KR101540740B1 - Adhesive resin composition and aluminum composite panel - Google Patents

Abstract

The present invention relates to an adhesive resin composition and an aluminum composite panel. The adhesive resin composition can exhibit excellent adhesive performance with aluminum, steel and the like, mechanical properties such as improved flexibility and impact resistance, and can exhibit higher moldability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an adhesive resin composition and an aluminum composite panel,

The present invention relates to an adhesive resin composition and an aluminum composite panel. More particularly, the present invention relates to an adhesive resin composition and an aluminum composite panel which can exhibit excellent adhesive properties with aluminum, steel and the like, mechanical properties such as improved flexibility and impact resistance, To an adhesive resin composition and an aluminum composite panel.

The polyolefin resin is lightweight, low in cost, and excellent in physical properties, and is used for various purposes. However, it is non-polar and has good compatibility with polar substrates such as nylon, polyester, aluminum, iron, paper and wood, The range of use has been limited.

In order to overcome this limitation of the polyolefin resin, various methods such as a method of chemically grafting the polar group to the main chain of the polyolefin to improve the adhesion, a method of mixing the polyolefin resin with another agent for imparting adhesiveness have been studied.

Particularly, various adhesive components are known for bonding a polymer layer of a multilayer film such as an aluminum composite panel or a metal layer such as aluminum. However, the previously known adhesive components for a multilayered film have problems such as insufficient adhesive force, low air and moisture barrier properties or mechanical properties, low flexibility or elasticity, low adhesive strength due to repeated deformation, And the like.

For example, Korean Patent Laid-Open Publication No. 2001-0071037 discloses an adhesive composition comprising an ethylene polymer and an adhesion promoter containing a reaction product of a carboxylic acid-grafted polyolefin and a polyamine. However, such a bonding composition has a limitation showing a high reactivity to a polar substrate, so that it has a certain limit to be applied to a multilayer film such as an aluminum composite panel in which various polymer resins or metal layers are laminated, and is applied to an extrusion step for producing a multilayer film But did not secure enough flexibility or elasticity.

Accordingly, there is a need to develop an adhesive material capable of exhibiting excellent adhesive performance with aluminum, steel, etc., improved mechanical properties such as flexibility and impact resistance, and exhibiting higher moldability.

Korean Patent Publication No. 2001-0071037

An object of the present invention is to provide an adhesive resin composition which can exhibit excellent adhesive performance with aluminum, steel and the like, mechanical properties such as improved flexibility and impact resistance, and can exhibit higher moldability.

The present invention also provides an aluminum composite panel including an adhesive layer capable of exhibiting excellent adhesive properties with aluminum, steel and the like, mechanical properties such as improved flexibility and impact resistance, and exhibiting higher moldability.

The present invention relates to a polyolefin resin composition comprising 20 to 40% by weight of a polyolefin resin; From 20 to 50% by weight of a copolymer of a polyolefin-based elastomer and a polyethylene resin in which a dicarboxylic acid or an acid anhydride thereof is grafted; 20 to 40% by weight of an ethylene vinyl acetate copolymer; And 1 to 20% by weight of impact-resistant polystyrene; and the peel strength to aluminum according to ASTM D882 is 10 kgf / 20 mm or more.

The present invention also provides an aluminum composite panel comprising an adhesive layer comprising the adhesive resin composition, a polyolefin resin layer and an aluminum layer.

Hereinafter, the adhesive resin composition and the aluminum composite panel according to the specific embodiment of the present invention will be described in more detail.

According to one embodiment of the invention, the polyolefin resin comprises 20 to 40% by weight; From 20 to 50% by weight of a copolymer of a polyolefin-based elastomer and a polyethylene resin in which a dicarboxylic acid or an acid anhydride thereof is grafted; 20 to 40% by weight of an ethylene vinyl acetate copolymer; And 1 to 20% by weight of impact-resistant polystyrene; and the peel strength to aluminum according to ASTM D882 is 10 kgf / 20 mm or more.

The present inventors have conducted studies on an adhesive material that is excellent in adhesion to metals such as steel and aluminum and can be applied to an aluminum composite panel or the like to provide a polyolefin elastomer in which a dicarboxylic acid or an acid anhydride thereof is grafted to a polyolefin resin And ethylene-vinyl acetate copolymer and impact-resistant polystyrene exhibit excellent adhesion with metals. In particular, they have improved elasticity and flexibility, and thus can achieve high moldability in the process of manufacturing a film. It was confirmed through experiment and completed the invention.

Particularly, the adhesive resin composition includes a polyolefin resin in which a dicarboxylic acid or an acid anhydride thereof is grafted, including a copolymer of a polyolefin-based elastomer and a polyethylene resin, in which a dicarboxylic acid or an acid anhydride thereof is grafted It is possible to obtain a high peel strength and to minimize the whitening phenomenon at a low temperature.

Such an adhesive resin composition may have a peel strength of 10 kgf / 20 mm or more with respect to aluminum according to ASTM D882, and preferably 12 to 25 kgf / 20 mm. The peel strength was measured based on ASTM D882 at a Peel speed of 50 mm / min and a specimen width of 20 mm.

The polyolefin resin contained in the adhesive resin composition of one embodiment is at least one polymer selected from the group consisting of low density polyethylene, high density polyethylene, polypropylene, propylene / ethylene copolymer and ethylene / propylene / alpha-olefin terpolymer Resin.

The low-density polyethylene may have a density of 0.890 g / cm 3 to 0.940 g / cm 3, and has many branched chains and low crystallinity. The high-density polyethylene has a density of 0.940 g / cm3 to 0.980 g / cm3, and has a low branching and high crystallinity.

As the polypropylene resin, a polypropylene polymer known to be commonly used in a molded resin product can be used without limitation, but a polypropylene resin having a melt index of 30 to 100 g / 10 min (ASTM D1238, 230 DEG C) Is preferably used.

The ethylene-propylene copolymer may be a block copolymer in which an ethylene repeating unit and a propylene repeating unit form a block, and may be a random copolymer in which the repeating units are randomly arranged. Such an ethylene-propylene copolymer may have a weight average molecular weight of 30,000 to 800,000.

The ethylene / propylene / alpha-olefin terpolymer preferably has a weight average molecular weight of 100,000 to 300,000.

A copolymer of a polyolefin elastomer and a polyethylene resin in which a dicarboxylic acid or an acid anhydride thereof is grafted in the adhesive resin composition of one embodiment is a copolymer of a polyolefin elastomer and a polyethylene resin in a main chain of a copolymer of a polyolefin elastomer and a polyethylene resin, Quot; means a polymer in which an acid or an acid anhydride thereof is grafted to form a branched chain.

The copolymer of the dicarboxylic acid or its acid anhydride-grafted polyolefin-based elastomer and the polyethylene resin can be obtained by melt-kneading a polyolefin (e.g., a polyolefin-based elastomer and a polyethylene resin) at 80 to 200 DEG C in the presence of a peroxide initiator using a twin screw extruder Based elastomer, polyethylene, and dicarboxylic acid or an acid anhydride thereof. When a copolymer of a polyolefin-based elastomer and a polyethylene resin in which a dicarboxylic acid or an acid anhydride thereof is grafted is prepared by the melt extrusion method as described above, the copolymer may be produced in the form of a composite, It can be easily obtained in the form of a pellet.

The peroxide initiator may generate a radical in a copolymer of a polyolefin elastomer and a polyethylene resin to enable a dicarboxylic acid or an acid anhydride graft reaction of the copolymer. Particularly, the peroxide initiator may be 2 , 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and [DTBPH, 2,5-Dimethyl 2,5-Di (t-butylperoxy) hexane].

The content of the peroxide initiator is preferably 0.02 to 7.0% by weight, more preferably 0.03 to 6.0% by weight, more preferably 0.03 to 5.0% by weight based on the total amount of the copolymer of the dicarboxylic acid or the acid anhydride grafted polyolefin elastomer and the polyethylene resin. And preferably 0.04 to 5.0% by weight. When the content of the peroxide initiator is less than 0.02% by weight, sufficient grafting reaction between the copolymer of the polyolefin-based elastomer and the polyethylene resin and the dicarboxylic acid or an acid anhydride thereof may be difficult to be achieved, By weight to 6.0% by weight or less.

The dicarboxylic acid may be selected from the group consisting of maleic acid, phthalic acid, itaconic acid, citraconic acid, alkenylsuccinic acid, cis-1,2,3,6 tetrahydrophthalic acid, 4-methyl-1,2,3,6 tetrahydrophthalic acid, The dianhydride of the dicarboxylic acid may be a dicarboxylic dianhydride of the above-mentioned examples.

The content of the dicarboxylic acid or its acid anhydride grafted from the copolymer of the dicarboxylic acid or its acid anhydride-grafted polyolefin-based elastomer and the polyethylene resin may be 0.1 wt% or more, preferably 0.1 wt% To 30% by weight. If the dicarboxylic acid or an acid anhydride thereof is grafted to less than 0.1 wt% in the copolymer, the compatibility between the adhesive resin compositions and the uniformity of the composition may be lowered. In addition, if the dicarboxylic acid or its acid anhydride is grafted to the copolymer in an amount exceeding 30% by weight, the adhesive strength, mechanical properties or flexibility of the adhesive composition may be deteriorated.

The grafting ratio of the dicarboxylic acid or an acid anhydride thereof can be measured from the results obtained by acid-base titration of a copolymer of the dicarboxylic acid or its acid anhydride-grafted polyolefin elastomer and a polyethylene resin. For example, about 1 g of the above-mentioned modified copolymer is placed in 150 ml of xylene saturated with water and refluxed for about 2 hours. A small amount of a 1% by weight thymol blue-dimethylformamide solution is added, and the solution is diluted with a 0.05N sodium hydroxide- Slightly excess titration to obtain a solution of a blue-brownish color. The solution was again back-adjusted with a 0.05N hydrochloric acid-isopropyl alcohol solution until it showed yellow color, and the acid value was determined. From this, the copolymer of polyolefin elastomer and polyethylene resin was grafted The amount of dicarboxylic acid can be calculated.

The copolymer of the polyolefin elastomer and the polyethylene resin in which the dicarboxylic acid or its acid anhydride is grafted may have a weight average molecular weight of 30,000 to 800,000.

Specific examples of the polyolefin-based elastomer include ethylene-octene rubber, ethylene butadiene rubber, ethylene-propylene rubber, ethylene / 1-butene random copolymer or Or a mixture of two or more thereof.

The ethylene / 1-butene random copolymer may contain repeating units derived from ethylene and 1-butene, respectively. The ethylene / 1-butene random copolymer may contain 70 to 90 mol% of repeating units derived from ethylene and 10 to 30 mol% of repeating units derived from 1-butene in order to further improve the adhesive performance. Particularly, the ethylene / 1-butene random copolymer containing 70 to 90 mol% of repeating units derived from ethylene and 10 to 30 mol% of repeating units derived from 1-butene can be obtained by reacting a hydrogenated petroleum resin or a hydrogenated Dicyclopentadiene- It has higher compatibility and can further improve the adhesion performance.

The content of the polyolefin elastomer may be 40 to 60 wt% based on the total weight of the copolymer of the polyolefin elastomer and the polyethylene resin in which the dicarboxylic acid or an acid anhydride thereof is grafted.

In the copolymer of the dicarboxylic acid or its acid anhydride-grafted polyolefin elastomer and the polyethylene resin, the polyethylene resin may be a low density polyethylene, a medium density polyethylene, a high density polyethylene, an ethylene / propylene copolymer and an ethylene / propylene / And an olefin terpolymer. The term " polymer resin " The content of the polyethylene resin may be 40 to 60% by weight based on the total weight of the copolymer of the polyolefin-based elastomer and polyethylene resin grafted with the dicarboxylic acid or an acid anhydride thereof.

The copolymer of the polyolefin elastomer and the polyethylene resin in which the dicarboxylic acid or the acid anhydride thereof is grafted can further improve the compatibility between the polyolefin resin, the ethylene vinyl acetate copolymer and the impact resistant polystyrene, Homogeneous composition and distribution can be obtained. In addition, the copolymer of the dicarboxylic acid or its acid anhydride-grafted polyolefin elastomer and the polyethylene resin may also improve adhesion of the adhesive resin composition to the metal.

The ethylene vinyl acetate copolymer contained in the adhesive resin composition may have a vinyl acetate content of 10 to 30% by weight. When the content of vinyl acetate is too low, the compatibility and optical properties with the polyolefin resin or the copolymer of the polyolefin-based elastomer and the polyethylene resin in which the dicarboxylic acid or its acid anhydride is grafted may be lowered, It is preferable to set it within the above-mentioned range.

The ethylene vinyl acetate copolymer may have a melt index of 2 g / 10 min to 60 g / 10 min. Such an ethylene vinyl acetate copolymer has a property of exhibiting a flexible behavior at a low temperature without adding a plasticizer and has a polar group and is particularly included in the adhesive resin composition to improve the adhesive strength, impact strength and heat sealing composition.

The impact resistant polystyrene contained in the adhesive resin composition means a homopolymer of styrene or alpha methyl styrene or a polymer of styrene and an unsaturated monomer such as ethylene, butene, butadiene or isoprene. Since the impact-resistant polystyrene has excellent impact resistance and adhesion at low temperatures, compared with polystyrene, the adhesive resin composition includes the impact-resistant polystyrene, so that the adhesion to a substrate such as steel can be significantly improved. An example of such impact-resistant polystyrene is a polymer obtained by grafting a styrene monomer and 1,3-butadiene.

On the other hand, the adhesive resin composition may further include at least one additive selected from the group consisting of an antioxidant, an adhesive property-imparting agent, and a fluorine compound.

The antioxidant may act as an oxidizing agent for removing the radical groups and decomposing peroxides. The antioxidant may prevent the oxidation induction time and the yellowing phenomenon. Specific examples of the antioxidant include a phenolic antioxidant, a phosphorus antioxidant, and a complex antioxidant.

In addition, the above-mentioned adhesive property-imparting agent not only makes the adhesive resin composition have higher adhesiveness, but also has high flexibility and elasticity so that high moldability can be ensured even in the production process of the coextruded multilayer film.

Specific examples of the adhesion-imparting agent include aromatic petroleum resin, aliphatic petroleum resin, copolymerized petroleum resin, hydrogenated petroleum resin, rosin acid, rosin ester, hydrogenated rosin resin, coumaroneindene resin, terpene resin, phenol resin , Polybutene, and mixtures of two or more thereof.

The petroleum resin is a light yellow or blackish brown thermoplastic resin having a molecular weight of 2000 or less and obtained by polymerizing an unsaturated hydrocarbon in a high-temperature pyrolysis fluid such as naphtha as a raw material with an acid catalyst.

The aromatic petroleum resin is a resin produced by using C9 as a main raw material among the oil produced in the olefin process during the naphtha cracking process, and has a softening point of about 80 to 150 DEG C and a molecular weight of about 600 to 1500. The main component of the aromatic petroleum resin is a copolymer of styrene vinyltoluene,? -Methylstyrene, and indene

The aliphatic petroleum resin is a resin which is produced by using C5 oil as a raw material among oil fractions produced in an olefin process during a naphtha cracking process, and has a softening point of about 70 to 100 ° C and a molecular weight of about 800 to 2000. The major component of the aliphatic petroleum resin is a copolymer such as isoprene or piperylene 2-methylbutene-1.

The copolymerized petroleum resin means a resin formed by copolymerizing the aromatic petroleum resin and the aliphatic petroleum resin.

The hydrogenated petroleum resin is a resin formed by adding hydrogen to the aromatic petroleum resin and the aliphatic petroleum resin. The properties of the hydrogenated petroleum resin become colorless and excellent in overall stability such as ultraviolet stability.

In addition, the fluorine compound may reduce the color transition time and may improve the compatibility of the olefin resins and reduce the gel incidence. As such a fluorine compound, for example, a polyolefin-based resin having a fluoropolymer content of 1 to 10% can be used, and it is preferable to master-mix and mix it to exhibit performance.

The adhesive resin composition may be prepared by mixing a copolymer of a polyolefin resin, a dicarboxylic acid or an acid anhydride thereof with a polyolefin elastomer and a polyethylene resin, an ethylene vinyl acetate copolymer and an impact resistant polystyrene, And melt-extruding the mixture at a temperature of 80 to 200 ° C using a twin-screw extruder. The adhesive resin composition may be produced in the form of a composite by the reaction extrusion method as described above, and may be obtained in the form of a pellet which is easy to mold in the form of a film or the like.

The additive may be contained in an amount of 0.1 to 20% by weight. When the content of the additive is too small, the effect of improving the physical properties of the adhesive resin composition may be insufficient. When the content of the additive is too large, the content of the polyolefin resin, copolymer of the modified polyolefin elastomer and polyethylene resin, ethylene vinyl acetate The mechanical properties may be deteriorated.

According to another embodiment of the present invention, there is provided an adhesive layer comprising the above-mentioned adhesive resin composition; A polyolefin resin layer; And an aluminum layer can be provided.

As described above, the present inventors have found that an adhesive layer comprising a copolymer of a polyurethane resin, a dicarboxylic acid or an acid anhydride thereof with a polyolefin elastomer and a polyethylene resin, an ethylene vinyl acetate copolymer, and an impact resistant polystyrene has mechanical properties And has excellent adhesion to aluminum and can be applied to an aluminum composite panel, and an aluminum composite panel including the adhesive layer, a polyolefin resin layer and an aluminum layer has been invented.

The polyolefin resin layer and the aluminum layer may be laminated via the adhesive layer, and the aluminum composite panel may include at least one of the polyolefin resin layer, the aluminum layer, and the adhesive layer.

A copolymer of a polyolefinic elastomer and a polyethylene resin in which the polyurethane resin, the dicarboxylic acid or an acid anhydride thereof is grafted, an ethylene vinyl acetate copolymer, an impact resistant polystyrene, an additive and the like can be used as the adhesive resin composition of the above- The contents described may be applied without limitation.

The configuration of the aluminum composite panel is the same as that of a typical composite panel except that the adhesive resin layer is formed using the adhesive resin composition described above, so that a further detailed description thereof will be omitted.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an adhesive resin composition capable of exhibiting excellent adhesion performance with aluminum, steel, etc., mechanical properties such as improved flexibility and impact resistance, exhibiting higher moldability, and an adhesive layer having the above- An aluminum composite panel may be provided.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph showing the degree of whitening at 100 deg. C of the multilayer film produced in Example 1. Fig.
2 is a photograph showing the degree of whitening of the multilayer film prepared in Comparative Example 1 at 100 ° C.
3 is a photograph showing the degree of whitening of the multilayer film prepared in Comparative Example 2 at 100 ° C.
4 is a photograph showing the degree of whitening of the multilayer film prepared in Comparative Example 3 at 100 ° C.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  1 and Comparative Example  1 to 3]: Adhesive Resin Composition and Production of Film

1. Degeneration Polyolefin  Manufacture of resin

Each component was mixed with the composition shown in the following Table 1, and the mixture was melt-kneaded using a 40 mm twin screw extruder in the presence of a peroxide initiator (2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexane) C11 / SC / PDV / Die = 80/120/170/170/170 / 170/170/170/160/160/160/140/160/170 ° C. at a discharge rate of 30 kg / To prepare a polyolefin resin.

In the introduction part C1, the temperature is set to 80 ° C to prevent the resin from melting at the inlet when the resin is supplied, and the temperature of the central part (C7) 170 < 0 > C.

(Unit: wt%) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 EVA 40 98 EOR 58 58 LLDPE 98 40 Peroxide 0.5 0.5 0.5 0.5 Maleic anhydride One One One One Fluorine compound 0.5 0.5 0.5 0.5

* EVA: ethylene vinyl acetate content of 15% by weight of VA

EOR: ethylene-octene rubber (weight average molecular weight: about 140,000, density: 0.857 g / cm3, glass transition temperature: -58 캜, melting point: 38 캜)

* LLDPE: weight-average molecular weight of about 80,000, density 0.920 g / ㎤, melt index 2.5g / 10min

Peroxide: 2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexane

* Fluorine compound: Fluoropolymer content 5%, MFI = 4

2. Preparation of Adhesive Resin Composition

Each component was mixed with the composition shown in the following Table 2, and the components were mixed using a twin-screw extruder (C1 to C11 / SC / PDV / Die = 80/120/170/170/170/170/170/170/160 / 160/160/140/160/170 캜 at a discharge rate of 30 kg / hr, 450 RPM to prepare an adhesive resin composition.

Composition (% by weight) Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 denaturalization
Polyolefin LLDPE / EBR-g-MAH 30 LLDPE-g-MAH 30 EVA-g-MAH 30 EVA / EBR-g-MAH 30 EVA 30 30 30 30 LDPE 24.4 24.4 24.4 24.4 Petroleum resin 5 5 5 5 HIPS 10 10 10 10 Antioxidant 0.3 0.3 0.3 0.3 Fluorine compound 0.3 0.3 0.3 0.3

* EVA: ethylene vinyl acetate content of 15% by weight of VA

* LDPE: weight average molecular weight of about 80,000, density of 0.916 g / cm3, melt index of 8 g / 10 min

* Petroleum resin: hydrogenated DCPD resin (Dicyclopentadiene)

* HIPS: polystyrene, 1,3-butadiene, homopolymer, density 1.05 g / cm3, MVR 9.5 ml / 10 min

* Antioxidant: Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane

* Fluorine compound: Fluoropolymer content 5%, MFI = 4

3. Preparation of multilayer film

Using the adhesive resin composition obtained in the above example, a three-layer film of two layers of LDPE / adhesive layer films was formed under the conditions of Line Speed = 5 m / min by a Multi Layer Film Molding Machine.

The operating conditions of the multi-layer film molding machine were as shown in Table 3 below.

CY1 CY2 CY3 AD1 EXTRUDER 1. TEMP (℃) 170 240 250 250 EXTRUDER 2. TEMP (℃) 170 240 250 250 FD1 FD2 DE1 DE2 DE3 FEED & DIES TEMP (℃) 250 250 250 250 250

1) EXTRUDER 1. TEMP, EXTRUDER 2. TEMP means the temperature of the three extruders used to form the two-layer film using each of the two films.

2) CY1 / CY2 / CY3 / AD1 means the part-by-part temperature of the cylinder inside the extruder. In the introduction portion CY1, the temperature was set at 170 占 폚 and lower than 250 占 폚, which is the temperature of the central portion CY3, in order to prevent the resin from sticking to the inlet at the time of charging.

3) FD1 / FD2 / DE1 / DE2 / DE3 is the temperature range of the extruder feed and die sections, and is set equal to the internal temperature of the extruder.

[ Experimental Example ]

One. Evaluation of moldability of multilayer film

3) the thickness and surface state of the film according to the roll winding speed, and 4) the occurrence of gelation. In the case of the multi-layer film produced in Examples and Comparative Examples, And the like.

In the manufacturing process of the three-layer film manufactured in Example 1, the feed of the raw material was smooth with the extruder, and the spreadability according to the melt index was good. In addition, the thickness and surface condition of each layer in the produced film were observed to be uniform and good, and the generation amount of Gel was remarkably decreased.

Thus, it has been confirmed that the adhesive resin composition of the present invention has improved flexibility and elasticity, and can achieve high moldability in the process of producing a coextruded multilayer film.

2. Evaluation of adhesive strength and peel strength of multilayer film

The multilayer films prepared in the above Examples and Comparative Examples were bonded to aluminum and SUS substrates respectively and peel strengths were measured on the basis of ASTM D882. In order to evaluate the adhesion at low temperature, And the degree of transfer relative to the area of the substrate was measured. The results are shown in Table 4 and FIG. 1 to FIG.

- Press temperature: Al-135 ℃. SUS-180 ° C

- Pressure: 25kg / cm ²

- Pressing time: 3min

- Peeling speed: 50mm / min

- Specimen width: 20mm

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Peel strength (kgf / 20 mm) 14 5 3 6

As shown in Table 1, according to the adhesive resin composition of Example 1, it can be confirmed that an adhesive layer having a peel strength of 14 kgf / 20 mm according to ASTM D882 can be manufactured. That is, from the above results, the adhesive resin composition to which the copolymer of the polyolefin-based elastomer and the polyethylene resin, in which the dicarboxylic acid or its acid anhydride was grafted, was used as the LLDPE-g-MAH, EVA-g-MAH, EVA / EBR -g-MAH, and the like.

As shown in Figs. 1 to 4, the multilayer film (Fig. 1) produced in the above Example 1 exhibited a higher adhesive strength than the films prepared in Comparative Examples (Fig. 2 to Fig. 4) , It can be confirmed that the adhesive layer is peeled off, not peeling off with the adhesive base material, which is usually evaluated as peeling of the most ideal adhesive layer. In addition, in Example 1, it can be confirmed that excellent adhesion can be maintained even at a low temperature with a peel strength of 14 kgf / 20 mm or more.

On the other hand, in the case of the comparative examples shown in Figs. 2 to 4, it was confirmed that the adhesive layer was not uniformly transferred to the release surface, or the resin layer was observed only on one side as shown in Fig. 3, and the adhesive strength to the aluminum substrate was low.

Claims (12)

20 to 40% by weight of a polyolefin resin;
From 20 to 50% by weight of a copolymer of a polyolefin-based elastomer and a polyethylene resin in which a dicarboxylic acid or an acid anhydride thereof is grafted;
20 to 40% by weight of an ethylene vinyl acetate copolymer;
1 to 20% by weight of impact resistant polystyrene; And
0.1 to 20% by weight of a fluorine compound, wherein the peel strength to aluminum according to ASTM D882 is 10 kgf / 20 mm or more,
The polyolefin elastomer may be one selected from the group consisting of ethylene-octene rubber, ethylene butadiene rubber, ethylene-propylene rubber and ethylene / 1-butene random copolymer. An adhesive resin composition comprising at least two kinds of compounds.
The method according to claim 1,
Wherein the polyolefin resin comprises at least one polymer resin selected from the group consisting of low density polyethylene, high density polyethylene, polypropylene, propylene / ethylene copolymer and ethylene / propylene / alpha-olefin terpolymer.
The method according to claim 1,
Wherein the dicarboxylic acid is selected from the group consisting of maleic acid, phthalic acid, itaconic acid, citraconic acid, alkenylsuccinic acid, cis-1,2,3,6 tetrahydrophthalic acid and 4-methyl-1,2,3,6-tetrahydrophthalic acid And at least one selected from the group consisting of polyolefin resin and polyolefin resin.
The method according to claim 1,
Wherein the copolymer of the dicarboxylic acid or its acid anhydride grafted polyolefin elastomer and the polyethylene resin has a weight average molecular weight of 30,000 to 800,000.
delete The method according to claim 1,
Wherein the polyolefin-based elastomer comprises 40 to 60 wt% based on the total weight of the copolymer of the polyolefin-based elastomer and the polyethylene resin, wherein the dicarboxylic acid or its acid anhydride is grafted.
The method according to claim 1,
Wherein the polyethylene resin comprises at least one polymer resin selected from the group consisting of low density polyethylene, medium density polyethylene, high density polyethylene, ethylene / propylene copolymer and ethylene / propylene / alpha-olefin terpolymer. .
The method according to claim 1,
Antioxidants; And an adhesion imparting agent; And at least one additive selected from the group consisting of an epoxy resin,
9. The method of claim 8,
The adhesive property-imparting agent may be at least one selected from the group consisting of aromatic petroleum resin, aliphatic petroleum resin, copolymerized petroleum resin, hydrogenated petroleum resin, rosin acid, rosin ester, hydrogenated rosin resin, coumarone resin, terpene resin, And at least one compound selected from the group consisting of the following.
9. The method of claim 8,
And the additive comprises 0.1 to 20 wt%.
An adhesive layer comprising the adhesive resin composition of claim 1;
A polyolefin resin layer; And
An aluminum composite panel comprising an aluminum layer.
12. The method of claim 11,
Wherein the polyolefin resin layer and the aluminum layer are laminated via the adhesive layer.

Images