CN103965539B - A kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane and preparation method thereof - Google Patents
A kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane and preparation method thereof Download PDFInfo
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- CN103965539B CN103965539B CN201410193726.1A CN201410193726A CN103965539B CN 103965539 B CN103965539 B CN 103965539B CN 201410193726 A CN201410193726 A CN 201410193726A CN 103965539 B CN103965539 B CN 103965539B
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
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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
- C08K5/20—Carboxylic acid amides
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
A kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane, is made up of the raw material of following weight parts: ldpe resin 90 ~ 96.5 parts, silicon-dioxide opening agent 0.5 ~ 2 part, hydrochloric acid 1 ~ 2 part, titanium dioxide 1 ~ 2 part, N-acetamido-4-vinylpridine 0.5 ~ 2 part, amine hydroxybenzene 0.5 ~ 2 part.The invention belongs to technical field of preservation of fresh, be mainly used in the packaging of fruit and vegetable food, the present invention is raw material based on Low Density Polyethylene, adds various modifying ingredients and carries out modification, reaches the object of the fresh keeping time extending fruit and vegetable food.Present invention also offers a kind of method preparing above-mentioned intelligent breathing preserving fruit and vegetable utilizing functional membrane, by adding Inorganic chemical composition, improving the air permeable effect of film, slowing down respiration, extend fresh keeping time.The present invention be a kind ofly possess ventilative balance adjustment simultaneously, ethylene gas is removed, the intelligent breathing preserving fruit and vegetable utilizing functional membrane of frosting resistance and antibacterial.
Description
Technical field
The present invention relates to chemical field, particularly relate to polymer chemistry, particularly a kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane and preparation method thereof.
Background technology
The Perserving materials used in product Freshkeeping Packaging field has polyethylene, polyvinyl chloride etc., wherein polyvinyl chloride is owing to having toxicity to a certain degree, therefore forbid the packaging for prepared food, and low density polyethylene films just plays increasing effect in product Freshkeeping Packaging field with its distinctive nontoxic property.Because the products such as fruits and vegetables fresh flower can discharge ethylene gas in the process of maturation, ethylene gas has the effect of accelerating the ripening, and is unfavorable for fresh-keeping to a certain extent.In addition, in preservation process, easily there is the accumulation of water droplet in film, also there will be the phenomenon of frosting under cryogenic, affect the attractive in appearance of food and mouthfeel in common food product packing film, is also unfavorable for the fresh-keeping of food simultaneously.Polyethylene preservative film in prior art, does not possess ventilative balance adjustment, ethylene gas is removed, frosting resistance and the function such as antibacterial, and tensile strength is weak, can not play the effect extending fresh keeping time.
Summary of the invention
The object of the present invention is to provide a kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane, described this intelligent breathing preserving fruit and vegetable utilizing functional membrane will overcome that polyethylene preservative film in prior art does not possess ventilative balance adjustment, ethylene gas is removed, frosting resistance and the function such as antibacterial, tensile strength are weak, can not the short technical problem of fresh keeping time.
This intelligent breathing preserving fruit and vegetable utilizing functional membrane of the present invention, is made up of the raw material of following weight parts: ldpe resin 90 ~ 96.5 parts, silicon-dioxide opening agent 0.5 ~ 2 part, hydrochloric acid 1 ~ 2 part, titanium dioxide 1 ~ 2 part, N-acetamido-4-vinylpridine 0.5 ~ 2 part, amine hydroxybenzene 0.5 ~ 2 part.
As the preferred embodiment of the present invention, described intelligent breathing preserving fruit and vegetable utilizing functional membrane is made up of the raw material of following weight parts: ldpe resin 93 ~ 96 parts, silicon-dioxide opening agent 0.8 ~ 1.5 part, hydrochloric acid 1.2 ~ 1.8 parts, titanium dioxide 1.4 ~ 1.9 parts, N-acetamido-4-vinylpridine 0.7 ~ 1.5 part, amine hydroxybenzene 0.9 ~ 1.6 part.
As preferred forms of the present invention, described intelligent breathing preserving fruit and vegetable utilizing functional membrane is made up of the raw material of following weight parts: ldpe resin 93.3 parts, silicon-dioxide opening agent 1.3 parts, hydrochloric acid 1.5 parts, titanium dioxide 1.7 parts, N-acetamido-4-vinylpridine 1 part, amine hydroxybenzene 1.2 parts.
Concrete, the density of described ldpe resin is between 0.915 ~ 0.940 gram/cc.
Concrete, described hydrochloric acid is solid.
Concrete, described silicon-dioxide opening agent is a kind of amorphous silica, be a kind of antiblocking agent, anticaking agent, opening agent efficiently, be used as the efficient opening agent of polyolefine IPP film, polyethylene ldpe film, BOPP BiOriented Polypropylene Films, CASNO:14808-60.
Present invention also offers a kind of method preparing above-mentioned intelligent breathing preserving fruit and vegetable utilizing functional membrane, described method specifically comprises following step: material allocation, material loading, extrude, inflation, cooling, printing, traction-folder are flat, volume film, cutting and packaging.
Material allocation: be mainly added ingredients in Low Density Polyethylene raw material, major ingredient basal component is Low Density Polyethylene, and auxiliary material basal component comprises technique sour, anti-fog and frosting auxiliary agent, antibacterial resin, silicon-dioxide opening agent and amine hydroxybenzene; Wherein technique acid is hydrochloric acid, and anti-fog and frosting auxiliary agent is titanium dioxide, and antibacterial resin is N ~ acetamido ~ 4 ~ vinyl pyridine, and the weight of main ingredient is 90 ~ 96.5:10 ~ 3.5, and wherein adjunct ingredient can adjust according to different effects.
Material loading, to extrude and inflation: mainly by multi-layer co-extruded principle, multilayer film is combined with each other, based on different formulas and temperature change and produce different film effect, be first then extrude the heating of material grain, after vane cooling stretches, by pressing from both sides rod, to flatten last rolling shaping.
Other step follow-up is identical with general polyethylene film production technique, and in the method for production of intelligent breathing preserving fruit and vegetable utilizing functional membrane of the present invention, the production technique temperature of whole production process is 160 ~ 170 DEG C.
This product attainable basic fundamental parameter is as follows: oxygen transmission rate: 5000 ~ 8000 milliliters/square metre (24 hours); Carbon dioxide transmission rate: 20000 ~ 25000 milliliters/square metre (24 hours); Vapor transmission rate: 24 ~ 28 grams/m; Ethylene gas removes speed: 3000 ~ 4000 milliliters/square metre (24 hours).
Principle of work of the present invention be based on Low Density Polyethylene gas regulating function and add the ethylene absorption effect of each composition, defrosting effect and antibacterial effect, according to respective weight part be process under the condition of 160 ~ 170 DEG C in production technique temperature by various composition, the main generation principle of permeability, the temperature control difference of various raw material and the difference of screw rod unique design and raw material proportion, make it be produced different space by the change of three layers of extrusion speed to cause and produce very trickle cold and hot change between film thus the smoke condition the produced function that film can be made waterproof and can breathe freely, making air can change discharge carbonic acid gas keeps humidity to have special-effect to removal ethylene gas.The condition of chemical element reaction is: the change produced due to temperature makes its molecular structure change and produce used the raw material of modification to make it draw in the process of stretching to form the process of extremely trickle air circulation and film can be made to produce gas purging effect.
The invention has the beneficial effects as follows: the invention belongs to technical field of preservation of fresh, main application is packaging intelligent breathing preserving fruit and vegetable utilizing functional membrane being used for product, improves fresh-keeping effect.The present invention, based on low density polyethylene films, adds various modifying ingredients and carries out modification, reaches the effect of the fresh keeping time extending product.The present invention by adding a certain amount of ethylene absorption material in the production of low density polyethylene films, reach the effect of removing ethylene gas, simultaneously by the gas permeability of this preservative film, make the carbon dioxide enrichment produced in product respiration, occupy the change point of ethylene gas reaction, play the effect that ethene suppressing gas produces.The respiration of product can consume oxygen and discharge carbonic acid gas, the principle that the present invention is based on gas regulation packaging is regulated the gas in film by the penetrating quality of preservative film, by adding Inorganic chemical composition, improve the air permeable effect of film, to reach the balance of oxygen and carbonic acid gas inside and outside a kind of film, namely in film, gas concentration lwevel is higher than the carbonic acid gas background concentration in air, and in film, oxygen concentration is lower than the oxygen background concentration in air, slow down respiration, extend fresh keeping time.
The present invention can possess gas regulating function simultaneously, absorb ethylene gas function, frosting resistance function and antibacterial: 1, the realization of gas regulating function is by adding inorganic component in Low Density Polyethylene, increases ventilation property and the selectivity of film; 2, the realization of absorption ethylene gas function is the composition by adding Absorbable rod ethylene gas in Low Density Polyethylene, and the many hollow structures in fresh-keeping function film of the present invention also have the function of ethylene adsorption; 3, the realization of frosting resistance function is by adding frosting resistance composition in Low Density Polyethylene, avoids the generation of frost; 4, the realization of antibacterial is by adding antimicrobial component in Low Density Polyethylene, plays the antibacterial effect in Freshkeeping Packaging.Intelligent breathing preserving fruit and vegetable utilizing function film strength of the present invention and toughness meet GBT4456-2008 (packaging polyethylene blown film) national standard.
Accompanying drawing explanation
Fig. 1 is the production technological process of intelligent breathing preserving fruit and vegetable utilizing functional membrane of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
Embodiment 1: a kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane, it is made up of the raw material of following weight parts: ldpe resin 93.5 parts, silicon-dioxide opening agent 0.5 part, hydrochloric acid 1 part, titanium dioxide 1 part, N-acetamido-4-vinylpridine 2 parts, amine hydroxybenzene 2 parts.
Embodiment 2: a kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane, it is made up of the raw material of following weight parts: ldpe resin 95 parts, silicon-dioxide opening agent 1 part, hydrochloric acid 1 part, titanium dioxide 1 part, N-acetamido-4-vinylpridine 1 part, amine hydroxybenzene 1 part.
Embodiment 3: a kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane, it is made up of the raw material of following weight parts: ldpe resin 93 parts, silicon-dioxide opening agent 2 parts, hydrochloric acid 2 parts, titanium dioxide 2 parts, N-acetamido-4-vinylpridine 0.5 part, amine hydroxybenzene 0.5 part.
As shown in Figure 1, the production method of intelligent breathing preserving fruit and vegetable utilizing functional membrane described by above-described embodiment, specifically comprises following step: material allocation, material loading, extrude, inflation, cooling, printing, traction-folder are flat, volume film, cutting and packaging.Material allocation: be mainly and add adjunct ingredient in Low Density Polyethylene raw material, major ingredient basal component is Low Density Polyethylene, and auxiliary material basal component comprises sour, the anti-fog and frosting auxiliary agent of technique and antibacterial resin, silicon-dioxide opening agent and amine hydroxybenzene; Wherein technique acid is hydrochloric acid, and anti-fog and frosting auxiliary agent is titanium dioxide, and antibacterial resin is N ~ acetamido ~ 4 ~ vinyl pyridine, and wherein adjunct ingredient can adjust according to different effects.Material loading, to extrude and inflation: mainly by multi-layer co-extruded principle, multilayer film is combined with each other, based on different formulas and temperature change and produce different film effect, be first then extrude the heating of material grain, after vane cooling stretches, by pressing from both sides rod, to flatten last rolling shaping.Other step follow-up is identical with general polyethylene film production technique.
The silicon-dioxide opening agent that above-described embodiment adopts and amine hydroxybenzene are from manufacturer: A.Schulman.
Embodiment 4: anti-mold effect is tested
1. testing method
The mensuration of ASTMG21-09 synthesized polymer material mildew resistance
2. experimental strain
Aspergillus niger (Aspergillusniger) ATCC16404, Chaetomium globosum (Chaetomiumglobasum) AS3.3601, G virens (Gliocladiumvirens) AS3.3987, penicillium funiculosum (Penicilliumfuniculosum) AS3.3875, Aureobasidium pullulans (Aureobasidiumpullulans) AS3.837.
3. test result
Remarks: according to the mensuration of ASTMG21-09 synthesized polymer material antifungal property, the mould-growth average evaluation that sample surfaces is observed is as follows: 0-does not grow 1-vestige growth (being less than 10%) 2-and slightly grows (10-30%) 3-moderate growth (30-60%) 4-severe growth (60%-covers comprehensively).Test sample adopts the product of embodiment 2 to test.
Embodiment 5: anti-(pressing down) bacterium test
1. testing method
ISO22196:2011 is in the measurement of plastics with the antibacterial activity of other pore-free surface
2. experimental strain
Streptococcus aureus ATCC6538P, intestinal bacteria ATCC8739
3. test result
Remarks: control sample is without anti-microbial property plastic film.Test sample adopts the product of embodiment 2 to test.
Embodiment 6: gas-premeable is tested
1. with reference to GB10457-2009 gas-premeable test method (pressure differential method).
2.
| Test item | Unit | Detected result |
| Water vapor transmission | g/(m 2·24h) | 10.6 |
| Permeability | cm 3/(m 2·24h·0.1Mpa) | 8433 |
| COZ permeability | cm 3/(m 2·24h·0.1Mpa) | 3.0×10 4 |
Note: test surfaces is sample internal surface.Test sample adopts the product of embodiment 2 to test.
Embodiment 7: test the removal effect to the ethylene gas that melon and fruit discharges.
1. use GC to analyze.
2.
Remarks: 1) get 2g (being accurate to 0.001g) sample in 20mL ml headspace bottle, seal immediately, in ml headspace bottle, 1ul Standard Gas of Ethylene is injected with gas-tight syringe, shake up, extract gas 100ul in ml headspace bottle and do stratographic analysis, place after 5 days, again extract gas 100ul in ml headspace bottle and do stratographic analysis.Ethene clearance X (%)=100x (starting point concentration is concentration after-5 days)/starting point concentration.Test sample adopts the product of embodiment 2 to test.
Finally should be noted that; above content is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; the simple modification that those of ordinary skill in the art carries out technical scheme of the present invention or equivalently to replace, does not all depart from essence and the scope of technical solution of the present invention.
Claims (4)
1. an intelligent breathing preserving fruit and vegetable utilizing functional membrane, it is characterized in that: be made up of the raw material of following weight parts: ldpe resin 90 ~ 96.5 parts, silicon-dioxide opening agent 0.5 ~ 2 part, hydrochloric acid 1 ~ 2 part, titanium dioxide 1 ~ 2 part, N-acetamido-4-vinylpridine 0.5 ~ 2 part, amine hydroxybenzene 0.5 ~ 2 part, the density of described ldpe resin is between 0.915 ~ 0.940 gram/cc, described hydrochloric acid is solid, and described silicon-dioxide opening agent is amorphous silica.
2. intelligent breathing preserving fruit and vegetable utilizing functional membrane according to claim 1, is characterized in that: be made up of the raw material of following weight parts: ldpe resin 93 ~ 96 parts, silicon-dioxide opening agent 0.8 ~ 1.5 part, hydrochloric acid 1.2 ~ 1.8 parts, titanium dioxide 1.4 ~ 1.9 parts, N-acetamido-4-vinylpridine 0.7 ~ 1.5 part, amine hydroxybenzene 0.9 ~ 1.6 part.
3. intelligent breathing preserving fruit and vegetable utilizing functional membrane according to claim 2, is characterized in that: be made up of the raw material of following weight parts: ldpe resin 93.3 parts, silicon-dioxide opening agent 1.3 parts, hydrochloric acid 1.5 parts, titanium dioxide 1.7 parts, N-acetamido-4-vinylpridine 1 part, amine hydroxybenzene 1.2 parts.
4. prepare a method for intelligent breathing preserving fruit and vegetable utilizing functional membrane as claimed in claim 1, it is characterized in that: comprise the step of a material allocation, the step of a material loading, a step extruded, an inflation step, one cooling step, one printing step, one draw-press from both sides flat step, one volume film step, one cutting step and one packaging step.
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| CN201410193726.1A CN103965539B (en) | 2013-06-25 | 2014-05-09 | A kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane and preparation method thereof |
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| CN201310254977.1 | 2013-06-25 | ||
| CN2013102549771A CN103304880A (en) | 2013-06-25 | 2013-06-25 | Intelligent breathing fruit and vegetable fresh-keeping film |
| CN2013102549771 | 2013-06-25 | ||
| CN201410193726.1A CN103965539B (en) | 2013-06-25 | 2014-05-09 | A kind of intelligent breathing preserving fruit and vegetable utilizing functional membrane and preparation method thereof |
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| CN106317540A (en) * | 2015-06-23 | 2017-01-11 | 大连瑞贤达塑胶有限公司 | Method for detecting penetration performance of fruit package nano preservative film |
| CN109354704A (en) * | 2018-09-10 | 2019-02-19 | 龙泽慧丰农业科技有限公司 | A kind of preservative film |
| CN110411117B (en) * | 2019-08-30 | 2024-10-11 | 长虹美菱股份有限公司 | Refrigerator fresh-keeping device based on gas regulation |
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| JP3067328B2 (en) * | 1991-10-22 | 2000-07-17 | 三菱化学株式会社 | Food packaging sheet or film |
| CN1262592C (en) * | 2002-07-08 | 2006-07-05 | 北京崇高纳米科技有限公司 | Fruit and vegetable fresh-keeping plastic film and method for making the same |
| KR20100049723A (en) * | 2008-11-04 | 2010-05-13 | 이규주 | Functional resin (PE, PP) film composed of functional pores |
| CN102030131A (en) * | 2010-11-10 | 2011-04-27 | 国家农产品保鲜工程技术研究中心（天津） | Fresh-keeping package for tropical fruits in south and application of fresh-keeping package in fruit and vegetable logistic fresh keeping |
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