CN110305351A - A kind of wet film of intelligence control of biodegradable and its preparation method and application - Google Patents
A kind of wet film of intelligence control of biodegradable and its preparation method and application Download PDFInfo
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- CN110305351A CN110305351A CN201810231480.0A CN201810231480A CN110305351A CN 110305351 A CN110305351 A CN 110305351A CN 201810231480 A CN201810231480 A CN 201810231480A CN 110305351 A CN110305351 A CN 110305351A
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- 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
- 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
Abstract
The invention belongs to function film fields, are related to a kind of wet film of intelligence control and its preparation method and application of biodegradable.The wet film of intelligence control of the biodegradable includes base and extra play, and the extra play is located at base one or both sides；Wherein, the base is porous membrane, and material is synthesis biodegradable macromolecule；The extra play is dense film, and material contains polyvinyl alcohol and helper component and optional crosslinking agent and/or antibacterial agent；The helper component is water-soluble metal salt, acid soluble metal oxide, cellulose and at least one of cellulose derivative and polyalcohol.There is the wet film of intelligence control of the invention intelligence to control wet ability, and have oxygen barrier property, the fruit and vegetable box that can be used for having fresh-keeping function and the refrigerator with fruit and vegetable preservation box.In addition, the film biodegradable, avoids and pollutes the environment.
Description
Technical field
The invention belongs to function film fields, a kind of wet film of intelligence control more particularly, to biodegradable and
Preparation method and application.
Background technique
Fruits and vegetables is the important food of the mankind, is that people obtain basic nutrition object (vitamin, minerals, composite carbon
Hydrate etc.) main source.Freshness requirement with the increasingly raising of people's living standard, to fresh fruit and vegetables
It is higher and higher.Fruits and vegetables remain to continue the vital movements such as breathing and transpiration after harvesting, and water can occur in storing process
Dispersion is become estranged the consumption of nutriment.Temperature is every to increase 10 DEG C, and fruits and vegetables respiratory intensity is increased by one times.Family's fruit and vegetable preserving method
It is that fruits and vegetables are placed in refrigerator to refrigerate, slows down fruits and vegetables breathing.In fruits and vegetables, moisture is important component, affects fruit and vegetable
Dish tenderness, freshness and taste.Ambient humidity, light and temperature is too low to will lead to fruits and vegetables loss of water and weightlessness, but the excessively high meeting of humidity is so that fruits and vegetables table
Face hydrogenesis, grows fungi, accelerates fruits and vegetables rotten and rotten.Therefore control fresh fruit of vegetables storage humidity is very
Important, it is beneficial to extend the fresh keeping time of fruits and vegetables.Using barrier film, the infiltration due to gases such as oxygen can be prevented,
Inhibit fresh fruit of vegetables respiration, is conducive to extend the fresh keeping time of fruits and vegetables.
Several functional films " temperature-sensitive moisture permeable membrane " on fruit and vegetable box for reducing moisture loss, " silicon filter in the market
Film ", the effect of " moisture permeable membrane " and unsatisfactory.Temperature-sensitive moisture permeable membrane film surface under high humidity low temperature is easy moisture condensation；Silicon filter
Film has moisture-keeping functions, but penetrability can not change with humidity；Moisture permeable membrane is that viscose solution is applied in paper-based substrate,
Performance meet the requirements but preparation process not environmentally, complex process, and it is exceeded to there may be in processing technology chlorinity
Problem.
CN105986511A disclose applied on the higher body paper of dry and wet intensity it is hydrophilic water conservation and good film-forming property it is natural
The technology of high molecular polymer, but cost is relatively high.CN104029449B discloses a kind of big vapor transfer rate coated film, and basal layer is
Eptfe membrane layer, coating are the ester emulsion copolymerized coating of polyurethane containing hemp stalk core super fine, the film
For automobile lamp shell, but do not have intelligence control wet performance.CN103507339A discloses a kind of moisture permeable membrane, which will
Regenerated cellulose is maintained in the substrate of non-woven fabrics, but does not have barrier gas performance.CN103107301A discloses a kind of nothing
Organic coating lithium ion battery separator includes multilayered structure, respectively porous flexible counterdie and the coating coated on counterdie two sides, applies
Layer includes polyvinyl alcohol and zeolite particles, and there is no metal salt components for the auxiliary element of the coating, and composite membrane does not have intelligence
Control wet function.CN1864829A discloses a kind of hydrophilic-hydrophobic bipolar composite membrane and preparation method thereof, which has the double-deck knot
Structure, bottom are porous support layer, and upper layer is the hydrophilic film of chloride containing lithium, which has high moisture-inhibiting and hinder by force other gas molecules
Gear effect, but it is moist not have intelligence control.WO2013066012A1 disclose a kind of perforated membrane containing inorganic particulate and
Comprising hydrophilic and hydrophobic substance Polymer Tie-layer, which is used to improve the thermal stability of lithium battery diaphragm, does not have intelligence
Control wet performance.WO2012133805A1 discloses a kind of moisture permeable membrane, porous substrate preferably polytetrafluoroethylene, price, and is somebody's turn to do
The high moisture-inhibiting performance of film is bad.US20030054155A1 discloses a kind of Waterproof Breathable composite membrane, and hydrophobic layer is polytetrafluoroethyl-ne
Alkene, hydrophilic layer are polyurethane, which has high moisture-inhibiting, but do not have intelligence control wet performance.
Summary of the invention
The purpose of the invention is to overcome drawbacks described above of the existing technology, provide a kind of intelligence control wet film,
Moisturizing in the case where low humidity has strong ventilating capability in the case where high humility, and has oxygen barrier property, in addition,
The film biodegradable, avoids and pollutes the environment.The present invention further provides the preparation method of the film,
It is this method simple process, at low cost.
The first aspect of the present invention provides a kind of wet film of intelligence control of biodegradable, including base and extra play,
The extra play is located at base one or both sides；Wherein,
The base is porous membrane, and material is synthesis biodegradable macromolecule, preferably polylactic acid, poly- to fourth
Succinate adipate, in poly terephthalic acid -co- succinic acid-butanediol ester and poly terephthalic acid -co- tetramethylene adipate
At least one, further preferably polylactic acid and/or poly terephthalic acid -co- succinic acid-butanediol ester；
The extra play is dense film, material contain polyvinyl alcohol and helper component and optional crosslinking agent and/
Or antibacterial agent；The helper component is water-soluble metal salt, acid soluble metal oxide, cellulose and cellulose derivative and more
At least one of first alcohol, preferably water-soluble metal salt and/or cellulose and cellulose derivative.
In the present invention, to realize that intelligence control is wet, the base need to be porous membrane, and the extra play need to be dense film.
The concept and term scope of the porous membrane and dense film are known to the skilled person.Dense thin as extra play
Film can be made by way of by the solution coating for containing additional layer component to substrate surface and drying.
According to the present invention, it is multilayer that the intelligence, which controls wet film, when intelligently controlling wet film is two layers, the extra play position
In base side, when intelligently controlling wet film is three layers, the extra play is located at base two sides, in case of need, described
It may be more than three layers of more layers that intelligence, which controls wet film, and extra play and base can be with arranged for interval.Wherein, the base is excellent
It is selected as single layer structure.
In the present invention, the aperture of the porous membrane is preferably 0.02-50 microns, and further preferably 0.05-10 microns,
More preferably 0.05-5 microns, most preferably 0.06-2 microns；Porosity is preferably 30%-80%, further preferably 40%-
70%；Hole of the aperture within the scope of the positive and negative an order of magnitude of average pore size accounts for 50% or more of all well, preferably accounts for all well
80% or more.The porous membrane can be directly obtained by commercially available, can also be by preparing, the method for preparing porous membrane
It is known to the skilled person, for example, biaxially oriented film is stretched on film drawer, obtains porous membrane.
Since the material of porous membrane is synthesis biodegradable macromolecule, the wet film of intelligence control of the invention
With biodegradable performance.Any synthesis biodegradable macromolecule for being capable of forming porous membrane in this field is available
In the present invention.
According to the present invention, the relative amount of the polyvinyl alcohol and helper component is limited with that can form dense film, preferably
Ground, on the basis of extra play total weight, the content of the polyvinyl alcohol is 50-99wt%, preferably 66-98wt%, further
Preferably 70-95wt%；The content of the helper component is 1-50wt%, preferably 2-34wt%, further preferably 5-
30wt%.
According to the present invention, the polyvinyl alcohol of higher molecular weight and alcoholysis degree is more advantageous to form dense film, it is preferable that institute
The weight average molecular weight for stating polyvinyl alcohol is 10000-500000, further preferably 20000-200000；Alcoholysis degree is preferably
70%-100%, further preferably 88%-99%.
In accordance with the present invention it is preferred that the water-soluble metal salt be sulfate, halide salt and metal hydroxides in extremely
Few one kind, preferably sodium sulphate, calcium sulfate crystal whiskers, sodium hydroxide, calcium chloride, sodium chloride, lithium chloride, lithium bromide, cesium fluoride and
At least one of at least one of lithium fluoride, further preferably sodium sulphate, calcium chloride and lithium chloride.
In accordance with the present invention it is preferred that the acid soluble metal oxide is preferably in aluminium oxide, calcium oxide and magnesia
It is at least one.
In accordance with the present invention it is preferred that the cellulose and cellulose derivative are nano-cellulose, cellulose ether, fiber
At least one of plain ester and cellulose ether-esters；Preferably hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, carboxylic
At least one of ethyl cellulose and hydroxypropyl methyl cellulose；Further preferably hydroxyethyl cellulose, hydroxy propyl cellulose
At least one of element and carboxymethyl cellulose.
In accordance with the present invention it is preferred that the polyalcohol is at least one of propylene glycol, glycerol, sorbierite and sucrose.
According to the present invention, crosslinking agent and antibacterial agent be it is optional containing component, it is wet thin that the addition of crosslinking agent can be such that intelligence controls
Film has better oxygen barrier property, and the addition of antibacterial agent, which can make intelligence control wet film, has anti-microbial property.
On the basis of the total weight of the extra play, the content of the crosslinking agent can be 0-10wt%, preferably 0.1-
7wt%, further preferably 2-6wt%；The crosslinking agent is preferably formaldehyde, glyoxal, malonaldehyde, butanedial, glutaraldehyde, horse
Come at least one of sour, maleic anhydride and sulfuric acid；Further preferably at least one of formaldehyde, glutaraldehyde and sulfuric acid, more
Preferably formaldehyde and sulfuric acid or glutaraldehyde and sulfuric acid, the crosslinking agent being used in compounding can further improve cross-linking efficiency and crosslinking
Effect, wherein the amount ratio of formaldehyde or glutaraldehyde and sulfuric acid can be 2-5:1.
On the basis of the total weight of the extra play, the content of the antibacterial agent can be 0-20wt%, preferably 0.1-
10wt%；The antibacterial agent be preferably nano zine oxide, titanium oxide, nano silver, Nanometer Copper, silk gum, quaternary ammonium salt, methyl hydroxybenzoate,
At least one at least one of potassium sorbate and chitosan, further preferably nano zine oxide, nano silver and quaternary ammonium salt
Kind, the quaternary ammonium salt is, for example, Cetylpyridinium Chloride.
Above-mentioned preferred component can get the film of more excellent moisture permeability and gas barrier property.
According to the present invention, the thickness of the base and extra play can determine as needed, generally, the thickness of the base
It can be 5-1000 microns, preferably 10-100 microns, further preferably 50-90 microns；The thickness of the extra play can be with
It is 0.5-100 microns, preferably 2-20 microns.
The intelligence that the second aspect of the present invention provides a kind of biodegradable controls the preparation method of wet film, including following
Step:
(1) each component for the extra play that above-mentioned intelligence controls wet film is sufficiently dissolved or is dispersed in water, be configured to molten
Liquid or dispersion liquid；
(2) solution obtained in step (1) or dispersion liquid are coated on the one side that above-mentioned intelligence controls the base of wet film
Or two sides；The intelligence is obtained after drying controls wet film.
Solution obtained in step (1) or dispersion liquid can be coated on by base using any conventional coating method,
Including but not limited to: brushing, showering, spraying.
According to the present invention, the mass concentration of the solution in step (1) or dispersion liquid can be 0.5%-30%, preferably
1%-10%, further preferably 5%-10%.
According to the present invention, the temperature dried in step (2) can be 50 DEG C -100 DEG C, preferably 60 DEG C -90 DEG C.It can be normal
Baking step, such as baking oven are completed in the various heating devices of rule.The time of drying can determine as needed, for example, 5-30min.
According to the present invention, crosslinking agent can be added when preparing the solution or dispersion liquid of extra play, can also be after the drying
Individually coating, or be added in two steps on above-mentioned two opportunity.The step of being individually coated with after the drying includes: individually to match crosslinking agent
Solution or dispersion liquid is made, the one side of the film after the solution containing crosslinking agent or dispersion liquid to be coated on to the drying of step (2)
Or two sides, the intelligence is obtained after drying again controls wet film；The mass concentration of the solution containing crosslinking agent or dispersion liquid
Preferably 0.5%-10%, further preferably 1%-5%.The condition dried again can be identical as first time drying condition.
The third aspect of the present invention provides above-mentioned intelligence and controls wet film and/or intelligently control as made from above-mentioned preparation method wet
Application of the film in vegetable and fruit fresh-keeping packaging.
There is the wet film of intelligence control of the invention intelligence to control wet ability, and fruits and vegetables humidity is kept when relative humidity is lower,
Increase moisture-inhibiting when relative humidity is higher to prevent fruit and vegetable moisture condensation from festering, and there is oxygen barrier property, can be used for having
There are the fruit and vegetable box of fresh-keeping function and the refrigerator with fruit and vegetable preservation box.In addition, the film biodegradable, avoids to environment
It pollutes.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.
In the present invention, intelligence controls the base of wet film and the thickness of extra play is measured by six water chestnut calibrator of Shanghai；Kong Jie
Structure includes that aperture and porosity are measured by mercury injection method, using instrument AutoporeIII-9420 type mercury injection apparatus.
Biaxially stretched polylactic acid film, Yi Sheng new material Co., Ltd, Shenzhen, 80 microns of thickness.
Poly terephthalic acid -co- tetramethylene adipate film, 55 microns of thickness.Wherein, poly terephthalic acid -co- oneself
Succinate adipate is bought from BASF Corp. of Germany, and the trade mark is Ecoflex C1800.Later on casting machine stream delay again it is two-way
Stretching obtains respective films.
Fine and close polylactic acid film, Yi Sheng new material Co., Ltd, Shenzhen, 80 microns of thickness.
Polyvinyl alcohol A, western Gansu Province chemical industry, trade mark PVA124, weight average molecular weight 105000, alcoholysis degree 99%.
Polyvinyl alcohol B, western Gansu Province chemical industry, trade mark PVA1788, weight average molecular weight 74800, alcoholysis degree 88%.
Sodium sulphate, Sinopharm Chemical Reagent Co., Ltd. analyze pure.
Calcium chloride, lark prestige, purity 98%.
Lithium chloride, lark prestige, purity 99%.
Lithium bromide, lark prestige, purity 99%.
Aluminium oxide, lark prestige, purity 90%.
Glycerol, lark prestige, purity 98%.
Hydroxypropyl cellulose, Sigma-Aldrich, ﹥ 95%.
Carboxyethyl cellulose, Sigma-Aldrich, ﹥ 95%.
Nano zine oxide, lark prestige, 99.5%, partial size 10-30nm.
Nano silver, lark prestige, 99.5%, partial size 10-30nm.
Potassium sorbate, Yi Nuokai, 99%.
Formaldehyde, lark prestige, 50% aqueous solution.
Glutaraldehyde, lark prestige, 50% aqueous solution.
Glyoxal, lark prestige, 50% aqueous solution.
Sulfuric acid, Sinopharm Chemical Reagent Co., Ltd. analyze pure.
Film one-way stretcher, Guangzhou is general same, MESI-LL.
Embodiment 1
By biaxially stretched polylactic acid film on film one-way stretcher, polylactic acid porous film is drawn at 60 DEG C.
7g polyvinyl alcohol A is added in 100mL distilled water, sufficiently dissolves, adds 2.1g sodium sulphate, 0.2g is nano oxidized
Zinc, 0.35g glutaraldehyde and 0.1g sulfuric acid, are stirred well to uniformly mixed, obtain coating liquid.This coating liquid is equably brushed
Polylactic acid porous film one side, then places it in baking oven, dries 10min at 70 DEG C, obtains intelligence and controls wet film A1,
Groundwork thickness is 80 microns, and aperture is 0.075 micron, and porosity 48%, aperture is in the positive and negative an order of magnitude model of average pore size
Hole in enclosing accounts for 80% of all well or more；Additional layer thickness is 10 microns.
Comparative example 1
Film is prepared according to method same as Example 1, unlike, sodium sulphate is not contained in coating liquid, is obtained thin
Film D1.
Comparative example 2
Film is prepared according to method same as Example 1, unlike, porous polylactic acid film is not used, and make
With fine and close polylactic acid film, film D2 is obtained.
Embodiment 2
By biaxially stretched polylactic acid film on film one-way stretcher, polylactic acid porous film is drawn at 60 DEG C.
7g polyvinyl alcohol A is added in 100mL distilled water, is sufficiently dissolved.0.7g hydroxypropyl cellulose is added, 0.2g receives
Rice zinc oxide, 0.35g formaldehyde and 0.1g sulfuric acid are stirred well to uniformly mixed, obtain coating liquid.By the uniform scrubbing brush of this coating liquid
It is coated in polylactic acid porous film one side, then places it in baking oven, dries 12min at 60 DEG C, intelligence is obtained and controls wet film
A2, groundwork thickness are 60 microns, and aperture is 0.032 micron, and porosity 30%, aperture is in the positive negative one number amount of average pore size
Hole in grade range accounts for 70% of all well or more；Additional layer thickness is 12 microns.
Embodiment 3
By biaxial tension poly terephthalic acid -co- tetramethylene adipate film on film one-way stretcher, in 60 DEG C
Under be drawn into poly terephthalic acid -co- tetramethylene adipate porous membrane.
7g polyvinyl alcohol A is added in 100mL distilled water, is sufficiently dissolved.Add 1.2g calcium chloride, 0.8g nano silver,
It is stirred well to uniformly mixed, obtains coating liquid.This coating liquid is equably brushed in poly terephthalic acid -co- adipic acid fourth
Diol ester porous membrane two sides, then places it in baking oven, dries 8min at 80 DEG C, and the film after being dried will contain
The 10mL aqueous solution of 0.25g formaldehyde and 0.08g sulfuric acid uniformly brushes film two sides after the drying, then dries at 80 DEG C
8min obtains intelligence and controls wet film A3, and groundwork thickness is 55 microns, and aperture is 0.062 micron, porosity 40%, aperture
Hole within the scope of the positive and negative an order of magnitude of average pore size accounts for 60% or more of all well；Additional layer thickness is 10 microns.
Embodiment 4
Film is prepared according to method same as Example 1, unlike, glutaraldehyde and sulfuric acid are not contained in coating liquid,
It obtains intelligence and controls wet film A4.
Embodiment 5
By biaxially stretched polylactic acid film on film one-way stretcher, polylactic acid porous film is drawn at 60 DEG C.
7.2g polyvinyl alcohol B is added in 100mL distilled water, sufficiently dissolves, adds 1.8g sodium sulphate, 0.18g nanometers
Zinc oxide, 0.36g glutaraldehyde and 0.1g sulfuric acid, are stirred well to uniformly mixed, obtain coating liquid.By the uniform scrubbing brush of this coating liquid
It is coated in polylactic acid porous film one side, then places it in baking oven, dries 10min at 70 DEG C, intelligence is obtained and controls wet film
A5, groundwork thickness are 75 microns, and aperture is 0.039 micron, and porosity 36%, aperture is in the positive negative one number amount of average pore size
Hole in grade range accounts for 75% of all well or more；Additional layer thickness is 11 microns.
Embodiment 6
By biaxially stretched polylactic acid film on film one-way stretcher, polylactic acid porous film is drawn at 60 DEG C.
4g polyvinyl alcohol A is added in 100mL distilled water, is sufficiently dissolved.1g lithium chloride is added, 0.15g is nano oxidized
Zinc, 0.2g formaldehyde and 0.06g sulfuric acid, are stirred well to uniformly mixed, obtain coating liquid.This coating liquid is equably brushed poly-
Lactic acid porous membrane one side, then places it in baking oven, dries 12min at 60 DEG C, obtains intelligence and controls wet film A6, base
Layer is with a thickness of 81 microns, and aperture is 0.042 micron, and porosity 40%, aperture is in the positive and negative an order of magnitude range of average pore size
Interior hole accounts for 80% of all well or more；Additional layer thickness is 8 microns.
Embodiment 7
Prepare film according to method same as Example 6, unlike, with etc. the lithium bromides of weight replace lithium chloride,
It obtains intelligence and controls wet film A7.
Embodiment 8
Prepare film according to method same as Example 2, unlike, with etc. the aluminium oxide of weight replace poly- hydroxypropyl
Cellulose obtains intelligence and controls wet film A8.
Embodiment 9
Prepare film according to method same as Example 2, unlike, with etc. the glycerol of weight replace poly- hydroxypropyl fibre
Dimension element obtains intelligence and controls wet film A9.
Embodiment 10
Prepare film according to method same as Example 2, unlike, with etc. the potassium sorbates of weight replace nano oxygen
Change zinc, obtains intelligence and control wet film A10.
Embodiment 11
Prepare film according to method same as Example 2, unlike, with etc. the glyoxals of weight replace formaldehyde, obtain
Wet film A11 is controlled to intelligence.
Embodiment 12
Prepare film according to method same as Example 2, unlike, with etc. the carboxyethyl celluloses of weight replace hydroxyl
Propyl cellulose obtains intelligence and controls wet film A12.
Test case
Moisture-vapor transmission test is carried out to above-mentioned film according to GB/T 1037-1988, is 25 DEG C in test temperature, thoroughly
It crosses under the test condition that surface humidity is respectively 50% and 90%, obtains the steam penetrating capacity (g/ of daily every square metre of film
m2/ day), data result is shown in Table 1.
Oxygen barrier property detection is carried out to above-mentioned film according to GB/T 19789-2005, obtains OTR oxygen transmission rate
[cm3·cm/(cm2SPa)], data result is shown in Table 1.
Table 1: the penetrability and gas barrier property test result of film
| Serial number | Moisture permeability (50%RH) | Moisture permeability (90%RH) | Gas barrier property (O2) |
| A1 | 142 | 1660 | 5.5×10-5 |
| D1 | 30 | 351 | 1.8×10-5 |
| D2 | 11 | 19 | 3.1×10-6 |
| A2 | 114 | 1372 | 7.4×10-5 |
| A3 | 128 | 1475 | 3.5×10-5 |
| A4 | 158 | 1731 | 1.9×10-4 |
| A5 | 122 | 1338 | 6.9×10-5 |
| A6 | 281 | 1307 | 7.3×10-5 |
| A7 | 242 | 1240 | 7.0×10-5 |
| A8 | 96 | 1304 | 6.1×10-5 |
| A9 | 117 | 1288 | 6.8×10-5 |
| A10 | 126 | 1200 | 5.8×10-5 |
| A11 | 104 | 1038 | 7.9×10-5 |
| A12 | 133 | 1245 | 7.0×10-5 |
Seen from table 1, the wet film of intelligence control of the invention has good oxygen-barrier property, and there is intelligence to control wet energy
Power, i.e., when humidity is lower, which is reduced, and the ability with moisturizing can keep fruits and vegetables humidity；Instead
It, at high humidity, which improves, and has strong ventilating capability, thus prevents fruit and vegetable
Moisture condensation is festered.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (15)
1. a kind of wet film of intelligence control of biodegradable, including base and extra play, the extra play are located at base side
Or two sides；Wherein,
The base is porous membrane, and material is synthesis biodegradable macromolecule, preferably polylactic acid, poly- to succinic acid
In butanediol ester, poly terephthalic acid -co- succinic acid-butanediol ester and poly terephthalic acid -co- tetramethylene adipate extremely
Few one kind, further preferably polylactic acid and/or poly terephthalic acid -co- succinic acid-butanediol ester；
The extra play is dense film, and material contains polyvinyl alcohol and helper component and optional crosslinking agent and/or resists
Microbial inoculum；The helper component is water-soluble metal salt, acid soluble metal oxide, cellulose and cellulose derivative and polyalcohol
At least one of.
2. intelligence according to claim 1 controls wet film, wherein the aperture of the porous membrane is 0.02-50 microns, excellent
It is selected as 0.05-10 microns；Porosity is 30%-80%, preferably 40%-70%；Aperture is in the positive negative one number amount of average pore size
Hole in grade range accounts for 50% of all well or more, preferably accounts for 80% or more of all well.
3. intelligence according to claim 1 controls wet film, wherein on the basis of extra play total weight, the polyvinyl alcohol
Content be 50-99wt%, preferably 66-98wt%；The content of the helper component is 1-50wt%, preferably 2-
34wt%.
4. intelligence according to claim 1 controls wet film, wherein the weight average molecular weight of the polyvinyl alcohol is 10000-
500000, preferably 20000-200000；Alcoholysis degree is 70%-100%, preferably 88%-99%.
5. intelligence according to claim 1 controls wet film, wherein
The water-soluble metal salt is at least one of sulfate, halide salt and metal hydroxides, preferably sodium sulphate, sulphur
At least one of sour calcium pyroborate, sodium hydroxide, calcium chloride, sodium chloride, lithium chloride, lithium bromide, cesium fluoride and lithium fluoride, into one
Step is preferably at least one of sodium sulphate, calcium chloride and lithium chloride；
The acid soluble metal oxide is at least one of aluminium oxide, calcium oxide and magnesia；
The cellulose and cellulose derivative be in nano-cellulose, cellulose ether, cellulose esters and cellulose ether-esters extremely
Few one kind；Preferably hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and hydroxypropyl methyl
At least one of cellulose；Further preferably in hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose extremely
Few one kind；
The polyalcohol is at least one of propylene glycol, glycerol, sorbierite and sucrose.
6. the wet film of intelligence control described at least one of -5 according to claim 1, wherein the total weight with the extra play is
Benchmark, the content of the crosslinking agent are 0-10wt%, preferably 0.1-7wt%.
7. the wet film of intelligence control described at least one of -5 according to claim 1, wherein the crosslinking agent is formaldehyde, second two
At least one of aldehyde, malonaldehyde, butanedial, glutaraldehyde, maleic acid, maleic anhydride and sulfuric acid；Preferably formaldehyde, glutaraldehyde and
At least one of sulfuric acid.
8. the wet film of intelligence control described at least one of -5 according to claim 1, wherein the total weight with the extra play is
Benchmark, the content of the antibacterial agent are 0-20wt%, preferably 0.1-10wt%.
9. the wet film of intelligence control described at least one of -5 according to claim 1, wherein the antibacterial agent is nano oxidized
At least one of zinc, titanium oxide, nano silver, Nanometer Copper, silk gum, quaternary ammonium salt, methyl hydroxybenzoate, potassium sorbate and chitosan；It is excellent
It is selected as at least one of nano zine oxide, nano silver and quaternary ammonium salt.
10. the wet film of intelligence control described at least one of -5 according to claim 1, wherein the base with a thickness of 5-
1000 microns, preferably 10-100 microns；The extra play with a thickness of 0.5-100 microns, preferably 2-20 microns.
11. the preparation method that a kind of intelligence of biodegradable controls wet film, comprising the following steps:
(1) each component that the intelligence as described in any one of claim 1-10 is controlled to the extra play of wet film sufficiently dissolve or
Person is dispersed in water, and is configured to solution or dispersion liquid；
(2) solution obtained in step (1) or dispersion liquid are coated on to the intelligence as described in any one of claim 1-10
The one or both sides of the base of wet film can be controlled；The intelligence is obtained after drying controls wet film.
12. preparation method according to claim 11, wherein the mass concentration of solution or dispersion liquid in step (1)
For 0.5%-30%, preferably 1%-10%.
13. preparation method according to claim 11, wherein the temperature dried in step (2) is 50 DEG C -100 DEG C, preferably
It is 60 DEG C -90 DEG C.
14. preparation method described in any one of 1-13 according to claim 1, wherein crosslinking agent is individually configured to solution
Or dispersion liquid, the one or both sides of the film after the solution containing crosslinking agent or dispersion liquid to be coated on to the drying of step (2), then
The intelligence is obtained after secondary drying controls wet film；The mass concentration of the solution containing crosslinking agent or dispersion liquid is preferably
0.5%-10%, further preferably 1%-5%.
15. the wet film of intelligence control described in any one of claim 1-10 and/or by any one of claim 11-14
Application of the wet film in vegetable and fruit fresh-keeping packaging is intelligently controlled made from the preparation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810231480.0A CN110305351A (en) | 2018-03-20 | 2018-03-20 | A kind of wet film of intelligence control of biodegradable and its preparation method and application |
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| CN114479147A (en) * | 2021-02-24 | 2022-05-13 | 陈雅婷 | Degradable plastic composite film |
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