CN110511415A - Using epoxy soybean oil acrylate as waterproof starch film of coating and preparation method thereof - Google Patents
Using epoxy soybean oil acrylate as waterproof starch film of coating and preparation method thereof Download PDFInfo
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- CN110511415A CN110511415A CN201910812840.0A CN201910812840A CN110511415A CN 110511415 A CN110511415 A CN 110511415A CN 201910812840 A CN201910812840 A CN 201910812840A CN 110511415 A CN110511415 A CN 110511415A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
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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
- 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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
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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
- C09D7/63—Additives non-macromolecular organic
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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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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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
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/04—Starch derivatives
- C08J2303/08—Ethers
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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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention discloses using epoxy soybean oil acrylate as waterproof starch film of coating and preparation method thereof, belong to field of packaging material.The waterproof starch film is using full starch base membrane material as sandwich layer, on sandwich layer two sides by the way of light solidifying coating combination interface modifying agent, forms epoxy soybean oil acrylate coating；Wherein, the epoxy soybean oil acrylate coating is prepared into photocuring solution by epoxy soybean oil acrylate, photoinitiator, interface modifier in a solvent, surface covering: photocuring solution being coated on starch film layer and is formed.Waterproof starch film produced by the present invention possesses good mechanical performance, transparency and waterproof performance, and has good adhesion between coating and film, has controllability good, and Environmental Safety, preparation process is easy, the advantages such as cost is relatively low.
Description
Technical field
The present invention relates to a kind of waterproof starch films, more particularly to a kind of using epoxy soybean oil acrylate as the anti-of coating
Water-starch film and preparation method thereof；The waterproof starch film is mainly used as packaging material.
Background technique
Starch-based material is cheap, and has good biocompatibility and biological degradability, has been applied to drug
In the fields such as release, packaging and agricultural.Attention with country to environmental protection, starch-based degradable packaging material have become people
Focus of attention.But the food during fresh-keeping packaging of food, other than external environment can generate steam, in packing box
Product can also generate steam, be packed if directlying adopt full starch film, due to the strongly hydrophilic of starch molecule, can be easy so that
Starch-based material is influenced by moisture, and leading to it, there are certain performance deficiencies, especially water vapour permeability and waterproofness
Can etc.；Meanwhile non-water-tight starch film is also difficult the moisture reservation of the food inside protective packaging and from outside moisture
Influence, to limit the application of starch-based packaging material.
In order to improve the moisture-proof and waterproofness of starch-based material, develop various mixing, synthesis and coating technology, such as with
Fat or grease mixing, mix with albumen/gelatin, are come with mineral filler, cellulose fibre, polysaccharide-based particle and self-reinforcing technology
Enhance its performance etc..But directly mixed with lyophobic dust, it is difficult to change the hydrophily of starch base mixing material, also Chang Fasheng
Phenomenon of phase separation, it is also difficult to play the advantage performance of each material；Except the content of non-starch is sufficiently low, hydrophobic polymer is being mixed
Independent phase is formed in object, starch is intended only as a kind of filler at this time.On the other hand, by adding chemistry filler, such as various nanometers
Filler, to improve the performance of starch-based material, but nano-filled object such as titanium oxide, zinc oxide, silica etc., not only cost
It is high, and can cause environmental pollution, it is not suitable for food packaging application, harm can be generated to human health.In addition, starch
Crosslinking technological needs to mix crosslinking agent with starch suspension in process of production, then casting film-forming, and this method is simultaneously uncomfortable
Industry manufacture is closed, because industrial starch membrane material is mainly to produce by extrusion casint.Surface covering method have it is easy to process,
At low cost, thickness control flexibly, the advantage of natural property that base material can be maximized etc., be conducive to the rear place of starch membrane material
Reason.
Chinese invention patent application 201810982787.4 discloses a kind of preparation method of nano-starch super-hydrophobic coat,
Specifically includes the following steps: first using ultrasonication starch, nano-starch dispersion liquid is prepared；Secondly, nano-starch is dispersed
Liquid is surface-treated with double bond containing silane coupling agent；Again, by surface treated nano-starch and vinylacetate
Emulsion polymerization synthesizes hydrophobic lotions；Finally, on the substrate surface by lotion dip-coating, drying is obtained with ultra-hydrophobicity
Coating.For the nano material that method of the invention uses for starch, low-surface energy substance is polyvinyl acetate, material therefor cost
It is cheap to be easy to get, there is good environmental-protecting performance, and there is good ultra-hydrophobicity using the coating of this method preparation, water is connect
Feeler is more than 151.6 °.And Chinese invention patent application 2018109634937 disclose a kind of light-cured type nano-cellulose/
The preparation method of AESO lotion, this method include following operating procedure: (1) dispersing nano-cellulose in deionized water, room
The lower magnetic agitation 1h of temperature, preparation of nano cellulose suspension；(2) photoinitiator Darocure 1173 is added to epoxy soybean
In oily acrylate, magnetic agitation 10min, prepares AESO oil phase at room temperature；(3) AESO oil is mutually pressed with nano-cellulose suspension
The ratio that mass ratio is 1:1~1:5 mixes, and carries out high speed emulsification at room temperature, and emulsive rate is 5000r/min~15000r/
Min, emulsification times are 5min~10min, and light-cured type nano-cellulose/AESO lotion is made.The present invention does not need addition and appoints
What surfactant can be obtained by the good light-cured type nano-cellulose/AESO lotion of stability.The lotion combines nanometer
The degradable characteristic of cellulose and AESO, can quickly solidify to form under UV illumination with good hydrophobicity and barrier properties for gases
The film layer of energy.But both methods is both needed to that starch or cellulose are first prepared into nano dispersion fluid, lotion preparation steps are numerous
It is trivial, and be solution system, it is difficult to industrialized production is carried out, and both films are the coatings as other matrix, and cannot
As an independent packaging film.
Chinese invention patent 2012100847451 discloses a kind of membrane encapsulation devices, opto-electronic device and its packaging method,
It is related to photoelectron technical field, can effectively obstructs water and oxygen, extends the service life of opto-electronic device.Membrane encapsulation devices packet
Include thin-film encapsulation layer；Thin-film encapsulation layer includes ultraviolet photocureable material layer；Ultraviolet photocureable material layer is by ultraviolet photocureable material
It is formed, ultraviolet photocureable material includes that the epoxy soybean oil acrylate that mass percentage is 25~95% and quality percentage contain
The ultraviolet initiator that amount is 5~75%.The present invention can be used for the encapsulation of opto-electronic device.It but at this stage, will be hydrophobic
Apply the coating to the research in hydrophilic full starch base membrane material almost without, this is because the hydrophilic property difference of the two,
It is easy to cause interface poor compatibility, generated fine crack makes hydrone be easier to permeate, and the infiltration of hydrone
Easily it is detached from coating and starch film, to limit application of the waterproof coating on hydrophilic material.
Therefore, how matrix of different nature effectively to be compounded, gives full play to each component advantage, be current solution starch film
The key for the problems such as waterproofness is poor, interface compatibility is poor between waterproof material and hydrophilic starch, this is to promoting the storage of China's food
It hides and the development of preservation technology, offer new packaging material etc. is of great significance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of raw material sources extensively,
Easy to process, transparent, the adhesive force of coating and starch film is strong, have both good mechanical performance with epoxy soybean oil acrylate
For the waterproof starch film and preparation method thereof of coating.
The purpose of the present invention is realized by following technical proposals:
Using epoxy soybean oil acrylate as the waterproof starch film of coating, using full starch base membrane material as sandwich layer, in sandwich layer two
Face forms epoxy soybean oil acrylate coating by the way of light solidifying coating combination interface modifying agent；Wherein, the ring
Oxygen soybean oil acrylate coating is prepared into light by epoxy soybean oil acrylate, photoinitiator, interface modifier in a solvent
Surface covering: photocuring solution is coated on starch film layer and is formed by curing solution；By epoxy soybean oil acrylate, light-initiated
Agent, interface modifier account for the 5~30wt%, 2~7wt% and 1~6wt% of photocuring solution materials quality respectively；
The interface modifier is one of KH550, KH560, KH570, KH792, DL602 and DL171 or a variety of.
To further realize the object of the invention, it is preferable that the starch is one of ative starch or a variety of；The original
Starch is tapioca, potato starch, wheaten starch and cornstarch；Either the starch is one in converted starch
Kind is a variety of；The converted starch is hydroxypropyl maize modified starch, carboxymethyl starch, esterification starch, oxidized starch, acid change
Property starch, etherification starch, crosslinked starch, cationic starch, graft starch and dialdehyde starch.
Preferably, the photoinitiator be Irgacure819, TEPO, TPO, TPO-L, 184,1173, in benzophenone
It is one or more.
Preferably, the full starch base membrane material is prepared using double screw extruder and chip mold extrusion.
Preferably, the sandwich layer with a thickness of 0.1~0.5mm.
Preferably, the two-sided overall thickness of the epoxy soybean oil acrylate coating is 2~10 μm.
It is described using epoxy soybean oil acrylate as the preparation method of the waterproof starch film of coating, comprising the following steps:
1) preparation of full starch base membrane material；
2) it configures photocuring solution: epoxy soybean oil acrylate, photoinitiator and interface modifier is dissolved in solvent
In, it is stirred at room temperature uniformly, is prepared into photocuring solution；
3) surface covering: the photocuring solution system is coated in the full starch base membrane material, is placed, is made light
Curing solution is evenly dispersed on starch membrane material surface, and the starch film containing photocuring solution surface layer is placed on ultraviolet light by exhaust
Lower exposure is made comprising using epoxy soybean oil acrylate as the waterproof starch film of coating.
Preferably, the preparation of the full starch base membrane material is squeezed out using screw extruder and chip mold and starch base is made
Membrane material, gained starch membrane material are adjusted under 57% relative humidities, reach water balance, then use ethyl acetate solution
Clean the dust on starch membrane material surface, drying for standby.
Preferably, the solvent is ethyl acetate；The stirring is magnetic agitation, and the time of stirring is 1.5~3h.
Preferably, described to be applied to rotary coating or dip-coating；15~30 DEG C of the temperature of the placement, humidity 40%
~65%, the time of placement is 1~2h；The ultraviolet light emission wavelength is 254nm, and light application time is 5~12min, illumination
Distance is 10~20cm.
Haake double screw extruder can be selected in screw extruder of the present invention, and the width of chip mold is 150mm, extruder
The control zone temperature of machine barrel is respectively 40 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 120 DEG C, 100 DEG C, 95 DEG C.
Compared with prior art, the invention has the following advantages:
1, the present invention is the waterproof starch film of coating for the first time by hydrophobicity epoxidized soybean oil using epoxy soybean oil acrylate
Acrylate coatings are in conjunction with the full starch based material of hydrophily, using the side of extrusion molding and light solidifying coating method combination interface modifying agent
Formula is prepared, and can effectively solve that hydrophobic coating is difficult in the full starch base membrane material of hydrophily coating and hydrophobic coating is easy to parent
The technical problem that water-starch basement membrane material is detached from, while can solve the problems, such as that general starch film transparency is low, prepared anti-pond
Powder film mechanical performance is strong, transparency improves.
2, the present invention has the function of waterproof by the waterproof starch film of coating of epoxy soybean oil acrylate, can be in food
During fresh-keeping packaging, the moisture attacks that effective protection starch film is not generated by external environment and food product inside improve anti-pond
Service life of powder film during packaging applications, while protecting the reservation of interior packing food moisture itself and from external water
The influence divided.
3, the present invention can be with ring using the interface modifier that epoxy soybean oil acrylate is related to as the waterproof starch film of coating
Covalent coupling reaction occurs for oxygen soybean oil acrylate, meanwhile, under photo curing condition, silicon can be generated in conjunction with moisture in air
Alcohol can occur dehydration condensation with the hydroxyl on starch membrane material surface, form compact two-phase interface connection type,
Gap between coating and starch membrane material two-phase disappears, so that there is good adhesive force between coating material and substrate,
Coating is prevented to be detached from.
4, the present invention directly can produce starch base membrane material with the powder prepared, to further decrease production cost, using crowded
Out plus light solidifying coating method prepares product has many advantages, such as that serialization degree is high, with short production cycle, and film-forming process is controllable, coating
Stability it is very good, obtained waterproof starch film thickness can be adjusted arbitrarily.
5, of the invention using epoxy soybean oil acrylate as the waterproof starch film of coating, for grinding for starch-based packaging material
Study carefully and using providing a kind of novel practical approach.
Specific embodiment
For a better understanding of the invention, below with reference to embodiment, the invention will be further described, but embodiment is not right
The scope of the present invention, which is constituted, to be limited.Unless stated otherwise, the present invention uses reagent, method and apparatus are normal for the art
Advise reagent, method and apparatus.Embodiment material therefor is commercially available.
Embodiment 1
It is a kind of using epoxy soybean oil acrylate as the waterproof starch film of coating, be prepared from the following steps:
(1) it the preparation and pre-treatment of full starch membrane material: is squeezed using the haake twin-screw of the chip mold with 150mm wide
Out machine (rheomex ptw24/40p,Screw diameter D=24mm, spiro rod length L=28D), tapioca raw material is thrown
Enter spout, squeezes out and tapioca membrane material is made.Extruder barrel has eight temperature-controlled areas, each temperature is respectively 40 DEG C,
60℃,90℃,120℃,120℃,100℃,95℃.Squeeze film is acquired using traction device, squeezes out the thickness of membrane material
About 0.2mm.Gained starch membrane material is placed on above drier pallet at room temperature (full equipped with 57%RH below drier pallet
And salting liquid) in 2 days, to reach water balance.Then the dust on starch membrane material surface is cleaned with ethyl acetate solution, drying is standby
With；
(2) preparation of photocuring solution system: proportionally by the epoxy soybean oil acrylate of 7wt%, the light of 6wt%
The interface modifier KH560 of initiator TEPO and 1wt% are dissolved in ethyl acetate, photocuring solution system are prepared into, in room
It is stirred evenly under temperature；
(3) surface covering: photocuring solution system is spun and coated in starch film layer, temperature is 25 DEG C, humidity is
50% condition places 2h, makes photocuring solution evenly dispersed on starch membrane material surface, then will contain photocuring solution surface layer
Starch film be placed under small-scale ultraviolet ray curing exposure (ultraviolet light emission wavelength 254nm, time for exposure 8min).It obtains final
Coated on both sides overall thickness is 5 μm, is placed on room by the waterproof starch film of coating of epoxy soybean oil acrylate for what is prepared
It is flat to reach moisture 2 days in (saturated salt solution of 57%RH being housed) below drier pallet above drier pallet under temperature
Weighing apparatus.
Embodiment 2
It is a kind of using epoxy soybean oil acrylate as the waterproof starch film of coating, be prepared from the following steps:
(1) it the preparation and pre-treatment of full starch membrane material: is squeezed using the haake twin-screw of the chip mold with 150mm wide
Out machine (rheomex ptw24/40p,Screw diameter D=24mm, spiro rod length L=28D), cornstarch raw material is thrown
Enter spout, squeezes out and cornstarch membrane material is made.Extruder barrel has eight temperature-controlled areas, each temperature is respectively 40 DEG C,
60℃,90℃,120℃,120℃,100℃,95℃.Squeeze film is acquired using traction device, squeezes out the thickness of membrane material
About 0.30mm.Gained starch membrane material, which is placed on above drier pallet at room temperature, (is equipped with 57%RH's below drier pallet
Saturated salt solution) in 2 days, to reach water balance.Then the dust on starch membrane material surface is cleaned with ethyl acetate solution, it is dry
It is spare；
(2) preparation of photocuring solution system: proportionally by the epoxy soybean oil acrylate of 10%wt, 4%wt
The interface modifier DL602 of photoinitiator TPO and 2%wt are dissolved in ethyl acetate, photocuring solution system are prepared into, in room
It is stirred evenly under temperature；
(3) surface covering: by the photocuring solution system dip-coating in starch film layer, temperature is 28 DEG C, humidity is
55% condition places 1.5h, makes photocuring solution evenly dispersed on starch membrane material surface, then will contain photocuring solution surface
The starch film of layer is placed on exposure (ultraviolet light emission wavelength 254nm, time for exposure 8min) under small-scale ultraviolet ray curing.It is final double
Finishing coat overall thickness is 6 μm, is placed on room temperature by the waterproof starch film of coating of epoxy soybean oil acrylate for what is prepared
Under drier pallet above 2 days in the saturated salt solution of 57%RH (below drier pallet be equipped with), to reach water balance.
Embodiment 3
It is a kind of using epoxy soybean oil acrylate as the waterproof starch film of coating, be prepared from the following steps:
(1) it the preparation and pre-treatment of full starch membrane material: is squeezed using the haake twin-screw of the chip mold with 150mm wide
Out machine (rheomex ptw24/40p,Screw diameter D=24mm, spiro rod length L=28D), by hydroxypropyl corn starch
Raw material puts into spout, squeezes out and hydroxypropyl corn starch membrane material is made.Extruder barrel has eight temperature-controlled areas, each temperature
Respectively 40 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 120 DEG C, 100 DEG C, 95 DEG C.Squeeze film is acquired using traction device, is squeezed out
The thickness of membrane material is about 0.25mm.Gained starch membrane material is placed on above drier pallet at room temperature and (fills below drier pallet
Have the saturated salt solution of 57%RH) in 2 days, to reach water balance.Then starch membrane material surface is cleaned with ethyl acetate solution
Dust, drying for standby；
(2) preparation of photocuring solution system: proportionally by the epoxy soybean oil acrylate of 15%wt, 6%wt
The interface modifier KH550 of photoinitiator Irgacure819 and 3%wt are dissolved in ethyl acetate, are prepared into photocuring solution
System is stirred at room temperature uniformly；
(3) surface covering: being 30 DEG C, humidity in temperature by photocuring solution system rotation dip-coating in starch film layer
For 55% condition, 1.2h is placed, makes photocuring solution evenly dispersed on starch membrane material surface, then will contain photocuring solution table
The starch film of surface layer is placed on exposure (ultraviolet light emission wavelength 254nm, time for exposure 7min) under small-scale ultraviolet ray curing.Finally
Coated on both sides overall thickness is 8 μm, is placed on room by the waterproof starch film of coating of epoxy soybean oil acrylate for what is prepared
It is flat to reach moisture 2 days in (saturated salt solution of 57%RH being housed) below drier pallet above drier pallet under temperature
Weighing apparatus.
Embodiment 4
It is a kind of using epoxy soybean oil acrylate as the waterproof starch film of coating, be prepared from the following steps:
(1) it the preparation and pre-treatment of full starch membrane material: is squeezed using the haake twin-screw of the chip mold with 150mm wide
Out machine (rheomex ptw24/40p,Screw diameter D=24mm, spiro rod length L=28D), by carboxymethyl starch raw material
Spout is put into, squeezes out and carboxymethyl starch membrane material is made.Extruder barrel has eight temperature-controlled areas, and each temperature is respectively 40
℃,60℃,90℃,120℃,120℃,100℃,95℃.Squeeze film is acquired using traction device, squeezes out the thickness of membrane material
Degree is about 0.28mm.Gained starch membrane material is placed on above drier pallet at room temperature (equipped with 57%RH below drier pallet
Saturated salt solution) in 2 days, to reach water balance.Then the dust on starch membrane material surface is cleaned with ethyl acetate solution, is done
It is dry spare；
(2) preparation of photocuring solution system: proportionally by the epoxy soybean oil acrylate of 18%wt, 6%wt
The interface modifier KH550 of photoinitiator TEPO and 5%wt are dissolved in ethyl acetate, are prepared into photocuring solution system, In
It stirs evenly at room temperature；
(3) surface covering: the photocuring solution system is spun and coated in the starch film layer, is 30 in temperature
DEG C, humidity be 60% condition, place 1h, make photocuring solution evenly dispersed on starch membrane material surface, then will contain photocuring
The starch film of solution surface layer is placed on exposure (ultraviolet light emission wavelength 254nm, the time for exposure under small-scale ultraviolet ray curing
6min).Final coated on both sides overall thickness is 7 μm, will be prepared using epoxy soybean oil acrylate as the anti-water-starch of coating
Film is placed on above drier pallet at room temperature in (equipped with the saturated salt solution of 57%RH below drier pallet) 2 days, to reach
To water balance.
Embodiment 5
1, contrast material:
(1) the full starch film of non-coating: using the haake double screw extruder of the chip mold with 150mm wide
(rheomex ptw24/40p,Screw diameter D=24mm, spiro rod length L=28D), by hydroxypropyl corn starch raw material
Spout is put into, squeezes out and hydroxypropyl corn starch membrane material is made.Extruder barrel has eight temperature-controlled areas, each temperature difference
It is 40 DEG C, 60 DEG C, 90 DEG C, 120 DEG C, 120 DEG C, 100 DEG C, 95 DEG C.Squeeze film is acquired using traction device, squeezes out membrane material
Thickness be about 0.25mm.Gained starch membrane material is placed on above drier pallet at room temperature and (is equipped with below drier pallet
The saturated salt solution of 57%RH) in 2 days, to reach water balance.
(2) starch-epoxy soybean oil acrylate blend film: for better and prepared anti-water-starch of the invention
Film carries out Contrast on effect, and according to art methods, (Chinese invention patent application 201810963493.7 (receive by a kind of light-cured type
Rice cellulose/AESO lotion preparation method) and a kind of 201810982787.4 (preparation sides of the super-hydrophobic coat containing nano-starch
Method) carry out the preparation of starch-epoxy soybean oil acrylate blend film, wherein by Chinese invention patent application
The preparation of nano-cellulose in 201810963493.7 (a kind of preparation methods of light-cured type nano-cellulose/AESO lotion)
Step replaces with the preparation of nano-starch in 201810982787.4 (a kind of preparation methods of the super-hydrophobic coat containing nano-starch)
Step, specific step is as follows.
1) 5g cornstarch is added in 100g water, after mixing evenly in 2 DEG C of progress ultrasonication 8h, obtains nano-starch
Dispersion liquid；2) photoinitiator KH550 is added in epoxidized soybean oil acrylic vinegar, at room temperature magnetic agitation, prepares light and draws
Send out the epoxidized soybean oil acrylic vinegar oil phase that agent concentration is 1%；3) by the resulting epoxy soybean oil acrylate oil phase of step 2)
In mass ratio be oily phase with the resulting nano-starch dispersion liquid of step 1): suspension=1:1 ratio mixes, and carries out at room temperature high
Speed emulsification, emulsive rate 5000r/min, emulsification times be 10min to get arrive light-cured type nano-starch lotion；It 4) will be newborn
After liquid is coated on PET stromal surface, under UV Light 7min can rapid film-forming, control film with a thickness of 0.3mm, so
After take off film.
(3) do not add the coating starch film of interface modifier:
1) using with 150mm wide chip mold haake double screw extruder (rheomex ptw24/40p,Screw diameter D=24mm, spiro rod length L=28D), hydroxypropyl corn starch raw material is put into spout, squeezes out and is made
Hydroxypropyl corn starch membrane material.Extruder barrel has eight temperature-controlled areas, each temperature is respectively 40 DEG C, 60 DEG C, 90 DEG C,
120℃,120℃,100℃,95℃.Squeeze film is acquired using traction device, the thickness for squeezing out membrane material is about 0.3mm.
Gained starch membrane material is placed on above drier pallet at room temperature and (saturated salt solution of 57%RH is housed) below drier pallet
In 2 days, to reach water balance.Then the dust on starch membrane material surface, drying for standby are cleaned with ethyl acetate solution；
2) preparation of photocuring solution system: proportionally by the epoxy soybean oil acrylate of 7%wt, the light of 6%wt
Initiator Irgacure819 is dissolved in ethyl acetate, and interface modifier is not added, and photocuring solution system is prepared into, in room temperature
Under stir evenly；
3) surface covering: being 25 in temperature by photocuring solution rotating coating or dip-coating in the starch film layer
DEG C, humidity be 50% condition, place 1.3h, make photocuring solution evenly dispersed on starch membrane material surface, then will consolidate containing light
The starch film for changing solution surface layer is placed on exposure (ultraviolet light emission wavelength 254nm, the time for exposure under small-scale ultraviolet ray curing
6min).Final coated on both sides overall thickness is 6 μm, will be prepared using epoxy soybean oil acrylate as the anti-pond of coating
Powder film is placed on above drier pallet at room temperature in (equipped with the saturated salt solution of 57%RH below drier pallet) 2 days, with
Reach water balance.
2, product made from embodiment 1,2,3,4 is subjected to interface attachment with the coating starch film of interface modifier is not added
Power measurement.
1) the adhesive force characterization of epoxy soybean oil acrylate coating is epoxy soybean oil acrylate coating and starch
The two-phase interface binding performance of membrane material will have a direct impact on the waterproof performance and service life of starch membrane material.Measure the side of adhesive force
Method pulls open method, cross-hatching, scratch and draws fork method." Portable adhesion-force tester is used according to ASTM D 4541-2009
Carrying out the standard test method of pull-off test " (portable to pull open method) test epoxy soybean oil acrylate coating is to starch membrane material
Adhesive force.Operating method is to take out billet, aluminium sheet and the sand paper that the test dedicated diameter of adhesive force is 20mm first, will be justified
The bottom surface of ingot and the surface of aluminium sheet are lain in above sand paper, the 4-5 oxide and impurity to remove surface of polishing, and epoxy is big
Soya bean oil acrylate starch membrane material is cut into the size that specification is 25*25mm, with epoxide resin AB structure glue by epoxidized soybean oil
The side of acrylate starch membrane material is sticked on aluminium sheet, and billet is sticked to the middle position of AESO starch membrane material another side, is used
Cotton swab dips the extra glue for overflowing and around billet, is placed for 24 hours at room temperature, starch membrane material is fixed on aluminium sheet.Lift
Quick coupling, the top of billet, which is passed through drawbench hole, connect it with quick coupling, after billet top connects, puts down fast
Quick coupling.It first returns to zero before test, pulling force is applied to billet by quick coupling, instrument starts to calculate display adhesive force, works as epoxy
When soybean oil acrylate coating takes off and is sticked on spindle from starch membrane material pull-up completely, the result of measurement is 100% effective.
2) test result is shown in Table 1.
From the data in table 1, it can be seen that with not plus compared with the coating starch film of interface modifier, the resulting waterproof starch film of embodiment
Interfacial adhesion significantly improve, it is prepared by the present invention to can be improved by the waterproof starch film of coating of epoxy soybean oil acrylate
Adhesion effect between coating and starch film matrix can effectively prevent being detached between waterproof coating and starch film.Probably due to not
It is physical absorption between epoxy soybean oil acrylate coating and starch membrane material, with faint model moral when interface modifier is added
Hua Li is connected, and there are apparent gaps between epoxy soybean oil acrylate coating and starch membrane material, therefore adhesive force is smaller.
After interface modifier is added, since the both ends of its molecule are logical with epoxy soybean oil acrylate coating and starch membrane material two-phase respectively
Too strong chemical bond connects, and forms compact two-phase interface connection type, and epoxy soybean oil acrylate coating applies
Gap between layer and starch membrane material disappears, and two-phase is combined closely, and increases the adhesive force of coating.
The influence of adhesive force between 1 different preventing water-starch film floating coat of table and starch film
3, product made from embodiment 1,2,3,4 and the starch film of non-coating, starch-epoxy soybean oil acrylate is total
Mixed film does not add the coating starch film of interface modifier to carry out mechanical performance and transparency measurement,
1) selection surface is used without breakage, uniformly the sample membrane material after equilibrium water conten according to national standard GB1302291
Test cut-off knife is cut into dumbbell shape batten (length and width of intermediate rectangular part is respectively 8mm, 2mm), using U.S. Instron
The ASTMD638 of company, 5566 type mechanical property testers select the mating 2422-003 air operated fixture of tester to measure.Ginseng
Number setting: rate of extension 10mm/min, the initial spacing 25mm of fixture.7 parallel tests measurement is carried out to each sample, is finally taken
Average value measures elongation at break (Elongation) and Young's modulus (Modulus).
2) smooth, smooth, flawless sample is chosen, the rectangular slat that specification is 30mm*10mm specification is cut into,
It is put into cuvette, sample is made to be close to cuvette inner wall.Using WFZ UV-3802 type ultraviolet specrophotometer, wavelength, which is arranged, is
600nm carries out transparency test to sample, and each sample does 3 groups of parallel tests.
3) test result is shown in Table 2.
From the data in table 2, it can be seen that compared with the starch film of non-coating, the elongation at break of the resulting waterproof starch film of embodiment
It significantly improving, Young's modulus slightly reduces, shows after epoxy soybean oil acrylate film binding interface modifier treatment,
The mechanical performance of starch film itself can be improved；Not plus the starch of the mechanical performance of the coating starch film of interface modifier and non-coating
Film it is suitable, and starch-epoxy soybean oil acrylate blend film mechanical performance decreases than the starch film of non-coating.In
During packaging applications, it is desirable that packaging film has certain flexibility, facilitates stretching, therefore improves the fracture elongation and drop of film
Low film Young's modulus is conducive to the application of waterproof starch film.
Compared with the starch film of non-coating, the transparency of the resulting waterproof starch film of embodiment increases, but does not add
The transparency of the coating starch film of interface modifier is slightly poorer than the starch film of non-coating；Starch-epoxy soybean oil acrylate is total
The transparency of mixed film is then worse.It may be epoxy soybean oil acrylate coating and starch membrane material when interface modifier not being added
Between poor adhesive force, there are apparent gap between epoxy soybean oil acrylate coating and starch membrane material, therefore increase light
Scattering, reduces the transmitance of light, to reduce the transparency of film.After interface modifier is added, due to the both ends of its molecule
It is connected respectively with epoxy soybean oil acrylate coating and starch membrane material two-phase by strong chemical bond, formation is tightly combined
Two-phase interface connection type, Adhesion enhancement reduces the dispersion of light so that the gap between two-phase disappears, increases the saturating of light
Rate is crossed, to improve the transparency of film.
It is prepared by the present invention to be provided with good mechanicalness by the waterproof starch film of coating of epoxy soybean oil acrylate
Energy and transparency, resultant effect are good.
The measuring mechanical property comparative situation of the different starch films of table 2
Note: transparence value is higher, indicates that the transparency of membrane material is lower
4, product made from embodiment 1,2,3,4 and the starch film of non-coating, starch-epoxy soybean oil acrylate is total
Mixed film does not add the coating starch film of interface modifier to carry out hindering wet measurement.
1) according to 1988 standard test method of national standard GB/T1037, using gravitational method with penetrability tester to sample into
Membrane material is prepared into the sample that diameter is 74mm with sampler by the measurement of row vapor water barriers performance, is added in moisture vapor transmission cup bottom
The sample membrane material of formulation circular rings are provided on moisture vapor transmission cup, side drying cylinder are taken out, in more creeling by 10ml distilled water
4A molecular sieve makes to test humid control in the range of 90% ± 2%RH, setup parameter: 38 DEG C of temperature, equilibration time 3h, surveying
Try area 33cm2, every class sample parallel testing 3 times, it is averaged.When observing and recording the steam tolerance of each sample simultaneously
Between, it is to terminate the time with film breakage.
2) weight percent after distilled water is immersed by measurement membrane material, and the water absorption rate of membrane material is assessed.In ring
At a temperature of border, membrane material sample (5 centimetres x5 centimetres) is put into the beaker equipped with 300ml distilled water (500ml), then with identical
Time interval sample is taken out, and with filter paper by the moisture of excess surface blot to weigh constant weight.Every class sample parallel testing 5
Secondary, the precision of balance is 0.01g, and water absorption rate is shown in following formula:
Water Absorption (%)=(Mt-M0)/M0×100
Wherein Mo and Mt is the weight of initial sample and the weight for being soaked for a period of time rear sample in water respectively.
3) test result is shown in Table 3.
The water-proof function test comparison situation of the different starch films of table 3
From the data in table 3, it can be seen that starch-epoxy soybean oil acrylate is blended film water and steams compared with the starch film of non-coating
Vapor permeability and water absorption rate decrease, and steam tolerance time extends；And pass through coating starch film moisture-vapor transmission and
Water absorption rate then further reduces, and steam tolerance time also further increases, and shows the mode of coating than directly mixing hydrophobicity
Substance is more effective.And after interface modifier is added in embodiment, steam tolerance time was even more to increase substantially, at 45~60 days
It is interior to be stabilized, not by moisture attacks.This is because when interface modifier not being added, epoxy soybean oil acrylate coating with
It is connected between starch membrane material by faint Van der Waals force, there are gap, hydrone is easy to penetrate into starch film two-phase interface
Material, and pass through strong covalent key connection after interface modifier is added, between epoxy soybean oil acrylate coating and starch membrane material,
Two-phase interface is completely embedded, and gap is not present, and hydrone is difficult to penetrate into starch membrane material.
Therefore had using prepared by the present invention using epoxy soybean oil acrylate as the waterproof starch film of coating significant
Waterproof effect, can be in food fresh keeping packaging process, and effective protection starch film is not by the water of external environment and food product inside generation
Vapour corrodes, and improves service life of waterproof starch film during packaging applications, while protecting interior packing food moisture itself
Reservation and influence from outside moisture.
To sum up, the present invention is prepared by using the mode of extrusion molding and light solidifying coating method combination interface modifying agent
Using epoxy soybean oil acrylate as the waterproof starch film of coating can solve current waterproof starch film be difficult to industrialized production and
Waterproof coating and hydrophilic starch membrane material easily occur mutually to separate and the problem of break-offs, while the waterproof that the present invention is prepared
Starch film is provided simultaneously with good mechanical performance, transparency, waterproof effect and adhesion effect, and comprehensive performance is good.These are good
Using effect and service life of the waterproof starch film prepared by the present invention during packaging applications can be improved in performance, protects simultaneously
The reservation of interior packing food moisture itself and influence from outside moisture, this will be helpful to the shelf for further increasing food
Phase.
The present invention is not constrained by above-described embodiment, and others are any to be made without departing from the spirit and principles of the present invention
Changes, modifications, substitutions, combinations, simplifications, should be equivalent alternative, be included within the scope of the present invention.
Claims (10)
1. a kind of using epoxy soybean oil acrylate as the waterproof starch film of coating, which is characterized in that be with full starch base membrane material
Sandwich layer forms epoxy soybean oil acrylate coating on sandwich layer two sides by the way of light solidifying coating combination interface modifying agent；
Wherein, the epoxy soybean oil acrylate coating is by epoxy soybean oil acrylate, photoinitiator, interface modifier molten
It is prepared into photocuring solution in agent, surface covering: photocuring solution being coated on starch film layer and is formed；By epoxidized soybean oil propylene
Acid esters, photoinitiator, interface modifier account for respectively photocuring solution materials quality 5~30wt%, 2~7wt% and 1~
6wt%；
The interface modifier is one of KH550, KH560, KH570, KH792, DL602 and DL171 or a variety of.
2. according to claim 1 using epoxy soybean oil acrylate as the waterproof starch film of coating, which is characterized in that institute
The starch stated is one of ative starch or a variety of；The ative starch is tapioca, potato starch, wheaten starch and corn
Starch；Either the starch is one of converted starch or a variety of；The converted starch is that hydroxypropyl is corn modified
Starch, esterification starch, oxidized starch, denaturated starch by acid, etherification starch, crosslinked starch, cationic starch, connects carboxymethyl starch
Branch starch and dialdehyde starch.
3. according to claim 1 using epoxy soybean oil acrylate as the waterproof starch film of coating, which is characterized in that institute
The photoinitiator stated is one of Irgacure819, TEPO, TPO, TPO-L, 184,1173, benzophenone or a variety of.
4. according to claim 1 using epoxy soybean oil acrylate as the waterproof starch film of coating, which is characterized in that institute
The full starch base membrane material stated is prepared using double screw extruder and chip mold extrusion.
5. according to claim 1 using epoxy soybean oil acrylate as the waterproof starch film of coating, which is characterized in that institute
The sandwich layer stated with a thickness of 0.1~0.5mm.
6. according to claim 1 using epoxy soybean oil acrylate as the waterproof starch film of coating, which is characterized in that institute
The two-sided overall thickness for the epoxy soybean oil acrylate coating stated is 2~10 μm.
7. described in any one of claims 1-6 using epoxy soybean oil acrylate as the preparation side of the waterproof starch film of coating
Method, it is characterised in that the following steps are included:
1) preparation of full starch base membrane material；
2) photocuring solution is configured: in a solvent by the dissolution of epoxy soybean oil acrylate, photoinitiator and interface modifier, In
It stirs evenly at room temperature, is prepared into photocuring solution；
3) surface covering: the photocuring solution system is coated in the full starch base membrane material, is placed, is made photocuring
Solution is evenly dispersed on starch membrane material surface, and the starch film containing photocuring solution surface layer is put and exposed under ultraviolet light by exhaust
Light is made comprising using epoxy soybean oil acrylate as the waterproof starch film of coating.
8. it is according to claim 1 using epoxy soybean oil acrylate as the preparation method of the waterproof starch film of coating,
It being characterized in that, the preparation of the full starch base membrane material is squeezed out using screw extruder and chip mold is made starch base membrane material,
Gained starch membrane material is adjusted under 57% relative humidities, reaches water balance, is then cleaned with ethyl acetate solution
The dust on starch membrane material surface, drying for standby.
9. it is according to claim 1 using epoxy soybean oil acrylate as the preparation method of the waterproof starch film of coating,
It is characterized in that, the solvent is ethyl acetate；The stirring is magnetic agitation, and the time of stirring is 1.5~3h.
10. it is according to claim 1 using epoxy soybean oil acrylate as the preparation method of the waterproof starch film of coating,
It is characterized in that, described is applied to rotary coating or dip-coating；15~30 DEG C of the temperature of the placement, humidity be 40%~
65%, the time of placement is 1~2h；The ultraviolet light emission wavelength be 254nm, light application time be 5~12min, illumination away from
From for 10~20cm.
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