CN103881230A - Nano composite polyethylene film as well as preparation method and application thereof - Google Patents
Nano composite polyethylene film as well as preparation method and application thereof Download PDFInfo
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- CN103881230A CN103881230A CN201410112767.3A CN201410112767A CN103881230A CN 103881230 A CN103881230 A CN 103881230A CN 201410112767 A CN201410112767 A CN 201410112767A CN 103881230 A CN103881230 A CN 103881230A
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- 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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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The invention discloses a nano composite polyethylene film as well as a preparation method and an application of the film. The preparation method comprises the following steps: (1) modifying TiO2 nano powder by using a titanate coupling agent to prepare modified TiO2 nano powder; (2) mixing and pelleting the modified TiO2 nano powder with low-density polyethylene; (3) extruding to form the nano composite polyethylene film. As the nano composite polyethylene film is prepared by modifying TiO2 nano powder by using the titanate coupling agent, subsequently mixing the modified TiO2 nano powder with the low-density polyethylene, pelleting twice and subsequently extruding, the process is simple, and the nano composite polyethylene film is good in strength, rigidity and toughness, can remarkably slow the degrading velocity of quality of penaeus vanmamei, and can prolong the expiration date in market.
Description
Technical field
The invention belongs to food fresh keeping material technology field, be specifically related to a kind of nano combined polyethylene film and its preparation method and application.
Background technology
Penaeus vannamei originates in pacific waters, South America, and early 1990s starts to introduce cultivation in China.Penaeus vannamei is subject to human consumer's welcome deeply because of the tender feature such as delicious and moderate of the thin body fertilizer of its shell, meat.But Penaeus vannamei belongs to perishable foodstuff, fishing for, transport, be very easily subject to bacteria attack in processing and storage and putrid and deteriorated, particularly after its death, under the effect of enzyme, carry out anaerobic degradation, along with the minimizing of glycogen and ATP, shrimp body starts hardening, and enter very soon the stiff phase, after the ATP in body has decomposed, shrimp becomes branch further to degrade, until putrid and deteriorated.In addition, in shrimp body, there is a large amount of polyphenoloxidase, can make shrimp surface produce bisphenol, and then be transformed into coloured quinones substance, and quinones substance has higher activity, very easily become melanochrome with amino acid or protein bound, thereby cause the black change of shrimp.
At present, the fresh keeping method of shrimps has ultra-violet sterilization, ozonize, sterilization by irradiation and adopts biological preservation agent solution fresh-keeping, but UV radiation technology for sterilization is generally surface disinfection, is limited in scope and has sterilization dead angle; Ozone technology price is higher, and has oxidisability easily to make by force sample decolouring; The dosage of the lethal microorganism of sterilization by irradiation is higher concerning operator, and security is low; Bio-preservative easily produces chemical residual, and food and environment are easily produced to pollution, and the fresh-keeping effect of these technology prawns is undesirable.
Publication number is the fresh keeping method that the patent documentation of CN102940300A discloses a kind of Penaeus vannamei, comprising: using sodium chloride solution as ionogen, electrolysis makes acidic electrolytic water, freezing and pulverizing, then Penaeus vannamei is laid on acidic electrolytic water trash ice.By the effective chlorine density of the low temperature of acidic electrolysis water-ice itself, low pH value and certain content, slow down the exogenous microbial growth in Penaeus vannamei surface, thereby play the storage time that extends Penaeus vannamei.Although the method can extend the storage time of Penaeus vannamei effectively, due to the existence of sodium-chlor, can destroy the original quality of white shrimp.
In order to extend the storage time of Penaeus vannamei, and farthest retain the original quality of Penaeus vannamei, after generally Penaeus vannamei being packed by wrapping material in prior art, carry out low temperature storage, the combination by packaging with refrigeration, plays freshening effect.
Interfacial effect, volume effect, quantum effect and macro quanta tunnel effect etc. that nano packaging material causes because of its quantum size, make polymer nanocomposites present the characteristic that is much different from general polymer matrix material, nanoparticle not only makes intensity, rigidity and the toughness of polymkeric substance significantly improve, and because its size is little, light transmission is good, there is property at aspects such as increasing matrix density, raising matrix light transmission, barrier, thermotolerance and resistance to deterioration, therefore have potential application widely in each field.
Summary of the invention
The invention provides a kind of preparation method of nano combined polyethylene film, the polyethylene film that the method makes can carry out Penaeus vannamei effectively fresh-keeping.
A preparation method for nano combined polyethylene film, comprises the following steps:
(1) adopt titanate coupling agent to TiO
2nanometer powder carries out modification, makes modification TiO
2nanometer powder;
(2) by modification TiO
2nanometer powder mixes with Low Density Polyethylene, granulation;
(3) extrusion molding makes described nano combined polyethylene film.
Described modification comprises:
(1) titanate coupling agent is added in solvent, regulate pH to 4～5, make metatitanic acid coupling agent solution;
(2) by TiO
2nanometer powder adds in titanate coupling agent solution, after having reacted except desolventizing, reaction product through vacuum-drying, pulverize, sieve, make described modification TiO
2nanometer powder.
Preferably, described solvent is the mixed solvent being made up of the third alcohol and water, also can select other solvent, and titanate coupling agent can disperse.
Preferably, the weight percent concentration of described titanate coupling agent solution is 20～30%.
Preferably, described TiO
2nanometer powder add-on is 10～20% of titanate coupling agent solution weight.
Preferably, temperature of reaction is controlled at 70～90 DEG C, and the reaction times is 50～60min, between the reaction period, stirs, and reacts fully.
Preferably, the described method except desolventizing is for revolving steaming, and temperature is controlled at 70～90 DEG C equally, utilizes ultrasonic can quickening to volatilize.
Preferably, described granulation comprises:
(1) by modification TiO
2nanometer powder mixes with Low Density Polyethylene, and granulation for the first time obtains one time master batch;
(2) master batch is mixed with Low Density Polyethylene, granulation for the second time, obtains secondary master batch;
Preferably, described modification TiO
2the weight percent that nanometer powder accounts for all raw materials is 1～2%.
The nano combined polyethylene film that the present invention also provides described preparation method to make.
Preferably, the thickness of described nano combined polyethylene film is 38～42 μ m.
The present invention provides again the application of nano combined polyethylene film in Penaeus vannamei is fresh-keeping.
Preferably, comprising: Penaeus vannamei is placed in to frozen water lethal, after cleaning drains, is placed in the packing bag that described nano combined polyethylene film is prepared from, after vacuum packaging, refrigerate.
Penaeus vannamei is carried out fresh-keeping by packaging and the composite fresh-keeping mode of refrigeration, nano combined polyethylene film of the present invention can play good freshening effect, makes the shelf life extension of Penaeus vannamei, and keeps good integrated quality.
In order to make Penaeus vannamei keep good texture characteristic, as preferably, the time of described Penaeus vannamei in frozen water is 15～20min.
In draining, owing to just taking out, if difference variation is too large, will destroy the texture characteristic of Penaeus vannamei from frozen water, as preferably, described Penaeus vannamei drains at 2～6 DEG C.
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) the present invention by titanate coupling agent to TiO
2nanometer is carried out modification, and then by the TiO after modification
2nanometer powder mixes with Low Density Polyethylene, prepares nano combined polyethylene film by extruding after secondary granulation, and technique is simple, and nano combined polyethylene film has good strength, rigidity and toughness.
(2) nano combined polyethylene film of the present invention is applied to the fresh-keeping packaging material of Penaeus vannamei, compares existing ldpe film wrapping material, and these wrapping material can significantly slow down the fall off rate of Penaeus vannamei quality, extends the shelf quality guaranteed period.
Brief description of the drawings
Fig. 1 is the impacts of the nano combined polyethylene film wrapping material of embodiment 1 on Penaeus vannamei sensory evaluation scores.
Fig. 2 is the impacts of the nano combined polyethylene film wrapping material of embodiment 1 on the black varying index of Penaeus vannamei.
Fig. 3 is the impacts of the nano combined polyethylene film wrapping material of embodiment 1 on Penaeus vannamei whiteness.
Fig. 4 is the impacts of the nano combined polyethylene film wrapping material of embodiment 1 on Penaeus vannamei texture characteristic.
Fig. 5 is the impacts of the nano combined polyethylene film wrapping material of embodiment 1 on Penaeus vannamei pH value.
Fig. 6 is the impacts of the nano combined polyethylene film wrapping material of embodiment 1 on Penaeus vannamei PPO enzymic activity.
Embodiment
Embodiment 1
(1) TiO
2the modification of nanometer
20: 72: 8 by titanate coupling agent (NDZ-201 in mass ratio, Nanjing Dao Ning Chemical Co., Ltd.): Virahol (analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group) and water mix, use again acetic acid (analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group) adjusting pH to 4～5, ultrasonic hydrolysis 15min, prepares metatitanic acid coupling agent solution.The modification TiO that titanate coupling agent solution quality per-cent is 10% will be accounted for
2nanometer (anatase titanium dioxide, particle diameter 40nm, Aladdin reagent company limited) be added among metatitanic acid coupling agent solution, at 80 DEG C of high-speed stirring 50min, 80 DEG C of ultrasonic volatilization 30min, revolve and steam isopropyl alcohol and water, and in 80 DEG C of vacuum drying ovens dry 12h, finally by pulverizer pulverize, sieving obtains modification TiO
2particle.
(2) preparation of nano combined polyethylene film
By above-mentioned modification TiO
2nanoparticle and Low Density Polyethylene (2426K, Sinopec Maoming branch office) in high-speed mixer, first mix 0.5h, then obtain master batch one time by twin screw extruder extruding pelletization, test conditions is set as follows: screw speed is 300r/min, be followed successively by 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C by feed end to four sections of temperature of die head, input speed is controlled at 1.5kg/h left and right.A master batch is mixed with Low Density Polyethylene in 1% ratio again, carry out secondary granulation, making containing massfraction is 1% modification TiO
2the secondary master batch of nanometer, secondary master batch is extruded to casting film-forming through single screw extrusion machine, test conditions is set as follows: screw speed is 40r/min, be followed successively by 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C by feed end to four sections of temperature of die head, be followed successively by 50r/min, 60r/min, 70r/min, 100r/min, 100r/min, 100r/min by near-lying mode head end to the deflector roll rotating speed away from die end, adding heated godet roll temperature is 90 DEG C, and take off roll rotating speed is 30r/min.The modification TiO making
2nano combined polyethylene film thickness is 40 ± 2 μ m, finally makes 20 × 18cm Penaeus vannamei modification TiO
2nano combined polyethylene packaging bag.
(3) experiment material
Choose the long and uniform Penaeus vannamei of body weight of body as experiment material, average quality 13.2g, it is fresh that vivaciously a body closely connects, and shrimp shell is without breakage, and shrimp is flexible not dryly to feel like jelly.
(4) packaging application
Choose 120 Penaeus vannameis, be immersed in frozen water 18min lethal, after cleaning, drain 12min in 4 DEG C.Average mark packs 6 ldpe film bags (control group) and above-mentioned modification TiO into
220 × 18cm modification TiO that nano combined polyethylene film is made
2in nano combined polyethylene packaging bag, after pack, use Vacuum Packaging Machine vacuum-pumping and sealing, storage at 4 DEG C.
Result shows, uses modification TiO of the present invention
2nano combined polyethylene packaging bag can effectively slow down the speed that after death Penaeus vannamei quality declines.The most obvious in the 6th day effect of storage, control group process Penaeus vannamei rotten corruption cannot eat, and Penaeus vannamei in nano packaging material group of the present invention is also in commodity sense organ tolerance interval, Shelf-life 30h.Specifically also can show, preserve after 8 days, nano-packaging Penaeus vannamei sensory evaluation scores is higher than contrast 31.2%, and black varying index is only contrast 68.0%, obvious difference.Whiteness is higher than contrast 6%, and hardness, elasticity, coherency, colloidality, chewiness, recovery are respectively 1.40,1.27,1.09,1.52,1.92,1.19 times of contrast.In addition modification TiO,
2the Penaeus vannamei retentiveness of nano combined polyethylene packaging bag is higher by 12.9% than control group, and pH value is low by 3.0%.PPO enzyme has participated in black change reaction, and modification TiO
2in Penaeus vannamei in nano combined polyethylene packaging bag, PPO enzymic activity is less than 85.0% of control group.
(1) TiO
2the modification of nanometer
20: 72: 8 by titanate coupling agent (NDZ-201 in mass ratio, Nanjing Dao Ning Chemical Co., Ltd.): Virahol (analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group) and water mix, use again acetic acid (analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group) adjusting pH to 4～5, ultrasonic hydrolysis 15min, prepares metatitanic acid coupling agent solution.The modification TiO that titanate coupling agent solution quality per-cent is 20% will be accounted for
2nanometer (anatase titanium dioxide, particle diameter 40nm, Aladdin reagent company limited) be added among metatitanic acid coupling agent solution, at 90 DEG C of high-speed stirring 60min, 80 DEG C of ultrasonic volatilization 30min, revolve and steam isopropyl alcohol and water, and in 80 DEG C of vacuum drying ovens dry 12h, finally by pulverizer pulverize, sieving obtains modification TiO
2particle.
(2) preparation of nano combined polyethylene film
By above-mentioned modification TiO
2nanoparticle and Low Density Polyethylene (2426K, Sinopec Maoming branch office) in high-speed mixer, first mix 0.5h, then obtain master batch one time by twin screw extruder extruding pelletization, test conditions is set as follows: screw speed is 300r/min, be followed successively by 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C by feed end to four sections of temperature of die head, input speed is controlled at 1.5kg/h left and right.A master batch is mixed with Low Density Polyethylene in 2% ratio again, carry out secondary granulation, making containing massfraction is 2% modification TiO
2the secondary master batch of nanometer, secondary master batch is extruded to casting film-forming through single screw extrusion machine, test conditions is set as follows: screw speed is 40r/min, be followed successively by 200 DEG C, 200 DEG C, 200 DEG C, 210 DEG C by feed end to four sections of temperature of die head, be followed successively by 50r/min, 60r/min, 70r/min, 100r/min, 100r/min, 100r/min by near-lying mode head end to the deflector roll rotating speed away from die end, adding heated godet roll temperature is 90 DEG C, and take off roll rotating speed is 30r/min.The modification TiO making
2nano combined polyethylene film thickness is 40 ± 2 μ m, finally makes 20 × 18cm Penaeus vannamei modification TiO
2nano combined polyethylene packaging bag.
(3) experiment material
Choose the long and uniform Penaeus vannamei of body weight of body as experiment material, average quality 13.2g, it is fresh that vivaciously a body closely connects, and shrimp shell is without breakage, and shrimp is flexible not dryly to feel like jelly.
(4) packaging application
Choose 120 Penaeus vannameis, be immersed in frozen water 15min lethal, after cleaning, drain 12min in 4 DEG C.Average mark packs 6 ldpe film bags (control group) and above-mentioned modification TiO into
220 × 18cm modification TiO that nano combined polyethylene film is made
2in nano combined polyethylene packaging bag, after pack, use Vacuum Packaging Machine vacuum-pumping and sealing, storage at 4 DEG C.
Result shows, uses modification TiO of the present invention
2nano combined polyethylene packaging bag can effectively slow down the speed that after death Penaeus vannamei quality declines.The most obvious in the 5th day effect of storage, control group process Penaeus vannamei rotten corruption cannot eat, and Penaeus vannamei in nano packaging material group of the present invention is also in commodity sense organ tolerance interval, Shelf-life 35h.Preserve after 8 days, nano-packaging Penaeus vannamei sensory evaluation scores is higher than contrast 36.3%, and black varying index is only contrast 57.2%, obvious difference.Whiteness is higher than contrast 7.3%, and hardness, elasticity, coherency, colloidality, chewiness, recovery are respectively 1.37,1.23,1.12,1.60,1.99,1.21 times of contrast.In addition modification TiO,
2the Penaeus vannamei retentiveness of nano combined polyethylene packaging bag is higher by 17.3% than control group, and pH value is low by 3.1%.PPO enzyme has participated in black change reaction, and modification TiO
2in Penaeus vannamei in nano combined polyethylene packaging bag, PPO enzymic activity is less than 77.1% of control group.
Claims (9)
1. a preparation method for nano combined polyethylene film, is characterized in that, comprises the following steps:
(1) adopt titanate coupling agent to TiO
2nanometer powder carries out modification, makes modification TiO
2nanometer powder;
(2) by modification TiO
2nanometer powder mixes with Low Density Polyethylene, granulation;
(3) extrusion molding makes described nano combined polyethylene film.
2. the preparation method of nano combined polyethylene film as claimed in claim 1, is characterized in that, described modification comprises:
(1) titanate coupling agent is added in solvent, regulate pH to 4～5, make metatitanic acid coupling agent solution;
(2) by TiO
2nanometer powder adds in titanate coupling agent solution, after having reacted except desolventizing, reaction product through vacuum-drying, pulverize, sieve, make described modification TiO
2nanometer powder.
3. the preparation method of nano combined polyethylene film as claimed in claim 2, is characterized in that, described TiO
2nanometer powder add-on is 10～20% of titanate coupling agent solution weight.
4. the preparation method of nano combined polyethylene film as claimed in claim 2, is characterized in that, described heated and stirred temperature is 70～90 DEG C, and the time is 50～60min.
5. the preparation method of nano combined polyethylene film as claimed in claim 2, is characterized in that, the described method except desolventizing is for revolving steaming.
6. the preparation method of nano combined polyethylene film as claimed in claim 1, is characterized in that, described granulation comprises:
(1) by modification TiO
2nanometer powder mixes with Low Density Polyethylene, and granulation for the first time obtains one time master batch;
(2) master batch is mixed with Low Density Polyethylene, granulation for the second time, obtains secondary master batch.
7. the preparation method of nano combined polyethylene film as claimed in claim 1, is characterized in that, described modification TiO
2the weight percent that nanometer powder accounts for all raw materials is 1～2%.
8. the nano combined polyethylene film that as described in as arbitrary in claim 1～7, preparation method makes.
9. the application of nano combined polyethylene film in Penaeus vannamei is fresh-keeping as claimed in claim 8.
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| CN201410112767.3A CN103881230A (en) | 2014-03-25 | 2014-03-25 | Nano composite polyethylene film as well as preparation method and application thereof |
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| CN201410112767.3A CN103881230A (en) | 2014-03-25 | 2014-03-25 | Nano composite polyethylene film as well as preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524332A (en) * | 2016-02-03 | 2016-04-27 | 河北麦森钛白粉有限公司 | Production process of fresh-keeping film based on titanium dioxide |
| CN107955252A (en) * | 2017-12-05 | 2018-04-24 | 苏州市农业科学院 | A kind of nanometer fruits and vegetables antifog film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467245A (en) * | 2002-07-08 | 2004-01-14 | 北京崇高纳米科技有限公司 | Fruit and vegetable fresh-keeping plastic film and method for making the same |
| CN102875868A (en) * | 2012-09-11 | 2013-01-16 | 大连巨峰包装制品有限公司 | Method for preparing food fresh-keeping film |
-
2014
- 2014-03-25 CN CN201410112767.3A patent/CN103881230A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467245A (en) * | 2002-07-08 | 2004-01-14 | 北京崇高纳米科技有限公司 | Fruit and vegetable fresh-keeping plastic film and method for making the same |
| CN102875868A (en) * | 2012-09-11 | 2013-01-16 | 大连巨峰包装制品有限公司 | Method for preparing food fresh-keeping film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524332A (en) * | 2016-02-03 | 2016-04-27 | 河北麦森钛白粉有限公司 | Production process of fresh-keeping film based on titanium dioxide |
| CN107955252A (en) * | 2017-12-05 | 2018-04-24 | 苏州市农业科学院 | A kind of nanometer fruits and vegetables antifog film and preparation method thereof |
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Application publication date: 20140625 |