Patent Application
20130101864
The invention relates to a antirust film and a preparation method thereof.
All metal preparations are faced with antirust problems. With the rapid development of industrial production, antirust method has been developed from the most simple plating, coating, vacuum packaging, painting, coating with antirust oil, to the method of Volatile Conosion Inhibitor (VCI), with an extensive application to rust inhibition of black metal and its products.
According to the current application situation of VCI antirust films, there are still many shortcomings:
{circle around (1)} The current antirust agents have acceptable rust inhibiting effect, but they are toxic and the release of gas has an impact on the human body, and the toxicity can not be ignored, endangering crowd safety; some antirust films only exhibit rust inhibiting effect on steel metals, but little on other metals.
{circle around (2)} Current antirust films usually adopt polyethylene. Because the tensile strength of polyethylene film is not very good, with polyethylene blown film equipment limitations, it is difficult to make super-wide thin-film and therefore is incompatible with the requirements of the rust inhibition of large-scale equipments, large-scale scientific instruments, aerospace equipments, and large-scale devices.
{circle around (3)} current antirust films adopts polyethylene as the main base and VCI as gas source of the antirust agent, due to poor performance of existing antirust agent, together with poor gas barrier property of polyethylene film, resulting in many antirust gas volatilizing from antirust bags made of films to bag outside, which not only waste the resources, but also make antirust time of the items can only reach 2 to 3 years; and as large-scale precision equipments and major aerospace facilities, they are required to be antirust over time in 10 years, so the existing antirust film can not meet this requirement.
□ As the antirust item is stored in the antirust bag made of antirust film, it saves a long time and is easy to breed mold and other colonies, although the VCI has antirust capabilities for metals, but can not kill the mold and other colony, therefore, for a especially long shelf of large-scale equipments, instruments and equipments, aerospace equipments, etc., when the existing antirust film open, you can find a lot of mold or other colonies.
□ With the development of science and technology, there will be more and more large-scale research equipments and aerospace equipments, precision instruments, and finishing equipments, antirust film have become increasingly demanding; However, following the market-use of polyethylene antirust film currently, we can not reach a very wide range, because of poor tensile strength causing leading to occurrence of bags breaking and air leaking, together with poor barrier property and short-time antirust of the film, which can not adapt to the large-scale equipments.
In order to overcome the disadvantages that the current VCI film barrier with poor barrier property, low endurance, can not be applied to large-scale equipments, the invention provides a multifunctional, long-acting antirust film, which has a good barrier property, maintains an antirust effect for a long time, and is effectively used in large-scale equipments. Also provided is a method for preparing the multifunctional, long-acting antirust film.
In order to solve the above technical problem, the invention adopts the following technical scheme:
a multifunctional, long-acting antirust film comprises: a nylon 6 thin-film layer, an adhesive layer, an antimicrobial layer and an antirust layer; the antimicrobial layer covers the antirust layer, the adhesive layer covers the antimicrobial layer, and the nylon 6 thin-film layer covers the adhesive layer;
in the multifunctional, long-acting antirust film, the nylon 6 thin-film layer accounts for from 25% to 32%, the adhesive layer accounts for from 6% to 8%, the antimicrobial layer accounts for from 30 to 35%, and the antirust layer accounts for from 26% to 35% of its total mass;
the antirust layer comprises from 23.5 to 26 parts by mass of a binary copolymer of PP, from 3 to 4 parts by mass of a thermoplastic elastomer, from 0.5 to 1 parts by mass of an antisticking agent and from 2 to 4 parts by mass of an antirust masterbatch;
the antimicrobial layer comprises from 27 to 29 parts by mass of polyethylene and from 3 to 6 parts by mass of an antimicrobial masterbatch.
As a preferred technical scheme, the adhesive layer uses a laminating adhesive for dry lamination machine.
Further, the nylon 6 thin layer uses a polyamide-6 thin film.
Further, in the antimicrobial agent layer, the polyethylene uses metallocene polyethylene.
Still further, in the antirust layer, the antirust masterbatch uses benzotriazole antirust masterbatch.
A method for preparing the multifunctional, long-acting antirust includes the following steps of:
(1) selecting materials: in the multifunctional, long-acting antirust film, the nylon 6 thin-film layer accounts for 25˜32%, the adhesive layer accounts for 6˜8%, the antimicrobial layer accounts for 30˜35%, and the antirust layer accounts for 26 to 35% of the total mass;
the antirust layer comprises from 23.5 to 26 parts by mass of a binary copolymer of PP, from 3 to 4 parts by mass of a thermoplastic elastomer, from 0.5 to 1 parts by mass of an antisticking agent and from 2 to 4 parts by mass of an antirust masterbatch;
the antimicrobial layer comprises from 27 to 29 parts by mass of polyethylene and from 3 to 6 parts by mass of an antimicrobial masterbatch.
(2) a process for preparing an antirust layer adopts a co-extruded biaxial stretching method, and specifically includes the following steps:
(2.1) melting, plasticizing and extruding: plasticizing and extruding the configured materials of a binary copolymer of PP, a thermoplastic elastomer, an antisticking agent and an antirust masterbatch using an extruder to obtain molten materials;
(2.2) filtering: filtering the molten materials;
(2.3) tape-casting: having the filtered molten material attached to the chill-roll surface, and forming a cast film with the aid of a quenching roll, water bath and a guide roll;
(2.4) stretching: taking the cast film off, stretching it in the longitudinal direction, and then stretching it in the transverse direction;
(2.5) cooling the stretched film and shaping it into a thin film; and
(2.6) traction winding-up: subjecting the thin film to edge trimming, thickness measuring and corona treatment, and then winding the thin film into a tubular film roll;
(3) applying an antimicrobial material to the antirust layer using a laminating machine; and
(4) applying an adhesive to the antimicrobial layer, then having a nylon 6 thin-film glued to the adhesive layer using a lamination machine, to form a multifunctional, long-acting antirust film.
As a preferred technical scheme: the step (3) includes the following steps:
(3.1) premixing polyethylene with an antimicrobial masterbatch, feeding the mixture into the hopper using a feeder, then into the extruder for melting and plasticizing the mixture, and filtering the molten mixture using a filter before entering the T-type die head;
(3.2) laminating: laminating the flake melt extruded from the die lip of the T-type die head to the antirust inhibitor layer uniformly; and
(3.3) Thickness measuring and edge trimming: measuring the thickness of the laminated film, winding it into a roll film, and subjecting the roll film to edge trimming treatment.
Still further, the antirust masterbatch is mixed and pelleted using a pressurized reciprocating twin-screw intermixing extruder.
The beneficial effects of the present invention is mainly embodied in: the VCI film has versatility and long-term effectiveness, wherein the antirust gas is non-toxic and environmentally friendly, and does no harm to the human body and the air. It can solve the antirust problems of black metal and non-ferrous metals and also the large-scale antirust problems of high-end facilities, such as large-scale equipments, aerospace equipments, and so on, and maintain antirust effect for at least 10 years. By adjusting the structure of the antirust film, it is achieved that: the gas in the antirust film bag does not leak, the mold and harmful colonies do not breed in the bag, the antirust parts have long-term antirust effect, and harmful bacteria do not grow on the antirust parts, without polluting the environment and affecting the health of staff.
The present invention is further described through the specific examples. However, the present invention is by no means limited to the listed examples herein:
Refer to
in the multifunctional, long-acting antirust film, the nylon 6 thin layer accounts for 25% to32%, the adhesive layer 2 accounts for 6% to 8%, the antimicrobial layer 3 accounts for 30% to 35%, and the antirust layer 4 accounts for 26% to 35% of its total mass;
the antirust layer 2 comprises from 23.5 to 26 parts by mass of a binary copolymer of PP, from 3 to 4 parts by mass of a thermoplastic elastomer, from 0.5 to 1 parts by mass of an antisticking agent and from 2 to 4 parts by mass of an antirust masterbatch;
the antimicrobial layer 3 comprises from 27 to 29 parts by mass of polyethylene and from 3 to 6 parts by mass of an antimicrobial masterbatch.
The adhesive layer 2 uses a laminating adhesive for dry lamination machine. The nylon 6 thin layer uses a polyamide-6 thin film. In the antimicrobial layer 3, the polyethylene uses metallocene polyethylene. In the antirust layer, the antirust masterbatch uses a benzotriazole antirust masterbatch.
In the multifunctional, long-acting antirust film of the present example, the nylon 6 thin layer accounts for 25%, the adhesive layer 2 accounts for 6%, the antimicrobial layer 3 accounts for 35%, and the antirust layer 4 accounts for 34% of its total mass.
The antirust layer 4 is BOPP film, which comprises the following components:
A a binary copolymer of PP, produced by the BSELL company, with a trade name of 7384PP, 23.5˜26 parts;
B a thermoplastic elastomer, produced by Dutch Shell Chemical Company, with a trade name of G1652, 3˜4 parts;
C an antisticking agent, produced by Suzhou Constab Engineering Plastics Company, with a trade name of AB6018PP, 0.5˜1 parts;
D an antirust masterbatch, benzotriazole antirust masterbatch, 2˜4 parts.
The antimicrobial layer 3 is a thin-film layer formed by laminating raw materials using a laminating machine, and the raw materials comprise the following components:
A metallocene polyethylene (mLLPE), produced by Exxon Chemical Company (USA), 27˜29 parts;
B an antimicrobial masterbatch, PE-BMFZ, produced by Shanghai Weilai New Material Co., Ltd., 3˜6 parts.
In order to improve the adhesive quality of lamination, metallocene polyethylene (mLLPE) is used as the substrate.
The adhesive layer 2 of the multifunctional, long-acting antirust film, is a binder layer laminated using a dry lamination machine, and the raw material is: a universal laminating adhesive for the dry lamination machine, non-toxic LH-7755A, reaching the food-grade standard of use, produced by Jintan City adhesive Plant.
The nylon 6 thin-film layer 1, in which nylon 6 is Polyamide-6, and the nylon 6 (polyamide-6) film is produced by Zhejiang Huisheng Plastic & Rubber Company.
In the example, the technical process for preparing the multifunctional, long-acting antirust film is as follows:
{circle around (1)} Currently, there are many kinds of VCI at home and abroad, with different properties. In order to obtain superior antirust properties, a safe, reliable and efficient VCI film is required. The selection of the VCI agent is one of the key technics of this application. The application selects benzotriazole as the VCI agent, whose antirust performance is very good and can meet very good levels of antirust requirements (such as the U.S. military standard MIL-1-22110). Benzotriazole has good thermal stability. It is non-toxic and does not have harmful physiological toxicity on human body. It can be extracted from the by-product produced during vitamin B6 production, with low cost.
The structural formula of Benzotriazole antirust agent is:
Molecular formula: C6H5N3
Molecular weight: 119.12;
Main properties: Benzotriazole is white to light pink needle-like crystals, and non-toxic; melting point is 9805 and boiling point is 204 □ (2.0 Kpa) or 159 □ (0.267 Kpa); benzotriazole is soluble in alcohol, benzene, toluene, chloroform and dimethylformamide, and slightly soluble in water.
Benzotriazole as the VCI agent is mixed with plastic particles to form a VCI masterbatch. Benzotriazole is capable of forming covalent bonds and coordinating bonds with metal atoms, and mostly cross-linked to each other to produce a chain polymer and form multilayer protective films on the metal surface, which protects the metal surface from oxidation reaction and plays an effective role in the rust inhibition.
The process for developing the antirust Masterbatch: currently, ordinary VCI masterbatch preparation adopts conventional mixing techniques, which requires long mixing time and high temperature and makes the VCI easy to decompose. The antirust films prepared by the conventional techniques have poor antirust effects and short antirust time. It is necessary to adopt an advanced antirust film and a novel masterbatch manufacturing technique to achieve high antirust effect.
In the invention, the VCI masterbatch is mixed and pelleted using a pressurized reciprocating twin-screw intermixing extruder, and the process for preparing the VCI masterbatch using the device has the following characteristics:
{circle around (1)} Since the device is equipped with two mandatory charging hoppers, antirust agents and additives may be added in two parts, and do not need to premix;
{circle around (2)} Increased torque and difficulty in filling caused by the addition of a large number of antirusts together with the base material are avoided;
{circle around (3)} The antirusts and additives can be dispersed well due to the Screw structure and operation mode of the device;
{circle around (4)} The true temperature of the melt can be measured with the pin of the device, so it is possible to impose strict and accurate control on mixing, with the result that the melt mixing time can be shortened and the VCI is not easy to break down.
Major device, materials, and technical parameters of the process for preparing the antirust masterbatch are as follows:
major device: pressurized reciprocating twin-screw intermixing extruder;
VCI: benzotriazole; additives: Cyclohexylamine Carbonate, sodium molybdate; base material: Polyolefin resin PP;
the antirust masterbatch is produced by mixing and extruding, and has a good antirust effect on more than ten metals, including steel, iron, copper, silver, aluminum, zinc, nickel, magnesium, and aluminum;
technical parameters: mixing temperature: 170˜180° C., mixing time: 35 min˜45min, the temperature controlled as follows:
temperature control of the pressurized reciprocating twin-screw intermixing extruder can be seen in Table 1:
plasticizing temperature control can be seen in Table 2:
Refer to
other solutions and work processes of the example are the same as the example 1.
Refer to
other solutions and work processes of the example are the same as the example 1.
Refer to
other solutions and work processes of the example are the same as the example 1.
Refer to
other solutions and work processes of the example are the same as the example 1.
Refer to
Other solutions and work processes of the example are the same as the example 1.
Refer to
(1) selecting materials: in the multifunctional, long-acting antirust film, the nylon 6 thin-film layer accounts for 25˜32%, the adhesive layer accounts for 6˜8%, the antimicrobial layer accounts for 30˜35%, and the antirust layer accounts for 26 to 35% of the total mass;
the antirust layer comprises from 23.5 to 26 parts by mass of a binary copolymer of PP, from 3 to 4 parts by mass of a thermoplastic elastomer, from 0.5 to 1 parts by mass of an antisticking agent and from 2 to 4 parts by mass of an antirust masterbatch;
the antimicrobial layer comprises from 27 to 29 parts by mass of polyethylene and from 3 to 6 parts by mass of an antimicrobial masterbatch.
(2) a process for preparing an antirust layer adopts a co-extruded biaxial stretching method, and specifically includes the following steps:
(2.1) melting, plasticizing and extruding: plasticizing and extruding the configured materials of a binary copolymer of PP, a thermoplastic elastomer, an antisticking agent and an antirust masterbatch using an extruder to obtain molten materials;
(2.2) filtering: filtering the molten materials;
(2.3) tape-casting: having the filtered molten material attached to the chili-roil surface, and forming a cast film with the aid of a quenching roll, water bath and a guide roll;
(2.4) stretching: taking the cast film off, stretching it in the longitudinal direction, and then stretching it in the transverse direction;
(2.5) cooling the stretched film and shaping it into a thin film; and
(2.6) traction winding-up: subjecting the thin film to edge trimming, thickness measuring and corona treatment, and then winding the thin film into a tubular film roll;
(3) applying an antimicrobial material to the antirust layer using a laminating machine; and
(4) applying an adhesive to the antimicrobial layer, then having a nylon 6 thin-film glued to the adhesive layer, to form a multifunctional, long-acting antirust film.
The step (3) includes the following steps:
(3.1) premixing polyethylene with an antimicrobial masterbatch, feeding the mixture into the hopper using a feeder, then into the extruder for melting and plasticizing the mixture, and filtering the molten mixture using a filter before entering the T-type die head;
(3.2) laminating: laminating the flake melt extruded from the die lip of the T-type die head to the antirust inhibitor layer uniformly; and
(3.3) thickness measuring and edge trimming: measuring the thickness of the laminated film, winding it into a roll film, and subjecting the roll film to edge trimming treatment.
The antirust masterbatch is mixed and pelleted using a pressurized reciprocating twin-screw intermixing extruder.
In the multifunctional, long-acting antirust film of the present example, the nylon 6 thin layer accounts for 25%, the adhesive layer 2 accounts for 6%, the antimicrobial layer 3 accounts for 35%, and the antirust layer 4 accounts for 34% of its total mass;
The preparation of the antirust layer adopts a co-extruded biaxial stretching method, where the production system is controlled by a computer, and the production process is:
raw materials preparation—melting, plasticizing and extruding—filtering the molten materials—extruding from the die head —chilling and shaping vertical stretching—horizontal stretching—cooling and shaping—Corona treatment—thickness measuring, tracting—constant breadth edge trimming—winding-up.
It is required that the melting temperature and plasticizing temperature are kept below 200° C., in order to prevent excessive gasification of the antirust masterbatch.
The antimicrobial layer is a laminated layer, which comprises PE as the base material and the antimicrobial agent masterbatch as the adjuvant. In order to improve the bond strength of the laminated layer, metallocene polyethylene (mLLPE) is used as the base material. The materials are coated on the antirust layer using the laminating machine, and the process includes the following steps:
(1) Preparing Raw Materials and Plasticizing Them:
mLLPE and the antimicrobial masterbatch are weighed with a batch meter and premixed. A feeder is used for feeding the premixed materials into the hopper, then into the extruder, in which the materials are melted and plasticized. The molten materials are filtered using a filter before entering the T-type die head. Homogeneous PE and antimicrobial mixed melt is laminated through a automatic adjustable die lip as flaky melt onto the antirust layer uniformly and with consistent thickness.
(2) Laminating:
the flake melt extruded from the die lip is uniformly laminated onto the BOPP antirust layer to form a BOPP/PE laminated film with required thickness;
(3) Thickness Measuring and Edge-Trimming
The actual thickness of the film is measured using an automatical thickness gauge, and the data obtained are automatically feedback to the mLLPE extruder, so as to adjust the opening size of the die lip in real time to control the extrusion amount of the melt, and thus ensure that the thickness error of the laminated film is within the allowable tolerance.
Then the BOPP/PE laminated film is winded into a rolling film. The rolling film is subjected to edge trimming and corona treatment (to increase the surface tension of the film), and ultimately, it is winded into a tubular film roll, and the tubular film roll is transported to the aging treatment area where the film roll is subjected to the aging treatment for 24 hours.
Temperature control of the extruder laminating machine is listed in the following table 3:
Temperature control of the die lip zones of the laminating machine is listed in the following table 4:
In the multifunctional, long-acting antirust film of the example, the upper layer is a thin-film layer comprising nylon 6 as the base material. The adhesive is applied to the BOPP/PE laminated layer using a dry laminating machine to form an adhesive layer, and then the nylon 6 thin-film layer covers the BOPP/PE laminated layer with the aid of the adhesive layer between, to complete the initial production of the multifunctional antirust film.
Then, the glued multifunctional antirust film is subjected to thickness measuring, edge trimming, corona treatment, winding-up, aging treatment, and product packaging before entering the bag-making workshop, where the antirust film is made into antirust bags to supply the orders from various manufacturers.
The multifunctional, long-acting antirust film greatly improves the technical properties, and its properties are beyond the ordinary antirust film. The technical parameters of the multifunctional, long-acting antirust film are as follows:
(1) film thickness: from 30 to 90 microns;
(2) Tensile strength: compared with ordinary antirust film with the same thickness, the tensile strength of the antirust film of the present invention increases by 31%;
(3) puncture resistance: compared with ordinary antirust film with the same thickness, the puncture resistance of the antirust film of the present invention increases by 33%;
(4) tear resistance: compared with ordinary antirust film with the same thickness, the tear resistance of the antirust film of the present invention increases by 30%;
(5) Heat-seal strength: compared with ordinary antirust film with the same thickness, the Heat-seal strength of the antirust film of the present invention increases by 28.7%;
(6) moisture permeability: 0 g/m2·H;
(7) Oxygen permeation ratio: 0 g/m2·H;
(8) Antirust time: More than 10 years;
(9) bacteria-inhibiting time: Long-acting effective.
Refer to
other solutions and work processes of the example are the same as the example 7.
Refer to
other solutions and work processes of the example are the same as the example 7.
Refer to
other solutions and work processes of the example are the same as the example 7.
Refer to
other solutions and work processes of the example are the same as the example 7.
Refer to
other solutions and work processes of the example are the same as with the example 7.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201010225078.5 | Jul 2010 | CN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CN10/76413 | 8/27/2010 | WO | 00 | 3/12/2012 |
