JP2001261903A - Adhesive resin composition based on modified ethylene/1- octene copolymer and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a adhesive resin composition good at adhesive strength in high speed molding in producing laminates by extrusion molding and also excellent in heat resisting adhesion. SOLUTION: This adhesive resin composition is obtained by including 5-95 wt.% modified ethylene/1-octene copolymer and 95-5 wt.% ethylene-based polymer; wherein the modified ethylene/1-octene copolymer contains 0.01-10 wt.% unsaturated carboxylic acid or its derivative and is obtained by modifying an ethylene/1-octene copolymer made by polymerization in the presence of a single site-catalyst containing a tetravalent transition metal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an adhesive resin which is excellent in molding processability, and has excellent adhesiveness to a substrate and its heat resistance, and excellent secondary workability such as stretchability, deep drawing and hot water resistance. The present invention relates to a composition and a laminate used for various uses such as for food packaging and industrial materials.

[0002]

2. Description of the Related Art Resins, food packaging and industrial materials are used.
Materials such as wood, woven fabric or non-woven fabric (hereinafter collectively referred to as "woven fabric, etc."), and metal are widely used as laminates with different materials utilizing their respective characteristics. Most of such laminates are manufactured by a method such as a glue lamination method, an extrusion lamination method, a co-extrusion lamination method, and a co-extrusion method via an adhesive component, but are used. Many of the adhesive components have an excellent initial adhesive strength, but have a problem that productivity is low because the adhesive strength tends to decrease when a molding speed is increased at the time of manufacturing a laminate, and furthermore, there is a problem of heat resistance of the adhesive strength. Inferior in durability, for example, when used as a food packaging material, the problem of delamination during molding into containers, high-temperature filling of contents, or high-temperature treatment such as boil sterilization or retort treatment. May occur.

In order to solve such a problem by improving the adhesive strength, an adhesive resin composition based on a resin obtained by polymerization using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst has been proposed. Various proposals have been made.
(For example, JP-A-6-206946, JP-A-6-206946)
206947, JP-A-6-207058,
JP-A-6-207062 and JP-A-9-176
391, etc.)

[0004]

SUMMARY OF THE INVENTION The present invention further improves the above-mentioned prior art, and provides good adhesive strength at the time of high-speed molding when producing a laminate by various molding methods, particularly extrusion molding. Another object of the present invention is to provide an adhesive resin composition having excellent heat resistance and heat resistance.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a modified polymer based on a specific ethylene copolymer gives good results. The invention has been reached. That is, the gist of the present invention is that the modified ethylene / 1-octene copolymer is 5 to 95% by weight,
A composition containing 95 to 5% by weight of an ethylene-based polymer, wherein the modified ethylene / 1-octene copolymer is
It is obtained by modifying an ethylene / 1-octene copolymer containing 0.01 to 10% by weight of an unsaturated carboxylic acid or a derivative thereof and polymerized using a single-site catalyst containing a tetravalent transition metal. The adhesive resin composition.

[0006] Another gist of the present invention is that an ethylene / 1-octene copolymer polymerized using a single-site catalyst containing a tetravalent transition metal has a temperature rising elution fractionation (TREF) elution curve. Is also present in the adhesive resin composition described above, which comprises a single peak, and further, the modified ethylene / 1-octene copolymer is formed using a single-site catalyst containing a tetravalent transition metal. The adhesive resin composition is obtained by modifying the polymerized ethylene / 1-octene copolymer in the molten state with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical generator. are doing.

Further, another gist of the present invention is to provide an adhesive layer comprising the above-mentioned adhesive resin composition and a substrate comprising at least one selected from the group consisting of resin, wood, woven or nonwoven fabric, and metal. And a laminate composed of layers, and in the laminate, the base material layer is a polyolefin-based resin, a saponified ethylene-vinyl acetate copolymer, a polyamide-based resin,
It also exists in a laminate made of at least one thermoplastic resin selected from the group consisting of a polyester resin, a polystyrene resin, a polyurethane resin, an acrylic resin, and a polycarbonate resin.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail by dividing into components, compositions, and laminates. 1. Constituent Component Modified Ethylene / 1-octene Copolymer The modified ethylene / 1-octene copolymer which is a component constituting the adhesive resin composition of the present invention is an unsaturated carboxylic acid or a derivative thereof (hereinafter collectively referred to as a “modifying agent”). ), Which is obtained by modifying an ethylene / 1-octene copolymer polymerized using a single-site catalyst containing 0.01 to 10% by weight and containing a tetravalent transition metal. It is a thing.

The ethylene / 1-octene copolymer before modification is a copolymer of ethylene and 1-octene, which is polymerized using a single-site catalyst containing a tetravalent transition metal. The proportion of ethylene units in the ethylene / 1-octene copolymer is preferably at least 60 mol%.

A single-site catalyst containing tetravalent transition metal (also called Kaminski catalyst) used for producing the ethylene / 1-octene copolymer includes a supported or unsupported metallocene compound and an organic aluminum compound.
Particularly, those based on a combination of alumoxanes are preferably used. The tetravalent transition metal compound used here is not particularly limited, for example, titanium, zirconium,
Nickel, palladium, hafnium, platinum and the like. Further, as the ligand of the transition metal, at least one of cyclopentadiene, indene, azulene, etc. which may have a substituent is used. Other ligands include monovalent anions such as chlorine and bromine, and C1 to C1.
About 8 alkyl groups, aryl groups, alkoxy groups, amide groups, phosphide groups and the like can be exemplified.

Specific examples of such a single-site catalyst include cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl) titanium dichloride, and dimethylsilyl. Tetramethylcyclopentadienyl-tert-butylamidozirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-tert-butylamidohafnium dichloride, dimethylsilyltetramethylcyclopentadienyl-pn-butylphenylamidozirconium chloride, methyl Phenyldyltetramethylcyclopentadienyl-tert-butylamidohafnium dichloride, indenyl titanium tris (dimethylamide), indenyl titanium tris ( Ethylamide), indenyl titanium tris (di -n- propyl amide), indenyl titanium bis (di -n- butylamide) (di -n
-Propylamide) and the like.

As a method for producing an ethylene / 1-octene copolymer using these catalysts, for example, a slurry method, a gas phase fluidized bed method (described in JP-A-59-23011), a solution method, or a high pressure method A bulk polymerization method or the like can be used. The specific manufacturing method is described in, for example,
JP-A-8-19309, JP-A-60-35005, JP-A-61-130314, JP-A-3-163
No. 088, etc., and these methods can be used as appropriate.

Further, the ethylene / 1-octene copolymer preferably has an elution curve of a temperature rise elution fractionation (TREF) consisting of a single peak. Temperature rise elution fractionation (TREF: Temperature Rising Elution)
Fractionation means that once the polymer is completely dissolved and then cooled, a thin polymer layer is formed on the surface of the inert substance, and then the temperature is raised continuously or stepwise to elute the component (polymer) Is collected and its concentration is continuously measured to determine the amount of the eluted component and the elution temperature. The elution curve is a graph in which the elution fraction is plotted on the vertical axis and the elution temperature is plotted on the horizontal axis, which can represent the composition distribution (molecular weight and crystallinity distribution) of the polymer. The method and apparatus for measuring temperature rise elution fractionation (TREF) are described in Journal of Applied Polymer S.
cience, 26, 4217-4231 (1981)
Year).

Since the polymer having a single peak in the elution curve by TREF has a narrow composition distribution and uniform crystallinity, the solid component mainly composed of a low polymer and the component which is easily eluted are reduced. Further, the adhesiveness, particularly the adhesive strength at the time of high-speed molding, is improved. When the elution curve by TREF has a plurality of peaks, the composition distribution and / or the crystallinity are non-uniform, so that the adhesive strength tends to decrease.

In the present invention, a modified ethylene / 1-based polymer obtained by the above-mentioned production method and preferably based on an ethylene / 1-octene copolymer having the above-mentioned characteristics.
An octene copolymer is used. This modified ethylene / 1-
The content of the unsaturated carboxylic acid or its derivative in the octene copolymer is 0.01 to 10% by weight, preferably 0.02% by weight.
-9% by weight, more preferably 0.03-8% by weight.

When the content of the unsaturated carboxylic acid or its derivative is 0.01% by weight or less, the adhesive strength becomes insufficient,
On the other hand, when the content is higher than 10% by weight, fish eyes are generated due to a concurrent crosslinking reaction, and the film tends to have poor appearance. The content of the unsaturated carboxylic acid can be measured by a calibration curve method using carbonyl absorption (1780 cm ^-1 ) of an infrared absorption spectrum.

As a method for introducing an unsaturated carboxylic acid or a derivative thereof into an ethylene / 1-octene copolymer, a method of modifying the unsaturated carboxylic acid or a derivative thereof by graft polymerization using this copolymer as a backbone polymer is used. Can be exemplified. Examples of the unsaturated carboxylic acid or a derivative thereof, such as acrylic acid, maleic acid, fumaric - Le acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Nadic ^TM (Endoshisu - bicyclo [2,2, 1] Hept-5-ene-2,3-dicarboxylic acid) and the like, and derivatives such as acid halides, amides, imides, anhydrides, esters and the like. Maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate
For example. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof are particularly preferable.

The modified ethylene used in the composition of the present invention
As a method for producing the 1-octene copolymer, for example, a melt modification method or a solution modification method is used. In the case of the melt modification method, a method in which an ethylene / 1-octene copolymer and an unsaturated carboxylic acid or a derivative thereof are preliminarily mixed with a radical generator and then melted in an extruder to carry out graft copolymerization, It is possible to use a method in which a mixture of a radical generator and an unsaturated carboxylic acid or a derivative thereof dissolved in a solvent or the like is added from a charging port to the ethylene / 1-octene copolymer melted in the vessel and graft copolymerized. it can. In the case of the solution denaturation method, a method in which an ethylene / 1-octene copolymer is dissolved in a solvent, and a radical generator and an unsaturated carboxylic acid or a derivative thereof are added thereto to carry out graft copolymerization can be used. In any case, it is preferable to carry out the reaction in the presence of a radical generator in order to graft copolymerize the unsaturated carboxylic acid or a derivative thereof efficiently.

The temperature at which the modification is carried out by the graft reaction is generally in the range of 60 to 350 ° C., and in the case of the melt modification method, the temperature is preferably in the range of 180 to 320 ° C. When the denaturation temperature is lower than 60 ° C., the graft reaction becomes difficult to occur or takes a long time. On the other hand, when the denaturation temperature is higher than this, the cross-linking reaction of the main chain of the backbone polymer cannot be ignored except for the graft reaction. However, as described above, fish eyes (bumps) are likely to be caused.

The amount of the radical generator used in the modification reaction is preferably in the range of usually 0.001 to 1 part by weight based on 100 parts by weight of the ethylene / 1-octene copolymer. Examples of the radical generator that can be used here include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,
5-di (peroxybenzoate) hexyne-3, lauroyl peroxide, 2,5-dimethyl-2,5-di (ter
t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert
Organic peroxides and peresters such as -butyl perbenzoate, tert-butyl perisobutyrate, tert-butyl perpivalate and cumyl perpivalate;
Alternatively, azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate may be used. Among them, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexane, 1,4-bis
Dialkyl peroxides such as (tert-butylperoxyisopropyl) benzene are preferable because of a good balance between the above-mentioned melting denaturation temperature and the radical generation temperature.

Ethylene Polymers Ethylene polymers suitable for use in the composition of the present invention include homopolymers of ethylene or copolymers of ethylene containing ethylene as a main component with α-olefins and vinyl esters. It is a polymer. Among them, an ethylene / α-olefin copolymer is preferred. As the α-olefin, an α-olefin containing no cyclic structure having 3 to 20 carbon atoms is preferable, for example, propylene, 1-butene, 1-hexene,
-Methyl-1-pentene, 1-octene, 1-decene,
Examples thereof include 1-tetradecene and 1-octadecene.
The α-olefin can be used alone or as a mixture of two or more kinds, and as the ethylene polymer, two or more kinds of polymers may be used in combination.

Specific examples of such an ethylene polymer include low-density polyethylene (LDPE), high-density polyethylene (HDPE), and medium-density polyethylene (MDP).
E), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), low crystalline ethylene
Butene-1 random copolymer (EBM), ethylene / propylene copolymer (EPR), ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer (EEA), and the like can be given.

The above-mentioned ethylene-based polymer includes:
The polymerization catalyst and production process are not particularly limited. 2. Adhesive Resin Composition The adhesive resin composition of the present invention contains 5 to 95% by weight of the above-mentioned specific modified ethylene / 1-octene copolymer and 95 to 5% by weight of the ethylene-based polymer. . When the content of the modified ethylene / 1-octene copolymer is less than 5% by weight, the adhesive strength is not at a practical level, and when the content exceeds 95% by weight, the moldability deteriorates. Absent.

The adhesive resin composition has a melt flow rate of 0.01 to 50 g / 10 minutes and a density of 0.85 g / min.
What is 0.95 g / cm < ³ > is preferable. This melt flow rate (hereinafter sometimes abbreviated as “MFR”) is JIS-K7210 (190 ° C. 21.18 N
Load), and this value is 0.0
It is preferably 1 to 50 g / 10 minutes. A more preferable range of the MFR is 0.03 to 45 g / 10 minutes,
More preferably, it is 0.05 to 40 g / 10 minutes.

When the MFR exceeds the above range, the moldability,
In particular, when a thin film such as a film is formed, film formation becomes unstable, which is not preferable. On the other hand, if it is less than 0.01 g / 10 minutes, the resin pressure at the time of molding increases, the extrusion molding speed tends to decrease, and the moldability tends to deteriorate and the appearance tends to deteriorate. Of the adhesive resin composition of the present invention,
The density measured according to JIS-K7210 is 0.85
０．９0.95 g / cm ³ , preferably 0.855 g / cm ^3.
More preferably, it is 0.94 g / cm ³ . If the density is out of the above range, the adhesive strength tends to decrease, and particularly, the adhesive strength during high-speed molding tends to decrease significantly.

In the adhesive resin composition of the present invention, in addition to the above-mentioned essential components, optional components such as olefin-based polymers such as propylene-based polymers may be added as long as the object of the present invention is not impaired. Coalescence and, if necessary, various additives,
For example, antioxidants, light stabilizers, ultraviolet absorbers, nucleating agents,
Neutralizing agents, lubricants, antiblocking agents, dispersants, flow improvers, release agents, coloring agents, fillers, and the like may be added.

The adhesive resin composition of the present invention is prepared by uniformly mixing the above-mentioned essential components and optional components using a tumbler blender, ribbon blender, V-type blender, Henschel mixer, etc., followed by a single-screw or twin-screw extruder. It can be prepared by melt-kneading with a mill roll, Banbury mixer, kneader, Brabender or the like. 3. Laminate Adhesive resin composition of the present invention, resin, wood, woven or non-woven, and on a substrate consisting of any one of metal, with or without an anchor coating agent, sequential extrusion lamination method, A laminate can be manufactured by laminating by sandwich extrusion lamination, surface coating, coextrusion lamination.

In addition, simultaneously with the extrusion of the base material and the adhesive resin composition, a base material made of another resin or the like may be co-extruded to form a three-layer (or more) laminate. If necessary, such a laminate can be further subjected to a stretching process to give a stretched product, or can be subjected to thermoforming such as vacuum forming, pressure forming, or the like, and can be formed into a container shape by co-extrusion blow molding. Can also. Among these molding methods, the adhesive resin composition of the present invention is suitable for producing a laminate by a coextrusion molding method or a laminate molding method.

The resin which can be used as the substrate is preferably a thermoplastic resin. Examples of the resin include a polyamide resin, a polyester resin, a saponified ethylene-vinyl acetate copolymer, a polyolefin resin, a polycarbonate resin, and polystyrene. Resins, acrylic resins, and the like. Using these resins, for example, an inflation film by a co-extrusion method in which one or more of the adhesive resin composition and the above resin are melted in an extruder, and supplied to a multilayer die and laminated in the die. A laminate such as a parison can be produced by a co-injection molding method in which a T-die film, a laminated sheet, a laminated pipe is produced, or a molten individual resin is injection-molded in the same mold with a time difference.

When using wood, woven fabric, or metal as the base material, the adhesive resin melted in the extruder is supplied to the die, and the lamination is performed simultaneously with the extrusion to cover and laminate the surface of the base material. Or a method in which a sheet made of an adhesive resin or a laminate in which an adhesive resin layer is formed on the surface in advance, and a method in which these substrates are pressed and laminated by a press or a hot roll, and used.

[0031]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. <Modified ethylene copolymer> 0.8% by weight of maleic anhydride and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (manufactured by NOF Corporation) were added to the ethylene polymer shown below. , Trade name "Perhexa 25B") to 0.0
4% by weight, and preliminarily mixed using a Henschel mixer.
The resulting mixture was melt-kneaded at ℃, extruded into strands, and pelletized to produce a modified ethylene copolymer.

The physical properties (MFR, density) and composition of the ethylene polymer used for the modification are as follows. The amount of the modifier added in the modified ethylene-based resin was determined by dissolving 0.5 g of the obtained modified ethylene-based resin in 50 ml of xylene at 120 ° C. and pouring the xylene solution into 400 ml of acetone. It was determined from the absorption intensity of the carbonyl group near 1780 cm ^-1 in the infrared absorption spectrum of the film obtained by press-molding the (purified resin), using a calibration curve separately prepared.

The contents of the modifier after modification are shown in the table. (Raw material ethylene copolymer) (1) Ethylene / 1-octene copolymer (metallocene catalyst) MFR: 3, density: 0.875 g / cm ³ , octene content: 22% by weight (2) ethylene / propylene Copolymer (vanadium catalyst) MFR: 3, density: 0.86 g / cm ³ , propylene content: 22% by weight (3) Ethylene / 1-butene copolymer (metallocene catalyst) MFR: 3.5 Density: 0.88 g / cm ³ , butene content: 20% by weight (4) Ethylene / 1-hexene copolymer (metallocene catalyst) MFR: 3.5, density: 0.88 g / cm ³ , hexene content : 28% by weight (5) Ethylene homopolymer (titanium catalyst) MFR: 2.5, density: 0.955 g / cm ³ (6) Ethylene / 1-butene copolymer (titanium catalyst) MFR: 2, density: 0.920g / cm ³ Butene content: 8 as the percent by weight ethylene polymer which is another component of the <ethylene polymer> adhesive resin composition was used for the next two ethylene copolymer. (1) Ethylene / butene copolymer (titanium catalyst) MFR: 2.1, density: 0.920 g / cm ³ , butene content: 7% by weight (2) Ethylene / butene copolymer (metallocene catalyst) MFR: 3.6, density: 0.880 g / cm ³ , butene content: 25% by weight <Production of adhesive resin composition> The modified ethylene-based polymer produced by the method described above and an ethylene copolymer Uniting with
After uniform mixing using a Henschel mixer at the ratios shown in the table, the mixture was melt-kneaded at a temperature of 190 ° C. in a twin-screw extruder having a diameter of 45 mm, extruded into strands, pelletized, and pelletized into an adhesive polymer composition. Was manufactured. <Production of Laminate> An adhesive resin layer was used as an intermediate layer, one of the outer layers was a linear low-density polyethylene resin (LLDPE) layer, and the other was a saponified ethylene-vinyl acetate copolymer (EVO).
A three-layer co-extruded blown film was manufactured as the H) layer or the polyamide resin (NY) layer under the following conditions.

(Inflation molding method)-Resin used LLDPE: SF8402 Nippon Polychem Co., Ltd. EVOH: F101A Kuraray Co., Ltd. NY: 1020CA2 Mitsubishi Engineering Plastics Co., Ltd.-Extruder diameter LLDPE / adhesive resin composition / EVOH or NY = 9
0/45/65 mmφ.Layer composition ratio LLDPE layer / adhesive layer / EVOH layer = 4/1/2 (total thickness = 70 μm) LLDPE layer / adhesive layer / NY layer = 4/1/2 (total thickness = 70 μm) Die temperature EVOH 210 ° C NY 220 ° C Laminate forming speed 30 m / min, 70 m / min <Example 1, Comparative Examples 1 to 6> Using the adhesive resin composition having the composition shown in the table, the above-mentioned inflation was performed. The laminate manufactured by the molding method was evaluated according to the following method. The results are shown in a table. <Evaluation method> (1) Initial adhesive strength Using a strip-shaped sample cut out from the laminate to a width of 5 mm, a polyamide resin layer or a saponified ethylene-vinyl acetate copolymer layer at one end was used according to JIS K6854. The adhesive resin composition layer was slightly peeled off in advance, and a peeling strength was measured by performing a T-shaped peeling test at a peeling rate of 50 mm / min in an atmosphere of 23 ° C. The results are shown in the table. (2) Heat-resistant adhesive strength A T-peel test was performed by the same method as the above-mentioned initial adhesive strength measurement, except that the atmosphere temperature was set to 100 ° C., and the peel strength was measured.

In this case, those having a peel strength of 30 g / 5 mm or more were evaluated as having good heat-resistant adhesive strength. <Evaluation of Results> A laminate (Example 1) using the adhesive resin composition based on the modified ethylene / 1-octene copolymer of the present invention was used when a modified polymer other than this was used (Comparative Example 1). 5) and unmodified (Comparative Example 6)
The adhesive strength to OH is particularly excellent when the molding speed is 70 m / min, and the adhesive strength at high temperatures is maintained. The adhesive strength to the polyamide resin is also good.

[0036]

[Table 1]

The adhesive resin composition of the present invention is excellent in molding processability, and has good initial adhesion to a substrate and its heat resistance, and is particularly excellent in high-speed molding such as 70 m / min. It shows adhesiveness.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Sato 2-5-2, Marunouchi, Chiyoda-ku, Tokyo Mitsui Chemicals, Inc. Functional Chemicals Company (72) Inventor Hiroyuki Nakayama 1 Tohocho, Yokkaichi-shi, Mie Prefecture (72) Inventor: Yoshinobu Yada, 1 Toho-cho, Yokkaichi-shi, Mie F-term (reference) 4F100 AB01B AB01C AK01B AK01C AK03B AK03C AK04A AK12B AK24A AK24C AK41C AK45B AK45C AK46B AK46C AK47 AK51B AK51C AK63 AK64 AK65 AK66A AK69B AK69C AL01A AL05A AL06A AP00B AP00C BA02 BA03 BA06 BA07 BA10B BA10C DG11B DG11C DG15B DG15C EH20 EH202 GB23 JB16B JB16C JJ03 JL08A JL11 YY00A 4J002 BB03X BB05X BB06X BB07X BB15X BN05W 4J028 AA01A AB01A AC08A AC10A BA00A BA01B BB00A BB01B BC25B EB02 EB07 EC02 EC03 FA01 FA02 FA04 FA06 GA26

Claims (5)

[Claims] 1. A composition comprising 5 to 95% by weight of a modified ethylene / 1-octene copolymer and 95 to 5% by weight of an ethylene polymer, wherein the modified ethylene / 1-octene copolymer Ethylene-1 polymerized using a single-site catalyst containing 0.01 to 10% by weight of an unsaturated carboxylic acid or a derivative thereof and containing a tetravalent transition metal
-An adhesive resin composition obtained by modifying an octene copolymer. 2. An ethylene / 1-octene copolymer polymerized using a single-site catalyst containing a tetravalent transition metal, wherein the temperature rise elution fractionation (TREF) elution curve consists of a single peak. The adhesive resin composition according to claim 1. 3. A modified ethylene / 1-octene copolymer obtained by polymerizing an ethylene / 1-octene copolymer polymerized by using a single-site catalyst containing a tetravalent transition metal in the presence of a radical generator. 2. A compound obtained by modification in a molten state with a saturated carboxylic acid or a derivative thereof.
Or the adhesive resin composition according to 2. 4. An adhesive layer comprising the adhesive resin composition according to claim 1, and at least one selected from the group consisting of resin, wood, woven or nonwoven fabric, and metal. And a base material layer. 5. A base material layer comprising a polyolefin resin, a saponified ethylene-vinyl acetate copolymer, a polyamide resin,
The laminate according to claim 4, wherein the laminate comprises at least one thermoplastic resin selected from the group consisting of a polyester resin, a polystyrene resin, a polyurethane resin, an acrylic resin, and a polycarbonate resin.