200,000, corn alcohol
The molecular weight of molten albumen is 25000-45000.
Further speaking, the mass fraction of curcumin is greater than 95% in the curcumin.
The preparation method of the edible Unidirectional water permeable polymeric membrane, comprising the following steps:
Stirring in deionized water, which is added, in gelatin makes gelatin water swelling, and Kappa-Carraginan is then added and stirs 25-40min,
Obtain solution A；Curcumin is dissolved in the ethanol solution that mass fraction is 95%, then this solution is added in solution A, and is added
Glycerol stirs 10-20min, adjusts pH value of solution to 6.8-7.5 to get hydrophilic coating solution is arrived, this solution is then poured on tetrafluoro second
It is obtained by drying on alkene plate to arrive hydrophilic film；
Zeins is added in the ethanol solution that mass fraction is 85% and is stirred under the conditions of 70-90 DEG C molten
20-40min is solved, continues stirring 5-12min after addition glycerol and obtains hydrophobic membrane solution；
Hydrophobic coating solution is uniformly coated in hydrophilic film after drying and obtains edible Unidirectional water permeable polymeric membrane.
Further speaking, the deionized water is added in two portions, and is used for gelatin water swelling for the first time, is being added for the second time
It is added after glycerol, the ratio being added twice is 1:1-1.5.
It further speaking, is 40-50 DEG C for the temperature of the deionized water of gelatin water swelling.
Further speaking, the hydrophilic coating solution is that preparation is reacted under the conditions of 70-90 DEG C.
Further speaking, the hydrochloric acid solution that hydrophilic film pH value of solution uses 2mol/L is adjusted.
Further speaking, the drying temperature of the hydrophilic film is 35-50 DEG C, drying time 3-5h.
Compared with prior art the beneficial effects of the present invention are:
The edible Unidirectional water permeable polymeric membrane of the present invention is made of hydrophobic outer film and internal layer hydrophilic film, and moisture is only capable of from hydrophobic
Layer is penetrated to hydrophilic layer, and cannot be penetrated from hydrophilic layer to hydrophobic layer, and the moisture that can effectively completely cut off in air plays well
Moisture-proof effect.The effect for also having both sustained release simultaneously, improves the anti-oxidant and bacteriostasis efficacy of food, can effectively extend food
Shelf life.
Internal layer hydrophilic film of the present invention is added with curcumin, can be used as intelligent indicator, curcumin can be sent out under alkaline condition
The conjugation that raw electron cloud deviates, pH will become red when being greater than 8；The alkalinity such as volatile amine can be generated when food apoilage
Gas can be such that food pH value increases, therefore we can use the freshness of the color change detection food of curcumin, and prompting disappears
Whether expense person's meat products, which is further adapted for, eats.
The hydrophobic membrane of zeins has the effect of sustained release, can extend the anti-oxidant and antibiotic effect of curcumin, and
And influence of the outer moisture to aquatic products can be effectively reduced, the intelligent measurement of external environmental interference curcumin can also be prevented.
Gelatin is made of the processing waste fish-skin of fish, and Kappa-Carraginan is by extracting in marine polysaccharide red algae, and corn alcohol is molten
Albumen be made of corn be a kind of edibility hydrophobic material, curcumin is a kind of common natural additive for foodstuff.These materials
Material is all with having green, and safety, free of contamination advantage especially can natural decomposition.Furthermore they are cheap, and source is wide
It is general, and filming performance is excellent.
The preparation method of the edible Unidirectional water permeable polymeric membrane of the present invention is simple, and in faint yellow, appearance is saturating for the packaging film of preparation
It is bright, have mechanical strength and flexibility good, completely cuts off the features such as vapor ability is strong.
The present invention will be further described combined with specific embodiments below.
Embodiment 1
Edible Unidirectional water permeable polymeric membrane, is made of hydrophobic outer film and internal layer hydrophilic film, the internal layer hydrophilic film by
The raw materials of following parts by weight forms: 1 part of gelatin, 1.2 parts of Kappa-Carraginan, 0.08 part of curcumin, 0.6 part of glycerol, mass fraction is
20 parts of 95% ethanol solution, 165 parts of deionized water.The hydrophobic outer film is made of the raw material of following parts by weight: corn
8 parts of alcohol soluble protein, mass fraction is 20 parts of ethanol solution, 3.2 parts of glycerol of 85%.
The molecular weight of the gelatin is greater than 300kd, and the molecular weight of Kappa-Carraginan is greater than 200,000, the molecule of zeins
Amount is 25000-45000.
The preparation method of edible Unidirectional water permeable polymeric membrane, comprising the following steps:
Under the conditions of 70 DEG C, stirring in the deionized water that temperature is 40 DEG C, which is added, in gelatin makes gelatin water swelling, then
Kappa-Carraginan is added and stirs 25min, obtains solution A；Curcumin is dissolved in the ethanol solution that mass fraction is 95%, then by this
Solution is added in solution A, and glycerol stirring 10min is added, and adjusts pH value of solution with the hydrochloric acid solution of 2mol/L and arrives to 6.8
Then this solution is poured on tetrafluoroethene plate by hydrophilic coating solution, 3h is dried under the conditions of 35 DEG C and obtains hydrophilic film；
By zeins be added to mass fraction be 85% ethanol solution in and stirring and dissolving under the conditions of 70 DEG C
20min, be added glycerol after continue stir 5min obtain hydrophobic membrane solution；
Hydrophobic coating solution is uniformly coated in hydrophilic film after drying and obtains edible Unidirectional water permeable polymeric membrane.
The deionized water is added in two portions, and is used for gelatin water swelling for the first time, is added after glycerol is added for the second time,
The ratio being added twice is 1:1.
Embodiment 2
Edible Unidirectional water permeable polymeric membrane, is made of hydrophobic outer film and internal layer hydrophilic film, the internal layer hydrophilic film by
The raw materials of following parts by weight forms: 4 parts of gelatin, 3.6 parts of Kappa-Carraginan, 0.2 part of curcumin, 3.8 parts of glycerol, mass fraction is
20 parts of 95% ethanol solution, 180 parts of deionized water.The hydrophobic outer film is made of the raw material of following parts by weight: corn
20 parts of alcohol soluble protein, mass fraction is 20 parts of ethanol solution, 8 parts of glycerol of 85%.
The molecular weight of the gelatin is greater than 300kd, and the molecular weight of Kappa-Carraginan is greater than 200,000, the molecule of zeins
Amount is 25000-45000.
The preparation method of edible Unidirectional water permeable polymeric membrane, comprising the following steps:
Under the conditions of 90 DEG C, stirring in the deionized water that temperature is 50 DEG C, which is added, in gelatin makes gelatin water swelling, then
Kappa-Carraginan is added and stirs 40min, obtains solution A；Curcumin is dissolved in the ethanol solution that mass fraction is 95%, then by this
Solution is added in solution A, and glycerol stirring 20min is added, and adjusts pH value of solution with the hydrochloric acid solution of 2mol/L and arrives to 7.5
Then this solution is poured on tetrafluoroethene plate by hydrophilic coating solution, 5h is dried under the conditions of 50 DEG C and obtains hydrophilic film；
By zeins be added to mass fraction be 85% ethanol solution in and stirring and dissolving under the conditions of 90 DEG C
40min, be added glycerol after continue stir 12min obtain hydrophobic membrane solution；
Hydrophobic coating solution is uniformly coated in hydrophilic film after drying and obtains edible Unidirectional water permeable polymeric membrane.
The deionized water is added in two portions, and is used for gelatin water swelling for the first time, is added after glycerol is added for the second time,
The ratio being added twice is 1:1.5.
Embodiment 3
Edible Unidirectional water permeable polymeric membrane, is made of hydrophobic outer film and internal layer hydrophilic film, the internal layer hydrophilic film by
The raw materials of following parts by weight forms: 1 part of gelatin, 3.6 parts of Kappa-Carraginan, 0.08 part of curcumin, 3 parts of glycerol, mass fraction is
20 parts of 95% ethanol solution, 180 parts of deionized water.The hydrophobic outer film is made of the raw material of following parts by weight: corn
20 parts of alcohol soluble protein, mass fraction is 20 parts of ethanol solution, 3.2 parts of glycerol of 85%.
The molecular weight of the gelatin is greater than 300kd, and the molecular weight of Kappa-Carraginan is greater than 200,000, the molecule of zeins
Amount is 25000-45000.
The preparation method of edible Unidirectional water permeable polymeric membrane, comprising the following steps:
Under the conditions of 90 DEG C, stirring in the deionized water that temperature is 50 DEG C, which is added, in gelatin makes gelatin water swelling, then
Kappa-Carraginan is added and stirs 25min, obtains solution A；Curcumin is dissolved in the ethanol solution that mass fraction is 95%, then by this
Solution is added in solution A, and glycerol stirring 20min is added, and adjusts pH value of solution with the hydrochloric acid solution of 2mol/L and arrives to 7.5
Then this solution is poured on tetrafluoroethene plate by hydrophilic coating solution, 5h is dried under the conditions of 50 DEG C and obtains hydrophilic film；
By zeins be added to mass fraction be 85% ethanol solution in and stirring and dissolving under the conditions of 90 DEG C
30min, be added glycerol after continue stir 5min obtain hydrophobic membrane solution；
Hydrophobic coating solution is uniformly coated in hydrophilic film after drying and obtains edible Unidirectional water permeable polymeric membrane.
The deionized water is added in two portions, and is used for gelatin water swelling for the first time, is added after glycerol is added for the second time,
The ratio being added twice is 1:1.2.
Embodiment 4
Edible Unidirectional water permeable polymeric membrane, is made of hydrophobic outer film and internal layer hydrophilic film, the internal layer hydrophilic film by
The raw material of following parts by weight forms: 2 parts of gelatin, 2 parts of Kappa-Carraginan, 0.1 part of curcumin, 2 parts of glycerol, mass fraction is 95%
20 parts of ethanol solution, 170 parts of deionized water.The hydrophobic outer film is made of the raw material of following parts by weight: the molten egg of corn alcohol
White 10 parts, mass fraction is 20 parts of ethanol solution, 4 parts of glycerol of 85%.
The molecular weight of the gelatin is greater than 300kd, and the molecular weight of Kappa-Carraginan is greater than 200,000, the molecule of zeins
Amount is 25000-45000.
The preparation method of edible Unidirectional water permeable polymeric membrane, comprising the following steps:
Under the conditions of 80 DEG C, stirring in the deionized water that temperature is 45 DEG C, which is added, in gelatin makes gelatin water swelling, then
Kappa-Carraginan is added and stirs 30min, obtains solution A；Curcumin is dissolved in the ethanol solution that mass fraction is 95%, then by this
Solution is added in solution A, and glycerol stirring 15min is added, and it is close to get arriving to 7 to adjust pH value of solution with the hydrochloric acid solution of 2mol/L
Then this solution is poured on tetrafluoroethene plate by moisture film solution, 4h is dried under the conditions of 40 DEG C and obtains hydrophilic film；
By zeins be added to mass fraction be 85% ethanol solution in and stirring and dissolving under the conditions of 80 DEG C
30min, be added glycerol after continue stir 10min obtain hydrophobic membrane solution；
Hydrophobic coating solution is uniformly coated in hydrophilic film after drying and obtains edible Unidirectional water permeable polymeric membrane.
The deionized water is added in two portions, and is used for gelatin water swelling for the first time, is added after glycerol is added for the second time,
The ratio being added twice is 1:1.3.
Experiment:
Three groups will be divided into after the freeze-drying of fresh oyster, under identical experiment condition after room temperature preservation 14 days, measured cold
Be lyophilized dry oyster physical index and chemistry and microbiological indicator such as table 1 and 2.Wherein control group does not use any packaging film, real
It tests 1 group to pack using hydrophilic film, 2 groups of experiment are packed using edible Unidirectional water permeable polymeric membrane described in the embodiment of the present invention 4.
The physical index of the freeze-drying oyster of table 1
After being packed as can be seen from Table 1 using film, freeze-drying oyster hardness is reduced, and mouthfeel improves.Test 2 groups of molten eggs of corn alcohol
White addition can completely cut off vapor, so reconstitution rate can be lower, but chewability and viscosity reduce, and can make that oyster mouthful is lyophilized
Sense improves.
The chemistry and microbiological indicator of the freeze-drying oyster of table 2
Above-mentioned three groups are not detected mould, saccharomycete, Escherichia coli.
As can be seen from Table 2, the freeze-drying oyster packed using the edible Unidirectional water permeable polymeric membrane of the present invention, preservation 14 days
Afterwards, Volatile Base Nitrogen (TVBN), total plate count, staphylococcus aureus quantity (Staphylococcus aureus) compare
It is all substantially reduced according to 1 group of group and experiment, illustrates the shelf life that can extend freeze-drying oyster.
Claims (9)
1. a kind of edible Unidirectional water permeable polymeric membrane, which is characterized in that it is made of hydrophobic outer film and internal layer hydrophilic film, it is described
Internal layer hydrophilic film is made of the raw material of following parts by weight: 1-4 parts of gelatin, 1.2-3.6 parts of Kappa-Carraginan, and curcumin 0.08-0.2
Part, 0.6-3.8 parts of glycerol, mass fraction is 20 parts of ethanol solution, 165-180 parts of deionized water of 95%.
2. edible Unidirectional water permeable polymeric membrane according to claim 1, which is characterized in that the hydrophobic outer film by with
The raw material of lower parts by weight forms: 8-20 parts of zeins, mass fraction is 20 parts of ethanol solution of 85%, glycerol 3.2-8
Part.
3. edible Unidirectional water permeable polymeric membrane according to claim 2, it is characterised in that: the molecular weight of the gelatin is greater than
300kd, the molecular weight of Kappa-Carraginan are greater than 200,000, and the molecular weight of zeins is 25000-45000.
4. a kind of preparation method of edible Unidirectional water permeable polymeric membrane, which comprises the following steps:
Stirring in deionized water, which is added, in gelatin makes gelatin water swelling, and Kappa-Carraginan is then added and stirs 25-40min, obtains molten
Liquid A；Curcumin is dissolved in the ethanol solution that mass fraction is 95%, then this solution is added in solution A, and glycerol is added
10-20min is stirred, pH value of solution is adjusted to 6.8-7.5 to get hydrophilic coating solution is arrived, this solution is then poured on tetrafluoroethene plate
It is upper obtained by drying to hydrophilic film；
By zeins be added to mass fraction be 85% ethanol solution in and stirring and dissolving under the conditions of 70-90 DEG C
20-40min, be added glycerol after continue stir 5-12min obtain hydrophobic membrane solution；
Hydrophobic coating solution is uniformly coated in hydrophilic film after drying and obtains edible Unidirectional water permeable polymeric membrane.
5. the preparation method of edible Unidirectional water permeable polymeric membrane according to claim 4, it is characterised in that: the deionization
Water is added in two portions, and is used for gelatin water swelling for the first time, is added after glycerol is added for the second time, the ratio being added twice is 1:
1-1.5。
6. the preparation method of edible Unidirectional water permeable polymeric membrane according to claim 5, it is characterised in that: inhaled for gelatin
The temperature of water swellable deionized water is 40-50 DEG C.
7. the preparation method of edible Unidirectional water permeable polymeric membrane according to claim 6, it is characterised in that: the hydrophilic film
Solution is that preparation is reacted under the conditions of 70-90 DEG C.
8. the preparation method of edible Unidirectional water permeable polymeric membrane according to claim 7, it is characterised in that: adjust hydrophilic film
PH value of solution uses the hydrochloric acid solution of 2mol/L.
9. the preparation method of edible Unidirectional water permeable polymeric membrane according to claim 8, it is characterised in that: the hydrophilic film
Drying temperature be 35-50 DEG C, drying time 3-5h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110839936A (en) * | 2019-11-28 | 2020-02-28 | 江苏中烟工业有限责任公司 | Tobacco sheet coating liquid and application thereof in heating cigarette core material |
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| FR3037791A1 (en) * | 2015-06-25 | 2016-12-30 | Oreal | PACKAGING ARTICLE COMPRISING AN ENVELOPE CONSISTING OF AT LEAST ONE FILM AND A COLORING, COLORLESS OR OXIDIZING COMPOSITION ANHYDROUS |
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| CN108163369A (en) * | 2017-11-02 | 2018-06-15 | 华南农业大学 | It is a kind of unidirectionally to hinder wet multilayer edible film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110839936A (en) * | 2019-11-28 | 2020-02-28 | 江苏中烟工业有限责任公司 | Tobacco sheet coating liquid and application thereof in heating cigarette core material |
| CN110839936B (en) * | 2019-11-28 | 2022-05-03 | 江苏中烟工业有限责任公司 | Tobacco sheet coating liquid and application thereof in heating cigarette core material |
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Inventor after: Kong Qing Inventor after: Yu Dongxing Inventor after: Yu Wanshuai Inventor after: Liu Jiaming Inventor before: Kong Qing Inventor before: Yu Dongxing Inventor before: Yu Wan Inventor before: Liu Jiaming |