CN114905804A - High-barrier gas-phase anti-rust film and preparation method thereof - Google Patents
High-barrier gas-phase anti-rust film and preparation method thereof Download PDFInfo
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- CN114905804A CN114905804A CN202210472482.5A CN202210472482A CN114905804A CN 114905804 A CN114905804 A CN 114905804A CN 202210472482 A CN202210472482 A CN 202210472482A CN 114905804 A CN114905804 A CN 114905804A
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Abstract
The invention belongs to the field of outer packaging materials, and discloses a high-barrier gas-phase anti-rust film and a preparation method thereof, wherein the anti-rust film mainly comprises an anti-rust layer serving as an inner layer of the anti-rust film, and a first buffer layer and a second buffer layer which serve as an outer layer and a secondary outer layer of the anti-rust film respectively, wherein a puncture-resistant layer and a high-barrier layer are arranged between the second buffer layer and the anti-rust layer, the anti-rust layer comprises anti-rust master batches, and the puncture-resistant layer is positioned between the high-barrier layer and the anti-rust layer. The coating has good oxygen-blocking and water-blocking functions, and meanwhile, the vapor phase corrosion inhibitor forms a protective molecular film on the surface of metal, can play a role in double protection of metal products, is particularly suitable for salty and humid zones, can achieve a good corrosion prevention effect, and also has lasting protection, good low-temperature flexibility and the like.
Description
Technical Field
The invention belongs to the field of external packaging materials, and particularly relates to a high-barrier gas-phase anti-rust film and a preparation method thereof.
Background
In the daily life and engineering application process, when some equipment is transported for a long distance or stored for a long time, an outer film is usually coated on the outer surface of the equipment and is mainly used for preventing the equipment from being affected with damp, oil-immersed or oxidized, a gas-phase anti-rust film is a metal protection packaging material which develops rapidly in the present year, and in a patent with the patent number of CN109291576A, a composite anti-rust packaging material and a production process are disclosed. However, the antirust films have the problems of poor barrier property, short antirust period and the like the antirust films of most types, and are difficult to be suitable for antirust packaging and storage of precise instruments or electronic elements in saline and wet areas.
Disclosure of Invention
In view of the above, the invention provides a high-barrier gas-phase anti-rust film and a preparation method thereof, so as to solve the problems that the existing anti-rust film is difficult to use in a saline wetland area and the application range of the existing anti-rust film is limited.
The technical scheme is as follows:
a high resistant separates gaseous phase antirust film, its key lies in: the anti-rust film comprises an anti-rust layer serving as an inner layer of the anti-rust film, and a first buffer layer and a second buffer layer which serve as an outer layer and a secondary outer layer of the anti-rust film respectively, wherein an anti-puncture layer and a high barrier layer are arranged between the second buffer layer and the anti-rust layer, the anti-rust layer comprises anti-puncture master batches, and the anti-puncture layer is located between the high barrier layer and the anti-rust layer.
Scheme more than adopting, the PE that will have rust-resistant master batch is as the inlayer, can be better form the protection film on packing metal object surface, play rust-resistant effect, and set up the puncture-resistant layer in the inboard of high separation, utilize its good puncture resistance and mechanical properties, avoid metal object sharp-pointed part to cause the injury to high separation layer, with this efficiency of maintaining high separation layer, and skin and time skin except can being used for satisfying some additional efficiency, can play the effect of protecting high separation layer equally, overall speaking, have good separation rust-resistant anticorrosive ability, and have better long-term protectiveness.
Preferably, the method comprises the following steps: the antirust layer, the first buffer layer and the second buffer layer are all polyethylene layers, a first bonding layer is arranged between the antirust layer and the puncture-resistant layer, and a second bonding layer is arranged between the high barrier layer and the second buffer layer. By adopting the scheme, the adjacent two layers are connected more tightly by using the adhesive, so that the oil resistance, the flexibility and the like of the whole anti-rust film are improved.
Preferably, the method comprises the following steps: the thickness of the anti-rust layer is 1-60 mu m, the thickness of the anti-puncture layer is 1-20 mu m, the thickness of the high barrier layer is 1-40 mu m, and the thickness of the first buffer layer is 1-60 mu m. By adopting the scheme, the total thickness of the protective layer can meet the protection requirements of most metal packages, the performance of each layer can be fully exerted, and the performance imbalance is avoided.
Preferably, the method comprises the following steps: the high barrier layer is made of ethylene/vinyl alcohol copolymer. The ethylene/vinyl alcohol copolymer as the high barrier layer material has not only good processability, but also excellent barrier property to gas, grease and solvent
Preferably, the method comprises the following steps: the first buffer layer has an antistatic agent therein. By adopting the scheme, the accumulation of static on the surface of the anti-rust film can be effectively reduced.
Preferably, the method comprises the following steps: the mass ratio of the antirust master batch in the antirust layer per unit area is 1-32%. The antirust master batch with the mass ratio is preferably selected, so that the cost is not obviously increased on the basis of ensuring that the antirust master batch has good antirust capacity, and the antirust master batch has good processability and certain mechanical strength.
Based on the high-barrier gas-phase antirust film, the application also provides a preparation method of the high-barrier gas-phase antirust film, and the technical scheme is as follows:
the preparation method of the high-barrier gas-phase antirust film is characterized by comprising the following steps of:
s1, mixing 40-90 parts of polyethylene, 1-20 parts of antirust master batch and 1-5 parts of an opening agent to form an antirust layer base material;
s2, selecting polyamide 6 as a raw material of the anti-puncture layer;
s3, selecting ethylene/vinyl alcohol copolymer as a high barrier layer raw material;
s4, mixing 50-90 parts of polyethylene and 3-30 parts of color master batch to form a second buffer layer base material;
s5, mixing 50-90 parts of polyethylene, 1-20 parts of antistatic agent and 1-5 parts of slipping agent to form a first buffer layer substrate;
s6, adding the base material and the raw material prepared in the steps S1-S5 and the adhesive for forming the first adhesive layer and the second adhesive layer into a multilayer blown film co-extrusion device for extrusion, wherein the melt extrusion temperature of the anti-rust layer is 160-230 ℃, the melt extrusion temperature of the first adhesive layer is 180-240 ℃, the melt extrusion temperature of the anti-puncture layer is 220-270 ℃, the melt extrusion temperature of the high barrier layer is 170-230 ℃, the melt extrusion temperature of the second adhesive layer is 170-240 ℃, the melt extrusion temperature of the second buffer layer is 170-230 ℃, and the melt extrusion temperature of the first buffer layer is 170-230 ℃.
By adopting the scheme, the production preparation efficiency can be relatively improved, and meanwhile, the integral performance of the anti-rust film can be ensured by preparing according to the parameters, so that the bonding of each layer is stable and reliable, and the layer is not easy to delaminate.
Preferably, the method comprises the following steps: in the step S6, the discharging traction speed of the multilayer blown film co-extrusion equipment is 10-20 m/min. By adopting the scheme, the stability of the finished antirust film can be effectively ensured within the traction speed range.
Preferably, the method comprises the following steps: the polyethylene comprises linear low density polyethylene and/or metallocene polyethylene and/or low density polyethylene. The single polyethylene or the combination of multiple polyethylenes can be selected for production according to production conditions and parameter requirements, and the method has more general practicability.
Compared with the prior art, the invention has the beneficial effects that:
the high-barrier gas-phase anti-rust film and the preparation method thereof provided by the invention have good oxygen-blocking and water-blocking functions, and meanwhile, the gas-phase corrosion inhibitor forms a protective molecular film on the surface of metal, so that the film can play double protection on metal products, is particularly suitable for salty and humid zones, can achieve good anti-corrosion effect, and also has lasting protection, good low-temperature flexibility and the like.
Drawings
FIG. 1 is a schematic view of a layered structure according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Referring to fig. 1, the high-barrier gas-phase anti-rust film comprises an anti-rust layer 1, an anti-puncture layer 3, a high-barrier layer 4, a second buffer layer 6 and a first buffer layer 7 which are sequentially arranged from inside to outside, wherein the anti-rust layer 1 contains anti-rust master batches, in the specific implementation, the main material of the anti-rust layer 1, the second buffer layer 6 and the first buffer layer 7 is Polyethylene (PE), the anti-puncture layer 3 is made of polyamide 6(PA6), the high-barrier layer 4 is made of ethylene/vinyl alcohol copolymer (EVOH), and in order to improve the adhesion between adjacent layered structures and prevent delamination, a first adhesive layer 2 is arranged between the anti-rust layer 1 and the anti-puncture layer 3, and a second adhesive layer 5 is arranged between the high-barrier layer 4 and the second buffer layer 6.
Because the antirust film is usually used for packaging metal devices, the metal devices are often provided with edges and sharp protrusions, polyamide 6(PA6) with better puncture resistance and mechanical property is used as the puncture-resistant layer 3 and is arranged on the inner side of the high barrier layer 4, so that the high barrier layer 4 can be prevented from being damaged, in addition, ethylene/vinyl alcohol copolymer (EVOH) has good gas barrier property, corrosion inhibition components in the antirust layer 1 can be prevented from volatilizing outwards and external oxygen can be prevented from permeating inwards, meanwhile, hydrocarbon-based functional groups carried by polyethylene adopted by the second buffer layer 6 and the first buffer layer 7 on the outer layer have good barrier property to water, and the condition that the gas barrier property of EVOH on the inner side is reduced due to water absorption is avoided.
The thickness of the high-barrier gas-phase antirust film in the application is 30-130 μm, and based on the total thickness, in order to give full play to the performance of each layer and avoid performance imbalance, the thickness of the antirust layer 1 is preferably selected as follows: 1-60 mu m, the anti-puncture layer 3 is 1-20 mu m thick, the high barrier layer 4 is 1-40 mu m thick, and the first buffer layer 7 is 1-60 mu m thick.
Further, in order to satisfy the use of precision instruments, an antistatic agent is added at the time of preparation of the first buffer layer 7 to prevent or reduce the accumulation of static electricity on the surface of the rust preventive film. In addition, the mass ratio of the antirust master batches in the antirust layer 1 in unit area is 1-32%, so that the antirust film can meet the long-term antirust use in salty and humid areas such as south China sea and the like, and the low-temperature flexibility of the antirust film is improved.
The application also synchronously provides a preparation method of the high-barrier gas-phase anti-rust film, which is characterized by comprising the following steps: firstly, mixing 40-90 parts of polyethylene, 1-20 parts of antirust master batch and 1-5 parts of an opening agent to form an antirust layer base material.
In the second step, polyamide 6(PA6) was chosen as the starting material for the puncture-resistant layer.
And thirdly, selecting ethylene/vinyl alcohol copolymer (EVOH) as a high barrier layer raw material.
And fourthly, mixing 50-90 parts of polyethylene and 3-30 parts of color master batch to form a second buffer layer base material.
And fifthly, mixing 50-90 parts of polyethylene, 1-20 parts of antistatic agent and 1-5 parts of slipping agent to form the first buffer layer base material.
And sixthly, adding the base material and the raw material prepared in the first step to the fifth step and the adhesive for forming the first bonding layer 2 and the second bonding layer 5 into a multilayer blown film co-extrusion device for extrusion, wherein the melt extrusion temperature of the anti-rust layer 1 is 160-230 ℃, the melt extrusion temperature of the first bonding layer 2 is 180-240 ℃, the melt extrusion temperature of the puncture-resistant layer 3 is 220-270 ℃, the melt extrusion temperature of the high barrier layer 4 is 170-230 ℃, the melt extrusion temperature of the second bonding layer 5 is 170-240 ℃, the melt extrusion temperature of the second buffer layer 6 is 170-230 ℃, the melt extrusion temperature of the first buffer layer 7 is 170-230 ℃, and the discharge traction speed is 10-20 m/min.
In the preparation process, the polyethylene in the first step, the fourth step and the fifth step can be linear low density polyethylene, or one or/and the combination of two or more of metallocene polyethylene and low density polyethylene, and the proper combination is selected according to specific situations, and the mass ratio can reach different performance requirements.
In the application, metallocene polyethylene, linear low-density polyethylene, polyamide 6, an opening agent, a color master batch and a slipping agent are selected from general products according to specific needs, no special requirements are needed, the adhesive is preferably maleic anhydride grafted low-density polyethylene, and the reliability of the adhesive performance can be improved.
Example one
In the specific implementation, 50 parts of metallocene polyethylene, 24 parts of linear low-density polyethylene, 10 parts of low-density polyethylene, 14 parts of antirust master batch and 2 parts of opening agent are preferably mixed in the first step to ensure good flexibility to form a base material of the antirust layer, and raw materials of the puncture-resistant layer and the high barrier layer are prepared according to the requirements of the second step and the third step.
In the fourth step, 60 parts of metallocene polyethylene, 17 parts of linear low-density polyethylene, 8 parts of low-density polyethylene and 15 parts of color master are selected and mixed to prepare the base material of the second buffer layer.
In the fifth step, 48 parts of metallocene polyethylene, 38 parts of linear low density polyethylene, 9 parts of low density polyethylene, 3 parts of antistatic agent and 2 parts of slipping agent are selected and mixed to form the base material of the first buffer layer.
In the embodiment, the multilayer blown film co-extruder with seven screws is adopted, and for each layer, the temperature of each section of the extruder is shown in table one:
TABLE-extruder temperatures in various zones are preferably indicated on the schematic scale (. degree. C.)
The rotating speed of each screw in the extruder corresponding to each layer of the anti-rust film is shown in the table II:
table two extruder screw working speed optimization schematic diagram (rpm) corresponding to each layer
| First buffer layer | Second buffer layer | Second adhesive layer | High barrier layer | Puncture resistant layer | First adhesive layer | Rust-proof layer |
| 55 | 40 | 45 | 20 | 33 | 65 | 45 |
And extruding at a drawing speed of 15.0m/min according to the parameters and the set layer thickness parameters to obtain the high-barrier gas-phase antirust film with the thickness of 100 micrometers, wherein the thickness of the antirust layer 1 is 25.5 micrometers, the thicknesses of the first adhesive layer 2 and the anti-puncture layer 3 are both 9 micrometers, the thickness of the high-barrier layer 4 is 12 micrometers, the thickness of the second adhesive layer 5 is 9 micrometers, and the thicknesses of the second buffer layer 6 and the first buffer layer 7 are respectively 15 micrometers and 20.5 micrometers.
Example 2: compared with the embodiment 1, the thickness ratio of each layer is ensured to be unchanged, and the rotating speed and the rolling speed of the screw rod are adjusted to obtain a finished film with the total thickness of 120 mu m.
Example 3: in the embodiment, the thickness ratio of each layer is changed by adjusting the blanking speed, and the rotating speed and the winding speed of the screw are adjusted to obtain the finished film with the total thickness of 50 μm, wherein the thickness of each layer is shown in table three. The preparation method comprises the following steps:
in the first step, 12 parts of metallocene polyethylene, 72 parts of low-density polyethylene, 14 parts of antirust master batch and 2 parts of opening agent are selected and mixed to form the base material of the antirust layer. The thickness of the rust-preventive layer 1 was 15 μm. In the fourth step, 13 parts of metallocene polyethylene, 72 parts of low-density polyethylene and 15 parts of color master are selected and mixed to prepare the base material of the second buffer layer. The thickness of the second buffer layer 6 was 5 μm. In the fifth step, 15 parts of metallocene polyethylene, 80 parts of low density polyethylene, 3 parts of antistatic agent and 2 parts of slipping agent are selected and mixed to prepare the base material of the first buffer layer 7, and the thickness of the first buffer layer 7 is 10 μm.
Comparative example 1: in comparison with example 3, the rust preventive layer in comparative example 1 was not added with a rust preventive agent, and the rest of the formulation and the production method were the same as in example 3.
Comparative example 2: having only three layers, namely, a three-layer PE rust preventive film was prepared: the first layer is formed by mixing 12 parts of metallocene polyethylene, 72 parts of low-density polyethylene, 14 parts of antirust master batches and 2 parts of an opening agent, and the second layer and the third layer are made of 100% pure low-density polyethylene.
Thickness (mum) of each layer of three different anti-rust films
| First layer | Second layer | Third layer | The fourth layer | The fifth layer | The sixth layer | The seventh layer | Total thickness of | |
| Example 1 | 25.5 | 9 | 9 | 12 | 9 | 15 | 20.5 | 100 |
| Example 2 | 30.6 | 10.8 | 10.8 | 14.4 | 10.8 | 18 | 24.6 | 120 |
| Example 3 | 15 | 5 | 5 | 5 | 5 | 5 | 10 | 50 |
| Comparative example 1 | 15 | 5 | 5 | 5 | 5 | 5 | 10 | 50 |
| Comparative example 2 | 16.6 | 16.7 | 16.7 | - | - | - | - | 50 |
The finished films obtained in examples 1 to 3, and comparative examples 1 and 2 were subjected to performance tests, the main test parameters including tensile strength, vapor phase corrosion inhibition ability, and rust-proof time, and the results are shown in table four.
Results of Performance test of four different anti-rust films
| Tensile Strength (MPa) | Gas phase corrosion inhibition capability | Antirust time (year) | |
| Example 1 | 28 | Superior food | ＞12 |
| Example 2 | 30 | Superior food | ＞14 |
| Example 3 | 25 | Youyou (an instant noodle) | 6～8 |
| Comparative example 1 | 28 | Good wine | ＜3 |
| Comparative example 2 | 18 | Good wine | ＜4 |
The high-barrier gas-phase rust preventive film obtained in example 1 was subjected to more detailed performance test measurements as shown in Table five.
Table five high-resistance gas phase antirust film finished product test result schematic table
As can be seen from the table five, the high-barrier gas-phase antirust film has good puncture resistance and barrier property (the oxygen transmission capacity and the water vapor transmission capacity are both small), and certainly has good long-term antirust protection capability.
Finally, it should be noted that the above-mentioned description is only a preferred embodiment of the present invention, and those skilled in the art can make various similar representations without departing from the spirit and scope of the present invention.
Claims (9)
1. A high resistant separates gaseous phase antirust film which characterized in that: the antirust film comprises an antirust layer (1) serving as an inner layer of an antirust film, and a first buffer layer (7) and a second buffer layer (6) serving as an outer layer and a secondary outer layer of the antirust film respectively, wherein an anti-puncture layer (3) and a high-barrier layer (4) are arranged between the second buffer layer (6) and the antirust layer (1), the antirust layer (1) comprises antirust master batches, and the anti-puncture layer (3) is located between the high-barrier layer (4) and the antirust layer (1).
2. The high-barrier gas-phase antirust film according to claim 1, characterized in that: the anti-rust layer (1), the first buffer layer (7) and the second buffer layer (6) are all polyethylene layers, a first bonding layer (2) is arranged between the anti-rust layer (1) and the puncture-resistant layer (3), and a second bonding layer (5) is arranged between the high barrier layer (4) and the second buffer layer (6).
3. The high-barrier gas-phase antirust film according to claim 1 or 2, characterized in that: the thickness of the anti-rust layer (1) is 1-60 mu m, the thickness of the anti-puncture layer (3) is 1-20 mu m, the thickness of the high barrier layer (4) is 1-40 mu m, and the thickness of the first buffer layer (7) is 1-60 mu m.
4. The high-barrier gas-phase antirust film according to claim 3, characterized in that: the high barrier layer (4) is prepared from ethylene/vinyl alcohol copolymer.
5. The high-barrier gas-phase antirust film according to claim 1 or 2, characterized in that: the first buffer layer (7) is internally provided with an antistatic agent.
6. The high-barrier gas-phase antirust film according to claim 1, characterized in that: the mass ratio of the antirust master batch in the antirust layer (1) per unit area is 1-32%.
7. A method for producing a high-barrier gas-phase antirust film as defined in any one of claims 1 to 6, comprising the steps of:
s1, mixing 40-90 parts of polyethylene, 1-20 parts of antirust master batch and 1-5 parts of an opening agent to form an antirust layer base material;
s2, selecting polyamide 6 as a raw material of the anti-puncture layer;
s3, selecting ethylene/vinyl alcohol copolymer as a high barrier layer raw material;
s4, mixing 50-90 parts of polyethylene and 3-30 parts of color master batch to form a second buffer layer base material;
s5, mixing 50-90 parts of polyethylene, 1-20 parts of antistatic agent and 1-5 parts of slipping agent to form a first buffer layer substrate;
s6, adding the base material and the raw material prepared in the steps S1-S5 and the adhesive for forming the first bonding layer (2) and the second bonding layer (5) into a multilayer blown film co-extrusion device for extrusion, wherein the melt extrusion temperature of the anti-rust layer (1) is 160-230 ℃, the melt extrusion temperature of the first bonding layer (2) is 180-240 ℃, the melt extrusion temperature of the anti-puncture layer (3) is 220-270 ℃, the melt extrusion temperature of the high barrier layer (4) is 170-230 ℃, the melt extrusion temperature of the second bonding layer (5) is 170-240 ℃, the melt extrusion temperature of the second buffer layer (6) is 170-230 ℃, and the melt extrusion temperature of the first buffer layer (7) is 170-230 ℃.
8. The method for preparing the high-barrier gas-phase antirust film according to claim 7, characterized in that: in the step S6, the discharging traction speed of the multilayer blown film co-extrusion equipment is 10-20 m/min.
9. The method for preparing a high-barrier gas-phase antirust film according to claim 7, characterized in that: the polyethylene comprises linear low density polyethylene and/or metallocene polyethylene and/or low density polyethylene.
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| CN117702125B (en) * | 2023-11-08 | 2024-05-28 | 宜兴维新科技有限公司 | Preparation method of rust-proof master batch composite vapor phase corrosion inhibitor for rust-proof film |
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