CN103144845B - The special paper-plastic composite film of fruit and vegetable normal-temperature fresh-keeping - Google Patents

The special paper-plastic composite film of fruit and vegetable normal-temperature fresh-keeping Download PDF

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Publication number
CN103144845B
CN103144845B CN201310063998.5A CN201310063998A CN103144845B CN 103144845 B CN103144845 B CN 103144845B CN 201310063998 A CN201310063998 A CN 201310063998A CN 103144845 B CN103144845 B CN 103144845B
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layer
bactericide
paper substrate
paper
fruit
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CN201310063998.5A
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CN103144845A (en
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李东立
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Shenyang Zhongqing New Materials Co Ltd
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Abstract

The present invention relates to a kind of fresh-keeping special-purpose non-toxic environment protection paper-plastic compound flexible packaging film of fruit and vegetable, the wrapping film is that barrier layer, bactericide releasing layer and regulating course are added between two layers of paper substrate, by the polarity and gas permeability that change barrier layer, regulating course, reach the purpose of control release bactericide, 5 20ppm gas phase bactericide can be discharged 30 90 days, with water conservation, sterilization, ventilative function.Main function is keeping fresh at normal temperature fruits and vegetables, extends the shelf life of fruit and vegetable.The freshness protection package be dropped after can with natural degradation, there is no any pollution to environment.

Description

The special paper-plastic composite film of fruit and vegetable normal-temperature fresh-keeping
Technical field
The present invention relates to a kind of water fruits and vegetables normal-temperature fresh-keeping paper-plastic composite film and preparation method thereof.The paper-plastic stick Film sets regulating course, bactericide releasing layer (adhesive layer), barrier layer using paper substrate as basement membrane between two layers of paper substrate, uses Prepared by solvent-free complex method, with sustained release sterilization, water conservation, ventilative function, for the fresh-keeping of water at normal temperature fruit vegetable.
Background technology
With the development and the improvement of people's living standards of Urbanization in China, metropolitan vegetables and fruit are increasingly Rely on other places supply, from the place of production into common people's hand, it is necessary to pluck, assemble by the place of production, transporting for long-distance, it is wholesale, several to supermarket Link, generally requires time of 2-4 days.Residence time of the fruits and vegetables in wholesale market and the shelf life in supermarket are general all longer, Due to lacking appropriate preservation technology, the loss late of China fruit and vegetable is 20% or so, and the loss late of developed country closely has 2.5%, the backwardness of this explanation China preservation technology.
Fruit dredges fresh-keeping key and is to prevent water loss, is wilted if fruit and vegetable fluid loss is more than more than 5%, loses Go commercial value;Plastic sheeting has relatively low moisture-vapor transmission, with preferable water retention property, therefore domestic and international fruit at present Thin fresh-keeping packaging material mainly uses plastic basis material, in order to increase the oxygen permeability of plastic basis material, is developed numerous Modified film technique, including various kinds of resin blending, the pore-creating of addition inorganic particulate, laser boring etc., but the fresh-keeping packaging material prepared Material typically is also limited to use under low temperature, and normal-temperature fresh-keeping effect is still undesirable, and reason is that the OTR oxygen transmission rate of plastics can not expire The requirement of high respiratory rate under sufficient fruits and vegetables normal temperature.Although the report of domestic many fruit and vegetable fresh-keeping packagings existing at present, this A little existing Fresh-Keeping Packaging Materials have following point:
Being limited to plastic basis material 1 existing Perserving materials, due to OTR oxygen transmission rate (0TR) highest of general plastic basis material more It is only capable of reaching 104ml/m2.day.atm, it is impossible to meet the requirement of fruit and vegetable metabolism at normal temperatures, be typically only capable of as fruit Perserving materials under vegetable low temperature, and it is poor to the fresh-keeping effect of fruits and vegetables under normal temperature, or even fruits and vegetables can be made to occur anaerobic respiration under normal temperature;
The moisture-vapor transmission (WVTR) of 2 existing plastics base Perserving materials is small, the water that fruits and vegetables metabolism is produced in freshness protection package Partial volume easily forms the internal environment of high humidity, causes bacteria breed, accelerates fruits and vegetables to rot;
If the gas permeability of 3 increase plastics fresh-keeping packagings is, it is necessary to which film thickness is reduced, this brings Packaging mechanics performance again Difficulty occurs for not enough the problem of so that processing film is molded, the preparation of freshness protection package.
In a word, the respiratory intensity of fruits and vegetables is big under fruits and vegetables normal temperature, and the requirement to fresh-keeping packaging material is high, and existing plastic basis material is protected Green wood material is typically suitable only for low temperature and used, or is suitable only for the low fruit and vegetable of respiratory intensity, for the high fruit of respiratory intensity Not but not preservation is played at normal temperatures with vegetables, accelerate fruits and vegetables to rot on the contrary.
The content of the invention
It is an object of the invention to provide a kind of fruits and vegetables normal temperature fresh-keeping packaging material, it is a kind of paper-plastic composite film, with paper Base is basement membrane, regulating course, bactericide releasing layer (adhesive layer), barrier layer is set between two layers of paper substrate, using solvent-free multiple Prepared by conjunction method, with sustained release sterilization, water conservation, ventilative function, can discharge 5-20ppm gas phase bactericide 30-90 days.
Difference of the invention with existing invention is:
Using plastic basis material 1 existing fruit fresh-keeping packaging material more, and the present invention uses plastic-paper composite base material, shared by paper substrate Ratio reduces the thickness of plastic basis material as far as possible more than 60% (W%);The reduction of plastic basis material thickness is beneficial to improve packaging material Oxygen permeability, to meet demand of the metabolic activity to oxygen under fruit normal temperature;And the decline of plastic basis material thickness causes mechanical property The not enough of energy makes up by paper substrate;
2 paper substrates have the effect of regulation package interior space humidity.Paper substrate be highly polar material, paper substrate short texture, because This OTR oxygen transmission rate is very big, even if really being dredged under normal temperature, respiratory intensity is high, and paper substrate can also meet high OTR oxygen transmission rate and (be more than 105ml/m2.day.atm).The thin paper-plastic composite film internal layer of contact fruit is paper substrate, and moisture will not condense into water droplet on paper substrate (condensation), paper substrate also has the effect of humidity in stabilising packaging:Paper substrate is similar to steam polarity, there is certain adsorptivity to moisture Can, paper substrate absorbs moisture when package interior moisture is high, and paper discharges moisture when humidity is low, and unnecessary moisture can Permeation composite membrane spills into the external world, and (moisture-vapor transmission of the composite membrane is in 1-10g/m2.day.atm between), package interior is not The problem of condensation or humidity are too high occurs;
3 existing packaging materials do not possess sterilizing function typically, and fruits and vegetables normal temperature fresh-keeping packaging material of the present invention, which is removed, to be had Outside high oxygen flow, permeation rate, also with sterilizing function, and the precursor substance for producing bactericide is using lactic acid and calcium sulfite Food grade accessory ingredients, after the moisture of fruits and vegetables respiration generation is touched, can discharge sulfur dioxide gas, the gas is fruits and vegetables Bactericide, allows to use in the world, meets the requirement of food security;
The 4 fruits and vegetables normal temperature fresh-keeping packaging materials are a kind of paper-plastic composite films, and its regulating course selects EVA (ethyl vinyl acetate second Enoate copolymer)-polyacrylate blending resin, be cast and form on paper substrate, by adjust the addition of polyacrylate come The polarity of layer is controlled to adjust, permeability of this layer to vapor and bactericide is adjusted by the change of polarity and thickness;In the layer The suitable blending ratio of middle polyacrylate is 5-50% (W%), and the thickness of this layer is 5-15 microns.
The barrier layer of the 5 fruits and vegetables normal temperature fresh-keeping packaging materials is from polyacrylates-polyethylene blending resin in outer layer paper Curtain coating is formed on base, and this layer is adjusted to vapor and oxygen by adjusting the change of addition and thickness of polyacrylate Transmitance, suppresses the transmission of bactericide;The suitable blending ratio of acrylate is 5-20% (W%), the thickness of this layer in this layer Spend for 5-15 microns.
The 6 fruits and vegetables normal temperature fresh-keeping packaging materials are prepared using solvent-free complex method, and production process is pollution-free.
The 7 fruits and vegetables normal temperature fresh-keeping packaging materials can discharge 5-20ppm gas phase bactericide 30-90 days, can repeat to make With 30-90 days.
Paper substrate, EVA resin, polyacrylate resin used in the 8 compound film preparations can be with natural degradations, polyethylene tree Fat also uses degradable, therefore the fruits and vegetables normal temperature fresh-keeping packaging material can be with natural degradation.
All raw materials selected by the present invention meet regulation of the country about packaging material for food, and the bactericide of release Concentration is low, does not have any Fungicide residue on packaged fruit, meets the requirement of food security.
In a word, the fruits and vegetables normal temperature fresh-keeping packaging material that prepared by the present invention can prevent fruits and vegetables water loss, kill on fruit Pathogen, disclosure satisfy that oxygen percent of pass under normal temperature needed for fruits and vegetables respiration, humidity suitable in control freshness protection package, can To significantly improve fruit and vegetable storage period at normal temperatures and shelf life;The concentration of sterilant of preservative film release and cycle are controllable, Bactericide noresidue on fruit, meets the requirement of food security;And fruits and vegetables normal temperature fresh-keeping packaging material production process is to environment Pollution-free, simple production process, production cost are low;Fruits and vegetables normal temperature fresh-keeping packaging material is reusable, can be dropped naturally after discarding Solution, it is environmentally safe.
Embodiment
By embodiment in detail below and application example, the invention will be further described.Following specific descriptions be for The present invention is readily appreciated, protection scope of the present invention is not intended to limit.
Comparative example 1
After the polybutyl methacrylate resin of 50 mass parts and 50 mass parts EVA resin melt blendings, in casting machine Upper casting film-forming, the thickness for controlling casting films is 35 microns, prepares inner side raw material film;By the polymethyl of 20 mass parts After acid butyl ester and the PE of 80 mass parts (low density polyethylene (LDPE)) melt blending, casting thickness is 35 microns of outside on casting machine Raw material film;After the lactic acid of 6 mass parts is mixed with the calcium sulfite of 4 mass parts, the polyurethane (PU) for being added to 90 mass parts is accounted for Tie in agent, prepare bactericide-polyurethane adhesive, bonded two raw material films with the binding agent, cut bag, obtain fruit Vegetable fresh-retaining bag.
Embodiment 1
After the butyl methacrylate resins of 50 mass parts and 50 mass parts EVA resin melt blendings, film is used as Resin raw material, on casting machine by blending resin curtain coating on 16.5 grammes per square metre paper, it is 5-7 microns to control casting thickness, is prepared EVA- acrylate films are coated into internal layer paper substrate;The polybutyl methacrylate of 20 mass parts and the PE of 80 mass parts is (low close Spend polyethylene) after melt blending, as the resin raw material of film, by resin curtain coating in 16.5 grammes per square metre paper on casting machine On, it is 5-7 microns to control casting thickness, is prepared into the outer coating of paper substrate layer by layer acrylate-PE films;By the lactic acid of 6 mass parts and 4 After the calcium sulfite mixing of mass parts, it is added in the polyurethane of 90 mass parts (PU) binding agent, prepares bactericide-polyurethane Binding agent, with the binding agent by two raw material films (paper substrate coats EVA- acrylate films and outer paper substrate layer by layer coat acrylate- PE films) coat side bond, the resin added of binding agent is 5-8g/m2, bag is then cut, fruit and vegetable is obtained normal Warm freshness protection package.
Embodiment 2-6
Preparation method is similar to Example 1, simply the thickness of the trade mark of feed change, proportion of composing and coated film, Specific data are shown in Table 1.
The OTR oxygen transmission rate of the plastics base freshness protection package prepared from comparative example 1 is less than 104ml/m2.day.atm, if this Fresh-keeping packed 1 kilogram of (300 × 400mm of appearance and size) fruits and vegetables, then be only capable of meeting less than 10ml/hr.kg respiratory intensities, general Preservation by low temperature fruits and vegetables can be used for, the respiratory intensity of general fruit to be in 20-50ml/hr.kg at normal temperatures, and the respiratory intensity of vegetables is more Greatly, therefore plastics base freshness protection package can cause anoxic in fruits and vegetables storage condition at room temperature, it is easier to which aging is rotted;Plastics base is fresh-keeping Bag is less than 1g/m to the transmitance of vapor2.day.atm (40-50 microns of thickness), the compatibility to water is relatively low, in freshness protection package Ponding breed bacteria easily occur causes fruits and vegetables to rot.
From embodiment 1-6 prepare fruits and vegetables normal temperature fresh-keeping packaging material oxygen gas permeability rate 104-106ml/ m2.day.atm between, moisture-vapor transmission 1-10g/m2.day.atm between, it can meet under fruits and vegetables normal temperature needed for respiration Oxygen supply, and can discharge 5-20ppm bactericide in freshness protection package, prevent fruits and vegetables from growing pathogen, play sterilization fresh-keeping Effect;By regulating course and barrier layer resin composition and thicknesses of layers change film gas permeability and bactericide rate of release and Cycle;The concentration of sterilant of release is very low in freshness protection package, is not remained on packaged fruit and vegetable after testing.
Upper example is applied in fruit freshness preserving with regard to the multifunctional fruit wrapping film of the invention prepared, herein not one by one Enumerate.
Those skilled in the art is it will be clearly understood that above preferred embodiment is simply illustrated to the present invention, not structure Into limitation of the present invention.Various variations and equivalence replacement are carried out to technical scheme, without departing from the technology of the present invention The principle and scope of scheme, all should cover among the scope of the claims in the present invention.

Claims (4)

1. a kind of paper-plastic stick wrapping film based on paper substrate, it is characterised in that according to order from inside outwards successively Layer, barrier layer, paper substrate are produced for paper substrate, regulating course, bactericide;
The regulating course be cast from ethylene-vinyl acetate copolymer-polyacrylate blending resin on internal layer paper substrate and Into controlling to adjust the polarity of layer by adjusting the addition of polyacrylate, the layer adjusted by the change of polarity and thickness To the permeability of vapor and bactericide;The suitable blending ratio of polyacrylate is 50W% in this layer, and the thickness of this layer is 5-15 microns;
The bactericide produces layer and is made up of bactericide precursor substance and binding agent, and wherein bactericide precursor substance accounts for the total matter of the layer The 10% of amount, binding agent selects EVA resin or polyurethane adhesive;The composition of bactericide precursor substance be lactic acid, calcium sulfite, Wherein lactic acid content accounts for the 50-60% of bactericide precursor substance;
The barrier layer is cast on outer layer paper substrate from polyacrylates-polyethylene blending resin and formed, by adjusting poly- third The change of the addition of olefin(e) acid ester and thickness adjusts transmitance of this layer to vapor and oxygen, suppresses the transmission of bactericide; The suitable blending ratio of polyacrylate is 5-20W% in this layer, and the thickness of this layer is 5-15 microns.
2. the paper-plastic stick wrapping film based on paper substrate described in claim 1, it is characterised in that polyacrylate bag Include polybutyl methacrylate, polymethyl methacrylate, polyethyl methacrylate, butyl polyacrylate.
3. the preparation method of the paper-plastic stick wrapping film based on paper substrate described in claim 1, is by being coated with tune The internal layer paper substrate of ganglionic layer, it is coated with the outer layer paper substrate of barrier layer and produces the solvent-free complex method of layer with bactericide and obtain.
4. the freshness protection package that a kind of paper-plastic stick wrapping film based on paper substrate as described in claim 1 is made, in dress Enter after fruits and vegetables, the gas phase that the vapor that fruits and vegetables respiration is produced can induce paper-plastic composite film release 5-20ppm is killed Microbial inoculum 30-90 days, water conservation, sterilization, ventilative function are played to fruit, improve the shelf life of water fruits and vegetables at normal temperatures.
CN201310063998.5A 2013-03-01 2013-03-01 The special paper-plastic composite film of fruit and vegetable normal-temperature fresh-keeping Expired - Fee Related CN103144845B (en)

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CN104109362A (en) * 2014-08-06 2014-10-22 昆明春叶塑料制成品有限公司 Environment-friendly biodegradable film for fruit and vegetable packaging and preparation method of film
CN105153825A (en) * 2015-08-14 2015-12-16 常德市金润新材料科技有限公司无锡新材料研究院 Moisture-retention waterborne coating as well as preparation method and application thereof
CN107097493A (en) * 2017-04-26 2017-08-29 广州市花都联华包装材料有限公司 A kind of constant humidity is guaranteed the quality flexible packaging film and its manufacture method
CN107522887B (en) * 2017-09-13 2020-07-21 常德金德新材料科技股份有限公司 Preservative film and preparation method thereof
CN107826460A (en) * 2017-11-09 2018-03-23 常德金德新材料科技股份有限公司 Fruits and vegetables fresh-keeping paper and preparation method thereof
CN115676134A (en) * 2022-10-27 2023-02-03 赵梓俨 g-C 3 N 4 Application of basic high-antibacterial high-barrier property modified atmosphere preservation plastic product
WO2024203673A1 (en) * 2023-03-28 2024-10-03 三井化学株式会社 Laminate and packaging material

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CN102862361A (en) * 2012-09-26 2013-01-09 北京印刷学院 Fruit and vegetable freshness retaining packaging material capable of releasing 1-methyl cyclopropene and preparation method thereof

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CN102173146A (en) * 2011-01-12 2011-09-07 北京印刷学院 Multifunctional multilayer composite film for fruit preservation and preparation method thereof
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Effective date of registration: 20181211

Address after: 110013 Shop No. 4001, 4002 and 4003, 118 Harbin Road, Shenhe District, Shenyang City, Liaoning Province - A115

Patentee after: Shenyang Zhongqing New Materials Co., Ltd.

Address before: 100013 Beijing Chaoyang District, Pingjie 12 District, 22nd Floor, 1092

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