KR19980068565A - Resin composition for extrusion lamination which can be directly bonded and has excellent low-temperature heat sealing composition and easy peeling property - Google Patents

Abstract

The present invention provides a polypropylene resin composition for extrusion lamination which is excellent in low-temperature heat sealing composition and easy peel and can be directly adhered to a substrate without a separate adhesive treatment, (D), 2 to 10 parts by weight of the component (E), and 0.001 to 10 parts by weight of the component (F) are contained in an amount of 5 to 20 parts by weight, 0.1 part by weight.

(A) a binary or ternary copolymer of propylene and ethylene or 1-butene, which satisfies the following conditions 1 to 3:

(1) ethylene or 1-butene alone or the sum of ethylene and 1-butene is 4 to 15 mol%

② When the melting temperature is below 135 ℃

③ Melt index is 5 ~ 25g / 10min (230 ℃)

(B) a low density polyethylene having a melt index of 1 to 15 g / 10 min (190 DEG C) and a density of 0.925 g /

(C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 캜) and a density of 0.915 g /

(D) an amorphous or low-crystalline ethylene-based? -Olefin random copolymer or a 1-butene? -Olefin random copolymer satisfying the following conditions 1 to 3:

(1) the? -Olefin has 2 to 20 carbon atoms

(2) a melt index of 0.1 to 30 g / 10 min (190 DEG C)

③ Density of 0.900g / ㎤ or less

(E) a modified polypropylene copolymer obtained by graft-modifying maleic anhydride, and satisfying the following conditions 1 to 2:

(1) an unsaturated carboxylic acid or a derivative thereof having a graft ratio of 0.1 to 10 mol%

② Intrinsic viscosity of 0.1-2 dl / g

(F) Release of crosslinking agent

The composition of the present invention has a wide range of heat sealing temperature at a low temperature, and is excellent in workability and easiness of peeling, and can be directly adhered to a substrate without a separate adhesive treatment.

Description

Resin composition for extrusion lamination which can be directly bonded and has excellent low-temperature heat sealing composition and easy peeling property

The present invention relates to a propylene resin composition, and more particularly to a propylene resin composition which has a wide range of heat sealing temperatures at low temperatures, excellent processability and easy peeling, And to provide a polypropylene resin composition for lamination.

Easy Peel Seal is the process of separating the heat-sealed packaging materials by using the power of the end-users of the product so that the contents can be easily opened. And a delamination peel seal using a difference in adhesion between various polymers in a co-extrusion process.

In general, the characteristics of the preferred isophyll are, in many respects, the most dominant view that must be achievable within the range of 600 to 1200 g / 15 mm. In addition, the ideal filler film or film should have a wide thermal bond temperature range and should be able to expect a reliable fill effect anywhere within that range, Can be expected from the sealing layer. The casting method using T-die and the extrusion lamination method are mainly used as the processing methods for imparting the characteristics of such an idle yarn, and the extrusion lamination method is mainly used. The extrusion lamination method is also referred to as an extrusion coating method. For example, the extrusion coating method is a method in which a raw resin is heated, melted and kneaded in an extruder, extruded from the extrusion die into a film state, coated on the surface of a substrate to be coated, The extrusion lamination process is widely used because it imparts properties such as moisture-proof property, gas barrier property, abrasion resistance, oil resistance and heat sealing property to a thin film substrate such as a film, sheet, paper, have.

Polyolefins such as low density polyethylene, medium density polyethylene, ethylene-vinyl acetate copolymer and ionomer resin are typically used as resins to be used in such extrusion lamination processing. Of these resins, excellent workability and low heat sealing temperature Low density polyethylene is mainly used. However, in the case of low-density polyethylene, it is not suitable to provide a resin composition excellent in easy-to-peel property. In the case of ethylene-vinyl acetate copolymer, a wide heat sealing temperature range can be expected. However, There is a problem of releasing acetic acid which is severely corroded by the extruder.

On the other hand, in recent years, polypropylene-based, expanded polystyrene-based, etc. are mainly used, and metal foil is often used to manufacture a packaging material for a multilayer sheet. However, since it is practically difficult to expect direct adhesion in forming a packaging material with different kinds of substrates In the actual processing step, a packaging material is manufactured using a separate adhesive (A / C). However, when an adhesive is used, there is a problem that adverse effect is exerted on the food due to the residual solvent.

Therefore, much research has been done to overcome these drawbacks, and the contents are as follows.

Japanese Patent Publication No. 60-49432 discloses a process for producing a film composed of an olefin layer, an easy-to-use filler layer and a processability improving layer. Japanese Patent Publication No. 61-29377 discloses a propylene copolymer, polybutene, ethylene-propylene- However, since the processability in extrusion laminating is poor, it is not suitable as an extrusion lamination resin.

Further, Japanese Patent Publication No. 3-4383 discloses a resin composition comprising a polyethylene, an ethylene-propylene random copolymer and an ethylene -olefin copolymer but is also not suitable as an extrusion lamination resin. US 4,189,519 discloses a resin composition comprising 10 to 50 parts by weight of an isotactic polybutene in an ethylene polymer and an ethylene-unsaturated ester copolymer, and polybutene, styrene-butadiene copolymer, low-density polyethylene, Polyethylene, and polyisobutene. However, these compositions have problems in that they can be thermally adhered to a high-density polyethylene-based resin but can not be adhered to a polypropylene-based resin. In US 4,916,190 and US 4,666,778, 10 to 30 parts by weight of an ethylene homopolymer or an ethylene copolymer, 55 to 60 parts by weight of a 1-butene homopolymer or 1-butene copolymer and 25 to 45 parts by weight of a propylene homopolymer or a propylene copolymer However, the resin composition is disadvantageous in that it is not suitable for sterilization of boiling and retort due to insufficient adhesive force and insufficient heat resistance.

Under these circumstances, the inventors of the present invention have found that it is possible to directly adhere to a substrate without any additional adhesive treatment, and it is possible to provide a polypropylene resin which is excellent in workability, high heat sealing temperature and narrow heat sealing temperature The present invention has been accomplished on the basis of the study by Koza et al.

(A), (B), (C), (D), (E) and (F) (D) is contained in an amount of 3 to 15 parts by weight, (E) is contained in an amount of 2 to 10 parts by weight, and (F) is contained in an amount of 5 to 20 parts by weight, Is 0.001 to 0.1 part by weight based on 100 parts by weight of the polypropylene resin composition. The polypropylene resin composition for extrusion lamination is excellent in low-temperature heat sealing composition and easy peel, and can be directly bonded to a substrate without any adhesive treatment.

(A) a binary or ternary copolymer of propylene and ethylene or 1-butene, which satisfies the following conditions 1 to 3:

(1) ethylene or 1-butene alone or the sum of ethylene and 1-butene is 4 to 15 mol%

② When the melting temperature is below 135 ℃

③ Melt index is 5 ~ 25g / 10min (230 ℃)

(B) a low density polyethylene having a melt index of 1 to 15 g / 10 min (190 DEG C) and a density of 0.925 g /

(C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 캜) and a density of 0.915 g /

(D) an amorphous or low-crystalline ethylene-based? -Olefin random copolymer or a 1-butene? -Olefin random copolymer satisfying the following conditions 1 to 3:

(1) the? -Olefin has 2 to 20 carbon atoms

(2) a melt index of 0.1 to 30 g / 10 min (190 DEG C)

③ Density of 0.900g / ㎤ or less

(E) a modified polypropylene copolymer obtained by graft-modifying maleic anhydride, and satisfying the following conditions 1 to 2:

(1) an unsaturated carboxylic acid or a derivative thereof having a graft ratio of 0.1 to 10 mol%

② Intrinsic viscosity of 0.1-2 dl / g

(F) Release of crosslinking agent

Other objects and applications of the present invention will become apparent to those skilled in the art from the following detailed description.

Hereinafter, the present invention will be described in more detail.

Examples of suitable substrates for extrusion lamination include PET, O-NYLON, OPP, cellophane, metal foil and the like. The extrusion lamination process first extrudes low-density polyethylene into the above- After lamination, a method of secondary lamination of a specific resin composition is mainly used. There is also a method in which a specific resin composition is extrusion-laminated directly on a substrate using an anchor coater agent (A / C agent) for special low-temperature processing.

However, the composition of the present invention is a resin composition capable of maintaining excellent film bonding strength by extrusion laminating directly on a substrate without using extrusion laminating of low-density polyethylene or using special anchor coater (A / C).

The present inventors have found out the following facts through extensive experiments for providing a resin composition for polypropylene extrusion lamination. That is, in order to have appropriate boiling and retort sterilization and low-temperature heat sealing composition, it is necessary to use a propylene random copolymer having a specific composition and to use specific low-density polyethylene and crosslinking release agent for excellent processability. Further, in order to impart an easy-to-peel property having a wide range of heat sealing temperatures at low temperatures, it is necessary to use a specific polybutene and an amorphous or low crystalline ethylene-based? -Olefin random copolymer or a 1-butene? , And it was found that the use of the two kinds of the present invention in combination with each other, rather than the single use, is further enhanced. It has also been found that a modified polypropylene copolymer obtained by graft-modifying maleic anhydride should be used in order to enable extrusion laminating directly on a substrate without using a special A / C agent to maintain excellent film bonding strength.

(A), (B), (C), (D), (E) and (F) in the crystalline polypropylene composition. (C) is 20 to 40 parts by weight, the content of (D) is 3 to 15 parts by weight, the content of (E) is 2 to 40 parts by weight, (F) in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of a polypropylene resin for extrusion laminating, which is excellent in low temperature heat sealing composition and easy peel and can be directly adhered to a substrate without a separate adhesive treatment Based resin composition can be provided.

(A) a binary or ternary copolymer of propylene and ethylene or 1-butene, which satisfies the following conditions 1 to 3:

(1) ethylene or 1-butene alone or the sum of ethylene and 1-butene is 4 to 15 mol%

② When the melting temperature is below 135 ℃

③ Melt index is 5 ~ 25g / 10min (230 ℃)

(B) a low density polyethylene having a melt index of 1 to 15 g / 10 min (190 DEG C) and a density of 0.925 g /

(C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 캜) and a density of 0.915 g /

(D) an amorphous or low-crystalline ethylene-based? -Olefin random copolymer or a 1-butene? -Olefin random copolymer satisfying the following conditions 1 to 3:

(1) the? -Olefin has 2 to 20 carbon atoms

(2) a melt index of 0.1 to 30 g / 10 min (190 DEG C)

③ Density of 0.900g / ㎤ or less

(E) a modified polypropylene copolymer obtained by graft-modifying maleic anhydride, and satisfying the following conditions 1 to 2:

(1) an unsaturated carboxylic acid or a derivative thereof having a graft ratio of 0.1 to 10 mol%

② Intrinsic viscosity of 0.1-2 dl / g

(F) Release of crosslinking agent

In the case of the crystalline polypropylene composition (A) among the components, a copolymer of ethylene, 1-butene or a mixture thereof is used as the propylene homopolymer because it is practically difficult to lower the heat sealing temperature to 135 ° C or less. When the content is less than 40 parts by weight, heat resistance is insufficient, which is not suitable for boiling and retort sterilization. When the content is 70 parts by weight or more, excellent heat resistance can be imparted due to a high temperature and a narrow heat- none.

The low-density polyethylene component as the component (B) is advantageous in that it is a problem that the polypropylene polymer has a deficiency of a processed nec-in (phenomenon in which the width of the extruded film is narrower than the width of the extruder die) And is contained in an amount of 5 to 20 parts by weight in order to improve the phenomenon of surging (unevenness in thickness occurring in the drawing direction because the extrusion amount is not constant). When the content of the component (B) is less than 5 parts by weight, the desired effect is difficult to achieve. When the amount of the component (B) is 20 parts by weight or more, the processability is excellent. However, I can not.

The polypropylene resin composition of the present invention contains polybutene (C) in an amount of 20 to 40 parts by weight in order to have a wide range of heat sealing temperatures at low temperatures. When the content is less than 20 parts by weight, . When the amount is more than 40 parts by weight, it is suitable as an oil-repellent composition, but it is not suitable as an extrusion lamination resin composition because of lowering of workability. The component (C) used herein preferably has a density of 0.915 g / cm 3 or less, preferably 0.911 g / cm 3 or less.

In addition, the composition of the present invention contains the component (D) in an amount of 3 to 15 parts by weight in addition to the components (A), (B) and (C) described above to provide a resin composition suitable for easy peeling without deteriorating workability. When the content of the component (D) is 3 parts by weight or less, improvement in workability and kneading effect can not be expected. When the content of the component (D) is 15 parts by weight or more, 3 to 15 parts by weight is preferable because it is not suitable for sterilization of boiling and retort due to insufficient heat resistance.

However, since the components (A), (B), (C) and (D) can not be bonded directly to a substrate without an adhesive, the composition of the present invention contains the component (E) in an amount of 2 to 10 parts by weight . When the content is less than 2 parts by weight, the adhesive strength is poor. When the content is more than 10 parts by weight, the adhesive strength is too high, which is not suitable for easy peeling, and therefore, it is preferably contained in an amount of 2 to 10 parts by weight.

On the other hand, in order to use the polypropylene resin composition of the present invention for extrusion lamination, melt flowability is important, which can be achieved by the following two methods. The first is a method of polymerizing a resin having a melt index of 10 g / 10 min or more by polymerization, and the second is a method of increasing the melt index by releasing a crosslinking agent. In the present invention, the latter method is adopted. However, the provision of polypropylene having a specific melt index, which is a feature of the present invention, is not limited to the above method.

The crosslinking agent releasing (F) that can be used in the present invention to provide a polypropylene resin having a specific melt index is not particularly limited, and examples thereof include methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide Ketone peroxides; Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide and diisopropylbenzene hydroperoxide; Benzoyl peroxide, benzoyl peroxide, 1,3-bis (tertiary-butylperoxyisopropylene) benzene, 2,5-dimethyl-2,5-di (tertiary butyl Diacyl peroxides such as peroxy) hexane; 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, and 2,2-di- (tertiary butylperoxy) butane; Alkyl peresters such as 2,2,4-trimethylpentyl peroxy neodecanoate and tert-butyl peroxy-neodecanoate; And percarbonates such as di-3-methoxybutyl peroxydicarbonate and tertiary oxybutyl peroxyisopropyl carbonate. However, the present invention is not limited to these examples.

When the amount of the crosslinking agent (F) is less than 0.001 parts by weight, it is difficult to increase the melt index by more than 15 g / 10 min. . When the amount is more than 0.1 part by weight, excessive decomposition of the polypropylene polymer deteriorates the basic properties of the polypropylene polymer. In addition, due to the lowered melt flowability of the components (B), (C) A phenomenon occurs.

The following examples illustrate the present invention.

The evaluation methods of various physical properties adopted in the following Examples and Comparative Examples were carried out by the following test methods.

1) The melt index was measured by the ASTM D-1238 method.

2) The processability was measured by measuring the difference between the die width at which the melt index was extruded and the laminating width after extrusion lamination.

3) The heat sealing temperature was 20 탆 thick laminated low-density polyethylene on a stretched nylon film having a thickness of 20 탆, followed by secondary extrusion lamination of the resin compositions of the present invention to a thickness of 23 짹 1 캜 and 50 짹 5% After the sample was allowed to stand in a constant temperature and humidity room for 24 hours, the two specimens were bonded to each other by five metal surfaces sloping at a pressure of 3 kg / ㎤ for a time of 1 second, and then subjected to a tensile test When the test was performed at a speed of 300 mm / min, a temperature at which a force of 600 g was applied was measured.

4) The heat resistance was determined by retort sterilization method using pressurized steam sterilizer manufactured by HI-TECH Co., Ltd. and pressurized sterilization at 110 ° C for 20 minutes, and the appearance of the film and the deformation of the heat sealing area were observed.

5) The degree of goodness of facial appearance and sensory strength of the posterior surface were measured.

6) The film adhesion strength was evaluated by extrusion laminating the resin compositions of the present invention to a thickness of 20 탆 on a stretched nylon film having a thickness of 20 탆 and then allowing the laminate to stand in a temperature and humidity chamber at 23 ± 1 ° C and 50 ± 5% The tensile strength of the specimens with a width of 20 mm was measured with a tensile testing machine at a speed of 300 mm / min.

[Example 1]

(A) having a melt index of 16 g / 10 min (230 캜), a melting temperature of 132 캜, a Vicat softening point of 124 캜, an ethylene content of 3.0 mol% and a 1-butene content of 5.0 mol% 15 parts by weight of a low-density polyethylene having a melt index of 8 g / 10 min (190 DEG C) and a density of 0.920 g / cm3 as a component (B), 50 parts by weight of a butene terpolymer powder having a melt index of 2 g / 10 parts by weight of an ethylene-propylene copolymer having an ethylene content of 70 mol% as a component (D), 10 parts by weight of a polybutene having a density of 0.911 g / 5 parts by weight of maleic anhydride-modified polypropylene copolymer modified with maleic anhydride graft ratio of 3% / g and 1,3-bis (tertiary-butylperoxy-isopropylene) benzene 0.01 , 0.1 parts by weight of a phenolic antioxidant and 0.1 parts by weight of calcium stearate, and the mixture was stirred with a Henschel mixer for about 5 minutes Followed by extrusion at 200 to 210 DEG C by an extruder to obtain a pellet-like composition. Various physical properties of the obtained composition were measured according to the above-described method, and the results are shown in Table 1.

[Examples 2 to 6]

Same as Example 1 except that the contents of (A), (B), (C), (D), (E) and (F) in Example 1 were changed as shown in the following Table 1 To obtain a composition, and the physical properties thereof were measured. The results are shown in Table 1.

[Example 7]

(A) having a melt index of 16 g / 10 min (230 캜), a melting point of 135 캜, a Vicat softening point of 126 캜 and a 1-butene content of 12 mol% Except that 50 parts by weight of a random binary copolymer powder was used. The results are shown in Table 1. < tb > < TABLE >

[Example 8]

A random binary copolymer of propylene-ethylene having a melt index of 16 g / 10 min (230 DEG C), a melting point of 132 DEG C, a Vickart softening point of 123 DEG C and an ethylene content of 7 mol% The composition was obtained in the same manner as in Example 1 except that 50 parts by weight of the powder was used. The properties of the composition were measured and the results are shown in Table 1.

[Example 9]

A composition was obtained in the same manner as in Example 1, except that low-density polyethylene having a melt index of 14 g / 10 min (190 캜) and a density of 0.920 g / cm 3 was used as the component (B) The results of measuring the physical properties thereof are shown in Table 1.

[Example 10]

A composition was obtained in the same manner as in Example 1, except that polybutene having a melt index of 18 g / 10 min (190 캜) and a density of 0.911 g / cm 3 was used as the component (C) in Example 1, The results of measuring the physical properties thereof are shown in Table 1.

[Example 11]

A composition was obtained in the same manner as in Example 1, except that an ethylene-1-butene copolymer having an ethylene content of 70 mol% was used as the component (D) in Example 1, Are shown in Table 1.

[Comparative Examples 1 to 10]

Same as Example 1 except that the contents of (A), (B), (C), (D), (E) and (F) in Example 1 were changed as shown in the following Table 1 To obtain a composition. The physical properties of the composition are shown in Table 1.

[Comparative Example 11]

(A) having a melt index of 4 g / 10 min (230 캜), a melting point of 135 캜, a Vicat softening point of 126 캜 and a 1-butene content of 12 mol% Except that 50 parts by weight of a random binary copolymer powder was used. The results are shown in Table 1. < tb > < TABLE >

[Comparative Example 12]

(A) having a melt index of 30 g / 10 min (230 캜), a melting point of 135 캜, a Vicat softening point of 126 캜 and a 1-butene content of 12 mol% Except that 50 parts by weight of a random binary copolymer powder was used. The results are shown in Table 1. < tb > < TABLE >

[Comparative Example 13]

A composition was obtained in the same manner as in Example 1, except that low-density polyethylene having a melt index of 25 g / 10 min (190 ° C) and a density of 0.920 g / cm 3 was used as the component (B) The results of measuring the physical properties thereof are shown in Table 1.

[Comparative Example 14]

A composition was obtained in the same manner as in Example 1 except that polybutene having a melt index of 0.2 g / 10 min (190 ° C) and a density of 0.911 g / cm 3 was used as the component (C) in Example 1 And the physical properties thereof are shown in Table 1.

[Comparative Example 15]

A composition was obtained in the same manner as in Example 1 except that polybutene having a melt index of 25 g / 10 min (190 ° C) and a density of 0.911 g / cm 3 was used as the component (C) in Example 1 And the physical properties thereof are shown in Table 1.

[Comparative Example 16]

Example 1 was carried out in the same manner as in Example 1, except that an ethylene-propylene copolymer having a melt index of 35 g / 10 min (190 ° C) and an ethylene content of 70 mol% was used as the component (D) The composition was obtained, and the physical properties thereof were measured. The results are shown in Table 1.

[Table 1]

division A B C D E F Melt Index Heat sealing temperature Film adhesion strength Processability Heat resistance Ease Weight portion g / 10 min ℃ g / 15mm ◎ Very good, ○ Good, × Bad Example 1 50 10 25 10 5 0.01 20 116 2500 ○ ◎ ◎ Example 2 50 10 30 5 5 0.01 19 118 2200 ○ ○ ◎ Example 3 45 20 20 10 5 0.01 20 115 2700 ◎ ○ ○ Example 4 50 20 20 5 5 0.01 18 120 2200 ◎ ○ ○ Example 5 50 10 25 10 5 0.003 16 116 2200 ○ ○ ◎ Example 6 50 10 25 10 5 0.08 32 116 2100 ◎ ○ ◎ Example 7 50 10 25 10 5 0.01 20 116 2600 ○ ◎ ◎ Example 8 50 10 25 10 5 0.01 20 115 2400 ◎ ○ ◎ Example 9 50 10 25 10 5 0.01 22 116 2500 ◎ ○ ◎ Example 10 50 10 25 10 5 0.01 23 116 2600 ◎ ○ ◎ Example 11 50 10 25 10 5 0.01 20 116 2700 ○ ◎ ◎ Comparative Example 1 50 10 25 10 5 12 116 2500 × ◎ ○ Comparative Example 2 55 10 25 10 0.01 18 120 150 ○ ○ × Comparative Example 3 50 10 25 10 5 0.0008 13 120 2500 × ○ ○ Comparative Example 4 50 10 25 10 5 0.15 47 120 2300 × ○ ○ Comparative Example 5 54.2 10 25 10 0.8 0.01 18 119 220 ○ ○ × Comparative Example 6 40 10 25 10 15 0.01 22 114 3000 × ○ × Comparative Example 7 68 10 15 2 5 0.01 20 124 2300 × ○ × Comparative Example 8 30 15 40 10 5 0.01 14 112 2200 × × ○ Comparative Example 9 50 3 32 10 5 0.01 16 118 2000 × ○ ○ Comparative Example 10 50 15 10 20 5 0.01 15 116 2400 ○ × × Comparative Example 11 50 10 25 10 5 0.01 10 118 2400 × ○ ○ Comparative Example 12 50 10 25 10 5 0.01 26 116 2200 × ○ ○ Comparative Example 13 50 10 25 10 5 0.01 22 116 2200 × × ○ Comparative Example 14 50 10 25 10 5 0.01 18 116 2400 × × ○ Comparative Example 15 50 10 25 10 5 0.01 26 116 2400 × × ○ Comparative Example 16 50 10 25 10 5 0.01 26 116 2400 × × ○

INDUSTRIAL APPLICABILITY As described above, the resin composition for extrusion lamination of the present invention is excellent in low-temperature heat-sealing composition and easy-to-peel property, and can be directly bonded to a substrate without any additional adhesive treatment.

Claims (1)

In the resin composition for extrusion lamination, (A), 5 to 20 parts by weight of the component (B), 20 to 40 parts by weight of the component (C), 3 to 15 parts by weight of the component (D), 2 to 10 parts by weight of the component And 0.001 to 0.1 part by weight of the component (F). (A) a binary or ternary copolymer of propylene and ethylene or 1-butene, which satisfies the following conditions 1 to 3: (1) ethylene or 1-butene alone or the sum of ethylene and 1-butene is 4 to 15 mol% ② When the melting temperature is below 135 ℃ ③ Melt index is 5 ~ 25g / 10min (230 ℃) (B) a low density polyethylene having a melt index of 1 to 15 g / 10 min (190 DEG C) and a density of 0.925 g / (C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 캜) and a density of 0.915 g / (D) an amorphous or low-crystalline ethylene-based? -Olefin random copolymer or a 1-butene? -Olefin random copolymer satisfying the following conditions 1 to 3: (1) the? -Olefin has 2 to 20 carbon atoms (2) a melt index of 0.1 to 30 g / 10 min (190 DEG C) ③ Density of 0.900g / ㎤ or less (E) a modified polypropylene copolymer obtained by graft-modifying maleic anhydride, and satisfying the following conditions 1 to 2: (1) an unsaturated carboxylic acid or a derivative thereof having a graft ratio of 0.1 to 10 mol% ② Intrinsic viscosity of 0.1-2 dl / g (F) Release of crosslinking agent