CN110328942A - Antistatic crosslinking heat shrink films of one kind and preparation method thereof - Google Patents
Antistatic crosslinking heat shrink films of one kind and preparation method thereof Download PDFInfo
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- CN110328942A CN110328942A CN201910737817.XA CN201910737817A CN110328942A CN 110328942 A CN110328942 A CN 110328942A CN 201910737817 A CN201910737817 A CN 201910737817A CN 110328942 A CN110328942 A CN 110328942A
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- antistatic
- heat shrink
- crosslinking
- shrink films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/001—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore a shaping technique combined with cutting, e.g. in parts or slices combined with rearranging and joining the cut parts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/21—Anti-static
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention discloses a kind of antistatic crosslinking heat shrink films, including outer layer, middle layer and the internal layer set gradually, the internal layer and outer layer weight percent include following components: 70~85% polyethylene, 10~20% modified poly ethylene, 1~5% antiblocking agent, 1~10% slipping agent, 1~5% antistatic agent, the polyethylene is low density polyethylene (LDPE), at least one of ultra-low density polyethylene and metallocene low density polyethylene (LDPE).It is compounded to obtain antistatic agent using surfactant antistatic agent and hydrophilic macromolecule antistatic agent, the lipophilic group of surfactant antistatic agent is in conjunction with low density polyethylene (LDPE), hydrophilic group then forms conductive layer on crosslinking heat shrink films surface, reduce the resistance of film surface, accelerate the release of its static charge inside, the coefficient of friction on crosslinking heat shrink films surface can also be reduced simultaneously, reduce and inhibit the generation of charge.The hydrophilic macromolecule antistatic agent of addition further increases the antistatic effect on crosslinking heat shrink films surface.
Description
Technical field
The present invention relates to heat-shrinkable film technology fields, more particularly to a kind of antistatic crosslinking heat shrink films and its preparation side
Method.
Background technique
Heat shrink films have preferable glossiness, tear-resistant effect, are widely used in food, daily as packaging material
The fields such as product, cosmetics, in addition to this, heat shrink films are also used as the surface that label is adhered to container, play products Presentation
The effect of information and brand promotion；Heat shrink films can also be used as the protective film of product, protection in various industrial circles simultaneously
Product is from the pollution and the infringement such as corrosion in transport, storage and process.
Existing heat shrink films are carrying out printing as packaging material and in use, electrostatic can be generated due to friction, and quiet
The adhesion of electricity is in anaerobic condition between acting on the layer structure that can make heat cross-linking film, and barrier prints the solidification and leaching of layer of ink internally
Dye causes the pattern dizzy dye of printing or falls off.When the electrification of the surface of heat shrink films, lesser paper scrap or floating can be adsorbed
Aerial dust and impurity, when as packaging material, the small impurity in this part will affect the heat sealability of packaging material
Can, and it is attached to the surface of packaging material, affect the displaying of content.In addition, in the process of heat shrink films, it is quiet
Electro ultrafiltration will lead to stick to each other between film, increase the difficulty of the processes such as trimming, winding and printing.
Summary of the invention
The main object of the present invention is to propose a kind of antistatic crosslinking heat shrink films, it is intended to solve existing heat shrink films and not have
There is antistatic property to lead to printed patterns dizzy dye or failure, absorption dust is easy when using as packaging material influences packaging
The technical issues of bag content is shown.
To achieve the above object, the present invention proposes a kind of antistatic crosslinking heat shrink films, including set gradually outer layer, in
Interbed and internal layer, the internal layer and outer layer weight percent include following components: 70~85% polyethylene, 10~20%
Modified poly ethylene, 1~5% antiblocking agent, 1~10% slipping agent, 1~5% antistatic agent；
The polyethylene is low density polyethylene (LDPE), at least one in ultra-low density polyethylene and metallocene low density polyethylene (LDPE)
Kind.
Preferably, the antistatic agent by surfactant antistatic agent and hydrophilic macromolecule antistatic agent compounding and
At, by weight percentage, the surfactant antistatic agent: the hydrophilic macromolecule antistatic agent=(0.5~3):
1。
Preferably, the surfactant antistatic agent is dodecyl diethanol amine, lauric acid diethanol amine, polyoxy second
Allylic alkylation amine, alkyl phenol, ethylene oxide sulfuric acid, polyol esters of fatty acids, at least one of organic phosphorus compound；The parent
Aqueous high molecular antistatic agent is polyether block amide analog copolymer, salt copolymer in carbonylation quaternary ammonium carboxylic acid, macromolecule transfevent
Bonding body, polyethylene glycol Copolymer polyamide, at least one of superhigh molecular weight polyethylene glycol.
Preferably, the middle layer weight percent includes following components: 80~95% polyethylene, 1~10%
Slipping agent, 1~10% cross-linked evocating agent.
Preferably, it is described it is antistatic crosslinking heat shrink films with a thickness of 10~35 μm.
The present invention also proposes a kind of preparation method of antistatic crosslinking heat shrink films as described in any of the above-described, including following
Step: outer layer, middle layer and internal layer raw material are uniformly mixed by mixing respectively by weight percentage；Plasticizing squeeze out, by outer layer, in
Interbed and internal layer raw material are separately added into extruder fusion plastification and obtain melt, and the melt enters co-extrusion die head co-extrusion and closes layer；One
Secondary inflation, the melt after layer is closed to co-extrusion are inflated to obtain film bubble, then carry out cooling and shaping and form membrane tube；Electron irradiation crosslinking, will
Membrane tube draws to electron irradiation crosslinking apparatus and generates activation crosslinking；Preheating, the membrane tube after crosslinking Treatment is carried out using baking oven
Preheating；Secondary inflation, the membrane tube after preheating carry out biaxial tension, are formed after stretching by vane cooling and shaping thin
Film；Post-processing carries out annealing and cooling treatment to the film, and the antistatic crosslinking is obtained after trimming is wound and is heat-shrinked
Film.
Preferably, it includes three-level vane that the vane is cooling, and first order vane air quantity is 1000~2000m3/ h, the second level
Vane air quantity is 1000~2000m3/ h, third level vane air quantity are 600~800m3/h。
Preferably, in described " membrane tube after preheating the carries out biaxial tension " step, transverse stretch ratio is 4.0~6.5,
Longitudinal stretching multiple is 4.8~6.8.
Preferably, in described " carrying out annealing and cooling treatment to the film " step, annealing temperature is 40 DEG C~80 DEG C,
Cooling temperature is 10 DEG C~30 DEG C.
Preferably, described " outer layer, middle layer and internal layer raw material are separately added into extruder fusion plastification and obtain melt, institute
State melt and enter co-extrusion die head co-extrusion and close layer " in step, the extruder includes three heated zones, feeding section 150~170
DEG C, melt 165~185 DEG C of section, 180~200 DEG C of homogenizing zone；The co-extrusion die head includes four heated zones, the heating zone
The temperature of section is equal are as follows: 180~200 DEG C.
This technology advantageous effect of the invention:
1. being compounded to obtain antistatic agent, table using surfactant antistatic agent and hydrophilic macromolecule antistatic agent
For the lipophilic group of face activating agent antistatic agent in conjunction with low density polyethylene (LDPE), hydrophilic group then forms conduction on crosslinking heat shrink films surface
Layer, reduces the resistance of film surface, accelerates the release of its static charge inside, while can also reduce rubbing for crosslinking heat shrink films surface
Coefficient is wiped, to reduce and inhibit the generation of charge.The hydrophilic macromolecule antistatic agent of addition further increases crosslinking heat and receives
The antistatic effect of contracting film surface can be conducted and be discharged by ionic conduction and be crosslinked since its molecular weight locomitivity is stronger
The electrostatic charge that heat shrink films generate, in addition hydrophilic macromolecule antistatic agent is on crosslinking heat shrink films surface in small stratiform point
Cloth is formed " shell-and-core structure ", reveals electrostatic charge as access, affected by environment smaller, be can be further improved crosslinking heat and is received
The antistatic effect of contracting film.
2. forming periosteum by using the film bubble cooling and shaping of an inflation, periosteum carries out electron irradiation, the film after crosslinking
Secondary inflation is carried out after pipe preheating and starts biaxial tension.The present invention carries out electron irradiation to the periosteum after an inflation, has
The degree of cross linking for improving to effect periosteum linear molecule chain, ensure that and be cross-linked with each other between outer layer, middle layer and internal layer, improve crosslinking
Secondary inflation molding is carried out after degree again, so that prepared antifog crosslinking heat shrink films not only have good thermal contraction performance,
And improve antifog crosslinking and be heat-shrinked film strength and mechanical performance, avoid easy delamination, be easily punctured, feel is partially hard, appearance
The problems such as easily slack and undisciplined.
3. passing through the cooling effect of three-level vane, it is ensured that the uniform thickness of antistatic crosslinking heat shrink films and preferable heat
Shrinking percentage, the air quantity of first order vane are 1000~2000m3/ h, using unheated air as cooling medium, to membrane tube play with
Cooling effect, makes the membrane tube by biaxial tension have preferable toughness, and second level vane and third level vane use low temperature
Gas is cooled down, and wherein the air quantity of second level vane is relatively large, is carried out Quench to membrane tube using cryogenic gas, is further mentioned
The percent thermal shrinkage of height crosslinking heat shrink films.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without creative efforts belongs to what the present invention protected
Range.
It is to be appreciated that if relating to directionality instruction (such as up, down, left, right, before and after ...) in the embodiment of the present invention,
Then directionality instruction is only used for explaining relative positional relationship, motion conditions etc. between component each under a certain particular pose,
If the particular pose changes, directionality instruction is also correspondingly changed correspondingly.
In addition, being somebody's turn to do " first ", " second " etc. if relating to the description of " first ", " second " etc. in the embodiment of the present invention
Description be used for description purposes only, be not understood to indicate or imply its relative importance or implicitly indicate indicated skill
The quantity of art feature." first " is defined as a result, the feature of " second " can explicitly or implicitly include at least one spy
Sign.It in addition, the technical solution between each embodiment can be combined with each other, but must be with those of ordinary skill in the art's energy
It is enough realize based on, will be understood that the knot of this technical solution when conflicting or cannot achieve when occurs in the combination of technical solution
Conjunction is not present, also not the present invention claims protection scope within.
The present invention proposes a kind of antistatic crosslinking heat shrink films, can be used as packaging material and carries out using thermal contraction performance
Preferably, while also there is good antistatic effect.
In an embodiment of the present invention, a kind of antistatic crosslinking heat shrink films, including set gradually outer layer, middle layer and
Internal layer, the internal layer and outer layer weight percent include following components: 70~85% polyethylene, 10~20% modification it is poly-
Ethylene, 1~5% antiblocking agent, 1~10% slipping agent, 1~5% antistatic agent；The polyethylene is low density polyethylene
Alkene, at least one of ultra-low density polyethylene and metallocene low density polyethylene (LDPE).
Specifically, the density range of polyethylene is 0.910~0.925g/cm3, molecular structure be on main chain with it is long,
The branched chain type molecule of short difference branch, has lower crystallinity and softening point (108 DEG C~126 DEG C), polyethylene is as crosslinking
The basis material of heat shrink films makes the crosslinking heat shrink films to complete have preferable intensity, the transparency and moisture resistance, guarantees
Its longer service life, and flexibility can also be increased, it is easy to process in production.Weight percent is 10~20%
Modified poly ethylene is then boundary strength, resistance to ag(e)ing and the heat resistance etc. in order to improve crosslinking heat shrink films, is heat-shrinked crosslinking
Film can adhere to more secured, service life extension when using as label material with product.Modified poly ethylene is specially third
Olefin(e) acid Grafted Polyethylene, the anhydride grafting modified polyethylene of horse Lay etc..
Antiblocking agent is specially silicone antiblocking agent, the mutual not phase of remaining component of silicone antiblocking agent and crosslinking heat shrink films
Molten, after internal layer raw material film forming, silicone antiblocking agent forms many hard knurs or micro-crack on the surface of inner layer material,
Make the inner layer material for being crosslinked heat shrink films that there is more coarse surface, to prevent it viscous with equipment in process
Even, wrapup procedure is more smooth, reduces the generation of crosslinking heat shrink films surface folding, the crosslinking heat shrink films that simultaneous processing is completed
Product is also not easy to stick together with other substances in storage and transportational process.1~10% slipping agent, which is added, can make crosslinking heat
The smooth effect in the surface of shrink film is preferable, while film surface has lower coefficient of friction, prevents raw material from melting in an extruder
When need electric current to be offered excessive, reduce production cost.The addition of antistatic agent can make to be crosslinked heat shrink films with preferable anti-
Electrostatic efficiency, the resistance of film surface is less than 1012 Ω cm, and interior layer component is in a molten state when processing, and antistatic agent molecule exists
The interface of interior layer component and process equipment forms orientations, and wherein lipophilic group is stretched to towards the inside of interior layer component, hydrophilic group
The outside of interior layer component, after the completion of solidification, the hydrophilic group in antistatic agent molecule is all located at air side, forms a unimolecule
Conductive layer has preferable antistatic effect.Additional amount is not to be exceeded 5%, otherwise can be precipitated on the surface of crosslinking heat shrink films
Lead to degradation.
Specifically, the antistatic agent by surfactant antistatic agent and hydrophilic macromolecule antistatic agent compounding and
At, by weight percentage, the surfactant antistatic agent: the hydrophilic macromolecule antistatic agent=(0.5~3):
1。
The lipophilic group of surfactant antistatic agent is in conjunction with low density polyethylene (LDPE), and hydrophilic group is then in crosslinking heat shrink films table
Face forms conductive layer, reduces the resistance of film surface, accelerates the release of its static charge inside, while can also reduce crosslinking and be heat-shrinked
The coefficient of friction of film surface, to reduce and inhibit the generation of charge.But it is located at the surfactant of crosslinking heat shrink films outer layer
Antistatic agent can be consumed constantly, the surfactant antistatic agent for causing it internal from the internal migrations of crosslinking heat shrink films not
In time, the antistatic effect for being crosslinked heat shrink films is influenced.Therefore, when adding surfactant antistatic agent, portion can be added
Divide hydrophilic macromolecule antistatic agent, further increases the antistatic effect on crosslinking heat shrink films surface.Hydrophilic macromolecule is anti-
After electrostatic agent is blended with low-density polyethylene body, since its molecular weight locomitivity is stronger, it can be conducted by ionic conduction
The electrostatic charge generated with release crosslinking heat shrink films, in addition hydrophilic macromolecule antistatic agent is on crosslinking heat shrink films surface in micro-
Small layered distribution constitutes conductive surface, and hydrophilic macromolecule antistatic agent is in spherical distribution at center, forms " shell core knot
Structure " reveals electrostatic charge as access, affected by environment smaller, can be further improved the antistatic effect of crosslinking heat shrink films
Fruit.When surfactant antistatic agent: the hydrophilic macromolecule antistatic agent=(0.5~3): when 1, in crosslinking heat shrink films
It is specifically used during antistatic effect it is best.
Further, the surfactant antistatic agent is dodecyl diethanol amine, lauric acid diethanol amine, polyoxy
Vinyl alkyl amine, alkyl phenol, ethylene oxide sulfuric acid, polyol esters of fatty acids, at least one of organic phosphorus compound；It is described
Hydrophilic macromolecule antistatic agent is polyether block amide analog copolymer, salt copolymer in carbonylation quaternary ammonium carboxylic acid, macromolecule transfer
Type bonding body, polyethylene glycol Copolymer polyamide, at least one of superhigh molecular weight polyethylene glycol.
Surfactant antistatic agent is dodecyl diethanol amine, lauric acid diethanol amine, polyoxyethylene alkyl amine, alkane
Base phenol, ethylene oxide sulfuric acid, polyol esters of fatty acids, at least one of organic phosphorus compound；Hydrophilic macromolecule resists quiet
Electric agent is polyether block amide analog copolymer, salt copolymer in carbonylation quaternary ammonium carboxylic acid, macromolecule transfevent bonding body, polyethylene glycol
Copolymer polyamide, at least one of superhigh molecular weight polyethylene glycol.Surfactant antistatic agent and hydrophilic macromolecule
The antistatic agent that both antistatic agents compounding is formed has lasting antistatic effect, after the molding of antistatic crosslinking heat shrink films
Antistatic property can be played, and affected by environment smaller.
Further, the middle layer weight percent includes following components: 80~95% polyethylene, 1~10%
Slipping agent, 1~10% cross-linked evocating agent.Polyethylene keeps the hardness of intermediate layer material and machinery strong as basis material
Degree, while it being also added with slipping agent, the smooth performance of intermediate layer material is improved, crosslinking heat shrink films can be improved in cross-linked evocating agent
Heat resistance, mechanical strength, rheological characteristic and storage stability etc., further extend the service life of crosslinking heat shrink films, specifically
It can be N, N~methylene-bisacrylamide cross-linked evocating agent.
Further, it is described it is antistatic crosslinking heat shrink films with a thickness of 10~35 μm.When antistatic crosslinking heat shrink films
Thickness less than 10 μm when, since with outer layer, internal layer and middle layer three-decker, layers of material is relatively thin, is not achieved antistatic
Requirement when crosslinking heat shrink films are specifically used to intensity and tensile strength；When the thickness of antistatic crosslinking heat shrink films is greater than 35
μm when, transparency it is lower and prepare needed for raw material it is more, the production cost increases.
The present invention also proposes a kind of preparation method of antistatic crosslinking heat shrink films as described in any of the above-described, including following
Step: outer layer, middle layer and internal layer raw material are uniformly mixed by mixing respectively by weight percentage；Plasticizing squeeze out, by outer layer, in
Interbed and internal layer raw material are separately added into extruder fusion plastification and obtain melt, and the melt enters co-extrusion die head co-extrusion and closes layer；One
Secondary inflation, the melt after layer is closed to co-extrusion are inflated to obtain film bubble, then carry out cooling and shaping and form membrane tube；Electron irradiation crosslinking, will
Membrane tube draws to electron irradiation crosslinking apparatus and generates activation crosslinking；Preheating, the membrane tube after crosslinking Treatment is carried out using baking oven
Preheating；Secondary inflation, the membrane tube after preheating carry out biaxial tension, are formed after stretching by vane cooling and shaping thin
Film；Post-processing carries out annealing and cooling treatment to the film, and the antistatic crosslinking is obtained after trimming is wound and is heat-shrinked
Film.
In the present embodiment, the raw material of outer layer, middle layer and internal layer is put into corresponding feeding cylinder after mixing respectively, then
Plasticizing is added into extruder in raw material in feeding cylinder to squeeze out, is squeezed out when each layer raw material carries out melting co-extrusion using individual
Machine, the melt after plasticizing completely enter in the taper co-extrusion die head of multilayer parallel, then carry out an inflation to melt and form film
Film bubble is put into sizing water jacket by bubble after the dimensionally stable of film bubble, and cooling and shaping under the action of cooling water, formation has
The membrane tube of multilayered structure draws periosteum to the line output window progress of electron irradiation crosslinking apparatus under the traction of traction device
Irradiation effectively improves the degree of cross linking of periosteum linear molecule chain so that the linear molecule chain of periosteum generates activation crosslinking, guarantees
It is cross-linked with each other between outer layer, middle layer and internal layer, and mechanical property to heat shrink films obtained, thermal stability, resistance to
Mill performance and creep resistance have different degrees of raising.Periosteum Jing Guo crosslinking Treatment is drawn via mechanical equipment to remote red
Pre-add heat treatment is carried out in outer enamel oven, using the heating of infra-red china baking oven so that the heating of periosteum is more uniform, is heated to
Start to carry out biaxial tension formation composite membrane higher than periosteum softening point and when being lower than the state of periosteum fusing point, be heat-treated by pre-add
Membrane tube temperature afterwards is 85~110 DEG C.Composite membrane is post-processed, is formed after eliminating composite membrane internal stress, then is cut off multiple
The antistatic crosslinking heat shrink films are obtained after closing the uneven part winding of film edge.
Specifically, it includes three-level vane that the vane is cooling, and first order vane air quantity is 1000~2000m3/ h, the second level
Vane air quantity is 1000~2000m3/ h, third level vane air quantity are 600~800m3/h.In order to effectively cool down membrane tube, it is ensured that
The thickness of heat shrink films is crosslinked uniformly with preferable percent thermal shrinkage, it is cold that membrane tube has to pass through the progress of three-level vane after secondary inflation
But, the air quantity of first order vane is 1000~2000m3/ h plays and cooling membrane tube using unheated air as cooling medium
Effect, make membrane tube by biaxial tension that there is preferable toughness, second level vane and third level vane use cryogenic gas
It is cooled down, wherein the air quantity of second level vane is relatively large, carries out Quench to membrane tube using cryogenic gas, further increases friendship
Join the percent thermal shrinkage of heat shrink films.
Further, in described " membrane tube after preheating the carries out biaxial tension " step, transverse stretch ratio 4.0-
6.5, longitudinal stretching multiple is 4.8-6.8.In this way, when transverse stretch ratio is 4.0-6.5, when longitudinal stretching multiple is 4.8-6,
Membrane tube can be with Uniform Tension, and the thickness uniformity and profile pattern are preferable, while can further refine crystal grain, and crystallization is strong
Degree correspondinglys increase, and the stretch modulus and intensity of membrane tube are preferable, and the mist degree of crosslinking heat shrink films obtained reduces, and glossiness mentions
It is high.
Specifically, annealing temperature is 40 DEG C~80 DEG C in " carrying out annealing and cooling treatment to the film " step,
Cooling temperature is 10 DEG C~30 DEG C.Remain with a large amount of internal stress inside crosslinking heat shrink films by biaxial tension, need into
Row post-processing, prevents crosslinking heat shrink films product from generating natural shrinking in storage and transportational process, and influence that product uses shows
As.Post-processing includes annealing and cooling treatment: wherein first being made annealing treatment, ensure that the further of composite membrane strand
Growth carries out thermal finalization to composite membrane using Double-side hot roller group, and the temperature of hot-rolling group is set in 40 DEG C~80 DEG C sections, then is adopted
The surface of crosslinking heat shrink films is cooled down with two-sided chilling roller or cold wind, the temperature of chilling roller is set in 10 DEG C~30 DEG C, so that
Strand after growth is quickly cooled down sizing, to improve the crystallinity of polymer molecule, improves the heat shrink films again
Mechanical performance and intensity.
Further, described " outer layer, middle layer and internal layer raw material are separately added into extruder fusion plastification and obtain melt,
The melt enters co-extrusion die head co-extrusion and closes layer " in step, the extruder includes three heated zones, feeding section 150~170
DEG C, melt 165~185 DEG C of section, 180~200 DEG C of homogenizing zone；The co-extrusion die head includes four heated zones, the heating zone
The temperature of section is equal are as follows: 180~200 DEG C.
The relatively low temperature setting of feeding section is 150~170 DEG C, is easy to cause crosslinking heat to receive this is because temperature is excessively high
Each layer raw material of contracting film is melted in early stage, undercompounding is occurred, is plasticized non-uniform phenomenon, is also resulted in each layer raw material and is being squeezed
It is decomposed during out, causes to skid, cause pressure oscillation of the raw material in extrusion process, reduce the production of crosslinking heat shrink films
Quality.The temperature for melting section has opposite raising compared with feeding section, is because each layer raw material of crosslinking heat shrink films is needed at this
Stage realizes the reason of plasticizing, only reaches the major part that 165~185 DEG C of temperature just can ensure that outer layer, middle layer and internal layer
Raw material is plasticized.And temperature of the temperature of homogenizing zone in three sections sets highest, is since raw material is melting section big portion
Divide plasticizing, only fraction macromolecule raw material does not start to be plasticized since itself plasticization temperature is higher, it enters to homogenizing zone, but
This part material not being plasticized will cause the unstable quality of crosslinking heat shrink films product, therefore set the plasticization temperature of homogenizing zone
It is 180~200 DEG C, extends the fusion time of raw material to realize abundant plasticizing.Co-extrusion die head of the invention includes conical mould head
And superposing die head, the temperature of co-extrusion die head heated zones are 180 DEG C~200 DEG C, ensure that the raw material of molten condition can be
It is uniformly distributed in the densely covered co-extrusion die head of pipeline, and is extruded into film in homogeneous thickness.
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, it should be understood that following real
It applies example to be only used to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Mixing, by weight percentage by the anhydride grafting modified poly- second of the horse Lay of the low density polyethylene (LDPE) of outer layer 85%, 10%
Alkene, 1% silicone antiblocking agent, 1% erucamide slip agent, 1% surfactant type antistatic agent functional master batches, 2%
Hydrophilic macromolecule antistatic master granule, the low density polyethylene (LDPE) of middle layer 95%, 3% slipping agent, 2% cross-linked evocating agent,
The low density polyethylene (LDPE) of internal layer 85%, the 10% anhydride grafting modified polyethylene of horse Lay, 1% silicone antiblocking agent, 1% mustard
Sour amide slipping agent, 1% surfactant type antistatic agent functional master batches, 2% hydrophilic macromolecule antistatic master granule mix respectively
It closes uniform；
Plasticizing squeezes out, and outer layer, middle layer and internal layer raw material are separately added into extruder fusion plastification and obtain melt, extruder
Including three heated zones, 160 DEG C of feeding section, melt 165 DEG C of section, 180 DEG C of homogenizing zone；Co-extrusion die head includes four heating zones
Section, the temperature of heated zones are equal are as follows: 185 DEG C, the melt enters co-extrusion die head co-extrusion and closes layer；
Inflation, the melt after layer is closed to co-extrusion are inflated to obtain film bubble, then carry out cooling and shaping and form membrane tube；
Membrane tube is drawn to electron irradiation crosslinking apparatus and generates activation crosslinking by electron irradiation crosslinking；
Preheating, the membrane tube after crosslinking Treatment is preheated using baking oven；
Secondary inflation, the membrane tube after preheating carry out biaxial tension, transverse stretch ratio 4.5, and longitudinal stretching multiple is
5.0, film is formed by vane cooling and shaping after stretching, cooling vane includes three-level vane, and first order vane air quantity is
1400m3/ h, second level vane air quantity are 1400m3/ h, third level vane air quantity are 600m3/h；
Post-processing carries out annealing and cooling treatment to the film, and annealing temperature is 50 DEG C, and cooling temperature is 20 DEG C.
The antistatic crosslinking heat shrink films are obtained after trimming is wound.
Embodiment 2
Mixing, by weight percentage by the ultra-low density polyethylene of outer layer 70%, 13% acrylic graft-modified poly- second
Alkene, 2% silicone antiblocking agent, 10% erucamide slip agent, 4% surfactant type antistatic agent functional master batches, 1%
Hydrophilic macromolecule antistatic master granule, the low density polyethylene (LDPE) of middle layer 80%, 10% slipping agent, 10% crosslinking cause
Agent, the ultra-low density polyethylene of internal layer 70%, 13% acrylic graft-modified polyethylene, 5% silicone antiblocking agent, 10%
Erucamide slip agent, 1% surfactant type antistatic agent functional master batches, 1% hydrophilic macromolecule antistatic master granule, point
Hun Hejunyun not；
Plasticizing squeezes out, and outer layer, middle layer and internal layer raw material are separately added into extruder fusion plastification and obtain melt, extruder
Including three heated zones, 170 DEG C of feeding section, melt 180 DEG C of section, 190 DEG C of homogenizing zone；Co-extrusion die head includes four heating zones
Section, the temperature of heated zones are equal are as follows: 195 DEG C, the melt enters co-extrusion die head co-extrusion and closes layer；
Inflation, the melt after layer is closed to co-extrusion are inflated to obtain film bubble, then carry out cooling and shaping and form membrane tube；
Membrane tube is drawn to electron irradiation crosslinking apparatus and generates activation crosslinking by electron irradiation crosslinking；
Preheating, the membrane tube after crosslinking Treatment is preheated using baking oven；
Secondary inflation, the membrane tube after preheating carry out biaxial tension, transverse stretch ratio 4.5, and longitudinal stretching multiple is
5.6, film is formed by vane cooling and shaping after stretching, cooling vane includes three-level vane, and first order vane air quantity is
1600m3/ h, second level vane air quantity are 1600m3/ h, third level vane air quantity are 700m3/h；
Post-processing carries out annealing and cooling treatment to the film, and annealing temperature is 60 DEG C, and cooling temperature is 25 DEG C.
The antistatic crosslinking heat shrink films are obtained after trimming is wound.
The beneficial effect of embodiment in order to better illustrate the present invention, the present invention are arranged one group of comparative example and test, with a thickness of
80 μm of the common crosslinking heat shrink films without antistatic treatment carry out performance detection, test to Examples 1 to 2 and comparative example
As a result as shown in the table:
Table 1 is crosslinked heat shrink films the performance test results
It can be seen that antistatic crosslinking heat shrink films of the present invention from the test result of table 1 and maintaining preferable drawing
While stretching intensity, elongation at break and tearing strength, sheet resistance is smaller, fights again after placing 6 months at room temperature quiet
The sheet resistance of electrical coupling heat shrink films is detected, and the testing result of sheet resistance is still smaller, is using a period of time
After remain to maintain preferable antistatic effect, therefore antistatic crosslinking heat shrink films provided by the invention keep it is good resist it is quiet
While electro ultrafiltration, mechanical strength is maintained in the preferable range of crosslinking heat shrink films.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by present specification, or directly/it is used in other indirectly
Relevant technical field is included in scope of patent protection of the invention.
Claims (10)
1. a kind of antistatic crosslinking heat shrink films, which is characterized in that described including outer layer, middle layer and the internal layer set gradually
Internal layer and outer layer weight percent include following components: 70~85% polyethylene, 10~20% modified poly ethylene, 1~
5% antiblocking agent, 1~10% slipping agent, 1~5% antistatic agent；
The polyethylene is low density polyethylene (LDPE), at least one of ultra-low density polyethylene and metallocene low density polyethylene (LDPE).
2. antistatic crosslinking heat shrink films according to claim 1, which is characterized in that the antistatic agent is by surface-active
Agent antistatic agent and hydrophilic macromolecule antistatic agent compound, and by weight percentage, the surfactant is antistatic
Agent: the hydrophilic macromolecule antistatic agent=(0.5~3): 1.
3. antistatic crosslinking heat shrink films according to claim 2, which is characterized in that the surfactant antistatic agent
For dodecyl diethanol amine, lauric acid diethanol amine, polyoxyethylene alkyl amine, alkyl phenol, ethylene oxide sulfuric acid, fat
Acid polyol ester, at least one of organic phosphorus compound；
The hydrophilic macromolecule antistatic agent is polyether block amide analog copolymer, and salt copolymer in carbonylation quaternary ammonium carboxylic acid is high
Molecule transfevent bonding body, polyethylene glycol Copolymer polyamide, at least one of superhigh molecular weight polyethylene glycol.
4. antistatic crosslinking heat shrink films according to claim 1, which is characterized in that the middle layer weight percent
Including following components: 80~95% polyethylene, 1~10% slipping agent, 1~10% cross-linked evocating agent.
5. antistatic crosslinking heat shrink films according to claim 1, which is characterized in that the antistatic crosslinking heat shrink films
With a thickness of 10~35 μm.
6. a kind of preparation method of antistatic crosslinking heat shrink films as claimed in claims 1-5, which is characterized in that including following
Step:
Outer layer, middle layer and internal layer raw material are uniformly mixed by mixing respectively by weight percentage；
Plasticizing squeezes out, and outer layer, middle layer and internal layer raw material are separately added into extruder fusion plastification and obtain melt, the melt into
Enter co-extrusion die head co-extrusion and closes layer；
Inflation, the melt after layer is closed to co-extrusion are inflated to obtain film bubble, then carry out cooling and shaping and form membrane tube；
Membrane tube is drawn to electron irradiation crosslinking apparatus and generates activation crosslinking by electron irradiation crosslinking；
Preheating, the membrane tube after crosslinking Treatment is preheated using baking oven；
Secondary inflation, the membrane tube after preheating carry out biaxial tension, form film by vane cooling and shaping after stretching；
Post-processing carries out annealing and cooling treatment to the film, and the antistatic crosslinking is obtained after trimming is wound and is heat-shrinked
Film.
7. the preparation method of antistatic crosslinking heat shrink films according to claim 6, which is characterized in that the vane is cooling
Including three-level vane, first order vane air quantity is 1000~2000m3/ h, second level vane air quantity are 1000~2000m3/ h, the
Three-level vane air quantity is 600~800m3/h。
8. the preparation method of antistatic crosslinking heat shrink films according to claim 6, which is characterized in that " the preheating
In membrane tube progress biaxial tension afterwards " step, transverse stretch ratio 4.0-6.5, longitudinal stretching multiple is 4.8-6.8.
9. the preparation method of antistatic crosslinking heat shrink films as claimed in claim 6, which is characterized in that described " to described thin
Film carries out annealing and cooling treatment " in step, annealing temperature is 40 DEG C~80 DEG C, and cooling temperature is 10 DEG C~30 DEG C.
10. the preparation method of antistatic crosslinking heat shrink films as claimed in claim 6, which is characterized in that it is described " by outer layer,
Middle layer and internal layer raw material are separately added into extruder fusion plastification and obtain melt, and the melt enters co-extrusion die head co-extrusion and closes layer "
In step, the extruder includes three heated zones, 150~170 DEG C of feeding section, melts 165~185 DEG C of section, homogenizing zone 180
~200 DEG C；
The co-extrusion die head includes four heated zones, and the temperature of the heated zones is equal are as follows: 180~200 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110722856A (en) * | 2019-10-22 | 2020-01-24 | 江阴升辉包装材料有限公司 | Puncture-resistant composite shrink film for refrigeration and preservation |
| CN111267449A (en) * | 2020-04-14 | 2020-06-12 | 汕头市明佳热收缩膜有限公司 | PEF heat shrinkable film and preparation method thereof |
| CN113276530A (en) * | 2021-04-19 | 2021-08-20 | 吕建忠 | Self-peeling type heat shrinkable film and preparation process thereof |
| CN114386281A (en) * | 2022-01-13 | 2022-04-22 | 北京卫星环境工程研究所 | An automatic design method of experimental heating circuit based on clustering |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5428873B2 (en) * | 1972-10-06 | 1979-09-19 | ||
| US4640856A (en) * | 1985-04-29 | 1987-02-03 | W. R. Grace & Co., Cryovac Div. | Multi-layer packaging film and receptacles made therefrom |
| CN1827362A (en) * | 2005-03-03 | 2006-09-06 | 优泊公司 | Label for in-mold molding and molded product using the label |
| CN106317569A (en) * | 2016-08-25 | 2017-01-11 | 太仓市鸿运包装材料有限公司 | Antistatic PE heat shrinkable film and preparing method thereof |
| CN107141553A (en) * | 2017-05-22 | 2017-09-08 | 安徽致达包装有限公司 | One kind punching PE heat-shrinkable films |
| CN107200918A (en) * | 2017-07-12 | 2017-09-26 | 肇庆市东盛益源包装材料有限公司 | A kind of PE heat shrink films and preparation method thereof |
| CN108516212A (en) * | 2018-03-30 | 2018-09-11 | 浙江众成包装材料股份有限公司 | A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films and preparation method thereof |
-
2019
- 2019-08-09 CN CN201910737817.XA patent/CN110328942B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5428873B2 (en) * | 1972-10-06 | 1979-09-19 | ||
| US4640856A (en) * | 1985-04-29 | 1987-02-03 | W. R. Grace & Co., Cryovac Div. | Multi-layer packaging film and receptacles made therefrom |
| CN1827362A (en) * | 2005-03-03 | 2006-09-06 | 优泊公司 | Label for in-mold molding and molded product using the label |
| CN106317569A (en) * | 2016-08-25 | 2017-01-11 | 太仓市鸿运包装材料有限公司 | Antistatic PE heat shrinkable film and preparing method thereof |
| CN107141553A (en) * | 2017-05-22 | 2017-09-08 | 安徽致达包装有限公司 | One kind punching PE heat-shrinkable films |
| CN107200918A (en) * | 2017-07-12 | 2017-09-26 | 肇庆市东盛益源包装材料有限公司 | A kind of PE heat shrink films and preparation method thereof |
| CN108516212A (en) * | 2018-03-30 | 2018-09-11 | 浙江众成包装材料股份有限公司 | A kind of multi-layer co-extruded low temperature polyolefin crosslinking heat shrink films and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 丁浩: "《塑料工业实用手册 上册》", 31 December 1995, 化学工业出版社 * |
| 王渊，王佩璋，陆晓中: "《高分子材料》", 31 January 2009, 中国轻工业出版社 * |
| 罗红旗: "《消失模模样数控加工切削机理研究》", 31 December 2018, 华中科技大学出版社 * |
| 陈申豪: "《包装材料》", 30 September 1989, 湖南大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110722856A (en) * | 2019-10-22 | 2020-01-24 | 江阴升辉包装材料有限公司 | Puncture-resistant composite shrink film for refrigeration and preservation |
| CN111267449A (en) * | 2020-04-14 | 2020-06-12 | 汕头市明佳热收缩膜有限公司 | PEF heat shrinkable film and preparation method thereof |
| CN113276530A (en) * | 2021-04-19 | 2021-08-20 | 吕建忠 | Self-peeling type heat shrinkable film and preparation process thereof |
| CN114386281A (en) * | 2022-01-13 | 2022-04-22 | 北京卫星环境工程研究所 | An automatic design method of experimental heating circuit based on clustering |
| CN114386281B (en) * | 2022-01-13 | 2022-09-13 | 北京卫星环境工程研究所 | Automatic design method for test heating loop based on clustering |
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