CN109703144B - Antistatic film and preparation method thereof - Google Patents
Antistatic film and preparation method thereof Download PDFInfo
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- CN109703144B CN109703144B CN201811622576.6A CN201811622576A CN109703144B CN 109703144 B CN109703144 B CN 109703144B CN 201811622576 A CN201811622576 A CN 201811622576A CN 109703144 B CN109703144 B CN 109703144B
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Abstract
The invention relates to the field of plastic films, in particular to an antistatic film and a preparation method thereof. The antistatic film has a three-layer structure comprising an inner layer, a middle layer and an outer layer; the middle layer preparation raw material comprises HDPE-II; the outer layer preparation raw material comprises HDPE-I; the density of HDPE-II is higher than the density of HDPE-I.
Description
Technical Field
The invention relates to the field of plastic films, in particular to an antistatic film and a preparation method thereof.
Background
Nowadays, plastic film products are widely applied to various industries of human society, and mainly made of PE (polyethylene) materials. The PE film, namely the polyethylene film, is commonly used as a packaging material for various products, and has the characteristics of rich raw material resources, moderate price, stable and reliable production process, superior product comprehensive performance and the like, so that the application range of the PE film is gradually expanded, and particularly in the field of packaging and protection films, the dosage of the PE film always accounts for the first of the general packaging materials.
Because the PE plastic film has excellent electrical insulation, static electricity is easy to generate by friction in the transportation and production processes. Static electricity can cause many problems, for example, charged particles can adsorb particles with opposite charges in the air, which causes the product to be unattractive, and dust adsorbed by static electricity can cause other problems such as malfunction of electronic devices, difficulty in heat sealing and the like. In order to solve the above problems, an antistatic agent is mainly used to prepare an antistatic film, and the antistatic film is a functional film capable of conducting static electricity accumulated on the surface through its high conductivity to achieve an antistatic effect, and usually has a resistance of 10-2Ω·cm-1010Omega cm. The preparation of the antistatic film has the obvious advantages of simple and convenient process and low price, and is the most widely applied method for producing the antistatic film at present. The method is that the antistatic agent is directly mixed into plastic particles (or powder) after being metered to produce the antistatic film, or the antistatic agent and other components are firstly mixed to prepare master batch, when the plastic film is produced, the master batch is mixed into the plastic particles to produce the antistatic film according to the conventional film forming method. The two processes are convenient and easy to implement. However, the two processes have some disadvantages, such as short antistatic time of the prepared antistatic film, poor compatibility between the antistatic agent and the film material, and the influence on the antistatic effect and the comprehensive properties such as strength and the like.
Disclosure of Invention
In view of the above technical problems, a first aspect of the present invention provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the middle layer preparation raw material comprises HDPE-II; the outer layer preparation raw material comprises HDPE-I; the density of HDPE-II is higher than the density of HDPE-I.
As a preferable technical scheme, the outer layer comprises, by weight, HDPE-I80-90, antistatic agent 10-20, opening agent 1-2, rheological agent 1-2, and color master copolymer 2-5.
As a preferred solution, the density of the antistatic agent is lower than the density of the HDPE-I.
As a preferable technical scheme, the melt index of the antistatic agent is 5-8 g/10min under the conditions that the temperature is 190 ℃ and the load is 2.16 kg.
As a preferred technical scheme, the melt index of the HDPE-I under the conditions of the temperature of 190 ℃ and the load of 2.16kg is not less than 0.05g/10 min.
As a preferable technical scheme, the preparation raw material of the middle layer comprises, by weight, HDPE-II100 and a rheological agent 1-2; the density of the HDPE-II is 0.960g/cm3～0.970g/cm3。
As a preferable technical scheme, the inner layer comprises raw materials for preparing LLDPE 90-95 parts by weight, an opening agent 1-2 parts by weight and a rheological agent 1-3 parts by weight; the LLDPE has a density of 0.918-0.925 g/cm3。
As a preferred technical scheme, the inner layer, the middle layer and the outer layer respectively comprise 30-40 parts by weight of the outer layer, 25-35 parts by weight of the middle layer and 30-40 parts by weight of the inner layer.
The second aspect of the present invention provides a method for preparing the antistatic film as described above, comprising the steps of:
(1) drying the antistatic agent at 50-80 ℃, and respectively stirring and mixing the raw materials of the components according to the formula proportion;
(2) melting the obtained mixture by a screw extruder according to the weight proportion of each layer, and extruding and blow-molding the mixture into a cylindrical film by a low-pressure die head;
(3) and carrying out post-treatment on the obtained cylindrical film to obtain the antistatic film.
A third aspect of the present invention provides the use of the antistatic film as described above in the field of buffer cushions.
Has the advantages that: the antistatic film provided by the invention has excellent mechanical properties such as tensile strength, elongation at break, tear strength, puncture strength and heat seal strength, and also has excellent processability, can be used for smoothly processing raw materials, is not easy to cause difficulty in melting and extruding the raw materials, is not easy to cause swing and shake in the process of blow molding of extruded melt, and has obviously reduced film breaking times per month compared with the conventional technology. In addition, the antistatic film provided by the invention has a high-efficiency antistatic effect, the prepared film has lower surface resistance, and the film is prevented from losing the antistatic effect after the antistatic agent on the surface of the film loses water absorption property due to the special arrangement in the film in the storage process, but the antistatic agent is promoted to continuously migrate to the surface of the film due to the difference between the density of the middle-outer layer raw material and the antistatic agent and other parameters, so that the antistatic effect of the film can be gradually improved while the effect of the antistatic agent is fully exerted.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about".
In view of the above technical problems, a first aspect of the present invention provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the middle layer preparation raw material comprises HDPE-II; the outer layer preparation raw material comprises HDPE-I; the density of HDPE-II is higher than the density of HDPE-I.
The antistatic film is characterized in that the main preparation raw materials of the middle layer and the outer layer of the three-layer asymmetric structure film are respectively different high-density polyethylene, and the density of the main preparation raw material high-density polyethylene of the middle layer is higher than that of the main preparation raw material high-density polyethylene of the outer layer, so that the migration of materials in the outer layer of the film to the middle layer of the film can be effectively prevented, and the migration direction of specific materials can be regulated and controlled. The HDPE (high density polyethylene) is thermoplastic polyolefin generated by ethylene copolymerization, is manufactured by a Ziegler-Natta polymerization method, and is characterized in that molecular chains have no branched chains, so that the molecular chains are regularly arranged and have higher density (generally 0.941-0.960 g/cm)3). The HDPE of the present invention may be prepared by methods well known to those skilled in the art, or may be commercially available (e.g., related products of Exxon Mobil, Dow Dupont, etc.).
The density in the present invention is a physical parameter well known to those skilled in the art and the density of HDPE is measured according to ASTM D-1505.
In some embodiments, the raw materials for preparing the outer layer comprise, by weight, 80-90 parts of HDPE-I, 10-20 parts of an antistatic agent, 1-2 parts of an opening agent, 1-2 parts of a rheological agent and 2-5 parts of a color masterbatch copolymer.
In some preferred embodiments, the HDPE-I is carried at a temperature of 190 ℃ under a load of 2.16kgThe melt index of (A) is not less than 0.05g/10 min; preferably, the HDPE-I has a density of 0.950g/cm3～0.960g/cm3(ii) a More preferably, the density is 0.956g/cm3. The density, melt index and other parameters of the high-density polyethylene have influence on the fluidity of the material in a molten state, the dispersion and mutual solubility effects of other materials and the like, and obviously influence the mechanical properties of the prepared film.
The melt index in the present invention is a value representing the fluidity of a plastic material at the time of processing, and is measured by melting plastic pellets into a plastic fluid at a certain temperature and pressure within 10 minutes, and then passing the plastic fluid through a circular tube having a diameter of 2.095mm in terms of the number of grams (g) of the plastic fluid. The larger the value, the better the processing fluidity of the plastic material, and the worse the processing fluidity. In the present invention, the melt indexes of the raw materials for preparing the outer layer, the middle layer and the inner layer are all measured under the same conditions according to the standard of ASTM D-1238.
Any object has its own electrostatic charge, which may be negative or positive, and the accumulation of electrostatic charge affects or even harms life or industrial production, and chemicals that guide/eliminate the accumulated harmful charge so that it does not cause inconvenience or harm to production/life are called antistatic agents. The antistatic agent is added into plastic or coated on the surface of a molded product to achieve the aim of reducing static accumulation. The antistatic agent has a hydrophilic group structure, and the hydrophilic group is exposed in the air to absorb moisture in the air and gradually form a water film layer on the surface of the film to release charges accumulated on the surface of the film so as to play an antistatic role. The antistatic agent in the present invention is an additive obtained by mixing an antistatic component with a polyethylene carrier. The antistatic agent of the present invention has an effective antistatic component of about 12%, and the polyethylene carrier has a density of not more than 0.9g/cm3The Linear Low Density Polyethylene (LLDPE) of (2) can be obtained commercially, for example, LLDPE (density of 0.812 g/cm) of the Japanese ocean under the trade name NH745S3) And the like.
In some embodiments, the density of the antistatic agentTo a density less than that of the HDPE-I; preferably, the antistatic agent has a density of 0.80g/cm3～0.90g/cm3(ii) a More preferably, it has a density of 0.85g/cm3。
In some preferred embodiments, the melt index of the antistatic agent under the same conditions is higher than that of the high density polyethylene used as the raw material for preparing the outer layer; preferably, the melt index of the antistatic agent is 5-8 g/10min under the conditions that the temperature is 190 ℃ and the load is 2.16 kg; further preferably, it has a melt index of 6.3g/10min at 190 ℃ under a load of 2.16 kg. The antistatic agents of the present invention are commercially available.
The color master batch copolymer is a special coloring agent for high molecular materials, is also called a pigment preparation, consists of basic elements such as pigment or fuel, carrier and additive, and is a copolymer obtained by uniformly loading an excessive amount of pigment or fuel into resin, and can be called a pigment concentrate. The color master copolymer mainly plays a role in coloring the film, the replacement of the raw materials of the color master copolymer does not influence other performances of the film, and the color master copolymer (or color master batch) can be selected from the color master copolymers (or color master batches) which are conventionally used for plastic films without special limitation, wherein the pigment/fuel is also not specially limited, and in one embodiment, the color master copolymer containing the pink 2367 pigment is adopted and is purchased from the market.
In some embodiments, the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agents 1-2 in parts by weight; the density of the HDPE-II is 0.960g/cm3～0.970g/cm3(ii) a In some preferred embodiments, the HDPE-II has a melt index of not less than 0.04g/10min at a temperature of 190 ℃ and a load of 2.16 kg; further preferably, the HDPE-II has a density of 0.967g/cm3。
The rheological agent is a plastic additive, can effectively reduce the apparent density of materials and the pressure of melt extrusion in a screw extruder, is favorable for avoiding the phenomena of melt fracture, sharkskin and the like, and is also favorable for reducing energy consumption. The type of rheological agent is not particularly limited in the present inventionBy way of limitation, conventional rheological agents for plastic film processing may be used. Preferably, the melt index of the rheological agent is 2-5 g/10min under the conditions that the temperature is 190 ℃ and the load is 2.16 kg; more preferably, the melt index of the rheological agent is 3g/10min under the conditions that the temperature is 190 ℃ and the load is 2.16 kg; even more preferably, the rheological agent has a density of 0.93g/cm3. The rheology agent of the present invention can be obtained commercially.
In some embodiments, the inner layer is prepared from raw materials including, by weight, 90-95 parts of LLDPE, 1-2 parts of an opening agent and 1-3 parts of a rheological agent; the LLDPE has a density of 0.918-0.925 g/cm3。
The LLDPE (linear low density polyethylene) in the present invention is a polymer obtained by gas phase fluidized bed polymerization of ethylene as a main raw material with a small amount of alpha-olefin (e.g., butene-1, octene-1, etc.) under high pressure or low pressure in the presence of a catalyst, wherein the catalyst does not include a metallocene catalyst. Compared with the conventional polyethylene, the linear low-density polyethylene has a small amount of short branched chains on the molecular chain, has higher linearity degree, and also has more regular molecular arrangement, higher crystallinity and heat resistance.
In some preferred embodiments, the LLDPE has a melt index of 0.1 to 0.5g/10min at a temperature of 190 ℃ under a load of 2.16 kg; more preferably, it has a melt index of 0.25g/10min at a temperature of 190 ℃ and a load of 2.16 kg; more preferably, the LLDPE has a density of 0.923g/cm3. The LLDPE of the present invention is commercially available.
The opening agent is an aid for reducing the frictional resistance between the material and the inner wall of the screw extruder in the melt extrusion process of the material, so that the film and the die wall are smoother, and the melt extrusion effect and the production processability of the material are improved. In some embodiments, the opening agent is a mixture of an amide-based opening agent and a polyethylene carrier, wherein the amide-based opening agent accounts for 10% of the total amount of the opening agent, and the polyethylene is Linear Low Density Polyethylene (LLDPE). In some embodiments, the amide-based opening agent is erucamide; preferably, the amide-based opening agents further comprise N, N' - [ ethylenebis (iminoethylenimine) ] distearamide; more preferably, the weight ratio of the erucamide to the N, N' - [ ethylene bis (imino ethylidene) ] distearamide is (1-3): (0.5 to 1.2); preferably, the ratio of 2: 1.
the applicant finds that the selection and the dosage of the opening agent have great influence on the mechanical properties such as tensile strength of the film and the processing performance of the film, and have more remarkable influence on the antistatic effect of the film, and the antistatic performance of the film is reduced when the selection of the type or the dosage of the opening agent is not proper. The reason for this is that, because the antistatic agent contains hydrophilic polar groups in its structure, it can generate forces such as hydrogen bonds with the polar groups such as amide in the amide-based opening agent, which can hinder the migration of the antistatic agent components to the film surface to some extent, and slow down the speed of the antistatic agent forming an antistatic layer on the film surface, and the number of amide groups in the amide-based opening agent, the length of the nonpolar fatty chain, etc. can be the influencing factors. Further, it is also possible that the opening agent migrates to the surface of the film to form an elastic film, like the antistatic agent, and prevents the exertion of the force of water absorption, antistatic property, etc. of the antistatic layer, because the molecular chain of the opening agent of the amide type is relatively short compared with the components such as high density polyethylene, and also contains polar parts such as amide groups, and the compatibility with the components such as polyamide is not good.
In some embodiments, the weight parts of the inner layer, the middle layer and the outer layer are respectively 30-40 parts of the outer layer, 25-35 parts of the middle layer and 30-40 parts of the inner layer; preferably, the weight ratio of the components is 35: 30: 35.
because the cylinder film is split in the preparation process of the antistatic film provided by the invention, the inner layer of the film participates in the heat sealing process when the buffer air cushion is prepared. The applicant finds that the proportion of the three layers in parts by weight needs to be controlled in the antistatic film provided by the invention, and the content of the inner layer in the antistatic film is required not to be too small, so that the heat sealing strength of the film is reduced, and the pressure maintaining performance of the film is affected. And the inner layer of the film can not use the high-density polyethylene which is the same as the middle layer and the outer layer of the film, and the linear low-density polyethylene with proper fluidity and density is needed to be used, so that the inner layer raw materials of the film can be fused and bonded at relatively low temperature in the heat sealing process, and can be rapidly cooled and solidified to seal the gas in the film, and the sealing property and the pressure maintaining effect of the film are obviously improved, so that the film is suitable for the use characteristics of buffer packaging.
The antistatic film is prepared from specific high-density polyethylene, linear low-density polyethylene, an antistatic agent and other raw materials, has a three-layer structure, and the antistatic agent on the outer layer of the film is extruded by internal molecular chains and gradually migrates to the surface of the film. The hydrophilic group of the antistatic agent is exposed in the air to absorb the moisture in the air, and a water film layer is gradually formed on the surface of the film to release the charges accumulated on the surface of the film, so that the antistatic effect is achieved. The carrier of the antistatic agent used in the invention has a density of not more than 0.90g/cm3The density of the antistatic agent is 0.85g/cm3The density of the outer layer and the middle layer is higher than 0.95g/cm3High density HDPE of (2). The density of HDPE used in the middle layer is higher than that of HDPE in the outer layer, and the antistatic agent and the carrier thereof gradually migrate outwards under the extrusion of the high-density HDPE molecules in the outer layer, so that an antistatic film is formed on the surface of the film. And because the middle layer adopts HDPE with higher density, the antistatic agent and the carrier thereof form a barrier wall, and the antistatic agent and the carrier thereof can only migrate to the outer layer surface but can not migrate to the middle layer or the inner layer.
The applicant finds that the arrangement of the density gradient helps to improve the antistatic effect of the film and effectively reduce the resistance value of the film, and the applicant unexpectedly finds that the antistatic effect of the film can be maintained for a long time by the arrangement and the matching of the density gradient and a specific opening agent and other components, and even the resistance value of the film is further gradually reduced with the passage of time, so that the antistatic effect of the film is better and better. However, the density of each raw material is not simply set to be smaller than that of the outer layer raw material, the density of the outer layer raw material is smaller than that of the middle layer raw material, so that the above effects can be achieved, when the density of the antistatic agent is too low or the density difference between the antistatic agent and the outer layer high-density polyethylene is too large, the dispersing effect between the antistatic agent and the high-density polyethylene is easily reduced, the antistatic agent is easily agglomerated, the antistatic performance of the film is poor, even a stress concentration point is formed inside the film due to uneven material dispersion and mixing, the antistatic effect cannot be improved, and the mechanical properties such as the tensile strength of the film are affected. And too big difference between middle layer raw materials density and outer layer raw materials density also can influence the action such as material in melting, flow, and the film bubble is easy to swing in the in-process of extruding the raw materials blow molding, and even the raw materials can not blow into the film bubble scheduling problem, influences the smooth machine-shaping of goods.
The second aspect of the present invention provides a method for preparing the antistatic film as described above, comprising the steps of:
(1) drying the antistatic agent at 50-80 ℃, and respectively stirring and mixing the raw materials of the components according to the formula proportion;
(2) melting the obtained mixture by a screw extruder according to the weight proportion of each layer, and extruding and blow-molding the mixture into a cylindrical film by a low-pressure die head;
(3) and carrying out post-treatment on the obtained cylindrical film to obtain the antistatic film.
Specifically, the following operations may be performed:
1. the antistatic material was placed in an oven at 60 ℃ and dried for 24H to ensure that there was no moisture in the material. The antistatic agent easily absorbs moisture in the air, so that poor bubble perforation on the surface of the film caused by the moisture is easily caused during extrusion blow molding when the film is not dried or is insufficiently dried, and the preparation process of the film is influenced.
2. The raw materials of all the components are mixed by a high-speed mixing stirring kettle according to the formula proportion, and the color master batch copolymer can be determined whether to be added according to different customer requirements.
3. The uniformly mixed materials are added into each screw electronic weighing hopper, the proportion of each layer and the revolution of the screw are controlled by the electronic weighing hopper, and the precision can be controlled to be 0.2 percent.
4. The film was extrusion blow-molded into a cylindrical film having a width of 400mm through a low-pressure die. The temperature of the three-layer extrusion screw of the machine table is set as follows:
| layer classification | Region 1 | Zone 2 | Zone 3 | Zone 4 | Zone 5 | Zone 6 | Head area |
| Outer layer | 190-200℃ | 200-210℃ | 200-210℃ | 200-210℃ | 200-210℃ | 200-210℃ | 190-200℃ |
| Middle layer | 190-200℃ | 200-210℃ | 200-210℃ | 200-210℃ | 200-210℃ | 200-210℃ | 190-200℃ |
| Inner layer | 180-185℃ | 180-190℃ | 180-190℃ | 180-190℃ | 180-190℃ | 180-190℃ | 190-200℃ |
5. And (5) making the cylindrical film into a bag and carrying out heat sealing to prepare the buffer air cushion.
A third aspect of the present invention provides the use of the antistatic film as described above in the field of buffer cushions.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, if not otherwise stated, the starting materials used are commercially available with an opening agent consisting of an amide-based opening agent and the same LLDPE carrier (90 wt% basis), and the masterbatch copolymer is a conventional masterbatch copolymer containing pink 2367.
Examples
Example 1
Embodiment 1 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I80, an antistatic agent 10, an opening agent 1, a rheological agent 1 and a color master copolymer 2 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and a rheological agent 1 in parts by weight; the inner layer is prepared from the raw materials of LLDPE90, an opening agent 1 and a rheological agent 1 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively outer layer 30, middle layer 25 and inner layer 30; the HDPE-I is a Taiwan rubber and plastic product with the trade name 9001 (the melt index is 0.05g/10min, and the density is 0.950 g/cm)3) (ii) a The HDPE-II is a product with the Japanese Mitsubishi code ES300 (the melt index is 0.04g/10min, and the density is 0.960 g/cm)3) (ii) a The LLDPE is a Canadian NOVA brand GX-4010P (melt index of 0.2g/10min, density of 0.918 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd100 (melt index 6.3g/10min, density 0.85 g/cm)3)。
The embodiment also provides a preparation method of the antistatic film, which comprises the following steps:
1. the antistatic material was placed in an oven at 60 ℃ and dried for 24H to ensure that there was no moisture in the material. The antistatic agent easily absorbs moisture in the air, so that poor bubble perforation on the surface of the film caused by the moisture is easily caused during extrusion blow molding when the film is not dried or is insufficiently dried, and the preparation process of the film is influenced.
2. The raw materials of all the components are mixed by a high-speed mixing stirring kettle according to the formula proportion, wherein the color master copolymer is a conventional color master copolymer containing No. 2367 pink.
3. The uniformly mixed materials are added into each screw electronic weighing hopper, the proportion of each layer and the revolution of the screw are controlled by the electronic weighing hopper, and the precision can be controlled to be 0.2 percent.
4. The film was extrusion blow-molded into a cylindrical film having a width of 400mm through a low-pressure die. The temperature of the three-layer extrusion screw of the machine table is set as follows:
| layer classification | Region 1 | Zone 2 | Zone 3 | Zone 4 | Zone 5 | Zone 6 | Head area |
| Outer layer | 195℃ | 205℃ | 205℃ | 205℃ | 205℃ | 205℃ | 195℃ |
| Middle layer | 195℃ | 205℃ | 205℃ | 205℃ | 205℃ | 205℃ | 195℃ |
| Inner layer | 185℃ | 185℃ | 185℃ | 185℃ | 185℃ | 185℃ | 195℃ |
5. And (5) making the cylindrical film into a bag and carrying out heat sealing to prepare the buffer air cushion. Note: the temperature in each zone of the screw extruder has a certain fluctuation (generally, a fluctuation of about 5 ℃).
Example 2
Embodiment 2 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I90, an antistatic agent 20, an opening agent 2, a rheological agent 2 and a color master copolymer 5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and a rheological agent 2 in parts by weight; the inner layer is prepared from raw materials including LLDPE 95, an opening agent 2 and a rheological agent 3 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively outer layer 40, middle layer 35 and inner layer 40; the HDPE-I is a product with a chemical mark of 5500S of Mitsui (melt index of 0.7g/10min, density of 0.958 g/cm)3) (ii) a The HDPE-II is a product with the Japanese Mitsubishi brand BU007 (melt index of 0.7g/10min, density of 0.970 g/cm)3) (ii) a The LLDPE is of a Mitsui chemical brand 2005HC (melt index 0.5g/10min, density 0.925 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 3
Embodiment 3 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a product with the Japanese Mitsubishi code ES300 (the melt index is 0.04g/10min, and the density is 0.960 g/cm)3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 4
Embodiment 4 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd100。
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 5
Embodiment 5 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 1: 1.2; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 6
Embodiment 6 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 3: 0.5; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 7
Embodiment 7 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 2: 1; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antibodyThe electrostatic agent is dupont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 8
Embodiment 8 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-II 85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-I100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 2: 1; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 9
Embodiment 9 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-I100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 2: 1; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 10
Embodiment 10 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is N, N' - [ ethylene-bis (imino ethylidene group)]Distearamide; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 11
Embodiment 11 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including HDPE-II 92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 2: 1; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 12
Embodiment 12 provides an antistatic film having a three-layer structure including an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of LG chemical mark XL1800 (melt index of 0.01g/10min, density of 0.95 g/cm)3) (ii) a The above-mentionedHDPE-II is a Letian chemical product with a trademark of 5001BL (melt index of 0.5g/10min, density of 0.967 g/cm)3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 2: 1; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 13
Embodiment 13 provides an antistatic film having a three-layer structure comprising an inner layer, a middle layer and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 1.5, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from raw materials including LLDPE92, an opening agent 1.5 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a Dow Dupont DGDA-1412NT product (the melt index is 0.75g/10min, the density is 1.14 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 2: 1; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Example 14
Example 14 provides an antistatic film having a three-layer structure including an inner layer, a middle layer, and an outer layer; the outer layer comprises the preparation raw materials of HDPE-I85, an antistatic agent 15, an opening agent 6, a rheological agent 1.5 and a color master copolymer 3.5 in parts by weight; the preparation raw materials of the middle layer comprise HDPE-II100 and rheological agent 1.5 in parts by weight; the inner layer is prepared from the raw materials of LLDPE92, an opening agent 6 and a rheological agent 2 in parts by weight.
The weight parts of the inner layer, the middle layer and the outer layer are respectively an outer layer 35, a middle layer 30 and an inner layer 35; the HDPE-I is a product of Sanjing chemical brand 7000F (melt index is 0.05g/10min, density is 0.956 g/cm)3) (ii) a The HDPE-II is a Letian chemical product with the grade of 5001BL (the melt index is 0.5g/10min, and the density is 0.967g/cm3) (ii) a The LLDPE is a product with an exxonmobil grade of 2230 (melt index of 0.25g/10min, density of 0.923 g/cm)3) (ii) a The amide-type opening agent in the opening agent is erucamide and N, N' - [ ethylene-bis (imino ethylidene group)]A mixture of distearamides in a weight ratio of 2: 1; the rheological agent is a product with the Wuhan hyper-branched resin science and technology company Limited brand of hyper c 100; the antistatic agent is DuPont sd 100.
This example also provides a method for preparing the antistatic film, which is the same as in example 1.
Evaluation of Performance
The films provided in the examples and comparative examples of the present invention were subjected to performance tests according to the respective standards, and the results thereof are shown in the following tables.
1. Tensile strength (MPa) and elongation at break (%) were measured according to GB/T1040.3-2006, and the results are shown in Table 1.
TABLE 1 tensile Property test
2. The films provided in the examples and comparative examples of the present application were subjected to the test of pants-type tear strength (KN/m), heat seal strength (N/15mm) and film puncture strength (N) according to the methods described in GB/T16578.1-2008 national standard, QB/T2358-1998 Enterprise Standard and GB/T9639.1-2008 national standard, respectively, and the results are shown in Table 2.
TABLE 2 tear Strength test results
3. According to IEC 61340-2-3: the films provided in the examples and comparative examples of the present application were subjected to the SGS third party film resistance performance test as described in 2016 standard, and the initial sheet resistance values obtained from the preparation of the antistatic film and the sheet resistance values after 3, 6 and 9 months, respectively, were tested. And whether the film swings, bubble is unstable and other conditions occur in the process of preparing the film during blow molding is observed and examined, the film breaking times per month are evaluated, and the average film breaking times per month is not higher than one time and is 10; the average membrane breaking frequency per month is 2-5, and the score is 8; the average membrane breaking times per month are 6-15, and the score is 5; the average membrane breaking frequency per month is 15-30, and the score is 3; the average number of membrane ruptures per month over 30 was scored as 1 and the results are shown in table 3 below.
TABLE 3 surface resistance Properties and processability test
From the test results, the antistatic film provided by the invention has excellent mechanical properties such as tensile strength, elongation at break, tearing strength, puncture strength, heat-sealing strength and the like, and also has excellent processing performance, the raw materials can be processed smoothly, the difficulty in melting and extruding the raw materials is not easy to occur, the extruded melt is not easy to swing and shake in the blow molding process, and the film breaking frequency per month is obviously reduced compared with the traditional technology. In addition, the antistatic film provided by the invention has a high-efficiency antistatic effect, the prepared film has lower surface resistance, and the film is prevented from losing the antistatic effect after the antistatic agent on the surface of the film loses water absorption property due to the special arrangement in the film in the storage process, but the antistatic agent is promoted to continuously migrate to the surface of the film due to the difference between the density of the middle-outer layer raw material and the antistatic agent and other parameters, so that the antistatic effect of the film can be gradually improved while the effect of the antistatic agent is fully exerted.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (6)
1. The antistatic film is characterized by having a three-layer structure, comprising an inner layer, a middle layer and an outer layer; the middle layer preparation raw material comprises HDPE-II; the outer layer preparation raw material comprises HDPE-I; the density of HDPE-II is higher than the density of HDPE-I;
the outer layer comprises 80-90 parts by weight of HDPE-I, 10-20 parts by weight of antistatic agent, 1-2 parts by weight of opening agent, 1-2 parts by weight of rheological agent and 2-5 parts by weight of color master copolymer;
the density of the antistatic agent is lower than the density of the HDPE-I;
the preparation raw materials of the middle layer comprise, by weight, HDPE-II100 and 1-2 of a rheological agent; the density of the HDPE-II is 0.960g/cm3～0.970g/cm3；
The inner layer comprises 90-95 parts by weight of LLDPE, 1-2 parts by weight of an opening agent and 1-3 parts by weight of a rheological agent; the LLDPE has a density of 0.918-0.925 g/cm3；
The melt index of the antistatic agent under the same condition is higher than that of the high-density polyethylene used as the raw material for preparing the outer layer.
2. The antistatic film of claim 1 wherein the antistatic agent has a melt index of 5 to 8g/10min at a temperature of 190 ℃ and a load of 2.16 kg.
3. The antistatic film of claim 1 wherein the HDPE-I has a melt index of not less than 0.05g/10min at a temperature of 190 ℃ and a load of 2.16 kg.
4. The antistatic film as claimed in claim 1, wherein the inner layer, the middle layer and the outer layer have the weight ratio of 30-40 parts of the outer layer, 25-35 parts of the middle layer and 30-40 parts of the inner layer.
5. The method for preparing an antistatic film according to any one of claims 1 to 4, comprising the steps of:
(1) drying the antistatic agent at 50-80 ℃, and respectively stirring and mixing the raw materials of the components according to the formula proportion;
(2) melting the obtained mixture by a screw extruder according to the weight proportion of each layer, and extruding and blow-molding the mixture into a cylindrical film by a low-pressure die head;
(3) and carrying out post-treatment on the obtained cylindrical film to obtain the antistatic film.
6. The use of the antistatic film according to any one of claims 1 to 4 in the field of cushion air cushions.
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