JP4945355B2 - Welding material and fuel tank using the same - Google Patents

Description

  The present invention relates to a welding material and a fuel tank using the same, and more specifically, various polyamide (PA) resins such as polyethylene resin, nylon 6,6, and various hydroxyl group-containing materials such as ethylene-vinyl alcohol copolymer (EVOH). Resins, various polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), various engineering plastics such as polyacetal (POM), polyphenylene ether (PPE), and polyphenylene sulfide (PPS), iron, aluminum, copper Further, the present invention relates to a welding material using a specific modified polyethylene resin composition which is excellent in adhesion to metals such as tin and various alloys, and a fuel tank using the same.

In recent years, various parts of automobiles are made into resin for the purpose of weight reduction and are put into practical use. In particular, the fuel tank is a large component, and if it is made of resin, it will contribute to reducing the weight of the vehicle body. Therefore, the mainstream is changing from metal ones to resin ones (hereinafter referred to as main parts). The resin fuel tank will be described in detail below.)
As such a resin fuel tank, for example, a fuel permeation prevention made of a polyamide resin (referred to as PA) or an ethylene-vinyl alcohol copolymer (referred to as EVOH) between a surface layer and an inner layer made of high-density polyethylene resin is used. It has a multi-layered material structure with layers sandwiched. However, the high-density polyethylene resin and PA or EVOH have poor adhesion, and generally an unsaturated carboxylic acid-modified polyethylene resin such as maleic anhydride is used for bonding the surface layer and inner layer to the PA or EVOH. ing.
The present applicants have proposed resin fuel tanks using these high-density polyethylene resins, EVOH and modified polyethylene resins, and adhesive resin compositions that can be used for the fuel tanks (for example, Patent Document 1, 2, 3, 4, 5).
In addition, a fuel tank having a structure including a high-density polyethylene layer, a binder layer, and an EVOH layer has been proposed (see, for example, Patent Document 6).
Furthermore, it is necessary to attach various accessory parts such as a fuel cut valve, a fuel vapor recovery valve, a fuel shut-off valve, a valve cover, a connector, a gutter joint, a fuel part, and a fuel supply part to the resin fuel tank body. These various accessory parts are made of polyamide resin, polyacetal resin, etc., and have poor adhesion and adhesion to the high-density polyethylene fuel tank body, and a modified polyolefin resin is disposed on the weld surface. In addition, a material (barrier material) having a fuel permeation preventive property such as polyamide resin or ethylene-vinyl alcohol copolymer is disposed so as to cover the modified polyolefin resin disposed on the welding surface between the accessory part and the fuel tank. Various techniques for preventing fuel diffusion have been proposed (see, for example, Patent Documents 7, 8, 9, 10, 11, 12).

As described above, the accessory parts such as the resin fuel tank main body and the fuel supply part itself can provide a certain degree of fuel permeation prevention by incorporating the resin layer having a barrier property into the multilayer structure. .
However, fuel diffusion also occurs at the joint (welded part) between the tank and accessory parts, and fuel diffusion from the joint (welded part) between the two is in a negligible amount. In order to reduce the amount, it is necessary to reduce the fuel permeation amount from the welded portion.

However, it is widely known that as a general polyethylene resin has a higher density, stress cracking resistance and creep rupture resistance tend to deteriorate, which is contrary to the above fuel permeation prevention performance. There is a correlation. Moreover, in a vehicle equipped with a direct fuel injection engine, a part of the fuel is returned to the tank, and the fuel temperature in the tank may rise to 60 to 80 ° C. Therefore, the stress cracking resistance of polyethylene resin In addition, both the creep rupture resistance and the fuel permeation prevention performance are promoted in the direction of deterioration. Furthermore, when it comes into contact with gasoline or gasohol, the interlayer adhesive strength between the polyethylene layer and the polyamide layer is lowered due to swelling of the polyethylene layer and the adhesive layer, and there is a problem that delamination and cracking occur.
Therefore, in order to use such a material as a constituent material of a fuel tank part which is an important safety part, it is difficult to say that the performance is sufficiently secured from the viewpoint of safety.
The modified polyolefin resin used for the welded surface is composed of a strong adhesive strength with a material having a fuel permeation-preventing property (barrier material) such as a polyamide resin or an ethylene-vinyl alcohol copolymer, However, there is a need for a balanced material that requires such strong welding (fusion) strength and sufficiently satisfies performance such as fuel permeation prevention and creep rupture resistance (long-term life performance). These modified polyethylene resins and welding materials did not satisfy these performances.
International Publication No. 2002/079323 Pamphlet US Pat. No. 5,643,997 US Pat. No. 5,902,655 JP 2006-176717 A JP 2006-176718 A JP 2002-264669 A JP 2000-008981 A JP 2002-370759 A Japanese Patent Laid-Open No. 20032-072399 JP 2004-293324 A Japanese Patent Laid-Open No. 2003-246028 JP 2005-193650 A

  In view of the above problems, the present invention not only maintains good fuel permeation resistance even when used in a high temperature atmosphere for a long period of time, but also creep rupture resistance and stress cracking resistance (long-term life performance). In addition, it is extremely excellent in the strong adhesive strength with the barrier material, and can constitute parts to be attached such as fuel supply parts attached to the fuel tank, while suppressing fuel diffusion from the welded part with the tank body It can be easily welded to the fuel tank, and it comes into contact with the fuel under harsh conditions such as gasoline, bioethanol, and gasohol in which methanol and ethanol are mixed with gasoline in an environment where the fuel temperature in the tank rises to 60-80 ° C. An object of the present invention is to provide a welding material that retains the welding strength afterwards and also has an excellent long-term life performance, and a fuel tank using the same.

  As a result of intensive studies to solve the above problems, the present inventors have selected a specific relatively high molecular weight modified polyethylene resin and a specific unmodified polyethylene resin having a wide molecular weight distribution, By using a modified polyethylene resin composition with high densification as the welding material, the performance and stress cracking resistance that are inversely related to creep rupture resistance (long-term life performance) and fuel permeation prevention performance are impaired. If such a welding material is a welding material that constitutes a part to be attached such as a fuel supply part for a fuel tank, fuel diffusion from the welding part with the tank body can be suppressed and fuel can be maintained. The present invention was completed by finding that it can be easily welded to a tank, maintains welding strength even after contact with fuel such as gasoline, and has excellent long-term life performance. It was.

That is, according to the first invention of the present invention, a welding material for welding to a fuel tank, the welding material is 0.5 to 95% by weight of the following modified polyethylene resin (X), Unmodified polyethylene resin (Y) 5-99.5 wt%, density 0.938-0.965 g / cm ³ , melt flow rate (temperature 190 ° C., load 2.16 kg) 0.05 A welding material containing the modified polyethylene resin composition (Z) of ˜1.0 g / 10 min is provided.
(X) Modified polyethylene resin: Polyethylene resin having a density of 0.910 to 0.965 g / cm ³ and a melt flow rate (temperature 190 ° C., load 2.16 kg) of 0.1 to 5.0 g / 10 min (A ) Modified polyethylene resin obtained by grafting at least one monomer selected from the group consisting of unsaturated carboxylic acids and derivatives thereof (Y) unmodified polyethylene resin: density is 0.930 to 0.965 g / cm ³ , Melt flow rate (temperature 190 ° C., load 2.16 kg) is 0.01 to 5.0 g / 10 min, melt flow rate ratio (high load melt flow rate HL-MFR: temperature 190 ° C., load 21.6 kg / melt flow) Rate MFR: Polyethylene resin with a temperature of 190 ° C. and a load of 2.16 kg satisfying 40 to 150

  According to a second invention of the present invention, in the first invention, the fuel tank comprises a multilayer laminated structure including a main material layer of high-density polyethylene, an adhesive material layer, and a barrier material layer. A welding material is provided.

  According to the third invention of the present invention, in the first or second invention, the melt flow rate ratio of the unmodified polyethylene resin (Y) (high load melt flow rate HL-MFR: temperature 190 ° C., load 21 6 kg / melt flow rate MFR: temperature 190 ° C., load 2.16 kg) is provided.

According to the fourth aspect of the present invention, in any one of the first to third aspects, the unmodified polyethylene resin (Y) has a density of less than 0.910 to 0.940 g / cm ³ and a temperature of 190. The polyethylene resin (B) has a high load melt flow rate of 0.05 to 10 g / 10 min at 25 ° C. and a load of 21.6 kg, a density of 0.940 to 0.970 g / cm ³ , and a temperature of 190. There is provided a welding material characterized by being a polyethylene resin composition comprising 75 to 40% by weight of a polyethylene resin (C) having a melt flow rate of 5 ° C. and a load of 2.16 kg at 5 to 600 g / 10 min.

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the unmodified polyethylene resin (Y) is a polyethylene resin produced by multistage polymerization. Material is provided.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, the welding material is based on 100 parts by weight of the modified polyethylene resin (X) and the unmodified polyethylene resin (Y). Furthermore, the welding material characterized by including 150 weight part or less of other polyethylene-type resin (D) is provided.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the modified polyethylene resin (X), the unmodified polyethylene resin (Y), and other polyethylene resins (D) There is provided a welding material characterized in that at least one resin is a polyethylene resin produced by a single site catalyst.

According to the eighth invention of the present invention, in any one of the first to seventh inventions, the modified polyethylene resin composition (Z) has a gasoline permeability of 50 mg / mm of a 1 mm thick sheet measured at 65 ° C. (Cm ² · 24 hr) or less, and a welding material characterized by satisfying an all-around notch tensile creep rupture time of 50 hours or more at 5.5 MPa measured at 80 ° C.

  According to a ninth aspect of the present invention, there is provided a welding material characterized in that the welding material according to any one of the first to eighth aspects constitutes a part attached to the fuel tank.

  According to a tenth aspect of the present invention, there is provided the welding material according to any one of the first to ninth aspects, wherein the welding material welds the fuel tank and its accessory parts.

  According to the eleventh aspect of the present invention, there is provided a component in which a laminated structure of at least two layers of a welding material layer and a barrier material layer according to any one of the first to tenth aspects is attached to a fuel tank. A welding material characterized in that it is constructed is provided.

  According to the twelfth aspect of the present invention, there is provided a fuel tank formed by welding the welding material according to any one of the first to eleventh aspects.

  According to a thirteenth aspect of the present invention, in the twelfth aspect, the fuel tank is composed of a multilayer laminated structure including a main material layer of high-density polyethylene, an adhesive material layer, and a barrier material layer. A fuel tank is provided.

The welding material of the present invention is a modified polyethylene-based resin that is selected from a specific relatively high molecular weight modified polyethylene resin and a specific unmodified polyethylene resin having a wide molecular weight distribution, and has a high molecular weight and a high density within a specific range. By using a resin composition as a welding material, the problem of fuel permeation prevention performance, stress cracking resistance, and creep rupture resistance (long-term life performance), which are in an inverse relationship, is eliminated, and fuel tanks, especially resin fuel It can be easily welded to the tank and maintains the welding strength even after coming into contact with fuel such as gasoline. Not only does it maintain good fuel permeation prevention even when used for a long time in a high-temperature atmosphere, Excellent resistance to creep fracture and stress cracking.
Further, by producing the unmodified polyethylene resin (Y) by multi-stage polymerization, a polymer having a desired wide molecular weight distribution can be easily obtained, so that a well-balanced welding material is provided.
Furthermore, when the above-mentioned welding material is used as a welding material constituting a part attached to the fuel tank such as a fuel supply part for a fuel tank, or at least two layers of a layer made of a welding material and a layer of a barrier material When the laminated structure is used as a welding material that constitutes a part attached to the fuel tank, a part of the fuel returns to the tank in a vehicle equipped with a direct fuel injection engine or the like, and the fuel temperature in the tank is 60 to 80 ° C. It is possible to provide a welding material that retains the welding strength even after coming into contact with the fuel under severe conditions such as gasoline, bioethanol, gasohol, etc., and has excellent long-term life performance.
Furthermore, the fuel tank of the present invention can provide a fuel tank excellent in long-term life performance while suppressing fuel diffusion from the welded portion with the tank body by using the above-mentioned welding material.

The present invention includes a modified polyethylene resin (X) obtained by modifying a polyethylene resin (A) satisfying a specific density and MFR, and an unmodified polyethylene resin (Y) satisfying a specific density, MFR and melt flow rate ratio. A welding material made of a modified polyethylene resin composition (Z), which contains another polyethylene resin (D) as required, and a fuel tank using the same.
Details will be described below.

[I] Welding material Component of modified polyethylene resin composition (Z) (1) Polyethylene resin (A)
The polyethylene resin (A) that is a raw material of the modified polyethylene resin (X) used in the present invention is an ethylene homopolymer having the following characteristics (a-1) density and (a-2) MFR or ethylene and α-olefin: Polyethylene produced by ionic polymerization such as high density polyethylene resin, linear low density polyethylene resin or linear ultra-low density polyethylene resin generally produced by ionic polymerization. The resin (A1) includes an ethylene (co) polymer (A2) such as low density polyethylene produced by radical polymerization.

Density characteristics (a-1) density polyethylene resin (A) is a 0.910~0.965g / cm ^3, preferably 0.915~0.960g / cm ^3, more preferably 0.920 to 0 .958 g / cm ³ . The density of the polyethylene resin (A) does not improve the adhesive strength of the modified polyethylene resin (X) is less than 0.910 g / cm ^3, fear Re occurs that resistance to gasoline permeation resistance decreases, the 0.965 g / cm ³ When exceeding, impact resistance and creep resistance will fall, and there exists a possibility that long-term life may not be satisfied.
Here, the density is a value measured based on the test method of JIS K6922-1 (1997).

Characteristic (a-2) Melt flow rate (MFR)
The melt flow rate (MFR) of the polyethylene resin (A) at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 5.0 g / 10 minutes, preferably 0.2 to 3.0 g / 10 minutes. Preferably it is 0.3-2.0 g / 10min. When the MFR of the polyethylene resin (A) is less than 0.1 g / 10 minutes, there is a possibility that the injection molding processability is lowered.
Here, MFR is a value measured under condition D (temperature 190 ° C., load 2.16 kg) based on the test method of JIS K6922-1 (1997).

The density of the polyethylene resin (A) can be controlled by the type and content of α-olefin, and the density tends to decrease as the content increases. MFR is a chain transfer agent such as hydrogen, process, etc. It is controlled by. These control methods are well known and commonly used by those skilled in the art.
The polyethylene resin (A) according to the present invention may be a mixture of two or more kinds of polyethylene resins (A) as long as the above conditions are satisfied.

  The polyethylene resin (A1) produced by ion polymerization and the ethylene (co) polymer (A2) produced by radical polymerization that can be preferably used will be described below.

(I) Polyethylene resin (A1)
The polyethylene resin (A1) produced by ionic polymerization that can be used in the present invention has a density of less than 0.910 to 0.940 g / cm ³ and an MFR in the range of 0.1 to 5.0 g / 10 minutes. A linear low density polyethylene resin composed of an ethylene / α-olefin copolymer, ethylene alone having a density of 0.940 to 0.965 g / cm ³ and an MFR of 0.1 to 5.0 g / 10 min. It includes a high-density polyethylene resin composed of a polymer or an ethylene / α-olefin 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, 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, and ethylene / 1-octene copolymer are economical. It is preferable from the viewpoint.

In order to produce the polyethylene resin (A1) produced by ionic polymerization that can be used in the present invention, preferably a specific Ziegler-type catalyst such as JP-B-55-14084 and JP-B-58-1708, It can be suitably produced by controlling the polymerization conditions such as polymerization temperature and pressure, co-catalyst and the like using a Philips catalyst or a single site catalyst.
In addition, the polyethylene resin (A1) is an ethylene olefin compound in the presence of a catalyst for olefin polymerization that includes an organoaluminum oxy compound and a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. And a C3-20 α-olefin copolymer are more preferred.

  The polyethylene resin (A1) produced by the ionic polymerization is not particularly limited to the production catalyst, process, etc., but the book “Polyethylene Technology Reader” (written by Kazuo Matsuura and Naotaka Mikami, published by the Industrial Research Council, 2001) P.). 123-160, p. It is possible to manufacture by the method described in 163-196 etc. That is, it can be produced in various polymerization apparatuses, polymerization conditions, etc. in each polymerization mode of Ziegler catalyst, Phillips catalyst, single site catalyst, etc., slurry method, solution method and gas phase method.

(Ii) Ethylene (co) polymer produced by radical polymerization (A2)
The ethylene (co) polymer (A2) produced by radical polymerization that can be used in the present invention is an ethylene homopolymer (low density polyethylene resin), an ethylene / vinyl ester copolymer, and ethylene by a high pressure radical polymerization method. And a copolymer of α, β-unsaturated carboxylic acid or a derivative thereof. These low-density polyethylene resins are produced by a known high-pressure radical polymerization method, and can be obtained by any method of a tubular method or an autoclave method. It may be manufactured.

The low density polyethylene resin preferably has a density of 0.910 to 0.935 g / cm ³ and a melt flow rate of 0.1 to 5.0 g / 10 min.

  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, and vinyl trifluoroacetate. It is 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, ethylene / butyl acrylate copolymer. Polymers, ethylene / (meth) acrylic acid such as ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer or alkyl ester copolymers thereof; ethylene / maleic anhydride / vinyl acetate copolymer, ethylene -A binary copolymer such as a maleic anhydride / methyl acrylate copolymer, an ethylene / maleic anhydride / ethyl acrylate copolymer, or a multi-component copolymer.

  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.

  As long as the polyethylene resin (A) used in the present invention satisfies the above physical properties, the polyethylene resin (A1) and (A2) may be appropriately mixed, or a blend with other polyethylene resins. It may be.

(2) Modified polyethylene resin (X)
The modified polyethylene resin (X) used in the present invention is obtained by adding at least one monomer selected from the group consisting of the following unsaturated carboxylic acids and derivatives thereof to the polyethylene resin (A) having the above-described characteristics by the following radical initiator or the like. , A grafted modified polyethylene resin.

(I) Unsaturated carboxylic acid or derivative monomer thereof At least one monomer selected from the group consisting of the unsaturated carboxylic acid or derivative thereof used in the present invention includes monobasic unsaturated carboxylic acid, dibasic unsaturated monomer. Saturated carboxylic acids and their metal salts, amides, imides, esters and anhydrides are mentioned. The number of carbon atoms of the monobasic unsaturated carboxylic acid is at most 20, preferably 15 or less. In addition, the carbon number of the dibasic unsaturated carboxylic acid is at most 30, preferably 25 or less, and the carbon number of this derivative is at most 30, 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 preferable, and maleic anhydride is particularly preferable. , 5-norbornene acid anhydride is preferred because of the excellent adhesion performance of the polyethylene resin composition.

  The blending amount is preferably 0.05 to 5.0 parts by weight, more preferably 0, for at least one monomer selected from the group consisting of unsaturated carboxylic acids or derivatives thereof with respect to 100 parts by weight of the resin component. 0.1 to 3 parts by weight, particularly preferably 0.2 to 2 parts by weight. If the blending amount of at least one monomer selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof is less than 0.05 parts by weight, it is not possible to obtain a sufficient welding performance as the original purpose. When the amount is more than parts by weight, unreacted monomers increase and the adhesion performance is impaired, which is not preferable.

(Ii) Radical initiator As the radical initiator used for grafting modification in the present invention, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane, lauroyl Peroxide, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy -M-isopropyl) benzene, di-t-butyldiperoxyisophthalate, n-butyl-4 Examples of the organic peroxide include 4-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, t-butylperoxyacetate, cyclohexanone peroxide, t-butylperoxylaurate, and acetyl peroxide. . Among these, a decomposition temperature for obtaining a half-life of 1 minute is preferably 160 to 200 ° C. If the decomposition temperature is too low, the decomposition reaction starts before the raw material polyethylene resin (A) is sufficiently plasticized in the extruder, so the reaction rate becomes low. Conversely, if the decomposition temperature is too high, the reaction occurs in the extruder. Not complete and the amount of unreacted unsaturated carboxylic acid and its derivatives increases.

  The blending amount of the radical initiator is preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the resin component. If it is less than 0.005 parts by weight, the grafting reaction is not sufficiently carried out and unreacted monomers increase, which is not preferable. On the other hand, when the amount is more than 0.5 parts by weight, gels and fish eyes frequently occur, which is not preferable.

(Iii) Modification method The production method of the modified polyethylene resin is as follows. At least one modification monomer selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof is added to 100 parts by weight of the polyethylene resin (A). Add 0 part by weight and 0.005 to 0.5 part by weight of radical initiator, and modify in melt-kneading or solvent using a single screw extruder and / or twin screw extruder or one or more reactors. Is achieved.
Specifically, a melt kneading method using an extruder, a Banbury mixer, a kneader, etc., a solution method dissolved in an appropriate solvent, a slurry method suspended in an appropriate solvent, or a so-called gas phase grafting method can be mentioned.
The treatment temperature is appropriately selected in consideration of the deterioration of the polyethylene resin (A), the decomposition of the unsaturated carboxylic acid or its derivative, the decomposition temperature of the peroxide used, etc., taking the melt kneading method as an example. When it mentions, it is 190-350 degreeC normally, and 200-300 degreeC is especially suitable.

In the production of the modified polyethylene resin (X) according to the present invention, for the purpose of improving its performance, as described in JP-A-62-10107, a known method such as the graft modification or A method of treating with an epoxy compound or a polyfunctional compound containing an amino group or a hydroxyl group after modification, and a method of removing unreacted monomers (unsaturated carboxylic acid and derivatives thereof) and various by-products by heating or washing. Can be adopted.
The higher the grafting 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 5.0% by weight.

Using the above radical initiator, the reaction to the polyethylene resin (A) occurs in parallel with the grafting reaction and the micro-crosslinking of the polyethylene at the same time. The precipitating reaction takes place preferentially to achieve a high monomer addition rate. On the other hand, when the resin temperature is less than 250 ° C., the fine crosslinking of the polyethylene resin preferentially occurs, so that gel and resin burn increase and the quality of the resulting modified polyethylene resin (X) decreases. Further, when the resin temperature exceeds 310 ° C., the deterioration of the polyethylene itself is accelerated, so that gels and resin burns increase drastically, which also deteriorates the quality.
In addition, since the reaction is carried out at such a high temperature, it is necessary to suppress the mixing of air into the extruder and the reactor as much as possible. In melt-kneading, it is also necessary to avoid the resin staying in the extruder for a long time. I must. For this reason, it is extremely preferable to perform nitrogen feed in the vicinity of the raw material resin inlet.

In producing the modified polyethylene resin (X) of the present invention, in order to suppress unnecessary side reactions and give priority to the grafting reaction to the polyethylene resin (A), a generally used antioxidant, etc. It is not preferable to add an additive. For example, the addition of an antioxidant for polyolefins may increase the amount of unreacted unsaturated carboxylic acid or derivative thereof by the antagonistic action of the antioxidant and the radical initiator.
Moreover, the addition of metal soaps may cause the metal soaps and unsaturated carboxylic acids or their derivatives to react, resulting in a decrease in the adhesive performance of the resulting modified polyethylene resin.

In the production of the modified polyethylene resin (X) of the present invention, it is preferable to modify the polyolefin resin material over a plurality of orders, and thereby a group consisting of unsaturated carboxylic acid and derivatives thereof, which are relatively expensive monomers. The modification rate of at least one modification monomer selected from the above is sufficiently increased to improve the economy, and a high modification rate can be achieved with a relatively small amount of modification monomer, and the adhesive performance is very excellent. Thus, it is possible to produce a high-quality modified polyolefin resin in which no unreacted modified monomer remains and no gel or resin burn occurs.
The graft modification rate obtained by the modification method in such melt kneading is generally in the range of about 0.2 to 2.5% by weight, and is the graft modification rate of the final modified polyethylene resin (X). The upper limit of is preferably as high as possible, but is generally in the range of 0.55 to 2.5% by weight. However, it is not particularly limited to this range, and a higher modification rate is desirable.

(3) Unmodified polyethylene resin (Y)
The unmodified polyethylene resin (Y) used in the present invention is a resin having the following characteristics (y-1) density, (y-2) MFR, (y-3) melt flow rate ratio, Ziegler catalyst, Philips Polyethylene resin having a wide molecular weight distribution produced by various polymerization apparatuses, polymerization conditions, etc. in each polymerization mode of a catalyst, a single site catalyst, etc., slurry method, solution method, gas phase method, preferably described later An ethylene homopolymer comprising a polyethylene resin (B) satisfying a specific density and MFR and a polyethylene resin (C) satisfying a specific density and MFR, or satisfying the above density, MFR and melt flow rate ratio And a polyethylene resin composed of an ethylene / α-olefin copolymer.

(I) Characteristics (y-1) density of unmodified polyethylene resin (Y) Density of unmodified polyethylene resin (Y) of the present invention is 0.930 to 0.965 g / cm ³ , preferably 0. .932 to 0.963 g / cm ³ , more preferably 0.945 to 0.960 g / cm ³ . When the density is less than 0.930 g / cm ³ , the fuel permeation prevention performance is lowered, and when it exceeds 0.965 g / cm ³ , the impact resistance is lowered.

(Y-2) Melt flow rate (MFR)
The melt flow rate (MFR) of 190 ° C. and a load of 2.16 kg of the unmodified polyethylene resin (Y) of the present invention is 0.01 to 5.0 g / 10 min, preferably 0.05 to 4. It is 0 g / 10 minutes, more preferably 0.1 to 3.0 g / 10 minutes. If the MFR is less than 0.01 g / 10 min, the moldability at the time of injection molding is extremely deteriorated, and if it exceeds 5.0 g / 10 min, the impact resistance and creep resistance may be lowered.

(Y-3) Melt flow rate ratio Melt flow rate ratio of unmodified polyethylene resin (Y) of the present invention (temperature 190 ° C, load 21.6 kg high load melt flow rate / temperature 190 ° C, load 2.16 kg) The melt flow rate) is 40 to 150 , preferably 50 to 150 , and more preferably 60 to 150 . In particular, it is desirable that it is 70-150. If the melt flow rate ratio is less than 40, the long-term life characteristics may deteriorate, and if it exceeds 270, the impact resistance may be lowered.
Here, the melt flow rate ratio is a ratio of a high load melt flow rate (HL-MFR) at a temperature of 190 ° C. and a load of 21.6 kg to a melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg. Thus, the molecular weight distribution is broadened. When the numerical value is large, it means that the molecular weight distribution is wide, and the mechanical strength such as impact resistance tends to decrease, but the molding processability is improved.
In the case of using a Ziegler catalyst, the above melt flow rate ratio is generally prepared by a method of controlling MFR using a chain transfer agent such as hydrogen, a method of controlling by multistage polymerization, and the like. It is done by combining. In addition, when a chromium-containing catalyst is used, the polymerization temperature and pressure, catalyst activation conditions, carrier type, etc. are generally used (Sensho "Polyethylene Technology Reader" (written by Kazuo Matsuura and Naotaka Mikami, (See, for example, pages 123 to 159 of the Industrial Research Society, 2001)).

(Ii) Configuration of Unmodified Polyethylene Resin (Y) One preferred embodiment of the present invention is that the unmodified polyethylene resin (Y) has a specific density, MFR and a polyethylene resin (B) satisfying a specific density. And made of a polyethylene resin (C) that satisfies MFR, and is composed of a multistage polymer or a mixture.

(Iii) Polyethylene resin (B)
The polyethylene resin (B) used in the present invention is a low density, high molecular weight polyethylene resin, and has the following characteristics (b-1) density and (b-2) high load melt flow rate. For example, linear low density polyethylene which is a copolymer of ethylene and α-olefin can be mentioned, and the α-olefin is not particularly limited as long as it is an α-olefin copolymerizable with ethylene. And those having 3 to 12 carbon atoms are preferable, and representative examples include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. A plurality of these may be used.

(B-1) Density The density of the polyethylene resin (B) used in the present invention is 0.910 to 0.940 g / cm ³ , preferably 0.915 to 0.935 g / cm ³ , and more preferably. Is 0.920 to 0.930 g / cm ³ . If the density is less than 0.910 g / cm ³ , the gasoline permeation resistance may decrease, and if it exceeds 0.940 g / cm ³ , the impact resistance and creep resistance may decrease.
(B-2) High load melt flow rate The high load melt flow rate (HL-MFR) of the polyethylene resin (B) used in the present invention is 0.05 to 10 g / 10 min, preferably 0.1 to 7 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes. If the HL-MFR is less than 0.05 g / 10 minutes, the injection moldability may be deteriorated. If it exceeds 10 g / 10 minutes, the impact resistance and creep resistance may be lowered.
The control of HL-MFR can be controlled by conventional means such as a method of controlling MFR using a chain transfer agent such as hydrogen, a method of controlling by polymerization temperature and pressure, and a combination thereof. The method is well known to those skilled in the art.

(Iv) Polyethylene resin (C)
The polyethylene resin (C) used in the present invention is a high density and low molecular weight polyethylene resin, and has the following characteristics (c-1) density and (c-2) MFR. Examples thereof include high-density polyethylene that is an ethylene homopolymer or an ethylene / α-olefin copolymer.

(C-1) Density The density of the polyethylene resin (C) used in the present invention is 0.940 to 0.970 g / cm ³ , preferably 0.943 to 0.965 g / cm ³ , and more preferably 0. 945 to 0.960 g / cm ³ . If the density is less than 0.940 g / cm ³ , impact resistance and creep resistance may be lowered, and if the density exceeds 0.970 g / cm ³ , impact resistance is lowered.
(C-2) MFR
The MFR (temperature 190 ° C., load 2.16 kg) of the polyethylene resin (C) used in the present invention is 5 to 600 g / 10 minutes, preferably 7 to 500 g / 10 minutes, more preferably 10 to 300 g / 10. Minutes. If the MFR is less than 5 g / 10 minutes, the moldability at the time of injection molding is extremely deteriorated, and if it exceeds 600 g / 10 minutes, impact resistance and creep resistance may be lowered.

(V) Blending ratio of polyethylene resin (B) and polyethylene resin (C) In unmodified polyethylene resin (Y), the blending ratio of polyethylene resin (B) and polyethylene resin (C) is polyethylene resin. (B) / polyethylene resin (C): 25-60 wt% / 75-40 wt%, preferably polyethylene resin (B) / polyethylene resin (C): 30-55 wt% / 70-45 % By weight, more preferably polyethylene resin (B) / polyethylene resin (C): 35-50% by weight / 65-50% by weight. When the polyethylene resin (B) is less than 25% by weight and the polyethylene resin (C) is more than 75% by weight, the notch creep rupture time may be deteriorated. If it exceeds 60% by weight and the polyethylene resin (C) is less than 40% by weight, the fluidity may decrease.

(Vi) Production of Unmodified Polyethylene Resin (Y) The unmodified polyethylene resin (Y) of the present invention has the above characteristics (y-1) density, (y-2) MFR, (y-3) melt flow rate. Ratio (b-1) density, (b-2) polyethylene resin (B) having melt flow rate and characteristic (c-1) density, (c-2) polyethylene resin having MFR As long as it is composed of (C), the production method is not particularly limited, and there is no limitation on the production method of each polymer comprising a polyethylene resin produced by multistage polymerization, an ethylene homopolymer, or a copolymer of ethylene and α-olefin. It may be a mixture. Among these, it is particularly preferable to produce by a multistage polymerization method because a polymer having a desired broad molecular weight distribution can be easily obtained.

  The multistage polymerization method is an industrial polyethylene resin production process for broadening the molecular weight distribution of the polyethylene resin. In order to broaden the molecular weight distribution of the polyethylene resin, there are a method of selecting an appropriate polymerization catalyst, a method of selecting an appropriate polymerization condition, and the like, but the molecular weight distribution of the polyethylene resin obtained by these methods is wide. Has a limit. In order to satisfy the performance required for the polyethylene resin of a specific application, a method of preparing a low molecular weight component on the one hand and a high molecular weight component on the other hand and blending each is practically used. In this method, polyethylene resins having different molecular weights are produced in each reactor using the above number of reactors, and the reactors are connected in series to continuously blend.

As an example of the production of these multistage polymerizations, for example, JP-A-08-301933 discloses an ethylene polymer comprising a high molecular weight component and a low molecular weight component in which a comonomer is selectively introduced on the high molecular weight side, Polyethylene with excellent fracture toughness has been presented. Further, polyethylene resins, pipes and pipe joints focusing on tie molecules are presented in Japanese Patent Application Laid-Open Nos. 09-286820, 11-228635, and 2003-064187. In addition, a tie molecule existence probability and a tie molecule formation probability, Japanese Patent Application Laid-Open No. 2000-109521, presents a polyethylene pipe that satisfies a relationship in which there is a component amount having a molecular weight of 100,000 or more by cross-fractionation and an elution temperature of 90 ° C. Table 2003-519496 discloses a multimodal polyethylene for producing a high molecular weight ethylene copolymer after a low molecular weight component ethylene homopolymer. Recently, polyethylene using 1-hexene as a comonomer, which is a bimodal polyethylene composed of a low molecular weight component and a high molecular weight component, has been proposed in Japanese Patent Publication Nos. 2003-504442 and 2003-53233. In all of the examples, after producing a low molecular weight ethylene homopolymer, a method for producing a high molecular weight ethylene / 1-hexene copolymer (referred to as reverse two-stage polymerization method) and a high molecular weight post-low molecular weight product are produced. It may be produced by a method (referred to as a sequential two-stage polymerization method).
In addition to the Ziegler catalyst, a polyethylene pipe comprising a high molecular weight component and a low molecular weight component in which the slope of the linear approximation of the temperature-molecular weight of cross fractionation is -0.5 to 0 using a metallocene catalyst is disclosed in It is presented in the 199719 publication.

In this invention, the method of manufacturing the polyethylene polymer of a polyethylene-type resin (B) component and the polyethylene polymer of a polyethylene-type resin (C) component by two-stage or more multistage polymerization is mentioned. As the catalyst, any of a Ziegler catalyst, a metallocene catalyst, and a Phillips catalyst may be used. In general, although a metallocene catalyst has a narrow composition distribution but a narrow molecular weight distribution, a Ziegler catalyst is preferably used. As an example of such a catalyst, there can be mentioned a catalyst described in JP-A No. 2003-105016.
By such a multistage polymerization method, a polymer having a desired wide molecular weight distribution can be easily produced. One of the most preferable methods for producing a polyethylene resin by multistage polymerization is as follows. In a polymerization apparatus in which two or more reactors are connected in series using a transition metal catalyst such as a Ziegler catalyst, in one or more reactors in the previous stage, A low-density, high-molecular weight polyethylene-based resin component (B) is added to a high-density, low-molecular-weight polyethylene-based resin component (C) in the subsequent reactor, or vice versa. The polyethylene resin component (C) is manufactured, and then it is manufactured by continuous suspension polymerization in the order of the low density, high molecular weight polyethylene resin component (B). The former is called forward multi-stage polymerization, and the latter is called reverse multi-stage polymerization, but reverse multi-stage polymerization requires equipment for purging unreacted hydrogen after the production of the polyethylene resin component (C). ) And the polyethylene resin component (C) are inferior in homogeneity, and the former sequential multistage polymerization is preferred.

The polymerization conditions in each reactor are not particularly limited as long as the desired components can be produced. Usually, the polymerization temperature is 50 to 110 ° C., and the residence time is 20 minutes to 6 hours. The pressure depends on the type of solvent used, but is 0.2 to 10 MPa.
In addition, in a polymerization apparatus in which two or three pipe loop reactors are connected in series, the polyethylene resin component (B) is converted into the polyethylene resin component (B) in the former one or two reactors, and the polyethylene resin component ( In the method of producing C) by continuous suspension polymerization, in the first and second stage reactors, the copolymerization of ethylene and α-olefin is carried out by weight ratio or fraction of hydrogen concentration to ethylene concentration. The polymerization reaction is carried out while adjusting the molecular weight according to the pressure ratio or the polymerization temperature or both, and while adjusting the density according to the weight ratio or partial pressure ratio of the α-olefin concentration to the ethylene concentration. Here, there are ethylene and hydrogen in the reaction mixture flowing from the reactor for producing the first-stage high molecular weight component, and α-olefin that also flows in, but the necessary ethylene and hydrogen are added for production.

The polymerization reaction mixture obtained by polymerization in the first stage reactor is transferred to the second stage reactor through a connecting pipe by differential pressure. For polymerization, any method such as a slurry polymerization method in which polymer particles are dispersed in a solvent, a solution polymerization method in which polymer particles are dissolved in a solvent, or a gas phase polymerization method in which polymer particles are dispersed in a gas phase can be applied. .
Examples of the hydrocarbon solvent used in the slurry polymerization method and the solution polymerization method include propane, n-butane, isobutane, n-pentane, isopentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, and xylene. Single or mixtures of activated hydrocarbons are used. In the case of slurry polymerization, propane, n-butane, and isobutane are preferable as the solvent in order to maintain the slurry state because the produced polyethylene polymer is hardly dissolved in the solvent even when the polymerization temperature is raised.
In polymerization using a solid Ziegler catalyst, hydrogen is usually used as a so-called chain transfer agent for adjusting the molecular weight. The hydrogen pressure is not particularly limited, but is usually 1.0 × 10 ^{−5 to} 1.0 × 10 ⁻¹ wt%, preferably 5.0 × 10 ^{−4 to} 5 as the hydrogen concentration in the liquid phase. 0.0 × 10 ⁻² wt%.

  In the production of the unmodified polyethylene resin (Y) of the present invention, as a method of mixing and producing each polymer, a blending method in which the degree of kneading is high is preferable, and a twin screw extruder, a single direction or a different direction, Examples thereof include a screw extruder, a Banbury mixer, a meshing or non-meshing continuous kneader, a Brabender kneader Brebender and the like.

When the unmodified polyethylene resin (Y) is produced by blending, in particular, as the component (B), a high load having a density of less than 0.910 to 0.940 g / cm ³ , a temperature of 190 ° C. and a load of 21.6 kg. A linear low density polyethylene resin (B ′) having a melt flow rate of 0.1 to 10 g / 10 min is used, and a density of 0.940 to 0.970 g / cm ³ as component (C), MFR (measurement temperature 190 ° C.) A method using a high density polyethylene resin (C ′) of 5 to 300 g / 10 min is preferable.

The linear low density polyethylene resin (B ′) is a linear low density polyethylene resin produced by ionic polymerization, and the density is less than 0.910 to 0.940 g / cm ³ , preferably the density is 0. It is desirable that the density is in the range of 915 to 0.935 g / cm ³ , more preferably 0.918 to 0.930 g / cm ³ . The high load melt flow rate (HL-MFR) is in the range of 0.05 to 10 g / 10 minutes, preferably 0.1 to 7 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes. . If the density is less than 0.910 g / cm ³ , the gasoline permeation resistance may decrease, and if it exceeds 0.940 g / cm ³ , the impact resistance and creep resistance may decrease. Further, when the high load melt flow rate (HL-MFR) is less than 0.05 g / 10 min, the moldability at the time of injection molding is extremely deteriorated, and when it exceeds 10 g / 10 min, the impact resistance and creep resistance are increased. There is a risk that

  The linear low-density polyethylene resin is a copolymer of ethylene and an α-olefin, and the α-olefin is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1- Examples include butene, 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, 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.

The linear low-density polyethylene resin (B ′) produced by ion polymerization is not particularly limited to the production catalyst, process, etc., but the book “Polyethylene Technology Reader” (written by Kazuo Matsuura and Naotaka Mikami, Kogyo) (Research Committee Publication, 2001) p. 123-160, p. It is possible to manufacture by the method described in 163-196 etc. 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.
In order to produce a linear low density polyethylene resin (B ′), it is preferable to use a specific Ziegler catalyst or a single site catalyst such as Japanese Patent Publication No. 55-14084 and Japanese Patent Publication No. 58-1708. It can be suitably produced by controlling polymerization conditions such as polymerization temperature and pressure, cocatalyst and the like.
A linear low-density polyethylene resin (B ′) is an olefin polymerization catalyst (generally a single-layer catalyst) containing an organoaluminum oxy compound and a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. In the case of a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a site-based catalyst, it is more preferable.

The high density polyethylene resin (C ′) has a density of 0.940 to 0.970 g / cm ³ , preferably a density of 0.945 to 0.965 g / cm ³ , and more preferably a density of 0.950 to 0.960 g / cm ³ . A range of cm ³ is desirable. The MFR is composed of an ethylene homopolymer or an ethylene / α-olefin copolymer in the range of 5 to 600 g / 10 minutes, preferably 7 to 500 g / 10 minutes, more preferably 10 to 300 g / 10 minutes. Includes high-density polyethylene resin.
If the density is less than 0.940 g / cm ³ , impact resistance and creep resistance may be lowered, and if the density exceeds 0.970 g / cm ³ , impact resistance is lowered.
Further, if the MFR is less than 5 g / 10 minutes, the moldability at the time of injection molding is extremely deteriorated, and if it exceeds 600 g / 10 minutes, impact resistance and creep resistance may be lowered.

The high-density polyethylene resin is composed of an ethylene homopolymer or an ethylene / α-olefin 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, 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.
The high-density polyethylene resin (C ′) produced by the above ion polymerization is not particularly limited to the production catalyst, process, etc., but the book “Polyethylene Technology Reader” (edited by Kazuo Matsuura and Naotaka Mikami, Industrial Research Committee) Publication, 2001) p. 123-160, p. It is possible to manufacture by the method described in 163-196 etc. 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.

In order to produce a high density polyethylene resin (C ′), the polymerization temperature is preferably determined using a specific Ziegler catalyst or a single site catalyst such as JP-B 55-14084 and JP-B 58-1708. It can be suitably produced by controlling polymerization conditions such as pressure, cocatalyst and the like.
The high-density polyethylene resin (C ′) is produced in the presence of an olefin polymerization catalyst containing an organoaluminumoxy compound and a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. And a copolymer obtained by copolymerizing a C3-20 α-olefin is further preferred.

(Vii) Other preferred unmodified polyethylene resin (Y)
Another preferred unmodified polyethylene resin (Y) of the present invention is an ethylene homopolymer or an ethylene / α-olefin copolymer, which is obtained by a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst. However, it is preferable to use a chromium-containing catalyst.

  The above-mentioned chromium-containing catalyst is preferably a supported catalyst essentially comprising a chromium compound, and the resulting composite composition is formed by supporting a chromium compound and a titanium compound and / or a fluorine compound on a dry inorganic oxide porous carrier. Is dried at a temperature of 100 to 300 ° C. in an inert gas or dry air, and then calcined at a temperature of 250 to 1,000 ° C. in a dry air or dry oxygen for about 6 hours to be activated. It will be used after.

Examples of the chromium compound include chromium oxide (CrO ₃ ), chromium acetylacetonate, dichromate nitrate, dichromate acetate, dichromium chloride, dichromate sulfate, and ammonium chromate.
Specific examples of the chromium-containing catalyst include chromium oxide, bis (cyclopentadienyl) chromium, and these magnesium-titanium composites. By using a chromium-containing catalyst, polyethylene having a broad molecular weight distribution and good injection moldability can be obtained as compared with titanium-based catalysts and metallocene-based catalysts.

  The inorganic oxide porous material carrier supported in the chromium-containing catalyst is desirably a carrier having an average particle diameter of 10 to 50 μm, and preferably an average particle diameter of 20 to 50 μm. Specifically, the average particle size is, for example, preferably in the range of 20-50 μm, 30-50 μm, and the carrier having a large particle size of 100 μm or more is less than 10%, less than 8-5%, Is preferably less than 10%, more preferably less than 10%, and particularly preferably less than 10% of the carrier having a large particle size of 80 μm or more. is there.

If the average particle size of the carrier is less than 10 μm, it is too fine as a carrier, so that it is not easy to handle and the polymerization stability may be impaired. When the average particle size exceeds 50 μm, there is a concern that the environmental stress crack resistance (ESCR property) and creep resistance when the polyethylene molded body is obtained are lowered.
The average particle size of the carrier is a value obtained by measuring the particle size distribution using a laser diffraction / scattering type particle size distribution measuring device and obtained by the arithmetic average diameter. As a measuring device, for example, LA-920 manufactured by Horiba, Ltd. The mold is preferable because of its excellent measurement accuracy.

The inorganic oxide porous body should have a specific surface area of 50 to 1,000 m ² / g, a pore diameter of 50 to 500 mm, and a pore volume of 0.5 to 3.0 cc / g. Is preferred.

Inorganic oxide porous materials include talc, silica, titania, alumina, magnesia, silica-titania, silica alumina, silica magnesia, silica chromia, silica chromia titania, silica titania alumina, tria, zirconia, silanized silica, aluminum phosphate Examples thereof include gels and other inorganic oxide porous bodies similar to these and mixtures of these carriers.
Particularly preferred are carriers formed from cogels and tergels, which are transition metal-containing carriers.
Examples of the transition metal-containing carrier include silica-titania (Si—Ti) cogel, Si—Zr cogel, Si—V cogel, AlPO ₄ —Ti cogel, silica-titania-chromium (Si—Ti—Cr) tagel, Si -Al-Ti tergel etc. are mentioned. Of the above-mentioned chromium-containing catalysts, silica-titania cogel-based catalysts and silica-titania-chromium (Si-Ti-Cr) tergel-based catalysts are preferred. Specific examples thereof include JP-A 61-031405 and JP-A 02- JP 160612, JP 11-071422, JP 11-106422, JP 11-506152, JP 2000-506152, JP 2001-515928, JP 2003-508593. No. publication, Japanese translations of PCT publication No. 2005-528512, etc. are mentioned.
Polyethylene resin having a melt flow rate ratio (HL-MFR / MFR) in the range of 40 to 270 by polymerization to a group under predetermined polymerization conditions by using a chromium-containing catalyst using a carrier containing the transition metal. Can be easily manufactured.

2. Modified polyethylene resin composition (Z)
The modified polyethylene resin composition (Z) of the present invention is composed of the above (X) component and (Y) component, and further contains another polyethylene resin (D) as necessary, and has the following properties (z-1 ) Density, (z-2) MFR, preferably further having properties (z-3) gasoline permeability, and (z-4) full notch tensile creep rupture time, used as welding material .

  The blending ratio of the modified polyethylene resin (X) and the unmodified polyethylene resin (Y) is 0.5 to 95% by weight of the modified polyethylene resin (X) and 5 to 99.unmodified polyethylene resin (Y). 5% by weight, preferably 0.5 to 50% by weight of the modified polyethylene resin (X) /99.5 to 50% by weight of the unmodified polyethylene resin (Y), more preferably the modified polyethylene resin (X) 0 0.5-30 wt% / unmodified polyethylene resin (Y) 99.5-70 wt%. If the modified polyethylene-based resin (X) is less than 0.5% by weight, there is a possibility that the adhesive strength with the barrier material may be insufficient, and if it exceeds 99.5% by weight, the creep resistance may be controlled. It becomes difficult and there is a high possibility that there is a problem in economic efficiency and practicality such as high cost.

Characteristic (z-1) Density The density measured based on JIS K6922-2 of the modified polyethylene resin composition (Z) of the present invention is 0.938 to 0.965 g / cm ³ , preferably 0.8. 939 to 0.962 g / cm ³ . When the density is less than 0.938 g / cm ³ , the fuel permeation resistance of the welded portion decreases. Further, it causes shear peeling and cracking at the interface with the barrier layer generated by dimensional change due to fuel swelling.

Characteristic (z-2) MFR
The MFR at a temperature of 190 ° C. and a load of 2.16 kg measured based on JIS K6922-2 of the modified polyethylene resin composition (Z) of the present invention is 0.05 to 1.0 g / 10 min, preferably Is 0.1 to 0.9 g / 10 min. When the MFR is less than 0.05 g / 10 min, the injection moldability when molding the welding material is deteriorated, and there is a possibility that poor welding to the fuel tank may occur. On the other hand, if it exceeds 1.0 g / 10 minutes, the impact resistance and creep resistance of the welding material are deteriorated, and there is a risk that poor welding to the fuel tank may occur.

Characteristic (z-3) Gasoline Permeability The gasoline permeability of a 1 mm thick sheet measured at 65 ° C. of the welding material of the present invention is preferably 50 mg / (cm ² · 24 hr) or less, more preferably 40 mg / (cm ² · 24 hr) or less, more preferably 30 mg / (cm ² · 24 hr) or less. When the gasoline permeability exceeds 50 mg / (cm ² · 24 hr), it remains within the range of the conventional technical level.
Here, the gasoline permeability is a value measured according to JIS Z0208 “Moisture permeability test method for moisture-proof packaging material (cup method)”. Specifically, it calculates | requires as follows.
A stainless steel cup with a diameter of 80 mm, a depth of 40 mm, and a thickness of 1 mm filled with 50 ml of commercially available gasoline (ENEOS regular gasoline made by Nippon Oil Corporation), and a stainless steel lid with a circular hole with a diameter of 60 mm, A 1 mm sheet of welding material is sandwiched between them. At this time, a 0.5 mm thick Teflon (registered trademark) packing is sandwiched and fixed between the stainless steel container and the welding material sheet. Next, the weight (W ₀ ) (mg) in this state is measured. Then, it is left in an oven at 65 ° C. for 24 hours, and the weight (W) (mg) is measured. The weight permeation amount, that is, gasoline permeation rate ( _TG ) (mg / (cm ² · 24 hr)) is defined by the following equation.
T _G = (W ₀ −W) /28.3

The gasoline permeability (T _G ) (mg / (cm ² · 24 hr)) can be improved by increasing the density of the resin constituting the welding material, but if the density is too high, the all-around notch creep since breaking time there is a fear to decrease the density in order to adjust them good balance is in the range of 0.938~0.965g / cm ^3, preferably 0.939~0.960g / cm ^3, further Preferably, it is selected within the range of 0.940 to 0.955 g / cm ³ .

Characteristic (z-4) All-around notch tensile creep rupture time The all-notch tensile creep rupture time at 5.5 MPa measured at 80 ° C. of the welding material of the present invention is preferably 50 hours or more, more preferably 60 hours. More preferably, it is 65 hours or more. If the all-around notch tensile creep rupture time at 5.5 MPa measured at 80 ° C. is less than 50 hours, the weld material is likely to creep rupture due to the stress caused by the increase in the internal pressure of the fuel tank, and fuel leaks from there. Extremely dangerous.

Here, the measurement of the all-around notch creep rupture time is a value measured in accordance with JIS K6774 “Polyethylene pipe for gas, Annex 5, All-around notch type tensile creep”. Specifically, it calculates | requires as follows.
A sheet having a thickness of 10 mm is produced by a 230 ° C. pressing method. From this sheet, a 6 mm × 6 mm × 60 mm square column is cut out, and a razor blade notch having a depth of 1 mm is put in the entire circumference of the center of the test piece using a notching jig. Next, after conditioning this test piece at 80 ° C. for 1 hour, a tensile creep test is performed with a load of 9 kg, and the time required until the test piece is completely broken is defined as a creep rupture time.

In addition to the above components (X) and (Y), the welding material of the present invention may contain other polyethylene-based materials for the purpose of improving MFR and density or gasoline permeability and / or creep rupture time as required. Resin (D) can be mix | blended.
The polyethylene resin (D) is a high-density polyethylene resin, linear low-density polyethylene resin or linear chain produced with a Ziegler-based catalyst, a Philips-based catalyst, a single-site-based catalyst or the like used as a raw material resin for the modified polyethylene. An ethylene (co) polymer such as a low-density polyethylene resin or a low-density polyethylene produced by radical polymerization can be used.
In particular, a polyethylene resin (a high density polyethylene resin, a linear low density polyethylene resin, or a linear ultra-low density polyethylene resin) using a single site catalyst is preferable.
The polyethylene resin based on the single site catalyst has a density of 0.900 to 0.965 g / cm ³ , preferably 0.911 to 0.940 g / cm ³ , more preferably 0.912 to 0.940 g / cm ^3. Measured based on JIS K6922-2, MFR at a temperature of 190 ° C. and a load of 2.16 kg is 0.01 to 5.0 g / 10 minutes, preferably 0, 05 to 4.0 g / 10 minutes, What is preferably 0.1 to 3.0 g / 10 min is preferable.

  The amount of component (D) is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 70 parts by weight or less with respect to 100 parts by weight of the total of component (X) and component (Y). It is. Within the above range, the density, MFR and the like can be easily adjusted within the scope of the present invention without impairing various physical properties.

  Furthermore, the welding material of the present invention is a welding material for welding to a fuel tank, and contains the modified polyethylene resin composition (Z) as an essential component, but does not impair the spirit of the present invention. The modified polyethylene-based resin composition may include engineering plastic, metal, or a mixture of these materials or inorganic fillers as other components.

  The engineering plastics include various polyamide (PA) resins such as nylon 6, nylon 6,6, nylon 11 and nylon 12, various hydroxyl group-containing resins such as ethylene-vinyl alcohol copolymer (EVOH) and polyvinyl alcohol (PVA). , Various polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin (AS), polycarbonate (PC), polyacetal ( POM), polyphenylene ether (PPE), polyphenylene sulfide (PPS) and the like.

  Examples of the metal include metals such as iron, aluminum, copper, tin, zinc, nickel, and titanium, and various alloys including these metals.

  Examples of the inorganic filler include talc, silica, calcium carbonate, and mica. Among them, fine powder talc and fine powder mica having a plate crystal structure with an average particle size of 0.5 to 10 μm are preferable. .

  Furthermore, various other thermoplastic resins and additives can be appropriately blended with the modified polyethylene resin composition (Z) of the present invention without departing from the object of the present 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. However, since metal soaps such as calcium stearate and zinc stearate have a concern that the adhesive strength with the barrier material is lowered, it is desirable to avoid blending these additives as much as possible.

[II] Use of welding material The welding material of the present invention maintains the welding strength even after contacting with fuel such as gasoline by satisfying the above characteristics, and is good even when used for a long time in a high temperature atmosphere. In addition to maintaining high fuel permeation prevention performance, it also has excellent creep rupture resistance and stress cracking resistance, suppressing fuel diffusion from the welded portion with the fuel tank body and improving long-term life performance. An excellent fuel tank can be provided.

The welding material of the present invention is a material that is welded by a vibration welding method, a heater heating method, an ultrasonic heating method, or the like by bringing a film, sheet, plate or the like made of the welding material into contact with the contact surface of the fuel tank.
In particular, the welding material of the present invention is a high-density polyethylene fuel tank, or a resin fuel tank composed of a multi-layer laminated structure including an adhesive layer and a barrier material layer as a main layer of high-density polyethylene described later. A remarkable effect is exhibited for a resin fuel tank whose surface is formed of at least high density polyethylene.

  In another aspect of the welding material of the present invention, when the fuel tank and the fuel tank accessory are welded, the fuel tank accessory is provided on the contact surface of the fuel tank via a film, sheet, or the like of the welding material. Are used by welding.

In another aspect of the welding material of the present invention, the welding material is a welding material constituting a part attached to the fuel tank, and the welding material constitutes all or part of the accessory part. is there.
That is, only the modified polyethylene resin composition of the present invention is used to manufacture a welding material that constitutes a part attached to a joint or the like, and the contact between the welding material that constitutes a part attached to a fuel tank such as the joint and the fuel tank It welds by welding a part.
Further, it is a welding material in which at least a contact portion of the joint with the fuel tank is made of a modified polyethylene resin composition.

Here, the parts attached to the fuel tank in the present invention are joints and the like welded to the fuel tank, specifically, inlets, various valves, fuel hoses, oil supply pipes connected to the fuel supply ports, and engines. Examples include connected supply pipes, canister connection nozzles, connectors, and separators.
As materials suitably used for these accessory parts, high density polyethylene, the welding material of the present invention, polyolefin resin such as polypropylene, various polyamides (PA) such as nylon 6, nylon 6,6, nylon 11 and nylon 12 are used. Resin, various hydroxyl group-containing resins such as ethylene-vinyl alcohol copolymer (EVOH) and polyvinyl alcohol (PVA), various polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylonitrile-butadiene-styrene Engineering products such as copolymer resin (ABS), acrylonitrile-styrene copolymer resin (AS), polycarbonate (PC), polyacetal (POM), polyphenylene ether (PPE), polyphenylene sulfide (PPS), etc. Stick, fiber-reinforced plastic composite materials, aluminum, iron, metals such as copper, and mixtures thereof, layered structure include composite materials.

Furthermore, another preferred embodiment of the welding material of the present invention is a welding material constituting an accessory part of a fuel tank having a laminated structure of at least two layers of the layer made of the welding material and the layer of the barrier material.
For example, welding material layer / barrier material layer, welding material layer / barrier material layer / welding material layer, welding material layer / barrier material layer / welding material / barrier material layer, / barrier material layer / welding material, Or the welding material which comprises the components attached to the fuel tank made into the laminated structure of inserting a dissimilar material between these layers is mentioned.
More specifically, [welding material layer / PA layer], [welding material layer / EVOH layer], [welding material layer / POM layer], [welding material layer / PA layer / welding material layer], welding material layer / EVOH layer / welding material layer], [welding material layer / PA layer / welding material layer / PA layer], [welding material layer / PA layer / welding material layer / PA layer / welding material layer], etc. PA: polyamide resin, EVOH: ethylene-vinyl acetate copolymer saponified product, POM: polyacetal resin).
The welding material composed of these laminated structures is arranged and welded so that the fuel tank and the welding material layer are in contact with each other.
Moreover, the welding material which consists of these laminated structures can be manufactured with shaping | molding methods, such as injection molding, such as two-color molding, and profile extrusion molding.

[III] Fuel Tank The fuel tank of the present invention is formed by welding the welding material to a fuel tank.
The fuel tank includes a conventional metal tank and a resin tank for the purpose of reducing the weight, but the welding material of the present invention has a good adhesion to both.
In particular, in resin tanks, the same kind of resin components as the resin tank body and the welding material are selected to exert a strong adhesive force, so gasoline permeability resistance, creep rupture resistance, and stress cracking resistance Etc. are improved in the same manner, and it has a feature that it can provide a comprehensively superior product. The resin fuel tank is mainly molded by blow molding, injection molding or the like.

The fuel tank of the present invention is preferably a resin fuel tank made of a high-density polyethylene or the like as a surface layer, and more preferably a multilayer laminated structure including a main material layer of high-density polyethylene and including an adhesive layer and a barrier material layer. It is the resin fuel tank comprised by these. A recycled material layer can be used for the resin fuel tank as desired.
Furthermore, the preferred specific resin fuel tank layer structure of the present invention has a three-layer structure of thermoplastic resin layer / adhesive layer / barrier layer such as high-density polyethylene, thermoplastic resin layer / adhesive layer / barrier layer. / Adhesive layer / thermoplastic resin layer 3 type 5 layer structure, thermoplastic resin layer / regrind layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer 4 type 6 layer structure 3 layers or more In addition, it can be used as a laminate comprising two types / two layers of an adhesive layer / barrier layer and two types / three layers of an adhesive layer / barrier layer / adhesive layer. The present invention can be applied not only to the fuel tank by the method but also to a bonded fuel tank made of tank shell parts manufactured by an injection molding method or a sheet molding method.

  Examples of the material preferably used for the barrier material layer include various polyamide (PA) resins such as nylon 6, nylon 6, 6, nylon 11, and nylon 12, ethylene-vinyl alcohol copolymer (EVOH), and polyvinyl. Various hydroxyl group-containing resins such as alcohol (PVA), various polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin ( AS, polycarbonate (PC), polyacetal (POM), polyphenylene ether (PPE), engineering plastics such as polyphenylene sulfide (PPS), and metal foils such as aluminum.

  The adhesive layer may be a conventional modified polyethylene resin modified with an unsaturated carboxylic acid such as maleic anhydride, or the modified polyethylene resin composition of the present invention.

Specific examples of the welding method with these fuel tanks include two-color molding, vibration welding method, die slide injection (DSI), die rotary injection (DRI) injection welding method, ultrasonic welding method, spin welding method, hot plate Examples include a welding method, a hot wire welding method, a laser welding method, and a high-frequency induction heating welding method.
The molding resin temperature at the time of welding by an injection welding method such as two-color molding, DSI, or SRI is 250 to 320 ° C, preferably 270 to 300 ° C. The mold temperature at that time is 30 to 120 ° C., preferably 50 to 100 ° C., and these are molded by a conventional method.

The fuel tank of the present invention is a fuel tank in which a welding material is welded to the fuel tank, and the other fuel tank is formed by welding the fuel tank and its accessory parts via the welding material of the present invention. This is a fuel tank.
Specifically, a welding material film, sheet, welding rod or the like is interposed on the contact surface between the fuel tank and its accessory parts, and welding is performed by a vibration welding method, a heater heating method, an ultrasonic heating method, or the like. is there.
The other fuel tank is a fuel tank formed by welding an accessory part containing the welding material of the present invention as a constituent material through a constituent material made of the welding material by the welding method.
Further, another fuel tank includes an attachment part including a laminated structure composed of at least two layers of a welding material layer of the present invention and a barrier material layer as a constituent material via a welding material layer composed of the welding material. A fuel tank or the like formed by welding.

The present invention will be described using examples, but the present invention is not limited to these examples.
The test methods and resin materials used in the examples are as follows.

1. Test method (1) Melt flow rate (MFR): Measured in accordance with condition D (temperature 190 ° C., load 2.16 kg) of JIS K6922-1 (1997).
(2) High load melt flow rate (HL-MFR): Measured in accordance with condition G (temperature 190 ° C., load 21.6 kg) of JIS K6922-1 (1997).
(3) Density: Measured according to JIS K6922-1 (1997).
(4) Gasoline permeability: Measured according to JIS Z0280. In measuring the gasoline permeability, a 1 mm sheet of adhesive material was prepared as follows. Using a T-die sheet molding machine manufactured by Create Plastic Co., Ltd., which combines a 50 mm single-screw extruder and a T die with a width of 200 mm and a lip of 1.5 mm, a resin temperature of 230 ° C., a chill roll temperature of 40 ° C., and a take-off speed of 0.7 m / min. Under the conditions, a sheet having a width of 180 mm and a thickness of 1 mm was produced. A circular test piece having a diameter of 80 mm was cut out from the adhesive material sheet, and the gasoline permeability at 65 ° C. was measured.
(5) All-around notch creep rupture time: Measured according to JIS K6774 Annex 5. Specifically, a 10 mm thick sheet of a modified polyethylene resin composition was produced by a 230 ° C. pressing method, and a 6 mm × 6 mm × 60 mm square column was cut out from this sheet, and a notched jig made by Create Plastic Co., Ltd. Using a (jig), a razor blade notch with a depth of 1 mm was put on the entire circumference of the center of the test piece to obtain a test piece. Next, this test piece was set in a lander method stress cracking tester manufactured by Orientec Co., Ltd., conditioned for 1 hour at 80 ° C., then a tensile creep test was performed with a 9 kg load, and the time until the test piece completely fractured was measured. Measured.
(6) Adhesive strength: Modern Machinery Co., Ltd., multilayer hollow molding machine, cylindrical shape of 3 types and 5 layers at a molding temperature of 200 ° C., blow pressure of 0.6 MPa, mold temperature of 20 ° C., cooling time of 120 sec. A hollow container (60 mmφ × 180 mm) was manufactured. The layer structure of the container is as follows: 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 _2.16 ) is 149) / welding material layer / nylon (Toray Industries, Inc. Amilan CM6246M) / welding material layer / high density polyethylene resin layer (Novatec HD HB111R, manufactured by Nippon Polyethylene Co., Ltd.), and the layer thickness is 1. It is 8 mm / 0.12 mm / 0.2 mm / 0.12 mm / 1.8 mm.
After that, a test piece was cut out in a strip shape with a width of 6 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 above blow molding, and the test piece was measured from the outer layer side of the test piece. The adhesive strength between the two layers (welding material) / the third layer (nylon) was measured. The measurement of the adhesive strength was performed by making a notch in the middle between the second layer and the third layer from the outer layer side of the test piece, and using a Tensilon UTM-III-500 manufactured by Toyo Baldwin Co., Ltd. at a tensile rate of 50 mm / min and 90 °. It was performed by the method of peeling.

2. Resin material (1) Modified polyethylene resin (X)
Modified polyethylenes (X-1) to (X-6) obtained in the following Production Examples 1 to 6 were used. The production conditions and properties of (X-1) to (X-6) are shown in Table 1.

(Production Example 1)
(I) Production of polyethylene resin (A1) 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 In addition, 100 g of tripropylaluminum was dropped over 100 minutes while maintaining at 90 ° C., 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 baked 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.
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 2 MPa. The solid catalyst is continuously supplied, and ethylene, 1-hexene and hydrogen are supplied so as to maintain a predetermined molar ratio to perform polymerization, and MFR = 3.2 g / 10 min, density 0.932 g / cm ³ powder A single site polyethylene resin (A1) was obtained.

(Ii) Production of Modified Polyethylene Resin (X-1) 100 parts by weight of the above powdered polyethylene resin (A1), 0.6 parts by weight of maleic anhydride and 2,5-dimethyl-di- (t-butylper After adding 0.02 part by weight of oxy) hexane and mixing with a Henschel mixer, using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd., melt kneading under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C., A single-site modified polyethylene resin (X-1) having an MFR of 2.1 g / 10 min, a density of 0.932 g / cm ³ , and a grafting rate of 0.42% by weight was obtained.

(Production Example 2)
(I) Production of polyethylene resin (A2) In accordance with the description in Example 1 of JP-B-55-14084, a Ziegler catalyst is used and slurry feed polymerization is used to adjust the feed amounts of comonomer and hydrogen to produce ethylene and butene. -1 was copolymerized to obtain a powdery high-density polyethylene resin (A2) having an MFR of 0.8 g / 10 min and a density of 0.950 g / cm ³ .
(Ii) Production of modified polyethylene resin (X-2) To 100 parts by weight of the above powdery high-density polyethylene resin (A2), 0.8 part by weight of maleic anhydride and 2,5-dimethyl-di- (t- After adding 0.02 part by weight of butylperoxy) hexane and mixing with a Henschel mixer, melt kneading using a modern machinery 50 mm single screw extruder under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. Thus, a modified polyethylene resin (X-2) having an MFR of 0.15 g / 10 min, a density of 0.950 g / cm ³ , and a grafting rate of 0.55 wt% was obtained.

(Production Example 3)
(I) Production of polyethylene resin (A3) Based on the description in Example 5 of JP-A-10-29824, ethylene and butene-1 were copolymerized by slurry polymerization using a Ziegler catalyst, and MFR = 2.2 g. / 10 min, a powdery linear low-density polyethylene resin (A3) having a density of 0.935 g / cm ³ was obtained.
(Ii) Production of Modified Polyethylene Resin (X-3) 100 parts by weight of the powdered linear low density polyethylene resin (A3), 0.8 parts by weight of maleic anhydride and 2,5-dimethyl-di- After adding 0.02 part 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. And kneaded to obtain a modified polyethylene resin (X-3) having an MFR of 0.50 g / 10 min, a density of 0.935 g / cm ³ , and a grafting rate of 0.55 wt%.

(Production Example 4)
(I) Production of polyethylene resin (A4) Based on the description in Example 5 of JP-A-10-29824, ethylene and butene-1 were copolymerized by slurry polymerization using a Ziegler catalyst, and MFR = 0.05 g. / 10 min, a powdery linear low-density polyethylene resin (A4) having a density of 0.923 g / cm ³ was obtained.
(Ii) Production of Modified Polyethylene Resin (X-4) 100 parts by weight of the above powdered linear low density polyethylene resin (A4), 0.6 parts by weight of maleic anhydride and 2,5-dimethyl-di- After adding 0.02 part 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. And kneaded to obtain a modified polyethylene resin (X-4) having an MFR of 0.01 g / 10 min, a density of 0.923 g / cm ³ , and a grafting rate of 0.42 wt%.

(Production Example 5)
(I) Production of polyethylene resin (A5) According to the description in Example 5 of JP-A-10-29824, ethylene and butene-1 were copolymerized by slurry polymerization using a Ziegler catalyst, and MFR = 9.0 g. / 10 min, a powdery linear low-density polyethylene resin (A5) having a density of 0.925 g / cm ³ was obtained.
(Ii) Production of Modified Polyethylene Resin (X-5) 100 parts by weight of the above powdered linear low density polyethylene resin (A5), 0.8 parts by weight of maleic anhydride and 2,5-dimethyl-di- After adding 0.02 part 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., conditions of screw rotation speed 50 rpm and resin temperature 280 ° C. And kneaded to obtain a modified polyethylene resin (X-5) having an MFR of 4.0 g / 10 min, a density of 0.925 g / cm ³ , and a grafting rate of 0.56 wt%.

(Production Example 6)
(I) Production of polyethylene resin (A6) Based on the description in Example 5 of JP-A-10-29824, ethylene and butene-1 were copolymerized by slurry polymerization using a Ziegler catalyst, and MFR = 2.0 g. / 10 min, a powdery linear low-density polyethylene resin (A6) having a density of 0.905 g / cm ³ was obtained.
(Ii) Production of Modified Polyethylene Resin (X-6) 100 parts by weight of the above powdered linear low density polyethylene resin (A6), 0.8 parts by weight of maleic anhydride and 2,5-dimethyl-di- After adding 0.02 part 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. To obtain a modified polyethylene resin (X-6) having an MFR of 0.88 g / 10 min, a density of 0.905 g / cm ³ , and a grafting rate of 0.57% by weight.

(2) Unmodified polyethylene resins (Y1) and (Y2)
(Y1-1) to (Y1-12) obtained in the following Production Examples 7 to 18 and (Y2-1) to (Y2-4) obtained in the following Production Examples 19 to 22 were used.

(Production Example 7)
Using a Ziegler catalyst described in Example 1 of JP-A-58-1708 and a two-stage polymerization process of a double-loop pipe reactor type slurry, a catalyst having an internal volume of 200 liters is used as a first stage reactor. A solid catalyst component and a predetermined amount of triethylaluminum (TEA) are continuously supplied from an organometallic compound supply line from a supply line, and a polymerization solvent (n-hexane), ethylene and hydrogen are supplied at a predetermined temperature at 90 ° C. The first-stage copolymerization was carried out continuously at a rate (production of polyethylene resin (C1) component). Next, a part of the polymerization product in the first-stage reactor was collected, and the physical properties of the polymerization product were measured and the results are shown in Table 2. The entire amount of the slurry polymerization product produced in the first stage reactor was introduced into the second stage reactor having an internal volume of 400 liters, and the polymerization was conducted at 70 ° C. while discharging the contents of the polymerizer at the required rate. A solvent (n-hexane), ethylene, 1-butene and hydrogen are supplied, and second-stage polymerization (polymerization of polyethylene resin (B1) component) is continuously performed, and finally an unmodified polyethylene resin (Y1-1). )
The value of (B1) component was calculated | required by the calculation based on an addition rule from the physical property of unmodified | denatured polyethylene-type resin (Y1-1), and the physical property of (C1) component obtained by the 1st stage reactor. Table 2 shows the physical property values of each component.

(Production Example 8)
(1) Production of linear low-density polyethylene resin (B1 ′) In accordance with the description in Example 1 of JP-A-58-1708, hydrogen and comonomer concentrations are prepared by slurry polymerization using a Ziegler catalyst. Then, ethylene and butene-1 were copolymerized to obtain a linear low density polyethylene resin (B1 ′) having an HL-MFR of 2.2 g / 10 min and a density of 0.927 g / cm ³ .

(2) Manufacture of high-density polyethylene resin (C1 ′) (i) Manufacture of catalyst As a solid catalyst component, a Ti-based catalyst by a dissolution precipitation method was used. The manufacturing method is as follows.
The inside of a 1 liter three-necked flask equipped with a stirrer and a condenser was sufficiently purged with nitrogen, and then dried hexane 250 ml, anhydrous magnesium chloride 11.4 g previously pulverized in a 3 liter vibration mill for 1 hour and n -110 ml of butanol was added and heated at 68 ° C for 2 hours to obtain a uniform solution (1a). After the solution (1a) was cooled to room temperature, 8 g of methylpolysiloxane having a kinematic viscosity at 25 ° C. of 25 cSt (centistokes) was added and stirred for 1 hour to obtain a uniform solution (1b). After the solution (1b) was cooled with water, 50 ml of titanium tetrachloride and 50 ml of dry hexane were dropped into the solution using an addition funnel over 1 hour to obtain a solution (1c). The solution (1c) was uniform, and the complex of the reaction product was not precipitated. The solution (1c) was heated at 68 ° C. for 2 hours while refluxing. About 30 minutes after the start of heating, precipitation of the reaction product complex (1d) was observed. This was collected, washed 6 times with 250 ml of dry hexane, and further dried with nitrogen gas to recover 19 g of the reaction product complex (1d). When the reaction product complex (1d) was analyzed, it contained 14.5% by weight of Mg, 44.9% by weight of n-butanol and 0.3% by weight of Ti, and the specific surface area was 17 m ² / g. 4.5 g of the reaction product complex (1d) was collected in a 1-liter three-necked flask equipped with a stirrer and a condenser under a nitrogen atmosphere, and 250 ml of dry hexane and 25 ml of titanium tetrachloride were added to this and refluxed. After heat treatment at 68 ° C. for 2 hours and cooling to room temperature, it was washed 6 times with 250 ml of dry hexane and dried with nitrogen gas to recover 4.6 g of the solid catalyst component (1e). When this solid catalyst component (1e) was analyzed, it contained 12.5% by weight of Mg, 17.0% by weight of n-butanol and 9.0% by weight of Ti, and the specific surface area was 29 m ² / g. When this solid catalyst component (1e) was observed with an SEM, the particle size was uniform and a shape close to a sphere.
(Ii) Production of polymer A polymerization vessel having an internal volume of 200 liters as a reactor, a solid catalyst component (1e) obtained by production of the catalyst from the catalyst supply line, and triethylaluminum (TEA) as an organometallic compound supply line The polymerization solvent (n-hexane), a predetermined amount of ethylene, 1-butene and hydrogen are supplied at 80 ° C. while continuously supplying the polymerization content at a required rate from Polymerization was continuously carried out under conditions of a total pressure of 1.1 MPa to obtain a polymer (C1 ′). The physical properties of the polymer (C1 ′) are as follows.
Density: 0.963 g / cm ³ , MFR: 100 g / 10 min

(3) Production of unmodified polyethylene resin (Y1-2) 50% by weight of the above-mentioned linear low density polyethylene resin (B1 ′) and 50% by weight of high density polyethylene resin (C1 ′) were blended to obtain a melt flow rate. An unmodified polyethylene resin (Y1-2) having a ratio of 103 was obtained. The results are shown in Table 3.

(Production Example 9)
(1) In accordance with the description in Example 1 of JP-B-2-35766, the feed amount of comonomer and hydrogen is adjusted by slurry polymerization using a Ziegler catalyst, and ethylene and butene-1 are copolymerized. A linear low-density polyethylene resin (B2 ′) having HL-MFR = 0.23 g / 10 min and a density of 0.927 g / cm ³ was produced.
(2) On the other hand, the high-density polyethylene resin (C2 ′) is adjusted with the comonomer and hydrogen feed amount in accordance with the production of the high-density polyethylene resin (C1 ′) of Production Example 8 above, Butene-1 was copolymerized to obtain a high-density polyethylene resin (C2 ′) having MFR = 280 g / 10 min and density of 0.964 g / cm ³ .
(3) Production of unmodified polyethylene resin (Y1-3) 48 wt% of the above-mentioned linear low density polyethylene resin (B2 ′) and 52 wt% of high density polyethylene resin (C2 ′) were blended to obtain a melt flow rate. An unmodified polyethylene resin (Y1-3) having a ratio of 250 was obtained. The results are shown in Table 4.

(Production Example 10)
(1) Production of Unmodified Polyethylene Resin (Y1-4) Feeding of comonomer and hydrogen by slurry two-stage polymerization using a Ziegler catalyst in accordance with the description in Example 1 of JP-A-54-7488 The amount is adjusted, ethylene and butene-1 are copolymerized, and a low-density polyethylene resin component (B2) 30 having HL-MFR = 0.15 g / 10 min and density of 0.915 g / cm ^{3 in} a first-stage reactor. In the second stage reactor, 70% by weight of the second resin component (C2) having a high density of MFR = 100 g / 10 min and a density of 0.943 g / cm ³ was produced, and an unmodified polyethylene resin (Y1-4) It was. The melt flow rate ratio of this unmodified polyethylene resin (Y1-4) was 100. The value of the component (C2) was determined by calculation based on the addition rule from the physical properties of the unmodified polyethylene resin (Y1-4) and the physical properties of the component (B2) obtained in the first-stage reactor. Table 5 shows the physical property values of each component.

(Production Example 11)
(1) In accordance with the description in Example 1 of JP-B-2-35766, ethylene and butene-1 are copolymerized by slurry polymerization using a Ziegler catalyst, and HL-MFR = 2.2 g / 10 min, density 0 935 g / cm ³ of a linear low density polyethylene resin (B3 ′) was obtained.
(2) On the other hand, the high density polyethylene resin (C3 ′) is obtained by copolymerizing ethylene and butene-1 by slurry polymerization based on the production of the high density polyethylene resin (C1 ′) of Production Example 8 above. = 100 g / 10 min. A high density polyethylene resin (C3 ′) having a density of 0.967 g / cm ³ was obtained.
(3) Production of unmodified polyethylene resin (Y1-5) 50% by weight of the above-mentioned linear low density polyethylene resin (B3 ′) and 50% by weight of high density polyethylene resin (C3 ′) are mixed to give an unmodified polyethylene system. Resin (Y1-5) was produced. The melt flow rate ratio of the unmodified polyethylene resin (Y1-5) was 105. The results are shown in Table 6.

(Production Example 12)
(1) In accordance with the description in Example 1 of JP-A No. 58-1708, ethylene and butene-1 are copolymerized by slurry polymerization using a Ziegler catalyst, and HL-MFR = 30 g / 10 min, density 0. 930 g / cm ³ of powdery linear low density polyethylene resin (B4 ′) was obtained.
(2) On the other hand, in accordance with the description in Example 1 of JP-A-58-1708, ethylene was homopolymerized by slurry polymerization using a Ziegler catalyst, and MFR = 5.0 g / 10 min, density 0.961 g / A powdery high density polyethylene resin (C4 ′) of cm ³ was obtained.
(3) Production of unmodified polyethylene resin (Y1-6) 50% by weight of the above powdered linear low density polyethylene resin (B4 ′) and 50% by weight of the powdered high density polyethylene resin (C4 ′) are mixed. An unmodified polyethylene resin (Y1-6) was obtained. The melt flow rate ratio of this unmodified polyethylene resin (Y1-6) was 47. The results are shown in Table 7.

(Production Example 13)
(1) Based on the description in Example 1 of JP-A-58-1708, ethylene and butene-1 were copolymerized by slurry polymerization using a Ziegler catalyst, and HL-MFR = 0.27 g / 10 min, density 0.929 g / cm ³ of powdery linear low density polyethylene resin (B5 ′) was obtained.
(2) On the other hand, in accordance with the description in Example 1 of JP-A-58-1708, ethylene and butene-1 were copolymerized by slurry polymerization using a Ziegler catalyst, and MFR = 320 g / 10 min, density 0. A powdery high-density polyethylene resin (C5 ′) of 963 g / cm ³ was obtained.
(3) Production of unmodified polyethylene resin (Y1-7) Mixing 46% by weight of the above powdered linear low density polyethylene resin (B5 ′) and 54% by weight of powdered high density polyethylene resin (C5 ′) An unmodified polyethylene resin (Y1-7) was obtained. The melt flow rate ratio of this unmodified polyethylene resin (Y1-7) was 290. The results are shown in Table 8.

(Production Example 14)
(1) In accordance with the description in Example 1 of JP-B-2-35766, the feed amount of comonomer and hydrogen is adjusted by slurry polymerization using a Ziegler catalyst, and ethylene and butene-1 are copolymerized. A linear low-density polyethylene resin (B6 ′) having HL-MFR = 0.22 g / 10 min and a density of 0.927 g / cm ³ was produced.
(2) On the other hand, the high-density polyethylene resin (C6 ′) is adjusted with the comonomer and hydrogen feed amount in accordance with the production of the high-density polyethylene resin (C1 ′) of Production Example 8 above, and is mixed with ethylene by slurry polymerization. Butene-1 was copolymerized to obtain a high density polyethylene resin (C6 ′) having MFR = 180 g / 10 min and density of 0.968 g / cm ³ .
(3) Production of unmodified polyethylene resin (Y1-8) 47% by weight of the above-mentioned linear low density polyethylene resin (B6 ′) and 53% by weight of high density polyethylene resin (C6 ′) were blended to obtain a melt flow rate. An unmodified polyethylene resin (Y1-8) having a ratio of 250 was obtained. The results are shown in Table 9.

(Production Example 15)
(1) In accordance with the description in Example 1 of JP-B-2-35766, the feed amount of comonomer and hydrogen is adjusted by slurry polymerization using a Ziegler catalyst, and ethylene and butene-1 are copolymerized. A linear low-density polyethylene resin (C7 ′) having an MFR = 16 g / 10 min and a density of 0.922 g / cm ³ was produced.
(2) Production of unmodified polyethylene resin (Y1-9) 50% by weight of the linear low density polyethylene resin (B1 ′) and 50% by weight of the linear low density polyethylene resin (C7 ′) were blended. An unmodified polyethylene resin (Y1-9) having a melt flow rate ratio of 85 was obtained. The results are shown in Table 10.

(Production Example 16)
(1) Production of unmodified polyethylene resin (Y1-10) 20% by weight of the above-mentioned linear low density polyethylene resin (B2 ′) and 80% by weight of high density polyethylene (C2 ′) are mixed to obtain an unmodified polyethylene resin. (Y1-10) was produced. The melt flow rate ratio of the unmodified polyethylene resin (Y1-10) was 95. The results are shown in Table 11.

(Production Example 17)
(1) Production of Unmodified Polyethylene Resin (Y1-11) 70% by weight of the above linear low density polyethylene resin (B1 ′) and 30% by weight of high density polyethylene (C1 ′) are mixed to obtain an unmodified polyethylene resin. (Y1-11) was produced. The melt flow rate ratio of the unmodified polyethylene resin (Y1-11) was 79. The results are shown in Table 12.

(Production Example 18)
(1) In accordance with the description in Example 1 of JP-B-2-35766, the feed amount of comonomer and hydrogen is adjusted by slurry polymerization using a Ziegler catalyst, and ethylene and butene-1 are copolymerized. A linear low-density polyethylene resin (B7 ′) having HL-MFR = 0.27 g / 10 min and a density of 0.929 g / cm ³ was produced.
(2) On the other hand, the high-density polyethylene resin (C8 ′) is prepared by adjusting the feed amount of comonomer and hydrogen in accordance with the production of the high-density polyethylene resin (C1 ′) of Production Example 8 above, and by ethylene by slurry polymerization. Butene-1 was copolymerized to obtain a high density polyethylene resin (C8 ′) having an MFR = 700 g / 10 min and a density of 0.967 g / cm ³ .
(3) Production of unmodified polyethylene resin (Y1-12) 52% by weight of the above-mentioned linear low-density polyethylene resin (B7 ′) and 48% by weight of high-density polyethylene (C8 ′) are mixed to produce an unmodified polyethylene-based resin. Resin (Y1-12) was manufactured. The melt flow rate ratio of the unmodified polyethylene resin (Y1-12) was 188. The results are shown in Table 13.

(Production Example 19)
(I) Preparation of Solid Catalyst A commercially available silica-supported chromium oxide catalyst (Grace, Inc., 969ID) was transferred to a firing tube at room temperature, dried under nitrogen, then calcined at 600 ° C. for 30 hours in dry air, and then nitrogen. Then, the temperature was returned to room temperature to obtain a solid catalyst having good fluidity.
(Ii) Slurry polymerization Using a continuous slurry polymerization apparatus, copolymerization of ethylene and 1-hexene was performed in a polymerization temperature of 100 ° C, a total pressure of 4.4 MPa, and an isobutane solvent. The solid catalyst is continuously supplied, and ethylene and 1-hexene are supplied so as to maintain a predetermined molar ratio to perform polymerization. MFR = 0.05 g / 10 min, density 0.945 g / cm ³ , melt flow rate A powdery polyethylene resin (Y2-1) having a ratio of 132 was obtained. The results are shown in Table 14.

(Production Example 20)
(I) Preparation of Solid Catalyst A commercially available silica-supported chromium oxide catalyst (Grace, Inc., 969MSB) was transferred to a calcining tube at room temperature, dried under nitrogen, then calcined at 730 ° C. for 18 hours under dry air, and then nitrogen. Then, the temperature was returned to room temperature to obtain a solid catalyst having good fluidity.
(Ii) Slurry polymerization Using a continuous slurry polymerization apparatus, ethylene and 1-hexene were copolymerized in an isobutane solvent at a polymerization temperature of 98 ° C, a total pressure of 4.4 MPa. The solid catalyst is continuously supplied, ethylene and 1-hexene are supplied so as to maintain a predetermined molar ratio, polymerization is performed, MFR = 0.22 g / 10 min, density 0.942 g / cm ³ _, melt flow rate A powdery polyethylene resin (Y2-2) having a ratio of 105 was obtained. The results are shown in Table 14.

(Production Example 21)
(I) Preparation of Solid Catalyst A commercially available silica-titania cogel-supported chromium oxide catalyst (Grace, Magnapore 963) was transferred to a firing tube at room temperature, dried under nitrogen, and then fired at 820 ° C. for 12 hours under dry air. Thereafter, the temperature was returned to room temperature under nitrogen to obtain a solid catalyst having good fluidity.
(Ii) Slurry polymerization Using a continuous slurry polymerization apparatus, copolymerization of ethylene and 1-hexene was performed in a polymerization temperature of 86 ° C, a total pressure of 4.4 MPa, and an isobutane solvent. The solid catalyst is continuously supplied, ethylene and 1-hexene are supplied so as to maintain a predetermined molar ratio, polymerization is performed, MFR = 0.21 g / 10 min, density 0.938 g / cm ³ , melt flow rate A powdery polyethylene resin (Y2-3) having a ratio of 101 was obtained. The results are shown in Table 14.

(Production Example 22)
(I) Preparation of Solid Catalyst A commercially available silica-supported chromium oxide catalyst (Grace, EP30X) was transferred to a calcining tube at room temperature, dried under nitrogen, then calcined at 820 ° C. for 18 hours under dry air, and then nitrogen. Then, the temperature was returned to room temperature to obtain a solid catalyst having good fluidity.
(Ii) Slurry polymerization Using a continuous slurry polymerization apparatus, ethylene and 1-hexene were copolymerized in an isobutane solvent at a polymerization temperature of 108 ° C, a total pressure of 4.4 MPa. The solid catalyst is continuously supplied, and ethylene and 1-hexene are supplied so as to maintain a predetermined molar ratio to perform polymerization. MFR = 0.85 g / 10 min, density 0.958 g / cm ³ , melt flow rate A powdery polyethylene resin (Y2-4) having a ratio of 71 was obtained. The results are shown in Table 14.

(3) Polyethylene resin (D)
Commercially available high density polyethylene (D1) and (D4) and single site polyethylene resins (D2) and (D3) produced in Production Examples 23 to 24 below were used.

(Production Example 23)
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 and tripropyl was maintained at 90 ° C. 100 g of aluminum was added dropwise 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 baked 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.
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 2 MPa. The solid catalyst is continuously supplied, and ethylene, 1-hexene and hydrogen are supplied so as to maintain a predetermined molar ratio to perform polymerization, and MFR = 2.2 g / 10 min, density 0.918 g / cm ³ powder A single site polyethylene resin (D2) was obtained.

(Production Example 24)
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 and tripropyl was maintained at 90 ° C. 100 g of aluminum was added dropwise 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 baked 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.
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 2 MPa. The solid catalyst is continuously supplied, and ethylene, 1-hexene and hydrogen are supplied so as to maintain a predetermined molar ratio for polymerization, and MFR = 2.3 g / 10 min, density 0.912 g / cm ³ powder A single site polyethylene resin (D3) was obtained.

Example 1
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the powdery unmodified polyethylene resin (Y1-1) are mixed. Further, 100 parts by weight of the mixture is mixed with pentaerythritol tetrakis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris After adding 0.1 part by weight of (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite and blending for 2 minutes with a Henschel mixer, 50 mm uniaxial made by Modern Machinery Co., Ltd. A modified polyethylene resin composition (Z) was obtained by melt-kneading using an extruder at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. Using this modified polyethylene resin composition (Z) as an adhesive material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 15.

(Example 2)
Unmodified polyethylene composed of 50% by weight of modified polyethylene resin (X-1), 50% by weight of powdered linear low density polyethylene resin (B1) and 50% by weight of powdered high density polyethylene resin (C1) (Y1-2) 50% by weight (however, the melt flow rate ratio is a blend of 50% by weight of powdered linear low-density polyethylene resin (B1) and 50% by weight of high-density polyethylene resin (C1). And 100 parts by weight of the mixture, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 wt. Parts, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, tris (2,4-di-t-butyl Enyl) 0.1 parts by weight of phosphite and 0.05 parts by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer, and then the screw rotation speed was adjusted to 80 rpm using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Then, the mixture was melt-kneaded under a resin temperature of 230 ° C. to obtain a modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as an adhesive material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 15.

(Example 3)
Unmodified polyethylene resin comprising 50% by weight of modified polyethylene resin (X-1), 48% by weight of powdered linear low density polyethylene resin (B2 ′) and 52% by weight of powdered high density polyethylene resin (C2 ′) (Y1-3) 50% by weight is mixed, and further 100 parts by weight of the mixture, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1% Parts, 0.1 part by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 0.1 part by weight of tris (2,4-di-t-butylphenyl) phosphite, Add 0.05 parts by weight of hydrotalcite, blend for 2 minutes with a Henschel mixer, and then screw using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. In a converter number 80 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as an adhesive material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 15. This Example 3 is a reference example.

Example 4
50% by weight of the modified polyethylene resin (X-2) and 50% by weight of the unmodified polyethylene resin (Y1-4) were mixed, and pentaerythritol tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, 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, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Was used for melt-kneading at a screw speed of 80 rpm and a resin temperature of 230 ° C. to obtain a modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as an adhesive material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 15.

(Example 5)
57% by weight of the modified polyethylene resin (X-1) described in Example 1 and 43% by weight of the unmodified polyethylene resin (Y1-5) are mixed, and further, a commercially available high density is added to 100 parts by weight of the mixture. 43 parts by weight of polyethylene (D1) (Novatec HE122R manufactured by Nippon Polyethylene Co., Ltd.) and 0.1 parts by weight of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, Tris (2,4-di-t-butylphenyl) phosphite 0.1 part by weight, hydrotal Add 0.05 parts by weight of the site, blend for 2 minutes with a Henschel mixer, and then use a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. At over rotational speed 80 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as an adhesive material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 15.

(Example 6)
40% by weight of the modified polyethylene resin (X-3) and 43% by weight of the unmodified polyethylene resin (Y1-5) are mixed, and further commercially available for 100 parts by weight of the mixture and further for 100 parts by weight of the mixture. High-density polyethylene (D1) (Novatec HE122R manufactured by Nippon Polyethylene Co., Ltd.) 43 parts by weight and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 weight Parts, 0.1 part by weight of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 0.1 part by weight of tris (2,4-di-t-butylphenyl) phosphite, Add 0.05 parts by weight of hydrotalcite and blend for 2 minutes with a Henschel mixer, then 50 mm single screw extrusion from Modern Machinery Co., Ltd. At a screw rotation speed 80rpm by using, kneaded at a resin temperature of 230 ° C., to obtain modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as an adhesive material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 15.

(Example 7)
The modified polyethylene resin (X-2) 53% by weight and the unmodified polyethylene resin (Y1-8) 47% by weight were mixed, and further, 100 parts by weight of the mixture, 33 parts by weight of the single site polyethylene (D2), Pentaerystol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) ) 0.1 parts by weight of propionate, 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.05 parts by weight of hydrotalcite were added and blended for 2 minutes with a Henschel mixer. Using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd., melt kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. Give Riechiren resin composition (Z). Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 16.

(Example 8)
The modified polyethylene resin (X-2) 71% by weight and the unmodified polyethylene resin (Y1-8) 29% by weight were mixed, and further, 43 parts by weight of the single site polyethylene (D2) with respect to 100 parts by weight of the mixture. Pentaerystol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) ) 0.1 part by weight of propionate, 0.1 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. Using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd., melt kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. Give Riechiren resin composition (Z). Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 16.

Example 9
The modified polyethylene resin (X-2) 53% by weight and the unmodified polyethylene resin (Y1-8) 47% by weight were mixed, and further, 100 parts by weight of the mixture, 33 parts by weight of the single site polyethylene (D3), Pentaerystol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) ) 0.1 part by weight of propionate, 0.1 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. Using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd., melt kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. Give Riechiren resin composition (Z). Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 16.

As is apparent from Tables 15 and 16, Examples 1 , 2 , and 4 to 6 (Example 3 is a reference example) within the scope of the present invention have an extremely high gasoline permeation rate and an all-around notch creep rupture time. It was excellent.
In particular, as shown in Examples 7 to 9, when the polyethylene resin (D) using a single site catalyst is used as the D component, the gasoline permeability is low, and particularly the notch creep rupture time and the adhesive strength are dramatically improved. Therefore, it is possible to provide an excellent accessory part and fuel tank.

(Comparative Example 1)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of a commercially available high-density polyethylene (D1) (Novatec HE122R manufactured by Nippon Polyethylene Co., Ltd.) were mixed, and pentaerythriol was further added to 100 parts by weight of the mixture. Stalltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Add 0.1 parts by weight, 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.05 parts by weight of hydrotalcite, blend for 2 minutes with a Henschel mixer, and then modern machinery Using a 50 mm single-screw extruder manufactured by Co., Ltd., melt kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. To obtain an adhesive material according to 17. Table 17 shows the results of measuring gasoline permeability, all-around notch creep rupture time, and adhesive strength.

(Comparative Example 2)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the unmodified polyethylene resin (Y1-6) are mixed, and pentaerythritol tetrakis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris After adding 0.1 part by weight of (2,4-di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite and blending for 2 minutes with a Henschel mixer, 50 mm uniaxial made by Modern Machinery Co., Ltd. A modified polyethylene resin composition (Z) was obtained by melt-kneading using an extruder at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. Table 17 shows the results of measurement and evaluation of gasoline permeability, all-around notch creep rupture time and adhesive strength using this modified polyethylene resin composition (Z) as an adhesive material.

(Comparative Example 3)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the unmodified polyethylene resin (Y1-7) described in Example 1 were mixed, and pentaerythritol tetrakis with respect to 100 parts by weight of the mixture. [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 1 part by weight, 0.1 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. ) Modified polyethylene-based resin composition (Z) using a 50 mm single screw extruder and melt kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. Obtained. Table 17 shows the results of measurement and evaluation of gasoline permeability, all-around notch creep rupture time and adhesive strength using this modified polyethylene resin composition (Z) as an adhesive material.

(Comparative Example 4)
As a resin fuel tank adhesive material, commercially available Adtex FT61AR3 manufactured by Nippon Polyethylene Co., Ltd. was measured for gasoline permeability, notch creep rupture time and adhesive strength. The results are shown in Table 17.

(Comparative Example 5)
As a resin fuel tank adhesive material, commercially available Adtex DH4100 manufactured by Nippon Polyethylene Co., Ltd. was measured for gasoline permeability, notch creep rupture time and adhesive strength. The results are shown in Table 17.

(Comparative Example 6)
As a resin fuel tank adhesive material, commercially available Mitsubishi Chemical Corporation Modic H511 was measured for gasoline permeability, notch creep rupture time and adhesive strength. The results are shown in Table 17.

As shown in Table 17, in Comparative Example 1 and Comparative Example 2, the density and MFR of the modified polyethylene resin composition (Y) are outside the scope of the present invention, and Comparative Example 1 has a large gasoline permeability. 50 mg / (cm ² · 24 hr), and Comparative Example 2 had a short notch creep rupture time (FNCT). In Comparative Example 3, the melt flow rate ratio of the unmodified polyethylene resin (Y) is outside the range of the present invention, and even in this material, the gasoline permeability is large and exceeds 50 mg / (cm ² · 24 hr). Met. Comparative Examples 4 to 6 were commercially available materials, but all had high gasoline permeability and exceeded 50 mg / (cm ² · 24 hr).

(Comparative Example 7)
50% by weight of the modified polyethylene resin (X-2) and 50% by weight of the unmodified polyethylene resin (Y1-9) are mixed, and pentaerythritol tetrakis [3- (3,3) is added to 100 parts by weight of the mixture. 5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris ( 2,4-di-t-butylphenyl) phosphite (0.1 part by weight) and hydrotalcite (0.05 part by weight) were added, blended for 2 minutes with a Henschel mixer, and then 50 mm single screw extrusion manufactured by Modern Machinery Co., Ltd. A modified polyethylene resin composition (Z) was obtained by melt-kneading using a machine at a screw speed of 80 rpm and a resin temperature of 230 ° C. Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 18.

(Comparative Example 8)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the unmodified polyethylene resin (Y1-10) are mixed. Further, 100 parts by weight of the mixture is mixed with pentaerythritol tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, 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, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Was used for melt-kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 18.

(Comparative Example 9)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the unmodified polyethylene resin (Y1-11) are mixed. Further, 100 parts by weight of the mixture is mixed with pentaerythritol tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, 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, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Was used for melt-kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 18.

(Comparative Example 10)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the unmodified polyethylene resin (Y1-12) are mixed, and pentaerythritol tetrakis [3- (3,5) is added to 100 parts by weight of the mixture. -Di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, 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, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Was used for melt-kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 18.

As shown in Table 18, in Comparative Example 7, the (y1) density of the unmodified polyethylene resin (Y) is outside the range of the present invention, and the gasoline permeability exceeds 50 mg / (cm ² .24 hr). It was a thing. In Comparative Examples 8 and 9, the blending composition ratio of the polyethylene resins B and C is outside the scope of the present invention. When the polyethylene A is small as in Comparative Example 8, the notch creep rupture time is shorter all around, When the amount is excessive as in Comparative Example 9, the gasoline permeability increases, and none of the materials intended by the present invention can be obtained.
Further, when the upper limit of the MFR ratio of the polyethylene resin Y was out of the range of the present invention as in Comparative Example 10 , the gasoline permeability was large.

(Comparative Example 11)
High-density polyethylene resin (density: 0.956 g / cm ³ , MFR: 0.8 g /%) used in the examples of WO20020779323A1 as a modified polyethylene-based resin (X-1) 50% by weight and an unmodified polyethylene-based resin 10 minutes, Ziegler catalyst used, melt flow rate ratio: 30, J-Rex-HD manufactured by Nippon Polyolefin Co., Ltd.) (Y1-13) 50% by weight, and further mixed with 100 parts by weight of the mixture, Erystol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) 0.1 parts by weight of propionate, 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite, hydro After adding 0.05 parts by weight of Lucite and blending for 2 minutes with a Henschel mixer, it was melt kneaded using a modern machinery 50 mm single screw extruder at a screw speed of 80 rpm and a resin temperature of 230 ° C. A modified polyethylene resin composition (Z) was obtained. Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 19.

(Comparative Example 12)
High-density polyethylene resin (density: 0.956 g / cm ³ , MFR: 0.8 g /%) used in the examples of WO20020779323A1 as a modified polyethylene-based resin (X-2) 50% by weight and an unmodified polyethylene-based resin 10 minutes, Ziegler-based catalyst used, melt flow rate ratio: 30, J-Rex-HD manufactured by Nippon Polyolefin Co., Ltd.) (Y1-13) 50% by weight, and further mixed with 100 parts by weight of the mixture. 33 parts by weight of site-based polyethylene resin (D2) and 0.1 part by weight of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, tris (2,4-di-t (Butylphenyl) phosphite (0.1 part by weight) and hydrotalcite (0.05 part by weight) were added, blended with a Henschel mixer for 2 minutes, and then a screw rotation speed of 80 rpm using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Then, the mixture was melt-kneaded at a resin temperature of 230 ° C. to obtain a modified polyethylene resin composition (Z). Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 19.

(Comparative Example 13)
With respect to 100 parts by weight of a mixture obtained by mixing 0.3% by weight of modified polyethylene resin (X-1) and 99.7% by weight of (Y1-1) as an unmodified polyethylene resin, pentaerythritol tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 0.1 Part by weight, 0.1 part by weight of tris (2,4-di-t-butylphenyl) phosphite, 0.05 part by weight of hydrotalcite were added, blended for 2 minutes with a Henschel mixer, and then Modern Machinery Co., Ltd. Using a 50 mm single screw extruder, melt-kneading at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C., the modified polyethylene resin composition (Z) It was. Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 19.

(Comparative Example 14)
With respect to 100 parts by weight of a mixture obtained by mixing 97% by weight of modified polyethylene resin (X-1) and 3% by weight of unmodified polyethylene resin (Y1-8), pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris ( 2,4-di-t-butylphenyl) phosphite (0.1 part by weight) and hydrotalcite (0.05 part by weight) were added, blended for 2 minutes with a Henschel mixer, and then 50 mm single screw extrusion manufactured by Modern Machinery Co., Ltd. A modified polyethylene resin composition (Z) was obtained by melt-kneading using a machine at a screw speed of 80 rpm and a resin temperature of 230 ° C. Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 19.

Comparative Examples 11 and 12 in Table 19 are high-density polyethylene resins (density: 0.956 g / cm ³ , MFR: 0.8 g / 10 minutes, used in Examples of WO20020779323A1 as unmodified polyethylene resins. Ziegler-based catalyst used, melt flow rate ratio: 30), and a material using a single-site polyethylene resin as the polyethylene resin D component, which corresponds to a supplementary test of the above material.
However, the material of Comparative Example 11 has a melt flow rate ratio of unmodified polyethylene resin of 30 and the molecular weight distribution is so narrow that it is outside the scope of the present invention. It was. In Comparative Example 12, a single-site polyethylene resin was further added to Comparative Example 11 as the polyethylene resin D component, and the notch creep rupture time of the entire circumference was improved. -4) It did not satisfy the characteristic that the notch creep rupture time was 50 hours or more.
Comparative Examples 13 and 14 are examples in which the blending ratio of the modified polyethylene resin (X) and the unmodified polyethylene resin (Y) is outside the range of the present invention. When the modified polyethylene resin (X) is excessive, the notch creep rupture time was very short.

(Comparative Example 15)
To 100 parts by weight of a mixture of 15% by weight of modified polyethylene resin (X-4) and 85% by weight of (Y1-1) as an unmodified polyethylene resin, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris ( 2,4-di-t-butylphenyl) phosphite (0.1 part by weight) and hydrotalcite (0.05 part by weight) were added, blended for 2 minutes with a Henschel mixer, and then 50 mm single screw extrusion manufactured by Modern Machinery Co., Ltd. A modified polyethylene resin composition (Z) was obtained by melt-kneading using a machine at a screw speed of 80 rpm and a resin temperature of 230 ° C. Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 20.

(Comparative Example 16)
With respect to 100 parts by weight of a mixture obtained by mixing 50% by weight of modified polyethylene resin (X-5) and 50% by weight of unmodified polyethylene resin (Y1-1), pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris ( 2,4-di-t-butylphenyl) phosphite (0.1 part by weight) and hydrotalcite (0.05 part by weight) were added, blended for 2 minutes with a Henschel mixer, and then 50 mm single screw extrusion manufactured by Modern Machinery Co., Ltd. A modified polyethylene resin composition (Z) was obtained by melt-kneading using a machine at a screw speed of 80 rpm and a resin temperature of 230 ° C. Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 20.

(Comparative Example 17)
To 100 parts by weight of a mixture of 15% by weight of modified polyethylene resin (X-6) and 85% by weight of (Y1-1) as an unmodified polyethylene resin, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris ( 2,4-di-t-butylphenyl) phosphite (0.1 part by weight) and hydrotalcite (0.05 part by weight) were added, blended for 2 minutes with a Henschel mixer, and then 50 mm single screw extrusion manufactured by Modern Machinery Co., Ltd. A modified polyethylene resin composition (Z) was obtained by melt-kneading using a machine at a screw speed of 80 rpm and a resin temperature of 230 ° C. Using this modified polyethylene resin composition (Z) as a welding material, gasoline permeability, all-around notch creep rupture time, and adhesive strength were measured and evaluated. The results are shown in Table 20.

  Comparative Examples 15 to 17 in Table 20 show that the density and MFR of the polyethylene resin (A), which is the raw material resin of the modified polyethylene resin (X), are outside the scope of the present invention. The formula creep rupture time (FNCT) did not satisfy 50 hours or more.

(Example 10)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the polyethylene resin (Y2-1) were mixed. Further, 100 parts by weight of the mixture was mixed with pentaerythritol tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris (2,4 -0.1 part by weight of di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes using a Henschel mixer, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. was used. Then, the material was melt-kneaded at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 21.

(Example 11)
40% by weight of the modified polyethylene resin (X-1) and 60% by weight of the polyethylene resin (Y2-2) are mixed, and further, 100 parts by weight of the mixture is mixed with pentaerythritol tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris (2,4 -0.1 part by weight of di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes using a Henschel mixer, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. was used. Then, the material was melt-kneaded at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 21.

(Example 12)
40% by weight of the modified polyethylene resin (X-2) and 60% by weight of the polyethylene resin (Y2-3) were mixed, and pentaerythritol tetrakis [3- (3,5-dioxy) was added to 100 parts by weight of the mixture. -T-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part by weight, tris (2,4 -0.1 part by weight of di-t-butylphenyl) phosphite and 0.05 part by weight of hydrotalcite were added and blended for 2 minutes using a Henschel mixer, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. was used. Then, the mixture was melt-kneaded at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 21.

(Example 13)
67% by weight of modified polyethylene resin (X-1) and 33% by weight of polyethylene resin (Y2-3) were mixed. Further, 100 parts by weight of the mixture was mixed with a commercially available unmodified polyethylene resin (Nippon Polyethylene Co., Ltd.). Manufactured by Novatec HB534N) (D4), 33 parts by weight, and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 parts by weight, hydrotalcite 0.05 parts by weight After blending for 2 minutes with a Henschel mixer, the number of screw rotations using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. At 0 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain a welding material. The results of measuring the physical properties are shown in Table 21.

(Example 14)
57% by weight of a modified polyethylene resin (X-1) and 43% by weight of a polyethylene resin (Y2-3) are mixed. Further, 100 parts by weight of the mixture is mixed with a commercially available unmodified polyethylene resin (Nippon Polyethylene Co., Ltd.). NOVATEC HB534N) (D4) 43 parts by weight, and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 parts by weight, hydrotalcite 0.05 parts by weight After blending for 2 minutes with a Henschel mixer, the number of screw rotations using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. At 0 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain a welding material. The results of measuring the physical properties are shown in Table 21.

(Example 15)
63% by weight of a modified polyethylene resin (X-1) and 37% by weight of a polyethylene resin (Y2-3) were mixed. Further, 100 parts by weight of the mixture was mixed with a commercially available unmodified polyethylene resin (Nippon Polyethylene Co., Ltd.). Manufactured by Novatec HB334R) (D5), 25 parts by weight, and pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 part by weight, octadecyl-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 parts by weight, hydrotalcite 0.05 parts by weight After blending for 2 minutes with a Henschel mixer, the number of screw rotations using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. At 0 rpm, and melt-kneaded at a resin temperature of 230 ° C., to obtain a welding material. The results of measuring the physical properties are shown in Table 21.

(Comparative Example 18)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the unmodified polyethylene resin (Y2-3) are mixed, and pentaerythritol tetrakis [3- (3,5) is added to 100 parts by weight of the mixture. -Di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, 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, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Was melt kneaded at a screw temperature of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 22.

(Comparative Example 19)
50% by weight of the modified polyethylene resin (X-1) and 50% by weight of the unmodified polyethylene resin (Y2-4) were mixed, and pentaerythritol tetrakis [3- (3,5) was added to 100 parts by weight of the mixture. -Di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, 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, and then a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. Was melt kneaded at a screw temperature of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 22.

(Comparative Example 20)
With respect to 100 parts by weight of the modified polyethylene resin (X-1), 100 parts by weight of a commercially available unmodified polyethylene resin (manufactured by Nippon Polyethylene Co., Ltd., Novatec HB534N) (D4), and pentaerythritol tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, After adding 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 parts by weight of hydrotalcite and blending for 2 minutes with a Henschel mixer, 50 mm unit made by Modern Machinery Co., Ltd. Using a shaft extruder, melt kneading was performed at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 22.

(Comparative Example 21)
85% by weight of unmodified polyethylene resin (Y2-3) is mixed with 15% by weight of modified polyethylene resin (X-4), and pentaerythritol tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, After adding 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 parts by weight of hydrotalcite and blending for 2 minutes with a Henschel mixer, 50 mm unit made by Modern Machinery Co., Ltd. Using a shaft extruder, melt kneading was performed at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 22.

(Comparative Example 22)
50% by weight of unmodified polyethylene resin (Y2-3) is mixed with 50% by weight of modified polyethylene resin (X-5), and pentaerythritol tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, After adding 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 parts by weight of hydrotalcite and blending for 2 minutes with a Henschel mixer, 50 mm unit made by Modern Machinery Co., Ltd. Using a shaft extruder, melt kneading was performed at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 22.

(Comparative Example 23)
85% by weight of unmodified polyethylene resin (Y2-3) is mixed with 15% by weight of modified polyethylene resin (X-6), and pentaerythritol tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 parts by weight, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 parts by weight, After adding 0.1 parts by weight of tris (2,4-di-t-butylphenyl) phosphite and 0.05 parts by weight of hydrotalcite and blending for 2 minutes with a Henschel mixer, 50 mm unit made by Modern Machinery Co., Ltd. Using a shaft extruder, melt kneading was performed at a screw rotation speed of 80 rpm and a resin temperature of 230 ° C. to obtain a welding material. The results of measuring the physical properties are shown in Table 22.

  As shown in Tables 21 and 22, Examples 10 to 15 within the scope of the present invention have a balance in which gasoline permeability, all-around notch creep rupture time (FNCT), and adhesive strength are excellent and balanced. It turns out to be a material. On the other hand, in Comparative Example 18, the density of the modified polyethylene resin composition (Z) is outside the range of the present invention, and the gasoline permeability is high. In Comparative Example 19, MFR is outside the range of the present invention, The notch creep rupture time (FNCT) was short. In addition, the modified polyethylene resin (X) alone has no unmodified polyethylene (Y) having a wide molecular weight distribution, and therefore has a short all-around notch creep rupture time (FNCT), both of which are unsuitable as a balanced welding material. Met. In Comparative Examples 21 to 23, the MFR and density of the polyethylene resin A, which is the raw material resin of the modified polyethylene resin (X), are outside the range of the present invention, and Comparative Example 21 has poor gasoline permeability. In Comparative Example 21, the MFR of the raw material resin was very low, and the injection moldability at the time of molding the welded part was significantly reduced. In Comparative Examples 22 and 23, the notch creep rupture time (FNCT) was short and the adhesive strength was low.

  The welding material of the present invention can be easily welded and joined to a fuel tank, particularly a resin fuel tank, and retains the welding strength even after coming into contact with fuel such as gasoline, and can be used for a long time in a high-temperature atmosphere. In addition to maintaining good fuel permeation-preventing properties, it also has excellent creep rupture resistance and stress cracking resistance, and when used as a constituent material for fuel supply parts for fuel tanks, It is possible to provide a fuel tank that suppresses the fuel diffusion from the joint portion and is also excellent in long-term life performance.

Claims (13)

A welding material for welding to a fuel tank, the welding material being 0.5 to 95% by weight of the following modified polyethylene resin (X) and 5 to 99.5 of the following unmodified polyethylene resin (Y). A modified polyethylene resin composition containing 0.9% by weight, a density of 0.938 to 0.965 g / cm ³ , and a melt flow rate (temperature 190 ° C., load 2.16 kg) of 0.05 to 1.0 g / 10 min. The welding material containing a thing (Z).
(X) Modified polyethylene resin: Polyethylene resin having a density of 0.910 to 0.965 g / cm ³ and a melt flow rate (temperature 190 ° C., load 2.16 kg) of 0.1 to 5.0 g / 10 min (A ) Modified polyethylene resin obtained by grafting at least one monomer selected from the group consisting of unsaturated carboxylic acids and derivatives thereof (Y) unmodified polyethylene resin: density is 0.930 to 0.965 g / cm ³ , Melt flow rate (temperature 190 ° C., load 2.16 kg) is 0.01 to 5.0 g / 10 min, melt flow rate ratio (high load melt flow rate HL-MFR: temperature 190 ° C., load 21.6 kg / melt flow) Rate MFR: Polyethylene resin with a temperature of 190 ° C. and a load of 2.16 kg satisfying 40 to 150   The welding material according to claim 1, wherein the fuel tank is formed of a multilayer laminated structure including a main material layer of high-density polyethylene, an adhesive material layer, and a barrier material layer.   Melt flow rate ratio of unmodified polyethylene resin (Y) (high load melt flow rate HL-MFR: temperature 190 ° C., load 21.6 kg / melt flow rate MFR: temperature 190 ° C., load 2.16 kg) is 70 to 150 The welding material according to claim 1 or 2, wherein: Polyethylene whose unmodified polyethylene resin (Y) has a density of less than 0.910 to 0.940 g / cm ³ , a temperature of 190 ° C., a high load melt flow rate of 21.6 kg and a load of 0.05 to 10 g / 10 min. Polyethylene resin (C) 75 having a resin (B) of 25 to 60% by weight, a density of 0.940 to 0.970 g / cm ³ , a temperature of 190 ° C., and a load flow of 2.16 kg of 5 to 600 g / 10 min. The welding material according to any one of claims 1 to 3, wherein the welding material is a polyethylene resin composition comprising -40% by weight.   The welding material according to any one of claims 1 to 4, wherein the unmodified polyethylene resin (Y) is a polyethylene resin produced by multistage polymerization.   The welding material further comprises 150 parts by weight or less of another polyethylene resin (D) with respect to 100 parts by weight of the modified polyethylene resin (X) and the unmodified polyethylene resin (Y). The welding material of any one of -5.   At least one of the modified polyethylene resin (X), the unmodified polyethylene resin (Y) and the other polyethylene resin (D) is a polyethylene resin produced by a single site catalyst. The welding material according to any one of claims 1 to 6. The modified polyethylene-based resin composition (Z) has a 1 mm-thick sheet measured at 65 ° C. with a gasoline permeability of 50 mg / (cm ² · 24 hr) or less, and an all-around notch tensile creep at 5.5 MPa measured at 80 ° C. The welding material according to any one of claims 1 to 7, wherein a fracture time satisfies 50 hours or more.   The welding material according to any one of claims 1 to 8, wherein the welding material constitutes a part attached to the fuel tank.   The welding material according to any one of claims 1 to 9, wherein the welding material welds the fuel tank and its accessory parts.   The welding material according to any one of claims 1 to 10, wherein a laminated structure of at least two layers of a layer made of a welding material and a barrier material layer constitutes a part attached to the fuel tank.   The fuel tank formed by welding the welding material of any one of Claims 1-11.   The fuel tank according to claim 12, wherein the fuel tank is composed of a multilayer laminated structure including a main material layer of high-density polyethylene, an adhesive material layer, and a barrier material layer.