KR102169618B1 - Adhesive composition, manufacturing method therfor, composite pipes and laminated sheet having the same - Google Patents

Abstract

The present invention relates to a method of preparing an adhesive composition, and more particularly, a step of obtaining a metal salt by mixing a compound containing at least one metal selected from groups I to III of the periodic table with a first organic acid; Adsorbing the second organic acid to the solid adsorbent; Mixing at least one of the solid adsorbent and the metal salt to which the second organic acid is adsorbed and an α, β-unsaturated carboxylic acid-α-olefin copolymer to obtain an adhesive precursor resin; By including the step of mixing and melt-kneading the adhesive precursor resin and α, β-unsaturated carboxylic acid-α-olefin copolymer; by including, it is possible to prepare an adhesive composition excellent in adhesion and durability.

Description

Adhesive composition, manufacturing method thereof, composite pipe using this adhesive composition, and laminated sheet {ADHESIVE COMPOSITION, MANUFACTURING METHOD THERFOR, COMPOSITE PIPES AND LAMINATED SHEET HAVING THE SAME}

The present invention relates to an adhesive composition and a method of manufacturing the same, and more particularly, to an adhesive composition having excellent adhesion between different materials, such as a corrosion-resistant metal, and a method of manufacturing the same.

In addition, the present invention also relates to a composite pipe and a laminated sheet using such an adhesive composition.

The mechanism by which the adhesive exhibits adhesiveness has not been fully elucidated, but it is known to exhibit adhesiveness when a component having the same or similar polarity, component, structure, and the like with the adherend is used.

Therefore, in the case of a heterogeneous material such as a metal and a polymer or a composite material, the bonding is difficult to perform with a conventional adhesive.

In addition, since most metals oxidize and corrode very easily and quickly in the air or in water, if necessary, corrosion-resistant coating is applied to solve the oxidation problem. However, since the corrosion-resistant coating changes the physical properties of the surface by lowering the polarity of the metal surface, it is difficult to use an existing adhesive depending on the type of the corrosion-resistant coating even if it is the same metal.

On the other hand, even a material that initially had sufficient adhesive strength may cause defects in the form of loss of adhesive strength due to failure to maintain physical properties or to damage its structure due to changes in physical properties upon completion of curing or hydrolysis or oxidation over time. have.

Therefore, it is required to develop an adhesive having excellent adhesion and durability to various materials. U.S. Patent No. 3,264,272 and U.S. Patent No. 3,969,434 propose a method for producing a polymer having a relatively high polarity that can be applied to an adhesive, but there is still no effective solution.

U.S. Patent No. 3,264,272 U.S. Patent No. 3,969,434

One problem to be solved by the present invention is to provide an adhesive having excellent adhesion with both polar and non-polar materials, and a method of manufacturing the same.

One problem to be solved by the present invention is to provide an adhesive having excellent plasticity and mechanical properties, and a manufacturing method thereof.

One problem to be solved by the present invention is to provide a composite pipe and a laminated sheet using this adhesive.

A method of preparing an adhesive composition according to an embodiment of the present invention includes the steps of: (S1) mixing a compound containing at least one metal selected from Groups I to III of the periodic table with a first organic acid to obtain a metal salt; (S2) adsorbing the second organic acid to the solid adsorbent; (S3) mixing at least one of the solid adsorbent and the metal salt to which the second organic acid is adsorbed and an α,β-unsaturated carboxylic acid-α-olefin copolymer to obtain an adhesive precursor resin; (S4) mixing and melt-kneading the adhesive precursor resin and the α,β-unsaturated carboxylic acid-α-olefin copolymer; may include.

According to an embodiment of the present invention, the metal may include at least one metal selected from the group consisting of Group I, IIa, IIb, and III of the periodic table.

According to an embodiment of the present invention, the metal may include at least one metal selected from the group consisting of Zn, Ni, Cr, Fe, Cu, Na, and Al.

According to an embodiment of the present invention, the first organic acid and the second organic acid may independently include at least one of acetic acid and formic acid.

According to an embodiment of the present invention, the solid adsorbent may include at least one of silica and carbon black.

According to an embodiment of the present invention, the solid adsorbent may be 0.5 to 15 parts by weight based on a total of 100 parts by weight of the adhesive precursor resin.

According to an embodiment of the present invention, the metal salt obtained in the step (S1) in the step (S2) may be further adsorbed onto the solid adsorbent.

According to an embodiment of the present invention, the α, β-unsaturated carboxylic acid may be at least one selected from the group consisting of acrylic acid, methacrylic acid, acetic acid, maleic acid, succinic acid, and itaconic acid.

According to an embodiment of the present invention, the α-olefin may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, and 4-methyl-1-pentene.

According to an embodiment of the present invention, the α, β-unsaturated carboxylic acid-α-olefin copolymer may have a melt index of 3 to 50 g/10min.

According to an embodiment of the present invention, the α, β-unsaturated carboxylic acid-α-olefin copolymer is maleic anhydride-polyethylene copolymer (MAH-g-PE), ethylene methyl acrylate (EMA) resin, ethylene methyl meta It may be at least one selected from the group consisting of acrylate (EMMA) resin and ethylene vinyl acetate (EVA) resin.

According to an embodiment of the present invention, when the adhesive precursor resin does not contain the solid adsorbent to which the second organic acid is adsorbed in the step (S3), the solid adsorbent to which the second organic acid is adsorbed is the step (S4). Can be added in.

Adhesive composition according to an embodiment of the present invention, α, β-unsaturated carboxylic acid-α-olefin copolymer; And at least one of a metal salt that is a reactant of a compound containing at least one metal selected from Groups I to III of the Periodic Table and a first organic acid, and a solid adsorbent to which a second organic acid is adsorbed.

Corrosion-resistant metal pipe according to an embodiment of the present invention, a metal pipe; A corrosion-resistant coating layer formed on the outer surface of the metal tube; And an adhesive composition prepared by the above-described manufacturing method and applied on the corrosion-resistant coating layer.

A laminated sheet according to an embodiment of the present invention includes: a first metal plate; An adhesive composition manufactured by the above-described manufacturing method and applied to the first metal plate; And a second metal plate bonded to the first metal plate by the adhesive composition, wherein the first and second metal plates may be steel plates or stainless steel plates, respectively.

A composite pipe according to an embodiment of the present invention includes a metal pipe made of thin stainless steel; An adhesive composition manufactured by the above manufacturing method and applied to the outer surface of a metal tube; And a resin layer bonded to the metal tube by the adhesive composition, and the resin layer may be made of an olefin resin such as polyethylene as a main component.

The manufacturing method of the adhesive composition of the present invention has a high reaction efficiency and thus the residual amount of the unreacted metal compound is small.

The adhesive composition prepared according to the manufacturing method of the adhesive composition of the present invention can exhibit excellent adhesion between metals and heterogeneous materials such as polymers.

The adhesive composition prepared according to the manufacturing method of the adhesive composition of the present invention may exhibit excellent adhesion between a metal having a corrosion-resistant coating and another member, for example, another metal or polymer.

The adhesive composition prepared according to the manufacturing method of the adhesive composition of the present invention is excellent in durability, so even if it takes a long time after bonding, there is little decrease in adhesion.

The composite pipe and the laminate sheet manufactured by using the adhesive composition according to the present invention have excellent bonding strength between metal and resin.

Hereinafter, the present invention will be described in detail. Prior to this, terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention. Therefore, since the configuration disclosed in the embodiments described in the present specification is only examples of the present invention and does not represent all the technical spirit of the present invention, various equivalents and modified examples that can replace them at the time of the present application It should be understood that there may be.

Hereinafter, the present invention will be described in detail.

A method for preparing an adhesive composition according to an embodiment of the present invention comprises the steps of (S1) mixing a compound containing at least one metal selected from Groups I to III of the periodic table with a first organic acid to obtain a metal salt; (S2) adsorbing the second organic acid to the solid adsorbent; (S3) mixing at least one of the solid adsorbent and the metal salt to which the second organic acid is adsorbed and an α, β-unsaturated carboxylic acid-α-olefin copolymer to obtain an adhesive precursor resin; (S4) mixing and melt-kneading the adhesive precursor resin and the α, β-unsaturated carboxylic acid-α-olefin copolymer; may include. Each step will be described below.

First, a metal salt is obtained by mixing a compound containing at least one metal selected from groups I to III of the periodic table with a first organic acid (S1).

After the metal salt reacts with the resin in the composition, the metal salt reacts with the hydrogen ion (H ⁺ ) of the portion corresponding to the acid group in the base resin, and should be easily removed from the adhesive resin. In addition, it is preferable that the interaction between the ionized carboxylic acid group and the metal ion is not disturbed by the ions of the metal salt initially introduced.

The metal contained in the metal salt may be at least one metal selected from groups I to III of the periodic table, and preferably at least one metal selected from the group consisting of groups I, IIa, IIb and III of the periodic table. May include, more preferably, at least one metal selected from the group consisting of Zn, Ni, Cr, Fe, Cu, Na, and Al, or more preferably may be an alkali metal. .

Metals can react with organic acids in the form of compounds containing metals.

The compound containing a metal may be, for example, an oxide of a metal.

The first organic acid is not particularly limited as long as it reacts with the metal to exhibit the desired function of the metal salt, and for example, at least one of acetic acid and formic acid may be used.

Next, the second organic acid is adsorbed onto the solid adsorbent (S2).

The solid adsorbent to which the second organic acid is adsorbed is uniformly dispersed in the composition so that the metal salt reacts with the resin uniformly.

The second organic acid may be the same as or different from the first organic acid, and for example, at least one of acetic acid and formic acid may be used.

The solid adsorbent may preferably be used that does not affect the adhesive component and the adherend, and may be uniformly dispersed in the composition while adsorbing the organic acid well, for example, may include at least one of silica and carbon black , Preferably, silica may be used.

Silica may have an average particle diameter of 0.08 to 0.3 μm. If the average particle diameter is less than 0.08 μm, dispersion is difficult, the adsorption of the metal salt becomes excessive, and the desorption of the adsorbed metal salt is difficult, so that the reaction rate may be lowered. If the average particle diameter is more than 0.3 μm, the total surface area may be reduced, and the amount of adsorbed metal salt may be reduced.

Silica may preferably have a surface area of 150 to 200 m ² /g. If the surface area is large, the adsorption amount can be increased, which is preferable, and in this respect, it may be preferable to use porous silica.

The solid adsorbent may be included in an amount of 0.5 to 15 parts by weight based on a total of 100 parts by weight of the adhesive precursor resin. If the content of the solid adsorbent is less than 0.5 parts by weight, it is difficult to uniformly disperse it, so that the reaction occurs locally and the uniformity of the adhesive composition may be lowered, and if it exceeds 15 parts by weight, it may act as an impurity.

In one embodiment according to the present invention, the metal salt obtained in step (S1) may be further adsorbed to the solid adsorbent if necessary. The reaction with the base resin can be further promoted by adsorbing metal salts.

Next, an adhesive precursor resin is obtained by mixing at least one of the solid adsorbent and the metal salt to which the second organic acid is adsorbed and an α, β-unsaturated carboxylic acid-α-olefin copolymer (S3).

When the adhesive composition is prepared by using an adhesive precursor resin, it may be more effective in uniform dispersion of a solid adsorbent and/or a metal salt in which an organic acid is adsorbed in the adhesive composition. If the adhesive composition is prepared by mixing the solid adsorbent and the metal salt with the entire base resin of the adhesive composition at once without going through the step of preparing the adhesive precursor resin, it becomes difficult to uniformly disperse the solid adsorbent and/or metal salt adsorbed with organic acids. The reaction may occur locally and the uniformity of the adhesive composition may be lowered.

The adhesive precursor resin is prepared using an α, β-unsaturated carboxylic acid-α-olefin copolymer, which is the base resin of the adhesive composition.

α, β-unsaturated carboxylic acid, one of the comonomers of α-olefin copolymer, α, β-unsaturated carboxylic acid, at least one selected from the group consisting of acrylic acid, methacrylic acid, acetic acid, maleic acid, succinic acid and itaconic acid will be used. I can.

The α-olefin, which is another one of the comonomers of the α, β-unsaturated carboxylic acid-α-olefin copolymer, may be an olefin having 2 to 8 carbon atoms, preferably ethylene, propylene, 1-butene, 1-pentene and 4 -At least one selected from the group consisting of methyl-1-pentene may be used.

The molar ratio of α, β-unsaturated carboxylic acid and α-olefin in the copolymer is preferably α, β-unsaturated carboxylic acid and: α-olefin = 0.1:99.9 to 20:80. The adhesive composition may exhibit excellent adhesion in the molar ratio range.

α, β-unsaturated carboxylic acid-α-olefin copolymer is, for example, maleic anhydride-polyethylene copolymer (MAH-g-PE), ethylene methyl acrylate (EMA) resin, ethylene methyl methacrylate (EMMA) resin , And at least one selected from the group consisting of ethylene vinyl acetate (EVA) resin may be used.

The melting index of the α, β-unsaturated carboxylic acid-α-olefin copolymer may be 3 to 50 g/10min, and may have excellent processability within the above range.

In one embodiment of the present invention, the weight ratio of the metal salt and the base resin in the adhesive precursor resin may be a metal salt: base resin = 20:80 to 50:50. If the base resin content is less than the above range, the adhesive strength of the adhesive composition may be lowered, and if the base resin content is greater than the above range, the metal salt content is relatively small and the degree of crosslinking is lowered, thereby deteriorating mechanical properties of the adhesive.

In an embodiment of the present invention, a metal oxide may be further mixed as needed in the adhesive precursor resin manufacturing process. By further adding a metal oxide, the adhesive strength of the adhesive can be further increased. As the metal oxide, an oxide of a metal included in the metal salt may be used.

Next, the adhesive precursor resin and the α, β-unsaturated carboxylic acid-α-olefin copolymer are mixed and melt-kneaded (S4).

In an embodiment of the present invention, in the case where the adhesive precursor resin does not contain the solid adsorbent to which the second organic acid is adsorbed in the step (S3), the solid adsorbent to which the second organic acid is adsorbed is the step (S4). Can be added in. By adding the solid adsorbent to which the organic acid has been adsorbed, it is possible to induce a uniform reaction of the organic acid and to strengthen the adhesion of the adhesive composition.

The α, β-unsaturated carboxylic acid-α-olefin copolymer may be the same as the resin used in the preparation of the adhesive precursor resin, or other resins may be used in the category of the α, β-unsaturated carboxylic acid-α-olefin copolymer described above.

Through the melt-kneading step, the metal salt is uniformly dispersed in the composition and reacts uniformly with the base resin to neutralize the base resin. The neutralization rate of the base resin is preferably 50 to 70% because it can exhibit excellent adhesion.

The melt-kneading process may be applied without particular limitation to a method known in the art, for example, may be performed through a low-speed mixer or a high-speed mixer, and may be performed at a temperature of 230 to 270°C.

In one embodiment of the present invention, additives known in the art may be further added without particular limitation as needed in the adhesive precursor resin manufacturing process or melt kneading process. For example, thickeners, antioxidants, leveling agents, dispersants, and the like can be used.

One embodiment of the present invention provides an adhesive composition prepared by the above-described manufacturing method. Adhesive composition according to an embodiment of the present invention is α, β-unsaturated carboxylic acid-α-olefin copolymer; And at least one of a metal salt that is a reactant of a compound containing at least one metal selected from Groups I to III of the Periodic Table and a first organic acid, and a solid adsorbent to which a second organic acid is adsorbed. Accordingly, the adhesive composition according to the present invention has excellent adhesion, and may exhibit excellent adhesion even between a material having low polarity or a heterogeneous material such as a metal and a polymer.

An embodiment of the present invention provides a metal tube to which the above-described adhesive composition is applied. For example, metal pipes; A corrosion-resistant coating layer formed on the outer surface of the metal tube; And it is manufactured by the above-described manufacturing method, it is possible to provide a corrosion-resistant metal tube comprising; an adhesive composition applied on the corrosion-resistant coating layer.

In one embodiment of the present invention, the corrosion-resistant coating layer may be a coating known in the art, for example, a chromium oxide film, an aluminum oxide film, or a zinc oxide film. For example, the metal tube on which the corrosion-resistant coating layer is formed according to the present invention may be a stainless steel tube in which a chromium oxide passivation film is formed on the surface of the metal tube including iron.

One embodiment of the present invention provides a laminated sheet to which the above-described adhesive composition is applied. For example, a first metal plate; Being prepared in the above-described manufacturing method, the adhesive composition applied to the first metal plate; And a second metal plate bonded to the first metal plate by an adhesive composition, wherein the first and second metal plates may be provided with a laminated sheet of a steel plate or a stainless steel plate, respectively.

On the other hand, the applicant of the present invention has developed a composite pipe that can be wound in an annular shape after being manufactured as a straight pipe and the circular cross-sectional shape does not change even after the pipe wound in an annular shape is reduced to a straight pipe, and this has been registered as Korean Patent Registration No. 1,166,886 ( All contents described in the patent registration publication are included in this specification). The composite pipe may be manufactured by using the adhesive composition according to the present invention. That is, the composite pipe is a metal pipe made of thin stainless steel; An adhesive composition prepared according to the present invention and applied to the outer surface of a metal tube; And a resin layer adhered to the metal tube by the adhesive composition and containing an olefin resin (eg, polyethylene) as a main component.

In addition, the Applicant also developed a method of manufacturing a composite pipe by inserting a stainless steel pipe coated with an adhesive into the inside of the steel pipe, expanding and combining the steel pipe and the stainless steel pipe, and forming a resin layer on the outer surface of the steel pipe. It has been registered as Patent Registration No. 1,870,573 (all the contents described in the registration gazette of this patent are included in this specification). In this composite pipe, instead of the adhesive, the adhesive composition according to the present invention can be used.

Hereinafter, examples will be described in detail to illustrate the present invention in detail.

Example 1

(1) Preparation of metal salt

At a temperature of 25°C, 50 g of ZnO was added to 73.8 g of acetic acid, shaken well, and allowed to stand for 2 hours, and then water was evaporated from this solution and precipitated zinc acetate (112.71 g) was obtained, and the obtained zinc acetate was clean water (distilled water). Washed three times with a wash to remove the remaining acetic acid and dried again at 110 ℃.

(2) Adsorption of organic acid to adsorbent

43.55 g of the obtained zinc acetate and 9.2 g of acetic acid were adsorbed on 0.7 g of silica and mixed with 162.15 g of zinc oxide (ZnO). (Total weight is 215.6g).

(3) Preparation of adhesive precursor resin

284.5 g of EMA resin, 215.5 g of silica adsorbed with the metal salt, and 10.0 g of zinc stearate were added to a mixer, and the silica was mixed until completely melted and adhered to the EMA resin to obtain an adhesive precursor resin. At this time, zinc stearate was added as a dispersant and a reaction enhancer.

(4) Preparation of adhesive composition

10 parts by weight of the obtained adhesive precursor resin and 90 parts by weight of the EMA resin were added to a mixer and mixed, and the mixture was introduced into an extruder and extruded under a vacuum of 1.0 bar at a temperature of 250° C. to prepare an adhesive composition.

The composition of the added ingredients is shown in Table 1 below.

Example 2

(1) Preparation of metal salt

It was carried out in the same manner as in Example 1.

(2) Adsorption of organic acid to adsorbent

9.2 g of acetic acid was adsorbed on 1.3 g of silica. (Total weight is 10.5g)

(3) Preparation of adhesive precursor resin

290.2 g of EMA resin, 165.4 g of zinc oxide, 44.4 g of zinc acetate, and 12.5 g of zinc stearate were added to a mixer, and uniformly mixed to obtain an adhesive precursor resin. At this time, zinc stearate was added as a dispersant and a reaction enhancer.

(4) Preparation of adhesive composition

90.5 wt% of EMA, 9.05 wt% of adhesive precursor resin and 0.45 wt% of acetic acid adsorbed silica (10 parts by weight of adhesive precursor resin, 0.5 parts by weight of acetic acid adsorbed silica) were added to an extruder and extruded to form an adhesive composition. Was prepared.

The composition of the added ingredients is shown in Table 2 below.

Example 3

(1) Preparation of metal salt

It was carried out in the same manner as in Example 1.

(2) Adsorption of organic acid to adsorbent

It was carried out in the same manner as in Example 1.

(3) Preparation of adhesive precursor resin

It was carried out in the same manner as in Example 1, except that 2.0 g of zinc stearate was added.

(4) Preparation of adhesive composition

8 parts by weight of the obtained adhesive precursor resin and 100 parts by weight of MAH-g-PE resin as a base resin were added to a mixer and mixed, and the mixture was introduced into an extruder and extruded under a vacuum of 1.0 bar at a temperature of 250°C. Was prepared.

The composition of the added ingredients is summarized in Table 3 below.

Experimental example

The melt index (MI), specific gravity, and tensile strength were measured for the adhesive compositions of Examples 1 to 3 and the base resin used in each composition, and are shown in Table 4. In addition, peel strength (Peel Strength, unit: N/10mm) between stainless steel and high density polyethylene (HDPE) and between stainless steel and steel was tested for the adhesive composition of Examples 1 to 3 and the base resin used in each composition. And (sample size 1cm X 10cm square), and the results are shown in Table 5 below.

As shown in Tables 4 to 5 below, it can be seen that the adhesive compositions according to Examples 1 to 3 show a significant difference in tensile strength and peel strength compared to the base resin.

Claims (16)

(S1) obtaining a metal salt by mixing a compound containing at least one metal selected from the group consisting of Zn, Ni, Cr, Fe, Cu, Na and Al with a first organic acid;
(S2) adsorbing the second organic acid to the solid adsorbent;
(S3) mixing at least one of the solid adsorbent and the metal salt to which the second organic acid is adsorbed and an α, β-unsaturated carboxylic acid-α-olefin copolymer to obtain an adhesive precursor resin;
(S4) mixing and melt-kneading the adhesive precursor resin and the α, β-unsaturated carboxylic acid-α-olefin copolymer; method for producing an adhesive composition comprising a.
The method of claim 1,
The metal salt is zinc acetate, the second organic acid in step (S2) is acetic acid and the solid adsorbent is silica,
The α, β-unsaturated carboxylic acid-α-olefin copolymer of steps (S3) and (S4) is ethylene methyl acrylate (EMA), a method for preparing an adhesive composition.
The method of claim 1,
The metal salt is zinc acetate, the second organic acid in step (S2) is acetic acid and the solid adsorbent is silica,
The α, β-unsaturated carboxylic acid-α-olefin copolymer in step (S3) is ethylene methyl acrylate (EMA), and the α, β-unsaturated carboxylic acid-α-olefin copolymer in step (S4) is maleic anhydride-polyethylene Copolymer (MAH-g-PE), a method for producing an adhesive composition.
The method of claim 1,
The first organic acid and the second organic acid independently of each other include at least one of acetic acid and formic acid, the method of manufacturing an adhesive composition.
The method of claim 1,
The solid adsorbent is a method of manufacturing an adhesive composition comprising at least one of silica and carbon black.
The method of claim 1,
The solid adsorbent is 0.5 to 15 parts by weight based on a total of 100 parts by weight of the adhesive precursor resin, the method of manufacturing an adhesive composition.
The method of claim 1,
In the step (S2), the metal salt obtained in the step (S1) is further adsorbed onto the solid adsorbent.
The method of claim 1,
The α, β-unsaturated carboxylic acid is at least one member selected from the group consisting of acrylic acid, methacrylic acid, acetic acid, maleic acid, succinic acid and itaconic acid, a method for producing an adhesive composition.
The method of claim 1,
The α-olefin is at least one member selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene, a method for producing an adhesive composition.
The method of claim 1,
The α, β-unsaturated carboxylic acid-α-olefin copolymer has a melt index of 3 to 50 g/10min.
The method of claim 1,
The α, β-unsaturated carboxylic acid-α-olefin copolymer is maleic anhydride-polyethylene copolymer (MAH-g-PE), ethylene methyl acrylate (EMA) resin, ethylene methyl methacrylate (EMMA) resin, and ethylene vinyl A method for producing an adhesive composition, which is at least one member selected from the group consisting of acetate (EVA) resin.
The method of claim 1,
In the case where the adhesive precursor resin does not include the solid adsorbent to which the second organic acid is adsorbed in the step (S3), the solid adsorbent to which the second organic acid is adsorbed is added in the step (S4). .
The method according to any one of claims 1 to 12,
The solid adsorbent is silica,
Silica has an average particle diameter of 0.08 to 0.3 μm and a surface area of silica of 150 to 200 m ² /g.
Steel pipe;
A stainless steel pipe inserted into the steel pipe;
An adhesive layer formed between the steel pipe and the stainless steel pipe and bonding the steel pipe and the stainless steel pipe; And
Including; a resin layer formed on the outer surface of the steel pipe,
The adhesive composition of the adhesive layer,
α, β-unsaturated carboxylic acid-α-olefin copolymer;
Zinc acetate, which is a reaction product of ZnO and acetic acid; And
Including; acetic acid adsorbed silica,
The α, β-unsaturated carboxylic acid-α-olefin copolymer is ethylene methyl acrylate (EMA) or consists of ethylene methyl acrylate (EMA) and maleic anhydride-polyethylene copolymer (MAH-g-PE),
The adhesive composition is prepared by further mixing and melt-kneading ethylene methyl acrylate (EMA) after making an adhesive precursor resin, or maleic anhydride-polyethylene copolymer (MAH-g-PE) after making an adhesive precursor resin. Prepared by melt-kneading,
The adhesive precursor resin is prepared by mixing the zinc acetate, acetic acid adsorbed silica, and ethylene methyl acrylate (EMA),
The adhesive composition has a peel strength of 98 to 142 N/10 mm between stainless steel and steel, and a tensile strength of 264 to 377 kg/cm ² when tested at a tensile rate of 10 mm/min.
Grater;
Stainless steel plate; And,
Including; an adhesive layer made by applying the adhesive composition to a steel plate or a stainless steel plate,
The adhesive composition,
α, β-unsaturated carboxylic acid-α-olefin copolymer;
Zinc acetate, which is a reaction product of ZnO and acetic acid; And
Including; silica adsorbed with acetic acid,
The α, β-unsaturated carboxylic acid-α-olefin copolymer is ethylene methyl acrylate (EMA) or consists of ethylene methyl acrylate (EMA) and maleic anhydride-polyethylene copolymer (MAH-g-PE),
The adhesive composition is prepared by further mixing and melt-kneading ethylene methyl acrylate (EMA) after making an adhesive precursor resin, or maleic anhydride-polyethylene copolymer (MAH-g-PE) after making an adhesive precursor resin. Prepared by melt-kneading,
The adhesive precursor resin is prepared by mixing the zinc acetate, acetic acid adsorbed silica, and ethylene methyl acrylate (EMA),
The adhesive composition has a peel strength of 98 to 142 N/10 mm between stainless steel and steel, and a tensile strength of 264 to 377 kg/cm ² when tested at a tensile speed of 10 mm/min.
Metal tubes made of thin stainless steel;
An adhesive layer made of an adhesive composition applied to the metal tube; And,
Including; a resin layer adhered to the metal tube by the adhesive layer,
The resin layer is made of HDPE,
The adhesive composition,
α, β-unsaturated carboxylic acid-α-olefin copolymer;
Zinc acetate, which is a reaction product of ZnO and acetic acid; And
Including; acetic acid adsorbed silica,
The α, β-unsaturated carboxylic acid-α-olefin copolymer is ethylene methyl acrylate (EMA) or consists of ethylene methyl acrylate (EMA) and maleic anhydride-polyethylene copolymer (MAH-g-PE),
The adhesive composition is prepared by further mixing and melt-kneading ethylene methyl acrylate (EMA) after making an adhesive precursor resin, or maleic anhydride-polyethylene copolymer (MAH-g-PE) after making an adhesive precursor resin. Prepared by melt-kneading,
The adhesive precursor resin is prepared by mixing the zinc acetate, acetic acid adsorbed silica, and ethylene methyl acrylate (EMA),
The adhesive composition has a peel strength of 132 to 166 N/10 mm between stainless steel and HDPE, and a tensile strength of 264 to 377 kg/cm ² when tested at a tensile rate of 10 mm/min.