WO2021088515A1 - 壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜及其制备方法 - Google Patents

壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜及其制备方法 Download PDF

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WO2021088515A1
WO2021088515A1 PCT/CN2020/114938 CN2020114938W WO2021088515A1 WO 2021088515 A1 WO2021088515 A1 WO 2021088515A1 CN 2020114938 W CN2020114938 W CN 2020114938W WO 2021088515 A1 WO2021088515 A1 WO 2021088515A1
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chitosan
acid
film
chlorokojic
composite
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French (fr)
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刘晓丽
夏文水
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/771—Organic compounds containing hetero rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • 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

Definitions

  • the invention relates to the technical field of food packaging materials, in particular to a chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film and a preparation method thereof.
  • cling film In daily life, cling film is often used to keep food fresh. At present, most of the most commonly used are polyethylene cling film, but because it is difficult to degrade, it will cause serious plastic waste pollution problems, and it will decompose after heating. Hazardous substances to the human body, etc. When the food is frozen and kept fresh, the cling film will freeze and stick to the food and cannot be removed. If you don't pay attention to it, you may accidentally eat it, which will seriously damage the health of the eater. Therefore, there is an urgent need to use other environmentally friendly, safe and harmless materials to replace harmful plastic wrap materials.
  • Chitosan is a natural alkaline polysaccharide with good biocompatibility and biodegradability.
  • the degradation products generally have no toxic side effects on the human body, do not accumulate in the body, and have no immunogenicity. It is widely selected as a fresh-keeping film material.
  • Chitosan also has a certain antibacterial effect, and has obvious inhibitory effect on bacteria, molds, fungi and yeasts.
  • chitosan also has good film-forming properties. In an appropriate solvent, chitosan molecules can be cross-linked to form hydrogen bonds, and the film-forming properties are good. It is regarded as an ideal material for the development of new natural antibacterial plastic wrap. .
  • Kojic acid is a common weakly acidic metabolite produced by some microorganisms such as Aspergillus and Acetobacter through aerobic fermentation. Due to its unique structure similar to catechol, it has anti-bacterial, anti-inflammatory, anti-tumor, and anti-oxidant effects, and is safe and non-toxic. In addition, kojic acid is also soluble in water and cannot be used by bacteria. It has the advantages of wide application range of pH, good thermal stability, not easy to decompose when heated, no irritation to the human body, and safe food. Chlorokojic acid is a product with strong antibacterial activity obtained after derivatization of the multifunctional skeleton of kojic acid. It is a good ligand for nucleophilic substitution and electrophilic substitution reaction, because it can chelate cell metabolism. The necessary metal cations have strong anti-bacterial and anti-fungal effects.
  • the technical problem to be solved by the present invention is to provide a chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film and its preparation method, which overcomes the water vapor barrier properties and mechanical properties of chitosan film in the prior art. Defects of poor strength.
  • the present invention provides a chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film.
  • the composite antibacterial fresh-keeping film at least includes a first composite film and a second composite film that are stacked ;
  • the first composite film is a composite film of chitosan and kojic acid, and the number average molecular weight of chitosan is 150-300KDa, and the degree of deacetylation is ⁇ 90%;
  • the second composite film is a composite film of chitosan and chlorine Dikojic acid composite membrane, and the number average molecular weight of chitosan is 400-800KDa, and the degree of deacetylation is ⁇ 85%.
  • chitosan with a number average molecular weight of 150-300KDa and 400-800KDa has good film-forming properties and antibacterial activity, while chitosan with a degree of deacetylation above 85% has more active amino groups. It can be more tightly combined with kojic acid and chlorokojic acid, so that the prepared composite membrane has better mechanical properties and water vapor barrier effects.
  • the mass ratio of kojic acid to chitosan is 0.05-0.15:0.5-1.2; in the second composite film, the mass ratio of chlorokojic acid to chitosan is 0.05 ⁇ 0.15:0.5 ⁇ 1.2.
  • first composite film and/or the second composite film further includes a plasticizer, and the mass ratio of the plasticizer to chitosan is 0.5-0.8:0.5-1.2.
  • the plasticizer is selected from at least one of glycerin, sorbitol, polyethylene glycol, and stearic acid.
  • the thickness of the first composite film and the second composite film can be set between several ⁇ m to several tens of ⁇ m, for example, 5 to 90 ⁇ m. Further, the thickness of the first composite film is 35.55 to 39.85 m, and the thickness of the second composite film is 36.68 to 41.06 m.
  • the composite antibacterial fresh-keeping film can be prepared by a variety of methods, including but not limited to cast film, extrusion film and the like.
  • the first composite film and/or the second composite film are cast films, which have the advantages of high production efficiency, good uniformity of the composite film, and stable performance.
  • Another aspect of the present invention provides a preparation method of chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film, which comprises the following steps:
  • chitosan/kojic acid mixed membrane liquid and chitosan/chlorokojic acid mixed membrane liquid among them, in the chitosan/kojic acid mixed membrane liquid, the number average molecular weight of chitosan is 150 ⁇ 300KDa, deacetylated Degree ⁇ 90%; In the chitosan/chlorokojic acid mixed membrane liquid, the number average molecular weight of chitosan is 400 ⁇ 800KDa, and the degree of deacetylation is ⁇ 85%;
  • the plasticizer is selected from at least one of glycerin, sorbitol, polyethylene glycol, and stearic acid.
  • the amount of the chitosan/chlorokojic acid composite membrane liquid is more than that of the chitosan/kojic acid composite membrane liquid.
  • the chitosan/chlorokojic acid composite membrane liquid is combined with the shell
  • the dosage ratio of the glycan/kojic acid composite membrane solution is 1 to 3:1, and the composite membrane has good antibacterial activity. When the ratio exceeds 3:1, the thickness of the film is larger and the drying time is longer, and the antibacterial activity of 2:1 is the highest, and the performance of the film is the best.
  • the drying conditions of the chitosan/kojic acid composite membrane solution are: the drying temperature is 35-55°C, and the drying time is 1 to 2 hours; the drying conditions of the chitosan/chlorokojic acid composite membrane solution are: drying temperature It is 55 ⁇ 75°C, and the time is 2 ⁇ 4h.
  • the chitosan/kojic acid composite membrane liquid and the chitosan/chlorokojic acid composite membrane liquid adopt different drying conditions. The reason is that the chitosan/kojic acid composite membrane liquid uses different drying conditions.
  • the number average molecular weight of sugar is 150-300KDa, and the amount of mixed membrane liquid is small, the required drying temperature is low, and the time is short.
  • the chitosan used has a number average molecular weight of 400-800KDa, which has a greater viscosity and a large amount of mixed membrane liquid, so the required drying temperature is higher and the time is longer. .
  • Chitosan is a natural alkaline polysaccharide extracted from shrimp and crab shells.
  • Kojic acid is produced by certain microorganisms. An organic acid produced by aerobic fermentation, safe to eat. After derivatization of kojic acid, chlorokojic acid with the same anti-corrosion properties can be obtained.
  • the 5-hydroxy- ⁇ -pyrone group on the molecular unit of kojic acid and chlorokojic acid can form a tightly combined multilayer film with the active amino group in the chitosan molecule through electrostatic interaction and hydrogen bonding, thereby The tightness between the components is strengthened, and the original mechanical properties and water vapor barrier properties of the chitosan film are further improved.
  • the casting method is used to prepare the composite membrane, which has the advantages of high production efficiency, good uniformity of the composite membrane, and stable performance.
  • the chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film of the present invention has good film-forming properties and mechanical properties, low water vapor transmission coefficient and good antibacterial activity, which can avoid A large amount of food moisture is lost and a better preservation effect is achieved.
  • the chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film of the present invention has a simple and rapid preparation method, and does not add any toxic substances, and is green and environmentally friendly.
  • Figure 1 is the X-ray diffraction pattern of the chitosan film prepared in Comparative Example 1 and the chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film prepared in Example 1.
  • This embodiment provides a chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film, and its preparation method includes the following steps:
  • chitosan 1/kojic acid mixed membrane solution Take 6 mL of chitosan 1/kojic acid mixed membrane solution and cast it on a 10 ⁇ 20 cm 2 glass plate to form a film, dry it in an oven at 35°C for 1 hour, and then add 12 mL of chitosan 2/chlorokojic acid on the surface Mix the membrane liquid, cast to form a membrane, dry for 2 hours at an oven temperature of 55°C, and uncover the membrane.
  • the chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film can be obtained.
  • This embodiment provides a chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film, and its preparation method includes the following steps:
  • chitosan 1/kojic acid mixed membrane solution Take 6 mL of chitosan 1/kojic acid mixed membrane solution and cast it on a 10 ⁇ 20 cm 2 glass plate to form a film, and dry it for 1.5 hours at an oven temperature of 40 °C, and then add 12 mL of chitosan 2/chlorinated koji to its surface
  • the acid is mixed with the film solution, cast to form a film, dried in an oven temperature of 60°C for 3 hours, and the film is peeled off.
  • the chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film can be obtained.
  • This embodiment provides a chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film, and its preparation method includes the following steps:
  • chitosan 1/kojic acid mixed membrane solution Take 6 mL of chitosan 1/kojic acid mixed membrane solution and cast it on a 10 ⁇ 20 cm 2 glass plate to form a film, dry it in an oven temperature of 50 °C for 2 hours, and then add 12 mL of chitosan 2/chlorokojic acid on the surface Mix the membrane liquid, cast to form a membrane, dry for 4 hours at an oven temperature of 70°C, and uncover the membrane.
  • the chitosan/kojic acid/chlorokojic acid composite antibacterial fresh-keeping film can be obtained.
  • This comparative example provides a pure chitosan 1 antibacterial fresh-keeping film, and its preparation method includes the following steps:
  • chitosan Dissolve 0.5 g of chitosan with a number average molecular weight of 157KDa and a degree of deacetylation of 90% in a 1% acetic acid solution. After stirring for 1 hour at 1000 r/min, sonicate it at an ultrasonic frequency of 35KHz for 1 hour until it is completely dissolved. Add 0.5 g glycerol, stir for 30 minutes at a stirring speed of 500r/min, then pour 18mL of chitosan 1 membrane solution on a glass plate, cast to form a film, put the glass plate in an oven at 45°C and dry for 1 hour to obtain the shell Glycan 1 antibacterial plastic wrap.
  • This comparative example provides a pure chitosan 2 antibacterial fresh-keeping film, and its preparation method includes the following steps:
  • This comparative example provides a pure chitosan 1 and chitosan 2 antibacterial composite fresh-keeping film, and its preparation method includes the following steps:
  • This comparative example provides a chitosan/kojic acid mixed antibacterial fresh-keeping film, and its preparation method includes the following steps:
  • This comparative example provides a chitosan2/chlorokojic acid mixed antibacterial fresh-keeping film, and its preparation method includes the following steps:
  • chitosan2/chlorokojic acid mixed membrane solution pour 18mL of chitosan2/chlorokojic acid mixed membrane solution on the glass plate, cast to form a film, put the glass plate in a 70°C oven and dry for 2h, then chitosan2/chlorokojic acid can be obtained Antibacterial fresh-keeping film with mixed liquid film.
  • TS tensile strength
  • TS represents the tensile strength (Mpa)
  • Fmax is the maximum tensile force that the film can withstand when it breaks
  • L represents the width of the film
  • W represents the thickness of the film.
  • L represents the initial length (mm) of the film
  • L0 represents the length (mm) of the film after stretching.
  • WVP represents the water vapor transmission coefficient [g ⁇ mm/(m 2 ⁇ h ⁇ kPa)]; d represents the thickness of the composite film (mm); ⁇ m represents the mass increase after stabilization (g); A represents the clipping The area of the membrane (m 2 ), ⁇ t represents the time interval (h) between each measurement, ⁇ p represents the fixed water vapor pressure difference (kPa) on both sides of the composite membrane, the experimental temperature is 25° C., and the relative humidity is maintained at 75%.
  • Table 1 shows the film thickness, mechanical properties and water vapor transmission coefficient of the antibacterial fresh-keeping films prepared in Comparative Examples 1-5 and Examples 1-3. It can be seen from Table 1 that compared with the group without kojic acid and chlorokojic acid in Comparative Examples 1-3, in Examples 1-3, with the increase of kojic acid and chlorokojic acid, the tensile strength of the film The strength and elongation at break gradually increase, while the water permeability coefficient gradually decreases. This is because the addition of kojic acid and chlorokojic acid destroys the intra- and intermolecular hydrogen bonds of chitosan, and at the same time forms new hydrogen bonds, which changes the properties of the membrane.
  • Table 2 shows the antibacterial properties of the antibacterial fresh-keeping films prepared in Comparative Examples 1-5 and Examples 1-3 of the present invention. It can be seen from the table that as the content of kojic acid and chlorokojic acid increase, the inhibition rate of the membrane on bacteria is significantly stronger than that without addition and gradually increases, and the inhibition rate against Escherichia coli and Staphylococcus aureus can be respectively Reaching 96% and 91%, it has a good inhibitory effect.

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Abstract

本发明公开了一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，所述复合抑菌保鲜膜至少包括层叠设置的第一复合膜和第二复合膜；其中，所述第一复合膜为壳聚糖与曲酸复合膜，且壳聚糖的数均分子量为150～300KDa，脱乙酰度≥90％；所述第二复合膜为壳聚糖与氯代曲酸复合膜，且壳聚糖的数均分子量为400～800KDa，脱乙酰度≥85％。本发明还公开了所述复合抑菌保鲜膜的制备方法。本发明的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，具有良好的成膜性和机械性能，有较低的水蒸气透过系数和良好的抑菌活性，可避免食品水分的大量流失和达到较好的保鲜效果。

Description

壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜及其制备方法 技术领域
本发明涉及食品包装材料技术领域，具体涉及一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜及其制备方法。
背景技术
在日常生活中常用保鲜膜对被食物进行保鲜，目前最常用的大多是聚乙烯材质的保鲜膜，但因其难以降解，会带来严重的塑料废弃物污染问题，并且加热后还会分解出对人体有害物质等。对食物进行冷冻保鲜时，保鲜膜会冻粘在食物上无法清除，稍不注意会发生误食的情况，严重损害了食用者健康。因此，迫切需要使用其它环保和安全无害的材料来代替有害保鲜膜材料。
天然多糖因其来源丰富、同时具有生物降解性和生物相容性和安全无毒等特性已引起研究人员的广泛关注。壳聚糖是一种天然碱性多糖，具有很好的生物相容性和生物降解性，降解产物一般对人体无毒副作用，在体内不蓄积，无免疫原性，被广泛选择用作保鲜膜材料。壳聚糖还具有一定的抑菌作用，对细菌、霉菌、真菌、酵母菌具有明显的抑制作用。此外，壳聚糖还具有很好的成膜性，在适当的溶剂中，壳聚糖分子间可以交联成氢键，成膜性能良好，被视为开发新型天然抑菌保鲜膜的理想材料。
曲酸是由一些微生物如曲霉属真菌(Aspergillus)和醋杆菌属(Acetobacter)等经过好氧发酵产生的一种常见的弱酸性代谢产物。由于曲酸特有的类似苯邻二酚的结构，所以具有抗菌抗病毒、抗发炎、抗肿瘤、抗氧化等作用，且安全无毒，此外，曲酸还具有易溶于水、细菌无法利用、pH适用范围广、热稳定性好，受热不易分解、对人体无刺激和食用安全等优点。氯代曲酸是曲酸的多功能骨 架经过衍生化后得到的具有较强抑菌活性的产物，它是进行亲核取代和亲电取代反应的良好的配体，因能鳌合菌体细胞代谢所必需的金属阳离子而具有较强的抗细菌和抗真菌的作用。
发明内容
本发明要解决的技术问题是提供一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜及其制备方法，克服了现有技术中壳聚糖膜自身较水蒸气阻隔性能和机械强度差的缺陷。
为了解决上述技术问题，本发明提供了一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，所述复合抑菌保鲜膜至少包括层叠设置的第一复合膜和第二复合膜；
其中，所述第一复合膜为壳聚糖与曲酸复合膜，且壳聚糖的数均分子量为150～300KDa，脱乙酰度≥90％；所述第二复合膜为壳聚糖与氯代曲酸复合膜，且壳聚糖的数均分子量为400～800KDa，脱乙酰度≥85％。
本发明中，数均分子量在150～300KDa、400～800KDa的壳聚糖具有较好的成膜性和抑菌活性，而脱乙酰度在85％以上的壳聚糖具有较多的活性氨基，能够和曲酸及氯代曲酸之间结合更紧密，使得所制备的复合膜具有较好的机械性能和水蒸气阻隔效果。
进一步地，所述第一复合膜中，曲酸的壳聚糖的质量比为0.05～0.15:0.5～1.2；所述第二复合膜中，氯代曲酸与壳聚糖的质量比为0.05～0.15:0.5～1.2。
进一步地，所述第一复合膜和/或第二复合膜中还包括增塑剂，所述增塑剂与壳聚糖的质量比为0.5～0.8:0.5～1.2。
进一步地，所述增塑剂选自甘油、山梨糖醇、聚乙二醇、硬脂酸中的至少一种。
本发明中，第一复合膜和第二复合膜的厚度可设置在几μm到几十μm之间，例如5～90μm。进一步地，所述第一复合膜的厚度为35.55～39.85μm，所述 第二复合膜的厚度为36.68～41.06μm。
本发明中，所述复合抑菌保鲜膜可采用多种方法制备而成，包括但不限于流延膜、挤压成膜等。优选地，所述第一复合膜和/或第二复合膜为流延膜，具有生产效率高、复合膜的均匀性好、性能稳定的优点。
本发明另一方面提供了一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备方法，包括以下步骤：
配置壳聚糖/曲酸混合膜液和壳聚糖/氯代曲酸混合膜液；其中，壳聚糖/曲酸混合膜液中，壳聚糖的数均分子量为150～300KDa，脱乙酰度≥90％；壳聚糖/氯代曲酸混合膜液中，壳聚糖的数均分子量为400～800KDa，脱乙酰度≥85％；
将壳聚糖/曲酸混合膜液流延成膜，干燥；接着在其表面上将壳聚糖/氯代曲酸混合膜液流延成膜，干燥，即得所述壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜。
进一步地，所述壳聚糖/曲酸混合膜液的配置方法为：
将壳聚糖溶于浓度为1％的乙酸溶液中，搅拌、超声至壳聚糖完全溶解，得到浓度为5～12g/L的壳聚糖溶液；按照增塑剂:壳聚糖＝0.5～0.8:0.5～1.2的比例向所述壳聚糖溶液中加入增塑剂，搅拌均匀，备用；
按照曲酸:壳聚糖＝0.05～0.15:0.5～1.2的比例，向上述溶液中加入曲酸，搅拌30～60min，搅拌速度为400～800r/min；超声分散5～10min，频率为35～50KHz；再静置1～2h，真空减压脱泡10～20min，即得到所述壳聚糖/曲酸混合膜液。
进一步地，所述壳聚糖/氯代曲酸混合膜液的配置方法为：
将壳聚糖溶于浓度为1％的乙酸溶液中，搅拌、超声至壳聚糖完全溶解，得到浓度为5～12g/L的壳聚糖溶液；按照增塑剂:壳聚糖＝0.5～0.8:0.5～1.2的比例向所述壳聚糖溶液中加入增塑剂，搅拌均匀，备用；
按照氯代曲酸:壳聚糖＝0.05～0.15:0.5～1.2的比例，向上述溶液中加入氯代曲酸，搅拌45～90min，搅拌速度为800～1000r/min；超声分散10～15min，频率为35～50KHz；再静置1～2h，真空减压脱泡15～25min，即得到所述壳聚糖/氯代曲酸混合膜液。
进一步地，所述增塑剂选自甘油、山梨糖醇、聚乙二醇、硬脂酸中的至少一种。
进一步地，流延成膜时，壳聚糖/氯代曲酸复合膜液的量多于壳聚糖/曲酸复合膜液，优选地，壳聚糖/氯代曲酸复合膜液与壳聚糖/曲酸复合膜液的用量比为1～3:1，此时该复合膜具有较好的抑菌活性。当比例超过3:1时，膜的厚度较大，干燥时间较长，而2:1时的抑菌活性最高，膜的性能最好。
进一步地，壳聚糖/曲酸复合膜液的干燥条件为：干燥温度为35～55℃，干燥时间为1～2h；壳聚糖/氯代曲酸复合膜液的干燥条件为：干燥温度为55～75℃，时间为2～4h。本发明中，壳聚糖/曲酸复合膜液与壳聚糖/氯代曲酸复合膜液采用不同的干燥条件，其原因是：壳聚糖/曲酸复合膜液中，所用的壳聚糖数均分子量为150～300KDa，且混合膜液量较少，所需干燥温度较低，时间较短。而壳聚糖/氯代曲酸复合膜液中，所用的壳聚糖数均分子量为400～800KDa，黏度更大，同时混合膜液量较多，因此所需干燥温度较高，时间较长。
本发明的有益效果：
1.本发明中利用同是天然生物防腐剂的壳聚糖和曲酸及其衍生物，壳聚糖是从虾蟹壳中提取出的一种天然碱性多糖，曲酸是由某些微生物好氧发酵产生的一种有机酸，食用安全。曲酸经衍生化后，可获得同样具有防腐特性的氯代曲酸。在常温下，曲酸和氯代曲酸分子单元上的5-羟基-γ-吡喃酮基可以和壳聚糖分子中的活性氨基通过静电作用及氢键形成紧密结合的多层膜，从而加强了各组分之间的紧密程度，进一步改善了壳聚糖膜原有的力学性能和水蒸气阻隔性能。同时采用流延法来制备复合膜，具有生产效率高、复合膜的均匀性好、 性能稳定的优点。
2.本发明的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，具有良好的成膜性和机械性能，有较低的水蒸气透过系数和良好的抑菌活性，可避免食品水分的大量流失和达到较好的保鲜效果。
3.本发明的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，制备方法简单、快速，且没有添加任何有毒物质，绿色环保。
附图说明
图1是是对比例1所制备的壳聚糖膜和实施例1所制备的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的X射线衍射图谱。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例1
本实施例提供了一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其制备方法包括以下步骤：
1、壳聚糖1溶液的制备
将数均分子量为157KDa，脱乙酰度为90％的壳聚糖0.5g溶于1％乙酸溶液中，在1000r/min下搅拌1h后，在超声频率为35KHz下超声1h至完全溶解，加入0.5g甘油，在搅拌速度为500r/min下搅拌30min，备用。
2、壳聚糖2溶液的制备
将数均分子量为495KDa，脱乙酰度为85％的壳聚糖0.5g溶于1％乙酸溶液中，在1500r/min下搅拌1.5h，在超声频率为40KHz下超声1.5h至完全溶解，加入0.5g甘油，在搅拌速度为800r/min下搅拌1h，备用。
3、壳聚糖1/曲酸混合膜液制备
将0.05g曲酸添加到壳聚糖1溶液中，在搅拌速度为400r/min下，搅拌30min，在频率为35KHz下超声脱气5min，静置1h后，真空减压脱泡10min。
4、壳聚糖2/氯代曲酸混合膜液制备
将0.05g氯代曲酸添加到上述壳聚糖2溶液中，在搅拌速度为800r/min下，搅拌45min，静置1h后，在频率为35KHz下超声脱泡10min，静置1h后，真空减压脱泡15min。
5、壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备
取6mL壳聚糖1/曲酸混合膜液在10×20cm 2玻璃板上流延成膜，在烘箱温度为35℃下干燥1h，之后在其表面加上12mL壳聚糖2/氯代曲酸混合膜液，流延成膜，在烘箱温度为55℃下干燥2h，揭膜。即可得到壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜。
实施例2
本实施例提供了一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其制备方法包括以下步骤：
1、壳聚糖1溶液的制备
将数均分子量为198KDa，脱乙酰度为92％的壳聚糖0.8g溶于1％乙酸溶液中，在1000r/min下搅拌1h，在超声频率为35KHz下超声1h至完全溶解，加入0.6g甘油，在搅拌速度为500r/min下搅拌30min，备用。
2、壳聚糖2溶液的制备
将数均分子量为525KDa，脱乙酰度为90％的壳聚糖0.8g溶于1％乙酸溶液中，在1500r/min下搅拌1.5h，在超声频率为40KHz下超声1.5h至完全溶解，加入0.6g甘油，在搅拌速度为800r/min下搅拌1h，备用。
3、壳聚糖1/曲酸混合膜液制备
将0.08g曲酸添加到壳聚糖1溶液中，搅拌速度为600r/min，搅拌时间为45min，超声分散，频率为40KHz，时间为8min，静置1.5h，真空减压脱泡15min。
4、壳聚糖2/氯代曲酸混合膜液制备
将0.08g氯代曲酸添加到上述壳聚糖2溶液中，在搅拌速度为900r/min下，搅拌60min，在频率为40KHz下超声脱泡12min，静置1.5h后，真空减压脱泡20min。
5、壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备
取6mL壳聚糖1/曲酸混合膜液在10×20cm 2玻璃板上流延成膜，在烘箱温度为40℃下干燥1.5h，之后在其表面加上12mL壳聚糖2/氯代曲酸混合膜液，流延成膜，在烘箱温度为60℃下干燥3h，揭膜。即可得到壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜。
实施例3
本实施例提供了一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其制备方法包括以下步骤：
1、壳聚糖1溶液的制备
将数均分子量为288KDa，脱乙酰度为95％的壳聚糖1.0g溶于1％乙酸溶液中，在1000r/min下搅拌1h，在超声频率为35KHz下超声1h至完全溶解，加入0.8g甘油，在搅拌速度为500r/min下搅拌30min，备用。
2、壳聚糖2溶液的制备
将数均分子量为789KDa，脱乙酰度为95％的壳聚糖1.0g溶于1％乙酸溶液中，在1500r/min下搅拌1.5h，在超声频率为40KHz下超声1.5h至完全溶解，加入0.8g甘油，在搅拌速度为800r/min下搅拌1h，备用。
3、壳聚糖1/曲酸混合膜液制备：
将0.10g曲酸添加到壳聚糖1溶液中，搅拌速度为800r/min，搅拌时间为60min；超声分散，频率为50KHz，时间为10min；静置2h，真空减压脱泡20min。
4、壳聚糖2/氯代曲酸混合膜液制备
将0.10g氯代曲酸添加到上述壳聚糖2溶液中，在搅拌速度为1000r/min下，搅拌90min；在频率为50KHz下超声脱泡15min，静置2h后，真空减压脱泡25min。
5、壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备
取6mL壳聚糖1/曲酸混合膜液在10×20cm 2玻璃板上流延成膜，在烘箱温度为50℃下干燥2h，之后在其表面加上12mL壳聚糖2/氯代曲酸混合膜液，流延成膜，在烘箱温度为70℃下干燥4h，揭膜。即可得到壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜。
对比例1
本对比例提供一种纯壳聚糖1抑菌保鲜膜，其制备方法包括以下步骤：
将数均分子量为157KDa，脱乙酰度为90％的壳聚糖0.5g溶于1％乙酸溶液中，在1000r/min下搅拌1h后，在超声频率为35KHz下超声1h至完全溶解，加入0.5g甘油，在搅拌速度为500r/min下搅拌30min，然后将18mL壳聚糖1膜液倒在玻璃板上，流延成膜，将玻璃板放入45℃烘箱中干燥1h，即可得到壳聚糖1抑菌保鲜膜。
对比例2
本对比例提供一种纯壳聚糖2抑菌保鲜膜，其制备方法包括以下步骤：
将数均分子量为495KDa，脱乙酰度为85％的壳聚糖0.5g溶于1％乙酸溶液中，在1000r/min下搅拌1h后，在超声频率为35KHz下超声1h至完全溶解，加入0.5g甘油，在搅拌速度为800r/min下搅拌1h，然后将18mL壳聚糖2膜 液倒在玻璃板上，流延成膜，将玻璃板放入60℃烘箱中干燥2h，即可得到壳聚糖2抑菌保鲜膜。
对比例3
本对比例提供一种纯壳聚糖1和壳聚糖2抑菌复合保鲜膜，其制备方法包括以下步骤：
将数均分子量为157KDa，脱乙酰度为90％的壳聚糖0.5g溶于1％乙酸溶液中，在1000r/min下搅拌1h后，在超声频率为35KHz下超声1h至完全溶解，加入0.5g甘油，在搅拌速度为500r/min下搅拌30min，备用。
将数均数均分子量为495KDa，脱乙酰度为85％的壳聚糖0.5g溶于1％乙酸溶液中，在1000r/min下搅拌1h后，在超声频率为35KHz下超声1h至完全溶解，加入0.6g甘油，在搅拌速度为800r/min下搅拌1h，备用。
将9mL壳聚糖1膜液和9mL壳聚糖2膜液倒在玻璃板上，流延成膜，将玻璃板放入65℃烘箱中干燥2h，即可得到壳聚糖1和壳聚糖2复合抑菌保鲜膜。
对比例4
本对比例提供一种壳聚糖1/曲酸混合抑菌保鲜膜，其制备方法包括以下步骤：
将数均分子量为157KDa，脱乙酰度为90％的壳聚糖0.8g溶于1％乙酸溶液中，在1000r/min下搅拌1h，在超声频率为35KHz下超声1h至完全溶解，加入0.6g甘油，在搅拌速度为500r/min下搅拌30min，备用。
再将0.08g曲酸添加到壳聚糖1溶液中，搅拌速度为600r/min，搅拌时间为45min，超声分散，频率为40KHz，时间为8min，静置1.5h，真空减压脱泡15min，即可得壳聚糖1/曲酸混合膜液。
然后将18mL壳聚糖1/曲酸混合膜液倒在玻璃板上，流延成膜，将玻璃板 放入50℃烘箱中干燥1.5h，即可得到壳聚糖1/曲酸混合膜液抑菌保鲜膜。
对比例5
本对比例提供一种壳聚糖2/氯代曲酸混合抑菌保鲜膜，其制备方法包括以下步骤：
将数均分子量为495KDa，脱乙酰度为85％的壳聚糖0.8g溶于1％乙酸溶液中，在1500r/min下搅拌1.5h，在超声频率为40KHz下超声1.5h至完全溶解，加入0.6g甘油，在搅拌速度为800r/min下搅拌1h，备用。
再将0.08g氯代曲酸添加到上述壳聚糖2溶液中，在搅拌速度为900r/min下，搅拌60min，在频率为40KHz下超声脱泡12min，静置1.5h后，真空减压脱泡20min，即可得壳聚糖2/氯代曲酸混合膜液。
然后将18mL壳聚糖2/氯代曲酸混合膜液倒在玻璃板上，流延成膜，将玻璃板放入70℃烘箱中干燥2h，即可得到壳聚糖2/氯代曲酸混合膜液抑菌保鲜膜。
性能测试
1.按照GB13022-91《塑料薄膜拉伸性能实验方法》用万能试验机对膜的拉伸强度和断裂伸长率进行测定，膜的厚度用测厚仪测定。
(1)抗拉强度(TS)计算如公式1所示：
TS＝F MAX/(L×W)     (公式1)
TS表示抗拉强度(Mpa)，Fmax是膜断裂时所承受的最大拉力，L表示膜的宽度，W表示膜的厚度。
(2)断裂伸长率(EB％)计算如公式2所示：
EB％＝(L-L 0)/L 0       (公式2)
L表示膜的初始长度(mm)，L0表示膜拉伸之后的长度(mm)。
2.按照GB1307-88《塑料薄膜和片材透水蒸气性试验方法-杯式法》对膜的水蒸气透过率进行测试。具体操作是，在透湿杯内加入干燥后的无水氯化钙，距离瓶口5mm，瓶口用所制备的保鲜膜扎紧并用石蜡密封，将其置于底部盛有饱和氯化钠溶液干燥器内，每隔一定时间取出称量瓶称重，直到前后两次的质量增加量相差小于5％时为止，称取三次，计算平均值，计算如公式3所示：
WVP＝Δm×d/(A×Δt×Δp)     (公式3)
其中，WVP表示水蒸气透过系数[g·mm/(m 2·h·kPa)]；d表示复合膜的厚度(mm)；Δm表示稳定后的质量增加量(g)；A表示剪取的膜的面积(m 2)，Δt表示每次测量间的时间间隔(h)，Δp表示复合膜两侧固定的水蒸气压差(kPa)，实验温度为25℃，相对湿度保持75％。
3.膜的抑菌性能由平板菌落计数法测试。
取一定量的(10 6CFU/mL)的大肠杆菌和金黄色葡萄球菌悬液滴加在抗菌保鲜膜表面上，涂抹均匀后，置于37±1℃的培养箱内培养4h。然后将其浸泡在PBS缓冲液的离心管中，在37±1℃恒温摇床上震荡10min后，将细菌洗脱PBS缓冲液中稀释。吸取60μL稀释后的PBS缓冲液涂布到琼脂培养基平板上，37±1℃下培养24h，每组重复3次。以未加保鲜膜的细菌悬液为对照组。
性能测试结果
表1对比例1-5和实施例1-3中所制备抑菌保鲜膜的膜厚度、机械性能和水蒸气透过系数
Figure PCTCN2020114938-appb-000001
Figure PCTCN2020114938-appb-000002
表1是对比例1-5和实施例1-3所制备的抑菌保鲜膜的膜厚度、机械性能和水蒸气透过系数。从表1可以看出，相比较于对比例1-3中未添加曲酸和氯代曲酸组，实施例1-3中，随着曲酸和氯代曲酸的增加，膜的抗拉强度和断裂伸长率逐渐增加，同时水透过系数逐渐降低。这是因为曲酸和氯代曲酸的加入，破坏了壳聚糖分子内和分子间的氢键作用，同时形成了新的氢键作用，使得膜的性能改变。
表2 对比例1-5和实施例1-3中所制备抑菌保鲜膜的抑菌性能
Figure PCTCN2020114938-appb-000003
表2是本发明对比例1-5和实施例1-3中所制备抑菌保鲜膜的抑菌性能。从表中可以看出，随着曲酸和氯代曲酸含量的增加，膜对细菌的抑制率要比未添加的明显增强并且逐渐增加，对大肠杆菌和金黄色葡萄球菌的抑制率可分别达到96％和91％，具有良好的抑制效果。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或 变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (10)

  1. 一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其特征在于，至少包括层叠设置的第一复合膜和第二复合膜；
    其中，所述第一复合膜为壳聚糖与曲酸复合膜，且壳聚糖的数均分子量为150～300KDa，脱乙酰度≥90％；所述第二复合膜为壳聚糖与氯代曲酸复合膜，且壳聚糖的数均分子量为400～800KDa，脱乙酰度≥85％。
  2. 如权利要求1所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其特征在于，所述第一复合膜中，曲酸与壳聚糖的质量比为0.05～0.15:0.5～1.2；所述第二复合膜中，氯代曲酸与壳聚糖的质量比为0.05～0.15:0.5～1.2。
  3. 如权利要求1所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其特征在于，所述第一复合膜和/或第二复合膜中还包括增塑剂，所述增塑剂与壳聚糖的质量比为0.5～0.8:0.5～1.2。
  4. 如权利要求3所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其特征在于，所述增塑剂选自甘油、山梨糖醇、聚乙二醇、硬脂酸中的至少一种。
  5. 如权利要求1所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其特征在于，所述第一复合膜的厚度为35.55～39.85μm，所述第二复合膜的厚度为36.68～41.06μm。
  6. 如权利要求1所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜，其特征在于，所述第一复合膜和/或第二复合膜为流延膜。
  7. 一种壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备方法，其特征在于，包括以下步骤：
    配置壳聚糖/曲酸混合膜液和壳聚糖/氯代曲酸混合膜液；其中，壳聚糖/曲 酸混合膜液中，壳聚糖的数均分子量为150～300KDa，脱乙酰度≥90％；壳聚糖/氯代曲酸混合膜液中，壳聚糖的数均分子量为400～800KDa，脱乙酰度≥85％；
    将壳聚糖/曲酸混合膜液流延成膜，干燥；接着在其表面上将壳聚糖/氯代曲酸混合膜液流延成膜，干燥，即得所述壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜。
  8. 如权利要求7所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备方法，其特征在于，所述壳聚糖/曲酸混合膜液的配置方法为：
    将壳聚糖溶于浓度为1％的乙酸溶液中，搅拌、超声至壳聚糖完全溶解，得到浓度为5～12g/L的壳聚糖溶液；按照增塑剂:壳聚糖＝0.5～0.8:0.5～1.2的比例向所述壳聚糖溶液中加入增塑剂，搅拌均匀，备用；
    按照曲酸:壳聚糖＝0.05～0.15:0.5～1.2的比例，向上述溶液中加入曲酸，搅拌30～60min，搅拌速度为400～800r/min；超声分散5～10min，频率为35～50KHz；再静置1～2h，真空减压脱泡10～20min，即得到所述壳聚糖/曲酸混合膜液。
  9. 如权利要求7所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备方法，其特征在于，所述壳聚糖/氯代曲酸混合膜液的配置方法为：
    将壳聚糖溶于浓度为1％的乙酸溶液中，搅拌、超声至壳聚糖完全溶解，得到浓度为5～12g/L的壳聚糖溶液；按照增塑剂:壳聚糖＝0.5～0.8:0.5～1.2的比例向所述壳聚糖溶液中加入增塑剂，搅拌均匀，备用；
    按照氯代曲酸:壳聚糖＝0.05～0.15:0.5～1.2的比例，向上述溶液中加入氯代曲酸，搅拌45～90min，搅拌速度为800～1000r/min；超声分散10～15min，频率为35～50KHz；再静置1～2h，真空减压脱泡15～25min，即得到所述壳聚糖/氯代曲酸混合膜液。
  10. 如权利要求7所述的壳聚糖/曲酸/氯代曲酸复合抑菌保鲜膜的制备方法，其特征在于，壳聚糖/曲酸复合膜液的干燥条件为：干燥温度为35～55℃，干燥时间为1～2h；壳聚糖/氯代曲酸复合膜液的干燥条件为：干燥温度为55～75℃，时间为2～4h。
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