CN107011531A - A kind of preparation method of anti-mildew fresh-keeping PVA coated films - Google Patents
A kind of preparation method of anti-mildew fresh-keeping PVA coated films Download PDFInfo
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- CN107011531A CN107011531A CN201710375076.6A CN201710375076A CN107011531A CN 107011531 A CN107011531 A CN 107011531A CN 201710375076 A CN201710375076 A CN 201710375076A CN 107011531 A CN107011531 A CN 107011531A
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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
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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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- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention belongs to field of packaging material, specifically related to a kind of preparation method of anti-mildew fresh-keeping PVA coated films, the present invention enters the interlayer structure of hydrotalcite-like materials, prepares houghite modified Nano particle using KF and BTA base butylbenzene natrium phenolsulfonicum as intercalator；Then houghite modified Nano particle is used for the coating of different substrate materials with PVA interaction generation PVA/ houghite modified Nano particles complex liquids, draws PVA coated films.PVA coated films prepared by the present invention have excellent water resistance, viscosity stability, and different substrate materials are respectively provided with stronger adhesive force, and hydrophobicity, oxygen-barrier property are excellent, can apply to flexible packaging and carry out anti-mildew fresh-keeping.
Description
Technical field
The invention belongs to field of packaging material, and in particular to a kind of preparation method of anti-mildew fresh-keeping PVA coated films.
Background technology
Preservative film is a kind of plastic packing product, is generally made up using ethene of masterbatch of polymerisation, is mainly used in micro-
The occasions such as the heating of ripple stove food, refrigerator food are preserved, fresh and prepared food packaging, family life, supermarket sales field, hotel and
Industrial food packaging applications are all widely used.Different according to material therefor and addition plasticiser, preservative film is divided into many
Type, is applicable to different occasions.Preservative film receives the favor of people with it the characteristics of convenient, economical, attractive in appearance.So
And, due to generally with the addition of plasticiser in process of production, influence of the preservative film to health also receives the concern of people.
One important technical requirements of flexible packaging are that to have good choke resistance moist, because the corruption of many food
Rotten is due to that oxygen and moisture penetration are crossed packaging material and entered in food, and the flourish to bacterium provides necessary bar
Part, as a result causes the oxidation deterioration of food.Therefore, the packaging material of the novel high barrier of Development and Production is flexible packaging circle
In terms of one important development.So-called high barrier material refers under standard state（23 DEG C, 65%RH）25.4 μ m thicks it is thin
Film oxygen permeating amount is in 5ml/M2.d it is following, and vapor transfer rate is in 2g/M2.d following material.Usual polyvinyl alcohol（PVA）, gather inclined dichloro
Ethylene copolymer（PVDC）Turn into three big high barrier hyaline membranes with polyacrylonitrile.
But it is due to that modified PVA coated film has that not water-fast, color is opaque, glue stability is poor, institute in the market
With current polyethylene coated film（PVA）R＆D direction in the modification of polyethylene coated liquid, China Aerospace Ke Gong groups 8511
PVA coating fluids are developed earliest（CN 95112745.4）, can only be coated with, expand in succession later on BOPP and PE
On MPE, PET, BOPP and CPP base material, and adhesion-tight is not peelable.Hainan match promise industry Wang Bo
（CN200510066498.2）Invent a kind of PVA strands and be condensed the PVA being made barrier coating fluids, coating by partially catalyzed
Thickness is 0.4-0.7 microns, far-infrared ray drying.2006, Hebei Barrier Packaging Materials Co., Ltd. successfully have developed new
Add the PVA high-obstructing coating liquids of inorganic nano-particle.
Hydrotalcite is a kind of natural ore deposit, and it is Mg that it, which constitutes structure proximate,6Al2（OH）16CO3·4H2O. the structure of hydrotalcite by
The class shepardite hydroxide layer of positively charged and electronegative interlayer composition.In shepardite, magnesium cation is in surrounding hydroxyl
Octahedral coordination, each octahedra public a line composition lamella.Part magnesium ion is taken by the trivalent aluminium ion isomorphous in shepardite
On behalf of hydrotalcite.Modified hydrotalcite is commonly referred to as hydrotalcite-like materials, and the carbanion of interlayer can be by many moon
Ion is replaced, such as nitrate anion, chlorion etc., and hydrotalcite after modified is houghite.
But following common shortcoming is still suffered from the prior art, i.e. the easy moisture absorption of PVA coating fluids, water resistance is poor, in height
Oxygen barrier declines under the conditions of wet；Coating fluid color is yellow, opaque, and the base material volume end face after coating is also obvious yellow,
As time went on, color burn；In coating process, because there is certain surface-active on PVA surfaces, is stirring or be coated with
Foam can be produced in drying process, defoamer selection is improper to cause the defect of coating barrier property.
So developing a kind of preparation method of the fresh-keeping PVA coated films of novel mildew resistant to solve the technical problem tool that the above is shared
There is important meaning.
The content of the invention
Present invention aim to address deficiency of the prior art, there is provided a kind of preparation side of anti-mildew fresh-keeping PVA coated films
Method, the present invention enters the interlayer structure of hydrotalcite-like materials using KF and BTA base butylbenzene natrium phenolsulfonicum as intercalator,
Prepare houghite modified Nano particle；Then houghite modified Nano particle generates PVA/ class water with PVA interactions
Talc modified Nanocomposites liquid is used for the coating of different substrate materials, draws PVA coated films.
The present invention is achieved through the following technical solutions above-mentioned purpose, a kind of preparation side of anti-mildew fresh-keeping PVA coated films
Method, comprises the following steps：
First, houghite modified Nano particle preparation section, comprises the following steps：
1）By Mg (NO3)2·6H2O、Al(NO3)3·6H2O is dispersed in water to be stirred under 200rpm rotating speed, is warming up to 60 DEG C；
Then it is added dropwise between the 2mol/L NaOH aqueous solution, maintenance system pH=9.5-11.0；Mg(NO3)2·6H2O and Al (NO3)3·
6H2O mole dosage ratio is 2:3；
2）Aging 6h is stirred at 60 DEG C, is then filtered, obtained sediment is put into the calcining furnace of nitrogen protection and calcined, by room temperature
Rise to 300~450 DEG C to be calcined, heating rate is 15 DEG C/min, calcination time is 8 hours, Temperature fall after the completion of calcining
To room temperature, product as hydrotalcite-like materials are obtained；
3）Take hydrotalcite-like materials 10g to be dispersed in the 100ml 0.02mol/L KF aqueous solution, then add 0.32g benzos three
Oxazolyl butylbenzene natrium phenolsulfonicum, is warming up under return stirring 24h, cooling, filtering, purifying water washing, nitrogen atmosphere and calcines to obtain class water
Talc modified nanoparticle precursor.Using KF and BTA base butylbenzene natrium phenolsulfonicum as intercalator in the present invention, class is entered
The interlayer structure of hydrotalcite material, so as to play the purpose being modified to hydrotalcite-like compound.
4）10g houghite modified Nano particle precursors are scattered in 200ml water, 10wt% KH- is then added dropwise
570 coupling agents, stir 5h at 60 DEG C, filtering, dry, grinding 400 mesh of sieving obtain houghite modified Nano particle.
2nd, PVA/ houghites modified Nano particle complex liquid preparation section, comprises the following steps：
1）Take 100ml purified waters to be added in reactor, stirred in adding 12g PVA17-99 under 400rpm rotating speed into water；
2）Then 0.2g plasticizer, 0.3g defoamers, 0.1-0.3g houghite modified Nano particles are added and is warming up to 80 DEG C, in
PVA17-99 is dispersed under 1000rpm rotating speed to be completely dissolved, then insulation reaction 2h, be cooled to room temperature and obtain PVA/ houghites
Modified Nano particle complex liquid.
3rd, anti-mildew fresh-keeping PVA coated films preparation section, will be added in PVA/ houghite modified Nano particle complex liquids
0.3Wt% Diethylenetriamine crosslinking agent, then using steel wire scraper for coating method base material one side or it is two-sided be coated, then
Dried again, obtain anti-mildew fresh-keeping PVA coated films.
It is preferred that, step 3 in houghite modified Nano particle preparation section）The temperature of the calcining is 660-700 DEG C.
It is preferred that, step 3 in houghite modified Nano particle preparation section）To take hydrotalcite-like materials 10g to be dispersed in
Ultrasonic disperse 0.5h at 40 DEG C in the 100ml 0.02mol/L KF aqueous solution, then adds 0.32g BTA base butylbenzene phenol sulphurs
Sour sodium, is warming up to return stirring 24h, and houghite is calcined to obtain for 660-700 DEG C under cooling, filtering, purifying water washing, nitrogen atmosphere
Modified Nano particle precursors.
It is preferred that, plasticizer described in PVA/ houghite modified Nano particle complex liquid preparation sections is phthalic acid
Dimethyl ester, BBP(Butyl Benzyl Phthalate or glycerine, preferably glycerine；
It is preferred that, defoamer described in PVA/ houghite modified Nano particle complex liquid preparation sections is polyoxyethylene polyoxy third
Alkene pentaerythrite ether or polyoxyethylene polyoxy propyl alcohol amidogen ether；
It is preferred that, it will be added in anti-mildew fresh-keeping PVA coated film preparation sections in PVA/ houghite modified Nano particle complex liquids
0.3Wt% Diethylenetriamine crosslinking agent ultrasound degassing 6h, then using steel wire scraper for coating method in base material one side or two-sided progress
Coating, then carries out drying at 60 DEG C, obtains anti-mildew fresh-keeping PVA coated films again.
It is preferred that, base material described in anti-mildew fresh-keeping PVA coated film preparation sections is PET, BOPP or PE.
The present invention enters the interlayer of hydrotalcite-like materials using KF and BTA base butylbenzene natrium phenolsulfonicum as intercalator
Structure, prepares houghite modified Nano particle；Then houghite modified Nano particle generates PVA/ with PVA interactions
Houghite modified Nano particle complex liquid is used for the coating of different substrate materials, draws PVA coated films.
PVA coated films prepared by the present invention have excellent water resistance, viscosity stability, effectively reduce polyvinyl alcohol painting
Cloth liquid with the change of time and temperature viscosity become it is big the drawbacks of, be conducive to the coating of coating fluid；And different substrate materials are respectively provided with
Stronger adhesive force, hydrophobicity, oxygen-barrier property are excellent, can apply to flexible packaging and carry out anti-mildew fresh-keeping.
Brief description of the drawings
Fig. 1 is houghite modified Nano particle SEM spectrum prepared by embodiment 1；
Fig. 2 is houghite modified Nano particle SEM spectrum prepared by embodiment 2；
Fig. 3 is the curve that PVA/ houghite modified Nano particle complex liquid water absorption rates prepared by embodiment 3 are changed over time.
Embodiment
To make the object, technical solutions and advantages of the present invention of greater clarity, with reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Embodiment 1
Prepare houghite modified Nano particle：
1) by 10g Mg (NO3)2·6H2O、Al(NO3)3·6H2O is dispersed in water to be stirred under 200rpm rotating speed, is warming up to
60℃；Then it is added dropwise between the 2mol/L NaOH aqueous solution, maintenance system pH=10.0-11.0；Mg(NO3)2·6H2O and Al
(NO3)3·6H2O mole dosage ratio is 2:3；
2) aging 6h is stirred at 60 DEG C, is then filtered, obtained sediment is put into the calcining furnace of nitrogen protection and calcined, by room temperature
Rise to 400 DEG C to be calcined, heating rate is 15 DEG C/min, calcination time is 8 hours, and room is naturally cooling to after the completion of calcining
Temperature, obtains product as hydrotalcite-like materials；
3) take hydrotalcite-like materials 10g to be dispersed in the 100ml 0.02mol/L KF aqueous solution, then add 0.32g benzos three
Oxazolyl butylbenzene natrium phenolsulfonicum, is warming up to return stirring 24h, is forged for 460-500 DEG C under cooling, filtering, purifying water washing, nitrogen atmosphere
Burn to obtain houghite modified Nano particle precursors；
4) 10g houghite modified Nano particle precursors are scattered in 200ml water, the KH-570 that 10wt% is then added dropwise is even
Join agent, stir 5h at 60 DEG C, filtering, dry at 90 DEG C, grinding 400 mesh of sieving obtain houghite modified Nano particle, scanning electricity
Mirror SEM is shown in Fig. 1.
Embodiment 2
Compared with Example 1, step 3）The pre-treatment of ultrasonic disperse is added, and calcining heat is improved, remaining and embodiment 1
It is identical；Differ only in the KF aqueous solution for taking hydrotalcite-like materials 10g to be dispersed in 100ml 0.02mol/L at 40 DEG C
Ultrasonic disperse 0.5h, then adds 0.32g BTA base butylbenzene natrium phenolsulfonicums, is warming up to return stirring 24h, cool, filter,
Houghite modified Nano particle precursors are calcined to obtain under purifying water washing, nitrogen atmosphere for 660-700 DEG C.
Houghite modified Nano particle scanning electron microscope sem prepared by embodiment 2 is shown in Fig. 2
It can be seen from Fig. 1 and Fig. 2 ESEM result in houghite modified Nano particle preparation process is prepared, insert
The preparation process of layer agent KF and BTA base butylbenzene natrium phenolsulfonicum to the houghite modified Nano particle finally prepared most
Whole pattern is very significant considering that, takes ultrasonic disperse and high-temperature calcination（660-700℃）The houghite prepared is modified
Nano-particle is preferable layer structure, and the houghite modified Nano prepared without ultrasonic pre-treatment and high-temperature calcination
Particle is granular structure, is unfavorable for preparing complex liquid with PVA progress.It is advantageous to carry out ultrasonic pre-treatment, and carry out height
Temperature calcining.
Embodiment 3
PVA/ houghite modified Nano particle complex liquids are prepared, are comprised the following steps：
1）Take 100ml purified waters to be added in reactor, stirred in adding 12g PVA17-99 under 400rpm rotating speed into water
Mix；
2）Then 0.2g glycerine, 0.3g polyoxyethylene polyoxypropylene pentaerythrites ether, 0.2g houghite modified Nanos are added
Particle (prepared by embodiment 2) is warming up to 80 DEG C, is completely dissolved, is then incubated in being dispersed to PVA17-99 under 1000rpm rotating speed
2h is reacted, room temperature is cooled to and obtains PVA/ houghite modified Nano particle complex liquids.
To PVA/ houghite modified Nano particles complex liquid using the test for pricking grace cup 3# progress viscosity（Unit is S）,
Room temperature prepare after measurement viscosity be 37.3,30 DEG C place 60h after viscosity be 39.0,30 DEG C placement 120h after viscosity be 41.0；10
DEG C place 60h after viscosity be 45.0,10 DEG C placement 120h after viscosity be 52.6；Result of the test shows PVA/ classes prepared by the present invention
Hydrotalcite-modified Nanocomposites liquid places viscosity for a long time at room temperature not to be increased substantially（It is changed into 41.0, increasing from 37.3
Long rate is only 1.1）；10 DEG C of low-temperature storage 120h viscosity also only increase by 1.41 times；So showing the PVA/ classes that the present invention is prepared
Hydrotalcite-modified Nanocomposites liquid effectively overcomes simple PVA coating fluid viscosities and constantly increases change great Rong with time and temperature
The phenomenon of the defect jelly easily occurred.
PVA/ houghite modified Nano particle complex liquids are coated in glass surface ware, after natural drying, at 60 DEG C
It is dried in vacuo 24h；It is then placed into constant temperature and humidity（30 DEG C, 75RH%）Vessel in measure its water absorption rate（Weight after water suction-dry
Dry rear weight）The percentage of weight after/drying, with the changing value of time water absorption rate as shown in figure 3, as a result showing preparation of the present invention
VA/ houghite modified Nano particle complex liquids in 48h water absorption rate be less than 10%, show the present invention changed by houghite
Property nano-particle PVA is modified realizes active hydroxyl groups on PVA strands and be blocked, reduce the interaction with water,
So as to which hydroscopicity is also not reaching to 10% in 48h.
Embodiment 4
Anti-mildew fresh-keeping PVA coated films are prepared, 0.3Wt% diethyl will be added in PVA/ houghite modified Nano particle complex liquids
Three amine crosslinkers, then use steel wire scraper for coating method respectively in thickness for 20 μm PET, BOPP（BOPP film uses preceding progress
Sided corona treatment）, PE substrate surfaces are coated（About 0.6-0.8 μm of coated film thickness, coating weight is 0.8g/m2, calculated with butt）,
Then 60 DEG C of curing 8h are carried out again, obtain anti-mildew fresh-keeping PVA coated films.Protected according to the method test in GB/T 8808-1988 is mould proof
The peel strength of fresh PVA coated films（Angle is 180 DEG C during stripping, is tested on universal electrical puller system, draw speed
300mm/min）, as a result PET, BOPP, PE peel strength are respectively 9.8,11.3,10.7 N/15mm.Pass through the stripping of three
Intensity can be seen that PVA/ houghite modified Nano particles complex liquid prepared by the present invention can have well with a variety of base materials
Adhesive force, application is wider.
Embodiment 5
The houghite modified Nano particle prepared using in embodiment 1 is prepared PVA/ houghite modified Nanos particle as raw material and answered
Liquid is closed, and with BOPP（BOPP film carries out sided corona treatment using preceding）Coated film is prepared into for base material.
The coated films prepared for base material of BOPP in embodiment 4 and the coated film prepared in embodiment 5 are used
Its 24h oxygen permeating amount of the OTR oxygen transmission rate test system and test of PERME-OX2/230 models, the painting as a result prepared for embodiment 4
Cloth film oxygen transit dose is 0.8cm3.m-2.24h-1.0.1MPa-1；Embodiment 5（I.e. with graininess houghite modified Nano grain
Son）The coated film oxygen transit dose prepared is 23 cm3.m-2.24h-1.0.1MPa-1；The 46cm of pure BOPP base materials3.m-2.24h-1.0.1MPa-1；So the houghite modification of selection preparation layer structure is received in the selection of houghite modified Nano particle
Rice corpuscles.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, embodiments of the present invention can be made with various changes, replace and change.
Claims (7)
1. a kind of preparation method of anti-mildew fresh-keeping PVA coated films, comprises the following steps：
First, houghite modified Nano particle preparation section, comprises the following steps：
1）By Mg (NO3)2·6H2O、Al(NO3)3·6H2O is dispersed in water to be stirred under 200rpm rotating speed, is warming up to 60 DEG C；
Then it is added dropwise between the 2mol/L NaOH aqueous solution, maintenance system pH=9.5-11.0；Mg(NO3)2·6H2O and Al (NO3)3·
6H2O mole dosage ratio is 2:3；
2）Aging 6h is stirred at 60 DEG C, is then filtered, obtained sediment is put into the calcining furnace of nitrogen protection and calcined, by room temperature
Rise to 300~450 DEG C to be calcined, heating rate is 15 DEG C/min, calcination time is 8 hours, Temperature fall after the completion of calcining
To room temperature, product as hydrotalcite-like materials are obtained；
3）Take hydrotalcite-like materials 10g to be dispersed in the 100ml 0.02mol/L KF aqueous solution, then add 0.32g benzos three
Oxazolyl butylbenzene natrium phenolsulfonicum, is warming up under return stirring 24h, cooling, filtering, purifying water washing, nitrogen atmosphere and calcines to obtain class water
Talc modified nanoparticle precursor；
4）10g houghite modified Nano particle precursors are scattered in 200ml water, the KH-570 that 10wt% is then added dropwise is even
Join and 5h is stirred at agent, 60 DEG C, filtering, dry, ground 400 mesh sieve obtain houghite modified Nano particle；
2nd, PVA/ houghites modified Nano particle complex liquid preparation section, comprises the following steps：
1）Take 100ml purified waters to be added in reactor, stirred in adding 12g PVA17-99 under 400rpm rotating speed into water；
2）Then 0.2g plasticizer, 0.3g defoamers, 0.1-0.3g houghite modified Nano particles are added and is warming up to 80 DEG C, in
PVA17-99 is dispersed under 1000rpm rotating speed to be completely dissolved, then insulation reaction 2h, be cooled to room temperature and obtain PVA/ houghites
Modified Nano particle complex liquid；
3rd, anti-mildew fresh-keeping PVA coated films preparation section, will add 0.3Wt% in PVA/ houghite modified Nano particle complex liquids
Diethylenetriamine crosslinking agent, then using steel wire scraper for coating method base material one side or it is two-sided be coated, then carry out again
Drying, obtains anti-mildew fresh-keeping PVA coated films.
2. preparation method according to claim 1, it is characterised in that：Walked in houghite modified Nano particle preparation section
Rapid 3）The temperature of the calcining is 660-700 DEG C.
3. preparation method according to claim 2, it is characterised in that：Walked in houghite modified Nano particle preparation section
Rapid 3）To take hydrotalcite-like materials 10g to be dispersed in the 100ml0.02mol/L KF aqueous solution ultrasonic disperse 0.5h at 40 DEG C, so
0.32g BTA base butylbenzene natrium phenolsulfonicums are added afterwards, are warming up to return stirring 24h, cooling, filtering, purifying water washing, nitrogen
Houghite modified Nano particle precursors are calcined to obtain under atmosphere for 660-700 DEG C.
4. preparation method according to claim 1, it is characterised in that：PVA/ houghite modified Nano particle complex liquid systems
Plasticizer is repefral, BBP(Butyl Benzyl Phthalate or glycerine described in standby process.
5. preparation method according to claim 1, it is characterised in that：PVA/ houghite modified Nano particle complex liquid systems
Defoamer is polyoxyethylene polyoxypropylene pentaerythrite ether or polyoxyethylene polyoxy propyl alcohol amidogen ether described in standby process.
6. preparation method according to claim 1, it is characterised in that：Will in anti-mildew fresh-keeping PVA coated film preparation sections
0.3Wt% Diethylenetriamine crosslinking agent ultrasound degassing 6h is added in PVA/ houghite modified Nano particle complex liquids, is then used
Steel wire scraper for coating method base material one side or it is two-sided be coated, then carry out again at 60 DEG C dry, obtain anti-mildew fresh-keeping PVA painting
Cloth film.
7. preparation method according to claim 1, it is characterised in that：Described in anti-mildew fresh-keeping PVA coated film preparation sections
Base material is PET, BOPP or PE.
Priority Applications (1)
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| CN107471695A (en) * | 2017-09-15 | 2017-12-15 | 青海祁连山包装科技有限公司 | A kind of preparation method for preventing halogen beef or mutton resistance corruption plastic film |
| CN109251450A (en) * | 2018-07-17 | 2019-01-22 | 王晚秀 | A kind of high barrier PVA group compound film and preparation method thereof |
| WO2019092454A1 (en) * | 2017-11-13 | 2019-05-16 | Scg Chemicals Co., Ltd. | Coating method and product thereof |
| WO2021061049A1 (en) * | 2019-09-23 | 2021-04-01 | Agency For Science, Technology And Research | A coating suspension |
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| CN105344335A (en) * | 2015-11-25 | 2016-02-24 | 福建师范大学 | Preparation method for LDHs/PVA composite membrane and application of LDHs/PVA composite membrane in heavy metal wastewater |
| CN106318060A (en) * | 2016-08-16 | 2017-01-11 | 中国船舶重工集团公司第七二五研究所 | Transparent anti-fouling membrane preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107471695A (en) * | 2017-09-15 | 2017-12-15 | 青海祁连山包装科技有限公司 | A kind of preparation method for preventing halogen beef or mutton resistance corruption plastic film |
| WO2019092454A1 (en) * | 2017-11-13 | 2019-05-16 | Scg Chemicals Co., Ltd. | Coating method and product thereof |
| CN109251450A (en) * | 2018-07-17 | 2019-01-22 | 王晚秀 | A kind of high barrier PVA group compound film and preparation method thereof |
| WO2021061049A1 (en) * | 2019-09-23 | 2021-04-01 | Agency For Science, Technology And Research | A coating suspension |
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| CN107011531B (en) | 2020-03-10 |
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