JP2008001802A - Adhesive resin composition and molded article made thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive resin composition having excellent fuel oil resistance, low-temperature impact strength and heat-resistance and excellent affinity or adhesiveness to various synthetic resin materials and metallic materials. <P>SOLUTION: The adhesive resin composition comprises (X) 5-35 wt.% modified polyethylene resin composition composed of (A') 100-70 wt.% modified high-density polyethylene resin produced by modifying (A) a high-density polyethylene resin having a density of 0.94-0.97 g/cm<SP>3</SP>and an MFR of 0.01-30 g/10 min, (B') 0-30 wt.% modified polyethylene resin produced by modifying (B) a polyethylene resin having a density of ≥0.91 g/cm<SP>3</SP>and an MFR of 0.01-10 g/10 min, (C) 19-35 wt.% straight-chain ultra-low density polyethylene resin having a density of 0.89-0.91 g/cm<SP>3</SP>and an MFR of 0.1-5 g/10 min and (D) 76-30 wt.% other unmodified polyethylene resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an adhesive resin composition containing a specific modified high-density polyethylene resin and a specific linear ultra-low-density polyethylene resin and a molded body using the same, and in particular, fuel oil resistance, impact resistance, heat resistance Adhesive resin with excellent compatibility with various synthetic resin materials, metal materials, especially barrier resin materials, etc., and useful in the packaging container field and industrial material field where various polyethylene resin materials are used The present invention relates to a composition and a molded body using the composition as an adhesive.

Techniques for graft polymerization of unsaturated carboxylic acids or their derivatives (eg, their anhydrides) to ethylene homopolymers or ethylene copolymers based on ethylene are already well known and manufactured industrially. It has been widely used for various applications.
Among them, modified polyethylene resins obtained by graft polymerization of acrylic acid, maleic acid or maleic anhydride are polar such as polyamide resin, ethylene-polyvinyl alcohol copolymer resin, thermoplastic polyester resin, polyvinyl chloride resin, and polyvinylidene chloride resin. It has been put to practical use as an adhesive material in coatings of various laminates, metal plates or metal pipes comprising a metal foil such as resin or aluminum foil.
Also, functions such as compatibility and compatibility with matrix resin in composite materials blended with additives such as various fillers, reinforcing agents, pigments, and polymer blend materials of different types of resins such as engineering plastics and polyolefin resins It is also used for the purpose of giving

Many modified polyethylene resins of this type have been proposed so far, but it is difficult to satisfy all the various performances demanded by the market with only a single modified polyethylene resin. Changing the type of polyethylene resin used as the raw material for the modified polyethylene resin, or blending the modified polyethylene resin with various other polyolefin resins, various elastomers, various polymers having polar groups, or compounds having polar groups Many have been proposed.
For example, a composition in which a soft resin such as an ethylene / propylene copolymer rubber or an ethylene / butene-1 copolymer rubber is blended with a modified polyolefin resin has been proposed (see, for example, Patent Documents 1 to 4). The composition which mix | blended other polymers, such as a thermoplastic polyester resin and a polyvinyl alcohol copolymer, with the polyethylene resin is proposed (for example, refer patent documents 5-7).

  Furthermore, a linear low density polyethylene resin (hereinafter sometimes referred to as LLDPE) having excellent properties such as environmental stress crack resistance (ESCR), heat sealability, and low temperature properties is used as a raw material for modified ethylene resins and modified polyethylene resins. It has been proposed that the above-described properties be imparted and heat resistance and adhesiveness be improved by using as a compounding material (see, for example, Patent Documents 8 to 12).

Among these proposals, according to Patent Document 8, a medium / low pressure copolymer having a density of 0.900 to 0.940 g / cm ³ and ethylene and 0.2 to 20 mol% of an α-olefin. A polyolefin-based resin composition in which at least one of (a) 30 to 100% by weight and another polyolefin resin (b) 70 to 0% by weight is graft-polymerized is disclosed. The object is to provide a polyolefin resin composition having excellent adhesion and environmental stress crack resistance (ESCR). However, as shown in Examples 1 to 6 described in Patent Document 8 and Table 1, the density of the medium / low pressure polyethylene resin used is 0.920 g / cm ³ , and as described later, The density range (0.870 to 0.910 g / cm ³ ) of the linear low super-density polyethylene resin (hereinafter sometimes referred to as VLDPE) according to the invention is not specifically disclosed. In addition, the total amount of graft-modified LLDPE and unmodified LLDPE in the composition described in Patent Document 8 is 80 to 100% by weight, and the composition ratio of these resins in the entire composition is extremely large. Furthermore, in this composition, what is sufficiently satisfactory in terms of fuel oil resistance, heat resistance and rigidity, which are the objects of the present invention, cannot be obtained.

Further, in Patent Document 9, for the same purpose as described above, from 99.9 to 65% by weight of unmodified LLDPE and from 0.1 to 35% by weight of graft-modified LLDPE or high-density polyethylene resin (hereinafter sometimes referred to as HDPE). A laminate of an ethylene-vinyl alcohol copolymer, a polyamide resin or a thermoplastic polyester resin and a polyolefin resin using the polyethylene resin composition is disclosed.
As unmodified LLDPE and graft modified LLDPE, (preferably, 0.915~0.930g / cm ^3, in the embodiment 0.926 g / cm ³⁾ density 0.910~0.960g / cm ³ linear polyethylene Resin is used.

Further, in Patent Document 10 and Patent Document 13, particularly, LLDPE having a density of 0.900 to 0.940 g / cm ³ is used to reduce the contamination of the obtained graft modified product and the crosslinking or oxidation reaction that occurs during graft modification. A production method for obtaining a modified product having high graft efficiency is disclosed. Patent Document 3 discloses a graft-modified polyolefin resin using VLDPE produced by a gas phase / low pressure method having a density of 0.910 g / cm ³ or less, a mixture of the polyolefin resin and a different material, and the like. . Among these different materials, polyolefin resins such as unmodified elastomers (for example, ethylene-propylene copolymer rubber), high-pressure low-density polyethylene resin, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, Examples thereof include polyamide resins and ethylene-vinyl alcohol copolymers.

Furthermore, in Patent Document 11, the product of the melt flow rate (hereinafter sometimes referred to as MFR) and the melt tension and the high pressure method low density polyethylene resin specified by MFR and the density are 0.880 to 0.900 g / cm. ³ is a material comprising an acrylic acid- or maleic anhydride graft-modified polyethylene resin, which is a copolymer of ethylene and α-olefin, which is excellent in molding processability and adhesiveness.
Patent Document 14 discloses that the density is 0.890 to 0.910 g / cm ³ , and the weight average molecular weight / number average molecular weight is 2, which has both good adhesiveness, heat sealability and heat resistance retention. To 15 and a product of melt tension at 160 ° C. and MFR of 4 or less, a modified polyethylene resin of a copolymer of ethylene and an α-olefin having 4 or more carbon atoms, the modified polyethylene resin and an unmodified polyethylene resin A modified polyethylene resin composition has been proposed.

Further, in Patent Document 15 and Patent Document 16, the density is 0.860 to 0.910 g / cm ³ , the boiling n-hexane insoluble content is 10% by weight or more, and the maximum peak temperature by the differential scanning calorimeter 1 to 40 parts by weight of rubber is added to 100 parts by weight of a copolymer of ethylene and α-olefin having a temperature of 100 ° C. or higher or a polyolefin resin containing the copolymer as a main component, Modified adhesive resins and laminates thereof have been proposed.

In Patent Document 17, 99 to 50% by weight of a polyethylene resin having a crystallinity of 40% or more or a polypropylene graft-modified product having a boiling n-hexane insoluble content of 80% or more and a crystallinity of 5 to 30%, and It is a multilayer laminate composed of a polyolefin resin composition and a polyamide resin layer composed of 1 to 50% by weight of an ethylene-α-olefin copolymer having a density of 0.870 to 0.910 g / cm ³ , and has interlaminar adhesion, particularly boiling. It has been proposed to provide a laminate with significantly improved interlayer adhesion when immersed in water. However, as the most preferable ethylene-α-olefin copolymer (crystallinity 5-30%, density 0.890-0.910 g / cm ³ ), the density polymerized by the vanadium catalyst is 0.870-0. a .900g / cm ^3, and the copolymerization ratio of ethylene is 85 to 95 mol%, yet crystallinity of 5-30% of the ethylene - cited butene-1 random copolymer.

And in patent document 18-patent document 23, fuel oil resistance (gasoline resistance) and impact resistance which could not be achieved even if any one of the above-mentioned modified polyethylene resins or compositions thereof was used were significantly improved. Fuel containers such as industrial cans and gasoline used for a long time at high temperatures, and related automobile parts, especially fuel containers made of multi-layer polyethylene resin for the purpose of preventing the permeation of fuel oil (for example, 3 types, 5 layers and 4 types) It has been proposed to provide a polyethylene resin composition particularly suitable for an adhesive layer between a barrier resin layer such as a polyamide resin or an ethylene-vinyl alcohol copolymer and a polyethylene resin layer.
Japanese Patent Publication No. 55-018251 Japanese Patent Laid-Open No. 61-132345 Japanese Patent Laid-Open No. 62-018258 Japanese Patent Publication No. 60-036217 JP-A-53-039341 Japanese Patent Laid-Open No. 52-122080 JP-A-52-103480 JP-A-57-170940 JP 59-068351 A Japanese Patent Laid-Open No. 61-276808 JP-A-62-025139 JP 62-119247 A JP 62-167308 A JP-A-62-010107 Japanese Patent Laid-Open No. 61-132345 JP-A 61-132337 Japanese Patent Publication No. 60-036942 Japanese Patent Publication No. 06-104761 Japanese Patent Publication No. 06-104762 Japanese Patent Publication No. 08-013532 Japanese Patent Publication No. 08-015333 Japanese Patent No. 2614352 Japanese Patent No. 2972844

However, when a fuel container made of a multilayer polyethylene resin using these resin compositions is actually filled with fuel oil and used in, for example, an automobile, the polyamide resin and the ethylene-vinyl alcohol are mixed with the passage of time. In general, the adhesive strength between a barrier material layer such as a polymer and a modified polyethylene resin layer tends to decrease. If this happens, the barrier material layer and the modified polyethylene resin layer peel in the worst case, and the fuel oil as the contents leaks from that point, which is extremely undesirable in terms of safety.
Further, when a multilayer polyethylene resin fuel container manufactured by direct blow molding is taken as an example, burrs of several% to several tens of% are usually generated. This burr is generally recycled and used from the viewpoints of resource saving, environmental protection and economy. For example, when a 4-type 6-layer polyethylene resin fuel container using an ethylene-vinyl alcohol copolymer that is practically used in the world market as a barrier material layer is manufactured by direct blow molding, Generally, it is effectively utilized by returning it to one layer (regrind material layer) in the fuel container.
In this regrind material layer, a polyethylene resin, a modified polyethylene resin, an ethylene-vinyl alcohol copolymer, various additives, and a filler are mixed. As in the case of nylon resin, it is known that the impact resistance of the resin used for the barrier material is significantly inferior to that of the high molecular weight high density polyethylene used for the main layer. Therefore, when using a burr containing a material with inferior impact resistance to obtain a multilayer blow container industrially and economically for the regrind material layer, if the modified polyethylene resin has low adhesive performance, The safety of the fuel container is remarkably lowered due to the deterioration of the property and the ethylene-vinyl alcohol copolymer is gelled. Further, in order to eliminate these problems, increasing the amount of the modified polyethylene resin composition increases the ratio of the modified polyethylene resin that is relatively easily deteriorated, which is one of the causes for the deterioration in heat resistance.

  The object of the present invention is to solve all of these drawbacks in view of the above problems, that is, not only good fuel oil resistance is maintained even when used for a long time in a high temperature atmosphere, but also impact resistance (particularly The impact resistance at low temperatures is also extremely excellent, and when used as a component material for a fuel container made of multi-layer polyethylene resin, the adhesive strength between the barrier material layer and the adhesive material layer is almost reduced even when filled with fuel oil. In addition, a material that has a remarkably excellent affinity between the mixed material and the barrier material when the burrs generated during the molding process are mixed with the constituent material of the fuel container made of the multilayer polyethylene resin and recycled, and a molded body using the material Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have determined that an appropriate amount of a modified polyethylene resin comprising a modified high-density polyethylene resin comprising a specific high-density polyethylene resin and a modified polyethylene resin comprising a specific polyethylene resin. Adhesive resin composition containing a specific amount of a specific linear ultra-low density polyethylene resin is excellent in fuel oil resistance and impact resistance, and hardly reduces the adhesive strength between the barrier material layer and the adhesive material layer. The present invention has been completed by finding that it can be an adhesive layer capable of greatly improving the heat deterioration resistance.

That is, according to the first invention of the present invention, the modified polyethylene resin composition (X) 5 to 35% by weight, the unmodified linear ultra-low density polyethylene resin (C) 19 to 35% by weight, and other Density of 0.93 to 0.95 g containing 76 to 30% by weight of unmodified polyethylene resin (D) (however, the total of (X) component + (C) component + (D) component is 100% by weight)) / Cm ³ , an adhesive resin composition having a melt flow rate of 0.1 to 5 g / 10 min,
Component (X) comprises (a1) a high density polyethylene resin (A) having a density of 0.94 to 0.97 g / cm ³ and (a2) a melt flow rate of 0.01 to 30 g / 10 min. Modified high-density polyethylene resin (A ′) grafted with at least one monomer selected from the group consisting of its derivatives (A ′) 100 to 70% by weight, and (b1) density 0.91 to less than 0.94 g / cm ³ , ( b2) Modified polyethylene resin (B ′) 0 obtained by grafting at least one monomer selected from the group consisting of unsaturated carboxylic acids and derivatives thereof onto polyethylene resin (B) having a melt flow rate of 0.01 to 10 g / 10 min. A modified polyethylene resin composition comprising -30% by weight,
Component (C) is an unmodified linear ultra-low density polyethylene resin having (c1) density of 0.86 to less than 0.91 g / cm ³ and (c2) melt flow rate of 0.1 to 30 g / 10 min. An adhesive resin composition is provided.

  According to the second invention of the present invention, in the first invention, at least one of the linear ultra-low density polyethylene resin (C) or the unmodified polyethylene resin (D) is produced by a single site catalyst. There is provided an adhesive resin composition characterized in that it is a cured resin.

According to a third invention of the present invention, in the first or second invention, the unmodified linear ultra-low density polyethylene resin (C) is (i) a density of 0.89 to 0.91 g / cm ³ , (ii) linear ultra-low density polyethylene resin (C1) having a melt flow rate of 0.1 to 10 g / 10 min, and (iii) density of 0.86 to 0.89 g / cm less than ^3, that is composed of (iv) a melt flow rate 0.5 to 30 g / 10min properties linear very low density polyethylene resin having a (C2) of less than 30 wt% linear very low density polyethylene resin An adhesive resin composition is provided.

  According to a fourth invention of the present invention, in any one of the first to third inventions, at least selected from the group consisting of grafted unsaturated carboxylic acid and derivatives thereof in the adhesive resin composition One type of monomer amount is 0.001 to 10% by weight, and an adhesive resin composition is provided.

  Moreover, according to 5th invention of this invention, the molded object characterized by using the adhesive resin composition of the invention in any one of 1-4 is provided.

  According to a sixth aspect of the present invention, in the fifth aspect, the molded body is a laminate, a packaging bag, a container, a fuel tank container, a food container, or an industrial chemical container. Is provided.

  The adhesive resin composition of the present invention comprises an appropriate amount of a modified polyethylene resin composed of a modified high density polyethylene resin composed of a specific high density polyethylene resin and a modified polyethylene resin composed of a specific polyethylene resin, and a specific linear form. By using an adhesive resin composition containing a specific amount of ultra-low density polyethylene resin, the amount of modified resin used can be greatly reduced, so it has excellent fuel oil resistance and impact resistance, and a barrier material layer It is possible to maintain the adhesive strength between the adhesive layers with almost no decrease, and to greatly improve the heat deterioration resistance, various polyolefin resins, various polyamide resins such as nylon 6,6, and ethylene-vinyl alcohol copolymer. Various hydroxyl group-containing resins such as polyethylene terephthalate resin and other polyester resins, polyvinyl chloride Le addition to various synthetic resin material such as various halogen-containing resins such as a resin, aluminum, excellent affinity or adhesion to the metal material such as iron. This adhesive resin composition is useful in the packaging container field and the industrial material field where various adhesive resin materials are used. In particular, a container using this adhesive resin composition as an adhesive layer has excellent initial adhesive strength and adhesive strength after being immersed in gasoline for a long time (excellent in fuel oil resistance), as well as low temperature impact resistance and heat resistance. In particular, when used as a component of a fuel container made of multi-layer polyethylene resin, not only good fuel oil resistance is maintained even when used for a long period of time, but also excellent in impact resistance and filled with fuel oil However, the adhesive strength between the barrier material layer and the adhesive material layer hardly decreases, and the material to be mixed and the barrier when the burrs generated during the molding process are mixed with the components of the fuel container made of multilayer polyethylene resin for recycling are used. It is a material that is also extremely excellent in affinity with the material.

The adhesive resin composition of the present invention includes a modified polyethylene resin (B ′) composed of a modified high-density polyethylene resin (A ′) of a specific high-density polyethylene (A) and another polyethylene (B). An adhesive resin composition comprising a polyethylene resin composition (X), an unmodified linear ultra-low density polyethylene resin (C), and another unmodified polyethylene resin (D).
Hereinafter, the components of the resin composition, the method for producing the adhesive resin composition, the molded body using the adhesive resin composition, and the like will be specifically described in detail.

[I] Component of resin composition Modified high-density polyethylene resin (A ')
The modified high-density polyethylene resin (A ′) used in the present invention has the following (a1) and (a2), and preferably, the high-density polyethylene resin (A) further having (a3) And a resin obtained by grafting at least one monomer selected from the group consisting of derivatives thereof in the presence of a radical generator.

(1) High density polyethylene resin (A)
The high density polyethylene resin (A) used as the raw material of the modified high density polyethylene resin (A ′) is an ethylene homopolymer or ethylene and α-olefin having the following (a1) and (a2), preferably (a3): And a copolymer. The α-olefin is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. , 1-decene. Two or more of them may be used in combination. Among these copolymers, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, and ethylene / 1-octene copolymer are economical. It is preferable from the viewpoint.

(A1) Density The density of the high-density polyethylene resin (A) is 0.94 to 0.97 g / cm ³ , preferably 0.945 to 0.965 g / cm ³ , more preferably 0.948 to 0.960 g / cm ³ . When the density of the high-density polyethylene resin (A) is less than 0.94 g / cm ³ , the rigidity of the extruded product using the target adhesive resin composition as a constituent material is remarkably lowered, and the fuel oil resistance is remarkably increased. Getting worse. Further, when the density of the high-density polyethylene resin (A) exceeds 0.97 g / cm ³ , there is a possibility that the impact resistance of the multilayer extruded product using the target polyethylene-based resin composition as a constituent material may be significantly lowered. .
Here, the density is a value measured according to JIS K6922-2.
In addition, these densities are generally controlled by controlling the polymerization conditions such as α-olefin content, polymerization temperature, pressure, process (slurry polymerization, gas phase polymerization) individually or mutually. Adjusted.

(A2) Melt flow rate The melt flow rate (hereinafter sometimes referred to as MFR) of the high-density polyethylene resin (A) is 0.01 to 30 g / 10 min, preferably 0.1 to 10 g / 10 min. More preferably, it is 0.5-5 g / 10min. When the MFR of the high-density polyethylene resin (A) is less than 0.01 g / 10 min, when the target adhesive resin composition is processed into a multilayer extruded product using the constituent material, an overload is applied to the motor of the processing machine. For this reason, the production efficiency is significantly reduced. Moreover, when MFR of a high-density polyethylene resin (A) exceeds 30 g / 10min, there exists a possibility that the intensity | strength of the multilayer extrusion molding which used the target adhesive resin composition for the structural material may fall remarkably.
Here, the melt flow rate is a value measured under a load of 190 ° C. and 2.16 kg in accordance with JIS K6922-2.
These MFRs are adjusted by controlling polymerization conditions such as a catalyst, a chain transfer agent such as hydrogen, polymerization temperature, pressure, and process individually or in combination with each other.

(A3) Viscosity curve index FCI
Regarding the (a3) viscosity curve index (hereinafter referred to as FCI) of the high-density polyethylene resin (A), the relationship between FCI and MFR preferably satisfies the following formula (1).
FCI ≦ −0.063 × log (MFR) +1.10 (1)
When the FCI satisfies the above range, in a multilayer extrusion molded article using the target adhesive resin composition as a constituent material, a significant improvement effect of the adhesive strength between the barrier material layer and the adhesive material layer can be expected.
Here, the viscosity curve index (FCI) of the high-density polyethylene resin (A) is a complex viscosity η ^* _0.1 at a measurement frequency of _0.1 rad / s obtained at 190 ° C. using a rotary rheometer. Defined by the logarithm ratio of the complex viscosity η ^* ₁₀ at a measurement frequency of 10 rad / s at 190 ° C. and expressed by FCI = log (η ^* _0.1 ) / log (η ^* ₁₀ ) .
In general, FCI correlates with the molecular weight distribution of the polyethylene resin, and when the molecular weight distribution becomes wide, FCI shows a large value, and when the molecular weight distribution becomes narrow, FCI tends to show a small value.
Therefore, FCI can be controlled by a catalyst (for example, narrower in the order of Phillips catalyst> Ziegler catalyst> metallocene catalyst), process (multistage polymerization becomes wider than single stage polymerization), or a combination thereof.

  The high-density polyethylene resin (A) according to the present invention is not particularly limited to the catalyst, the process and the like as long as the above parameters are satisfied. The book “Polyethylene Technology Reader” (written by Kazuo Matsuura and Naotaka Mikami, industrial research) P. 1). It can be produced by the method described in 123-160. That is, it can be produced with various polymerization apparatuses, polymerization conditions, and catalysts in each polymerization mode of Ziegler catalyst, single site catalyst, etc., slurry method, solution method, and gas phase method. More specifically, in order to produce the high-density polyethylene resin (A) of the present invention, a polymerization temperature, preferably using a specific Ziegler catalyst or a single site catalyst such as JP-B-55-14084, It can be suitably produced by controlling polymerization conditions such as pressure, cocatalyst and the like.

(2) Unsaturated carboxylic acid and its derivative As unsaturated carboxylic acid and its derivative used when manufacturing the modified high-density polyethylene resin (A ′) of the present invention, monobasic unsaturated carboxylic acid and dibasic unsaturated Carboxylic acids and their metal salts, amides, imides, esters and anhydrides are mentioned. Of these, the number of carbon atoms of the monobasic unsaturated carboxylic acid is generally 20 or less, preferably 15 or less. Moreover, the carbon number of the derivative is usually at most 20 or less, preferably 15 or less. Further, the carbon number of the dibasic unsaturated carboxylic acid is generally 30 or less, preferably 25 or less. The carbon number of the derivative is usually 30 or less, preferably 25 or less. Among these unsaturated carboxylic acids and derivatives thereof, acrylic acid, methacrylic acid, maleic acid and anhydrides thereof, 5-norbornene-2,3-dicarboxylic acid and anhydrides thereof, and glycidyl methacrylate are particularly preferable. And 5-norbornenoic anhydride are preferred.

(3) Radical generator The radical generator used when producing the modified high-density polyethylene resin (A ') of the present invention is not particularly limited, but an organic peroxide is preferable. As the organic peroxide, those having a half-life decomposition temperature of 100 ° C. or more are suitable. Suitable organic peroxides include dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-di- (t-butylperoxy) hexane, 2,5-dimethyl-2. , 5- (t-butylperoxy) hexane-3, lauroyl peroxide, t-butylperoxybenzoate, and the like.

(4) Production of modified high-density polyethylene resin (A ′) The modified high-density polyethylene resin (A ′) according to the present invention comprises the above-described high-density polyethylene resin (A), an unsaturated carboxylic acid and / or a derivative thereof. , And is produced by uniformly mixing and processing with a radical generator. Specific examples include a melt-kneading method using an extruder, a Banbury mixer, a kneader, a solution method in which the solution is dissolved in an appropriate solvent, a slurry method in which the suspension is suspended in an appropriate solvent, or a so-called gas phase grafting method.
The treatment temperature is appropriately selected in consideration of the deterioration of the high-density polyethylene resin (A), the decomposition of the unsaturated carboxylic acid or its derivative, the decomposition temperature of the peroxide used, etc. For example, the temperature is usually 190 to 350 ° C, and 200 to 300 ° C is particularly preferable.
In producing the modified high-density polyethylene resin (A ′) according to the present invention, for the purpose of improving its performance, an already known method as described in Patent Document 14, for example, an epoxy compound during or after the graft modification described above Alternatively, a method of treating with a polyfunctional compound containing an amino group or a hydroxyl group, and a method of removing unreacted monomer (unsaturated carboxylic acid or derivative thereof) or by-product components by heating or washing, etc. Can do.
The higher the graft amount of the at least one monomer selected from the group consisting of the unsaturated carboxylic acid and its derivative, the better, but generally it is in the range of 0.001 to 10% by weight.

2. Modified polyethylene resin (B ')
The modified polyethylene resin (B ′) used in the present invention contains at least one monomer selected from the group consisting of unsaturated carboxylic acids and derivatives thereof in the polyethylene resin (B) having the following (b1) and (b2): , A resin obtained by grafting in the presence of a radical generator.

(1) Polyethylene resin (B)
The polyethylene resin (B) used as the raw material of the modified polyethylene resin (B ′) is an ethylene homopolymer having the following (b1) and (b2) produced by a Ziegler catalyst, a Phillips catalyst, a single site catalyst or the like. , Ethylene / α-olefin copolymers, linear low density polyethylene and the like. The α-olefin of the copolymer of ethylene and α-olefin is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, Examples include 4-methyl-1-pentene, 1-octene, and 1-decene. Two or more of them may be used in combination. Among these copolymers, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, and ethylene / 1-octene copolymer are economical. It is preferable from the viewpoint.

(B1) Density The (b1) density of the polyethylene resin (B) of the present invention is 0.91 to less than 0.94 g / cm ³ , preferably 0.915 to 0.938 g / cm ³ , more preferably 0.916. ˜0.937 g / cm ³ , more preferably 0.917 to 0.936 g / cm ³ . When the density is less than 0.91 g / cm ³ , the rigidity of the extruded product using the target adhesive resin composition as a constituent material is remarkably lowered, and the fuel oil resistance is remarkably deteriorated. In addition, when the density of the polyethylene resin (B) exceeds 0.94 g / cm ³ , there is a possibility that the delamination strength between the polyethylene resin composition / barrier material layers of the multilayer extruded product as the final product cannot be improved. Therefore, it is desirable to select within these ranges.
Here, the density is a value measured according to JIS K6922-2.

(B2) MFR
The (b2) MFR of the polyethylene resin (B) of the present invention is 0.01 to 10 g / 10 min, preferably 0.1 to 7 g / 10 min, more preferably 0.3 to 5 g / 10 min. When the MFR of the polyethylene resin (B) is less than 0.01 g / 10 min, an overload is applied to the motor of the processing machine when the target adhesive resin composition is processed into a multilayer extruded product using the constituent material. There is a risk that production efficiency will be significantly reduced. On the other hand, if the MFR of the polyethylene resin (B) is larger than 10 g / 10 min, the strength of the multilayer extruded product using the target adhesive resin composition as a constituent material may be significantly reduced.
Here, MFR is a value measured under a load of 190 ° C. and 2.16 kg in accordance with JIS K6922-2.

(2) Other raw materials The unsaturated carboxylic acid, its derivative and radical generator used in the modified polyethylene resin (B ′) of the present invention are the same as those used in the modified high-density polyethylene resin (A ′). It does not matter. Moreover, the manufacturing method of modified polyethylene resin (B ') is performed similarly to manufacture of the said modified high density polyethylene resin (A').
The higher the graft amount of at least one monomer selected from the group consisting of the unsaturated carboxylic acid and its derivative, the better, but generally it is in the range of 0.001 to 10% by weight.

3. Modified polyethylene resin composition (X)
In the modified polyethylene resin composition (X) of the present invention, the modified high-density polyethylene resin (A ′) is 100 to 70% by weight and the modified polyethylene resin (B ′) is 0 to 30% by weight, preferably (A ′). Component 95 to 80% by weight / (B ′) Compounded resin with component 5 to 20% by weight.
When the modified high-density polyethylene resin (A ′) is less than 70% by weight and the modified polyethylene resin (B ′) is more than 30% by weight in the modified polyethylene resin composition (X), the adhesive resin composition of the present invention. In addition, there is a concern that the fuel oil resistance of the multi-layer extrusion molded article using the target adhesive resin composition as a constituent material may deteriorate the adhesion strength between the barrier material layer and the adhesive material layer. Occurs.
In the modified polyethylene resin composition (X) of the present invention, each of the high-density polyethylene resin (A) and the other polyethylene resin (B) as raw materials is a group consisting of an unsaturated carboxylic acid and a derivative thereof alone. At least one monomer selected from the above may be graft-modified, or after the high-density polyethylene resin (A) and the other polyethylene resin (B) are mixed in advance, the mixture is grafted by the same method. It may be denatured.
In any of the above cases, the amount of the grafted monomer in the modified polyethylene resin composition (X) according to the present invention is preferably 0.001 to 10% by weight, more preferably 0.01%. -7% by weight, more preferably 0.05-5% by weight. If the ratio of the grafted monomers in the resin composition is less than 0.001% by weight as the total amount thereof, the various effects of the present invention cannot be exhibited sufficiently. On the other hand, even if it exceeds 10% by weight, the effect of the present invention cannot be further improved, and on the contrary, there is a concern of promoting gelation at the time of modification and deterioration of heat resistance deterioration.

4). Linear ultra-low density polyethylene resin (C)
The linear ultra-low density polyethylene resin (C) used in the present invention is an ethylene / α-olefin copolymer having the following (c1) and (c2). The α-olefin is a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1- Examples include octene and 1-decene. Two or more of them may be used in combination. Among these copolymers, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer, performance and This is preferable from the viewpoint of economy.

(C1) Density The (c1) density of the linear ultra-low density polyethylene resin (C) used in the present invention is 0.86 to 0.91 g / cm ³ , preferably 0.88 to 0.909 g / cm ^{3. 3} , more preferably 0.89 to 0.908 g / cm ³ . When the density is less than 0.86 g / cm ³ , there is a concern that the fuel oil resistance of the extruded body using the target adhesive resin composition as a constituent material is significantly lowered. On the other hand, when the density exceeds 0.91 g / cm ³ , there is a concern that the adhesive strength between the barrier material layer and the adhesive material layer of the multilayer extruded product using the target adhesive resin composition as a constituent material remains at the level of the prior art. Occurs.
Here, the density is a value measured according to JIS K 6922-2.

(C2) MFR
The (c2) MFR of the linear ultra-low density polyethylene resin (C) used in the present invention is 0.1 to 10 g / 10 min, preferably 0.3 to 5.0 g / 10 min, more preferably 0.5 to 4. 0.0 g / 10 min. When the MFR is less than 0.1 g / 10 min, when processing the target adhesive resin composition into a multilayer extrusion molded product using the constituent material, the processing machine motor is overloaded and the production efficiency is significantly reduced. Let On the other hand, if the MFR exceeds 10 g / 10 min, the strength of the multilayer extruded product using the target adhesive resin composition as a constituent material may be significantly reduced.
Here, MFR is a value measured under a load of 190 ° C. and 2.16 kg in accordance with JIS K6922-2.

In the present invention, two kinds of the above-mentioned unmodified linear ultra-low density polyethylene resin (C) may be mixed and used. For example, (i) a density of 0.89 to 0.91 g / cm ³ , ( ii) 70% by weight or more of a linear ultra-low density polyethylene resin (C1) having a melt flow rate of 0.1 to 10 g / 10 min; and (iii) a density of 0.86 to less than 0.89 g / cm ³ , ( iv) A linear ultra-low density polyethylene resin (C2) having a melt flow rate of 0.5 to 30 g / 10 min may be used by mixing with a linear ultra-low density polyethylene resin of less than 30% by weight.

(I) above the density of the linear very low density polyethylene resin (C1) is a 0.89~0.91g / cm ^3, preferably 0.893~0.909g / cm ^3, more preferably 0.895 to 0.908 g / cm ³ . When the density is less than 0.89 g / cm ³ , there is a concern that the fuel oil resistance of the extruded product using the target adhesive resin composition as a constituent material is significantly lowered. On the other hand, when the density exceeds 0.91 g / cm ³ , there is a concern that the adhesive strength between the barrier material layer and the adhesive material layer of the multilayer extruded product using the target adhesive resin composition as a constituent material remains at the level of the prior art. Occurs.
Moreover, (ii) MFR is 0.1-10 g / 10min, Preferably it is 0.3-5.0 g / 10min, More preferably, it is 0.5-4.0 g / 10min. When the MFR is less than 0.1 g / 10 min, when processing the target adhesive resin composition into a multilayer extrusion molded product using the constituent material, the processing machine motor is overloaded and the production efficiency is significantly reduced. Let On the other hand, if the MFR exceeds 10 g / 10 min, the strength of the multilayer extruded product using the target adhesive resin composition as a constituent material may be significantly reduced.

The (iii) density of the linear ultra-low density polyethylene resin (C2) is 0.86 to less than 0.89 g / cm ³ , preferably 0.863 to 0.887 g / cm ³ , and more preferably Is 0.865 to 0.885 g / cm ³ . When the density is less than 0.86 g / cm ³ , there is a concern that the fuel oil resistance and the fuel swellability of the extrusion molded body using the target adhesive resin composition as a constituent material are remarkably lowered. On the other hand, when the density exceeds 0.89 g / cm ³ , the adhesive strength between the barrier material layer and the adhesive material layer of the multilayer extrusion molded article using the target adhesive resin composition as a constituent material may remain at the level of the prior art. Arise.
Moreover, (iv) MFR is 0.5-30 g / 10min, Preferably it is 0.7-25 g / 10min, More preferably, it is 0.8-20 g / 10min. When the MFR deviates from the above range, the adhesive strength between the barrier material layer and the adhesive material layer of the multilayer extrusion molded article using the target adhesive resin composition as the constituent material remains at the level of the prior art particularly after immersion in the fuel oil. Concerns arise.

The blending ratio of the linear ultra-low density polyethylene resin (C1) and the linear ultra-low density polyethylene resin (C2) is such that (C1) is 70% by weight or more and (C2) is less than 30% by weight, preferably (C1) is selected in the range of 70 to 95% by weight, (C2) in the range of 30 to 5% by weight, more preferably (C1) in the range of 85 to 95% by weight / (C2) in the range of 5 to 15% by weight.
When the linear ultra-low density polyethylene resin (C1) is less than 70% by weight among the unmodified linear ultra-low density polyethylene resin (C), the fuel oil resistance of the adhesive resin composition of the present invention is There are cases where performance improvement cannot be expected. When the linear ultra-low density polyethylene resin exceeds 30% by weight, the adhesive strength between the barrier material layer and the adhesive material layer of the multilayer extrusion molded article using the target adhesive resin composition as a constituent material is conventionally It will remain at the level of technology.
The unmodified linear ultra-low density polyethylene resin (C) of the present invention is obtained by polymerizing each of the linear ultra-low density polyethylene resin (C1) and the linear ultra-low density polyethylene resin (C2) alone. Or a linear ultra-low density polyethylene resin and a linear chain obtained by polymerization under suitable conditions using a mixed catalyst comprising two or more types of complex catalyst components, or multistage polymerization. You may use the thing corresponded to the mixture of an ultra-low density polyethylene resin.

The linear ultra-low density polyethylene resin (C) of the present invention is produced by a Ziegler catalyst, a Phillips catalyst, a single site catalyst or the like. For example, the book “Polyethylene Technology Reader” (written by Kazuo Matsuura and Naotaka Mikami, (Research Committee Publication, 2001) p. It can be produced by the method described in 179-195.
In particular, using a ligand having a cyclopentadienyl skeleton and a transition metal compound of Group IV of the Periodic Table (referred to as a metallocene catalyst or a single site catalyst) in the gas phase It can be produced by a production process such as a polymerization method, a solution polymerization method, a slurry polymerization method, a high-pressure ion polymerization method, etc. As preferable constituent requirements, it is preferable to satisfy the following properties (a) to (d): .

(A) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5
(B) The difference between the temperature T _{25 at} which 25% of the total elution is obtained from the integral elution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) and the temperature T _{75 at} which 75% of the total is eluted. T ₇₅ −T ₂₅ and density d satisfy the relationship of the following formula (2) −670 × d + 644 ≧ T ₇₅ −T ₂₅ ≧ −300 × d + 280 (2)
(C) The amount of orthodichlorobenzene (ODCB) soluble component X (weight%), density d and melt flow rate (MFR) at 25 ° C. satisfies the relationship of the following formula (3) X <9.8 × 10 ³ × (0.9300-d + 0.008logMFR) ² +2.0 (3)
(D) There are multiple peaks in the elution temperature-elution volume curve by the continuous temperature rising elution fractionation method (TREF).

The properties (i) to (d) above will be described in detail below.
(A) Molecular weight distribution The molecular weight distribution (Mw / Mn) of the linear ultra-low density polyethylene resin (C) used in the present invention is preferably 1.5 to 4.5, more preferably 2.0 to 4.0. More preferably, it is 2.3 to 3.5. When Mw / Mn is less than 1.5, when the target adhesive resin composition is processed into an extruded product using a constituent material, the processing machine motor is overloaded, so the production efficiency is significantly reduced. Let In addition, when Mw / Mn exceeds 4.5, the adhesive strength between the barrier material layer and the adhesive material layer of the multilayer extruded product using the target adhesive resin composition as a constituent material is significantly higher than that of the prior art. There is a possibility that a significant improvement effect cannot be obtained.
The above (a) molecular weight distribution depends on the type of catalyst in the polymerization of ethylene and α-olefin, the type of promoter, the polymerization temperature, the amount of chain transfer agent, the residence time in the polymerization reactor, the number of polymerization reactors, etc. It can be adjusted and preferably increased or decreased by adjusting the mixing ratio of the high molecular weight component and the low molecular weight component, which is a technique well known to those skilled in the art.
That is, when the polymerization temperature and the amount of chain transfer agent are changed during the polymerization reaction, polymer components having different molecular weights are generated, and as a result, the molecular weight distribution of the entire polymer can be changed. It is also possible to increase or decrease the molecular weight distribution by performing polymerization with different polymerization conditions in multiple stages.
Here, Mw / Mn is obtained by calculating a weight average molecular weight (Mw) and a number average molecular weight (Mn) by usual gel permeation chromatography (hereinafter referred to as GPC) and calculating a ratio (Mw / Mn) thereof. This is the required value.

(B) Elution amount by TREF 25% of the total amount obtained from the integrated elution curve of the elution temperature-elution amount curve by the linear temperature elution fractionation method (TREF) of the linear ultra-low density polyethylene resin (C) used in the present invention. It is preferable that the difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which the elution is performed and the temperature T _{75 at} which 75% of the total is eluted satisfy the relationship of the formula (2),
−670 × d + 644 ≧ T ₇₅ −T ₂₅ ≧ −300 × d + 280 (2)
More preferably, the relationship of the formula (2 ′) is satisfied.
−670 × d + 639 ≧ T ₇₅ −T ₂₅ ≧ −300 × d + 285 (2 ′)

The difference T ₇₅ -T ₂₅ between the temperature T _{25 at} which 25% of the total elution is obtained from the integral elution curve of the elution temperature-elution amount curve by TREF and the temperature T _{75 at} which 75% of the total is eluted is, for example, ethylene-based The integral elution curve shown in FIG. 1, which is an elution curve showing the elution temperature and the elution amount of the copolymer, is obtained as a difference between a temperature T _{25 at} which 25% of the copolymer is eluted and a temperature T _{75 at} which 75% of the copolymer is eluted. By satisfying this relationship, performance such as adhesion strength and heat resistance between the barrier material layer and the adhesive material layer of the multilayer extrusion molded article using the target adhesive resin composition as a constituent material is improved.
The difference T ₇₅ -T ₂₅ obtained from the integral elution curve of the elution temperature-elution amount curve by TREF is the distribution state of the comonomer (α-olefin) in the copolymer (distribution of the number of branches in the copolymer). The distribution of α-olefin in the copolymer can be controlled by selecting the polymerization conditions, which is a technique well known to those skilled in the art. For example, the composition distribution tends to become wider when multistage polymerization is performed, tends to become wider when a plurality of catalysts are used, tends to become narrower when the polymerization temperature is raised, and becomes wider when the amount of α-olefin at the time of polymerization is increased. There is a tendency, and these can be combined appropriately to obtain a desired composition distribution.

Here, the measuring method of TREF is as follows.
First, the sample concentration is added to ODCB obtained by adding an antioxidant (for example, butylhydroxytoluene) to the sample so that the sample concentration becomes 0.05% by weight, and the sample is heated and dissolved at 140 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 4 ° C./h, and the sample is deposited on the surface of the glass beads. Next, the sample is sequentially eluted while increasing the column temperature at a constant rate of 50 ° C./hr while allowing ODCB to flow through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent is continuously detected by measuring the absorption with respect to a wave number of 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene with an infrared detector. From this value, the concentration of the ethylene (co) polymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. According to the TREF analysis, since a change in elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, it is possible to detect a relatively fine peak that cannot be detected by a fractionation method.

(C) Orthodichlorobenzene (ODCB) soluble content The amount of orthodichlorobenzene (ODCB) soluble content X (wt%), density d and melt flow rate of the linear ultra-low density polyethylene resin (C) used in the present invention at 25 ° C. (MFR) preferably satisfies the relationship of formula (3),
X <9.8 × 10 ³ × (0.9300−d + 0.008logMFR) ² +2.0 (3)
More preferably, the relationship of Formula (3 ′) is satisfied,
X <7.4 × 10 ³ × (0.9300−d + 0.008logMFR) ² +2.0 (3 ′)
More preferably, the relationship of the formula (3 ″) is satisfied.
X <5.6 × 10 ³ × (0.9300−d + 0.008logMFR) ² +2.0 (3 ″)

The ODCB soluble component at 25 ° C. is a highly branched component and a low molecular weight component contained in the ethylene (co) polymer. It is desirable that the content of the ODCB-soluble component is an amount that satisfies the above relational expression. The amount of ODCB solubles is affected by the α-olefin content and molecular weight of the entire copolymer, ie, density and MFR. Therefore, the fact that the density and the amount of soluble components of MFR and ODCB satisfy the above relationship indicates that there is little uneven distribution of α-olefins contained in the entire copolymer.
Further, the amount of the orthodichlorobenzene (ODCB) soluble component at 25 ° C. increases as the number of low molecular weight components having a molecular weight of about several thousand or less increases as the number of branches of the copolymer increases. Therefore, the ODCB soluble component tends to increase as the amount of α-olefin during polymerization increases, and tends to increase as the amount of low molecular weight components increases, and can be easily controlled by using a single-site catalyst. Is possible.

Here, the amount X of soluble ODCB at 25 ° C. is measured by the following method. 0.5 g of the sample is heated in 20 ml of ODCB at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. This solution is allowed to stand at 25 ° C. overnight, and then filtered through a Teflon (registered trademark) filter to collect the filtrate. For this filtrate, which is a sample solution, the absorption peak intensity around the wave number of 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene is measured by an infrared spectrometer, and the sample concentration is calculated using a calibration curve prepared in advance. From this value, the ODCB soluble content at 25 ° C. can be determined.

(D) Number of peaks in elution temperature-elution amount curve by continuous temperature elution fractionation method (TREF) Elution temperature by linear temperature elution fractionation method (TREF) of linear ultra-low density polyethylene resin (C) used in the present invention -It is preferable that a plurality of peaks in the elution amount curve exist. In particular, as shown in FIG. 2, which is an elution curve showing the elution temperature and the elution amount of the ethylene copolymer, there are a plurality of TREF peaks, and the high temperature side of the peak is more preferably between 85 ° C. and 100 ° C. It is desirable to exist. The presence of this high temperature peak improves the heat resistance. A special ethylene / α-olefin copolymer in which a plurality of peaks substantially appear in the elution temperature-elution amount curve obtained by TREF shown in FIG. 2 is most preferable.
Copolymer of ethylene and α-olefin obtained in the presence of a general metallocene catalyst, that is, a ligand having a cyclopentadienyl skeleton and a transition metal compound of Group IV of the periodic table In the elution temperature-elution amount curve obtained by TREF, the normal linear ultra-low density polyethylene resin is an ethylene and α-olefin having substantially only one peak as shown in FIG. And a special ethylene / α-olefin copolymer in which a plurality of such copolymers appear.
The presence of a plurality of peaks in the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) means that the main structure of the branched structure of the comonomer (α-olefin) in the copolymer is single. Indicates that there are multiple types, not types.
In order to make the main structure of the branched structure of the comonomer (α-olefin) in the copolymer into a plurality of types instead of a single type, it is achieved by combining a plurality of copolymer components having different composition distributions. can do. That is, it can be carried out by using a multistage polymerization or a catalyst having a plurality of types of active sites.
Here, the measurement method of TREF is the same as the measurement in (b) above.

  The linear ultra-low density polyethylene resin (C) of the present invention comprises at least one catalyst (metallocene catalyst or single catalyst) containing a ligand having a cyclopentadienyl skeleton and a transition metal compound of Group IV of the periodic table. It can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, or a high-pressure ion polymerization method. A catalyst obtained by mixing the following compounds (i) to (iv) for the production of the linear ultra-low density polyethylene resin (C) satisfying (a) to (d) which are particularly preferable constituents: It is suitably manufactured by using

(I) Compound represented by the following general formula (I) Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹ _4- pqr (I)
(In formula (I), Me ¹ represents zirconium, titanium, or hafnium, R ¹ and R ³ each represent a hydrocarbon group having 1 to 24 carbon atoms, and R ² represents a 2,4-pentanedionato ligand or a compound thereof. Derivative, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof, X ¹ represents a halogen atom, and p, q and r are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦, respectively. 4, an integer indicating a range of 0 ≦ p + q + r ≦ 4)
(Ii) Compound represented by the following general formula (II) Me ² R ⁴ _m (OR ⁵ ) _n X ² _zm-n (II)
(In the formula (II), Me ² is a group I-III element of the periodic table, R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom (however, X ² Is a hydrogen atom, Me ² is limited to a group III element in the periodic table), z is a valence of Me ² , and m and n are 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively. And an integer indicating the range of 0 ≦ m + n ≦ z)
(Iii) Organocyclic compound having conjugated double bond (iv) Modified organoaluminum oxy compound and / or boron compound containing Al—O—Al bond

In the compound represented by the general formula (I) of the catalyst component (i), Me ¹ represents zirconium, titanium, or hafnium in the general formula (I), and any one of these transition metals is used. It is not limited to these, and a plurality can be used. R ¹ and R ³ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group Aryl groups such as a group; aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neophyll group. These may be branched. R ² represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine. p, q, and r are integers satisfying the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ P + q + r ≦ 4, respectively.

Examples of the compound represented by the general formula of the catalyst component (i) include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrabutoxytitanium, tetrabutoxyhafnium and the like. In particular, Zr (OR) ₄ compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium are preferable, and a mixture of two or more of these may be used.

  Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof include tetra (2,4-pentandionato) zirconium. , Tri (2,4-pentandionato) chloride zirconium, di (2,4-pentandionato) dichloride zirconium, (2,4-pentandionato) trichloride zirconium, di (2,4-pentandionato) Diethoxide zirconium, di (2,4-pentanedionato) di-n-propoxide zirconium, di (2,4-pentandionato) di-n-butoxide zirconium, di (2,4-pentane) Diato) dibenzylzirconium, di (2,4-pentanedionato) dineophilylzirconium, tetra ( Benzoylmethanato) zirconium, di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (dibenzoylmethanato) di-n-butoxidezirconium, di (dibenzo) Ilacetonato) diethoxide zirconium, di (dibenzoylacetonato) di-n-propoxide zirconium, di (dibenzoylacetonato) di-n-butoxide zirconium and the like.

In the compound represented by the general formula (II) of the catalyst component (ii), in the general formula (II), Me ² represents a group I-III element of the periodic table, and lithium, sodium, potassium, magnesium, calcium Zinc, boron, aluminum and the like. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8, specifically, a methyl group, an ethyl group, a propyl group, or isopropyl. Group, alkyl group such as butyl group; alkenyl group such as vinyl group, allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, Examples include aralkyl groups such as a styryl group, a benzhydryl group, a phenylbutyl group, and a neophyll group. These may be branched. X ² represents a halogen atom such as fluorine, iodine, chlorine and bromine or a hydrogen atom. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , and m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

  As the organic cyclic compound having a conjugated double bond of the catalyst component (iii), one cyclic ring having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. Or a cyclic hydrocarbon compound having 2 or more and a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially 1 to 6 hydrocarbon residues (typically A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group having 1 to 12 carbon atoms; one ring having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds, or Organosilicon compound having a cyclic hydrocarbon group having 2 or more and a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially 1 to 6 hydrocarbon residue or alkali Metal salt (sodium salt or Organosilicon compounds substituted with lithium salt) is included. Particularly preferred are those having a cyclopentadiene structure in any of the molecules.

Suitable examples of the catalyst component (iii) include cyclopentadiene, indene, azulene or alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Moreover, the compound which these compounds couple | bonded (bridge | crosslinked) through the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.
The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula (III).
A _L SiR _4-L (III)
In general formula (III), A represents the cyclic hydrocarbon group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, and a propyl group. An alkyl group such as isopropyl group and butyl group; an alkoxy group such as methoxy group, ethoxy group, propoxy group and butoxy group; an aryl group such as phenyl group; an aryloxy group such as phenoxy group; an aralkyl group such as benzyl group; Represents a hydrocarbon residue or hydrogen having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

  Specific examples of the organic cyclic hydrocarbon compound of the catalyst component (iii) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7 -Cyclopolyene having 5 to 24 carbon atoms or substituted cyclopolyene such as dimethylindene, cycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadienylsilane, tris Examples include cyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

  Examples of the modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component (iv) include a modified organoaluminum oxy compound usually referred to as aluminoxane obtained by reacting an alkylaluminum compound with water. And a compound containing usually 1 to 100, preferably 1 to 50 Al—O—Al bonds in the molecule. The modified organoaluminum oxy compound may be linear or cyclic.

  The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferable. The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is usually 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1/1.

  Examples of the boron compound of the catalyst component (iv) include triethylaluminum triethylammonium tetra (pentafluorophenyl) borate tetra (pentafluorophenyl) borate, dimethylanilinium dimethylanilinium tetra (pentafluorophenyl) borate, and penta (pentafluoro). Phenyl) borate, butylammonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (3,5-difluorophenyl) borate and the like. .

The catalyst may be used by mixing and contacting the catalyst components (i) to (iv), but it is preferable to use the catalyst supported on an inorganic carrier and / or a particulate polymer carrier (v).
Examples of the inorganic carrier and / or particulate polymer carrier (v) include carbon materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like.

Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or a mixture thereof may be mentioned, and SiO ₂ —Al ₂ O ₃ , Examples thereof include SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, and SiO ₂ —Cr ₂ O ₃ . Among these, those having as a main component at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ are preferable. Further, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl methacrylate, polystyrene, polynorbornene, Examples include various natural polymers and mixtures thereof.

  The inorganic carrier and / or the particulate polymer carrier (v) can be used as they are, but these carriers are preferably used as a pretreatment as an organoaluminum compound or a modified organoaluminum oxy compound containing an Al—O—Al bond. It can also be used after contacting with.

  The linear ultra-low density polyethylene resin (C) according to the present invention further has a melting point (measurement method will be described later) by a differential scanning calorimeter of 50 to 122 ° C., preferably 66 to 121 ° C. is there. When the melting point is lower than 50 ° C., the resulting composition is insufficient in terms of heat resistance. On the other hand, when the temperature is higher than 122 ° C., the adhesive strength between the barrier material layer and the adhesive material layer of the multilayer extrusion molded article using the target adhesive resin composition as a constituent material remains at the level of the prior art.

5. Other unmodified polyethylene resin (D)
As other unmodified polyethylene resin (D), a high density polyethylene having a density of 0.94 g / cm ³ or more by a Ziegler catalyst, a Phillips catalyst, a single site catalyst or the like, a density of 0.91 to 0.94 g / cm ³ is used. Examples include ethylene / α-olefin copolymers (linear low density polyethylene) and ethylene (co) polymers produced by a high pressure radical polymerization method.
These other polyethylene resins (D) are blended for the preparation of the addition amount of the modified polyethylene-based resin composition and reduce the role of improving heat deterioration resistance and impact resistance of the adhesive resin composition. Without limitation, the density, MFR, and the like can be adjusted.

  The α-olefin as the ethylene-α · olefin copolymer of the unmodified polyethylene resin (D) is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, Examples thereof include 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. Two or more of them may be used in combination. Among these copolymers, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 4-methyl-1-pentene copolymer, and an ethylene / 1-octene copolymer are used for adhesion strength and It is preferable from the viewpoint of economy.

  The ethylene (co) polymer obtained by the high pressure radical polymerization method is an ethylene homopolymer (low density polyethylene resin), an ethylene / vinyl ester copolymer, and ethylene and an α, β-unsaturated carboxylic acid or Examples thereof include copolymers with derivatives thereof. These low-density polyethylene resins and the like are produced by a known high-pressure radical polymerization method, and may be produced by any method of a tubular method or an autoclave method.

  The ethylene-vinyl ester copolymer is composed mainly of ethylene, and vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. And a copolymer. Among these, vinyl acetate is particularly preferable. A copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomers is preferred. Furthermore, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight.

Typical copolymers of ethylene and α, β-unsaturated carboxylic acid ester include ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, and ethylene / butyl acrylate. Copolymer, ethylene / (meth) acrylic acid such as ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer or alkyl ester copolymer thereof; ethylene / maleic anhydride / vinyl acetate copolymer, Examples thereof include binary copolymers or multiple copolymers such as ethylene / maleic anhydride / methyl acrylate copolymer, ethylene / maleic anhydride / ethyl acrylate copolymer, and metal salts thereof.
That is, as these comonomers, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid-n-butyl, methacrylic acid- Examples thereof include n-butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, and lauryl methacrylate. Among these, alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate are particularly preferable. In particular, the (meth) acrylic acid ester content is in the range of 3 to 30% by weight, preferably 5 to 20% by weight.
Moreover, K, Na, Li, Ca, Zn, Mg, Al etc. are mentioned as a metal of the said metal salt.

The unmodified polyethylene resin (D) usable in the present invention has an MFR measured under a load of 190 ° C. and 2.16 kg in accordance with JIS K6922-2, preferably 0.01 to 50 g / 10 min, preferably 0.1 30 g / 10 min, more preferably 0.3 to 10 g / 10 min, and the density measured according to JIS K6922-2 is 0.910 to 0.965 g / cm ³ , preferably 0.915 to 0.960 g / Suitable is cm ³ , more preferably in the range of 0.917 to 0.955 g / cm ³ .

[II] Adhesive Resin Composition The adhesive resin composition of the present invention comprises a modified high-density polyethylene resin (A ′) of 100 to 70% by weight and a modified polyethylene resin (B ′) of 0 to 30% by weight. Polyethylene resin composition (X): 5 to 35% by weight, unmodified linear ultra-low density polyethylene resin (C): 19 to 35% by weight, and other unmodified polyethylene resin (D): 76 to 30% by weight The composition ratio of preferable constituent components is 10 to 34% by weight of the modified polyethylene resin composition (X), 20 to 33% by weight of linear ultra-low density polyethylene (C), and other polyethylene resins ( D) 70 to 33% by weight, more preferably 15 to 33% by weight of the modified polyethylene resin composition (X), linear ultra-low density polyethylene (C) 23 to 30% by weight, other polyethylene resin (D) 62 In the range of 37 wt%.
If the modified polyethylene resin composition (X) is less than 5% by weight, the adhesive strength is not improved, and if it exceeds 35% by weight, the heat-resistant deterioration performance is lowered. In addition, when the composition ratio of the unmodified linear ultra-low density polyethylene resin (C) is less than 19% by weight, the various improving effects of the present invention such as adhesive strength after gasoline immersion cannot be sufficiently exhibited. On the other hand, if the composition ratio of the unmodified linear ultra-low density polyethylene resin (C) exceeds 35% by weight, the fuel oil resistance and fuel swellability of the adhesive resin composition of the present invention are deteriorated and the desired adhesion is achieved. There is a possibility that the rigidity of the multilayer extrusion molded article using the functional resin composition as a constituent material is lowered.

The adhesive resin composition of the present invention has an MFR of 0.1 to 5 g / 10 min, preferably 0.2 to 4.0 g / 10 min measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-2. More preferably, the density is 0.3 to 3.0 g / 10 min, and the density measured according to JIS K6922-2 is 0.93 to 0.95 g / cm ³ , preferably 0.930 to 0.945 g / cm. ³ and more preferably those in the range of 0.930 to 0.942 g / cm ³ .
If the MFR of the adhesive resin composition is less than 0.1 g / 10 min, an overload is applied to the motor of the processing machine when the adhesive resin composition is processed into a multi-layer extruded product using the constituent material. Significantly reduce production efficiency. Further, if the MFR of the adhesive resin composition is larger than 5 g / 10 min, the strength of the multilayer extruded product using the adhesive resin composition as a constituent material may be remarkably lowered, and the parison may be used during direct blow molding. As a result, the drawdown property of the molded article may be increased, and the thickness distribution of the obtained molded product may be extremely uneven. Further, when the density of the adhesive resin composition is less than 0.93 g / cm ³ , there is a possibility that the fuel oil resistance of an extruded product using the adhesive resin composition as a constituent material is significantly deteriorated. On the other hand, if the density of the adhesive resin composition is higher than 0.95 g / cm ^{3, the} impact resistance of the multilayer extrusion molded article using the target adhesive resin composition as a constituent material may be significantly lowered.

  Moreover, various additives can be suitably mix | blended with this adhesive resin composition in the range which does not deviate from the objective of this invention. Examples of the additive include an antioxidant, a neutralizing agent, a lubricant, an antiblocking agent, an antistatic agent, a pigment, a weathering stabilizer, a nucleating agent, a flame retardant, and a filler.

[III] Production of Adhesive Resin Composition The adhesive resin composition of the present invention was dry blended at a predetermined mixing ratio with each component constituting the adhesive resin composition using a Henschel mixer, a tumbler blender, or the like. Thereafter, an adhesive resin composition adjusted to a uniform composition can be produced by adding melt kneading usually using a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a mixing roll, or the like.
In order to obtain a multilayer extruded product using the adhesive resin composition of the present invention as a constituent material, the melt-kneading operation can be omitted. That is, it is a method of obtaining a multilayer extrusion molded article by dry blending each component constituting the adhesive resin composition at a predetermined mixing ratio and then directly feeding it into a multilayer extrusion molding machine.

[IV] Molded Article Using Adhesive Resin Composition The adhesive resin composition of the present invention obtained as described above can be applied to containers such as industrial cans and fuel oil tanks such as gasoline. The article can be easily shaped into a desired shape by a blow molding method implemented as the molding method, and an article excellent in impact resistance can be obtained. Besides the blow molding method, various parts can be obtained by an injection molding method or a press molding method as a cap or various industrial members.
Moreover, since the adhesive resin composition of the present invention has affinity and adhesiveness with a barrier material such as an ethylene-vinyl alcohol copolymer, it is a laminate of three or more layers, two or two layers or two or three layers. These applications can be applied not only to the above-mentioned blow molded article but also to a film molded article, a sheet molded article, and the like.

[V] Container The adhesive resin composition of the present invention can be suitably used for containers such as fuel tanks. Barrier resin in a multilayer fuel oil tank made of ethylene-vinyl alcohol copolymer, polyamide resin, or the like, which has been put into practical use as a means for preventing permeation of fuel oil from automobile fuel tanks in recent years. Since the adhesive resin composition of the present invention has both excellent impact resistance (especially impact resistance at low temperature) and fuel oil resistance as an adhesive layer of the material and the main material (mainly high molecular weight high density polyethylene resin) Useful for.
In addition, the adhesive resin composition of the present invention can be used between the barrier material layer and the adhesive layer even when it is filled with fuel oil when the burrs generated during the molding process are used for the constituent material (regrind material) of the multilayer polyethylene. Adhesive strength is hardly reduced, and the burrs generated during molding are mixed with the components of the multi-layer polyethylene resin fuel container, and the compatibility between the mixed material and the barrier material when recycled is remarkably excellent. Demonstrate the effect.

  More specific laminates include three-layer three-layer structure of thermoplastic resin layer / adhesive material layer / barrier resin material layer such as high-density polyethylene, thermoplastic resin layer / adhesive material layer / barrier resin material layer / Adhesive layer / thermoplastic resin layer 3 type 5 layer laminate, thermoplastic resin layer / adhesive layer / regrind layer / barrier resin layer / adhesive layer / thermoplastic layer 4 A laminated body having a layer structure is exemplified.

The fuel tank container preferably used is composed of a main material layer of high-density polyethylene described below, an adhesive layer of the adhesive resin composition of the present invention, a barrier resin material layer, and a regrind material layer. Is preferred.
(1) High-density polyethylene The high-density polyethylene used for the main material layer of the fuel tank container of the present invention has a density of 0.93 g / cm ³ or more by a Ziegler catalyst, a Phillips catalyst, a single site catalyst, etc., preferably The range of 0.94 to 0.965 g / cm ³ , the melt flow rate is 0.01 to 30 g / min, preferably 0.02 to 10 g / 10 min, more preferably 0.03 to 5 g / min, 190 ° C. The ratio (MI _21.6 / MI _2.16 ) of the melt flow rate MI _21.6 measured at a load of _21.6 kg to the melt flow rate MI _2.16 measured at 190 ° C. and a load of 2.16 kg is 50 to 50 It is desirable to be in the range of 200, preferably 60-170.
(2) Adhesive The adhesive for the fuel tank container of the present invention is composed of the adhesive resin composition.
(3) Barrier resin material As the barrier resin material layer of the fuel tank container of the present invention, an ethylene-vinyl alcohol copolymer, a polyamide resin such as nylon 6, nylon 6, 6, nylon 11, nylon 12, etc., Polyester resins such as polyethylene terephthalate and polybutylene terephthalate, engineering plastics such as polyphenylene sulfide and liquid crystal polyester resin, polyvinylidene chloride resins, mixtures thereof, polymer alloys and the like are used.
(4) Regrind material The regrind layer used in the fuel tank container of the present invention is a fuel tank container made of a laminate containing the high-density polyethylene, adhesive, and barrier resin material. It is used by crushing and recycling burrs and defective products.

  The thickness of each layer of the fuel tank container is selected in the range of 0.1 to 10 mm, preferably 0.3 to 8 mm, more preferably 0.5 to 7 mm for the main material layer and / or the regrind material layer. . The thicknesses of the adhesive layer and the barrier resin material layer are each selected in the range of 10 μm to 5 mm, preferably 20 μm to 4 mm, more preferably 30 μm to 3 mm. The container is manufactured based on a conventional method by blow molding, injection molding, rotational molding, or the like.

The present invention will be described below through examples, but the present invention is not limited to these examples.
In addition, the test method used in the Example and adjustment of the resin material are as follows.

1. Test method (1) Density: Measured according to JIS K6922-2.
(2) MFR: Measured according to JIS K6922-2.
(3) Charpy impact value: measured at −40 ° C. in accordance with JIS K7111.
(4) FCI measurement method: The FCI measurement method of the high-density polyethylene resin (A) is as follows.
The measuring device uses a rotating rheometer UDS-200 manufactured by Paar Physica Co., Ltd., and MP306 (a flat plate having a diameter of 25 mm) is used as a fixing jig. The measurement temperature is 190 ° C., the strain is 10%, the distance between the flat plates is 2.1 mm, and the complex viscosity η ^* _{0.1 at a} frequency of _0.1 rad / s and the complex viscosity η ^* ₁₀ at a frequency of 10 rad / s are measured. . FCI was calculated from the ratio of η ^* _0.1 and η ^* ₁₀ .
(5) Mw / Mn measurement method: The Mw / Mn measurement method of the linear ultra-low density polyethylene resin is as follows.
The measuring apparatus uses Waters Co., Ltd. Gel Permeation Chromatography 150 Cplus, the column is connected with two Shodex HT-806M manufactured by Showa Denko Co., Ltd. in series, and the detector is a differential manufactured by Miran Co. Refractometer type 1A is used. The measurement temperature is 140 ° C., the eluent is 0.05% by weight of 2,4,6-trimethylphenol dissolved in 1,2,4-trichlorobenzene, and the operation is performed at a flow rate of 1.0 ml / min. . The sample is weighed 3.0 mg and used by dissolving in 3.0 ml of the solvent having the same composition as the eluent by shaking at 150 ° C. for 2 hours, and the injection volume of the sample solution is 300 μl. Mw / Mn was calculated from the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by the above measurement.
(6) Melting | fusing point measuring method: Melting | fusing point measurement of a linear ultra low density polyethylene resin is as follows.
The measuring apparatus uses a differential scanning calorimeter DSC7 manufactured by Perkin Elmer Co., Ltd. About 5 mg of a sample is set in the measuring apparatus, and the temperature is raised from room temperature to 200 ° C. at a rate of temperature increase of 10 ° C./min. Held for 5 minutes, then lowered to 0 ° C. at a rate of 10 ° C./min, and further the maximum endothermic peak temperature when the temperature was raised at a rate of 10 ° C./min. The temperature at the apex was set to the maximum peak temperature Tm1.
(7) TREF: The sample was injected while maintaining the column at 140 ° C., the temperature was lowered to 25 ° C. at 0.1 ° C./min, the polymer was deposited on the glass beads, and the column was heated under the following conditions. The polymer concentration eluted at each temperature was detected with an infrared detector.
Solvent: ODCB, flow rate: 1 ml / min, heating rate: 50 ° C./hour, detector: infrared spectrometer (wavelength 2925 cm ⁻¹ )
Column: 0.8cm x 12cmL (filled with glass beads)
Sample concentration: 1 mg / ml
(8) ODCB soluble content (X) amount: 0.5 g of a sample is heated in 20 ml of ODCB at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. The solution is allowed to stand at 25 ° C. overnight and then filtered through a Teflon (registered trademark) filter to collect the filtrate. The filtrate, which is a sample solution, was measured for the absorption peak intensity near the wave number of 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene using an infrared spectrometer, and the sample concentration was calculated using a calibration curve prepared in advance. From this value, the ODCB soluble content at 25 ° C. was determined.
(9) Oxidation induction period (OIT): The oxidation induction period (OIT) measurement of the modified polyethylene resin composition of the present invention is as follows.
The measuring apparatus uses EXSTAR6000-TG / DTA-6200 manufactured by Seiko Instruments Inc., and approximately 5 mg of the same sample used for the melting point measurement is set in the measuring apparatus. Next, while introducing nitrogen at a rate of 100 mL / min into the chamber, the temperature is raised from room temperature to 210 ° C. at a rate of temperature increase of 20 ° C./min, and then held at that temperature for 5 minutes. Here, nitrogen introduction is stopped at a constant temperature, and oxygen introduction is started at a rate of 50 mL / min. The time at this time is t1. After the introduction of oxygen, the oxidative deterioration of the modified polyethylene resin composition begins, and a phase transition based on the oxidative deterioration is observed depending on the current value. When the time at the intersection of the tangents of the current value during the oxidative degradation is defined as t2, it is defined as OIT = t2−t1 (minutes).
(10) Degree of fuel swelling: Among the multipurpose test pieces described in JIS K 7139, a compression molded test piece having a size of 80 mm × 10 mm × 4 mm is prepared. The length (L0) in the longitudinal direction of the test piece is measured in advance at room temperature, and then immersed in commercial regular gasoline manufactured by Shin Nippon Oil Co., Ltd. at 65 ° C. for 1000 hours. The longitudinal length (L1) after 1000 hours is measured at room temperature, and the fuel swelling degree (SR) defined below is calculated.
SR = (L1-L0) / L0 × 100 (%)

2. Raw materials used (1) Modified high-density polyethylene resin (A ')
As the modified high-density polyethylene resin (A ′), modified resins obtained in the following (A1 ′) and (A2 ′) production examples were used.

(A1 'production example)
In accordance with the description in Example 1 of JP-B-55-14084, a comonomer amount and a hydrogen feed amount are adjusted by slurry polymerization using a Ziegler catalyst, and MFR 0.8 g / copolymerized from ethylene and butene-1 100 parts by weight of high density polyethylene resin (A1) having properties of 10 min, density 0.954 g / cm ³ and FCI = 1.09, 0.3 part by weight of maleic anhydride and 2,5-dimethyl-di- (t -Butylperoxy) After adding 0.01 parts by weight of hexane and mixing with a Henschel mixer, melting was performed using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. Kneaded to obtain a modified high-density polyethylene (A1 ′) having an MFR of 0.2 g / 10 min and a density of 0.953 g / cm ³ (anhydrous maleic acid). Acid graft amount = 0.2 wt%). The results are shown in Table 1.

(A2 'production example)
In accordance with the description in Example 1 of JP-A-58-1708, a comonomer amount and a hydrogen feed amount are adjusted by slurry two-stage polymerization using a Ziegler catalyst, and ethylene and butene-1 are copolymerized. To 100 parts by weight of a high-density polyethylene resin (A2) having an MFR of 0.8 g / 10 min, a density of 0.955 g / cm ³ , and an FCI = 1.14, 0.3 parts by weight of maleic anhydride and 2,5-dimethyl-di- ( After adding 0.01 parts by weight of t-butylperoxy) hexane and mixing with a Henschel mixer, using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. By melt-kneading, a modified high-density polyethylene (A2 ′) having an MFR of 0.2 g / 10 min and a density of 0.954 g / cm ³ was obtained (maleic anhydride graph). Amount = 0.2% by weight). The results are shown in Table 1.

(2) Modified polyethylene resin (B ')
As the modified high-density polyethylene resin (B ′), the modified resin obtained in the following (B ′) production example was used.
(B 'production example)
To 100 parts by weight of linear low-density polyethylene resin (B) having an MFR of 0.8 g / 10 min and a density of 0.927 g / cm ³ (ethylene / 1-hexene copolymer: trade name Novatec LL SF720G manufactured by Nippon Polyethylene Co., Ltd.) Then, 0.3 parts by weight of maleic anhydride and 0.01 parts by weight of 2,5-dimethyl-di- (t-butylperoxy) hexane were added, mixed with a Henschel mixer, and then 50 mm unit manufactured by Modern Machinery Co., Ltd. Using a screw extruder, melt kneading was carried out under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. to obtain (B ′) modified polyethylene resin having an MFR of 0.2 g / 10 min and a density of 0.927 g / cm ³ (anhydrous maleic acid). Acid graft amount = 0.2 wt%). The results are shown in Table 1.

(3) Linear ultra-low density polyethylene resin (C)
The resin obtained in the following production example was used as a linear ultra-low density polyethylene resin (C1).
(Production example of linear ultra-low density polyethylene resin (C1))
(I) Preparation of solid catalyst To a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ), 75 g of indene and 88 g of methylbutylcyclopentadiene were added. While maintaining the temperature at 100 ° C., 100 g of tripropylaluminum was dropped over 100 minutes, and then reacted at the same temperature for 2 hours. After cooling to 40 ° C., 3200 ml of a toluene solution of methylalumoxane (concentration 2.5 mmol / ml) was added and stirred for 2 hours. Next, 2000 g of silica (Grace, # 952, surface area 300 m ² / g) preliminarily fired at 450 ° C. for 5 hours is added, stirred at room temperature for 1 hour, blown with nitrogen at 40 ° C. and dried under reduced pressure, and fluidized. A good solid catalyst was obtained.
(Ii) Gas phase polymerization Using a continuous fluidized bed gas phase polymerization apparatus, copolymerization of ethylene and 1-hexene was performed at a polymerization temperature of 65 ° C and a total pressure of 20 kgf / cm ² G. The solid catalyst was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to maintain a predetermined molar ratio, and polymerization was performed to obtain a linear ultra-low density polyethylene resin C1. Table 2 shows the physical property values of this resin.

(C2) Linear ultra-low-density polyethylene resin: A commercially available linear ultra-low-density polyethylene resin using a Ziegler-based catalyst (trade name: Nackflex GRSN-1539NT7, manufactured by Nihon Unicar Corporation) was used as C2. Table 2 shows the physical property values of this resin.
(C3) Linear ultra-low density polyethylene resin: A commercially available linear ultra-low density polyethylene resin (trade name: Engage 8200, manufactured by Dupont Dow Elastomer Japan Ltd.) using a single site catalyst was used as C3. Table 2 shows the physical property values of this resin.

(4) Unmodified polyethylene resin (D)
The following resins were used as the unmodified polyethylene resin (D).
(D1) Unmodified polyethylene resin: A commercially available linear low-density polyethylene (trade name: Novatec LL SF720G, manufactured by Nippon Polyethylene Co., Ltd.) using a Ziegler catalyst was used as the unmodified polyethylene resin D1. Table 2 shows the physical property values of this resin.
(D2) Unmodified polyethylene resin: A commercially available high-density polyethylene (trade name: Novatec HD HS430P, manufactured by Nippon Polyethylene Co., Ltd.) using a Ziegler catalyst was used as the unmodified polyethylene resin (D2). Table 2 shows the physical property values of this resin.

(Example 1)
13 parts by weight of modified high-density polyethylene resin (A1 ′), 2 parts by weight of modified polyethylene resin (B ′), 25 parts by weight of linear ultra-low density polyethylene resin (C1) and 30 parts by weight of unmodified polyethylene resin (D1), Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′ is added to 100 parts by weight of the mixture mixed at a ratio of 30 parts by weight of the unmodified polyethylene resin (D2). , A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 Part by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer. Using a 50 mm single-screw extruder manufactured by N Machinery Co., Ltd., melt kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C., the target adhesive resin composition described in Table 3 (hereinafter referred to as an adhesive) There are things).
Next, using a NB-150 continuous multilayer hollow molding machine manufactured by Nippon Steel Co., Ltd., a molding temperature of 210 ° C., a blow pressure of 0.6 MPa, a mold temperature of 20 ° C., and a cooling time of 180 sec. A rectangular parallelepiped hollow container (850 mm × 600 mm × 210 mm) was produced. The container is composed of a high-density polyethylene resin layer (Novatec HD HB111R manufactured by Nippon Polyethylene Co., Ltd., density 0.944 g / cm ³ , MFR 0.04 g / min, melt flow ratio (MI _21.6 / MI) from the outer layer side. _2.16 ) is 149) / regrind material layer / adhesive material layer / ethylene-vinyl alcohol copolymer layer (Eval F101B manufactured by Kuraray Co., Ltd.) / Adhesive material layer / high-density polyethylene resin layer (Japanese polyethylene ( Novatec HD HB111R) with a layer thickness of 1.3 mm / 4.0 mm / 0.2 mm / 0.3 mm / 0.2 mm / 4.0 mm. Among these, the composition ratios of the high-density polyethylene resin, the adhesive, and the ethylene-vinyl alcohol copolymer in the regrind layer are 87.2% by weight, 6.5% by weight, and 6.3% by weight, respectively.
Thereafter, a test piece was cut out in a strip shape with a width of 10 mm and a length of 100 mm in the MD direction from the flat portion of the bottom surface in the deep drawing direction of the container obtained by the blow molding described above, and manufactured by Nippon Oil Corporation. Was immersed in commercial regular gasoline of 1800 hours at 65 ° C.
Furthermore, the adhesive strength between the third layer (adhesive resin composition) / fourth layer (ethylene-vinyl alcohol copolymer) was measured from the outer layer side of the test piece before and after the gasoline immersion. The measurement of the adhesive strength was performed by making a notch in the middle of the third layer and the fourth layer from the outer layer side of the test piece, using a Tensilon UTM-III-500 manufactured by Toyo Baldwin Co., Ltd., and 90 ° at a tensile speed of 50 mm / min. It was performed by the method of peeling. The results are as shown in Table 3.

(Example 2)
17 parts by weight of modified high-density polyethylene resin (A1 ′), 3 parts by weight of modified polyethylene resin (B ′), 25 parts by weight of linear ultra-low density polyethylene resin (C1) and 30 parts by weight of unmodified polyethylene resin (D1), Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′ is added to 100 parts by weight of the mixture mixed at a ratio of 25 parts by weight of the unmodified polyethylene resin (D2). , A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 Part by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer. Using emission Machinery Co. 50mm single screw extruder at a screw rotation number 80 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Example 3)
17 parts by weight of modified high-density polyethylene resin (A1 ′), 3 parts by weight of modified polyethylene resin (B ′), 25 parts by weight of linear ultra-low density polyethylene resin (C2) and 30 parts by weight of unmodified polyethylene resin (D1), Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′ with respect to 100 parts by weight of the mixture mixed at a ratio of 25 parts by weight of the unmodified polyethylene resin (D2) , A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 Part by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer. Using emission Machinery Co. 50mm single screw extruder at a screw rotation number 80 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

Example 4
26 parts by weight of modified high-density polyethylene resin (A1 ′), 4 parts by weight of modified polyethylene resin (B ′), 25 parts by weight of linear ultra-low density polyethylene resin (C1) and 27 parts by weight of unmodified polyethylene resin (D1), Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′ with respect to 100 parts by weight of the mixture mixed at a ratio of 18 parts by weight of the unmodified polyethylene resin (D2) , A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 Part by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer. Using emission Machinery Co. 50mm single screw extruder at a screw rotation number 80 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Example 5)
26 parts by weight of modified high-density polyethylene resin (A1 ′), 4 parts by weight of modified polyethylene resin (B ′), 20 parts by weight of linear ultra-low density polyethylene resin (C1) and 36 parts by weight of unmodified polyethylene resin (D1), Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′ with respect to 100 parts by weight of the mixture mixed at a ratio of 14 parts by weight of the unmodified polyethylene resin (D2) , A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 Part by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer. Using emission Machinery Co. 50mm single screw extruder at a screw rotation number 80 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Example 6)
26 parts by weight of modified high-density polyethylene resin (A1 ′), 4 parts by weight of modified polyethylene resin (B ′), 20 parts by weight of linear ultra-low density polyethylene resin (C1), linear ultra-low density polyethylene resin (C3) 5 parts by weight, 21 parts by weight of the unmodified polyethylene resin (D1), and 100 parts by weight of the mixture mixed at a ratio of 24 parts by weight of the unmodified polyethylene resin (D2), and further 3,3 ′, 3 ″, 5,5 ', 5 "-hexa-tert-butyl-a, a', a"-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5- 0.14 parts by weight of di-t-butyl-4-hydroxyphenyl) propionate, 0.12 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.05 parts by weight of hydrotalcite added After blending for 2 minutes with a Henschel mixer, melt kneading was performed at a resin temperature of 230 ° C. using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. at a resin temperature of 230 ° C. A functional resin composition was obtained.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Example 7)
17 parts by weight of modified high-density polyethylene resin (A2 ′), 3 parts by weight of modified polyethylene resin (B ′), 25 parts by weight of linear ultra-low density polyethylene resin (C1) and 30 parts by weight of unmodified polyethylene resin (D1) Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a with respect to 100 parts by weight of the mixture mixed at a ratio of 25 parts by weight of the unmodified polyethylene resin (D2) ', A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 14 parts by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.05 part by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer. At a screw rotation speed 80rpm by using the Dan Machinery Co. 50mm single screw extruder, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Comparative Example 1)
26 parts by weight of modified high-density polyethylene resin (A1 ′), 4 parts by weight of modified polyethylene resin (B ′), 10 parts by weight of linear ultra-low density polyethylene resin (C1) and 53 parts by weight of unmodified polyethylene resin (D1), Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′ with respect to 100 parts by weight of the mixture mixed at a ratio of 7 parts by weight of the unmodified polyethylene resin (D2) , A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 Part by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added, blended for 2 minutes with a Henschel mixer, At a screw rotation speed 80rpm by using Machinery Co. 50mm single screw extruder, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Comparative Example 2)
17 parts by weight of modified high-density polyethylene resin (A1 ′), 3 parts by weight of modified polyethylene resin (B ′), 40 parts by weight of linear ultra-low density polyethylene resin (C1) and 5 parts by weight of unmodified polyethylene resin (D1), Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′ with respect to 100 parts by weight of the mixture mixed at a ratio of 35 parts by weight of the unmodified polyethylene resin (D2) , A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 Part by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added, blended for 2 minutes with a Henschel mixer, At a screw rotation speed 80rpm by using Machinery Co. 50mm single screw extruder, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Comparative Example 3)
40 parts by weight of modified high-density polyethylene resin (A1 ′), 5 parts by weight of modified polyethylene resin (B ′), 20 parts by weight of linear ultra-low density polyethylene resin (C1) and 35 parts by weight of unmodified polyethylene resin (D1) Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,4) with respect to 100 parts by weight of the mixture mixed at a ratio 6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.14 parts by weight, tris (2,4-di-) (t-Butylphenyl) phosphite 0.12 parts by weight and hydrotalcite 0.05 parts by weight were added and blended for 2 minutes with a Henschel mixer. There at a screw rotation speed 80rpm by, kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

(Comparative Example 4)
17 parts by weight of modified high-density polyethylene resin (A1 ′), 3 parts by weight of modified polyethylene resin (B ′), 75 parts by weight of unmodified polyethylene resin (D1) without blending linear ultra-low density polyethylene resin (C1) Further, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a with respect to 100 parts by weight of the mixture mixed at a ratio of 5 parts by weight of the unmodified polyethylene resin (D2) ', A "-(mesitylene-2,4,6-triyl) tri-p-cresol 0.15 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 14 parts by weight, 0.12 part by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended with a Henschel mixer for 2 minutes. At a screw rotation speed 80rpm by using Narry Co. 50mm single screw extruder, and melt-kneaded at a resin temperature of 230 ° C., to obtain the desired adhesive resin composition according to Table 3.
Four types and six layers of hollow containers were molded in the same manner as in Example 1, and the adhesive strength before and after immersion in fuel oil was measured. The results are as shown in Table 3.

As can be seen from the examples in Table 3, the adhesive resin composition of the present invention can greatly reduce the amount of the modified resin used, and therefore has excellent fuel oil resistance and impact resistance, and has a barrier material layer. In addition, the adhesive strength between the adhesive layers can be maintained without substantially lowering, and the heat deterioration resistance can be greatly improved.
In particular, in the case of a resin material that satisfies the relational expression of FCI and MFR as a modified high-density polyethylene resin (A), or a resin material that uses a mixture of two types of linear ultra-low density polyethylene (C), the initial adhesive strength And excellent adhesion strength (fuel oil resistance, fuel swellability, etc.) after being immersed in gasoline for a long time, impact resistance and heat resistance at low temperatures, especially when used as a component of a fuel container made of multi-layer polyethylene resin Even when used for a long time, not only good fuel oil resistance is maintained, but also excellent in impact resistance. Also, even when fuel oil is filled, the adhesive strength between the barrier material layer and the adhesive material layer is hardly reduced, and burrs generated during molding are mixed with the components of the fuel container made of multilayer polyethylene resin and recycled. It was a material that was remarkably excellent in the affinity between the mixed material and the barrier material and the heat deterioration resistance.

  On the other hand, when the linear ultra-low density polyethylene (C) of Comparative Example 1 was less than the range of the present invention, the Charpy impact value and the adhesive strength (before and after gasoline immersion) were lowered. When the blending amount of the linear ultra-low density polyethylene (C) of Comparative Example 2 is more than the range of the present invention, the fuel swelling degree is high. When the blending amount of the modified resin composition (I) of Comparative Example 3 was more than the range of the invention, the value of the oxygen induction period (OIT) was small and the heat deterioration resistance was poor. When the linear ultra-low density polyethylene (C) of Comparative Example 4 was not used, the Charpy impact value and the adhesive strength (before and after gasoline immersion) were lowered.

  By using the adhesive resin composition of the present invention as an adhesive layer, various polyolefin resins, various polyamide resins such as nylon 6,6, various hydroxyl group-containing resins such as ethylene-vinyl alcohol copolymer, polyethylene terephthalate resin, etc. In addition to various synthetic resin materials such as various polyester resins and various halogen-containing resins such as polyvinyl chloride resins, it has excellent affinity or adhesion to metal materials such as aluminum and iron, and various adhesive resin materials are used. It is useful in the field of packaging containers and industrial materials. In particular, it is an adhesive resin composition that is excellent in initial adhesive strength and adhesive strength after being immersed in gasoline for a long time, that is, excellent in fuel oil resistance and excellent in impact resistance and heat resistance at low temperatures. For industrial cans and fuel tanks It has a remarkable effect as an adhesive for containers. In particular, the fuel tank container using the resin composition of the present invention not only maintains good fuel oil resistance even when used for a long time, but also has excellent impact resistance. When used as a component material, the adhesive strength between the barrier material layer and the adhesive material layer is hardly reduced even when fuel oil is filled, and the burrs generated during the molding process are added to the component material of the fuel container made of multilayer polyethylene resin. It is a material that is remarkably excellent in the affinity between the material to be mixed and the barrier material and the heat deterioration resistance when mixed and recycled.

It is a figure of the elution curve showing the elution temperature and elution amount of the linear ultra-low density polyethylene (C) which satisfy | fills requirement (b). It is a figure of the elution curve showing the elution temperature and elution amount of the linear ultra-low density polyethylene (C) which satisfy | fills requirement (d). It is a figure of the elution curve showing the elution temperature and elution amount of a linear ultra low density polyethylene (C) by a general metallocene catalyst.

Claims (6)

Modified polyethylene resin composition (X) 5 to 35 wt%, unmodified linear ultra-low density polyethylene resin (C) 19 to 35 wt%, and other unmodified polyethylene resin (D) 76 to 30 wt% ( However, the density is 0.93 to 0.95 g / cm ³ , the melt flow rate is 0.1 to ⁵ g / cm, and the total of (X) component + (C) component + (D) component is 100% by weight) An adhesive resin composition for 10 minutes,
Component (X) comprises (a1) a high density polyethylene resin (A) having a density of 0.94 to 0.97 g / cm ³ and (a2) a melt flow rate of 0.01 to 30 g / 10 min. Modified high-density polyethylene resin (A ′) grafted with at least one monomer selected from the group consisting of its derivatives (A ′) 100 to 70% by weight, and (b1) density 0.91 to less than 0.94 g / cm ³ , ( b2) Modified polyethylene resin (B ′) 0 obtained by grafting at least one monomer selected from the group consisting of unsaturated carboxylic acids and derivatives thereof onto polyethylene resin (B) having a melt flow rate of 0.01 to 10 g / 10 min. A modified polyethylene resin composition comprising -30% by weight,
Component (C) is an unmodified linear ultra-low density polyethylene resin having (c1) density of 0.86 to less than 0.91 g / cm ³ and (c2) melt flow rate of 0.1 to 30 g / 10 min. An adhesive resin composition characterized by the above.   The adhesive resin according to claim 1, wherein at least one of the linear ultra-low density polyethylene resin (C) or the unmodified polyethylene resin (D) is a resin produced with a single-site catalyst. Composition. The unmodified linear ultra-low density polyethylene resin (C) has the following properties: (i) density 0.89 to 0.91 g / cm ³ , (ii) melt flow rate 0.1 to 10 g / 10 min. A linear ultra-low density polyethylene resin (C1) of 70% by weight or more, (iii) a density of 0.86 to less than 0.89 g / cm ³ , and (iv) a melt flow rate of 0.5 to 30 g / 10 min. 3. The adhesive resin composition according to claim 1, wherein the adhesive resin composition is composed of a linear ultra-low density polyethylene resin comprising less than 30% by weight of an ultra-low density polyethylene resin (C2).   The amount of at least one monomer selected from the group consisting of grafted unsaturated carboxylic acids and derivatives thereof in the adhesive resin composition is 0.001 to 10% by weight. 4. The adhesive resin composition according to any one of 3 above.   The molded object using the adhesive resin composition of any one of Claims 1-4.   The molded body according to claim 5, wherein the molded body is a laminate, a packaging bag, a container, a fuel tank container, a food container, or an industrial chemical container.

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