CN107814967A - Anti-mildew fresh-keeping film and preparation method thereof - Google Patents
Anti-mildew fresh-keeping film and preparation method thereof Download PDFInfo
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- CN107814967A CN107814967A CN201711080784.3A CN201711080784A CN107814967A CN 107814967 A CN107814967 A CN 107814967A CN 201711080784 A CN201711080784 A CN 201711080784A CN 107814967 A CN107814967 A CN 107814967A
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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
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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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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
- 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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- 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
- 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
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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Abstract
The present invention relates to a kind of anti-mildew fresh-keeping film and preparation method thereof, the anti-mildew fresh-keeping film includes basement membrane, silicone rubber coating and anti-mildew fresh-keeping coating；The basement membrane is provided with air-vent, and the silicone rubber coating is respectively formed in the both side surface of the basement membrane with the anti-mildew fresh-keeping coating, and the raw material percentage composition by weight of the silicone rubber coating includes following component：Silicon rubber 52%~63%, polyurethane 20%~25%, polyacrylic acid γ methacryloxypropyl trimethoxy silanes 12%~18%, carborundum 5%~10%, titanium dioxide 3%~8% and monovalence silver source 1%~3%.When the anti-mildew fresh-keeping film is used for packaging material, when packing the products such as fruits and vegetables, fruits and vegetables need not carry out any anticorrosive mildewproof sterilization fresh-keeping processing in itself, clean fruits and vegetables need to be only placed in the packaging product such as anti-mildew fresh-keeping film, by packing product antimycotic antiseptic function in itself and ethene airing function, have the function that, to placing thing anti-mildew fresh-keeping in packaging product, effectively to extend freshness of the fruits and vegetables in storage is transported, market application foreground is wide.
Description
Technical field
The present invention relates to technical field of preservation of fresh, more particularly to a kind of anti-mildew fresh-keeping film and preparation method thereof.
Background technology
The condition of the shorter article storage of the Storage periods such as fruits and vegetables is harsher, otherwise will be sent out because of microorganism amount reproduction
Change of mildewing makes it no longer fresh, loses original value.The fresh-keeping mode in industry is simply wrapped generally by preservative film at present
Wrap up in the purpose for completely cut off external oxygen and moisture, reaching fresh-keeping.But the fresh-keeping effect of this fresh-keeping mode is bad, especially uses
When preserving fruit and vegetable utilizing, the respiration of fruits and vegetables itself, which produces, easily to be caused bacteria breed in preservative film inwall condensation and goes mouldy, together
When accelerate fruits and vegetables maturation rot.
The content of the invention
Based on this, it is necessary to provide preferable anti-mildew fresh-keeping film of a kind of fresh-keeping effect and preparation method thereof.
A kind of anti-mildew fresh-keeping film, including basement membrane, silicone rubber coating and anti-mildew fresh-keeping coating；The basement membrane is provided with air-vent,
The silicone rubber coating is respectively formed in the both side surface of the basement membrane with the anti-mildew fresh-keeping coating, the silicone rubber coating
Raw material percentage composition by weight includes following component：Silicon rubber 52%~63%, polyurethane 20%~25%, polyacrylic acid γ-
Methacryloxypropyl trimethoxy silane 12%~18%, carborundum 5%~10%, titanium dioxide 3%~8% and one
Valency silver source 1%~3%.
In one of the embodiments, the silicon rubber is selected from methyl silicone rubber, methyl vinyl silicone rubber, aminomethyl phenyl
One or more in vinylsiloxane rubber and fluorosioloxane rubber.
In one of the embodiments, the silicon rubber consists of the following components in percentage by weight：70%~80% first
Base vinylsiloxane rubber and 20%~30% fluorosioloxane rubber.
In one of the embodiments, the monovalence silver source is silver nitrate.
In one of the embodiments, the aperture of the air-vent is 0.5~0.7nm.
In one of the embodiments, the distribution density of the air-vent is 20~40/cm2。
In one of the embodiments, the raw material percentage composition by weight of the anti-mildew fresh-keeping coating includes following component：
Matrix resin 20%~50%, solvent 20%~70%, mould inhibitor 0.65%~25.5%, water-keeping material 0.3%~4% and help
Agent 0.2%~2%.
In one of the embodiments, the matrix resin is selected from polyurethane, acrylic acid esters co-polymer, ethyl vinyl acetate
At least one of the polyvinyl alcohol of vinyl esters copolymer, polyvinyl acetate copolymer and degree of hydrolysis more than 85%；It is described
Water-keeping material is selected from least one of hydroxy acrylate, glycerine, porous inorganic material and high hydroscopic resin
In one of the embodiments, the mass ratio of the mould inhibitor and the water-keeping material is 4~6:1.
The preparation method of above-mentioned anti-mildew fresh-keeping film, comprises the following steps：
The raw material of the silicone rubber coating and n-hexane blending slurrying are obtained into Silicone Rubber Based Coatings；
The matrix resin and the solvent are well mixed, obtain mixed liquor；Institute is sequentially added in the mixed liquor
State water-keeping material, the auxiliary agent and the mould inhibitor and be well mixed, obtain anti-mildew fresh-keeping coating；
The basement membrane a surface coated silastic coating and carry out heat treatment and form silicone rubber coating, will be described mould proof
Antistaling coating is coated on the surface away from the silicone rubber coating on the basement membrane and carries out heat treatment and makes the anti-mildew fresh-keeping
Coating forms the anti-mildew fresh-keeping coating, obtains the anti-mildew fresh-keeping film.
Ethene is a Plant Hormone, and can accumulate gradually release in the development of the gardening plants such as fruit vegetable, when release
When ethene reaches a certain amount of around fruits and vegetables, will accelerate fruit and vegetable from it is ripe with it is rotten, reduce the commodity value of fruits and vegetables.
In fruit vegetables storing environment, ethene can also change carbon dioxide and cause fruits and vegetables metabolic disorder to the effect of fruits and vegetables.Therefore tradition
Preservative film can not be effectively reduced ethylene concentration around fruits and vegetables, and in order to ensure often saturating with being effectively isolated for external environment
Gas is very low, causes ethylene concentration to gradually step up, and accelerates the rotten speed of fruits and vegetables, have impact on fresh-keeping effect, shortens fresh-keeping
Duration.The anti-mildew fresh-keeping film of the present invention close to fruits and vegetables, can suppress in packaging in face where anti-mildew fresh-keeping coating when packing fruits and vegetables
The growth of mould, in the case where fruits and vegetables are without preceding processing, it are not easy to generation and go mouldy.Fruits and vegetables itself discharge in anti-mildew fresh-keeping film
Ethene can be discharged from the air-vent of basement membrane, and basement membrane is provided with the gas permeability of anti-mildew fresh-keeping coating side and is provided with silicon rubber more than basement membrane
The gas permeability of gel coating side, even if obtained anti-mildew fresh-keeping film has good one-way ventilating performance.Silicon rubber is a kind of comprehensive
The macromolecular material of excellent performance is closed, strand is given by silicon original and alternately formed with oxygen atom, has good gas permeability, will
Itself and polyurethane, polyacrylic acid γ-methacryloxypropyl trimethoxy silane blending and modifying, and it is inorganic to add carborundum
Powder forms organic-inorganic hybrid films and further improves gas separating property.Titanium dioxide can degrade second under photocatalysis simultaneously
Alkene, make basement membrane both sides generation ethylene concentration poor, so as to provide the power that ethene spreads to silicone rubber coating, promote on the inside of basement membrane
Ethene constantly to external diffusion, significantly improve the percent of pass of ethene, reduce the percent of pass of other gases.Monovalence silver ion
On the one hand π-complex compound assist absorption ethene can be formed with ethene, promotes the ethene on the inside of basement membrane to external diffusion, on the other hand two
Titanium oxide can reduce the compound of electron-hole pair after Ag is doped with, and improve photocatalysis efficiency, can more efficiently remove fruit
Ethene around vegetable, ethylene concentration is maintained very low level, nor affect on the respiration of fruits and vegetables, therefore improve fresh-keeping
Effect, extend fresh-keeping duration.
Further, the water-keeping material in anti-mildew fresh-keeping film has very strong water imbibition, and the saturating of basement membrane is reached in vapor
By water vapor adsorption before stomata, and after finite concentration is reached, the slowly release vapor, and then effectively into anti-mildew fresh-keeping film
Suppress the moisture loss of fruits and vegetables, the presence of mould inhibitor can prevent fruits and vegetables etc. from going mouldy.So that locate in anti-mildew fresh-keeping film
In the state that low ethylene concentration and vapor balance, effectively further avoiding anti-mildew fresh-keeping film inwall condensation makes anti-mildew fresh-keeping
The bacterial multiplication of film is accelerated and ethene is accumulated in inside anti-mildew fresh-keeping film the problem of causing fruits and vegetables accelerated ageing, more preferable so as to realize
Fresh-keeping effect.
Embodiment
To enable objects, features and advantages of the present invention more obvious understandable, below to the specific embodiment party of the present invention
Formula is described in detail.Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still this hair
Bright to be implemented with being much different from other modes described here, those skilled in the art can be without prejudice in the present invention
Similar improvement is done in the case of culvert, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
The arbitrary and all combination of the Listed Items of pass.
The anti-mildew fresh-keeping film of an embodiment of the present invention, including basement membrane, silicone rubber coating and anti-mildew fresh-keeping coating；Basement membrane is set
There is air-vent, silicone rubber coating is respectively formed in the both side surface of basement membrane with anti-mildew fresh-keeping coating, and the raw material of silicone rubber coating is pressed
Weight percentage includes following component：Silicon rubber 52%~63%, polyurethane 20%~25%, polyacrylic acid γ-methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane 12%~18%, carborundum 5%~10%, titanium dioxide 3%~8% and monovalence silver source
1%~3%.
Specifically, silicon rubber is selected from methyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber and fluorine
One or more in silicon rubber.
Preferably, silicon rubber consists of the following components in percentage by weight：70%~80% methyl vinyl silicone rubber and
20%~30% fluorosioloxane rubber, ethene removal effect is more preferable when coordinating with other components.
Preferably, monovalence silver source is silver nitrate, more effectively ethylene adsorption and can promote titanium dioxide in silicone rubber coating
Titanium is degraded, and improves the keeping property of anti-mildew fresh-keeping film.
Preferably, the aperture of air-vent is 0.5~0.7nm.Preferably, the distribution density of air-vent be 20~40/
cm2.When the aperture of air-vent and density within the above range, the gas separating property of basement membrane can be effectively improved so that
The transmitance of ethene is more than the transmitance of hydrone, so further better ensures that in anti-mildew fresh-keeping film and is in low ethylene concentration
And the state of vapor balance.
In one embodiment, the raw material of anti-mildew fresh-keeping coating percentage composition by weight includes following component：Matrix resin
20%~50%, solvent 20%~70%, mould inhibitor 0.65%~25.5%, water-keeping material 0.3%~4% and auxiliary agent 0.2%
~2%.Found by studying, the water-keeping material of the anti-mildew fresh-keeping film slowly can discharge vapor into anti-mildew fresh-keeping film, enter
And ensure the humidity in anti-mildew fresh-keeping film, therefore after water-keeping material is added, it is necessary to suitably improve mould inhibitor content, prevent
Fungus growth.So select said ratio.Preferably, the mass ratio of mould inhibitor and water-keeping material is 4~6:1.
Preferably, basement membrane is PET film (pet film), PP films (polypropylene film), PA6
Film (polyamide 6 film), eva film (ethene-polyvinyl acetate copolymer film), (ethylene-vinyl alcohol is common for EVOH films
Homopolymer film), PVA film (polyvinyl alcohol film) or PLA films (linear aliphatic polyesters-polylactic acid film).
It is furthermore preferred that basement membrane is PET film and PP films.PET and PP remains to keep under conditions of temperature is up to 120 DEG C
Excellent performance, and then antistaling coating can be avoided to carry out heat treatment and form the problem of anti-mildew fresh-keeping coating causes basement membrane to destroy.More
Preferably, the thickness of basement membrane is 12~22 μm.
In one of the embodiments, matrix resin is selected from polyurethane, acrylic acid esters co-polymer, ethene-vinyl acetate
Polyvinyl alcohol (the letter of lipin polymer (abbreviation EVA), polyvinyl acetate copolymer (abbreviation PVAC) and degree of hydrolysis more than 85%
At least one of claim PVA).Wherein, degree of hydrolysis, also referred to as alcoholysis degree, and degree of hydrolysis is more than 85% polyvinyl alcohol, its is water-soluble
Property is fine.
Preferably, polyvinyl alcohol of the degree of hydrolysis in matrix resin more than 85% is selected from polyvinyl alcohol 1788, polyvinyl alcohol
At least one of 2088 and polyvinyl alcohol 2488.Polyvinyl alcohol 1788, polyvinyl alcohol 2088 and polyvinyl alcohol 2488 are water
The good polyvinyl alcohol of dissolubility.By taking polyvinyl alcohol 1788 as an example, it is that the degree of polymerization is 1700, and degree of hydrolysis is 88% polyethylene
Alcohol.
Further, water-keeping material is selected from hydroxy acrylate, glycerine, high hydroscopic resin, porous inorganic material and water
At least one of the polyvinyl alcohol of Xie Du less than 80%.
In one of the embodiments, high hydroscopic resin can be hydrolysis starch, graft acrylamide, high substituted degree crosslinking carboxylic
Methylcellulose, cross-linked carboxymethyl cellulose graft acrylamide, cross-linking type hydroxyethyl cellulose graft acrylamide polymer,
At least one of the polyvinyl alcohol of low-density cross-linked type polyethylene alcohol and degree of hydrolysis less than 80%.Further, porous, inorganic
Material can be porous silica, zeolite etc..
Further, matrix resin is the group of the polyvinyl alcohol of polyvinyl acetate copolymer and degree of hydrolysis more than 80%
Close, and water-keeping material is the combination of high hydroscopic resin and porous inorganic material；Wherein, high hydroscopic resin is that degree of hydrolysis is less than 80%
Polyvinyl alcohol.Contain polyvinyl alcohol in such matrix resin and in high hydroscopic resin, pass through polyvinyl alcohol when both act on
Intermolecular interaction, enable to high hydroscopic resin to be connected with matrix resin closer, avoiding the addition of high hydroscopic resin causes
The problem of hole increases between matrix resin.
Further, porous inorganic material is porous silica.And the quality of high hydroscopic resin and porous inorganic material
Than for 1:0.5~1.Further, polyvinyl acetate copolymer and degree of hydrolysis are more than 80% polyethylene in matrix resin
The mass ratio of alcohol is 1:0.5~1.
Preferably, the thickness of anti-mildew fresh-keeping coating is 0.5~10 μm, and the thickness of silicone rubber coating is 3~8 μm.
Preferably, this patent has been obtained scattered more uniform in aforementioned body resin by research in substantial amounts of mould inhibitor
And the mould inhibitor that performance is more stable, mould inhibitor is in sorbate, citrate, dehydroacetic acid salt, xanthoxlin and catechin
At least one.Alternatively, sorbate, citrate, dehydroacetic acid salt are its sodium salt or sylvite.
Further, the weight percentage in anti-mildew fresh-keeping coating, sorbate are 0.2%~4%, citric acid
Salt is 0.2%~6%, and dehydroacetic acid salt is 0%~2%, and xanthoxlin is 0~6%, and catechin is 0.25%~7.5%.Research
It was found that adding catechin in sorbate and citrate, anti-mold effect can be effectively improved, main cause is that catechin is water-soluble
Easily polymerization forms unformed tannin to liquid, and tannin is easily oxidized, and especially hydrolyzes weak base in sorbate and citrate etc.
Property under the conditions of aoxidize faster, therefore can be combined with protein play kill mould effect.Within the range, the group of each mould inhibitor
It is preferable to close anti-mold effect.
Further, the weight percentage in anti-mildew fresh-keeping coating, sorbate are 2%~4%, citric acid
Salt is 2%~6%, and dehydroacetic acid salt is 1%~2%, and xanthoxlin is 3~4%, and catechin is 4%~7.5%.Add simultaneously
Xanthoxlin and dehydroacetic acid salt act synergistically as mould inhibitor, reach preferable anti-mold effect.
Further, mould inhibitor is the combination of sorbate, citrate, dehydroacetic acid salt, xanthoxlin and catechin,
And sorbate, citrate, dehydroacetic acid salt, the mass ratio of xanthoxlin and catechin are 1:1~2:0.5~0.8:1~2:1
~2.
In one of the embodiments, solvent is selected from least one of water and ethanol.Using polyurethane, polyvinyl alcohol,
The water-soluble preferable resin such as ethylene-vinyl acetate analog copolymer, polyvinyl acetate copolymer, solvent can be water, with up to
To environmental protection and reduce the effect of cost.Preferably, solvent is that volume ratio is 1:The combination of 1 second alcohol and water.
In one of the embodiments, auxiliary agent is in surfactant, emulsifying agent, wetting agent, defoamer and sagging inhibitor
At least one.Wherein, surfactant is Tween 80 and sapn etc., and surfactant can be such that mould inhibitor divides in matrix resin
Dissipate more uniform.Emulsifying agent may advantageously facilitate water-soluble poor resin and form stable aqueous emulsion.
The anti-mildew fresh-keeping film of present embodiment face where anti-mildew fresh-keeping coating when packing fruits and vegetables close to fruits and vegetables, can suppress
The growth of mould in packaging, in the case where fruits and vegetables are without preceding processing, it are not easy to generation and go mouldy.In anti-mildew fresh-keeping film fruits and vegetables from
The ethene of body release can be discharged from the air-vent of basement membrane, and gas permeability of the basement membrane provided with anti-mildew fresh-keeping coating side is set more than basement membrane
There is the gas permeability of silicone rubber coating side, even if obtained anti-mildew fresh-keeping film has good one-way ventilating performance.Silicon rubber is
A kind of macromolecular material of excellent combination property, strand are given by silicon original and alternately formed with oxygen atom, have well saturating
Gas, by itself and polyurethane, polyacrylic acid γ-methacryloxypropyl trimethoxy silane blending and modifying, and add carbon
SiClx inorganic powder forms organic-inorganic hybrid films and further improves gas separating property.Titanium dioxide energy under photocatalysis simultaneously
Enough degrading ethylenes, make basement membrane both sides generation ethylene concentration poor, so as to provide the power that ethene spreads to silicone rubber coating, promote
Ethene on the inside of basement membrane significantly improves the percent of pass of ethene constantly to external diffusion, reduces the percent of pass of other gases.One
On the one hand valency silver ion can form π-complex compound assist absorption ethene with ethene, promote the ethene on the inside of basement membrane to external diffusion, separately
One side titanium dioxide can reduce the compound of electron-hole pair after Ag is doped with, and improve photocatalysis efficiency, can be more efficient
Ground removes the ethene around fruits and vegetables, ethylene concentration is maintained very low level, nor affects on the respiration of fruits and vegetables, therefore carries
High fresh-keeping effect, extends fresh-keeping duration.
Further, the water-keeping material in anti-mildew fresh-keeping film has very strong water imbibition, and the saturating of basement membrane is reached in vapor
By water vapor adsorption before stomata, and after finite concentration is reached, the slowly release vapor, and then effectively into anti-mildew fresh-keeping film
Suppress the moisture loss of fruits and vegetables, the presence of mould inhibitor can prevent fruits and vegetables etc. from going mouldy.So that locate in anti-mildew fresh-keeping film
In the state that low ethylene concentration and vapor balance, effectively further avoiding anti-mildew fresh-keeping film inwall condensation makes anti-mildew fresh-keeping
The bacterial multiplication of film is accelerated and ethene is accumulated in inside anti-mildew fresh-keeping film the problem of causing fruits and vegetables accelerated ageing, more preferable so as to realize
Fresh-keeping effect.
Present invention also offers the preparation method of the above-mentioned anti-mildew fresh-keeping film of an embodiment, comprise the following steps S1~
S4。
Step S1：Basement membrane provided with air-vent is provided.
Specifically, punched by laser drilling on basement membrane and form air-vent.Alternatively, the aperture of air-vent is
0.5~0.7nm, the distribution density of air-vent is 20~40/cm2。
Step S2：The raw material of silicone rubber coating and n-hexane blending slurrying are obtained into Silicone Rubber Based Coatings.
Specifically, the mass percent concentration of n-hexane is 99.2%~99.5% in Silicone Rubber Based Coatings.
Step S3：Matrix resin and solvent are well mixed, obtain mixed liquor, water conservation material is sequentially added in mixed liquor
Material, auxiliary agent and mould inhibitor are simultaneously well mixed, and obtain anti-mildew fresh-keeping coating.
Specifically, step S3 specifically includes following steps：In rotating speed it is 100~300 revs/min by matrix resin and solvent
Under be stirred and heated to 30~65 DEG C mixing 5~15min, in mixed liquor in rotating speed be 200~400 revs/min under successively plus
Enter water-keeping material and auxiliary agent stirs 30~60min, mould inhibitor is added dropwise under being then 500~800 revs/min in rotating speed, is added dropwise anti-
Mould dose of time control is in 1~2h, so that mould inhibitor is fully dispersed.
Step S4：Basement membrane a surface coated silastic coating and carry out heat treatment and form silicone rubber coating, will be mould proof
Antistaling coating is coated on the surface away from silicone rubber coating on basement membrane and carries out heat treatment to form anti-mildew fresh-keeping coating mould proof
Fresh-keeping coating, obtain anti-mildew fresh-keeping film.
Further, the condition of heat treatment is to handle 5~10s in 80~120 DEG C.
The preparation method of present embodiment is environment friendly and pollution-free, and the anti-mildew fresh-keeping film being prepared is used for packaging material packaging fruit
During the products such as vegetable, fruits and vegetables need not carry out any anticorrosive mildewproof sterilization fresh-keeping processing in itself, need to only be placed on clean fruits and vegetables mould proof
In the packaging product such as preservative film, by packing product antimycotic antiseptic function in itself and ethene airing function, reach and packaging is produced
The effect of placement thing anti-mildew fresh-keeping in product, effectively extends freshness of the fruits and vegetables in storage is transported, and is advantageous to fruits and vegetables fortune
Defeated wrapping enterprise widelys popularize, and market application foreground is wide.
It is specific embodiment below.
Embodiment 1
PP films are provided.It is 0.6nm air-vents that the PP films, which cross laser drilling and punch to obtain aperture,.Point of air-vent
Cloth density is 25/cm2。
The raw material of silicone rubber coating and n-hexane blending slurrying are obtained into Silicone Rubber Based Coatings, the raw material of silicone rubber coating is by weight
Amount percentage includes：Silicon rubber 52%, polyurethane 21%, polyacrylic acid γ-methacryloxypropyl trimethoxy silane
13%th, carborundum 6%, titanium dioxide 6% and monovalence silver source 2%, wherein silicon rubber is made up of methyl silicone rubber, and monovalence silver source is
Silver chlorate.
The raw material of anti-mildew fresh-keeping coating is provided, percentage composition by weight includes：Polyvinyl acetate copolymer 25%, hydrolysis
Spend the polyvinyl alcohol 25% for 88%, volume ratio 1:1 ethanol water mixed solvent 20%, potassium sorbate 4%, sodium citrate
The polyvinyl alcohol 4% for being 78% for 6%, sodium dehydroacetate 2%, xanthoxlin 6%, catechin 7.5%, degree of hydrolysis and tell
Temperature 80 is 0.5%.By polyvinyl alcohol that polyvinyl acetate copolymer and degree of hydrolysis are 88% ethanol water in the mixed solvent in
Rotating speed is to be stirred and heated to 50 DEG C under 300 revs/min to be well mixed, and obtains mixed liquor.In mixed liquor in rotating speed be 300
Hydroxy acrylate and Tween 80 stirring 60min are sequentially added under rev/min, is added dropwise under being then 800 revs/min in rotating speed anti-
Mould dose of potassium sorbate, sodium citrate, sodium dehydroacetate, xanthoxlin and catechin, the time control that mould inhibitor is added dropwise are 1~2h
It is interior, it is well mixed, cooling obtains anti-mildew fresh-keeping coating.
Silicone Rubber Based Coatings are coated in a surface of basement membrane, silicone rubber coating is formed then at 120 DEG C of processing 1.2s, will be mould proof
Antistaling coating, then at 120 DEG C of processing 1.2s, is obtained containing anti-mildew fresh-keeping coated in the surface away from silicone rubber coating on basement membrane
The PE preservative films of coating.
Embodiment 2
The experimental procedure of embodiment 2 is substantially the same manner as Example 1, and difference is in the raw material in silicone rubber coating, silicon
Rubber is made up of methyl phenyl vinyl silicone rubber.
Embodiment 3
The experimental procedure of embodiment 3 is substantially the same manner as Example 1, and difference is in the raw material in silicone rubber coating, and one
Valency silver source is silver nitrate.
Embodiment 4
The experimental procedure of embodiment 4 is substantially the same manner as Example 3, and difference is in the raw material in silicone rubber coating, silicon
Rubber is made up of 76% methyl vinyl silicone rubber and 24% fluorosioloxane rubber.
Embodiment 5
The experimental procedure of embodiment 5 is substantially the same manner as Example 1, and difference is the group of the raw material of anti-mildew fresh-keeping coating
Into：Percentage composition includes by weight：Polyurethane 20%, volume ratio 1:1 ethanol water mixed solvent 70%, potassium sorbate are
0.2%th, sodium citrate 0.2%, catechin 0.25%, hydroxy acrylate 4% and Tween 80 are 0.5%.
Embodiment 6
The experimental procedure of embodiment 6 is substantially the same manner as Example 1, and difference is the group of the raw material of anti-mildew fresh-keeping coating
Into：Percentage composition includes by weight：Acrylic acid esters co-polymer 20%, ethylene-vinyl acetate analog copolymer 15%, volume ratio
For 1:1 ethanol water mixed solvent 40%, potassium sorbate 2%, sodium citrate 2%, sodium dehydroacetate 1.6%, Chinese prickly ash
Element is 2%, catechin 2%, glycerine 1.2% and Tween 80 are 0.2%.
Embodiment 7
The experimental procedure of embodiment 7 is substantially the same manner as Example 6, and difference is the portion of the raw material of anti-mildew fresh-keeping coating
It is grouped into：Potassium sorbate is 2%, sodium citrate 4%, sodium dehydroacetate 1%, xanthoxlin 4%, catechin 1%, third
Triol 2%.
Embodiment 8
The experimental procedure of embodiment 8 is substantially the same manner as Example 7, and difference is the portion of the raw material of anti-mildew fresh-keeping coating
It is grouped into：The polyvinyl alcohol that degree of hydrolysis is 78% 4% replaces with the polyvinyl alcohol 1% and porous silica that degree of hydrolysis is 78%
3% combination.
Embodiment 9
The experimental procedure of embodiment 9 is substantially the same manner as Example 7, and difference is the portion of the raw material of anti-mildew fresh-keeping coating
It is grouped into：The polyvinyl alcohol that degree of hydrolysis is 78% 4% replaces with the polyvinyl alcohol 2% and porous silica that degree of hydrolysis is 78%
2% combination.
Embodiment 10
The experimental procedure of embodiment 10 is substantially the same manner as Example 1, difference in embodiment 10 basement membrane it is ventilative
The aperture in hole is 10nm.
Embodiment 11
The experimental procedure of embodiment 11 is substantially the same manner as Example 9, and difference is in the raw material in silicone rubber coating, and one
Valency silver source is silver nitrate, and silicon rubber is made up of 76% methyl vinyl silicone rubber and 24% fluorosioloxane rubber
The experimental procedure of comparative example 1~3 is substantially the same manner as Example 1, and difference is, is not provided with the basement membrane of comparative example 1
Silicone rubber coating；Polyurethane and carborundum are not contained in the raw material of the silicone rubber coating of comparative example 2；The silicon rubber of comparative example 3 applies
Monovalence silver source is not contained in the raw material of layer；Titanium dioxide is not contained in the raw material of the silicone rubber coating of comparative example 4.
Fresh apple is wrapped up respectively using PE preservative films made from embodiment 1~11 and comparative example 1~4 to be tested, and
Observe apple cosmetic variation situation.The one side for having anti-mildew fresh-keeping coating during test directly contacts with apple.Test condition is：Environment
Temperature 45 C (in order to shorten test period, it is the temperature higher than normal temperature to set test temperature), humidity 65%, test object：Apple
Fruit, testing time：15 days, it the results are shown in Table 1.
Table 1
Anti-mildew fresh-keeping film made from embodiment 1 is existed using mould proof fresh-keeping layer as internal layer and by internal layer of silicone rubber coating respectively
Through performance test is carried out to ethylene gas when volatilization temperature is 100 DEG C, the volatilization time is 60 minutes, respectively obtains the saturating of ethene
It is 100cm to cross rate3/m2DPa and 30cm3/m2·d·Pa。
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of anti-mildew fresh-keeping film, it is characterised in that including basement membrane, silicone rubber coating and anti-mildew fresh-keeping coating；The basement membrane is set
There is air-vent, the silicone rubber coating is respectively formed in the both side surface of the basement membrane, the silicon with the anti-mildew fresh-keeping coating
The raw material of rubber coating percentage composition by weight includes following component：Silicon rubber 52%~63%, polyurethane 20%~25%, gather
Acrylic acid γ-methacryloxypropyl trimethoxy silane 12%~18%, carborundum 5%~10%, titanium dioxide 3%
~8% and monovalence silver source 1%~3%.
2. anti-mildew fresh-keeping film according to claim 1, it is characterised in that the silicon rubber is selected from methyl silicone rubber, methyl
One or more in vinylsiloxane rubber, methyl phenyl vinyl silicone rubber and fluorosioloxane rubber.
3. anti-mildew fresh-keeping film according to claim 2, it is characterised in that the silicon rubber by following percentage by weight group
It is grouped into：70%~80% methyl vinyl silicone rubber and 20%~30% fluorosioloxane rubber.
4. anti-mildew fresh-keeping film according to claim 1, it is characterised in that the monovalence silver source is silver nitrate.
5. anti-mildew fresh-keeping film according to claim 1, it is characterised in that the aperture of the air-vent is 0.5~0.7nm.
6. anti-mildew fresh-keeping film according to claim 5, it is characterised in that the distribution density of the air-vent is 20~40
Individual/cm2。
7. anti-mildew fresh-keeping film according to claim 1, it is characterised in that the raw material by weight hundred of the anti-mildew fresh-keeping coating
Content is divided to include following component：Matrix resin 20%~50%, solvent 20%~70%, mould inhibitor 0.65%~25.5%, guarantor
Water material 0.3%~4% and auxiliary agent 0.2%~2%.
8. anti-mildew fresh-keeping film according to claim 7, it is characterised in that the matrix resin is selected from polyurethane, acrylic acid
Lipin polymer, ethylene-vinyl acetate analog copolymer, polyvinyl acetate copolymer and degree of hydrolysis are more than 85% polyethylene
At least one of alcohol；The water-keeping material is in hydroxy acrylate, glycerine, porous inorganic material and high hydroscopic resin
At least one.
9. anti-mildew fresh-keeping film according to claim 7, it is characterised in that the quality of the mould inhibitor and the water-keeping material
Than for 4~6:1.
10. the preparation method of the anti-mildew fresh-keeping film described in a kind of any one of claim 1~9, it is characterised in that including following step
Suddenly：
The basement membrane provided with the air-vent is provided；
The raw material of the silicone rubber coating and n-hexane blending slurrying are obtained into Silicone Rubber Based Coatings；
The matrix resin and the solvent are well mixed, obtain mixed liquor；The guarantor is sequentially added in the mixed liquor
Water material, the auxiliary agent and the mould inhibitor are simultaneously well mixed, and obtain anti-mildew fresh-keeping coating；
The basement membrane a surface coated silastic coating and carry out heat treatment and form silicone rubber coating, by the anti-mildew fresh-keeping
Coating is coated on the surface away from the silicone rubber coating on the basement membrane and carries out heat treatment and makes the anti-mildew fresh-keeping coating
The anti-mildew fresh-keeping coating is formed, obtains the anti-mildew fresh-keeping film.
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| CN112500751A (en) * | 2020-10-29 | 2021-03-16 | 鲸果科技(杭州)有限公司 | Photocatalytic preservative coating and super-fresh paper coated with same |
| CN114103335A (en) * | 2020-08-28 | 2022-03-01 | 扬中市华龙橡塑电器有限公司 | Silicate insulation board of high-efficient use |
| CN114481634A (en) * | 2022-01-29 | 2022-05-13 | 贵州省材料产业技术研究院 | Degradable silicone rubber film and preparation method thereof |
| CN115467191A (en) * | 2022-09-21 | 2022-12-13 | 珠海正业包装有限公司 | Research and development of environment-friendly anti-mildew corrugated paper |
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| CN112500751A (en) * | 2020-10-29 | 2021-03-16 | 鲸果科技(杭州)有限公司 | Photocatalytic preservative coating and super-fresh paper coated with same |
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