WO2018227656A1 - 可食膜成膜液及其制备方法和可食膜及其制备方法 - Google Patents

可食膜成膜液及其制备方法和可食膜及其制备方法 Download PDF

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Publication number
WO2018227656A1
WO2018227656A1 PCT/CN2017/090429 CN2017090429W WO2018227656A1 WO 2018227656 A1 WO2018227656 A1 WO 2018227656A1 CN 2017090429 W CN2017090429 W CN 2017090429W WO 2018227656 A1 WO2018227656 A1 WO 2018227656A1
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edible film
film
film forming
edible
forming liquid
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French (fr)
Inventor
王喆
户帅锋
王怀雨
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/12—Agar or agar-agar, i.e. mixture of agarose and agaropectin; 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
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/12—Agar-agar; 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
    • 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
    • C08J2405/04—Alginic 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the technical field of packaging materials, in particular to a edible film forming liquid, a preparation method thereof and an edible film and a preparation method thereof.
  • the use of edible film packaging to replace plastic packaging has become a new trend in the development of food packaging.
  • the edible film is easily degraded by microorganisms in the natural environment, and can reduce environmental pollution.
  • the edible film Using food raw materials as the substrate, the edible film has the characteristics of safe, non-toxic and edible, and can be widely used in food packaging, pharmaceutical packaging and cosmetics, especially for children's food, convenience food, beverage or pharmaceutical powder packaging and skin care products.
  • the product packaging In the product packaging.
  • the edible film can be classified into a polysaccharide edible film, a protein edible film, a lipid edible film, or a plurality of materials to prepare a composite edible film according to different film forming substrates.
  • the formula of edible film is various, but there are problems of too long preparation time. Generally, only the process of coating film formation in the preparation process requires drying for several hours, the production efficiency is very low, and it cannot be used for edible film. Large-scale industrial preparation.
  • the technical problem to be solved by the present invention is to provide an edible film which is rapid in film formation and can be efficiently produced, and a preparation method thereof.
  • a edible film forming solution comprising 8-22 parts by mass of solute and 78-92 parts by mass of distilled water, the solute comprising the following components marine polysaccharide, fish gelatin, glycerin, wherein marine polysaccharide: fish gelatin : The mass ratio of glycerol is (1-8): (5-15): (0.5-2.5).
  • the marine polysaccharide is at least one of sodium alginate, carrageenan, agar, chitosan, and carboxymethyl chitosan.
  • the edible film forming solution is a pseudoplastic fluid.
  • the sodium alginate: fish gelatin: glycerol mass ratio is (1-2.5): (5-10): (0.5-2.5)
  • the carboxymethyl chitosan The mass ratio of fish gelatin:glycerol is (3-5): (5-12): (0.5-2.5).
  • the invention also provides a preparation method of the edible film forming liquid solution as described above, comprising the following steps:
  • the fish gelatin protein is dissolved in distilled water to obtain a fish gelatin protein solution
  • the fish gelatin solution and glycerin were added to the hydrogel and stirred and mixed.
  • the step of agitating and mixing further comprises the step of vacuum degassing.
  • the vacuum degassing time is from 0.5 to 2 h.
  • the agitation mixing time is 15-45 min.
  • the present invention also provides an edible film prepared from the edible film forming solution as described above.
  • the edible film has a thickness of from 10 to 60 ⁇ m.
  • the present invention also provides a method for preparing an edible film as described above, comprising the steps of:
  • Preheating a heating zone of the film forming machine pouring the edible film forming liquid into a film forming tank of the film forming machine, casting the edible film forming liquid, and forming the edible film into
  • the film solution is uniformly coated and dried by heating to form an edible film.
  • the film forming machine is a drum casting machine or a steel belt casting machine.
  • the drying time is > 15 min; preferably, the drying time is 30 min.
  • the heating zone of the preheating film forming machine is preheated to 50-80 °C.
  • the edible film forming solution is cast, and the step of coating the edible film forming solution uniformly is to cast the edible film forming solution on a drum or steel On the belt, the edible film forming solution was uniformly coated using a doctor blade.
  • a gap between the scraper and the drum or the steel strip is 1-5 mm, and a gap between the scraper and the drum or the steel strip is formed and edible
  • the thickness of the film is related.
  • the invention provides a film forming liquid for edible film, a preparation method thereof and an edible film and a preparation method thereof.
  • a film forming substrate involved in a film forming liquid of a edible film is marine polysaccharide and fish collagen derived from the sea.
  • Food raw materials such as protein, natural non-toxic, rich in source, can achieve efficient use of marine resources, and the edible film can be widely used in food packaging, cosmetics and cosmetic packaging; in the present invention, by studying the ratio of each component, A new method for preparing an edible film forming liquid and a new film forming method are proposed, so that the film forming speed of the edible film is greatly improved, and the demand for large-scale industrial production can be satisfied; the edible film tensile resistance of the present invention The strength, elongation at break, and water vapor transmission coefficient can meet the packaging material requirements of food packaging, pharmaceutical packaging, and cosmetic packaging.
  • the edible film of the present invention can be stably stored in a humidity environment of 30%-80%. .
  • the invention provides a basic formula of a film forming liquid of an edible film, and can also add different functional additives on the basis of the formula, so that the edible film has various specific functions.
  • the edible film forming liquid is a pseudoplastic fluid.
  • the fish gelatin protein is evenly distributed in the network structure formed by sodium alginate hydrogel, and a certain force is also formed between the sodium alginate molecule and the fish gelatin protein molecule, so that the film forming liquid system remains stable.
  • Glycerin is added as a plasticizer to maintain a certain flexibility after the film-forming liquid is dried to form a film.
  • the gap between the scraper and the drum is set to 3 mm
  • the temperature of the heating zone is set to 50-80 ° C
  • the film-forming knife is filmed
  • the film is automatically wound up and stored at 30%. -80% humidity in the environment.
  • the thickness, tensile properties, transparency, and haze of the edible film were measured.
  • the thickness detection method is to randomly select 10 points on the edible film, measure with a vernier caliper, and take the arithmetic mean.
  • the tensile property testing method refers to GB13022-91 to cut the film into a strip shape of 15 mm width. The clamping distance was set to 50 mm and the stretching rate was 50 mm/min. The test was carried out by an XLW intelligent electronic tensile testing machine. The measurement result was 10 times or more. Calculate the tensile strength according to the following formula:
  • Ts is the tensile strength (MPa); F is the maximum tension (N) that the sample is subjected to when fractured; S is the cross-sectional area (m 2 ) of the sample.
  • the light transmittance and haze of the film were tested by a WGT-S transmittance/haze meter. Film samples were tested more than 8 times.
  • the water vapor transmission coefficient was measured by a PERMATRAN-W1/5 moisture permeability meter at a relative humidity of 100% and a temperature of 37.8 ° C. Each sample was measured 6 times and averaged.
  • the water vapor transmission coefficient formula is calculated as:
  • the film was prepared by a roller casting machine, and the film formation liquid from the above edible film was introduced into the heating zone to form a edible film. After drying for 15 minutes, the thickness of the edible film was 35 ⁇ 2 ⁇ m, and the tensile strength Ts was 21.35 MPa. The elongation EB was 22.32%, the light transmittance was 92%, and the water vapor transmission coefficient was 8.47 ⁇ 10 -10 g/m ⁇ s ⁇ Pa.
  • the same edible film forming solution was poured into a plexiglass container, and it took 4 hours from the blast drying oven at 60 ° C to the formation of the edible film, and the film thickness was 110 ⁇ m. It can be seen that, compared with the conventional laboratory oven blast drying method, the method of the invention greatly reduces the formation time of the edible film, enables the film to be produced in a large-scale pipeline, and the thickness after film formation is thinner and more Meet the needs of food packaging.
  • the edible film was stored for 16 weeks without significant changes in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • the film formation liquid from the above edible film enters the heating zone of the steel strip casting machine to form an edible film, and is dried for 30 minutes.
  • the thickness of the edible film was measured to be 40 ⁇ 2 ⁇ m, the tensile strength Ts was 31.35 MPa, the elongation at break EB was 42.32%, the light transmittance was 95%, and the water vapor transmission coefficient was 9.61 ⁇ 10 -10 g/m. ⁇ s ⁇ Pa.
  • the forming time of the edible film required 5 hours and the film thickness was 92.3 ⁇ m.
  • the edible film was stored for 26 weeks with no significant change in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • the heating zone was introduced into the edible film to form a drying time of about 30 minutes.
  • the thickness of the edible film was measured to be 30 ⁇ 2 ⁇ m, the tensile strength Ts was 31.35 MPa, the elongation at break EB was 42.32%, the light transmittance was 95%, and the water vapor transmission coefficient was 9.61 ⁇ 10 -10 g/m. ⁇ s ⁇ Pa.
  • the forming time of the edible film required 7 hours, and the film thickness was 86.7 ⁇ m.
  • the edible film was stored for 20 weeks without significant changes in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • the heating zone of the steel strip casting machine pouring the edible film forming liquid into the film forming tank of the steel strip casting machine, and casting the edible film forming liquid by a doctor blade
  • the distance between the scraper and the steel strip is set to 2 mm
  • the temperature of the heating zone is set to 50-70 ° C
  • the edible film is formed by drying, the film is creased, and the film is automatically wound up and stored at 30%-80. % humidity in the environment.
  • the heating zone was introduced into the edible film to form a drying time of about 30 minutes.
  • the thickness of the edible film was measured to be 30 ⁇ 2 ⁇ m, the tensile strength Ts was 31.35 MPa, the elongation at break EB was 42.32%, the light transmittance was 95%, and the water vapor transmission coefficient was 9.61 ⁇ 10 -10 g/m. ⁇ s ⁇ Pa.
  • the forming time of the edible film was 5.7 hours, and the film thickness was 86.7 ⁇ m.
  • the edible film was stored for 14 weeks without significant changes in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • the heating zone of the steel strip casting machine pouring the edible film forming liquid into the film forming tank of the steel strip casting machine, and casting the edible film forming liquid by a doctor blade
  • the distance between the scraper and the steel strip is set to 2 mm
  • the temperature of the heating zone is set to 50-70 ° C
  • the edible film is formed by drying, the film is creased, and the film is automatically wound up and stored at 30%-80. % humidity in the environment.
  • the heating zone was introduced into the edible film to form a drying time of about 35 minutes.
  • the thickness of the edible film was measured to be 30 ⁇ 2 ⁇ m, the tensile strength Ts was 36.35 MPa, the elongation at break EB was 52.85%, the light transmittance was 91%, and the water vapor transmission coefficient was 1.03 ⁇ 10 -10 g/m. ⁇ s ⁇ Pa.
  • the forming time of the edible film was 6.2 hours, and the film thickness was 123.4 ⁇ m.
  • the edible film was stored for 16 weeks without significant changes in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • the edible film forming liquid is a pseudoplastic fluid.
  • the heating zone of the steel strip casting machine pouring the edible film forming liquid into the film forming tank of the steel strip casting machine, and casting the edible film forming liquid by a doctor blade
  • the distance between the scraper and the steel strip is set to 2 mm
  • the temperature of the heating zone is set to 50-70 ° C
  • the drying is performed for 30 min to form a edible film.
  • the film is creased and automatically wound up and stored at 30%. -80% humidity in the environment.
  • the heating zone was introduced into the edible film to form a drying time of about 26 minutes.
  • the thickness of the edible film was measured to be 37 ⁇ 2 ⁇ m, the tensile strength Ts was 38.74 MPa, the elongation at break EB was 55.31%, the light transmittance was 88%, and the water vapor transmission coefficient was 1.21 ⁇ 10 -10 g/m. ⁇ s ⁇ Pa.
  • the forming time of the edible film was 5.6 hours, and the film thickness was 90.7 ⁇ m.
  • the edible film was stored for 26 weeks with no significant change in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • the edible film forming liquid is a pseudoplastic fluid.
  • the heating zone of the steel strip casting machine pouring the edible film forming liquid into the film forming tank of the steel strip casting machine, and casting the edible film forming liquid by a doctor blade
  • the distance between the scraper and the steel strip is set to 2 mm
  • the heating zone temperature The degree is set to 50-70 ° C, dried to form a edible film, the filming knife is filmed, automatically wound up, and stored in an environment of 30%-80% humidity.
  • the heating zone was introduced into the edible film to form a drying time of about 30 minutes.
  • the thickness of the edible film was measured to be 29 ⁇ 1 ⁇ m, the tensile strength Ts was 28.93 MPa, the elongation at break EB was 43.25%, the light transmittance was 93%, and the water vapor transmission coefficient was 7.29 ⁇ 10 -9 g/m ⁇ s ⁇ Pa.
  • the forming time of the edible film was 6.5 hours, and the film thickness was 110.3 ⁇ m.
  • the edible film was stored for 13 weeks without significant changes in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • the heating zone was introduced into the edible film to form a drying time of about 40 minutes.
  • the thickness of the edible film was measured to be 33 ⁇ 2 ⁇ m, the tensile strength Ts was 38.35 MPa, the elongation at break EB was 62.85%, the light transmittance was 85%, and the water vapor transmission coefficient was 1.28 ⁇ 10 -10 g/m. ⁇ s ⁇ Pa.
  • the forming time of the edible film was 5.6 hours, and the film thickness was 90.7 ⁇ m.
  • the edible film was stored for 18 weeks with no significant change in performance. After being sterilized by ultraviolet sterilization, the edible film was stored for 40 weeks under the condition of room temperature of 50%, and the performance did not change significantly.
  • 1% acetic acid solution is prepared into a 3% chitosan solution, poured on the steel strip of the casting film forming machine, and part of the solution flows out of the steel strip. It is not suitable to form a film. Because the dry matter content is low, the viscosity of the solution is not enough. During the movement of the steel strip, the solution flows and can only form a film in the flat container.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

公开了可食膜成膜液及其制备方法和可食膜及其制备方法，可食膜成膜液包含8-22质量份的溶质和78-92质量份的蒸馏水，所述溶质包括海洋多糖、鱼胶蛋白、甘油，上述原料天然无毒，来源丰富，制成的可食膜能应用于食品包装、药品及化妆品包装；该可食膜抗张强度、断裂伸长率、水蒸气透过系数都能够满足食品、药品、化妆品包装对于包装材料的要求，能够稳定贮藏于30％-80％的湿度环境中。

Description

可食膜成膜液及其制备方法和可食膜及其制备方法 技术领域
本发明涉及包装材料技术领域，具体涉及可食膜成膜液及其制备方法和可食膜及其制备方法。
背景技术
近年来，随着人们环保意识的增强及对食品品质要求的提高，采用可食膜包装取代塑料包装已经成为食品包装发展的一个新趋势。可食膜在自然环境中容易被微生物降解，能够减少对环境的污染。以食品原料为基材，使得可食膜具有安全无毒可食的特性，可以广泛应用于食品包装，药品包装和化妆品领域，特别是儿童食品、方便食品、饮品或药品冲剂包装和护肤品等产品包装中。
可食膜根据成膜基材的不同，可以分为多糖可食膜、蛋白可食膜、脂质可食膜，也可以多种材料共混制备复合可食膜。目前可食膜的配方多种多样，但是都存在制备时间过长的问题，一般仅制备过程中涂布成膜这一步工艺，就需要干燥几小时，生产效率十分低下，无法用于可食膜的大规模产业化制备。
发明内容
本发明所要解决的技术问题是提供一种成膜快速、能高效生产的可食膜及其制备方法。
本发明所采取的技术方案是：
一种可食膜成膜液，包含8-22质量份的溶质和78-92质量份的蒸馏水，所述溶质包括以下组分海洋多糖、鱼胶蛋白、甘油，其中，海洋多糖：鱼胶蛋白：甘油的质量比为(1-8)：(5-15)：(0.5-2.5)。
在一些优选的实施方式中，所述海洋多糖为海藻酸钠、卡拉胶、琼胶、壳聚糖和羧甲基壳聚糖中的至少一种。
在一些优选的实施方式中，所述可食膜成膜液为假塑性流体。
在一些优选的实施方式中，所述海藻酸钠：鱼胶蛋白：甘油的质量比为(1-2.5)：(5-10)：(0.5-2.5)，所述羧甲基壳聚糖：鱼胶蛋白：甘油的质量比为(3-5)：(5-12)：(0.5-2.5)。
本发明还提供了一种如上所述的可食膜成膜液的制备方法，包括以下步骤：
取海洋多糖溶于蒸馏水中，得到水凝胶；
取鱼胶蛋白溶于蒸馏水中，得到鱼胶蛋白溶液；
向所述水凝胶中加入所述鱼胶蛋白溶液和甘油，搅拌混合。
在一些优选的实施方式中，所述搅拌混合后还包括真空脱气的步骤。
在一些优选的实施方式中，所述真空脱气的时间为0.5-2h。
在一些优选的实施方式中，所述搅拌混合的时间为15-45min。
本发明还提供了一种可食膜，由如上所述的可食膜成膜液制备得到。
在一些优选的实施方式中，所述可食膜的厚度为10-60μm。
本发明还提供了一种如上所述的可食膜的制备方法，包括以下步骤：
制备可食膜成膜液；
预热制膜机的加热区，将所述可食膜成膜液倒入所述制膜机的制膜槽中，将所述可食膜成膜液流延，将所述可食膜成膜液涂布均匀，通过加热干燥，形成可食膜。
在一些优选的实施方式中，所述制膜机为滚筒流延机或钢带流延机。
在一些优选的实施方式中，所述干燥的时间≥15min；优选地，所述干燥的时间为30min。
在一些优选的实施方式中，所述预热制膜机的加热区是将其预热至50-80℃。
在一些优选的实施方式中，将所述可食膜成膜液流延，将所述可食膜成膜液涂布均匀的步骤是将所述可食膜成膜液流延在滚筒或钢带上，使用刮刀将所述可食膜成膜液涂布均匀。
在进一步优选的实施方式中，所述刮刀与所述滚筒或所述钢带之间的间隙为1-5mm，所述刮刀与所述滚筒或所述钢带之间的间隙与形成的可食膜的厚度有关。
本发明的有益效果是：
本发明提供了可食膜成膜液及其制备方法和可食膜及其制备方法，首先可食膜成膜液中所涉及到的成膜基材为来源于海洋中的海洋多糖和鱼胶原蛋白等食品原料，天然无毒，来源丰富，能够实现海洋资源的高效利用，制成的可食膜能够广泛应用于食品包装、化妆品及化妆品包装；本发明中通过研究各组分的配比、提出新的制备可食膜成膜液的方法以及提出新的制膜方法，使得可食膜的成膜速度大幅提升，能够满足大规模产业化生产的需求；本发明所述可食膜抗张强度、断裂伸长率、水蒸气透过系数都能够满足食品包装、药品包装及化妆品包装的包装材料要求，此外，本发明所述可食膜能够稳定贮藏于30％-80％的湿度环境中。
本发明提供的一种可食膜的成膜液基本配方，还可以在该配方基础上添加不同的功能助剂，使可食膜具备多样的特异性功能。
具体实施方式
实施例1：
(1)取4g海藻酸钠加一定量的蒸馏水中，在60℃条件下机械搅拌30分钟，得到质量分数为4％的海藻酸钠水凝胶备用。
(2)取20g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为20％的鱼胶蛋白溶液。
(3)将500mL质量分数为4％的海藻酸钠水凝胶和500mL质量分数为20％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌30分钟，得到总干物质为12％的可食膜成膜液，该可食膜成膜液为假塑性流体。鱼胶蛋白均匀分布在海藻酸钠水凝胶形成的网状结构中，海藻酸钠分子与鱼胶蛋白分子之间也形成一定的作用力，使成膜液体系保持稳定。加入甘油作为增塑剂，使成膜液干燥成膜后保持一定的柔韧性。
(4)将所述可食膜成膜液置于真空环境中除气30分钟。
(5)预热滚筒流延机的加热区，将所述可食膜成膜液倒入滚筒流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在滚筒上，所述刮刀与所述滚筒之间的间隙为设定为3mm，加热区温度设定为50-80℃，干燥，形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
(6)将上述可食膜成膜液倒在有机玻璃容器中，置于60℃鼓风干燥箱中烘干，所形成的膜作为对照组，比较两种不同成膜方式加工的薄膜的成型时间以及厚度。
对可食膜进行厚度、拉伸性能、透明度、雾度检测。
厚度检测方法是在可食膜上随机选取10个点，用游标卡尺测量，取算术平均值。拉伸性能检测方法参照GB13022-91将膜剪切成15mm宽的长条状。设定夹距为50mm，拉伸速率为50mm/min，通过XLW智能电子拉力试验机测试。测定结果10次以上。按以下公式计算抗拉强度：
Figure PCTCN2017090429-appb-000001
式中：Ts为抗拉强度(MPa)；F为样品断裂时所承受的最大张力(N)；S为试样横截面积(m2)。
通过WGT-S透光率/雾度测定仪对薄膜的透光率和雾度进行测试。薄膜样品均测试8次以上。
通过PERMATRAN-W1/5透湿仪，在相对湿度为100％，温度为37.8℃条件下测定水蒸气透过系数，每个样品测定6次，取平均值。水蒸气透过系数公式计算为:
PV＝WVTR×n/Δp
式中PV为水蒸气透过系数g/(m·s·Pa)；WVTR为膜的水蒸气透过率(g/(m2·d))，由仪器测出；n为膜的厚度(mm)；Δp为测试压力(约0.2MPa)。
采用滚筒流延机制备成膜，从上述可食膜成膜液进入加热区至可食膜成型，经过15min 干燥，测得可食膜厚度为35±2μm，抗张强度Ts为21.35MPa，断裂伸长率EB为22.32％，透光率为92％，水蒸气透过系数为到8.47×10-10g/m·s·Pa。
而对照组中，同样的可食膜成膜液倒在有机玻璃容器中，从置于60℃鼓风干燥箱中至可食膜形成需要4个小时，膜厚110μm。由此可见，相对于传统的实验室烘箱鼓风干燥法而言，本发明所述方法大大降低了可食膜形成时间，使薄膜能够大规模流水线式生产，膜成型后的厚度更薄，更符合食品包装需求。
在环境湿度为50％的室温条件下，可食膜经过16周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
实施例2：
(1)取10g羧甲基壳聚糖加一定量的蒸馏水中，在60℃条件下机械搅拌30分钟，得到质量分数为10％的羧甲基壳聚糖水凝胶备用。
(2)取16g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为20％的鱼胶蛋白溶液。
(3)将500mL质量分数为10％的羧甲基壳聚糖水凝胶和500mL质量分数为16％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌30分钟，得到总干物质含量为13％的可食膜成膜液，该可食膜成膜液为假塑性流体。
(4)将上述可食膜成膜液置于真空环境中除气30分钟。
(5)预热钢带流延机的加热区，将所述可食膜成膜液倒入钢带流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在钢带上，所述刮刀与所述钢带之间的间隙设定为2mm，加热区温度设定为50-70℃，干燥形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
(6)将上述可食膜成膜液倒在有机玻璃容器中，置于60℃鼓风干燥箱中烘干，所形成的膜作为对照组，比较两种不同成膜方式加工的薄膜的成型时间以及厚度。
从上述可食膜成膜液进入钢带流延机的加热区至可食膜成型，经过30min干燥时间。测得可食膜厚度为40±2μm，抗张强度Ts为31.35MPa，断裂伸长率EB为42.32％，透光率为95％，水蒸气透过系数为到9.61×10-10g/m·s·Pa。而对照组中，可食膜的成型时间需要5个小时，膜厚92.3μm。
在环境湿度为50％的室温条件下，可食膜经过26周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
实施例3：
(1)取2g海藻酸钠和4g羧甲基壳聚糖加一定量的蒸馏水中，在60℃条件下机械搅拌30分钟，得到质量分数为6％的混合水凝胶备用。
(2)取20g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为20％的鱼胶蛋白溶液。
(3)将500mL质量分数为6％的水凝胶和500mL质量分数为20％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌15分钟，得到干物质含量为13％的可食膜成膜液，该可食膜成膜液为假塑性流体。
(4)将上述可食膜成膜液置于真空环境中除气30分钟。
(5)预热滚筒流延机的加热区，将所述可食膜成膜液倒入滚筒流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在滚筒上，刮刀与滚筒之间的间隙设定为2mm，加热区温度设定为50-80℃，干燥形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
(6)将上述可食膜成膜液倒在有机玻璃容器中，置于70℃鼓风干燥箱中烘干，所形成的膜作为对照组，比较两种不同成膜方式加工的薄膜的成型时间以及厚度。
从上述可食膜成膜液进入加热区至可食膜成型，经过大约30min的干燥时间。测得可食膜厚度为30±2μm，抗张强度Ts为31.35MPa，断裂伸长率EB为42.32％，透光率为95％，水蒸气透过系数为到9.61×10-10g/m·s·Pa。而对照组中，可食膜的成型时间需要7个小时，膜厚86.7μm。
在环境湿度为50％的室温条件下，可食膜经过20周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
实施例4：
(1)取8g卡拉胶加一定量的蒸馏水中，在80℃条件下机械搅拌30分钟，得到质量分数为4％的卡拉胶水凝胶备用。
(2)取20g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为20％的鱼胶蛋白溶液。
(3)将500mL质量分数为8％的卡拉胶水凝胶和500mL质量分数为20％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌45分钟得到总干物质含量为14％的可食膜成膜液，该可食膜成膜液为假塑性流体。
(4)将上述可食膜成膜液置于真空环境中除气2小时。
(5)预热钢带流延机的加热区，将所述可食膜成膜液倒入钢带流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在钢带上，刮刀与钢带之间的间距设定为2mm，加热区温度设定为50-70℃，干燥形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
从上述可食膜成膜液进入加热区至可食膜成型，经过大约30min的干燥时间。测得可食膜厚度为30±2μm，抗张强度Ts为31.35MPa，断裂伸长率EB为42.32％，透光率为95％，水蒸气透过系数为到9.61×10-10g/m·s·Pa。对照组中，可食膜的成型时间需要5.7个小时，膜厚86.7μm。
在环境湿度为50％的室温条件下，可食膜经过14周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
实施例5：
(1)取4g卡拉胶和4g海藻酸钠加一定量的蒸馏水中，在80℃条件下机械搅拌30分钟，得到质量分数为8％的混合水凝胶备用。
(2)取14g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为14％的鱼胶蛋白溶液。
(3)将800mL质量分数为8％水凝胶和400mL质量分数为14％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌30分钟。得到总干物质含量为10％的可食膜成膜液。
(4)将上述可食膜成膜液置于真空环境中除气30分钟。
(5)预热钢带流延机的加热区，将所述可食膜成膜液倒入钢带流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在钢带上，刮刀与钢带之间的间距设定为2mm，加热区温度设定为50-70℃，干燥形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
从上述可食膜成膜液进入加热区至可食膜成型，经过大约35min的干燥时间。测得可食膜厚度为30±2μm，抗张强度Ts为36.35MPa，断裂伸长率EB为52.85％，透光率为91％，水蒸气透过系数为到1.03×10-10g/m·s·Pa。对照组中，可食膜的成型时间需要6.2个小时，膜厚123.4μm。
在环境湿度为50％的室温条件下，可食膜经过16周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
实施例6：
(1)取4g海藻酸钠和6g壳聚糖加一定量的1％乙酸溶液中，在80℃条件下机械搅拌30分钟，得到质量分数为4％的混合水凝胶备用。
(2)取16g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为16％的鱼胶蛋白溶液。
(3)将500mL质量分数为10％的混合水凝胶和500mL质量分数为16％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌30分钟，得到总干物质含量为13％的可食膜成膜液，该可食膜成膜液为假塑性流体。
(4)将上述可食膜成膜液置于真空环境中除气30分钟。
(5)预热钢带流延机的加热区，将所述可食膜成膜液倒入钢带流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在钢带上，刮刀与钢带之间的间距设定为2mm，加热区温度设定为50-70℃，干燥30min，形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
从上述可食膜成膜液进入加热区至可食膜成型，经过大约26min的干燥时间。测得可食膜厚度为37±2μm，抗张强度Ts为38.74MPa，断裂伸长率EB为55.31％，透光率为88％，水蒸气透过系数为到1.21×10-10g/m·s·Pa。对照组中，可食膜的成型时间需要5.6个小时，膜厚90.7μm。
在环境湿度为50％的室温条件下，可食膜经过26周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
实施例7：
(1)取10g琼胶加入水中，在80℃条件下机械搅拌30分钟，得到质量分数为10％的混合水凝胶备用。
(2)取10g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为10％的鱼胶蛋白溶液。
(3)将500mL质量分数为10％的混合水凝胶和500mL质量分数为10％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌30分钟，得到总干物质含量为10％的可食膜成膜液，该可食膜成膜液为假塑性流体。
(4)将上述可食膜成膜液置于真空环境中除气30分钟。
(5)预热钢带流延机的加热区，将所述可食膜成膜液倒入钢带流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在钢带上，刮刀与钢带之间的间距设定为2mm，加热区温 度设定为50-70℃，干燥形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
从上述可食膜成膜液进入加热区至可食膜成型，经过大约30min的干燥时间。测得可食膜厚度为29±1μm，抗张强度Ts为28.93MPa，断裂伸长率EB为43.25％，透光率为93％，水蒸气透过系数为7.29×10-9g/m·s·Pa。对照组中，可食膜的成型时间需要6.5个小时，膜厚110.3μm。
在环境湿度为50％的室温条件下，可食膜经过13周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
实施例8：
(1)取4g羧甲基壳聚糖，4g卡拉胶和4g海藻酸钠加一定量的蒸馏水中，在80℃条件下机械搅拌30分钟，得到质量分数为12％的混合水凝胶备用。
(2)取10g鱼胶蛋白加入到一定量的蒸馏水中，搅拌10分钟溶解，得到质量分数为10％的鱼胶蛋白溶液。
(3)将500mL质量分数为12％水凝胶和500mL质量分数为10％的鱼胶蛋白水溶液共混，加入20mL甘油后在60℃条件下搅拌30分钟。得到总干物质含量为11％的可食膜成膜液，该可食膜成膜液为假塑性流体。
(4)将上述可食膜成膜液置于真空环境中除气30分钟。
(5)预热滚筒流延机的加热区，将所述可食膜成膜液倒入钢带流延机的制膜槽中，采用刮刀将所述可食膜成膜液流延在滚筒上，刮刀与滚筒之间的间距设定为2mm，加热区温度设定为50-70℃，干燥形成可食膜，起膜刀起膜，自动收卷，贮藏于30％-80％湿度的环境中。
从上述可食膜成膜液进入加热区至可食膜成型，经过大约40min的干燥时间。测得可食膜厚度为33±2μm，抗张强度Ts为38.35MPa，断裂伸长率EB为62.85％，透光率为85％，水蒸气透过系数为到1.28×10-10g/m·s·Pa。对照组中，可食膜的成型时间需要5.6个小时，膜厚90.7μm。
在环境湿度为50％的室温条件下，可食膜经过18周贮藏，性能无明显变化。经过紫外灭菌处理的可食膜，在环境湿度为50％的室温条件下，可食膜经过40周贮藏，性能无明显变化。
对比例1：
1％的醋酸溶液配制成3％的壳聚糖溶液，倒在流延制膜机的钢带上，部分溶液流出钢带， 不宜形成薄膜。因为干物质含量较低，溶液的粘度不够，在钢带运动过程中，溶液流动，只能在平板容器中成膜。

Claims (15)

  1. 一种可食膜成膜液，其特征在于，包含8-22质量份的溶质和78-92质量份的蒸馏水，所述溶质包括以下组分海洋多糖、鱼胶蛋白、甘油，其中，海洋多糖：鱼胶蛋白：甘油的质量比为(1-8)：(5-15)：(0.5-2.5)。
  2. 根据权利要求1的可食膜成膜液，其特征在于，所述海洋多糖为海藻酸钠、卡拉胶、琼胶、壳聚糖和羧甲基壳聚糖中的至少一种。
  3. 根据权利要求1或2的可食膜成膜液，其特征在于，所述可食膜成膜液为假塑性流体。
  4. 权利要求1-3任一项所述的可食膜成膜液的制备方法，其特征在于，包括以下步骤：
    取海洋多糖溶于蒸馏水中，得到水凝胶；
    取鱼胶蛋白溶于蒸馏水中，得到鱼胶蛋白溶液；
    向所述水凝胶中加入所述鱼胶蛋白溶液和甘油，搅拌混合。
  5. 根据权利要求4所述的可食膜成膜液的制备方法，其特征在于，所述搅拌混合后还包括真空脱气的步骤。
  6. 根据权利要求5所述的可食膜成膜液的制备方法，其特征在于，所述真空脱气的时间为0.5-2h。
  7. 根据权利要求4-6任一项所述的可食膜成膜液的制备方法，其特征在于，所述搅拌混合的时间为15-45min。
  8. 一种可食膜，其特征在于，由权利要求1-3任一项所述的可食膜成膜液制备得到。
  9. 根据权利要求8所述的可食膜，其特征在于，所述可食膜的厚度为10-60μm。
  10. 权利要求8或9所述的可食膜的制备方法，其特征在于，包括以下步骤：
    制备可食膜成膜液；
    预热制膜机的加热区，将所述可食膜成膜液倒入所述制膜机的制膜槽中，将所述可食膜成膜液流延，将所述可食膜成膜液涂布均匀，通过加热干燥，形成可食膜。
  11. 根据权利要求10所述的可食膜的制备方法，其特征在于，所述制膜机为滚筒流延机或钢带流延机。
  12. 根据权利要求10所述的可食膜的制备方法，其特征在于，所述干燥的时间≥15min。
  13. 根据权利要求10-12任一项所述的可食膜的制备方法，其特征在于，所述预热制膜机的加热区是将其预热至50-80℃。
  14. 根据权利要求10所述的可食膜的制备方法，其特征在于，将所述可食膜成膜液流延，将所述可食膜成膜液涂布均匀的步骤是将所述可食膜成膜液流延在滚筒或钢带上，使用刮刀将所述可食膜成膜液涂布均匀。
  15. 根据权利要求14所述的可食膜的制备方法，其特征在于，所述刮刀与所述滚筒或所述钢带之间的间隙为1-5mm。
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