WO2018120704A1 - Mildew-proof preservative film and preparation method therefor - Google Patents

Mildew-proof preservative film and preparation method therefor Download PDF

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Publication number
WO2018120704A1
WO2018120704A1 PCT/CN2017/090900 CN2017090900W WO2018120704A1 WO 2018120704 A1 WO2018120704 A1 WO 2018120704A1 CN 2017090900 W CN2017090900 W CN 2017090900W WO 2018120704 A1 WO2018120704 A1 WO 2018120704A1
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mold
proof
agent
mildew
fresh
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PCT/CN2017/090900
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French (fr)
Chinese (zh)
Inventor
余赞
钟文
田璐
罗臻
张勇军
韦雪雪
钱正宇
杜建军
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常德金德新材料科技股份有限公司
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Priority to ZA201800718A priority Critical patent/ZA201800718B/en
Publication of WO2018120704A1 publication Critical patent/WO2018120704A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
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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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
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    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • 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
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
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    • 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
    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08J2431/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2431/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to the technical field of food storage, in particular to an anti-mild plastic wrap film and a preparation method thereof.
  • An anti-mild plastic wrap film comprising a base layer and a mildew-proof fresh-keeping coating layer disposed on the base layer, wherein the raw material of the mildew-proof fresh-keeping coating is a mildew-proof fresh-keeping paint, and the anti-mold and fresh-keeping paint is content by weight
  • the composition includes the following components: resin 20% to 60%, solvent 30% to 70%, mold inhibitor 0.5% to 10%, and auxiliary agent 0.3% to 5%, wherein the resin is polyurethane, acrylate copolymer, poly At least one of vinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate copolymer, and vinyl acetate-butyl ester copolymer, the solvent It is at least one of water and ethanol.
  • the above-mentioned mildew-proof plastic wrap film has a dense surface and no pores, and is added with an anti-fungal agent, thereby having a good effect of keeping moisture constant and preventing mildew.
  • the mildew-proof plastic wrap is especially suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles.
  • the surface of the mold-proof plastic wrap coated with the anti-mold and fresh-keeping coating is used as the inner surface, which can promote the contact between the anti-mold and fresh-keeping coating and the fresh-keeping articles in the mold-proof plastic wrap, thereby improving the fresh-keeping effect.
  • the acrylate copolymer is selected from the group consisting of methyl methacrylate-acrylic acid Ethyl ester-butyl acrylate copolymer, at least one of methyl methacrylate-butyl acrylate-acrylic acid copolymer, methyl methacrylate-butyl acrylate-acrylic acid-N-methylol acrylamide copolymer.
  • the antifungal agent is a natural extract antifungal agent
  • the natural extract antifungal agent is selected from the group consisting of gingerol, catechin, citric acid, allicin, chitosan, At least one of sorbic acid, turmeric root alcohol, citron essential oil, Mengzong bamboo extract, geranol and nisin.
  • the resin is an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate copolymer And at least one of the vinyl acetate-butyl ester copolymer, the anti-mold coating further comprises not more than 3% of a neutralizing agent by weight, the neutralizing agent being selected from the group consisting of sodium hydrogencarbonate, three At least one of ethylamine and ammonia in water.
  • the anti-mold agent is a non-natural extract anti-fungal agent
  • the non-natural extract anti-mold agent is selected from the group consisting of sodium diacetate, potassium sorbate, sodium sorbate, potassium citrate, Sodium citrate, calcium propionate, sodium ascorbate, potassium ascorbate, sodium salicylate, salicylamine, lauryl alanine, sodium isophora, carson, paraben, fumaric acid and lysobacteria At least one of the molds.
  • the antifungal agent is a natural extract antifungal agent and a non-natural extract antifungal agent, and the natural extract antifungal agent and the non-natural extract are resistant.
  • the mass ratio of the fungicide is from 0.4 to 1.5:1.
  • the mold proof coating has a thickness of 0.5 to 10 ⁇ m.
  • the base layer is a PET film, a PP film, a PA6 film, an EVA film, an EVOH film, a PVA film, or a PLA film.
  • a method for preparing a moldproof plastic wrap film comprising the following steps:
  • the method for preparing the mold-proof fresh-keeping paint comprises the following steps: providing a raw material, comprising: 20% to 60% of a resin, 30% to 70% of a solvent, and 0.5% to 10% of an antifungal agent according to a weight percentage % and auxiliary agent 0.3% to 5%; wherein the resin is polyurethane, acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, At least one of a polyvinyl acetate copolymer and a vinyl acetate-butyl ester copolymer, the solvent being at least one of water and ethanol; mixing the resin, the solvent and the auxiliary agent uniformly, Obtaining a mixed liquid; mixing the mixed liquid and the anti-fungal agent to obtain the anti-mold and fresh-keeping paint;
  • the preparation method of the above-mentioned mildew-proof plastic wrap, the resin forming a network structure in the anti-mold and fresh-keeping coating, and the anti-mold agent-preserving resin in the network structure, the obtained anti-mold fresh-keeping coating has a good function of maintaining moisture constant and preventing mildew Effect.
  • the mildew-proof plastic wrap is especially suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles.
  • the anti-fungal agent in the preparation step of the mildew-proof fresh-keeping paint, is added to the mixed solution in a dropping manner to be mixed with the mixed liquid.
  • Figure 1 is a structural view of an anti-mold and plastic wrap film of an embodiment
  • FIG. 2 is a flow chart showing a method of preparing a mildew-proof fresh-keeping paint according to an embodiment.
  • an anti-mold coating film 1 of an embodiment includes a base layer 11 and an anti-mold coating 12 disposed on the base layer 11.
  • the raw material of the mildew-proof fresh-keeping coating 12 is a mildew-proof fresh-keeping paint.
  • the base layer 11 is a PET film (polyethylene terephthalate film), a PP film (polypropylene film), a PA6 film (polyamide 6 film), and an EVA film (ethylene-polyvinyl acetate copolymer film).
  • EVA film ethylene-polyvinyl acetate copolymer film
  • EVOH film ethylene-vinyl alcohol copolymer film
  • PVA film polyvinyl alcohol film
  • PLA film linear aliphatic polyester-polylactic acid film.
  • the base layer 11 is a PET film and a PP film. PET and PP can maintain excellent performance at temperatures up to 120 ° C, which can avoid the problem of the base layer 11 being damaged by heat treatment of the safety coating to form a mildew-proof coating.
  • the base layer 11 has a thickness of 12 to 22 ⁇ m.
  • the mold-preserving coating 12 has a thickness of 0.5 to 10 ⁇ m. If the thickness of the mildew-proof fresh-keeping coating 12 is insufficient, the resin cannot be effectively formed into a film, and the effect of preventing mildew and fresh-keeping is not reflected. The thickness of the mildew-proof fresh-keeping coating 12 is too thick, which not only increases the cost, but also cannot be completely dried during heat treatment, and there is a problem such as back sticking. Like, and when it is not completely dry, since the outer surface is partially dried, and the inside is still in a liquid state, in the process of continuing to air dry, the cracking of the coating is likely to occur due to the natural drying of the interior, which is also extremely great. Reduce the effect of mildew-proof and fresh-keeping coatings.
  • the present invention provides an anti-mild and fresh-keeping coating of an embodiment.
  • the mildew-proof fresh-keeping coating comprises the following components in a weight percentage: 20% to 60% of the resin, 30% to 70% of the solvent, 0.5% to 10% of the antifungal agent, and 0.3% to 5% of the auxiliary agent.
  • the resin is polyurethane, acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate copolymer and vinyl acetate. At least one of the butyl ester copolymers.
  • a resin is selected from a resin which is compatible with the antifungal agent and is soluble in a water solvent, so that the antifungal agent can be sufficiently dispersed in the resin to ensure the effect of the antifungal agent, and the disadvantage of toxic solvents contaminating the environment can be avoided.
  • the resin is at least one of a polyurethane, an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, and modified polyvinylidene chloride.
  • the chemical properties of these resins are higher than those of ethylene vinyl acetate.
  • the copolymer, polyvinyl acetate copolymer and vinyl acetate-butyl ester copolymer are more stable, and are more safe for use when the plastic wrap is in contact with food.
  • the resin in the component is a host material, and the resin is a high-performance polymer, which is not mildewed by itself, and the surface of the coating is dense and has no pores, thereby maximally limiting the adsorption of water molecules and Dissolved, and the strong cohesive force between the molecules can inhibit the movement of water molecules in it, thereby effectively inhibiting the ingress and egress of moisture into and out of the coating, thereby preventing the loss of moisture and moisture, maintaining a constant moisture and moisturizing effect.
  • the acrylate-based copolymer is selected from the group consisting of methyl methacrylate-ethyl acrylate-butyl acrylate copolymer, methyl methacrylate-butyl acrylate-acrylic acid copolymer, methyl methacrylate-butyl acrylate- At least one of an acrylic acid-N-methylol acrylamide copolymer.
  • methyl methacrylate-ethyl acrylate-butyl acrylate copolymer it is obtained by copolymerization of three monomers of methyl methacrylate, ethyl acrylate and butyl acrylate.
  • the polyvinyl alcohol is selected from at least one of polyvinyl alcohol 1788, polyvinyl alcohol 2088, and polyvinyl alcohol 2488.
  • Polyvinyl alcohol 1788, polyvinyl alcohol 2088 and polyvinyl alcohol 2488 are all water-soluble polyvinyl alcohols. Taking polyvinyl alcohol 1788 as an example, it is a polyvinyl alcohol having a degree of polymerization of 1,700 and a degree of alcoholysis of 88%.
  • the modified polyvinylidene chloride is at least one selected from the group consisting of acrylate-modified polyvinylidene chloride and urethane-modified polyvinylidene chloride.
  • the water solubility of polyurethane modified polyvinylidene chloride is significantly improved.
  • the solvent is at least one of water and ethanol. Both water and ethanol are environmentally friendly and non-toxic solvents. They are used in the mold-proof plastic wrap 1 to be in direct contact with food, etc., avoiding the use of toxic solvents for the packaging of polyurethane, polyvinyl alcohol, ethylene vinyl acetate copolymer, A water-soluble resin such as a polyvinyl acetate copolymer, and the solvent is preferably water to achieve environmental protection and cost reduction.
  • the antifungal agent is at least one of a natural extract antifungal agent and a non-natural extract antifungal agent.
  • the natural extract antifungal agent is selected from the group consisting of gingerol, catechin, citric acid, allicin, chitosan, sorbic acid, turmeric root alcohol, citron essential oil, Mengzong bamboo extract, geranol and lactic acid chain ball At least one of the bacterins.
  • the non-natural extract fungicide is selected from the group consisting of sodium diacetate, potassium sorbate, sodium sorbate, potassium citrate, sodium citrate, calcium propionate, sodium ascorbate, potassium ascorbate, sodium salicylate, and salicylate. At least one of bacteriocin, dodecylalanine, isovitamin C sodium, carson, paraben, fumaric acid, and lysogen.
  • the antifungal agent is a natural extract type fungicide and a non-natural extract type fungicide.
  • the use of the two antifungal agents in this way is advantageous for increasing the amount of the antifungal agent entering the resin, thereby improving the antifungal effect.
  • the antifungal agent is a natural extract antifungal agent and a non-natural extract antifungal agent
  • the mass ratio of the natural extract antifungal agent and the non-natural extract antifungal agent is 0.4 to 1.5. :1.
  • the natural extract antifungal agent has good mildew resistance under alkaline conditions, and the polyurethane itself is weakly alkaline.
  • the antifungal agent contains a natural extract antifungal agent
  • the resin is an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymerization
  • the anti-mold coating further comprises not more than 3% of a neutralizing agent by weight, and the neutralizing agent is selected From at least one of sodium hydrogencarbonate, triethylamine and aqueous ammonia, the concentration of the aqueous ammonia is not less than 3 mol/L. It will be appreciated that the neutralizing agent can be concentrated aqueous ammonia. It can be understood that the antifungal agent is a non-natural extract antifungal agent
  • the auxiliary agent includes at least one of a surfactant, an emulsifier, a wetting agent, an antifoaming agent, and an anti-settling agent.
  • the surfactant is Tween and Span, and the surfactant can make the antifungal agent more uniformly dispersed in the resin.
  • the emulsifier is advantageous for promoting the formation of a stable aqueous emulsion of a poorly water-soluble resin.
  • the resin is dissolved in a solvent and the film forming property is adjusted by an auxiliary agent, and the distribution ratio of the control group is controlled to form a surface-dense, non-porous coating, thereby maximally limiting water molecules.
  • Adsorption and dissolution, and the cohesive force between the polymers can inhibit the movement of water molecules therein, thereby effectively inhibiting the ingress and egress of moisture into and out of the coating to maintain a constant moisture and moisturizing effect.
  • the resin and the antifungal agent have good mutual solubility, so that the antifungal agent is sufficiently dispersed in the resin to ensure the effect of the antifungal agent, and the disadvantage of toxic solvent polluting the environment can be avoided.
  • the anti-fungal agent can enter the cell through the cell membrane of the microorganism to destroy the microorganism or prevent it from germinating to prevent the growth of the mold, thereby achieving a long-term stable preservation effect.
  • a method for preparing the above-mentioned mildew-proof fresh-keeping paint of the present invention comprises the following steps.
  • Step S110 providing a raw material, which comprises 20% to 60% by weight of the resin, 30% to 70% of the solvent, 0.5% to 10% of the antifungal agent, and 0.3% to 5% of the auxiliary agent.
  • Step S120 mixing the resin, the solvent and the auxiliary agent uniformly to obtain a mixed liquid.
  • the temperature at which the resin, the solvent and the auxiliary agent are mixed in the step S120 is 30 to 65 °C.
  • the step S120 includes the steps of dissolving the resin in a solvent, stirring at a rotation speed of 100 to 300 rpm and heating to 30 to 65 ° C; adding an auxiliary agent, continuing at a rotation speed of 200 to 400 rpm. Stir for 30 to 60 minutes to obtain a mixed solution.
  • the temperature and stirring intensity are controlled in such a way that the mixture is uniformly mixed.
  • the antifungal fresh-keeping paint further comprises not more than 3% of the neutralizing agent by weight
  • the step S120 further comprises the step of: adding the mixed liquid and adding the medium
  • the agent is used to adjust the pH of the mixture to 7-8.
  • Adding a neutralizing agent to adjust the pH of the mixture is to control the pH of the system, so that the pH of the system is as close as possible to the neutrality so that the pH of the coating is close to neutral, thereby improving its environmental friendliness.
  • Step S130 mixing the mixed solution and the anti-mold agent to obtain a mildew-proof fresh-keeping paint.
  • the mixture and the anti-fungal agent are uniformly mixed, so that the anti-mold agent is uniformly dispersed inside the resin, and the problem that the anti-fungal agent is dissolved in the free state and the effective content of the anti-fungal agent is decreased when the anti-mold agent is formed, thereby reducing the anti-mold effect.
  • the antifungal agent enters the cell through the cell membrane of the microorganism to destroy the microorganism or prevent it from germinating to prevent the growth of the mold, thereby achieving a long-term stable preservation effect.
  • the anti-fungal agent is added to the mixed solution in a dropping manner to be mixed with the mixed liquid, so that the anti-fungal agent is more fully dispersed in the resin, and the anti-fungal agent is prevented from being freed in the solvent as much as possible, thereby improving the anti-fungal agent.
  • Effective content More preferably, when the antifungal agent is a natural extract antifungal agent and a non-natural extract antifungal agent, the two antifungal agents are separately and simultaneously added to the mixed solution to prevent the two kinds. The addition of the anti-fungal agent causes the latter anti-fungal agent to be present in the solvent in a free state, so that a better knot cannot be achieved. The problem with the effect.
  • the conditions for mixing the mixed solution and the anti-mold agent in step S130 are mixed at 30 to 65 ° C for 1 to 2 h. It can be understood that when the antifungal agent is added by dropping, after the end of the antifungal agent is added, the mixed solution and the antifungal agent are continuously mixed for 1 to 2 hours. Step S130 is stirred and mixed at a number of revolutions of 500 to 800 rpm.
  • the preparation method of the above-mentioned mildew-proof fresh-keeping paint has the advantages of simple process and easy realization, and the obtained mold-preserving and fresh-keeping paint has good film forming property, and can form a surface-tight and non-porous anti-mold and fresh-keeping coating, thereby maximally limiting the adsorption of water molecules. And dissolve, and the cohesive force between the polymers can inhibit the movement of water molecules therein, thereby effectively inhibiting the ingress and egress of moisture into and out of the coating, thereby achieving a constant moisture retention and moisturizing effect.
  • the anti-mold agent is uniformly dispersed inside the resin, and the problem that the anti-fungal agent is dissolved in water in a free state to cause a decrease in the anti-fungal agent content when the coating is formed and the anti-mold effect is reduced is avoided.
  • the antifungal agent enters the cell through the cell membrane of the microorganism to destroy the microorganism or prevent it from germinating to prevent the growth of the mold, thereby achieving a long-term stable preservation effect.
  • the mildew-proof fresh-keeping coating is particularly suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles.
  • the invention also provides a preparation method of the moldproof and preservative film of an embodiment.
  • the preparation method comprises the steps of: preparing a mildew-proof fresh-keeping paint; applying a mildew-proof fresh-keeping paint on the base layer and performing heat treatment to form a mildew-proof and fresh-keeping coating on the mildew-proof fresh-keeping paint, and obtaining the mold-proof and fresh-keeping film.
  • the preparation method of the above-mentioned mildew-proof plastic wrap film the resin in the anti-mold fresh-keeping coating is cross-linked to form a network structure, and the anti-mold agent is uniformly dispersed in the network structure of the resin, and the obtained anti-mold and fresh-keeping coating has a dense surface, no The pores, therefore, the mildew-proof fresh-keeping coating has a good effect of maintaining a constant moisture; the anti-fungal agent is uniformly dispersed inside the resin, and can effectively prevent mildew, thereby achieving better preservation effect.
  • the coating amount of the mildew-proof fresh-keeping coating applied to the base layer 11 is 1 to 10 g/m 2 , that is, the coating amount of the mildew-proof fresh-keeping coating on the base layer 11 unit area, thereby controlling the mildew-proof fresh-keeping coating 12
  • the thickness is 0.5 to 10 ⁇ m.
  • the heat treatment is carried out at 80 to 120 ° C for 5 to 10 s.
  • the resin undergoes a crosslinking reaction under such conditions to form a dense network structure, so that the coating has an effect of preventing moisture from entering and leaving. Due to the limited thickness of the coating, the heat treatment time is too long and will affect the performance of the coating.
  • the heat treatment conditions are respectively carried out at 80 to 85 ° C, 90 to 100 ° C, 105 to 120 ° C, 90 to 100 ° C, and 80 to 85 ° C for 1 to 2 s.
  • the coating is heat treated in the temperature region, and the temperature region is The gradient distribution makes the coating gradually warm up in the early stage of film formation, and gradually lowers the temperature in the later stage of film formation, thereby improving the compactness of the coating and ensuring that the coating does not crack.
  • the conditions of the heat treatment are respectively treated at 80 ° C, 90 ° C, 120 ° C, 100 ° C and 85 ° C for 1.2 s.
  • the anti-mold and anti-fresh film 1 has a surface which is dense and non-porous, and has an anti-fungal agent added thereto, thereby having a good effect of keeping moisture constant and preventing mildew.
  • the mildew-proof plastic wrap 1 is particularly suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles.
  • the mold-proof plastic wrap film 1 is coated with the surface of the mildew-proof fresh-keeping coating 12 as an inner surface, the anti-mold fresh-keeping coating 12 can be brought into contact with the fresh-keeping articles in the mildew-proof plastic wrap film 11, thereby improving the freshness preservation. effect.
  • the raw materials are provided in a weight percentage including: polyurethane resin 60%, water 30%, gingerol 5%, and Tween 4%.
  • the polyurethane resin was dissolved in water, stirred at 300 rpm and heated to 50 ° C; an auxiliary was added, and stirring was continued for 50 min at 300 rpm to obtain a mixed solution.
  • the pH of the mixture after adding triethylamine was 7.
  • Gingerol was added to the mixture by stirring at a rotation speed of 600 rpm, and after the addition of the gingerol was completed, the mixture and the gingerol were continuously stirred and mixed at a rotation speed of 600 rpm. Cool down and get anti-mold and fresh-keeping paint.
  • the mold-proof fresh-keeping paint was coated on the PET film at a coating amount of 10 g/m 2 , and then treated at 80 ° C, 90 ° C, 120 ° C, 100 ° C, and 85 ° C for 1.2 s, respectively, to obtain a mold-proof plastic wrap.
  • the raw materials are provided in a percentage by weight: polyvinyl alcohol 2488 resin 47%, water 40%, sorbic acid and turmeric root alcohol total 8%, Tween 2% and sodium hydrogencarbonate 3%.
  • the polyvinyl alcohol 2488 resin was dissolved in water, stirred at a rotation speed of 100 rpm and heated to 65 ° C; an auxiliary was added, and stirring was continued for 30 minutes at a rotation speed of 200 rpm to obtain a mixed solution.
  • the pH of the mixture after adding sodium hydrogencarbonate was 8.
  • the mildew-proof fresh-keeping paint was coated on the PP film at a coating amount of 1 g/m 2 , and then treated at 85 ° C, 95 ° C, 110 ° C, 90 ° C, and 80 ° C for 2 s, respectively, to obtain a mold-proof plastic wrap.
  • the raw materials are provided in a weight percentage including: polyurethane modified polyvinylidene chloride resin 20%, water 70%, dodecylalanine 0.5%, and Tween 5%.
  • the polyurethane modified polyvinylidene chloride resin was dissolved in water, stirred at 200 rpm and heated to 60 ° C; an auxiliary was added, and stirring was continued for 50 min at a rotation speed of 400 rpm to obtain a mixed solution.
  • the mold-proof fresh-keeping paint was coated on the EVA film at a coating amount of 5 g/m 2 , and then treated at 83 ° C, 100 ° C, 105 ° C, 95 ° C and 82 ° C for 1 s, respectively, to obtain a mold-proof plastic wrap.
  • the raw materials are provided in the weight percentage including: vinyl acetate-butyl ester copolymer 40%, water and ethanol (volume ratio 1:1) total 48%, Mengzong bamboo extract and isovitamin C sodium (Meng Zongzhu extract and different The mass ratio of vitamin C sodium is 1:1) total 10%, Span 1.5% and concentrated ammonia 0.4%.
  • epoxy resin is not suitable for use in contact with foods and the like, and the present invention aims to solve the anti-mildew and fresh-keeping effects of foods and tobacco leaves. If it is at the expense of food safety hazards, it cannot be considered a technical problem. If you continue to choose to retain epoxy resin, someone raises a question about this, can you pass the defense?
  • the vinyl acetate-butyl ester copolymer was dissolved in water, stirred at 300 rpm and heated to 40 ° C; an auxiliary was added, and stirring was continued for 50 min at 300 rpm to obtain a mixed solution.
  • the pH of the mixture after the addition of concentrated aqueous ammonia was 7.5.
  • the Mengzong bamboo extract and the isovitamin C sodium were separately and simultaneously added to the mixture by stirring at a rotation speed of 800 rpm. After the addition of the anti-fungal agent, the mixture, Mengzong bamboo extract and iso-vitamin C sodium were mixed. Continue mixing at a speed of 800 rpm for 2 h. Cool down and get anti-mold and fresh-keeping paint.
  • the mold-proof fresh-keeping paint was coated on the PA6 film at a coating amount of 8 g/m 2 , and further treated at 90 ° C for 10 s to obtain a mold-proof plastic wrap.
  • Example 5 is substantially the same as Example 4, except that the antifungal agent of Example 5 is replaced with berberol and potassium ascorbate, and the mass ratio of cedarol and potassium ascorbate is 0.428:1; Covered on the substrate and treated at 120 ° C for 5 s to obtain a mildew-proof coating.
  • Example 6 is basically the same as Example 4, except that the antifungal agent of Example 6 is replaced with berberol and potassium ascorbate, and the mass ratio of cedarol and potassium ascorbate is 0.67:1; Covered on the substrate, and then treated at 80 ° C for 8 s to obtain a mold-proof plastic wrap.
  • Example 7 was basically the same as Example 4 except that the antifungal agent of Example 7 was replaced with allicin and salicylamine, and the mass ratio of allicin to salicylamine was 1.5:1.

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Abstract

A mildew-proof preservative film, comprising a base layer and a mildew-proof preservative coating provided on the base layer. The mildew-proof preservative coating is made from a mildew-proof preservative paint. The paint comprises the following components in percentage by weight: 20-60% of resin, 30-70% of solvent, 0.5-10% of mildew preventive, and 0.3-5% of additive. The resin is at least one of polyurethane, an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, an ethylene-vinyl acetate copolymer, a polyvinyl acetate copolymer, and a vinyl acetate-butyl ester copolymer; and the solvent is at least one of water and ethanol. A preparation method for the mildew-proof preservative film comprises the following steps: uniformly mixing the resin, the solvent, and the additive to obtain a mixed liquid; uniformly mixing the mixed liquid and mildew preventive to obtain a paint; then coating the base layer with the paint, and conducting heat treatment so that the paint forms a coating, so as to obtain the mildew-proof preservative film.

Description

防霉保鲜膜及其制备方法Anti-mild plastic wrap and preparation method thereof 技术领域Technical field
本发明涉及食物存储技术领域，特别是涉及一种防霉保鲜膜及其制备方法。The invention relates to the technical field of food storage, in particular to an anti-mild plastic wrap film and a preparation method thereof.
背景技术Background technique
食品和烟叶等储存期较短的物品存放的条件比较苛刻，否则就会因为微生物大量繁殖发生霉变使其不再新鲜，失去原有的价值。目前行业内普遍使用燥剂和强氧化剂以达到保鲜作用，以干燥剂来营造一个相对缺水的环境，抑制霉菌的生长；以强氧化剂来杀灭霉菌。但这两种方法均存在不足。强氧化剂对人体和环境不友好；而干燥剂在吸收空气中的水分同时也会吸收食品中的水分，进而造成食品脱水的问题。Foods and tobacco leaves and other items with short shelf life are stored in harsh conditions. Otherwise, microbial growth will cause the mold to become no longer fresh and lose its original value. At present, desiccant and strong oxidant are widely used in the industry to achieve the preservation effect, and a desiccant is used to create a relatively water-deficient environment to inhibit the growth of mold; a strong oxidant is used to kill mold. But both methods are inadequate. Strong oxidants are not friendly to the human body and the environment; while the desiccant absorbs the moisture in the air and also absorbs the water in the food, which causes the problem of dehydration of the food.
发明内容Summary of the invention
基于此，有必要提供一种保持水分恒定且能防止霉变的防霉保鲜膜及其制备方法。Based on this, it is necessary to provide a mold-preserving film which keeps the moisture constant and can prevent mildew and a preparation method thereof.
一种防霉保鲜膜，包括基层和和设于所述基层上的防霉保鲜涂层，所述防霉保鲜涂层的原料为防霉保鲜涂料，所述防霉保鲜涂料按重量百分含量包括如下组分：树脂20％～60％、溶剂30％～70％、防霉剂0.5％～10％和助剂0.3％～5％，其中所述树脂为聚氨酯、丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种，所述溶剂为水和乙醇中的至少一种。An anti-mild plastic wrap film comprising a base layer and a mildew-proof fresh-keeping coating layer disposed on the base layer, wherein the raw material of the mildew-proof fresh-keeping coating is a mildew-proof fresh-keeping paint, and the anti-mold and fresh-keeping paint is content by weight The composition includes the following components: resin 20% to 60%, solvent 30% to 70%, mold inhibitor 0.5% to 10%, and auxiliary agent 0.3% to 5%, wherein the resin is polyurethane, acrylate copolymer, poly At least one of vinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate copolymer, and vinyl acetate-butyl ester copolymer, the solvent It is at least one of water and ethanol.
上述防霉保鲜膜，采用的防霉保鲜涂层表面致密、无孔隙，而且添加有防霉剂，因而具有较好的保持水分恒定和防止霉变的效果。该防霉保鲜膜特别适用于水果、面包和烟叶等储存期较短、易短时霉变和需及时食用物品的保鲜。特别的，使用时将防霉保鲜膜涂覆有防霉保鲜涂层的表面作为内表面，可促进防霉保鲜涂层与防霉保鲜膜内的保鲜物品接触，进而可提高保鲜效果。The above-mentioned mildew-proof plastic wrap film has a dense surface and no pores, and is added with an anti-fungal agent, thereby having a good effect of keeping moisture constant and preventing mildew. The mildew-proof plastic wrap is especially suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles. In particular, when the mold is used, the surface of the mold-proof plastic wrap coated with the anti-mold and fresh-keeping coating is used as the inner surface, which can promote the contact between the anti-mold and fresh-keeping coating and the fresh-keeping articles in the mold-proof plastic wrap, thereby improving the fresh-keeping effect.
在其中一个实施例中，所述丙烯酸酯类共聚物选自甲基丙烯酸甲酯-丙烯酸 乙酯-丙烯酸丁酯共聚物、甲基丙烯酸甲酯-丙烯酸丁酯-丙烯酸共聚物、甲基丙烯酸甲酯-丙烯酸丁酯-丙烯酸-N-羟甲基丙烯酰胺共聚物中的至少一种。In one embodiment, the acrylate copolymer is selected from the group consisting of methyl methacrylate-acrylic acid Ethyl ester-butyl acrylate copolymer, at least one of methyl methacrylate-butyl acrylate-acrylic acid copolymer, methyl methacrylate-butyl acrylate-acrylic acid-N-methylol acrylamide copolymer.
在其中一个实施例中，所述防霉剂为天然提取物类防霉剂，所述天然提取物类防霉剂选自姜辣素、儿茶素、柠檬酸、大蒜素、壳聚糖、山梨酸、姜黄根醇、香樟精油、孟宗竹提取物、日柏醇和乳酸链球菌素中的至少一种。In one embodiment, the antifungal agent is a natural extract antifungal agent, and the natural extract antifungal agent is selected from the group consisting of gingerol, catechin, citric acid, allicin, chitosan, At least one of sorbic acid, turmeric root alcohol, citron essential oil, Mengzong bamboo extract, geranol and nisin.
在其中一个实施例中，所述树脂为丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种时，所述防霉保鲜涂料按重量百分含量还包括不超过3％的中和剂，所述中和剂选自碳酸氢钠、三乙胺和氨水中的至少一种。In one embodiment, the resin is an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate copolymer And at least one of the vinyl acetate-butyl ester copolymer, the anti-mold coating further comprises not more than 3% of a neutralizing agent by weight, the neutralizing agent being selected from the group consisting of sodium hydrogencarbonate, three At least one of ethylamine and ammonia in water.
在其中一个实施例中，所述防霉剂为非天然提取物类防霉剂，所述非天然提取物类防霉剂选自双乙酸钠、山梨酸钾、山梨酸钠、柠檬酸钾、柠檬酸钠、丙酸钙、抗坏血酸钠、抗坏血酸钾、水杨酸钠、水杨菌胺、十二烷基丙氨酸、异维生素C钠、卡松、尼泊金酯、富马酸和溶菌霉中的至少一种。In one embodiment, the anti-mold agent is a non-natural extract anti-fungal agent, and the non-natural extract anti-mold agent is selected from the group consisting of sodium diacetate, potassium sorbate, sodium sorbate, potassium citrate, Sodium citrate, calcium propionate, sodium ascorbate, potassium ascorbate, sodium salicylate, salicylamine, lauryl alanine, sodium isophora, carson, paraben, fumaric acid and lysobacteria At least one of the molds.
在其中一个实施例中，所述防霉剂为天然提取物类防霉剂和非天然提取物类防霉剂两种，所述天然提取物类防霉剂和所述非天然提取物类防霉剂的质量比为0.4～1.5:1。In one embodiment, the antifungal agent is a natural extract antifungal agent and a non-natural extract antifungal agent, and the natural extract antifungal agent and the non-natural extract are resistant. The mass ratio of the fungicide is from 0.4 to 1.5:1.
在其中一个实施例中，所述防霉保鲜涂层的厚度为0.5～10μm。在其中一个实施例中，所述基层为PET薄膜、PP薄膜、PA6薄膜、EVA薄膜、EVOH薄膜、PVA薄膜或PLA薄膜。In one embodiment, the mold proof coating has a thickness of 0.5 to 10 μm. In one embodiment, the base layer is a PET film, a PP film, a PA6 film, an EVA film, an EVOH film, a PVA film, or a PLA film.
一种防霉保鲜膜的制备方法，包括如下步骤：A method for preparing a moldproof plastic wrap film, comprising the following steps:
制备防霉保鲜涂料，所述防霉保鲜涂料的制备方法包括如下步骤：提供原料，按重量百分含量包括：树脂20％～60％、溶剂30％～70％、防霉剂0.5％～10％和助剂0.3％～5％；其中所述树脂为聚氨酯、丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种，所述溶剂为水和乙醇中的至少一种；将所述树脂、所述溶剂和所述助剂混合均匀，得到混合液；将所述混合液和所述防霉剂混合均匀，得到所述防霉保鲜涂料；Preparing a mildew-proof fresh-keeping paint, the method for preparing the mold-proof fresh-keeping paint comprises the following steps: providing a raw material, comprising: 20% to 60% of a resin, 30% to 70% of a solvent, and 0.5% to 10% of an antifungal agent according to a weight percentage % and auxiliary agent 0.3% to 5%; wherein the resin is polyurethane, acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, At least one of a polyvinyl acetate copolymer and a vinyl acetate-butyl ester copolymer, the solvent being at least one of water and ethanol; mixing the resin, the solvent and the auxiliary agent uniformly, Obtaining a mixed liquid; mixing the mixed liquid and the anti-fungal agent to obtain the anti-mold and fresh-keeping paint;
将所述防霉保鲜涂料涂覆于基层上并进行热处理使所述防霉保鲜涂料形成 防霉保鲜涂层，得到所述防霉保鲜膜。Applying the mildew-proof fresh-keeping coating to the base layer and performing heat treatment to form the mold-proof fresh-keeping coating The mold-proof and fresh-keeping coating is obtained to obtain the mold-proof plastic wrap.
上述防霉保鲜膜的制备方法，防霉保鲜涂层中树脂形成网状结构，防霉剂分散树脂的网状结构中，得到的防霉保鲜涂层具有较好的保持水分恒定和防止霉变的效果。该防霉保鲜膜特别适用于水果、面包和烟叶等储存期较短、易短时霉变和需及时食用物品的保鲜。The preparation method of the above-mentioned mildew-proof plastic wrap, the resin forming a network structure in the anti-mold and fresh-keeping coating, and the anti-mold agent-preserving resin in the network structure, the obtained anti-mold fresh-keeping coating has a good function of maintaining moisture constant and preventing mildew Effect. The mildew-proof plastic wrap is especially suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles.
在其中一个实施例中，所述防霉保鲜涂料的制备步骤中，所述防霉剂以滴加方式加入所述混合液以与所述混合液混合。In one embodiment, in the preparation step of the mildew-proof fresh-keeping paint, the anti-fungal agent is added to the mixed solution in a dropping manner to be mixed with the mixed liquid.
附图说明DRAWINGS
图1为一实施例的防霉保鲜膜的结构图；Figure 1 is a structural view of an anti-mold and plastic wrap film of an embodiment;
图2为一实施例的防霉保鲜涂料的制备方法的流程图。2 is a flow chart showing a method of preparing a mildew-proof fresh-keeping paint according to an embodiment.
具体实施方式detailed description
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳的实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate the understanding of the present invention, the present invention will be described more fully hereinafter with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the understanding of the present disclosure will be more fully understood.
参照图1，一实施例的防霉保鲜膜1，包括基层11和和设于基层11上的防霉保鲜涂层12。防霉保鲜涂层12的原料为防霉保鲜涂料。Referring to Fig. 1, an anti-mold coating film 1 of an embodiment includes a base layer 11 and an anti-mold coating 12 disposed on the base layer 11. The raw material of the mildew-proof fresh-keeping coating 12 is a mildew-proof fresh-keeping paint.
优选的，基层11为PET薄膜(聚对苯二甲酸乙二醇酯薄膜)、PP薄膜(聚丙烯薄膜)、PA6薄膜(聚酰胺6薄膜)、EVA薄膜(乙烯-聚醋酸乙烯酯共聚物薄膜)、EVOH薄膜(乙烯-乙烯醇共聚物薄膜)、PVA薄膜(聚乙烯醇薄膜)或PLA薄膜(线形脂肪族聚酯-聚乳酸薄膜)。更优选的，基层11为PET薄膜和PP薄膜。PET和PP在温度高达120℃的条件下仍能保持优良的性能，进而可避免保险涂料进行热处理形成防霉保鲜涂层导致基层11破坏的问题。Preferably, the base layer 11 is a PET film (polyethylene terephthalate film), a PP film (polypropylene film), a PA6 film (polyamide 6 film), and an EVA film (ethylene-polyvinyl acetate copolymer film). EVOH film (ethylene-vinyl alcohol copolymer film), PVA film (polyvinyl alcohol film) or PLA film (linear aliphatic polyester-polylactic acid film). More preferably, the base layer 11 is a PET film and a PP film. PET and PP can maintain excellent performance at temperatures up to 120 ° C, which can avoid the problem of the base layer 11 being damaged by heat treatment of the safety coating to form a mildew-proof coating.
更优选的，基层11的厚度为12～22μm。More preferably, the base layer 11 has a thickness of 12 to 22 μm.
优选的，防霉保鲜涂层12的厚度为0.5～10μm。防霉保鲜涂层12的厚度不够则树脂不能有效成膜，则防霉保鲜的效果不能体现。而防霉保鲜涂层12的厚度过厚，不仅成本增加，而且在热处理时不能完全干燥，会出现返粘等不良现 象，且在未完全干燥时，由于外表面已部分干燥，而内部仍成液态，在继续风干的过程中，由于内部自然干燥的原因很容易出现涂层开裂的情况，这也会极大的降低防霉保鲜涂层的效果。Preferably, the mold-preserving coating 12 has a thickness of 0.5 to 10 μm. If the thickness of the mildew-proof fresh-keeping coating 12 is insufficient, the resin cannot be effectively formed into a film, and the effect of preventing mildew and fresh-keeping is not reflected. The thickness of the mildew-proof fresh-keeping coating 12 is too thick, which not only increases the cost, but also cannot be completely dried during heat treatment, and there is a problem such as back sticking. Like, and when it is not completely dry, since the outer surface is partially dried, and the inside is still in a liquid state, in the process of continuing to air dry, the cracking of the coating is likely to occur due to the natural drying of the interior, which is also extremely great. Reduce the effect of mildew-proof and fresh-keeping coatings.
本发明提供了一实施例的防霉保鲜涂料。The present invention provides an anti-mild and fresh-keeping coating of an embodiment.
所述防霉保鲜涂料，按重量百分含量包括如下组分：树脂20％～60％、溶剂30％～70％、防霉剂0.5％～10％和助剂0.3％～5％。The mildew-proof fresh-keeping coating comprises the following components in a weight percentage: 20% to 60% of the resin, 30% to 70% of the solvent, 0.5% to 10% of the antifungal agent, and 0.3% to 5% of the auxiliary agent.
其中所述树脂为聚氨酯、丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种。如此树脂选用与防霉剂互溶性好且能溶于水溶剂的树脂，不仅可使防霉剂充分分散在树脂中，保证防霉剂的效果，而且还可避免有毒溶剂污染环境的缺点。The resin is polyurethane, acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate copolymer and vinyl acetate. At least one of the butyl ester copolymers. Such a resin is selected from a resin which is compatible with the antifungal agent and is soluble in a water solvent, so that the antifungal agent can be sufficiently dispersed in the resin to ensure the effect of the antifungal agent, and the disadvantage of toxic solvents contaminating the environment can be avoided.
更优选的，所述树脂为聚氨酯、丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯和改性聚偏二氯乙烯中的至少一种，这些树脂化学性质较乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物更稳定，其用于保鲜膜与食品接触时，更具有安全保障。More preferably, the resin is at least one of a polyurethane, an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, and modified polyvinylidene chloride. The chemical properties of these resins are higher than those of ethylene vinyl acetate. The copolymer, polyvinyl acetate copolymer and vinyl acetate-butyl ester copolymer are more stable, and are more safe for use when the plastic wrap is in contact with food.
所述组分中树脂为主体材料，所述树脂均为性能良好的高聚物，本身不会霉变，制成的涂层表面致密，无孔隙，因而能够最大限度的限制水分子的吸附和溶解，而分子间强大的凝聚力能够抑制水分子在其中移动，进而有效的抑制水分进出涂层，达到防止丢失水分和吸收水分、保持水分恒定和保鲜保湿的效果。The resin in the component is a host material, and the resin is a high-performance polymer, which is not mildewed by itself, and the surface of the coating is dense and has no pores, thereby maximally limiting the adsorption of water molecules and Dissolved, and the strong cohesive force between the molecules can inhibit the movement of water molecules in it, thereby effectively inhibiting the ingress and egress of moisture into and out of the coating, thereby preventing the loss of moisture and moisture, maintaining a constant moisture and moisturizing effect.
优选的，丙烯酸酯类共聚物选自甲基丙烯酸甲酯-丙烯酸乙酯-丙烯酸丁酯共聚物、甲基丙烯酸甲酯-丙烯酸丁酯-丙烯酸共聚物、甲基丙烯酸甲酯-丙烯酸丁酯-丙烯酸-N-羟甲基丙烯酰胺共聚物中的至少一种。以甲基丙烯酸甲酯-丙烯酸乙酯-丙烯酸丁酯共聚物为例，其由甲基丙烯酸甲酯、丙烯酸乙酯和丙烯酸丁酯三种单体共聚而成。Preferably, the acrylate-based copolymer is selected from the group consisting of methyl methacrylate-ethyl acrylate-butyl acrylate copolymer, methyl methacrylate-butyl acrylate-acrylic acid copolymer, methyl methacrylate-butyl acrylate- At least one of an acrylic acid-N-methylol acrylamide copolymer. Taking methyl methacrylate-ethyl acrylate-butyl acrylate copolymer as an example, it is obtained by copolymerization of three monomers of methyl methacrylate, ethyl acrylate and butyl acrylate.
优选的，聚乙烯醇选自聚乙烯醇1788、聚乙烯醇2088和聚乙烯醇2488中的至少一种。聚乙烯醇1788、聚乙烯醇2088和聚乙烯醇2488均是水溶性很好的聚乙烯醇。以聚乙烯醇1788为例，其为聚合度为1700，醇解度为88％的聚乙烯醇。 Preferably, the polyvinyl alcohol is selected from at least one of polyvinyl alcohol 1788, polyvinyl alcohol 2088, and polyvinyl alcohol 2488. Polyvinyl alcohol 1788, polyvinyl alcohol 2088 and polyvinyl alcohol 2488 are all water-soluble polyvinyl alcohols. Taking polyvinyl alcohol 1788 as an example, it is a polyvinyl alcohol having a degree of polymerization of 1,700 and a degree of alcoholysis of 88%.
优选的，改性聚偏二氯乙烯选自丙烯酸酯改性聚偏二氯乙烯和聚氨酯改性聚偏二氯乙烯中的至少一种。聚氨酯改性聚偏二氯乙烯的水溶性能显著提升。Preferably, the modified polyvinylidene chloride is at least one selected from the group consisting of acrylate-modified polyvinylidene chloride and urethane-modified polyvinylidene chloride. The water solubility of polyurethane modified polyvinylidene chloride is significantly improved.
其中，溶剂为水和乙醇中的至少一种。水和乙醇均为对环保无毒的溶剂，其用于防霉保鲜膜1能与食品等直接接触，避免了采用有毒溶剂对包装物采用聚氨酯、聚乙烯醇、乙烯醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物等水溶性较好的树脂，溶剂优选为水，以达到环保和降低成本的作用。Wherein the solvent is at least one of water and ethanol. Both water and ethanol are environmentally friendly and non-toxic solvents. They are used in the mold-proof plastic wrap 1 to be in direct contact with food, etc., avoiding the use of toxic solvents for the packaging of polyurethane, polyvinyl alcohol, ethylene vinyl acetate copolymer, A water-soluble resin such as a polyvinyl acetate copolymer, and the solvent is preferably water to achieve environmental protection and cost reduction.
其中，防霉剂为天然提取物类防霉剂和非天然提取物类防霉剂中的至少一种。优选的，天然提取物类防霉剂选自姜辣素、儿茶素、柠檬酸、大蒜素、壳聚糖、山梨酸、姜黄根醇、香樟精油、孟宗竹提取物、日柏醇和乳酸链球菌素中的至少一种。优选的，非天然提取物类防霉剂选自双乙酸钠、山梨酸钾、山梨酸钠、柠檬酸钾、柠檬酸钠、丙酸钙、抗坏血酸钠、抗坏血酸钾、水杨酸钠、水杨菌胺、十二烷基丙氨酸、异维生素C钠、卡松、尼泊金酯、富马酸和溶菌霉中的至少一种。The antifungal agent is at least one of a natural extract antifungal agent and a non-natural extract antifungal agent. Preferably, the natural extract antifungal agent is selected from the group consisting of gingerol, catechin, citric acid, allicin, chitosan, sorbic acid, turmeric root alcohol, citron essential oil, Mengzong bamboo extract, geranol and lactic acid chain ball At least one of the bacterins. Preferably, the non-natural extract fungicide is selected from the group consisting of sodium diacetate, potassium sorbate, sodium sorbate, potassium citrate, sodium citrate, calcium propionate, sodium ascorbate, potassium ascorbate, sodium salicylate, and salicylate. At least one of bacteriocin, dodecylalanine, isovitamin C sodium, carson, paraben, fumaric acid, and lysogen.
优选的，防霉剂为天然提取物类防霉剂和非天然提取物类防霉剂两种。如此采用两种防霉剂有利于提高进入树脂中的防霉剂含量，进而提高防霉效果。优选的，防霉剂为天然提取物类防霉剂和非天然提取物类防霉剂两种时，天然提取物类防霉剂和非天然提取物类防霉剂的质量比为0.4～1.5:1。Preferably, the antifungal agent is a natural extract type fungicide and a non-natural extract type fungicide. The use of the two antifungal agents in this way is advantageous for increasing the amount of the antifungal agent entering the resin, thereby improving the antifungal effect. Preferably, when the antifungal agent is a natural extract antifungal agent and a non-natural extract antifungal agent, the mass ratio of the natural extract antifungal agent and the non-natural extract antifungal agent is 0.4 to 1.5. :1.
天然提取物类防霉剂在碱性条件下的防霉性能较好，而聚氨酯本身为弱碱性。优选的，防霉剂含有天然提取物类防霉剂时，且树脂为丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种时，防霉保鲜涂料按重量百分含量还包括不超过3％的中和剂，所述中和剂选自碳酸氢钠、三乙胺和氨水中的至少一种，所述氨水的浓度不低于3mol/L。可以理解，中和剂可为浓氨水。可以理解，防霉剂为非天然提取物类防霉剂，也可添加中和剂。The natural extract antifungal agent has good mildew resistance under alkaline conditions, and the polyurethane itself is weakly alkaline. Preferably, when the antifungal agent contains a natural extract antifungal agent, and the resin is an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymerization When at least one of the polyvinyl acetate copolymer and the vinyl acetate-butyl ester copolymer, the anti-mold coating further comprises not more than 3% of a neutralizing agent by weight, and the neutralizing agent is selected From at least one of sodium hydrogencarbonate, triethylamine and aqueous ammonia, the concentration of the aqueous ammonia is not less than 3 mol/L. It will be appreciated that the neutralizing agent can be concentrated aqueous ammonia. It can be understood that the antifungal agent is a non-natural extract antifungal agent, and a neutralizing agent may also be added.
优选的，助剂包括表面活性剂、乳化剂、润湿剂、消泡剂及防沉降剂中的至少一种。其中，表面活性剂为吐温和司盘等，表面活性剂可使防霉剂在树脂中分散更加均匀。乳化剂有利于促进水溶性较差的树脂形成稳定的水乳液。Preferably, the auxiliary agent includes at least one of a surfactant, an emulsifier, a wetting agent, an antifoaming agent, and an anti-settling agent. Among them, the surfactant is Tween and Span, and the surfactant can make the antifungal agent more uniformly dispersed in the resin. The emulsifier is advantageous for promoting the formation of a stable aqueous emulsion of a poorly water-soluble resin.
上述防霉保鲜涂料，树脂溶于溶剂中并通过助剂调节其成膜性，控制组分配比，使其能形成表面致密、无孔隙的涂层，因此能够最大限度的限制水分子 的吸附和溶解，而高分子间的凝聚力能够抑制水分子在其中的移动，进而有效的抑制水分进出涂层，达到保持水分恒定和保鲜保湿的效果。此外，树脂与防霉剂互溶性好，使得防霉剂充分分散在树脂中，保证防霉剂的效果，而且还可避免有毒溶剂污染环境的缺点。The above-mentioned mildew-proof fresh-keeping paint, the resin is dissolved in a solvent and the film forming property is adjusted by an auxiliary agent, and the distribution ratio of the control group is controlled to form a surface-dense, non-porous coating, thereby maximally limiting water molecules. Adsorption and dissolution, and the cohesive force between the polymers can inhibit the movement of water molecules therein, thereby effectively inhibiting the ingress and egress of moisture into and out of the coating to maintain a constant moisture and moisturizing effect. In addition, the resin and the antifungal agent have good mutual solubility, so that the antifungal agent is sufficiently dispersed in the resin to ensure the effect of the antifungal agent, and the disadvantage of toxic solvent polluting the environment can be avoided.
防霉剂能通过微生物的细胞膜进入细胞内进而消灭微生物或者阻止其发芽以防止霉菌生长，进而达到长期稳定的保鲜效果。The anti-fungal agent can enter the cell through the cell membrane of the microorganism to destroy the microorganism or prevent it from germinating to prevent the growth of the mold, thereby achieving a long-term stable preservation effect.
参照图2，本发明上述防霉保鲜涂料的制备方法，包括以下步骤。Referring to Fig. 2, a method for preparing the above-mentioned mildew-proof fresh-keeping paint of the present invention comprises the following steps.
步骤S110：提供原料，按重量百分含量包括：树脂20％～60％、溶剂30％～70％、防霉剂0.5％～10％和助剂0.3％～5％。Step S110: providing a raw material, which comprises 20% to 60% by weight of the resin, 30% to 70% of the solvent, 0.5% to 10% of the antifungal agent, and 0.3% to 5% of the auxiliary agent.
步骤S120：将树脂、溶剂和助剂混合均匀，得到混合液。Step S120: mixing the resin, the solvent and the auxiliary agent uniformly to obtain a mixed liquid.
具体的，步骤S120中树脂、溶剂和助剂混合的温度为30～65℃。Specifically, the temperature at which the resin, the solvent and the auxiliary agent are mixed in the step S120 is 30 to 65 °C.
具体的，步骤S120包括以下步骤：将树脂溶于溶剂中，在转速为100～300转/分钟下搅拌并加热至30～65℃；加入助剂，在转速为200～400转/分钟下继续搅拌30～60min，得到混合液。如此控制温度和搅拌强度，促使混合液混合均匀。Specifically, the step S120 includes the steps of dissolving the resin in a solvent, stirring at a rotation speed of 100 to 300 rpm and heating to 30 to 65 ° C; adding an auxiliary agent, continuing at a rotation speed of 200 to 400 rpm. Stir for 30 to 60 minutes to obtain a mixed solution. The temperature and stirring intensity are controlled in such a way that the mixture is uniformly mixed.
具体的，防霉剂含有天然提取物类防霉剂时，防霉保鲜涂料按重量百分含量还包括不超过3％的中和剂，步骤S120还包括步骤：得到混合液后加入所述中和剂以调节混合液的pH值为7～8。加入中和剂调节混合液的pH是为了控制体系的酸碱度，使得体系的酸碱度尽量接近中性以使涂料的酸碱度接近中性，进而提高其环保性。Specifically, when the antifungal agent contains the natural extract antifungal agent, the antifungal fresh-keeping paint further comprises not more than 3% of the neutralizing agent by weight, and the step S120 further comprises the step of: adding the mixed liquid and adding the medium The agent is used to adjust the pH of the mixture to 7-8. Adding a neutralizing agent to adjust the pH of the mixture is to control the pH of the system, so that the pH of the system is as close as possible to the neutrality so that the pH of the coating is close to neutral, thereby improving its environmental friendliness.
步骤S130：将混合液和防霉剂混合均匀，得到防霉保鲜涂料。Step S130: mixing the mixed solution and the anti-mold agent to obtain a mildew-proof fresh-keeping paint.
将混合液和防霉剂混合均匀，使得防霉剂均匀分散在树脂内部，避免防霉剂以游离态溶于水中导致形成涂层时防霉剂的有效含量下降进而降低防霉效果的问题。防霉剂通过微生物的细胞膜进入细胞内进而消灭微生物或者阻止其发芽以防止霉菌生长，进而达到长期稳定的保鲜效果。The mixture and the anti-fungal agent are uniformly mixed, so that the anti-mold agent is uniformly dispersed inside the resin, and the problem that the anti-fungal agent is dissolved in the free state and the effective content of the anti-fungal agent is decreased when the anti-mold agent is formed, thereby reducing the anti-mold effect. The antifungal agent enters the cell through the cell membrane of the microorganism to destroy the microorganism or prevent it from germinating to prevent the growth of the mold, thereby achieving a long-term stable preservation effect.
优选的，防霉剂以滴加方式加入混合液以与混合液混合，以使防霉剂更充分的分散在树脂中，而尽可能的避免防霉剂游离在溶剂中，进而提高防霉剂的有效含量。更优选的，防霉剂为天然提取物类防霉剂和非天然提取物类防霉剂两种时，将该两种防霉剂单独且同时滴加至混合液中，以防止该两种防霉剂先后加入导致后者防霉剂更多的以游离态存在于溶剂中，致使不能达到较好的结 合效果的问题。Preferably, the anti-fungal agent is added to the mixed solution in a dropping manner to be mixed with the mixed liquid, so that the anti-fungal agent is more fully dispersed in the resin, and the anti-fungal agent is prevented from being freed in the solvent as much as possible, thereby improving the anti-fungal agent. Effective content. More preferably, when the antifungal agent is a natural extract antifungal agent and a non-natural extract antifungal agent, the two antifungal agents are separately and simultaneously added to the mixed solution to prevent the two kinds. The addition of the anti-fungal agent causes the latter anti-fungal agent to be present in the solvent in a free state, so that a better knot cannot be achieved. The problem with the effect.
优选的，步骤S130中混合液和防霉剂混合的条件为于30～65℃下混合1～2h。可以理解，防霉剂以滴加方式加入时，在防霉剂滴加结束后，将混合液和防霉剂继续混合1～2h。步骤S130在转速为500～800转/分钟下搅拌混合。Preferably, the conditions for mixing the mixed solution and the anti-mold agent in step S130 are mixed at 30 to 65 ° C for 1 to 2 h. It can be understood that when the antifungal agent is added by dropping, after the end of the antifungal agent is added, the mixed solution and the antifungal agent are continuously mixed for 1 to 2 hours. Step S130 is stirred and mixed at a number of revolutions of 500 to 800 rpm.
上述防霉保鲜涂料的制备方法，工艺简单，易于实现，得到的防霉保鲜涂料成膜性好，可形成表面致密、无孔隙的防霉保鲜涂层，因而能够最大限度的限制水分子的吸附和溶解，而高分子间的凝聚力能够抑制水分子在其中的移动，进而有效的抑制水分进出涂层，达到保持水分恒定和保鲜保湿的效果。此外，防霉剂均匀分散在树脂内部，避免防霉剂以游离态存在溶于水中导致形成涂层时防霉剂含量下降进而降低防霉效果的问题。防霉剂通过微生物的细胞膜进入细胞内进而消灭微生物或者阻止其发芽以防止霉菌生长，进而达到长期稳定的保鲜效果。The preparation method of the above-mentioned mildew-proof fresh-keeping paint has the advantages of simple process and easy realization, and the obtained mold-preserving and fresh-keeping paint has good film forming property, and can form a surface-tight and non-porous anti-mold and fresh-keeping coating, thereby maximally limiting the adsorption of water molecules. And dissolve, and the cohesive force between the polymers can inhibit the movement of water molecules therein, thereby effectively inhibiting the ingress and egress of moisture into and out of the coating, thereby achieving a constant moisture retention and moisturizing effect. In addition, the anti-mold agent is uniformly dispersed inside the resin, and the problem that the anti-fungal agent is dissolved in water in a free state to cause a decrease in the anti-fungal agent content when the coating is formed and the anti-mold effect is reduced is avoided. The antifungal agent enters the cell through the cell membrane of the microorganism to destroy the microorganism or prevent it from germinating to prevent the growth of the mold, thereby achieving a long-term stable preservation effect.
该防霉保鲜涂料特别适用于水果、面包和烟叶等储存期较短、易短时霉变和需及时食用物品的保鲜。The mildew-proof fresh-keeping coating is particularly suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles.
本发明还提供了一实施例的防霉保鲜膜的制备方法。该制备方法包括以下步骤：制备防霉保鲜涂料；将防霉保鲜涂料涂覆于基层上并进行热处理使防霉保鲜涂料形成防霉保鲜涂层，得到所述防霉保鲜膜。The invention also provides a preparation method of the moldproof and preservative film of an embodiment. The preparation method comprises the steps of: preparing a mildew-proof fresh-keeping paint; applying a mildew-proof fresh-keeping paint on the base layer and performing heat treatment to form a mildew-proof and fresh-keeping coating on the mildew-proof fresh-keeping paint, and obtaining the mold-proof and fresh-keeping film.
上述防霉保鲜膜的制备方法，防霉保鲜涂层中树脂发生交联反应形成网状结构，防霉剂均匀分散于树脂的网状结构中，得到的防霉保鲜涂层，表面致密，无孔隙，因而该防霉保鲜涂层具有较好的保持水分恒定的效果；防霉剂均匀分散在树脂内部，还能有效防止霉变，进而达到较好的保鲜效果。The preparation method of the above-mentioned mildew-proof plastic wrap film, the resin in the anti-mold fresh-keeping coating is cross-linked to form a network structure, and the anti-mold agent is uniformly dispersed in the network structure of the resin, and the obtained anti-mold and fresh-keeping coating has a dense surface, no The pores, therefore, the mildew-proof fresh-keeping coating has a good effect of maintaining a constant moisture; the anti-fungal agent is uniformly dispersed inside the resin, and can effectively prevent mildew, thereby achieving better preservation effect.
优选的，防霉保鲜涂料涂覆于基层11的涂覆量为1～10g/m2，即为防霉保鲜涂料在基层11单位面积上的涂覆量，从而控制防霉保鲜涂层12的厚度为0.5～10μm。Preferably, the coating amount of the mildew-proof fresh-keeping coating applied to the base layer 11 is 1 to 10 g/m 2 , that is, the coating amount of the mildew-proof fresh-keeping coating on the base layer 11 unit area, thereby controlling the mildew-proof fresh-keeping coating 12 The thickness is 0.5 to 10 μm.
优选的，热处理的条件为于80～120℃处理5～10s。树脂在该条件下发生交联反应形成致密的网状结构，使得涂层具有防止水分进出的效果。由于涂层的厚度有限，热处理的时间太长将会影响涂层的性能。Preferably, the heat treatment is carried out at 80 to 120 ° C for 5 to 10 s. The resin undergoes a crosslinking reaction under such conditions to form a dense network structure, so that the coating has an effect of preventing moisture from entering and leaving. Due to the limited thickness of the coating, the heat treatment time is too long and will affect the performance of the coating.
优选的，热处理的条件为依次于80～85℃、90～100℃、105～120℃、90～100℃和80～85℃下分别处理1～2s。如此涂料在该温度区域中热处理，该温度区域呈 梯度分布，使得涂料成膜前期逐渐升温，成膜后期逐渐降温，进而提高涂层的致密性和保证涂层不会开裂。更优选的，热处理的条件为依次于80℃、90℃、120℃、100℃和85℃下分别处理1.2s。Preferably, the heat treatment conditions are respectively carried out at 80 to 85 ° C, 90 to 100 ° C, 105 to 120 ° C, 90 to 100 ° C, and 80 to 85 ° C for 1 to 2 s. The coating is heat treated in the temperature region, and the temperature region is The gradient distribution makes the coating gradually warm up in the early stage of film formation, and gradually lowers the temperature in the later stage of film formation, thereby improving the compactness of the coating and ensuring that the coating does not crack. More preferably, the conditions of the heat treatment are respectively treated at 80 ° C, 90 ° C, 120 ° C, 100 ° C and 85 ° C for 1.2 s.
上述防霉保鲜膜1，采用的防霉保鲜涂层表面致密、无孔隙，而且添加有防霉剂，因而具有较好的保持水分恒定和防止霉变的效果。该防霉保鲜膜1特别适用于水果、面包和烟叶等储存期较短、易短时霉变和需及时食用物品的保鲜。特别的，使用时将防霉保鲜膜1涂覆有防霉保鲜涂层12的表面作为内表面，可促进防霉保鲜涂层12与防霉保鲜膜11内的保鲜物品接触，进而可提高保鲜效果。The anti-mold and anti-fresh film 1 has a surface which is dense and non-porous, and has an anti-fungal agent added thereto, thereby having a good effect of keeping moisture constant and preventing mildew. The mildew-proof plastic wrap 1 is particularly suitable for the preservation of fruits, breads and tobacco leaves, such as short storage period, short-term mildew and timely consumption of articles. In particular, when the mold-proof plastic wrap film 1 is coated with the surface of the mildew-proof fresh-keeping coating 12 as an inner surface, the anti-mold fresh-keeping coating 12 can be brought into contact with the fresh-keeping articles in the mildew-proof plastic wrap film 11, thereby improving the freshness preservation. effect.
以下为具体实施例。The following are specific examples.
实施例1Example 1
提供原料，按重量百分含量包括：聚氨酯树脂60％、水30％、姜辣素5％、吐温4％。The raw materials are provided in a weight percentage including: polyurethane resin 60%, water 30%, gingerol 5%, and Tween 4%.
将聚氨酯树脂溶于水中，在转速为300转/分钟下搅拌并加热至50℃；加入助剂，在转速为300转/分钟下继续搅拌50min，得到混合液。加入三乙胺后混合液的pH值为7。The polyurethane resin was dissolved in water, stirred at 300 rpm and heated to 50 ° C; an auxiliary was added, and stirring was continued for 50 min at 300 rpm to obtain a mixed solution. The pH of the mixture after adding triethylamine was 7.
将姜辣素以滴加方式在转速为600转/分钟下搅拌下加入混合液，姜辣素滴加结束后，将混合液和姜辣素继续在转速为600转/分钟下搅拌混合1。降温，得到防霉保鲜涂料。Gingerol was added to the mixture by stirring at a rotation speed of 600 rpm, and after the addition of the gingerol was completed, the mixture and the gingerol were continuously stirred and mixed at a rotation speed of 600 rpm. Cool down and get anti-mold and fresh-keeping paint.
将防霉保鲜涂料按10g/m2的涂覆量涂覆在PET薄膜上，再依次于80℃、90℃、120℃、100℃和85℃下分别处理1.2s，得到防霉保鲜膜。The mold-proof fresh-keeping paint was coated on the PET film at a coating amount of 10 g/m 2 , and then treated at 80 ° C, 90 ° C, 120 ° C, 100 ° C, and 85 ° C for 1.2 s, respectively, to obtain a mold-proof plastic wrap.
实施例2Example 2
提供原料，按重量百分含量包括：聚乙烯醇2488树脂47％、水40％、山梨酸和姜黄根醇总量8％、吐温2％和碳酸氢钠3％。The raw materials are provided in a percentage by weight: polyvinyl alcohol 2488 resin 47%, water 40%, sorbic acid and turmeric root alcohol total 8%, Tween 2% and sodium hydrogencarbonate 3%.
将聚乙烯醇2488树脂溶于水中，在转速为100转/分钟下搅拌并加热至65℃；加入助剂，在转速为200转/分钟下继续搅拌30min，得到混合液。加入碳酸氢钠后混合液的pH值为8。The polyvinyl alcohol 2488 resin was dissolved in water, stirred at a rotation speed of 100 rpm and heated to 65 ° C; an auxiliary was added, and stirring was continued for 30 minutes at a rotation speed of 200 rpm to obtain a mixed solution. The pH of the mixture after adding sodium hydrogencarbonate was 8.
将山梨酸和姜黄根醇以滴加方式在转速为800转/分钟下搅拌下加入混合 液，山梨酸和姜黄根醇滴加结束后，将混合液、山梨酸和姜黄根醇继续在转速为500～800转/分钟下搅拌混合2h。降温，得到防霉保鲜涂料。Adding sorbic acid and turmeric root alcohol in a dropping manner at a rotation speed of 800 rpm After the dropwise addition of the liquid, sorbic acid and turmeric root alcohol, the mixture, sorbic acid and turmeric root alcohol were continuously stirred and mixed at a rotational speed of 500 to 800 rpm for 2 hours. Cool down and get anti-mold and fresh-keeping paint.
将防霉保鲜涂料按1g/m2的涂覆量涂覆在PP薄膜上，再依次于85℃、95℃、110℃、90℃和80℃下分别处理2s，得到防霉保鲜膜。The mildew-proof fresh-keeping paint was coated on the PP film at a coating amount of 1 g/m 2 , and then treated at 85 ° C, 95 ° C, 110 ° C, 90 ° C, and 80 ° C for 2 s, respectively, to obtain a mold-proof plastic wrap.
实施例3Example 3
提供原料，按重量百分含量包括：聚氨酯改性聚偏二氯乙烯树脂20％、水70％、十二烷基丙氨酸0.5％和吐温5％。The raw materials are provided in a weight percentage including: polyurethane modified polyvinylidene chloride resin 20%, water 70%, dodecylalanine 0.5%, and Tween 5%.
将聚氨酯改性聚偏二氯乙烯树脂溶于水中，在转速为200转/分钟下搅拌并加热至60℃；加入助剂，在转速为400转/分钟下继续搅拌50min，得到混合液。The polyurethane modified polyvinylidene chloride resin was dissolved in water, stirred at 200 rpm and heated to 60 ° C; an auxiliary was added, and stirring was continued for 50 min at a rotation speed of 400 rpm to obtain a mixed solution.
将十二烷基丙氨酸以滴加方式在转速为500转/分钟下搅拌下加入混合液，十二烷基丙氨酸滴加结束后，将混合液和十二烷基丙氨酸继续在转速为500～800转/分钟下搅拌混合1.5h。降温，得到防霉保鲜涂料。Add the lauryl alanine to the mixture by stirring at 500 rpm, and after the dropwise addition of dodecyl alanine, continue the mixture and lauryl alanine. The mixture was stirred and mixed at a rotation speed of 500 to 800 rpm for 1.5 hours. Cool down and get anti-mold and fresh-keeping paint.
将防霉保鲜涂料按5g/m2的涂覆量涂覆在EVA薄膜上，再依次于83℃、100℃、105℃、95℃和82℃下分别处理1s，得到防霉保鲜膜。The mold-proof fresh-keeping paint was coated on the EVA film at a coating amount of 5 g/m 2 , and then treated at 83 ° C, 100 ° C, 105 ° C, 95 ° C and 82 ° C for 1 s, respectively, to obtain a mold-proof plastic wrap.
实施例4Example 4
提供原料，按重量百分含量包括：醋酸乙烯酯-丁酯共聚物40％、水和乙醇(体积比1:1)总量48％、孟宗竹提取物和异维生素C钠(孟宗竹提取物和异维生素C钠的质量比为1:1)总量10％、司盘1.5％和浓氨水0.4％。经过多次考虑，环氧树脂不适宜用作与食品等相接触，本发明旨在解决的是食品和烟叶等的防霉保鲜效果。若以食品安全隐患为代价，则不能算是解决了技术问题。若继续选择保留环氧树脂，有人针对此处提出质疑，是否能够通过申辩呢？The raw materials are provided in the weight percentage including: vinyl acetate-butyl ester copolymer 40%, water and ethanol (volume ratio 1:1) total 48%, Mengzong bamboo extract and isovitamin C sodium (Meng Zongzhu extract and different The mass ratio of vitamin C sodium is 1:1) total 10%, Span 1.5% and concentrated ammonia 0.4%. After many considerations, epoxy resin is not suitable for use in contact with foods and the like, and the present invention aims to solve the anti-mildew and fresh-keeping effects of foods and tobacco leaves. If it is at the expense of food safety hazards, it cannot be considered a technical problem. If you continue to choose to retain epoxy resin, someone raises a question about this, can you pass the defense?
将醋酸乙烯酯-丁酯共聚物溶于水中，在转速为300转/分钟下搅拌并加热至40℃；加入助剂，在转速为300转/分钟下继续搅拌50min，得到混合液。加入浓氨水后混合液的pH值为7.5。The vinyl acetate-butyl ester copolymer was dissolved in water, stirred at 300 rpm and heated to 40 ° C; an auxiliary was added, and stirring was continued for 50 min at 300 rpm to obtain a mixed solution. The pH of the mixture after the addition of concentrated aqueous ammonia was 7.5.
将孟宗竹提取物和异维生素C钠单独且同时以滴加方式在转速为800转/分钟下搅拌下加入混合液，防霉剂滴加结束后，将混合液、孟宗竹提取物和异维生素C钠继续在转速为800转/分钟下搅拌混合2h。降温，得到防霉保鲜涂料。The Mengzong bamboo extract and the isovitamin C sodium were separately and simultaneously added to the mixture by stirring at a rotation speed of 800 rpm. After the addition of the anti-fungal agent, the mixture, Mengzong bamboo extract and iso-vitamin C sodium were mixed. Continue mixing at a speed of 800 rpm for 2 h. Cool down and get anti-mold and fresh-keeping paint.
将防霉保鲜涂料按8g/m2的涂覆量涂覆在PA6薄膜上，再于90℃处理10s，得到防霉保鲜膜。 The mold-proof fresh-keeping paint was coated on the PA6 film at a coating amount of 8 g/m 2 , and further treated at 90 ° C for 10 s to obtain a mold-proof plastic wrap.
实施例5Example 5
实施例5与实施例4基本相同，不同之处在于，实施例5的防霉剂替换为日柏醇和抗坏血酸钾，且日柏醇和抗坏血酸钾的质量比为0.428:1；将防霉保鲜涂料涂覆在基底上，再于120℃处理5s，得到防霉保鲜涂层。Example 5 is substantially the same as Example 4, except that the antifungal agent of Example 5 is replaced with berberol and potassium ascorbate, and the mass ratio of cedarol and potassium ascorbate is 0.428:1; Covered on the substrate and treated at 120 ° C for 5 s to obtain a mildew-proof coating.
实施例6Example 6
实施例6与实施例4基本相同，不同之处在于，实施例6的防霉剂替换为日柏醇和抗坏血酸钾，且日柏醇和抗坏血酸钾的质量比为0.67:1；将防霉保鲜涂料涂覆在基底上，再于80℃处理8s，得到防霉保鲜膜。Example 6 is basically the same as Example 4, except that the antifungal agent of Example 6 is replaced with berberol and potassium ascorbate, and the mass ratio of cedarol and potassium ascorbate is 0.67:1; Covered on the substrate, and then treated at 80 ° C for 8 s to obtain a mold-proof plastic wrap.
实施例7Example 7
实施例7与实施例4基本相同，不同之处在于，实施例7的防霉剂替换为大蒜素和水杨菌胺，且大蒜素和水杨菌胺的质量比为1.5:1。Example 7 was basically the same as Example 4 except that the antifungal agent of Example 7 was replaced with allicin and salicylamine, and the mass ratio of allicin to salicylamine was 1.5:1.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (10)

  1. 一种防霉保鲜膜，其特征在于，包括基层和设于所述基层上的防霉保鲜涂层，所述防霉保鲜涂层的原料为防霉保鲜涂料，所述防霉保鲜涂料按重量百分含量包括如下组分：树脂20％～60％、溶剂30％～70％、防霉剂0.5％～10％和助剂0.3％～5％，其中所述树脂为聚氨酯、丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种，所述溶剂为水和乙醇中的至少一种。An anti-mild plastic wrap film, comprising: a base layer and a mildew-proof fresh-keeping coating layer disposed on the base layer; the raw material of the anti-mold and fresh-keeping coating layer is a mildew-proof fresh-keeping paint, and the anti-mold and fresh-keeping paint is by weight The percentage includes the following components: 20% to 60% of the resin, 30% to 70% of the solvent, 0.5% to 10% of the antifungal agent, and 0.3% to 5% of the auxiliary agent, wherein the resin is a copolymer of polyurethane and acrylate. At least one of a substance, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, an ethylene-vinyl acetate copolymer, a polyvinyl acetate copolymer, and a vinyl acetate-butyl ester copolymer, The solvent is at least one of water and ethanol.
  2. 如权利要求1所述的防霉保鲜膜，其特征在于，所述丙烯酸酯类共聚物选自甲基丙烯酸甲酯-丙烯酸乙酯-丙烯酸丁酯共聚物、甲基丙烯酸甲酯-丙烯酸丁酯-丙烯酸共聚物、甲基丙烯酸甲酯-丙烯酸丁酯-丙烯酸-N-羟甲基丙烯酰胺共聚物中的至少一种。The mold proof wrap film according to claim 1, wherein the acrylate copolymer is selected from the group consisting of methyl methacrylate-ethyl acrylate-butyl acrylate copolymer, methyl methacrylate-butyl acrylate. At least one of an acrylic copolymer, a methyl methacrylate-butyl acrylate-acrylic acid-N-methylol acrylamide copolymer.
  3. 如权利要求1所述的防霉保鲜膜，其特征在于，所述防霉剂为天然提取物类防霉剂，所述天然提取物类防霉剂选自姜辣素、儿茶素、柠檬酸、大蒜素、壳聚糖、山梨酸、姜黄根醇、香樟精油、孟宗竹提取物、日柏醇和乳酸链球菌素中的至少一种。The mold-proof plastic wrap according to claim 1, wherein the anti-fungal agent is a natural extract antifungal agent, and the natural extract anti-fungal agent is selected from the group consisting of gingerol, catechin, and lemon. At least one of acid, allicin, chitosan, sorbic acid, turmeric root alcohol, citron essential oil, Mengzong bamboo extract, geranol and nisin.
  4. 如权利要求3所述的防霉保鲜膜，其特征在于，所述树脂为丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种时，所述防霉保鲜涂料按重量百分含量还包括不超过3％的中和剂，所述中和剂为碳酸氢钠、三乙胺和氨水中的至少一种。The mold-proof plastic wrap according to claim 3, wherein the resin is an acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene vinyl acetate. In at least one of a copolymer, a polyvinyl acetate copolymer, and a vinyl acetate-butyl ester copolymer, the mold proof coating further comprises not more than 3% of a neutralizing agent by weight, wherein The agent is at least one of sodium hydrogencarbonate, triethylamine and aqueous ammonia.
  5. 如权利要求1所述的防霉保鲜膜，其特征在于，所述防霉剂为非天然提取物类防霉剂，所述非天然提取物类防霉剂选自双乙酸钠、山梨酸钾、山梨酸钠、柠檬酸钾、柠檬酸钠、丙酸钙、抗坏血酸钠、抗坏血酸钾、水杨酸钠、水杨菌胺、十二烷基丙氨酸、异维生素C钠、卡松、尼泊金酯、富马酸和溶菌霉中的至少一种。The mold-proof plastic wrap according to claim 1, wherein the anti-fungal agent is a non-natural extract anti-mold agent, and the non-natural extract anti-fungal agent is selected from the group consisting of sodium diacetate and potassium sorbate. , sodium sorbate, potassium citrate, sodium citrate, calcium propionate, sodium ascorbate, potassium ascorbate, sodium salicylate, salicylamine, lauryl alanine, sodium isophora, carson, ni At least one of p-gold ester, fumaric acid, and lysogen.
  6. 如权利要求1所述的防霉保鲜膜，其特征在于，所述防霉剂为天然提取物类防霉剂和非天然提取物类防霉剂两种，所述天然提取物类防霉剂和所述非天然提取物类防霉剂的质量比为0.4～1.5:1。 The mold-proof plastic wrap according to claim 1, wherein the anti-fungal agent is a natural extract antifungal agent and a non-natural extract anti-fungal agent, and the natural extract anti-mold agent The mass ratio of the non-natural extract antifungal agent is from 0.4 to 1.5:1.
  7. 如权利要求1所述的防霉保鲜膜，其特征在于，所述防霉保鲜涂层的厚度为0.5～10μm。The mold-proof plastic wrap according to claim 1, wherein the mold-preserving coating has a thickness of 0.5 to 10 μm.
  8. 如权利要求1～7任一项所述的防霉保鲜膜，其特征在于，所述基层为PET薄膜、PP薄膜、PA6薄膜、EVA薄膜、EVOH薄膜、PVA薄膜或PLA薄膜。The mold-preserving and preservative film according to any one of claims 1 to 7, wherein the base layer is a PET film, a PP film, a PA6 film, an EVA film, an EVOH film, a PVA film or a PLA film.
  9. 一种防霉保鲜膜的制备方法，其特征在于，包括如下步骤：A method for preparing a moldproof plastic wrap film, comprising the steps of:
    制备防霉保鲜涂料，所述防霉保鲜涂料的制备包括如下步骤：提供原料，按重量百分含量包括：树脂20％～60％、溶剂30％～70％、防霉剂0.5％～10％和助剂0.3％～5％；其中所述树脂为聚氨酯、丙烯酸酯类共聚物、聚乙烯醇、聚偏二氯乙烯、改性聚偏二氯乙烯、乙烯-醋酸乙烯酯类共聚物、聚醋酸乙烯酯共聚物和醋酸乙烯酯-丁酯共聚物中的至少一种，所述溶剂为水和乙醇中的至少一种；将所述树脂、所述溶剂和所述助剂混合均匀，得到混合液；将所述混合液和所述防霉剂混合均匀，得到所述防霉保鲜涂料；Preparing a mildew-proof fresh-keeping paint, the preparation of the mildew-proof fresh-keeping paint comprises the following steps: providing a raw material, which comprises: 20% to 60% of resin, 30% to 70% of solvent, 0.5% to 10% of mildewproof agent by weight percentage And the additive is 0.3% to 5%; wherein the resin is polyurethane, acrylate copolymer, polyvinyl alcohol, polyvinylidene chloride, modified polyvinylidene chloride, ethylene-vinyl acetate copolymer, poly At least one of a vinyl acetate copolymer and a vinyl acetate-butyl ester copolymer, wherein the solvent is at least one of water and ethanol; and the resin, the solvent and the auxiliary agent are uniformly mixed to obtain Mixing liquid; mixing the mixed liquid and the anti-fungal agent to obtain the anti-mold and fresh-keeping paint;
    将所述防霉保鲜涂料涂覆于基层上并进行热处理使所述防霉保鲜涂料形成防霉保鲜涂层，得到所述防霉保鲜膜。Applying the mildew-proof fresh-keeping paint to the base layer and performing heat treatment to form the mold-proof fresh-keeping paint to form a mold-proof fresh-keeping coating, and obtaining the mold-proof and preservative film.
  10. 如权利要求9所述的防霉保鲜膜的制备方法，其特征在于，所述防霉保鲜涂料的制备步骤中，所述防霉剂以滴加方式加入所述混合液以与所述混合液混合。 The method for preparing a mold-proof plastic wrap according to claim 9, wherein in the preparing step of the anti-mold coating, the anti-fungal agent is added to the mixed solution in a dropping manner to form the mixed solution. mixing.
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