JP5244779B2 - Biodiesel fuel container materials and molded products - Google Patents

Description

  The present invention relates to a material for a biodiesel fuel container and a molded article. More specifically, the present invention relates to long-term durability, elution resistance, and mechanical strength when molded into a fuel container that directly or indirectly contacts biodiesel fuel. The present invention relates to a material for a biodiesel fuel container excellent in various characteristics such as the above, and a molded article manufactured using the material.

  Recently, movements to regulate carbon dioxide emissions are accelerating in order to prevent global warming, which is thought to be due to an increase in carbon dioxide. Under such circumstances, as a measure for reducing carbon dioxide emissions, attention has been paid to using biomass as fuel instead of petroleum fuel. Biomass is an organic compound photo-synthesized from carbon dioxide and water by solar energy, and it is considered that the increase of carbon dioxide can be suppressed by using this as a fuel.

  Under such circumstances, the use of biodiesel fuel (BDF), which is a biomass fuel, for diesel vehicles is being actively promoted. Biodiesel fuel is a vegetable oil methyl ester (fatty acid methyl ester) as the main component, rapeseed oil, sunflower oil, soybean oil, corn oil and these waste edible oils are esterified with methanol, A typical example is a liquid fuel in which glycerin produced as a by-product is separated and removed, and the kinematic viscosity is reduced to about twice that of light oil. Waste cooking oil and the like are easily available, but cannot be used as fuel for diesel automobiles as they are because of their physical properties such as high viscosity.

Biodiesel fuel is usually used by mixing with light oil. However, biodiesel fuel contains trace amounts of methanol, triglyceride, acid, etc., and container materials that are not easily affected by these substances are required. ing. In addition, biodiesel fuel itself has a property of easily deteriorating materials such as resin as compared with light oil.
In fuel containers and container parts that are in direct or indirect contact with such biodiesel fuel, excellent fuel oil resistance (hereinafter referred to as biodiesel fuel resistance) is required for biodiesel fuel.
For example, as a material related to biodiesel fuel resistance, Japanese Patent Application Laid-Open No. 2004-059720 (Patent Document 1) discloses 100 parts by weight of polyoxymethylene, 0.01 to 2.0 parts by weight of an antioxidant, hindered amine light. A polyoxymethylene resin composition comprising 0.01 to 2.0 parts by weight of a stabilizer and / or 0.01 to 2.0 parts by weight of at least one hydrotalcite represented by a specific chemical formula, and The molded part has been proposed.
However, since the above composition uses polyoxymethylene, it is not always satisfactory in terms of moldability and price.

In addition, JP-T-2001-527109 (Patent Document 2) is stabilized by a sterically hindered amine or its N-hydroxy or N-oxyl derivative for producing plastic products and molded products for storage and transfer of vegetable oil esters. Plastic products for storing and transporting vegetable oil esters, in particular vegetable oil methyl esters, have been proposed, and compounds of a specific structural formula are exemplified as suitable compounds for their use ing.
However, it cannot be said that all of the sterically hindered amines exemplified in Patent Document 2 or their N-hydroxy or N-oxyl derivative compounds sufficiently satisfy various performances in compatibility with polyethylene. In this case, the practical performance cannot be fully demonstrated at an excellent level. That is, when an amine compound having a poor affinity with polyethylene is used, the compound bleeds out after a long period of time, or the impact resistance of the obtained molded product is lowered. Even if the material is used, a suitable molded product is not necessarily obtained with respect to various properties such as long-term durability, elution resistance, and mechanical strength.

On the other hand, Japanese Patent Application Laid-Open No. 04-080215 (Patent Document 3) is a polymer having a specific structure having a hindered amine group in the molecular side chain, and has an excellent light stabilizing effect when blended with itself or other polymer materials. A material having very good transparency, film-forming property and appearance when formed into a film has been proposed, and an ethylene copolymer of ethylene and a vinyl compound represented by a specific chemical formula is described.
However, when the ethylene copolymer is formed into a molded article that is in direct or indirect contact with biodiesel fuel, there is no mention of whether or not various properties such as long-term durability, elution resistance, and mechanical strength can be improved. There is no suggestion, and its usefulness in the application field is not clear.
Japanese Patent Laid-Open No. 05-170931 (Patent Document 4) describes a resin composition in which an ethylene copolymer composed of ethylene and a vinyl compound having a hindered amine is blended with polyethylene.
However, the resin composition is used as a material for water supply and drainage transfer pipes, and has various properties such as long-term durability, elution resistance, and mechanical strength when used for molded articles that come into direct or indirect contact with biodiesel fuel. There is no description or suggestion as to whether or not it can be improved, and its usefulness in the field of use is unclear.

JP 2004-059720 A JP-T-2001-527109 Japanese Patent Laid-Open No. 04-080215 JP 05-170931 A

  The present invention is satisfactory in terms of solving the above-mentioned problems, and has good moldability to a molded product that is in direct or indirect contact with biodiesel fuel, and is low in price, but has long-term durability of the molded product. Another object of the present invention is to provide a biodiesel fuel container material that is excellent in various properties such as elution resistance and mechanical strength.

  As a result of intensive research to solve the above problems, the present inventors have copolymerized a specific polyethylene and a vinyl compound unit having a specific structure with an ethylene unit in the main chain as a material for a biodiesel fuel container. It was found that a biodiesel fuel container excellent in various properties such as long-term durability, elution resistance, and mechanical strength can be obtained by using a material containing an ethylene-vinyl compound copolymer. It came to be completed.

According to the first aspect of the present invention, the density is 0.920 to 0.970 g / cm ³ , and the melt flow rate (HLMFR; measured at a temperature of 190 ° C. and a load of 21.6 kg) is 0.1 to 100 g / 10. A biodiesel fuel container material containing 0.1 to 10 parts by weight of an ethylene-vinyl compound copolymer (II) with respect to 100 parts by weight of polyethylene (I), The compound (II) is a copolymer of ethylene (A) and a vinyl compound (B) represented by the following general formula, and the ratio of (B) to the sum of (A) and (B) is 0.00. The melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg is 0.1 to 200 g / 10 min. Biodiesel fuel capacity Use material is provided.

(In formula, R < ₁ > and R < ₂ > is a hydrogen atom or a methyl group, and R < ₃ > represents a hydrogen atom or a C1-C4 alkyl group.)

Further, according to the second invention of the present invention, in the first invention, the ethylene-vinyl compound copolymer (II) is isolated without being continuous with two or more vinyl compounds (B) in the copolymer. The biodiesel fuel container material is provided, wherein the ratio is 83% or more based on the total amount of the vinyl compound (B).
According to the third invention of the present invention, in the first or second invention, the vinyl compound (B) is 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy- 1,2,2,6,6-pentamethylpiperidine, 4-acryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6 A biodiesel fuel container material characterized by being a compound selected from the group consisting of 6-tetramethylpiperidine and 4-acryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine Is done.
According to the fourth invention of the present invention, in any one of the first to third inventions, the proportion of the vinyl compound (B) unit is that of the polyethylene (I) and the ethylene-vinyl compound copolymer (II). A biodiesel fuel container material is provided that is 10 to 5000 ppm based on the total amount.
Furthermore, according to the fifth invention of the present invention, in any one of the first to fourth inventions, the polyethylene (I) has a density of 0.930 to 0.965 g / cm ³ and an HLMFR of 1 to 10 g / 10. A material for a biodiesel fuel container is provided.

On the other hand, according to the sixth invention of the present invention, there is provided a biodiesel fuel container manufactured using any one of the materials of the first to fifth inventions.
Moreover, according to the 7th invention of this invention, the biodiesel fuel container component manufactured using the material in any one of the 1st-5th invention is provided.

  According to the present invention, as a biodiesel fuel container material, a specific polyethylene and an ethylene-vinyl compound copolymer having an ethylene unit in the main chain and a copolymerized vinyl compound unit having a specific structure are used. It is excellent in properties such as long-term durability, elution resistance, and mechanical strength when it is made into a molded product such as a fuel container that is in direct or indirect contact with biodiesel fuel. Become. In addition to biodiesel fuel containers, it can be used in a wide range of fields including various container fields due to its material properties.

The present invention is described in detail below.
The biodiesel fuel container material of the present invention has a density of 0.920 to 0.970 g / cm ³ , and a melt flow rate (HLMFR; measured at a temperature of 190 ° C. and a load of 21.6 kg) of 0.1 to 100 g / 10. It contains 0.1 to 10 parts by weight of ethylene-vinyl compound copolymer (II) with respect to 100 parts by weight of polyethylene (I), and ethylene-vinyl compound copolymer (II) A copolymer of ethylene (A) and a vinyl compound (B) represented by the following general formula, wherein the ratio of (B) to the sum of (A) and (B) is 0.001 to 2.0 mol. The melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg of the copolymer is 0.1 to 200 g / 10 min.

(In formula, R < ₁ > and R < ₂ > is a hydrogen atom or a methyl group, and R < ₃ > represents a hydrogen atom or a C1-C4 alkyl group.)

Hereinafter, the (I) component, the (II) component, other optional components, the molding method of the molded product, the molded product characteristics, etc. of the material of the present invention will be described in detail.
In the present invention, the biodiesel fuel is, as described above, mainly composed of vegetable oil methyl ester (fatty acid methyl ester), rapeseed oil, sunflower oil, soybean oil, corn oil, and waste foods thereof. This is a liquid fuel in which the oil is esterified with methanol as a raw oil, and glycerin produced as a by-product is separated and removed to lower the kinematic viscosity to about twice that of light oil. Biodiesel fuel contains a small amount of methanol, triglyceride, acid, etc., so it is easier to deteriorate the material such as resin compared to light oil, but it can be suppressed by blending light oil to some extent. it can. According to the present invention, even when light oil is mixed at 70% by volume or less, preferably 60% by volume or less, excellent effects such as durability can be exhibited.

1. Biodiesel Fuel Container Material (1) Polyethylene (I) Polyethylene (I) constituting the biodiesel fuel container material of the present invention has a density of 0.920 to 0.970 g / cm ³ and a temperature of 190 ° C. The polyethylene has a melt flow rate (HLMFR) measured at a load of 21.6 kg of 0.1 to 100 g / 10 min.

In the present invention, the density of polyethylene (I) is 0.920 to 0.970 g / cm ³ , preferably 0.930 to 0.965 g / cm ³ , more preferably 0.940 to 0.960 g / cm ³ . is there. When the density is less than 0.920 g / cm ³ , the rigidity of the molded container is small, and it is difficult to maintain the strength of the thin product. On the other hand, those having a density exceeding 0.970 g / cm ³ are substantially difficult to produce. Here, the density is a value measured according to JIS K6922-1, 2: 1997.
A desired density can be obtained by changing the density depending on the kind and amount of the comonomer copolymerized with ethylene.

The melt flow rate (HLMFR) of polyethylene (I) according to the present invention is measured at a temperature of 190 ° C. and a load of 21.6 Kg, and is preferably 1 to 100 g / 10 min, preferably 2 to 50 g / 10 minutes, more preferably 5 to 20 g / 10 minutes. If the HLMFR is less than 1 g / 10 min, the surface skin of the molded container tends to be rough in the case of blow molding, and the fluidity decreases in the case of injection molding. On the other hand, if it exceeds 100 g / 10 minutes, it becomes easy to draw down the parison in blow molding, it becomes difficult to adjust the thickness distribution of the blow molded container, and in the case of injection molding, impact resistance is lowered. Here, HLMFR is a value measured according to JIS K6922-2: 1997 “Plastics—Polyethylene (PE) molding and extrusion materials—Part 2: How to make test pieces and properties”. .
This HLMFR can be adjusted by the ethylene polymerization temperature, the use of a chain transfer agent, and the like, and a desired product can be obtained while balancing with other physical properties. That is, the molecular weight can be decreased by increasing the polymerization temperature of ethylene and α-olefin, and as a result, the HLMFR can be increased, and the molecular weight can be increased by decreasing the polymerization temperature, and as a result, the HLMFR can be decreased. Can do. In addition, when using a Ziegler catalyst, the molecular weight can be lowered by increasing the amount of hydrogen (chain transfer agent amount) that coexists in the copolymerization reaction of ethylene and α-olefin, resulting in an increase in HLMFR. The molecular weight can be increased by reducing the amount of hydrogen (chain transfer agent amount) to be produced, and as a result, HLMFR can be reduced.

Furthermore, the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight of the polyethylene (I) according to the present invention is measured by gel permeation chromatography (GPC), preferably 5.0 to 50.0. More preferably, it is 5.5-45.0, More preferably, it is 6.5-40.0. When Mw / Mn is less than 5.0, melt molding tends to occur in the extruded parison in blow molding, and melt fracture tends to occur particularly during high-speed molding. When the Mw / Mn exceeds 50.0, in blow molding, if the HLMFR value is low, the parison tends to be rough, the blow molded container tends to be rough, and if the HLMFR value is high, the parison There is a portion where the surface skin is abnormally shined, and the air bleeding property is deteriorated at the time of blow molding, and the surface of the molded container tends to be rough.
Mw / Mn by GPC measurement can be adjusted by the type of catalyst, the type of cocatalyst, the polymerization temperature, the residence time in the polymerization reactor, the number of polymerization reactors, etc. It can be adjusted according to the speed. Preferably, it can be increased or decreased by adjusting the composition ratio of the high molecular weight component and the low molecular weight component, polymer components having different molecular weights are produced by changing the polymerization temperature and the amount of chain transfer agent during the polymerization reaction, As a result, the molecular weight distribution of the entire polymer can be changed. It is also possible to increase or decrease the molecular weight distribution by performing polymerization with different polymerization conditions in multiple stages.

The measurement conditions and measurement method of GPC, and the molecular weight calculation method are as follows.
Use (i) Measurement Conditions c _o Tazu Inc. Model 150C, subjected to GPC measurement under the following conditions to determine the weight average molecular weight (Mw).
Column: 1 Shodex HT-G manufactured by Showa Denko KK and 2 HT-806Ms of the same Solvent: 1,2,4-trichlorobenzene Temperature: 140 ° C.
Flow rate: 1.0 ml / min Injection volume: 300 μl
(Ii) Sample preparation Approximately 3 mg of a sample and 3.0 ml of a solvent are weighed into a commercially available 4 ml screw top vial, and shaken at 150 ° C. for 2 hours using a SSC-9300 type stirrer manufactured by Senshu Scientific.
(Iii) Calculation of molecular weight GPC chromatographic data is loaded into a computer at a frequency of 1 point / second, processed according to the description in Chapter 4 of “Size Exclusion Chromatography” written by Sadao Mori and Kyoritsu Publishing Co., and the Mw value is calculated. calculate.
(Iv) Column calibration Column calibration was performed by using monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66 manufactured by Showa Denko KK 0.0, S-28.5, S-5.05), n-eicosane and 0.2 mg / l each solution of n-tetracontane, a series of monodisperse polystyrene measurements were taken and their elution peaks A curve obtained by fitting the logarithm of time and molecular weight with a quartic polynomial is used as a calibration curve.
In addition, the molecular weight of polystyrene is converted into the molecular weight of polyethylene using the following formula.
M _PE = 0.468 × M _PS

Specific examples of polyethylene according to the present invention include, for example, ethylene homopolymer, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, Other α-carbon atoms having about 2 to 18 carbon atoms such as 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, 1-octadecene, etc. Binary or ternary copolymers with olefins, etc., specifically, ethylene homopolymers such as branched low density polyethylene and linear high density polyethylene, ethylene-propylene copolymers, ethylene- 1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1- Heptene copolymers, include ethylene-based resin of an ethylene-1-octene copolymers, these ethylene polymers are more than two may be used together.
Moreover, when it aims at modification | reformation, the copolymerization with diene is also possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like. The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content therein is 0 to 40 mol%, preferably 0 to 30 mol%.
These ethylene polymers preferably have a molecular weight of 2,000 to 500,000 in terms of weight average molecular weight, more preferably 5,000 to 450,000, and 10,000 to 400,000. Those are particularly preferred.

As the polymerization catalyst for the ethylene polymer, various catalysts such as a Ziegler catalyst, a chromium catalyst, and a metallocene catalyst are used, and any of them can be used.
Specifically, any catalyst that is composed of a solid catalyst component and an organometallic compound and that is suitable for slurry-based olefin polymerization such that hydrogen exhibits a chain transfer action of olefin polymerization can be used. Preferred is a heterogeneous catalyst in which polymerization active sites are localized.
The solid catalyst component is not particularly limited as long as it is used as a solid catalyst for olefin polymerization containing a transition metal compound. As the transition metal compound, compounds of elements of Group 4 to Group 10 of the periodic table, preferably Group 4 to Group 6, can be used, and specific examples include Ti, Zr, Hf, V, Cr. And compounds such as Mo.

Examples of the Ziegler catalyst include those described in JP-A-53-78287, JP-A-54-2183, JP-A-55-71707, JP-A-58-225105, and the like. System.
Examples of the chromium-based catalyst include, for example, JP 2002-080521 A, JP 2006-512454 A, WO 94/13708 International Publication Pamphlet, JP 2002-020212 A, and JP 2003-096127 A. Examples thereof include catalyst systems described in Japanese Unexamined Patent Application Publication Nos. 2003-183287, 2003-313225, and 2006-182917.
The metallocene catalyst is a kind of so-called single-site catalyst having a relatively single active site, and representative examples thereof include transition metal metallocene complexes such as zirconium or titanium biscyclopenta. A catalyst obtained by reacting a dienyl complex with methylaluminoxane or the like as a co-catalyst can be mentioned, and it is a homogeneous or heterogeneous catalyst in which various complexes, co-catalysts, supports and the like are variously combined.
Examples of the metallocene catalyst include JP-A-58-19309, 59-95292, 59-23011, 60-35006, 60-35007, 60-35008, and 60-35009. No. 61-130314 and JP-A-3-163088, and the like.

The polyethylene can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. Among the polymerization conditions of the ethylene polymer, the polymerization temperature can be selected from the range of 0 to 300 ° C. The polymerization pressure can be selected from the range of atmospheric pressure to about 100 kg / cm ² . It is selected from aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, etc. in a state where oxygen and water are substantially cut off. It can be produced by polymerizing ethylene and α-olefin in the presence of an inert hydrocarbon solvent.
In the above polymerization, hydrogen supplied to the polymerization vessel is consumed as a chain transfer agent, determines the average molecular weight of the produced ethylene-based polymer, and partly dissolves in a solvent and is discharged from the polymerization vessel. The solubility of hydrogen in the solvent is small, and the hydrogen concentration near the polymerization active point of the catalyst is low unless a large amount of gas phase is present in the polymerization vessel. Therefore, if the hydrogen supply amount is changed, the hydrogen concentration at the polymerization active point of the catalyst changes rapidly, and the molecular weight of the produced ethylene polymer changes following the hydrogen supply amount in a short time. Therefore, a more homogeneous product can be produced by changing the hydrogen supply rate in a short cycle. Moreover, the aspect of changing the hydrogen supply amount is preferably changed discontinuously rather than continuously because the effect of broadening the molecular weight distribution can be obtained.
In the polyethylene according to the present invention, it is important to polymerize by changing the hydrogen supply amount, but other polymerization conditions such as polymerization temperature, catalyst supply amount, supply amount of olefin such as ethylene, 1-butene It is also important to change the supply amount of the comonomer and the like, the supply amount of the solvent, etc., simultaneously with the change of hydrogen or separately.

(2) Ethylene-vinyl compound copolymer (II) The ethylene-vinyl compound copolymer (II) is obtained by copolymerization of ethylene (A) and a vinyl compound (B) represented by the following general formula. .

（式中、Ｒ_１及びＲ_２は上記と同じである。）

(In the formula, R ₁ and R ₂ are the same as above.)

The concentration of the vinyl compound (B) having a hindered amine group in the side chain in the ethylene-vinyl compound copolymer (II) (determined by a known nitrogen analysis) is determined between ethylene (A) and the vinyl compound (B). A vinyl compound (B) unit is 0.001-2.0 mol% with respect to the sum, Preferably it is 0.01-1.5 mol%.
Since this copolymer has an excellent long-term durability effect, the vinyl compound (B) unit is 0.001 mol with respect to all the structural units of the copolymer (that is, a vinyl compound having a hindered amine group in the side chain). %, A sufficient effect is exhibited. When the content exceeds 2.0 mol%, mechanical properties such as impact resistance may be deteriorated.
Furthermore, the ethylene-vinyl compound copolymer (II) according to the present invention preferably has a ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight determined using GPC in the range of 3 to 120. A particularly preferred range is 5 to 20.

  For the production of the ethylene-vinyl compound copolymer (II), ethylene and a vinyl compound monomer represented by the following general formula are used.

In the formula, R ₁ and R ₂ are a hydrogen atom or a methyl group, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the vinyl compound represented by the above general formula, R ₁ and R ₂ are more preferably a hydrogen atom, and R ₃ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
The vinyl compound monomer of the above formula can be synthesized by a known method, for example, the method described in JP-B-47-8539 and JP-A-48-65180.

Typical examples of vinyl compound monomers of the above formula are as follows.
4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-acryloyloxy-1-ethyl-2,2,6 , 6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine, 4 -Methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1-ethyl-2,2,6 6-tetramethylpiperidine, 4-methacryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine, 4-crotono Aryloxy-2,2,6,6-tetramethylpiperidine, among 4-crotonoyloxy-oxy-1-propyl-2,2,6,6-tetramethylpiperidine above, the following compounds are preferred.
4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-acryloyloxy-1-ethyl-2,2,6 , 6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine Furthermore, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-acryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1- Propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine Gin is preferred.

  The ethylene-vinyl compound copolymer (II) needs to have an MFR (according to the measurement method described in JIS-K-6760) in the range of 0.1 to 200 g / 10 minutes. A preferred range is 0.5 to 20 g / 10 minutes, more preferably 1 to 5 g / 10 minutes. When the MFR is less than 0.1 g / 10 minutes, the compatibility with commercially available polyolefin resins and the like is poor, and when blending is used, it causes visible defects such as fish eyes and blisters. If the MFR exceeds 200, even if the copolymer has a large molecular weight, bleeding or blooming due to diffusion loss occurs, or when blended with other polymer materials such as polyolefin, It causes a decrease in strength.

Further, the ethylene-vinyl compound copolymer (II) does not have two or more vinyl compounds (B) continuous in the copolymer and is present in a specific amount, and the proportion of the vinyl compound (B) is the vinyl compound (B). The total amount is preferably 83% or more. The presence confirmation of the vinyl compound (B) is performed as follows.
^{According to a} known method by ¹³ C-NMR (for example, JNM-GSX270 Spectrometer manufactured by JEOL Ltd.) (see, for example, “Chemistry Dossier (1)” pages 53 to 56 (1986)), polyacrylic acid Ethyl (see “Polymer Analysis Handbook”, page 969 (1985), published by Asakura Shoten) and ethylene-hydroxyethyl acrylate copolymer (Eur. Poly. J. Vol. 25, No. 4, pages 411 to 418 (1989)) The 22.9 ppm peak in the TMS standard was isolated from the branch point of the isolated vinyl compound (B) unit to the methylene group at the α-position, and two vinyl compounds having a continuous 35.7 ppm peak (B ) It belongs to the methylene group sandwiched between the branch points of the unit. Using these two signals, the ratio of the vinyl compound (B) unit present in isolation in the copolymer (II) of ethylene (A) and vinyl compound (B) can be calculated by the following formula. it can.

  Based on the above, the proportion of two or more vinyl monomers having a hindered amine group in the side chain that do not continue and exist in isolation is estimated, and the presence ratio is based on the total amount of vinyl compound (B) in the copolymer. It is preferably 83% or more. If the proportion of vinyl compound units having hindered amine groups in the side chain is less than 83%, the content of vinyl compound units having hindered amine groups in the side chain is less than 83%. The characteristic of having durability is hardly exhibited.

The ethylene-vinyl compound copolymer can be produced by a known method, for example, a method described in JP-A-4-80215.
That is, the ethylene-vinyl compound copolymer is obtained by radical polymerization of ethylene (A) and vinyl compound (B) at a pressure of 1000 to 5000 kg / cm ² and a temperature of 100 to 400 ° C.

(3) Ratio of both components of polyethylene (I) and ethylene-vinyl compound copolymer (II) The biodiesel fuel container material of the present invention is an ethylene-vinyl compound with respect to 100 parts by weight of polyethylene (I). It is suitable to blend 0.1 to 10 parts by weight of copolymer (II), preferably 0.5 to 8 parts by weight, more preferably 1 to 5 parts by weight. When the ethylene-vinyl compound copolymer (II) is less than 0.1 parts by weight, the biodiesel fuel resistance and long-term durability are lowered, and when it exceeds 10 parts by weight, the impact resistance tends to be lowered.

  The ratio of the vinyl compound (B) unit contained in the biodiesel fuel container material of the present invention is the vinyl compound (B) unit relative to the total amount of polyethylene (I) and ethylene-vinyl compound copolymer (II). Is preferably 10 to 5000 ppm, more preferably 100 to 3000 ppm. When the proportion of the vinyl compound (B) unit is out of the lower limit of the above range, the biodiesel fuel resistance and long-term durability are lowered, and when the proportion is out of the upper limit, the impact resistance tends to be lowered.

  The polyethylene (I) and the ethylene-vinyl compound copolymer (II) are pelletized by mechanical melting and mixing with a pelletizer or homogenizer according to a conventional method, and then molded by various molding machines to obtain a desired molding. Product. In addition, the biodiesel fuel container material obtained by the above method includes other olefin polymers and rubbers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, antistatic agents in accordance with conventional methods. Antifogging agents, antiblocking agents, processing aids, color pigments, pearl pigments, glittering materials, polarizing pearl pigments, crosslinking agents, foaming agents, neutralizing agents, thermal stabilizers, crystal nucleating agents, inorganic or organic fillers, Known additives such as flame retardants can be blended. As a coloring method, a compound added in a necessary amount to the base resin or a master batch added at a high concentration may be post-blended. The crystal nucleating agent may be added at the time of blow molding in a master batch.

  In addition, as an additive, for example, an antioxidant (phenolic, phosphorus-based, sulfur-based), a lubricant, an antistatic agent, a light stabilizer, an ultraviolet absorber, or the like can be appropriately used in combination of one or more. As the filler, calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc. can be used. . In any case, various additives may be blended with the above material as necessary, and kneaded with a kneading extruder, a Banbury mixer, or the like to obtain a molding material.

(4) Flexural modulus The flexural modulus of the biodiesel fuel container material of the present invention is measured according to JIS K6922-2: 2005. The bending elastic modulus of the material of the present invention is 500 MPa or more, preferably 700 to 3000 MPa, more preferably 700 to 2000 MPa. If the flexural modulus is in this range, the rigidity will not be insufficient when the fuel container is made thin. The flexural modulus can be adjusted by changing the density of polyethylene (I).

(5) Low temperature impact resistance The Charpy impact strength of the biodiesel fuel container material of the present invention is based on JIS K-7111 (2004), a type 1 test piece is produced, and the striking direction is edgewise and notched. Is measured as TYPE A (0.25 mm) in dry ice / alcohol at −40 ° C.
The material of the present invention has a Charpy impact strength at −40 ° C. of 7 kJ / m ² or more, preferably 7.5 kJ / m ² , more preferably 8 kJ / m ² . When the Charpy impact strength at −40 ° C. is less than 7 kJ / m ² , the low-temperature impact strength tends to be insufficient, and the drop strength tends to be weak. The low temperature impact strength can be increased by increasing the molecular weight of polyethylene (I) and can be decreased by decreasing the molecular weight.

(6) Long-term durability The long-term durability of the biodiesel fuel container material of the present invention is evaluated by the following long-term durability tests 1 and 2.
In the long-term durability test 1, a test piece having a thickness of 2 mm is prepared in accordance with JIS K6922-2: 2005, and an immersion test is performed in warm water at 80 ° C. Further, 50 cc of the test solution is injected into a cup with an inner diameter of 65 mmφ, the opening is sealed with a test piece after immersion in warm water, and a one-side immersion test of biodiesel fuel is performed at 100 ° C. As evaluation of long-term durability, the molecular weight of the test piece after fuel immersion is measured by GPC.
In the long-term durability test 2, a test piece having a thickness of 2 mm is prepared in accordance with JIS K6922-2: 2005, and an exposure test in accordance with JIS K7350-4: 1996 is performed. Further, 50 cc of the test solution is injected into a cup having an inner diameter of 65 mmφ, the opening is sealed with a test piece after the exposure test, and a single-sided immersion test of biodiesel fuel is performed at 100 ° C. As evaluation of long-term durability, the molecular weight of the test piece after fuel immersion is measured by GPC.
The ratio of the polyethylene molecular weight after long-term immersion in biodiesel fuel to the molecular weight of polyethylene before long-term immersion in biodiesel fuel is 75% or more, preferably 80% or more, more preferably 85% or more. When the ratio of the molecular weight after long-term immersion in biodiesel fuel to the molecular weight of polyethylene before long-term immersion in biodiesel fuel is less than 70%, impact strength and tensile strength are reduced, and the performance as a fuel container can be maintained. Disappear.

2. Biodiesel fuel container and container parts The biodiesel fuel container material of the present invention is preferably a blow molded product by a blow molding method, particularly a blow molded product by a direct blow molding machine, a rotary blow molding machine or a multilayer blow molding machine. Can be made into fuel containers (hereinafter also referred to as hollow plastic molded product containers) and container parts (fuel pipes, fuel pumps, etc.). Further, a hot parison stretch blow molding machine, a cold parison stretch blow molding machine, injection blow molding, and the like are also possible.
The size of the container is not particularly limited, but is preferably about 10 to 2000 ml. Further, the shape of the container is not particularly limited. The obtained container is a plastic molded product having biodiesel fuel resistance and excellent long-term durability. In addition to moldability, it is excellent in touch, etc., handleability, drop impact strength, impact resistance, etc. It can be suitably used as a biodiesel fuel container or the like because it does not cause problems such as whitening when an external force is applied to the container and deforms.
In the present invention, a container part is a part attached to a fuel container, such as a lid (cap), an internal solution supply port, a discharge port, etc., a valve, a pipe, a handle, a fuel pump, a reinforcing part, an inlet, and an opening. Examples include various parts such as a liner. This part can be integrally attached to the container by welding and welding to the fuel container.

The hollow plastic molded product container has a structure having at least one layer of polyethylene resin, and preferably has a multilayer structure, but may have a single layer structure made of polyethylene resin.
When the hollow plastic molded product container has a multilayer structure, it is preferable to have a permeation reduction barrier layer, and a barrier layer is usually used as the permeation reduction barrier layer.
When the layer structure of the hollow plastic molded product container is two or more layers, the innermost layer and the outermost layer are preferably made of a polyethylene resin.
The hollow plastic molded article container preferably has a multilayer structure that includes at least one barrier layer to reduce permeation of volatile materials and includes a permeation-reducing barrier layer made of a polar barrier polymer. For example, when the wall of the plastic fuel container (tank) has a multi-layer structure, there is an advantage that a barrier layer (which alone is not sufficient in moldability and mechanical strength) can be fixed between two layers made of polyethylene resin. is there. As a result, particularly during coextrusion blow molding, the moldability of a material having two or more layers of polyethylene resin is improved primarily under the influence of the improved moldability of the polyethylene resin. Further, in the hollow plastic molded product container, the base layer may be coated on the surface of the polyethylene resin layer by a treatment such as fluorination, surface coating or plasma polymerization.

A particularly preferred embodiment of the hollow plastic molded article container is a four-type six-layer structure including the following layers from the inside to the outside. That is, a polyethylene resin layer, an adhesive layer, a barrier layer, an adhesive layer, a recycled material layer, and a polyethylene resin layer.
Below, the structure of each layer in the said aspect and a layer structure ratio are demonstrated in detail.

(1) Layer structure of hollow plastic molded product container (a) Outermost layer The resin (a) constituting the outermost layer of the hollow plastic molded product container is a polyethylene-based resin that satisfies the above predetermined requirements.

(B) Innermost layer The resin (b) constituting the innermost layer of the hollow plastic molded product container is a polyethylene resin that satisfies the above-mentioned predetermined requirements, and may be the same as or different from the resin (a). It may be.

(C) Barrier layer The resin (c) that forms the barrier layer of the hollow plastic molded product container is selected from ethylene vinyl alcohol resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, etc. It is preferable to consist of alcohol resin. More preferably, the ethylene vinyl alcohol resin has a saponification degree of 93% or more, desirably 96% or more, and an ethylene content of 25 to 50 mol%.

(D) Adhesive layer The resin (d) that forms the adhesive layer of the hollow plastic molded product container is selected from high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and the like graft-modified with unsaturated carboxylic acid or a derivative thereof. In particular, it is preferably made of high-density polyethylene graft-modified with an unsaturated carboxylic acid or a derivative thereof.
Content of unsaturated carboxylic acid or its derivative (s) is 0.01-5 weight%, Preferably it is 0.01-3 weight%, More preferably, it is 0.01-1 weight%. When the graft modification amount is less than 0.01% by weight, sufficient adhesion performance is not exhibited, and when it exceeds 5% by weight, unsaturated carboxylic acid that does not contribute to adhesion adversely affects adhesion.

(E) Recycled material layer The resin that forms the recycled material layer of the hollow plastic molded product container includes a polyethylene resin (a) that forms the outermost layer, a polyethylene resin (b) that forms the innermost layer, and a barrier layer. It is a composition containing resin (c) and resin (d) which forms an adhesive layer. The blending amount of each component is preferably (a) component 10 to 30% by weight, (b) component 30 to 50% by weight, (c) component 1 to 15% by weight, and (d) component 1 to 15% by weight. .
As each component of (a) to (d), a new article can be used, but unnecessary parts such as scrap and burrs of the multilayer laminate including each layer composed of the components (a) to (d) are recovered and re-used. Such recycled products can be used as component raw materials for each component. For example, a regrind resin obtained by pulverizing a hollow plastic molded product (such as an automobile fuel tank product) once molded, used, and used is used. When a recycled product is used, all the components (a) to (d) can be supplied from the recycled product, or can be mixed with a new product.
When using molding burrs or unused parisons that are generated during the production of multilayer laminates as recycled materials, the compatibility of various components may decrease, so further mixing the compatibilizer and the resin that constitutes the adhesive layer May be.

(F) Layer composition ratio of hollow plastic molded product container The thickness composition of each layer of the hollow plastic molded product container is 10 to 30% of the outermost layer, 20 to 50% of the innermost layer, and 1 to 15% of the barrier layer by thickness ratio. The adhesive layer is 1 to 15%, and the recycled material layer is 30 to 60% (however, the sum of all layer thickness components is 100%).
The layer composition ratio of the outermost layer is 10 to 30%, preferably 10 to 25%, more preferably 10 to 20%. When the layer composition ratio of the outermost layer is less than 10%, the impact performance is insufficient, and when it exceeds 30%, the molding stability of the hollow plastic molded product container is impaired.
The layer composition ratio of the innermost layer is 20 to 50%, preferably 35 to 50%, more preferably 40 to 50%. If the outer layer has a layer composition ratio of less than 20%, a lack of rigidity of the hollow plastic molded product becomes obvious, and if it exceeds 50%, molding stability of the hollow plastic molded product is impaired.
The layer composition ratio of the barrier layer is 1 to 15%, preferably 1 to 10%, more preferably 1 to 5%. When the layer composition ratio of the barrier layer is less than 1%, the barrier performance is insufficient, and when it exceeds 15%, the impact performance is insufficient.
The layer composition ratio of the adhesive layer is 1 to 15%, preferably 1 to 10%, more preferably 1 to 5%. When the layer composition ratio of the adhesive layer is less than 1%, the adhesive performance is unsatisfactory, and when it exceeds 15%, the rigidity of the hollow plastic molded product becomes insufficient.
The composition ratio of the recycled material layer is 30 to 60%, preferably 35 to 50%, more preferably 35 to 45%. If the layer composition ratio of the recycled material layer is less than 30%, the molding stability of the hollow plastic molded product is impaired, and if it exceeds 60%, the impact performance is insufficient.

  The hollow plastic molded product container is preferably a four-type six-layer hollow plastic molded product that is laminated in this order from the outermost layer, the recycled material layer, the adhesive layer, the barrier layer, the adhesive layer, and the innermost layer. By sandwiching the barrier layer with an adhesive layer, a high level of barrier properties is exhibited. By having the recycled material layer between the outermost layer and the adhesive layer, the effects of cost reduction by reducing raw material costs and maintaining the rigidity of the hollow plastic molded product container are exhibited.

(2) Production of hollow plastic molded product container and container parts The production method of the hollow plastic molded product container is not particularly limited, and can be produced by an extrusion blow molding method using a conventionally known multilayer hollow molding machine. . For example, after a constituent resin of each layer is heated and melted by a plurality of extruders, a molten parison is extruded by a multilayer die, then the parison is sandwiched between molds, and air is blown into the interior of the parison, thereby forming a multilayer hollow plastic A molded product is produced. The fuel pipe which is a container part can be formed by extrusion molding or injection molding. Other container parts can also be formed by hollow molding, injection molding, extrusion molding or the like.
Furthermore, for hollow plastic molded product containers and container parts, antistatic agents, antioxidants, neutralizers, lubricants, antiblocking agents, antifogging agents, organic or inorganic materials are used as long as the purpose is not impaired as required. Known additives such as pigments, fillers, inorganic fillers, UV inhibitors, dispersants, weathering agents, crosslinking agents, foaming agents, flame retardants and the like can be added.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. In addition, the measuring method used in the Example is as follows.

(1) Density: Measured according to JIS K6922-1 and 2: 1997.
(2) Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg: measured in accordance with JIS K6922-2: 1997.
(3) Melt flow rate (HLMFR) at a temperature of 190 ° C. and a load of 21.6 kg: measured in accordance with JIS K6922-2: 1997.
(4) GPC measurement conditions and measurement method, and molecular weight calculation method:
Use (i) Measurement Conditions c _o Tazu Inc. Model 150C, subjected to GPC measurement under the following conditions to determine the weight average molecular weight (Mw).
Column: 1 Shodex HT-G manufactured by Showa Denko KK and 2 HT-806Ms of the same Solvent: 1,2,4-trichlorobenzene Temperature: 140 ° C.
Flow rate: 1.0 ml / min Injection volume: 300 μl
(Ii) Sample preparation Approximately 3 mg of a sample and 3.0 ml of a solvent were weighed into a commercially available 4 ml screw top vial, and shaken at a temperature of 150 ° C. for 2 hours using a SSC-9300 type stirrer manufactured by Senshu Kagaku.
(Iii) Calculation of molecular weight GPC chromatographic data is loaded into a computer at a frequency of 1 point / second, processed according to the description in Chapter 4 of “Size Exclusion Chromatography” written by Sadao Mori and Kyoritsu Publishing Co., and the Mw value is calculated. Calculated.
(Iv) Column calibration Column calibration was performed by using monodisperse polystyrene (S-7300, S-3900, S-1950, S-1460, S-1010, S-565, S-152, S-66 manufactured by Showa Denko KK 0.0, S-28.5, S-5.05), n-eicosane and 0.2 mg / l each solution of n-tetracontane, a series of monodisperse polystyrene measurements were taken and their elution peaks A curve obtained by fitting a logarithmic relationship between time and molecular weight with a quartic polynomial was used as a calibration curve.
In addition, the molecular weight of polystyrene was converted into the molecular weight of polyethylene using the following formula.
M _PE = 0.468 × M _PS
(5) Flexural modulus: measured in accordance with JIS K6922-2: 2005.
(6) Charpy impact strength: In accordance with JIS K-7111 (2004), a type 1 test piece was prepared, the edge direction was edgewise, and the notch type was type A (0.25 mm).
As a result, it was measured at −40 ° C. in dry ice / alcohol.
(7) Long-term durability test 1: In accordance with JIS K6922-2: 2005, a test piece having a thickness of 2 mm was prepared, and an immersion test was performed in warm water at 80 ° C. Furthermore, 50 cc of the test solution was injected into a cup having an inner diameter of 65 mmφ, the opening was sealed with a test piece after immersion in warm water, and a one-side immersion test of biodiesel fuel was performed at 100 ° C. As evaluation of long-term durability, the molecular weight of the test piece after fuel immersion was measured by GPC. The ratio of the molecular weight of polyethylene after 504 hours of immersion in biodiesel fuel (molecular weight retention) to the molecular weight of polyethylene before immersion in biodiesel fuel is 75% or more, and x is less than 75%. did.

(11) Long-term durability test 2: A test with a thickness of 2 mm was prepared according to JIS K6922-2: 2005, and an exposure test according to JIS K7350-4: 1996 was performed. Furthermore, 50 cc of the test solution was injected into a cup having an inner diameter of 65 mmφ, the opening was sealed with a test piece after the exposure test, and a single-sided immersion test in biodiesel fuel was performed at 100 ° C. As evaluation of long-term durability, the molecular weight of the test piece after fuel immersion was measured by GPC. The ratio of the molecular weight of polyethylene after 504 hours of immersion in biodiesel fuel (molecular weight retention) to the molecular weight of polyethylene before immersion in biodiesel fuel is 75% or more, and x is less than 75%. did.

Resin used (1) Polyethylene (I)
The following were used.
High density polyethylene HB111R (density = 0.945 g / cm ³ , HLMFR = 6 g / 10 min) manufactured by Nippon Polyethylene
High density polyethylene HJ221 manufactured by Nippon Polyethylene (density = 0.949 g / cm ³ , HLMFR = 13 g / 10 min)
High-density polyethylene 4261AG (density = 0.945 g / cm ³ , HLMFR = 6 g / 10 min) manufactured by Basel
(2) Ethylene-vinyl compound copolymer (II)
Using a stirring autoclave type continuous reactor, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine dissolved in ethylene and ethyl acetate and tertiary butyl peroxypidine dissolved in normal hexane as a catalyst. Valate was continuously fed and copolymerized at a polymerization pressure of 2000 kg / cm ² and a polymerization temperature of 200 ° C. The resulting copolymer had a melt flow rate of 2.7 g / 10 minutes and a 4-acryloyloxy-2,2,6,6-tetramethylpiperidine unit content of 5.0% by weight (0.69 mol%). The ratio of the isolated substance was 85% as measured by ¹³ C-NMR. This ethylene-vinyl compound copolymer was used as “copolymer (a)”.

Test liquid used As the test liquid for the long-term durability tests 1 and 2, the following test liquid (A) or (B) was used.
The test liquid (A) used Vetable oil methyl ester (CAS No. 68990-52-3) manufactured by DIESTER INDUSTRIE as biodiesel fuel.
The test liquid (B) is 30% by volume of Vetable oil methyl ester (CAS No. 68990-52-3) manufactured by DIESTER INDUSTRIES as biodiesel fuel, and 70% by volume of ENEOS premium light oil manufactured by Nippon Oil Corporation as light oil. A mixture with was used.

[Example 1]
The materials shown in Table 1 were used as materials, test pieces were prepared, and various performance evaluations were performed. The results are shown in Table 1.

[Examples 2-3]
Except for the conditions shown in Table 1, test pieces were prepared in the same manner as in Example 1, and various performance evaluations were performed. The results are shown in Table 1.

[Comparative Examples 1 to 7]
The procedure was the same as in Example 1 except for the conditions shown in Table 1.
In Comparative Example 1, instead of the ethylene-vinyl compound copolymer (II) of Example 1, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (Flectol TMQ, CAS manufactured by FLEXSYS) was used. No. 26780-96-1, molecular weight of about 500), Comparative Examples 2 and 3 are CHIMASSORB manufactured by Ciba Specialty Chemicals instead of the ethylene-vinyl compound copolymer (II) of Example 1. 944 was used. The results are shown in Table 1.

[Examples 4 to 6]
As shown in Table 2, the same procedure was carried out as in Examples 1 to 3, except that the test solution (A) was replaced with the test solution (B). The results are shown in Table 2.

"Evaluation"
In Examples 1 to 3 that satisfy the requirements of the present invention, as a result of a long-term durability test using biodiesel fuel, the weight average molecular weight is hardly changed, and molecular cleavage or the like that is considered to be caused by oxidative degradation or the like is unlikely to occur. I understand.
On the other hand, Comparative Example 1 uses polymerized 2,2,4-trimethyl-1,2-dihydroquinoline corresponding to Example 13 of JP-T-2001-527109 (Patent Document 2). It can be seen that the long-term durability is inferior to that of the examples. Moreover, Comparative Example 2 and 3 used CHIMASSORB 944 instead of the ethylene-vinyl compound copolymer (II) of Example 1, and it turns out that long-term durability is also inferior to an Example. Comparative examples 4-6 do not use ethylene-vinyl compound copolymer (II), and it turns out that long-term durability is inferior to an Example. In Comparative Example 7, the ethylene-vinyl compound copolymer (II) was used in an amount exceeding 10 parts by weight with respect to 100 parts by weight of polyethylene (I), resulting in a decrease in impact resistance.
Further, as shown in Examples 4 to 6, the resin material of the present invention is less likely to change in weight average molecular weight even with respect to a mixture of biodiesel fuel and light oil, and is considered to be caused by oxidation degradation or the like. It turns out that etc. are hard to occur.

  The biodiesel fuel container material of the present invention can be applied to the production of molded articles that are in direct or indirect contact with biodiesel fuel, and is a fuel container excellent in various properties such as long-term durability, elution resistance, and mechanical strength, and A fuel container part can be obtained. Moreover, since it can be used in a wide range of fields including various container fields due to its characteristics, it is very useful in industry.

Claims (7)

To 100 parts by weight of polyethylene (I) having a density of 0.920 to 0.970 g / cm ³ and a melt flow rate (HLMFR; measured at a temperature of 190 ° C. and a load of 21.6 kg) of 0.1 to 100 g / 10 min. In contrast, a biodiesel fuel container material containing 0.1 to 10 parts by weight of an ethylene-vinyl compound copolymer (II),
The ethylene-vinyl compound copolymer (II) is a copolymer of ethylene (A) and a vinyl compound (B) represented by the following general formula, and (B) with respect to the sum of (A) and (B). ) Is 0.001 to 2.0 mol%, and the melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg of the copolymer is 0.1 to 200 g / 10 min. A material for a biodiesel fuel container, characterized in that it exists.

(In formula, R < ₁ > and R < ₂ > is a hydrogen atom or a methyl group, and R < ₃ > represents a hydrogen atom or a C1-C4 alkyl group.)   In the ethylene-vinyl compound copolymer (II), two or more vinyl compounds (B) are present in isolation without being continuous, and the proportion thereof is based on the total amount of the vinyl compound (B). It is 83% or more, The material for biodiesel fuel containers of Claim 1 characterized by the above-mentioned.   Vinyl compound (B) is 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-acryloyloxy-1- Ethyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, and 4-acryloyloxy-1-butyl-2,2,6 The material for a biodiesel fuel container according to claim 1 or 2, wherein the material is a compound selected from the group consisting of 1,6-tetramethylpiperidine.   The ratio of the vinyl compound (B) unit is 10 to 5000 ppm with respect to the total amount of polyethylene (I) and ethylene-vinyl compound copolymer (II). The material for biodiesel fuel containers as described. The polyethylene (I) has a density of 0.930 to 0.965 g / cm ³ and an HLMFR of 1 to 50 g / 10 minutes, for a biodiesel fuel container according to any one of claims 1 to 4 material.   The biodiesel fuel container manufactured using the material in any one of Claims 1-5.   The biodiesel fuel container part manufactured using the material in any one of Claims 1-5.