KR101004088B1 - Eco-friendly volatile corrosion inhibitor stretch film and preparation method thereof - Google Patents

Abstract

PURPOSE: An environment-friendly volatile anti-corrosive stretch film is provided to enable applications to environment-friendly volatile anti-corrosive master batch, ferrous metals or nonferrous metals and to ensure excellent mechanical properties. CONSTITUTION: An environment-friendly volatile anti-corrosive stretch film comprises an anticorrosive adhesive layer and an anticorrosive support layer. The anticorrosive adhesive layer includes 1~10 parts by weight volatile anti-corrosive masterbatch made by mixing a polymer resin and amine molybdenum, 70~95 parts by weight base resin, and 1~10 parts by weight adhesive.

Description

Eco-friendly volatile corrosion inhibitor stretch film and preparation method

The present invention relates to an environmentally friendly vaporizable rust-preventive stretch film and a method for producing the same.

To date, metal-related packaging materials emphasize simple functions such as corrosion protection, and use methods such as anti-rust paper, anti-rust film, anti-rust solution, anti-rust grease, anti-rust oil, anti-rust powder, etc. to prevent corrosion that greatly affects quality. have. However, the method used to prevent corrosion of the metal has disadvantages such as inconvenience in use, increased packaging cost, and low productivity.

Complementing these shortcomings, vaporizing rust preventive stretch products have been proposed mainly in developed countries for the advancement and automation of packaging methods. The vaporizable rust preventive stretch product is manufactured using a vaporizable rust preventive agent. The vaporizable rust preventive agent (Volatile Corrosion Inhibitor master batch) refers to a material that inhibits corrosion by vaporizing at room temperature to coat a metal surface.

The vaporizing rust preventive agent is prepared by mixing materials that are easily vaporized at room temperature, and prevents the primary mechanism of corrosion by preventing vaporized particles from flowing from the cathode to the anode by forming a fine film on the metal surface. Can be. Vaporizable rust inhibitor particles are usually formed by adsorbing a thin protective layer of 1 molecule thickness onto a metal surface. The metal ions thus formed no longer react with moisture and oxygen.

Vaporizable rust inhibitors utilize the property that more or less vaporizable rust inhibitor particles are automatically released in the evaporation zone as the temperature increases and decreases. Accurately calculated vaporization rust preventive treatments maintain the most suitable evaporation pressure to ensure proper dispersion of particles in enclosed spaces (spaces that do not drastically explode into packaging gaps) as well as lower corrosion rates for metals. There is a natural dynamic equilibrium between the vaporized vaporizable rust inhibitor particles and the vaporized rust inhibitor particles that are not vaporized and condensed. This equilibrium requires protection from the flow of air that vaporizing rust inhibitors can lose in creating complete protection. In a confined space, the vaporizable rust preventive system is in equilibrium with the atmosphere in the package, thereby creating a rust preventive environment of the vaporizable rust preventive inside the package. Vaporizable rust inhibitors bound to the metal surface block the process of corrosion and have the same effect on low and high humidity.

Often, vaporizable rust inhibitors are divided into ferrous metal vaporization rust inhibitors and nonferrous metal vaporization rust inhibitors. Ferrous metal vaporization rust inhibitors contain sodium nitrate or nitrate ions. Typical vaporizing rust inhibitors include a mixture of sodium nitrite and urotropine, a mixture of sodium nitrite and carbamide, ammonium benzoate, or nitrite dicyclohexylamine nitrite (DICAN). Used. In some cases, nitrite urotropine (UN) compounds are used. In others, sodium nitrite and carbamide mixtures and sodium benzoate or ammonium benzoate are already applied. Among them, DICAN is now widely used as a ferrous metal vaporizing rust inhibitor.

Although non-ferrous metal vaporizing rust inhibitors have been used in the past, chromium salts (Chromates) have been used. However, chromium is very toxic and has a low vapor pressure. Therefore, it has been replaced by NO ₂ compounds. This is because the protection of various metals is possible. In addition, aminonitro benzoate and aminodinitro benzoate are also known to have versatility. In particular, benzotriazole (C ₆ H ₅ N ₃ ) has been used in copper alloys, which has a mechanism of action that forms insoluble complex salts with copper.

DICAN, DIPAN, Nitrous acid, salt, and sodium nitrite, which are currently used as materials of rust inhibitors, are designated as environmentally harmful substances and thus have many problems to be used as vaporizing rust inhibitors. In addition, the film using the vaporizable rust preventive material has a thickness of 40 ㎛ or more, the film containing the vaporizable rust preventive material has a problem that not only decreases the adhesive force, but also increases the manufacturing cost.

Accordingly, the film can be used for both ferrous and non-ferrous metals without using environmentally harmful substances and without emitting toxic substances such as carcinogens during vaporization, and it can be used for environmentally harmless substances, even if the film is made thin. There is a need for a vaporizable antirust stretch film that does not weaken its mechanical properties.

The object of the present invention for solving the problems of the prior art described above is harmless to the human body because it does not emit toxic substances during vaporization, and can be applied to both environmentally friendly vaporizable rust-proof masterbatch, ferrous metals or non-ferrous metals, the thickness of the film The present invention provides a method for producing a vaporizable antirust stretch film and a vaporizable antirust stretch film having a thin and excellent mechanical properties.

Vaporizable rustproof masterbatch according to one feature of the present invention for achieving the above object is made by mixing a polymer resin and amine molybdenum, the vaporizable rustproof masterbatch is used for corrosion protection of iron or nonferrous metals.

The vaporizable rust preventive masterbatch may further include benzotriazole and additives.

The polymer resin is preferably 75 to 85 parts by weight and amine molybdenum is mixed at 15 to 25 parts by weight.

In addition, the vaporizable rust-preventive stretch film according to another feature of the present invention is a vapor-resistant rust masterbatch made by mixing a polymer resin and amine molybdenum, a base resin 1 and an anti-rust adhesive layer mixed with an adhesive; And an antirust support layer made of a base resin 2.

The vaporizable rustproof masterbatch is 1 to 10 parts by weight, the base resin 1 is preferably 70 to 95 parts by weight and the adhesive is 1 to 10 parts by weight.

The vaporizable rust preventive stretch film may be formed of two or more layers.

It is preferable that the thickness of the said vaporization antirust stretch film is 10-60 micrometers.

It is preferable that the tensile force of the said vaporization antirust stretch film is 200-600 kgf / cm <^2> , and elongation rate is 300-1,000% or more.

In addition, the method for producing a corrosion-resistant vaporized anti-corrosive stretch film for iron or non-ferrous metals according to another aspect of the present invention, 1) the dough prepared by mixing and kneading the vaporizable rust-proof masterbatch, the base resin 1 and the adhesive of the present invention 1 and kneading the base resin 2 to obtain a dough 2; And 2) combining the dough 1 and dough 2 while extruding using an extruder.

The vaporizable rustproof masterbatch of step 1) is 1 to 10 parts by weight, the base resin 1 is preferably 70 to 95 parts by weight and the adhesive is added in 1 to 10 parts by weight.

It is preferable that the said vaporizable antirust masterbatch is made by mixing a polymer resin and amine molybdenum.

The amine molybdenum is prepared by dropping a solution 1 obtained by mixing ammonium hydroxide and molybdenum into a solution 2 prepared by mixing one selected from dicyclohexylamine or 2-ethylamine with phosphoric acid; It is preferably prepared by mixing and reacting one selected from dicyclohexylamine or 2-ethylamine with Solution 1 in which ammonium hydroxide and molybdenum are mixed.

In the present invention, instead of harmful substances such as nitrite, dicyclohexylamine nitrite, cyclohexyl carbonate, which is harmful to the human body, by using amine molybdenum, an environmentally friendly substance, an antirust masterbatch is made and added thereto to prepare a vaporizable antirust stretch film. The mechanical properties similar to those of conventional rust-preventive films can be achieved with respect to ferrous or nonferrous metals. This has the significance of greatly improving the stability of the human body, which is the limitation of the conventional rust-preventive film, and has the characteristics that can have the tensile strength, the elongation rate required as a vaporizable rust-preventive stretch film.

In addition, the vaporizable antirust stretch film of the present invention can be produced in a thin thickness, so that the amount of material used can be reduced, which is economical. As described above, the vaporizable antirust stretch film of the present invention has advantages such as human stability, stable mechanical properties, and low production cost, and thus may be usefully used in a field in which a vaporizable antirust stretch film is used.

1 is a view briefly illustrating a process for preparing the amine molybdenum of the present invention.
Figure 2 is for producing a vaporizable antirust masterbatch of the present invention.
3 and 4 are schematic diagrams of vaporizable rust preventive stretch films prepared using the vaporizable rust preventive masterbatch of the present invention.
5 is a result of examining the corrosion inhibitory effect of the metal plate using the vaporizable rust-proof film of the present invention.
Figure 6 is a schematic diagram of a device for producing a stretch film using a vaporizable rustproof masterbatch of the present invention.

Applicant, while studying a method for producing a vaporizable antirust stretch film that is harmless to the human body, it is possible to manufacture a vaporizable antirust stretch film using amine molybdenum, while confirming that the physical properties as a vaporizable antirust stretch film can be satisfied. The invention has been completed.

Hereinafter, the present invention will be described in detail.

Hereinafter, the vaporizable antirust masterbatch of the present invention will be described.

The vaporizable antirust masterbatch of the present invention is made by mixing a polymer resin and an amine molybdenum.

When ferrous or non-ferrous metals are exposed to air, corrosion occurs due to reaction with oxygen or moisture in the air. In order to prevent this, forming a thin protective layer on the surface of the ferrous or non-ferrous metals by using a vaporizing anti-corrosive material or a rust preventive agent desirable. In the art for the convenience of use and ease of manufacture, to prepare and use the masterbatch containing the rust inhibitor or rust inhibitor. The masterbatch is prepared by mixing the materials to be blended in advance, and in the present invention, a vaporizable rust preventive material or a rust preventive agent is mixed with a polymer resin to prepare a vaporizable rust preventive masterbatch.

The polymer resin, such as the polyolefin series used in the vaporizable rustproof masterbatch, may serve as a support for amine molybdenum, which is a main component of the rust preventive agent.

Amine molybdenum, which is a main component of the rust preventive agent, is a substance that can be released from the film and vaporized as the air temperature increases, and is an environmentally friendly and harmless component.

The vaporizable masterbatch using the polymer resin and the amine molybdenum is preferably mixed at 75 to 85 parts by weight and 15 to 25 parts by weight, respectively. At this time, when the amine molybdenum is less than 15 parts by weight, it is difficult to have a sufficient corrosion protection function according to the low amount of the main component of the rust preventive agent, and when it exceeds 25 parts by weight, it is possible to perform a sufficient corrosion protection function, Since the compatibility of the rust preventive stretch film may be degraded, it is not preferable.

In order to enhance the rust prevention effect of the vaporizable rustproof masterbatch, benzotriazole may be further added. The benzotriazole is a rust preventive substance used in the past, and is somewhat toxic to humans, and thus the use amount is restricted. Therefore, in the present invention, the content of benzotriazole is preferably less than 2 parts by weight, preferably 1 to 1.5 parts by weight.

In addition, the vaporizing antirust masterbatch may further include an additive, in order to increase the stability of the material, an additive may be an antioxidant, heat stabilizer or antistatic agent. The antioxidant, heat stabilizer or antistatic agent may be used a material commonly used in the art. The amount of the additive used is preferably 0.1 to 0.3 parts by weight.

EMBODIMENT OF THE INVENTION Hereinafter, the vaporizable rustproof stretch film manufactured using the vaporizable rustproof masterbatch of this invention is demonstrated.

Vaporizable anti-rust stretch film according to another feature of the present invention is a vaporizable anti-rust masterbatch made by mixing a polymer resin and amine molybdenum, a base resin 1 and an anti-rust adhesive layer mixed with an adhesive; And an antirust support layer made of a base resin 2.

In general, when wrapped by attaching ferrous or non-ferrous metals to the rust preventive film, it is not possible to protect the portion existing on the inner surface. However, in the case of the vaporizable antirust stretch film of the present invention, an antirust material such as amine molybdenum capable of bonding with a metal surface is vaporized in the vaporizable rust preventive stretch film, which is bonded to the metal surface of the inner surface and is present on the inner surface. Prevents contact with oxygen or moisture.

At this time, the vaporizable rust-proof masterbatch is 1 to 10 parts by weight, the base resin 1 is 70 to 95 parts by weight and the pressure-sensitive adhesive is 1 to 10 parts by weight, the vaporizable masterbatch is 1 to 5 parts by weight, base resin 1 It is more preferable that 80-95 weight part of silver and an adhesive are 5-10 weight part. At this time, the content of the vaporizable rustproof masterbatch is a content for serving as a vaporizable rustproof stretch film, although the vaporizable rustproof masterbatch may have a high antirust effect even if it exceeds 10 parts by weight, the tensile strength and elongation rate of the vaporizable rustproof stretch film and It is not preferable because it can affect the adhesive force.

In addition, the base resin may be a mixture of one or more resins to increase mechanical properties such as elongation, tensile strength. Preferably, the base resin may be used by mixing at least one resin such as polyolefin, polyethylene, or ethylene vinyl acetate.

The vaporizable rust preventive stretch film may be formed of two or more layers. The vaporization antirust stretch film which has an antirust support layer and an antirust adhesion layer of the said two-layer structure is formed. The film may have a rustproof adhesive layer formed on both surfaces of the rustproof support layer according to the use, and may have a three-layer structure.

The vaporizable rust-preventive stretch film is preferably made thin for convenience of use and to reduce production costs and to prevent a decrease in adhesion. It is preferable that it is 10-60 micrometers, and, as for the thickness of the said film, it is more preferable that it is 20-50 micrometers.

At this time, when the thickness of the film is less than 10 ㎛, due to the thin thickness of the vaporized rust-preventive stretch film of the present invention is difficult to have the desired tensile strength and elongation, if 60 ㎛, may have an appropriate tensile strength and elongation, but the manufacturing cost increases Problems that the adhesive strength is lowered may occur.

Tensile force and elongation of the film required in the present invention is preferably suitable for use in iron or nonferrous metals, preferably tensile strength is 200 ~ 600 kgf / cm ² , elongation is 300 ~ 1,000%. More preferably, the tensile strength is 250 to 400 kgf / cm ² , and the elongation is 500 to 700%.

Hereinafter, the method of manufacturing the vaporization antirust stretch film of this invention is demonstrated.

In addition, in order to manufacture a vaporizable rust-preventive stretch film of the present invention, step 1) is prepared by kneading the dough 1 and the base resin 2, which are prepared by mixing and kneading the vaporizable rust-preventive masterbatch and the base resin 1 of the present invention. It is a step to obtain the dough 2.

Base resins 1 and 2 used in preparing the vaporizable rust-preventive stretch film are synthetic resins excellent in tensile strength and elongation, and preferably polyolefin, polyethylene, or ethylene vinyl acetate may be used.

The vaporizable rust preventive masterbatch is made of a mixture of a polymer resin and amine molybdenum, and the amine molybdenum is a substance that can be released from the film and vaporized with increasing temperature, and the amine molybdenum is an environmentally friendly and harmless component.

At this time, the vaporizable rust-proof master batch is 1 to 10 parts by weight, the base resin 1 is 70 to 95 parts by weight, the pressure-sensitive adhesive is preferably added to 1 to 10 parts by weight, preferably the vaporizable master batch is 1 to 5 parts by weight. The base resin 1 is 80 to 95 parts by weight and the pressure-sensitive adhesive is 5 to 10 parts by weight. The amine molybdenum is preferably used synthetically.

The amine molybdenum is prepared by dropping a solution 1 obtained by mixing ammonium hydroxide and molybdenum into a solution 2 prepared by mixing one selected from dicyclohexylamine or 2-ethylamine with phosphoric acid;

It is preferably prepared by mixing and reacting one selected from dicyclohexylamine or 2-ethylamine with Solution 1 in which ammonium hydroxide and molybdenum are mixed.

The amine molybdenum produced by the above process has a thick, large oval shape, and has a long, soft tail having a length of 0.7-1.3 cm.

The mixed material of step 1) may be kneaded at an appropriate time and temperature so that the mixing is performed well.

The kneading speed can be adjusted according to the kneading time and the kneading temperature, the preferred kneading speed is preferably 3 ~ 5 × 10 ³ rpm.

In this case, when the kneading speed is less than 3 × 10 ³ rpm, it is not preferable to take too long kneading time, and when the kneading speed exceeds 5 × 10 ³ rpm, it is not preferable because the loss of the vaporizable rust preventive material is concerned.

In addition, the dough 2 produced using the base resin 2 may be a support layer of the rust-preventing adhesive layer, and the base resin 2 does not contain a rust preventive agent. Kneading temperature and the kneading speed of the base resin 2 is the same as the dough.

Next, step 2) is a step of bonding while extruding the dough 1 and dough 2 using an extruder.

The dough prepared by applying the appropriate kneading time, kneading temperature and kneading speed can be prepared in the form of a thin stretch film using an extruder. The stretch film manufactured using the extruder may be cooled at room temperature or may be cooled through a cooling apparatus. The method for cooling the stretch film is not particularly limited.

The kneading material 1 and the kneading material 2 are kneaded in different parts, and the kneading material 1 and the kneading material 2 are simultaneously extruded and combined to form a vaporizable anti-rust stretch film having a rust-preventing support layer and an anti-rust adhesive layer having a two-layer structure. The film may have a rustproof adhesive layer formed on both sides of the support layer, depending on the application, it may be a three-layer structure, and may further include an adhesive layer if necessary.

The vaporizable rust-preventive stretch film produced through the above process is preferably made thin for ease of stretch operation, reduced production costs, improved adhesion. More preferably, it is prepared to a thickness of 10 ~ 60 ㎛. The T-die method is used to manufacture a stretch film having a thin thickness as described above. The process proceeds at a high temperature of 220 to 230 ° C. in the process, and the high temperature is a vaporizable rust preventive film of a vaporizable rust preventive film. It is undesirable because there is a risk of vaporizing the masterbatch. Accordingly, in the present invention, a vaporizable rust preventive stretch film may be manufactured using a blown type method.

Air blown molding is a blown type process, which melts a resin by means of an extruder, blows air into a tube to make a tube, passes through a roll, and cools the product with air. Refers to the molding method to obtain.

Hereinafter, the present invention will be described in detail with reference to a preferred embodiment so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Production Example  1: Type 1 Amine Molybdenum

Ammonium hydroxide (100 mL) and molybdenum (20 g) were mixed and sufficiently stirred until it became a bluish-clear transparent liquid to prepare 20% ammonium molybdate solution 1. Dicyclohexylamine (10 mL) and phosphoric acid (4 mL) were added to a beaker, followed by stirring sufficiently to prepare Solution 2.

The solution 1 was slowly added dropwise to the solution 2 using a separatory funnel and stirred, and the mixed solution slowly became white crystals and became transparent. The solution in which the crystals were formed was separated by filtration and dried to obtain an amine molybdenum powder.

Production Example  2: amine molybdenum type 2

Amine molybdenum was prepared in the same manner as in Preparation Example 1, except that 2-ethylamine (5 ml) was used instead of dicyclohexylamine.

Production Example  3: amine molybdenum type 3

Dicyclohexylamine (20 mL) and ammonium molybdate (13 mL) were mixed and heated to 80 ° C. for at least 1 hour to obtain a clear solution. It is cooled to 15 ° C. or lower to obtain a white precipitate, which is filtered and dried to obtain a white powder.

Example  1-9 and Comparative example  1-7: Preparation of Vaporizable Antirust Masterbatch

Using a polyethylene resin, the amine molybdenum or VCI 600 of the Preparation Examples 1 to 3, benzotriazole, antioxidants and heat stabilizers with reference to Table 1 below to prepare a vaporizable antirust masterbatch.

1 part by weight of benzotriazole, 0.2 parts by weight of antioxidant and heat stabilizer, about 85-70 parts by weight of polyethylene resin and Examples 1-3 of the above-mentioned amine molybdenum or VCI 600 (obtained from Rustec, component: cyclohexylamine benzoate ) Was mixed to 15 to 30 parts by weight, and kneaded at 120 ℃ for 15 minutes. This was injected into the injection molding machine, and cooled to prepare a vaporizable rustproof masterbatch. See Table 1 below for the contents of the ingredients for preparing each example.

Examples and
Comparative example
chief ingredient
Polyethylene resin
(Parts by weight)
chief ingredient
content
(Parts by weight)
Benzotriazole
(Parts by weight)
Antioxidant
Heat stabilizer
(Parts by weight)
Example 1
Production Example 1
84.8
14
One
0.2
Example 2
Preparation Example 2
84.8
14
One
0.2
Example 3
Preparation Example 3
84.8
14
One
0.2
Example 4
Production Example 1
79.8
19
One
0.2
Example 5
Preparation Example 2
79.8
19
One
0.2
Example 6
Preparation Example 3
79.8
19
One
0.2
Example 7
Production Example 1
74.8
23.5
1.5
0.2
Example 8
Preparation Example 2
74.8
23.5
1.5
0.2
Example 9
Preparation Example 3
74.8
23.5
1.5
0.2
Comparative Example 1
Production Example 1
69.8
28.5
1.5
0.2
Comparative Example 2
Preparation Example 2
69.8
28.5
1.5
0.2
Comparative Example 3
Preparation Example 3
69.8
28.5
1.5
0.2
Comparative Example 4
VCI 600
84.8
15
0
0.2
Comparative Example 5
VCI 600
79.8
20
0
0.2
Comparative Example 6
VCI 600
74.8
25
0
0.2
Comparative Example 7
VCI 600
69.8
30
0
0.2

Table 1 showed the best kneading property when 15 to 25 parts by weight of the amine molybdenum, which is the main component of the vaporizable rustproof masterbatch, and it was found that the kneading property was good when mixed with 20 parts by weight of the amine molybdenum. there was. However, compatibility was not good when the amount of amine molybdenum added exceeded 25 parts by weight. In the following experimental example, the vaporizable rust preventive masterbatch was prepared by using a vaporizable rust preventive masterbatch prepared with 20 parts by weight of amine molybdenum as a main component.

Example  10: vaporization antirust Stretch  film

A vaporizable rust preventive stretch film was prepared using a blown extruder equipped with two or more cylinders. In detail, first, 95 parts by weight of polyethylene resin, 2 parts by weight of the vaporizable antirust masterbatch of Example 4, and 8 parts by weight of pressure-sensitive adhesive are mixed in one cylinder, and 95 parts by weight of polyethylene resin and 5 parts by weight of vaporizable rust preventive agent are mixed in another cylinder. While extruding each dough, to form a different layer in each layer to produce a vaporizable rust-preventive stretch film.

Example  11: vaporization antirust Stretch  film

A vaporizable rust preventive stretch film was prepared in the same manner as in Example 10 except that the vaporizable rust preventive masterbatch of Example 5 was used.

Example  12: vaporization antirust Stretch  film

A vaporizable rust preventive stretch film was prepared in the same manner as in Example 10, except that the vaporizable rust preventive masterbatch of Example 6 was used.

Experimental Example  1: Evaluation of Manufacturing Efficiency of Amine Molybdenum

The production efficiency of the amine molybdenum prepared by Preparation Examples 1 to 3 was analyzed. The results are shown in Table 2 below.

Production Example 1
Preparation Example 2
Preparation Example 3
yield
○
○
×
material cost
○
○
◎
water
○
○
◎
productivity
○
○
×

◎: Very good, ○: Excellent, △: Normal, ×: Poor

As shown in Table 2, it was found that amine molybdenum was prepared in similar efficiency in Preparation Examples 1 and 2. Preparation Examples 1 and 2 have a complicated manufacturing process, but have a high synthesis yield and excellent process productivity, making them most suitable for amine molybdenum production. In addition, although the yield and productivity were low in Preparation Example 3, there was an advantage that the purity and material cost is lower than Preparation Examples 1 and 2.

Experimental Example  2: vaporization antirust masterbatch Dough , Extrudability , Cutting property  And evaluate processability

In order to see if phase separation or agglomeration occurs in the process of mixing the resin and the additive, kneading property is extruded to examine whether it is easy to extrude the mixed resin after kneading the resin and the additive. Afterwards, in order to evaluate whether it is easy to cut the resin into pellets, the cutting property and all of the above were evaluated to evaluate the processability of the vaporizable antirust masterbatch. In order to evaluate this, the following experiment was conducted.

The results are shown in Table 3 below.

Dough
Extrudability
Cutting property
Machinability
Example 4
○
○
○
○
Example 5
○
○
○
○
Example 6
○
○
○
○
Comparative Example 5
○
△
○
△
(Slight vaporization loss)

○: Good △: Normal ×: Poor

As shown in Table 3, Examples 4 to 6, the addition amount of the main component is 20 parts by weight, all kneading, compressibility, cutting properties and workability was good. On the other hand, while Comparative Example 5 had good kneading property and cutting property, the extrusion property was normal, and it was found that the workability was not preferable because a slight vaporization loss of the rust inhibitor was observed.

Experimental Example  3: Optimum vaporization antirust masterbatch Dough time , Dough Temperature  And Kneading speed  Measure

In order to investigate the optimum kneading time, kneading temperature and kneading speed for producing a vaporizable rust-proof masterbatch of the present invention, the following experiment was conducted.

The following experiment will be described with reference to FIG. 2.

79.8% polyethylene resin, 19.0% amine molybdenum type 1, 1% benzotriazole and 0.2% additive were mixed in the kneader. The kneading time, the kneading temperature and the kneading speed of the vaporizable antirust masterbatch were measured in the kneader. The results are shown in Tables 4 to 6 below.

Experimental Example  3-1: Dough time

Dough temperature: 115 ℃, dough speed: 4 × 10 ³ rpm

Mixing time
Dough
Mixed state
Vaporization loss
Perfection(%)
5 minutes
imperfection
Bad
Very good
52
10 minutes
Good
Great
Very good
78
15 mins
Very good
Great
Very good
94
20 minutes
Very good
Very good
Great
94
25 mins
Very good
Very good
Good
88
30 minutes
Very good
Very good
imperfection
76

※ Completeness = dough state (40%) + mixed state (30%) + vaporization loss (30%)

※ For each item: Very good-Excellent-Good-Incomplete-Defective

As shown in Table 4, the vaporized rust preventive masterbatch was incomplete in the state of dough less than 5 minutes after the start of kneading in the kneader, and the mixed state was also judged poor. After 10 minutes of kneading, the dough was in good condition, but the overall degree of completeness was insufficient. After 15 minutes, the kneading and mixing were good, and the high degree of completion was obtained due to good evaluation in the vaporization loss. In kneader, more than 20 minutes after kneading, the efficiency was lowered. The kneading time in kneader was 15-20 minutes, which showed the highest degree of completeness, and was also excellent in efficiency.

Experimental Example  3-2: Dough Temperature

Kneading time: 15 minutes, kneading speed: 4 × 10 ³ rpm

Kneader temperature
Dough
Mixed state
Vaporization loss
Perfection(%)
100 ℃
Good
Great
Very good
78
110 ℃
Great
Very good
Very good
92
120 ℃
Very good
Very good
Great
94
130 ℃
Very good
Very good
Good
88
140 ℃
Very good
Very good
Bad
76
150 ℃
Very good
Very good
Bad
76

※ Completeness = dough state (40%) + mixed state (30%) + vaporization loss (30%)

※ For each item: Very good-Excellent-Good-Incomplete-Defective

As shown in Table 5, the temperature of the kneader showed a high degree of completeness at 110 ~ 120 ℃, at a temperature higher than the kneading state and mixing state is very good, but vaporization loss occurs, it can be seen that inefficient.

Experimental Example  3-3: Dough speed

The kneading speed was measured with a kneading temperature of 120 ° C. and a kneading time of 15 minutes.

Dough speed
(× 10 ³ rmp)
Dough
Mixed state
Vaporization loss
Perfection
(%)
One
Good
Good
Very good
78
3
Very good
Very good
Great
94
5
Very good
Very good
Great
94
7
Very good
Very good
Good
88
9
Very good
Very good
imperfection
82
10
Very good
Very good
imperfection
82

※ speed is adjusted by dial gauge

※ Completeness = dough state (40%) + mixed state (30%) + vaporization loss (30%)

※ For each item: Very good-Excellent-Good-Incomplete-Defective

As shown in Table 6, the kneading speed of the kneader did not find a big difference due to optimization of other conditions. Only differences in vaporization loss existed. Optimum conditions were formed at a kneading speed of 3 to 5 × 10 ³ rpm.

Experimental Example  4: vaporization antirust Stretch  Process stabilization of film

In the case of a general stretch film, it is manufactured by a T-die method through a casting facility, but the present invention introduces a blown type extrusion. Accordingly, the following experiment was conducted to select a base resin suitable for blown extrusion and to find an optimal extrusion process for each base resin.

First, 90 parts by weight of polyethylene resin, 2 parts by weight of the vaporizable rustproof masterbatch of Example 5, and 8 parts by weight of the pressure-sensitive adhesive are mixed in one cylinder, and resins I, II, and III are respectively referred to the other cylinders by referring to Tables 7 and 8 below. 95 parts by weight and 5 parts by weight of a vaporizable rust inhibitor were added and kneaded.

While extruding the respective dough, to produce the film 1 to 5 by combining what is produced in a different layer in one layer. The appearance, processability, workability and blocking properties of the prepared film were measured and shown in Table 9 below.

Type of Resin Used

Resin Ⅰ
Resin II
Resin III
Kinds
Linear low density poly ethylene (LLDPE)
LLDPE
(Linear low density poly ethylene)
m-LLDPE
(metallocene linear low density polyethylene)
Density (g / cm 3)
0.926
0.918
0.915
Melt Flow Index (g / 10min)
2.5
2.0
3.7
Melting Point (℃)
110-130
110-130
114

Resin Mixing Condition

film
Resin Ⅰ
Resin II
Resin III
UV agent
One
○


○
2

○

○
3


○
○
4
○

○
○
5

○
○
○

film
Exterior
Processing Castle
Workability
Blocking property
One
○
○
△
○
2
○
◎
○
△
3
○
△
◎
×
4
○
◎
◎
○
5
△
○
◎
○

◎: Excellent, ○: Good, △: Normal, ×: Poor

Experimental Example  5: vaporization antirust Stretch  Antirust effect measurement of film

In order to evaluate the rust resistance of the vaporizing antirust stretch film of the present invention, the following experiment was conducted.

 The experiment was conducted according to the neutral salt spray test method (KS D 9502), and the determination method was determined by the 'post-test appearance' of b of 16 KS D 9502 determination method.

Stainless, steel and aluminum metal specimens were coated with reference to the films in Table 10 below and each sample was placed in a salt spray (Jungdo Testing Ins., ISO-NM). Each sample was sprayed with a 0.5% saline solution, and the temperature was measured for 2 weeks at 35 ° C. in the salt sprayer and 47 ° C. in the air saturator.

The results are shown in FIG. 5.

Sample 1
Sample 2
Sample 3
Sample 4
Uncovered
stainless
1-1
2-1
3-1
4-1
5-1
steel
1-2
2-2
3-2
4-2
5-2
aluminum
1-3
2-3
3-3
4-3
5-3

As shown in FIG. 5, the appearance of the stainless metal specimens was not changed by the salt spray irrespective of the type of film and the coating of the film, and the aluminum specimen had corrosion only on the surface of the sample 3 and the control plate not coated with the film. It was.

In case of steel, which showed the greatest effect of salt spray, rust occurred in the order of Sample 4, Sample 1, and Sample 2.In case of Sample 3, the rust began to occur from the initial salt spray test and the entire surface after 2 weeks of salt spraying. Rust occurred in about one third of.

In the case of Sample 3, there is a trace of moisture permeation into the film, and it is judged that the moisture permeability (permeability) of the film is not good.

Experimental Example  6: vaporization antirust Stretch  Evaluation of Film Properties

In order to evaluate the physical properties of the vaporizable rust-preventive stretch film of the present invention, the maximum physical property test (Ultimate test), the physical property test (Quality test), the puncture test (Puncture test) and the retention test (Retention test) was performed.

Maximum physical property test to measure the pull force (tensile force) at the point of failure by pulling up to the point at which the film breaks, elongation (%) while rewinding the film 100 m, test rate (M / min), average sound level ( dB), tensile force (kgf / ㎠), unwinding strength (kg), average elongation (%) and the standard deviation of the average elongation was measured to conduct a general property test to analyze the general quality of the film.

In addition, when the punch pin is attached and the film is stretched up to 200%, the punching test for the maximum value is measured, and the punching pin is removed and replaced with the extension pin, and then the punching test is performed. When the elongation rate reached 200%, the extension pin was protruded for 1 minute, and the restoring force test was performed to measure and record the holding force of the film to measure and record the deviation from the maximum restoring point to the end point.

The test methods described above were performed based on the Dow method, and each sample was run three times to obtain an average value of the results. The results are shown in Tables 11 to 14 below.

Maximum Property Test

Film 1
Film 2
Film 3
Film 4
Film 5
Testing speed (m / min)
150
150
150
150
150
Tensile force (kgf / ㎠)
43.97
40.37
52.79
50.70
49.18
Elongation (%)
495.53
481.38
546.25
537.12
538.18

< Physical property  Test>

Film 1
Film 2
Film 3
Film 4
Film 5
Elongation (%)
150
150
150
150
150
Testing speed (m / min)
150
150
150
150
150
Average sound level (dB)
86.4
85.9
87.2
84.7
85.1
Tensile force (kgf / ㎠)
32.75
34.64
39.36
41.03
42.67
Unwinding Strength (kg)
6.51
5.62
7.28
5.52
5.71
Standard Deviation
4.54
4.69
4.32
4.51
4.63

<Puncture Test>

Film 1
Film 2
Film 3
Film 4
Film 5
Elongation (%)
150
150
150
150
150
Testing speed (m / min)
150
150
150
150
150
medium
1.09
1.26
1.26
1.28
1.25

<Resilience Test>

Film 1
Film 2
Film 3
Film 4
Film 5
Elongation (%)
150
150
150
150
150
Test rate (M / min)
150
150
150
150
150
Average maximum value (Lbs)
1.69
1.99
2.02
2.09
1.93
Mean, ending value (Lbs)
1.44
1.65
1.72
1.76
1.63
Max-ending value (D)
0.25
0.34
0.30
0.33
0.30

The maximum physical property test is a measure of the maximum force when the film is stretched until it breaks at a constant speed (test speed), and in this experiment, the tensile force of the prepared stretch film is measured.

The general test is a measure of the strength (tensile force) and the unwinding strength when the film is uniformly stretched (elongation rate). Indicates.

The puncture test is an experiment in which a film is stretched at a constant speed and then pressurized on the film with a pointed device to determine whether a hole is formed in the film. If the value is less than 0.9, it is judged to be drilled. When the rust-preventive stretch film was wound on the actual equipment, the result of the perforation test showed a value of 0.9 or more because it should not be perforated when the edge was wound. This value is important because it should not be punctured when winding the edges with the stretch film.

The resilience test is a numerical representation of the stress recovery test, the force to return to its original state.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the technical idea of the present invention, which also belong to the appended claims. Of course

Claims (12)

delete delete delete An anticorrosive pressure-sensitive adhesive layer in which a vaporizable antirust masterbatch formed by mixing a polymer resin and an amine molybdenum, a base resin 1 and an adhesive; And
An antirust support layer consisting of base resin 2 containing metallocene-linear low density polyethylene (m-LLDPE) and linear low density polyethylene (LLDPE), or metallocene-linear low density polyethylene (m-LLDPE);
Vaporizable rust preventive stretch film comprising a. The method of claim 4, wherein
The vaporizable rust-proof masterbatch is 1 to 10 parts by weight, the base resin 1 is 70 to 95 parts by weight, and the pressure-sensitive adhesive is 1 to 10 parts by weight vaporized rust preventive stretch film, characterized in that. The method of claim 4, wherein
The vaporizable rust-preventive stretch film comprises two or more layers. The method of claim 4, wherein
The vaporizable rustproof stretch film has a thickness of 10 to 60 µm. The method of claim 4, wherein
The vaporizing rust-preventive stretch film is a tensile strength of 200 ~ 600 kgf / cm ² , elongation is 300 to 1,000% or more evaporable rust preventive stretch film. In the method of manufacturing a vaporizable antirust stretch film for preventing corrosion of ferrous or nonferrous metals,
1) Vaporized antirust masterbatch containing polymer resin and amine molybdenum, base resin 1 and dough 1 prepared by kneading adhesive, metallocene-linear low density polyethylene (m-LLDPE) and linear low density polyethylene (LLDPE), Or kneading base resin 2 containing metallocene-linear low density polyethylene (m-LLDPE); And
2) combining the dough 1 and the dough 2 while extruding;
Vaporizable antirust stretch film production method comprising a. 10. The method of claim 9,
The vaporizing rust-proof masterbatch of the step 1) is 1 to 10 parts by weight, the base resin 1 is 70 to 95 parts by weight and the pressure-sensitive adhesive is characterized in that 1 to 10 parts by weight of the vaporizing rust-resistant stretch film manufacturing method. 10. The method of claim 9,
The vaporizable rust preventive master batch is a method of producing a vaporizable rust preventive stretch film, characterized in that the mixture of the polymer resin and amine molybdenum. The method of claim 11,
The amine molybdenum,
Prepared by dropping a solution 1 obtained by mixing ammonium hydroxide and molybdenum into a solution 2 prepared by mixing one kind selected from dicyclohexylamine or 2-ethylamine with phosphoric acid;
A method for producing a vaporizable rust-preventive stretch film, characterized in that it is prepared by mixing and reacting one selected from dicyclohexylamine or 2-ethylamine with solution 1 in which ammonium hydroxide and molybdenum are mixed.

Images