JP5997879B2 - Resin multilayer container - Google Patents

Description

  The present invention relates to a resin multilayer container, and more particularly to a resin multilayer container having improved surface slipperiness and puncture resistance. More specifically, it exhibits optimal slipperiness in each process such as the manufacturing process, filling process, and packaging process of the resin multilayer container, and the filled content is excellent in liquid drainage, and is transported, stored, and used. The present invention relates to the improvement of a resin multilayer container that does not impair the sealing performance sometimes.

  Resin multilayer containers filled with viscous contents such as ketchup and mayonnaise (hereinafter sometimes simply referred to as “multilayer containers” or “containers”) are mainly blown by a direct blow method. Often manufactured by being extruded and subsequently blow molded into the shape of a container in a cooling mold. The structure of the resin material is a multilayer structure in which a polyolefin resin such as a polypropylene resin is used as a surface layer (inner layer and / or outer layer), and a barrier layer such as an ethylene vinyl alcohol copolymer is provided in an intermediate layer. The ones are common.

  For example, Japanese Patent Laid-Open No. 1-139347 (Patent Document 1) discloses a tube container in which at least an outer layer contains linear low density polyethylene and high pressure method low density polyethylene and has a gas barrier resin layer. No. 10-166530 (Patent Document 2) discloses at least ethylene in which an inner surface resin layer is polymerized using a metallocene catalyst in a tube container in which a surface resin layer, an intermediate layer, and an inner surface resin layer are sequentially laminated. The container is made of a resin layer of -α-olefin copolymer, and the intermediate layer is a vapor deposition layer of an inorganic oxide.

  Resin multilayer containers are required to have slipperiness on the container surface as well as transparency and gloss. In other words, in the case of resin multilayer containers, environment such as line, temperature, humidity, etc., such as container molding process, container transfer process, content filling process such as food by the user, transfer process after filling the contents, container packaging process, etc. In each of the processes with different conditions, it is required to exhibit good slipperiness in order to ensure stable continuous production. For example, in a container forming process line or a container alignment line in a content filling process, even if containers contact each other, slipperiness is required so as not to affect the work and production speed in the process or the next process. . Moreover, in the transfer line after the container is filled with the contents, slipping between the transfer conveyor and the container is required in order to ensure smooth transfer. Furthermore, in the container packaging line, since the packaging of the container with the exterior film is usually performed at a high speed, the slipperiness between the container surface and the wrap film is required. Since each of these processes and lines has different environmental conditions such as temperature and humidity, an appropriate slip property of the surface of the resin multilayer container is required under various environmental conditions. Further, in order to improve the liquid drainage of the contents filled in the container, the slipperiness of the inner surface of the resin multilayer container is required.

  In order to improve the slipperiness of the resin multilayer container, conventionally, a lubricant is mainly added to the raw material resin of the outermost layer or the innermost layer. The lubricant is usually added to a raw material resin by a master batch method or kneaded.

As the lubricant, for example, fatty acid amide is widely used, and specifically, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide (behenic acid amide) and the like are used. Among these, the lubricant having a low melting point is, for example, oleic acid amide, and by adding this, good slipperiness is exhibited when the temperature of the container is low. A lubricant having a relatively high melting point is, for example, behenic acid amide. By adding this, a good slip property can be obtained when the container becomes hot, such as when the contents such as food are filled at high temperature. It can be demonstrated. These lubricants have been used in a mixture of two or more. For example, in JP 2009-214914 A (Patent Document 3), in a multilayer container filled with non-oil content, an unsaturated aliphatic amide and a saturated aliphatic amide are blended into a polyolefin resin layer on the inner surface of the container. Is disclosed. Japanese Unexamined Patent Publication No. 2010-189052 (Patent Document 4) discloses a multilayer container filled with oil-based contents, which has a polyolefin-based resin layer on the outermost surface layer and the innermost surface layer, and the innermost surface layer is a linear low density polyethylene. It is disclosed that the outermost surface layer contains a lubricant such as an unsaturated aliphatic amide. Japanese Patent Laid-Open No. 6-72422 (Patent Document 5) discloses that in a multilayer container including an outermost layer of a polyolefin resin and a gas barrier layer, two or more kinds of lubricants having different melting points from the polyolefin resin of the outermost layer. Is disclosed. Furthermore, JP-A-2005-307122 (Patent Document 6) discloses oleic acid amide, stearic acid amide, and erucic acid amide as slip agents (lubricants) made from natural product-derived oils and fats.

  Furthermore, in the multilayer container made of resin, when the multilayer container is packaged or packed, when packed and transported, or when the container is stored, the containers or the container and various members come into contact with each other. Or, in some cases, may be shocked. Due to these contacts and impacts, the bottom and body of the container may be damaged, and the sealing performance of the container may be lost. In particular, if the piercing resistance of the resin multilayer container is insufficient, the container is likely to break during transport and storage in winter, and the reliability of product distribution is impaired, so improvement is required. It was.

  In addition, in a resin multilayer container, if the surface gloss is inferior, the state of the filled contents may not be intuitively grasped, and therefore improvement has been demanded.

JP-A-1-139347 Japanese Patent Laid-Open No. 10-166530 JP 2009-214914 A JP 2010-189052 A Japanese Patent Laid-Open No. 6-72422 JP-A-2005-307122

  The problem of the present invention is that containers, containers and devices, containers and packaging films or containers are used under different lines and environmental conditions from the container molding process, the container transfer process, the contents filling process, and the packaging process. To provide a resin multilayer container having appropriate slipperiness between the contents, improved liquid drainage of the contents filled in the container, sufficient puncture resistance, and excellent surface gloss. It is in.

  As a result of diligent research on solving the above problems, the present inventors have determined that the surface layer (the innermost layer and / or the outermost layer) of the resin multilayer container is a polyolefin-based resin composition containing a specific unsaturated fatty acid amide. It was found that the problem can be solved by using the product, and the present invention was completed.

That is, according to the present invention, (A) low density polyethylene, (B) high density polyethylene, (C) an ethylene-based polyolefin obtained using a metallocene catalyst, and (D) an unsaturated cis structure carbon double bond A resin multilayer container comprising as a surface layer a layer made of a resin composition containing a fatty acid amide,
The resin composition has the following I and II:
(I) When the total of (A), (B) and (C) is 100% by mass, (C) is 8 to 40% by mass; and (II) (A), (B) and (C) (D) is 100 to 4000 ppm with respect to the total mass of
The above-mentioned resin multilayer container characterized by satisfying the above is provided.

  In addition, according to the present invention, the following resin multilayer containers (1) to (13) are provided as embodiments.

(1) The fatty acid amide having the (D) unsaturated cis structure carbon double bond is the following (D ₁ ), (D ₂ ) and (D ₃ ):
_{(D 1) H 2 N-} CO - (- CH 2 -) n -CH = CH - (- CH 2 -) n -CH 3 ( where, n is in the range of 6 ≦ n ≦ 10 integer);
_{(D 2) H 2 N-} CO - (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3 ( however, m is an integer in the range of 6 ≦ m ≦ 10) And (D ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10); ;
The above-mentioned resin multilayer container containing at least one fatty acid amide represented by a formula selected from the group consisting of:

(2) The fatty acid amide having the (D) unsaturated cis-structured carbon double bond is a fatty acid amide represented by the formula (D ₁ ), and the (D ₂ ) or (D ₃ ) The said resin multilayer container which is a mixture with the at least 1 sort (s) of fatty acid amide represented by a formula.

(3) The above-mentioned resin multilayer container in which m in the fatty acid amide represented by the formula (D ₂ ) is m = n + 1 or m = n−1.

(4) k in fatty acid amide of the formula of the above (D ₃₎ is said of the resin multilayer container is k = n.

(5) The fatty acid amide having the (D) unsaturated cis structure carbon double bond is a fatty acid amide represented by the above formula (D ₁ ) and the following (D ₁₁ ):
(D ₁₁ ) H ₂ N—CO — (— CH ₂ —) _j —CH═CH — (— CH ₂ —) _j —CH ₃ (where j is an integer in the range of 6 ≦ j ≦ 10, j ≠ n);
The said resin multilayer container which is a mixture with the fatty acid amide represented by this formula.

(6) The above resin multilayer, wherein (D) the fatty acid amide having an unsaturated cis structure carbon double bond contains a compound having 2 to 4 bonds of unsaturated cis structure carbon double bonds in the molecular structure. container.

(7) The resin multilayer container, wherein the resin composition further contains a saturated fatty acid amide.

(8) The said resin multilayer container whose said surface layer is one or both of the outermost layer or the innermost layer.

(9) The said resin multilayer container further provided with a barrier layer.

(10) The said resin multilayer container whose said barrier layer is an ethylene vinyl alcohol copolymer or polyglycolic acid.

(11) The resin multilayer container further including a recovery layer.

(12) The resin multilayer container, wherein the resin multilayer container includes a surface layer, a barrier layer, an adhesive layer, and a recovery layer.

(13) The above-mentioned resin multilayer container comprising the outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer.

According to the present invention, (A) low density polyethylene, (B) high density polyethylene, (C) an ethylene-based polyolefin obtained using a metallocene catalyst, and (D) a fatty acid having an unsaturated cis structure carbon double bond A resin multilayer container provided with a layer made of a resin composition containing an amide as a surface layer,
The resin composition has the following I and II:
(I) When the total of (A), (B) and (C) is 100% by mass, (C) is 8 to 40% by mass; and (II) (A), (B) and (C) (D) is 100 to 4000 ppm with respect to the total mass of
By using the above-mentioned resin multi-layer container satisfying the requirements, the container can be used in different lines and environmental conditions from the container molding process, the container transfer process, the content filling process, and the packaging process. Can exhibit appropriate slipperiness between each other, between the container and the device, between the container and the packaging film or between the container and the contents, and the liquid drainage of the contents filled in the container is improved, and There is an effect that it is possible to provide a resin multilayer container having sufficient puncture resistance and excellent surface gloss.

I. Resin composition forming surface layer The resin multilayer container of the present invention has a surface layer, specifically, one or both of the outermost layer and the innermost layer of the container are (A) low density polyethylene, (B) high density polyethylene, It is characterized in that it is formed from a resin composition containing (C) an ethylene-based polyolefin obtained using a metallocene catalyst, and (D) an aliphatic amide having an unsaturated cis structure carbon double bond. .

1. (A) Low-density polyethylene (A) Low-density polyethylene contained in the surface layer of the resin multilayer container of the present invention means a commonly used low-density polyethylene, and generally has a density of 0.910 to 0.930 g / It is polyethylene of cm ³ , preferably 0.912 to 0.928 g / cm ³ . In addition, the density of polyethylene is measured according to JIS K6922-2.

  (A) The low density polyethylene has an MFR (temperature 190 ° C., load 21.18 N), preferably 0.1 to 10 g / 10 minutes, more preferably 0.3 to 5 g / 10 minutes, and still more preferably 0.5. Those within a range of ˜2 g / 10 min can be used. The low-density polyethylene (A) has a polydispersity (Mw / Mn), which is an index of molecular weight distribution, preferably 1.2 or more, more preferably 1.5 or more, and still more preferably 1.7 or more. In this case, the improvement in moldability is effective. The upper limit of polydispersity (Mw / Mn) is about 3.0. In addition, MFR of polyethylene is measured according to JIS K6922-2, and polydispersity (Mw / Mn) is measured according to JIS K7252.

  (A) As low-density polyethylene, in addition to so-called Ziegler-Natta catalyst, high-pressure polyethylene (soft polyethylene), linear low-density polyethylene (LLDPE), and other olefin monomers such as ethylene Copolymers can also be used. (A) Although a synthetic product can be used as the low density polyethylene, a commercially available product may be used. Commercially available products include Novatec LD (registered trademark) manufactured by Nippon Polyethylene Co., Ltd., and low density polyethylene manufactured by Mitsui DuPont Polychemical Co., Ltd.

  The content of (A) low-density polyethylene in the resin composition is not particularly limited, but is usually 30 to 70% by mass when the total of (A), (B) and (C) is 100% by mass, Preferably it is 35-65 mass%, More preferably, it is the range of 40-60 mass%. If the content of the low-density polyethylene (A) in the resin composition is too small, the melt viscosity of the resin in the blow molding extrusion described later becomes small, causing problems in molding such as difficulty in handling blow bubbles, or a container The surface gloss may be reduced. When the content of the (A) low density polyethylene in the resin composition is too large, the slipperiness may be lowered or the puncture resistance may be lowered.

2. (B) High-density polyethylene (B) The high-density polyethylene contained in the surface layer of the resin multilayer container of the present invention is generally a polyethylene having a density of 0.942 g / cm ³ or more. Usually, it is polyethylene with a density of 0.980 g / cm ³ or less, preferably 0.945 to 0.970 g / cm ³ , more preferably 0.948 to 0.965 g / cm ³ . (B) The high density polyethylene has an MFR (temperature 190 ° C., load 21.18 N), preferably 0.1 to 10 g / 10 minutes, more preferably 0.3 to 5 g / 10 minutes, and still more preferably 0.5. Those within a range of ˜2 g / 10 min can be used. In addition, those having a polydispersity (Mw / Mn) of preferably 2.5 or more, more preferably 3.0 or more, and even more preferably 3.5 or more are effective in improving moldability. . The upper limit of polydispersity (Mw / Mn) is about 5.5.

  (B) A synthetic product can be used as the high-density polyethylene, but it can also be selected from commercially available products. Examples of commercially available products are low-pressure high-density polyethylene obtained using a so-called Ziegler-Natta catalyst, Novatec HD (registered trademark) manufactured by Nippon Polyethylene Co., Ltd., Hi-Zex (registered trademark) manufactured by Prime Polymer Co. There is.

  The content of (B) high-density polyethylene in the resin composition is not particularly limited, but when the total of (A), (B) and (C) is 100% by mass, usually 5 to 60% by mass, Preferably it is 10-55 mass%, More preferably, it is the range of 12-50 mass%. If the content of the (B) high-density polyethylene in the resin composition is too small, the rigidity of the container may be insufficient or the puncture resistance may be reduced. If the content of the (B) high-density polyethylene in the resin composition is too large, drawdown may occur when the container is molded, or melt fracture may occur in the parison used for blow molding.

3. (C) Ethylene-based polyolefin obtained by using a metallocene catalyst A resin multilayer container having a layer composed of a resin composition containing (A), (B), (C) and (D) of the present invention as a surface layer In the resin composition, when the total of (A), (B) and (C) is 100% by mass, the ethylene-based polyolefin obtained using the (C) metallocene catalyst is 8 to 40% by mass. It is characterized by being.

  (C) Ethylene-based polyolefin obtained by using a metallocene catalyst (hereinafter sometimes referred to as “metallocene-catalyzed ethylene-based polyolefin”) is ethylene or a mixture containing ethylene as a main component and α-olefin as a subcomponent. It is an ethylene-based polyolefin obtained by polymerizing a monomer in the presence of a metallocene catalyst. Therefore, the ethylene-based polyolefin obtained using the (C) metallocene catalyst contains polyethylene or an ethylene / α-olefin copolymer obtained by carrying out a polymerization reaction in the presence of the metallocene catalyst.

The metallocene catalyst is a general term for a metallocene, that is, a catalyst comprising a transition metal component composed of a complex composed of two substituted or unsubstituted cyclopentadienyl rings and various transition metals, and an organoaluminum component, particularly an aluminoxane. It is. Examples of the transition metal component include metals of groups IVb, Vb or VIb of the periodic table, particularly zirconium or hafnium. The transition metal component in the catalyst is generally represented by the following formula (Cp) ₂ MR ₂
(Wherein Cp is a substituted or unsubstituted cyclopentadienyl ring, M is a transition metal, and R is a halogen atom or an alkyl group) is generally used. .

  The aluminoxane is obtained by reacting an organoaluminum compound with water, and includes a linear aluminoxane and a cyclic aluminoxane. These aluminoxanes can be used alone or in combination with other organic aluminum.

  A polymerization method of ethylene or ethylene and α-olefin using a metallocene catalyst is known in many publications, and is synthesized by polymerization in an organic solvent, a liquid monomer or a gas phase method in the presence of the metallocene catalyst. However, any of these known methods satisfying the above conditions can be used for the purpose of the present invention.

  In the case of a copolymer of ethylene and an α-olefin, the α-olefin is preferably one having 3 to 10 carbon atoms, and propylene, butene-1, pentene-1, hexene-1, 4-methyl. Examples thereof include pentene-1, heptene-1, octene-1. These α-olefins are preferably present in the copolymer in an amount of 3 to 15 mol%.

The metallocene-catalyzed ethylene-based polyolefin is characterized by a narrow molecular weight distribution. In the present invention, the polydispersity (Mw / Mn), which is an index of the molecular weight distribution, is preferably 4.0 or less, more preferably 3.5. In the following, more preferably 3.2 or less is used. For the purpose of improving moldability, those having relatively long chain branches introduced during polymerization or in subsequent steps are also preferably used. The metallocene-catalyzed ethylene-based polyolefin usually has a density of about 0.890 to 0.920 g / cm ³ , preferably about 0.892 to 0.918 g / cm ³ and an MFR of 0.1 to 10 g / 10 minutes. It is preferably about 0.3 to 5 g / 10 minutes.

  The presence of the (C) metallocene-catalyzed ethylene-based polyolefin in the resin composition can be confirmed by the following method. That is, a resin pellet is cut into a glass having a thickness of 100 μm to form a sample, which is laid on a scanning electron microscope SEM and measured with an analyzer that distributes the generated fluorescent X-rays. The presence of a peak corresponding to the energy of. The resin pellets may be scraped from the surface layer, or may be a surface layer obtained by separating the layers of a resin multilayer container.

  (C) Although a metallocene catalyst ethylene-type polyolefin can use a synthetic product, it can also select and use from a commercial item. Examples of commercially available products include Exelen (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., Harmolex (registered trademark) and Kernel (registered trademark) manufactured by Nippon Polyethylene Corporation.

  When (C) metallocene catalyst ethylene-based polyolefin in the resin composition is less than 8% by mass when the total of (A), (B) and (C) is 100% by mass, the resin product obtained The stab resistance of the multilayer container may be insufficient, or the surface gloss may be lowered. If the (C) metallocene-catalyzed ethylene-based polyolefin in the resin composition similarly exceeds 40% by mass, the slipping property of the resulting resin multilayer container may be deteriorated, and the surface gloss may be further lowered. (C) The metallocene-catalyzed ethylene-based polyolefin can be contained in the resin composition in an amount of preferably 9 to 35% by mass, more preferably 10 to 32% by mass.

4). (D) Fatty acid amide having an unsaturated cis-structured carbon double bond The resin composition containing (A), (B), (C) and (D) in the present invention comprises (A ), (B) and (C), 100 to 4000 ppm of (D) fatty acid amide having an unsaturated cis structure carbon double bond. (D) A fatty acid amide having an unsaturated cis-structured carbon double bond (hereinafter sometimes referred to as “(D) unsaturated fatty acid amide”) functions as a lubricant. The unsaturated fatty acid amide (D) is an unsaturated fatty acid amide having at least one carbon double bond in the molecular structure of the fatty acid amide. When it is an unsaturated fatty acid amide having a plurality of carbon double bonds in the molecular structure of the fatty acid amide, the unsaturated fatty amide in which all of the carbon double bonds are carbon double bonds of an unsaturated cis structure It is. If the unsaturated fatty acid amide has a carbon double bond having a trans structure, the uniform blending of the resin material may be insufficient, or the unsaturated fatty acid amide having the trans structure may precipitate on the surface of the container. In some cases, the slipperiness is deteriorated, the surface gloss is deteriorated, and the puncture strength is lowered.

  The content of the unsaturated fatty acid amide (D) is preferably 150 to 3900 ppm, more preferably 200 to 3800 ppm, still more preferably 250 to 3700 ppm, and particularly preferably 300 to 3600 ppm. If the content of the unsaturated fatty acid amide (D) is too small, the slipping property will be insufficient, and during the manufacture of the container, during transportation or during filling of the contents, it may be caused by contact or collision with containers or devices. There is a risk of the occurrence of defective products, production line stoppage, equipment failure, and the like. Moreover, if the slipperiness of the innermost layer of the container is insufficient, the contents may not be filled smoothly, or the contents may be insufficiently drained when used by consumers. When there is too much content of unsaturated fatty acid amide of (D), the surface gloss of the obtained container may become small, or the stickiness during conveyance work may increase. When the unsaturated fatty acid amide of (D) is a mixture of fatty acid amides having two or more kinds of unsaturated cis structure carbon double bonds as described later, the total amount of the mixture needs to be included in the above range. There is.

  (D) The fatty acid amide having an unsaturated cis structure carbon double bond is preferably a fatty acid amide having an unsaturated cis structure carbon double bond having one unsaturated cis structure carbon double bond in the molecular structure. is there.

  (D) The fatty acid amide having an unsaturated cis-structured carbon double bond may be an unsaturated fatty acid amide having a plurality of unsaturated cis-structured carbon double bonds in the molecular structure. A compound having 6 or less carbon bonds, more preferably 5 or less bonds, and still more preferably 4 or less bonds. Therefore, the fatty acid amide having an unsaturated cis structure carbon double bond (D) most preferably used in the present invention is an unsaturated cis structure having 1 to 4 unsaturated cis structure carbon double bonds in the molecular structure. It is a fatty acid amide having a carbon double bond.

Examples of the fatty acid amide having an unsaturated cis structure carbon double bond (D) having an unsaturated cis structure carbon double bond include the following formulas (D ₁ ) to (D ₃ ):
_{(D 1) H 2 N-} CO - (- CH 2 -) n -CH = CH - (- CH 2 -) n -CH 3 ( where, n is in the range of 6 ≦ n ≦ 10 integer);
(D ₂ ) H ₂ N—CO — (— CH ₂ —) _m−2 —CH═CH — (— CH ₂ —) _m —CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10) And (D ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10); ;
And at least one fatty acid amide compound represented by the formula selected from the group consisting of: (Hereinafter, (the fatty acid amide represented by the formula _{D 1),} there may be referred to as "formula _{(D 1)} fatty acid amide of the" further may be simply referred to as a "formula _{(D 1)". (D} 2) The same applies to the fatty acid amide represented by the formula (D ₃ ).)

  Preferred examples of the fatty acid amide having an unsaturated cis structure carbon double bond (D) having one unsaturated cis structure carbon double bond include the following compounds.

Formula _{(D 1) H 2 N-} CO - (- CH 2 -) n -CH = CH - (- CH 2 -) n -CH 3 ( where, n is in the range of 6 ≦ n ≦ 10 integer):
cis-8,9-hexadecenoamide [H ₂ N—CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₆ —CH ₃ ] (corresponding to n = 6)
cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to n = 7)
cis-10, 11-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₈ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ] (corresponding to n = 8)
cis-11,12-ethaeicosenoamide [H ₂ N—CO — (— CH ₂ —) ₉ —CH═CH — (— CH ₂ —) ₉ —CH ₃ ] (corresponding to n = 9)
cis-12, 13- tetraeicosenoamide (corresponding to n = 10) _{[H 2 N-CO - (-} CH 2 -) 10 -CH = CH - (- - CH 2) 10 -CH 3 ]

Formula (D ₂ ) H ₂ N—CO — (— CH ₂ —) _{m− 2} —CH═CH — (— CH ₂ —) _m —CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10) ):
cis-6,7-tetradecenoamide _{[H 2 N-CO - (-} CH 2 -) 4 -CH = CH - (- CH 2 -) 6 -CH 3 ] (corresponding to m = 6)
cis-7,8-hexadecenoamide [H ₂ N—CO — (— CH ₂ —) ₅ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to m = 7)
cis-8,9-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ] (corresponding to m = 8)
cis-9,10-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₉ —CH ₃ ] (corresponding to m = 9)
cis-10, 11- ethaeicosenoamide (corresponding to m = 10) _{[H 2 N-CO - (-} CH 2 -) 8 -CH = CH - (- - CH 2) 10 -CH 3 ]

Formula (D ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10):
cis-12,13-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₀ —CH═CH — (— CH ₂ —) ₆ —CH ₃ ] (corresponding to k = 6)
cis-13,14-docosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₁ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to k = 7)
cis-14,15- tetracosenoamide (corresponding to k = 8) _{[H 2 N-CO - (-} CH 2 -) 12 -CH = CH - 8 -CH 3 (- - CH 2) ]
cis-15,16-hexacosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₃ —CH═CH — (— CH ₂ —) ₉ —CH ₃ ] (corresponding to k = 9)
cis-16,17- octacosenoamide (corresponding to k = 10) _{[H 2 N-CO - (-} CH 2 -) 14 -CH = CH - (- - CH 2) 10 -CH 3 ]

Examples of the fatty acid amide having an unsaturated cis structure carbon double bond, which is a compound having 2 to 4 bonds of unsaturated cis structure in the molecular structure, include, for example, an unsaturated cis structure in the molecular structure. The following compounds having 4 carbon double bonds are listed.
cis-5,6-8,9-11,12-14,15-arachidonic acid amide [H ₂ N—CO — (— CH ₂ —) ₃ —CH═CH—CH ₂ —CH═CH—CH ₂ — _{CH = CH-CH 2 -CH =} CH - (- CH 2 -) 4 -CH 3 ]

Examples of the (D) fatty acid amide having an unsaturated cis structure carbon double bond include the fatty acid amides of the above formulas (D ₁ ) to (D ₃ ), or a plurality of unsaturated cis structures in the molecular structure. If one type of fatty acid amide selected from fatty acid amides having a carbon double bond is used, a sufficient effect can be obtained, but two or more types of (D) unsaturated cis-structured carbon double bonds can be obtained. A mixture of fatty acid amides may be used. The mixture of fatty acid amides preferably contains the fatty acid amide of the above formula (D ₁ ).

Therefore, a preferred mixture of (D) fatty acid amides having an unsaturated cis-structured carbon double bond is represented by the above formula (D ₁ ) fatty acid amide and the above formula (D ₂ ) or (D ₃ ). A mixture with at least one fatty acid amide. The proportion of the fatty acid amide of the formula (D ₁ ) in the mixture is usually 0.05 to 99.95% by mass, preferably 0.1 to 99.9% by mass, more preferably 0.5 to 99.5% by mass. %, More preferably in the range of 1 to 99% by mass. Therefore, the ratio of the fatty acid amide, which is the above formula (D ₂ ) or formula (D ₃ ), or a mixture of formula (D ₂ ) and formula (D ₃ ) is usually 99.95 to 0.05% by mass, preferably Is in the range of 99.9 to 0.1% by mass, more preferably 99.5 to 0.5% by mass, and still more preferably 99 to 1% by mass.

In particular, (D) a mixture of fatty acid amides having an unsaturated cis-structured carbon double bond is a fatty acid amide of the above formula (D ₁ ), ie H ₂ N—CO — (— CH ₂ —) _n —CH═ CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10) and the fatty acid amide of the above formula (D ₂ ), that is, H ₂ N—CO— ( —CH ₂ —) _{m− 2} —CH═CH — (— CH ₂ —) _m —CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10), and m = n + 1 or m = n It is preferable that it is a mixture with this fatty acid amide which is -1.

In particular,
The formula (D ₁ ) corresponds to cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (n = 7 And the formula (D ₂ ) is cis-6,7-tetradecenoamide [H ₂ N—CO — (— CH ₂ —) ₄ —CH═CH — (— CH ₂ —) ₆ —CH ₃ ] (m = Corresponding to n-1) or cis-8,9-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ] ( m = 8 = corresponding to n + 1) and the like.

Further, (D) a mixture of fatty acid amides having an unsaturated cis-structured carbon double bond is a fatty acid amide of the above formula (D ₁ ), that is, H ₂ N—CO — (— CH ₂ —) _n —CH═ CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10) and the fatty acid amide of the above formula (D ₃ ), that is, H ₂ N—CO— ( —CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10) and k = n It is preferable that it is a mixture.

In particular,
The formula (D ₁ ) corresponds to cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (n = 7 And the formula (D ₃ ) is cis-13,14-docosenoamide [H ₂ N—CO — (— CH ₂ —) ₁₁ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (k = Corresponding to 7 = n) and the like can be preferably used.

Further, (D) a mixture of fatty acid amides having an unsaturated cis-structured carbon double bond is a mixture of two or more compounds belonging to the fatty acid amide of the above formula (D ₁ ) and having different values of n. be able to. That is, (D ₁ ) H ₂ N—CO — (— CH ₂ —) _n —CH═CH — (— CH ₂ —) _n —CH ₃ (where n is an integer in the range of 6 ≦ n ≦ 10) And (D ₁₁ ) H ₂ N—CO — (— CH ₂ —) _j —CH═CH — (— CH ₂ —) _j —CH ₃ (where j is an integer in the range of 6 ≦ j ≦ 10) , J ≠ n) can be used.

Specifically, for example, the formula (D ₁ ) is cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ (Corresponding to n = 7), and the formula (D ₁₁ ) is cis-10,11-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₈ —CH═CH — (— CH ₂ —) ₈ -CH ₃ ] (corresponding to j = 8) is preferably used.

Furthermore, (D) a fatty acid amide having an unsaturated cis-structured carbon double bond containing 2 to 4 unsaturated cis-structured carbon double bonds in the molecular structure may be used alone or in combination with other (D) It can also be used as a mixture with a fatty acid amide having a saturated cis structure carbon double bond. As the other (D) fatty acid amide having an unsaturated cis structure carbon double bond, the fatty acid amides of the above formulas (D ₁ ) to (D ₃ ) are preferably used, and in particular, the fatty acid amide of the formula (D ₁ ) Amides are preferred. Specifically, cis-5,6-8,9-11,12-14,15-arachidonic acid amide [H ₂ N—CO — (— CH ₂ —) ₃ —CH═CH—CH ₂ —CH═ _{CH-CH 2 -CH = CH-} CH 2 -CH = CH - (- CH 2 -) 4 and -CH _3], a mixture such as is preferably used in the cis-9,10-octadecenoamide is a formula _{(D 1)} it can.

5. (D) Method for Producing Fatty Acid Amide Having Unsaturated cis-Structure Carbon Double Bond The unsaturated fatty acid amide (D) contained in the resin composition in the present invention may be a commercially available product or a commercially available product. May be obtained by separating the desired unsaturated fatty acid amide by extraction or the like. However, for example, fatty acid amides of the formula _{(D 2), i.e., (D 2) H 2 N} -CO - (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH ₃ (where m is an integer in the range of 6 ≦ m ≦ 10) can be produced by the following method.

The following (formula a) having a CH ₃ O—CO— terminal group and a hydroxyl group terminal or a carboxylic acid terminal at the α, ω positions and a (m−1) -linked methylene group (—CH ₂ —) _m−1 ):
(Formula _{a) CH 3 O-CO -} (- CH 2 -) m-1 -OH
As a starting material. ((Formula a) illustrates a compound having a hydroxyl terminal.)

The hydroxyl terminal of the compound represented by the formula (a) is bromine-substituted using carbon tetrabromide (CBr ₄ ), and then methyl cyanide (CH ₃ ) using triphenylphosphine (PPh ₃ , triphenylphosphine). CN) bromine is reacted with PPh ₃ in a solvent and the following (formula b):
(Formula b) [CH ₃ O—CO — (— CH ₂ —) _m−1 -PPh ₃ ] ⁺ + Br ⁻
To obtain an ionic intermediate represented by:

The ionic intermediate (formula b) is reacted with decyl aldehyde to make the PPh ₃ group an alkyl group terminal having a carbon double bond with an unsaturated cis structure (formula c):
(Formula _{c) CH 3 O-CO -} (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3
The α, ω structural compound represented by

Next, lithium hydroxide is reacted with the CH ₃ O—CO— terminal group of the α, ω structure compound of the formula (c) to form a hydroxyl terminal, which is saturated with ammonium in a solvent of oxalyl chrolide and methylene chloride. To the amide group terminal by reaction with (Formula d):
(Wherein _{d) H 2 N-CO -} (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3
A fatty acid amide having an unsaturated cis structure carbon double bond represented by

  By changing the carbon number m (where m is an integer in the range of 6 ≦ m ≦ 10), a fatty acid amide having an unsaturated cis structure carbon double bond having a desired carbon number can be obtained using this synthetic route. Can be obtained.

In the synthesis of fatty acid amide having an unsaturated carbon double bond, as is well known, a compound having an unsaturated cis structure carbon double bond and a compound having an unsaturated trans structure carbon double bond can be obtained simultaneously. Therefore, chromatographic development is performed using a mixed solvent having a concentration gradient of 100% (initial development) to 40% of ethyl acetate and hexane to separate isomers of unsaturated cis structure and unsaturated trans structure. . At that time, using a proton ¹ H-NMR nuclear magnetic resonance apparatus, identification according to the chemical shift value was performed on the fractionated solution at each chromatography development time based on the Aldorich standard substance, and fractionation was performed. Identify the liquid. The fraction solution is dried under reduced pressure to recover the desired fatty acid amide having an unsaturated cis structure carbon double bond.

6). Other compounding agents The resin composition according to the present invention is optionally further blended with other inorganic fillers, heat stabilizers, light stabilizers, water repellents, antistatic agents, antiblocking agents, release agents. Various additives such as a coupling agent and an oxygen absorber can be contained.

  In addition, the resin composition of the present invention can be used as other compounding agents within a range not impairing the object of the present invention, as desired, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid. Other polymers such as methyl copolymers, maleic anhydride modified polyolefins can be included. The content of these various additives and other polymers is usually 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less in the resin composition.

  As various additives, other lubricants other than the unsaturated fatty acid amide of the formula (D) can also be used. As the other lubricant, a saturated fatty acid amide is preferable. By using the saturated fatty acid amide in combination, effects such as further improvement of slipperiness and surface gloss can be achieved. As the saturated fatty acid amide, a compound usually used as a lubricant can be used, for example, butyramide, valeric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, Examples thereof include palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, and preferably stearic acid amide and behenic acid amide.

  When the saturated fatty acid amide is contained, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, based on the total content of the unsaturated fatty acid amide of the formula (D) and the saturated fatty acid amide. More preferably, it is 6% by mass or less, and the lower limit of the content is about 0.5% by mass, and if it is 1% by mass, a sufficient effect can be realized. Moreover, the total content of the unsaturated fatty acid amide of the formula (D) and the saturated fatty acid amide is in the range of 100 to 4000 ppm with respect to the total mass of (A), (B) and (C). Is preferred.

II. Resin multilayer container The resin multilayer container of the present invention is a resin multilayer container provided with a layer made of the resin composition as a surface layer. The resin multilayer container of the present invention includes a resin multilayer container having a multilayer structure of two layers, three layers, four layers, five layers or more having a layer made of the resin composition as a surface layer.

1. Surface layer As a surface layer in a resin multilayer container, there are an outermost layer and an innermost layer of the container. The resin multilayer container of the present invention comprises a layer made of the resin composition, that is, a layer made of the resin composition containing the (A), (B), (C) and (D). The outermost layer or the innermost layer may be provided in one or both of the outermost layer and the innermost layer.

  By arranging the layer composed of the resin composition of the present invention in the outermost layer of the resin multilayer container, the slipperiness of the outer surface of the container is improved, so that the container is being manufactured, transported or filled with contents. In addition, it is possible to prevent the occurrence of defective products, the stop of the production line, the failure of the device, etc. due to contact or collision with containers or devices, and the surface gloss is also excellent.

  By arranging the layer composed of the resin composition of the present invention in the innermost layer of the resin multilayer container, the slipperiness of the inner surface of the container is improved, so that the contents can be filled smoothly or the consumer's There are effects such as excellent liquid drainage of the contents during use.

  By arranging the layer composed of the resin composition of the present invention in the outermost layer and the innermost layer of the resin multilayer container, the effects of both the case of arranging in the outermost layer and the case of arranging in the innermost layer are combined. Can be realized.

2. Barrier layer The resin multilayer container of the present invention preferably further comprises a barrier layer in order to enhance the storage stability of the contents. As the barrier layer, those having gas barrier properties such as oxygen barrier properties and carbon dioxide gas barrier properties, and barrier properties against water or water vapor can be used. The barrier layer is not particularly limited, and a resin film layer on which a metal or an inorganic oxide is deposited, a metal foil, a barrier resin layer, or the like can be used depending on the type of container.

  Preferable examples of the barrier resin forming the barrier layer include partially saponified products of ethylene vinyl alcohol copolymer or ethylene-vinyl acetate copolymer (hereinafter, these may be collectively referred to as “EVOH”). be able to. Furthermore, since it is excellent not only in oxygen gas barrier properties but also in carbon dioxide gas barrier properties, polyglycolic acid can be used as the gas barrier resin. Moreover, aromatic polyamide (MXD6) formed from metaxylylenediamine and adipic acid, polyvinylidene chloride, and the like can be used.

  As EVOH, an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%, more preferably 30 to 50 mol%, a saponification degree of 90 mol% or more, A saponified copolymer obtained by saponification is preferably used in an amount of 95 mol% or more, more preferably 97 mol% or more, particularly preferably 99 mol% or more. This EVOH has a molecular weight sufficient to form a film, and generally has an MFR (190 ° C., 21.18 N) of 6 g / 10 min or less, preferably 5 g / 10 min or less, more preferably 4 g / 10. Is less than a minute.

3. Adhesive Layer In the resin multilayer container of the present invention, an adhesive layer can be interposed between the respective layers for the purpose of increasing the delamination strength. The adhesive layer is preferably one that can be extruded and exhibits good adhesion to each resin layer. When the resin multilayer container is a multilayer blow molded container manufactured by blow molding, which will be described later, an adhesive layer may not be interposed from the viewpoint of heat resistance and molding processability. For applications where characteristics, impact resistance, etc. are desired, an adhesive layer is preferably interposed.

  Examples of the adhesive layer include acid-modified polyolefins such as maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene; glycidyl group-containing ethylene copolymers, thermoplastic polyurethanes, ethylene-vinyl acetate copolymers, polyamide / ionomers, polyacrylimides, etc. Can be mentioned.

  If desired, the adhesive layer may contain various additives such as an inorganic filler, a plasticizer, a heat stabilizer, a light stabilizer, and a dye.

4). Recovery Layer The resin multilayer container of the present invention is preferably provided with a recovery layer in order to increase the strength of the container and increase the recyclability of resources.

  The recovery layer is a material that is recovered from the resin multilayer container itself of the present invention (such as burrs, unnecessary portions of product containers, or products recovered from bottles that are out of product specifications), or the resin multilayer container of the present invention. It is a layer containing the material recovered in the process as a main component. In particular, when the resin multilayer container of the present invention is manufactured by blow molding, which will be described later, the head (hereinafter referred to as “bag portion”) of the molded container after introducing blow air into the parison that is a preformed product. It is necessary to cut out the bag portion, but the cut bag portion can be made into a collection layer using a collected resin powdered by a crusher as a raw material. Further, it contains as a main component a resin recovered by cutting away the portion other than the bag portion of the blow molded container, a parison before molding, and materials and raw materials for forming each layer of the resin multilayer container. It may be a thing.

  The recovery layer may further contain raw materials for forming each layer of the resin multilayer container of the present invention, for example, various resin raw materials, compounding agents, adhesives, and the like.

5. Multilayer container The resin multilayer container of the present invention comprises a layer made of the resin composition containing the above (A), (B), (C) and (D) as a surface layer, preferably a layer structure. As a resin multilayer container including a surface layer, a barrier layer, an adhesive layer, and a recovery layer. More preferably, it is a resin multilayer container having a layer structure comprising an outermost layer / adhesive layer / barrier layer / adhesive layer / collection layer / innermost layer.

  The thickness of the resin multilayer container of the present invention is not particularly limited, but the total thickness of the container body (side wall) is usually in the range of 20 μm to 5 mm, preferably 100 μm to 3 mm, more preferably 200 μm to 1 mm. .

  The thickness of the surface layer relative to the total thickness (meaning the total thickness of the outermost layer and / or the innermost layer) is usually 50 to 90% with respect to the total thickness. In addition, since the ratio of this thickness is substantially equivalent to the ratio of mass, it represents below by the mass%.

  The surface layer is preferably 55 to 85% by mass, more preferably 60 to 80% by mass. A collection layer is 5-30 mass% normally, Preferably it is 10-25 mass%, More preferably, it is 15-25 mass%. A barrier layer is 1-10 mass% normally, Preferably it is 2-8 mass%, More preferably, it is 3-6 mass%. The total amount of the adhesive layer is usually 0.005 to 2% by mass, preferably 0.007 to 1.5% by mass, and more preferably 0.008 to 1.2% by mass.

  The ratio of the outermost layer (outermost layer and innermost layer) in the resin multilayer container of the present invention to the entire outermost layer is not particularly limited, but is usually 10 to 80% by mass, preferably 15 to 75% by mass, and more preferably. Is 20 to 70% by mass, particularly preferably 25 to 65% by mass.

  In the resin multilayer container of the present invention, the thickness of the entire container may be uniform, but the thickness may be changed depending on the part. In general, it is preferable to increase the thickness of the bottom of the multilayer container.

Volume of the resin multilayer container of the present invention is not particularly limited, is preferably 100～3000Cm ^3, more preferably 200～2000Cm ^3, more preferably a resin multilayered container having a volume in the range of 300～1000Cm ³ .

[Surface friction coefficient]
The resin multilayer container of the present invention is a container excellent in slipperiness by including as a surface layer a layer composed of a resin composition containing the above (A), (B), (C) and (D). . When the surface layer is one or both of the outermost layer and the innermost layer, the slipperiness of the outer surface and / or inner surface of the resin multilayer container can be improved. The slipperiness of the resin multilayer container can be evaluated by a surface sliding friction coefficient measured by a method according to JIS K7125. Specifically, after the container is fully filled with water at a temperature of 23 ° C., a two-layer sealing material (aluminum / LDPE) is used, and the LDPE side of the sealing material is placed on the mouth of the container and heat-welded. And seal the mouth of the container. The mouth portion of the container is provided with a thread for screwing a lid onto the outer peripheral portion of the mouth portion. A wire for pulling the container is fixed to the lid, and then the lid is screwed to the mouth of the container. The container is placed horizontally on a stainless steel flat plate, and the maximum tensile load when the wire attached to the mouth of the container is pulled horizontally by about 2 cm at a speed of 86 mm / min using a tensile and compression tester. A value is obtained, and the load value is divided by the total weight of the container to obtain the surface sliding friction coefficient of the container. If the sliding friction is 0.40 or less, it can be said that the sliding property is good, and is preferably 0.38 or less, more preferably 0.35 or less.

[Puncture strength]
The resin multilayer container of the present invention has excellent puncture resistance by including, as a surface layer, a layer made of the resin composition containing the above (A), (B), (C) and (D). Container. The puncture resistance of the resin multilayer container can be evaluated by measuring the puncture strength by a method according to JIS T8051. Specifically, the body in the range 90 to 130 mm above the bottom of the container is cut into a ring, and a sheet obtained by cutting the ring is used as a sample, and a temperature of 23 ° C. is used using a Tensilon universal testing machine (compression testing machine). In an air-conditioned atmosphere, measure the maximum piercing load (unit N) when a piercing jig with a tip of 3 mm and a radius of curvature of 1.5 mm is pierced perpendicularly at a piercing speed of 500 mm / min. Evaluation can be made by taking the value converted into the sample thickness of 390 μm as the puncture strength of the container. If the puncture strength is 30 N or more, it can be said that the puncture resistance is excellent, and is preferably 33 N or more.

[Surface gloss]
The resin multilayer container of the present invention is a container having an excellent surface gloss by providing a layer made of the resin composition containing the above (A), (B), (C) and (D) as a surface layer. is there. The surface gloss of the resin multilayer container can be measured by a method according to JIS Z8528. Specifically, a normal direction (T direction) 60 mm and a longitudinal direction (L direction) 80 mm are cut out from a body part 20 to 100 mm above the bottom of the container to make a sample, and in a conditioned atmosphere at a temperature of 23 ° C., a gloss meter The gloss (60 ° gloss value (%)) of the sample is measured in the T direction and the L direction, and the average value of the measured values in the T direction and the L direction is defined as the surface gloss of the container. If the surface gloss is 40 or more, it can be said that the gloss is good, and is preferably 43 or more, more preferably 45 or more.

III. Container production method The resin multilayer container of the present invention is a blow molded container (including stretch blow molded containers), an injection molded container, a packaging bag produced by folding and bonding from a film or sheet, and a sheet formed by vacuum molding and / or. Or it can be made into various shapes, such as a tray and a cup formed by pressure forming. Among these, blow molded containers are preferable, and direct blow molded containers are more preferable.

  The resin multilayer container of the present invention forms containers of various shapes by blow molding (including stretch blow molding), injection molding, bending or bonding of a film or sheet, vacuum forming and / or pressure forming of a sheet. Can be manufactured. For example, a resin multilayer container which is a packaging bag can be manufactured by sealing three or four sides of a multilayer sheet or film manufactured in advance. In addition, a resin multilayer container having a shape such as a tray or a cup can be manufactured from a multilayer sheet or film manufactured in advance by a sheet forming method (vacuum forming and / or pressure forming).

  Among these, it is preferable to manufacture a resin multilayer container by blow molding, and a multilayer parison (hereinafter sometimes referred to as “multilayer parison”) is blow-molded in a split mold having a container-shaped cavity wall. Thus, a multilayer container which is a blow molded product is manufactured. The blow molding may be performed by a cold parison method in which a multilayer parison is manufactured and then cooled to room temperature or room temperature and heated to a predetermined temperature when blow molding is performed, or a multilayer parison is manufactured and subsequently blow molded. The hot parison system to be performed may be used. The multi-layer parison can be produced by multi-layer injection molding, but a method of producing a tubular (hereinafter sometimes referred to as “tubular” or “pipe”) multi-layer parison by melt coextrusion is preferred. It is preferable to produce the multi-layer parison by direct blow molding in which blow molding is performed continuously. Hereinafter, the case where the resin multilayer container of the present invention is manufactured by direct blow molding will be described.

1. Manufacture of multilayer parison As a method of manufacturing a multilayer parison having a predetermined multilayer structure by coextrusion, there are methods such as a coextrusion method using a tubular die, a coextrusion method using a T die, and a coextrusion method by inflation molding. Although a so-called container-shaped container is manufactured by blow molding, a cylindrical (pipe-shaped) multilayer parison is preferably manufactured by a coextrusion method using a tubular die. When producing a multi-layer parison by co-extrusion using a tubular die, use the number of extruders corresponding to the type of resin, and expand the resin corresponding to each layer into a tubular shape while melting the resin in the die passage. Are joined together in the order of the laminated body. When the innermost layer and the outermost layer, which are the surface layers, are made of the same type of resin, they are further branched through a branch channel so as to sandwich the resin raw materials forming other layers, and then merged in an extrusion die, and are tubular Resin is extruded from a die head having a shape in a state of being laminated in a predetermined layer configuration. The temperature of the die head is usually 120 to 240 ° C, preferably 130 to 230 ° C, more preferably 140 to 220 ° C. As the shape of the diorifice, it is possible to use a circular or flat shape. According to the co-extrusion method using a tubular die, it is possible to relatively easily change the thickness of the multilayer parison.

  As described above, the multilayer parison can also be manufactured by co-injection molding. Using a molding machine equipped with a plurality of injection cylinders, the melted surface layer (outermost layer and / or outer layer and / or from a single gate in a single parison injection mold cavity in a single clamping operation. The resin composition forming the innermost layer) and the resin material forming the other layer are co-injected to form a bottomed multilayer parison. The barrier layer may not be present on a part or all of the bottom of the multilayer parison. Generally, since the thickness of the bottom portion is larger than the thickness of the body portion, the barrier property can be exhibited even if the bottom portion is substantially only the resin composition layer. By disposing the barrier layer only on the trunk, it is easy to prevent the mechanical strength of the multilayer container from being lowered and to control the thickness of the barrier layer uniformly.

2. Blow molding In blow molding, a cylindrical multilayer parison coextruded by the above method is sandwiched between split molds, the lower end is fused and closed, and the upper end is cut, and then a pressurized fluid is applied from the opened upper end. After blowing into a container shape, the upper part (head or bag part) of the unnecessary container mouth is cut out to obtain a resin multilayer container.

As the mold for blow molding, either a mirror-finished one or a sandblasted one can be used, and the surface temperature of the mold is generally preferably in the range of 10 to 50 ° C. Moreover, it is preferable to use sterilized air as the fluid for blow molding, and the pressure is suitably in the range of 1.0 to 15 kg / cm ² .

  The resin multilayer container of the present invention can also be produced by stretch blow molding. In the stretch blow molding process, the multilayer parison is adjusted to a temperature at which it can be stretched, and then inserted into a cavity of a blow molding die, and a pressurized fluid such as air is blown to perform stretch blow molding. In order to perform the stretching in the length direction, a stretching rod may be used. Stretch blow molding can be performed by either a hot parison system or a cold parison system. The total draw ratio is usually 6 to 9 times, 8 to 9.5 times for a pressure resistant container, 6 to 7.5 times for a heat resistant container, and 7 to 8 times for a large container.

  When manufacturing a heat-resistant resin multilayer container suitable for hot filling of contents, the temperature of the blow molding mold is set to 100 ° C or higher in order to prevent thermal shrinkage and deformation of the container during hot filling. The temperature may be raised and heat treatment (heat setting) may be performed in the mold. The mold temperature is 100 to 165 ° C., preferably 145 to 155 ° C. for a general heat resistant container, and 160 to 165 ° C. for a high heat resistant container. The heat treatment time varies depending on the thickness of the multilayer container and the heat treatment temperature, but is usually 1 to 30 seconds, preferably 2 to 20 seconds.

  EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the examples. The measurement methods of the properties or physical properties of the resin raw materials and containers in the examples and comparative examples are as follows.

[Density and MFR]
Resin density and MFR (temperature 190 ° C., load 21.18 N) were measured in accordance with JIS K6922-2.

[Crystal melting point]
The crystal melting point of the resin was measured according to JIS K7122.

[Polydispersity (Mw / Mn)]
The polydispersity (Mw / Mn), which is an index of the molecular weight distribution of the resin, was measured according to JIS K7252.

[Surface friction coefficient]
The surface sliding friction coefficient of the container was measured by a method according to JIS K7125. Specifically, after the container is fully filled with water at a temperature of 23 ° C., a two-layer sealing material (aluminum / LDPE) is used, and the LDPE side of the sealing material is placed on the mouth of the container and heat-welded. The container mouth was sealed. The mouth portion of the container is provided with a thread for screwing a lid onto the outer peripheral portion of the mouth portion. A wire for pulling the container was fixed to the lid, and then the lid was screwed onto the mouth of the container. The container was placed horizontally on a stainless steel plate. Using a tensile and compression tester manufactured by Imada Manufacturing Co., Ltd., product name SV50, attaching a wire to the mouth of the container and obtaining the maximum tensile load value when pulled horizontally about 2 cm at a speed of 86 mm / min. Dividing by weight gave the surface sliding friction coefficient of the container.

[Puncture strength]
The puncture strength of the container was measured by a method according to JIS T8051 for the container used for measuring the surface sliding friction coefficient. Specifically, the body portion 90 to 130 mm above the bottom of the container was cut into a ring, and a sheet obtained by cutting the ring was used as a sample. Using a Tensilon universal testing machine RC-121OA manufactured by Orientec Co., Ltd., in a conditioned atmosphere at a temperature of 23 ° C., a piercing jig having a tip of 3 mm and a radius of curvature of 1.5 mm was pierced on the surface of the sample at a speed of 500 mm / The maximum puncture load (unit N) when pierced at a right angle in minutes and penetrated was measured, and the value converted to the sample thickness of 390 μm was taken as the puncture strength of the container.

[Surface gloss]
The surface gloss of the container was measured by a method according to JIS Z8528 for the container used for measuring the surface sliding friction coefficient. Specifically, a normal direction (T direction) of 60 mm and a vertical direction (L direction) of 80 mm were cut out from a body part 20 to 100 mm above the bottom of the container to prepare a sample. In an air-conditioned atmosphere at a temperature of 23 ° C., the gloss (60 ° gloss value (%)) of the sample is measured in the T direction and L direction using a commercially available gloss meter, and the average value of the measured values in the T direction and L direction is measured in the container. The surface was glossy.

[Example 1]
Using a plurality of extruders and multi-layer dies, a cylindrical parison whose layer structure is the outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer is extruded, and the contents are output by a rotary direct blow molding machine. A resin multilayer container having a multilayer structure of 500 cm ³ (hereinafter referred to as “multilayer container”) was molded. The weight of the multilayer container was 20 g.

(1) Surface layer (outermost layer and innermost layer):
(A) Low density polyethylene: trade name Novatec LD (registered trademark) manufactured by Nippon Polyethylene Co., Ltd. [density 0.924 g / m ³ , MFR (temperature 190 ° C., load 21.18 N) 0.7 g / 10 min, crystalline melting point 113 ° C., polydispersity (Mw / Mn) = 2] 55% by mass,
(B) High-density polyethylene: trade name Novatec HD (registered trademark) manufactured by Nippon Polyethylene Co., Ltd. [density 0.960 g / m ³ , MFR (temperature 190 ° C., load 21.18 N) 0.7 g / 10 min, crystalline melting point 135 ° C., polydispersity (Mw / Mn) = 4] 25% by mass, and (C) metallocene-catalyzed ethylene-based polyolefin: trade name Harmolex [density 0.908 g / m ³ , MFR (temperature) manufactured by Nippon Polyethylene Co., Ltd. 190 ° C., load 21.18 N) 0.9 g / 10 min, crystal melting point 125 ° C., polydispersity (Mw / Mn) = 3] 20% by mass,
[However, the mass% of (A), (B) and (C) is a value when the total of (A), (B) and (C) is 100 mass%. ]
And
(D) Fatty acid amide having an unsaturated cis structure carbon double bond: cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ — CH ₃ ; unsaturated fatty acid amide of formula (D ₁ ) 98% by mass, cis-5,6-8,9-11,12-14,15-arachidonic acid amide [H ₂ N—CO — (— CH ₂ −) ₃ —CH═CH—CH ₂ —CH═CH—CH ₂ —CH═CH—CH ₂ —CH═CH — (— CH ₂ —) ₄ —CH ₃ ] 2% by mass 390 ppm [provided that , (D) is the total content (ppm) of (A), (B) and (C) relative to the total mass. The same applies to the following examples and comparative examples. ]

(2) Barrier layer: Trade name EVAL manufactured by Kuraray Co., Ltd. [EVOH having an ethylene content of 44% in molar ratio. Density 1.140 g / cm ³ , MFR (temperature 190 ° C., load 21.18 N) 1.7 g / 10 min, crystal melting point 165 ° C.]

(3) Recovery layer: Resin (recovered resin) obtained by excising the container head (bag part) produced when direct blow molding the multilayer container manufactured according to the present embodiment and pulverizing it with a crusher Used as raw material.

(4) Adhesive layer: maleic anhydride-modified polyolefin manufactured by Mitsubishi Chemical Corporation, trade name Modic (registered trademark)

  The thickness ratio (mass ratio) of the layers (1) to (4) was 74: 4: 21: 1.

  Table 1 shows the results of measurement of the surface sliding friction coefficient (hereinafter referred to as “sliding friction”), puncture strength, and surface gloss of the molded container.

[Example 2]
(D) Fatty acid amide having an unsaturated cis structure carbon double bond is converted to 99.8% by mass of cis-9,10-octadecenoamide [formula (D ₁ )] and cis-8,9-octadecenoamide [H ₂ N— CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ; unsaturated fatty acid amide of formula (D ₂ )] A multilayer container was molded in the same manner as in Example 1 except that the amount was changed to 387 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 3]
(D) Fatty acid amide having an unsaturated cis-structured carbon double bond is converted into cis-9,10-octadecenoamide [formula (D ₁ )] 90.0% by mass and cis-8,9-octadecenoamide [formula (D ₂ )] A multilayer container was formed in the same manner as in Example 1 except that the mixture was changed to a mixture with 10.0% by mass and the total content was changed to 3500 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 4]
(D) Fatty acid amide having an unsaturated cis structure carbon double bond is converted to cis-9,10-octadecenoamide [formula (D ₁ )] 85.0% by mass, cis-6,7-tetradecenoamide [H ₂ N— CO — (— CH ₂ —) ₄ —CH═CH — (— CH ₂ —) ₆ —CH ₃ ; unsaturated fatty acid amide of formula (D ₂ )] 15.0% by mass A multilayer container was molded in the same manner as in Example 1 except that the amount was changed to 350 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 5]
(D) The fatty acid amide having an unsaturated cis structure carbon double bond was changed to cis-8,9-octadecenoamide [formula (D ₂ )] (single), and the content was changed to 400 ppm, A multilayer container was formed in the same manner as in Example 1. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 6]
(D) Fatty acid amide having an unsaturated cis structure carbon double bond is converted to 98.0% by mass of cis-9,10-octadecenoamide [formula (D ₁ )] and cis-13,14-docosenoamide [H ₂ N— CO — (— CH ₂ —) ₁₁ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ; unsaturated fatty acid amide of formula (D ₃ )] A multilayer container was molded in the same manner as in Example 1 except that the amount was changed to 1500 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 7]
(D) Fatty acid amide having an unsaturated cis-structured carbon double bond is converted into cis-13,14-docosenoamide [formula (D ₃ )] 95.0% by mass, cis-9,10-octadecenoamide [formula (D ₁ )] A multilayer container was molded in the same manner as in Example 1 except that the mixture was changed to a mixture with 5.0% by mass and the content was changed to 250 ppm. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 8]
(D) Fatty acid amide having an unsaturated cis-structured carbon double bond is converted to 95.0% by mass of cis-9,10-octadecenoamide [formula (D ₁ )] and cis-13,14-docosenoamide [formula (D ₃ )] It was changed to a mixture with 3.0% by mass, and behenic acid amide, which is a saturated fatty acid amide, was added at a rate of 2.0% by mass, and the total content of these fatty acid amides was changed to 1000 ppm. Except for this, a multilayer container was formed in the same manner as in Example 1. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 9]
(D) Fatty acid amide having an unsaturated cis-structured carbon double bond is converted to 92.0% by mass of cis-9,10-octadecenoamide [formula (D ₁ )] and cis-13,14-docosenoamide [formula (D ₃ )] It was changed to a mixture with 3.0% by mass, further containing stearic acid amide, which is a saturated fatty acid amide, at a rate of 5.0% by mass, and the total content of these fatty acid amides was changed to 1000 ppm. Except for this, a multilayer container was formed in the same manner as in Example 1. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Comparative Example 1]
(D) The fatty acid amide having an unsaturated cis structure carbon double bond corresponds to trans-9,10-octadecenoamide [corresponding to the trans form of the unsaturated fatty acid amide of the formula (D ₁ ). ] A multilayer container was molded in the same manner as in Example 5 except that it was changed to (single). Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Comparative Example 2]
trans-9,10-octadecenoamide [corresponds to the trans form of the unsaturated fatty acid amide of the formula (D ₁ ). ] (Single) was changed to a mixture of trans-9,10-octadecenoamide 98.0% by mass and stearic acid amide 2.0% by mass, which is a saturated fatty acid amide, in the same manner as in Comparative Example 1. A multilayer container was formed. Table 1 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

  From the results in Table 1, (A) low-density polyethylene, (B) high-density polyethylene, (C) an ethylene-based polyolefin obtained using a metallocene catalyst, and (D) a fatty acid having an unsaturated cis structure carbon double bond A resin multilayer container including a layer made of a resin composition containing an amide as a surface layer, wherein the resin composition has a total of (I) (A), (B) and (C) of 100% by mass Example 1 sometimes (C) satisfies 8-40% by mass; and (II) (D) satisfies 100-4000 ppm with respect to the total mass of (A), (B) and (C). The resin multi-layer container of ˜9 has a surface sliding friction coefficient of 0.25 to 0.32, a good surface sliding property, a puncture strength of 34 N, an excellent puncture resistance, and a surface gloss. It was found that the gloss was good at 43 to 54.

  On the other hand, the resin multilayer container of Comparative Examples 1 and 2 containing a fatty acid amide having an unsaturated trans structure carbon double bond instead of the fatty acid amide having an unsaturated cis structure carbon double bond (D) The puncture resistance is equivalent to that of the resin multilayer container of Examples 1 to 9, but the surface sliding friction coefficient is as large as 0.45 or 0.42, there is a sticky feeling, and the surface gloss is as low as 39, The gloss was not good.

[Example 10]
The surface layer was changed to (A) 55% by mass of low-density polyethylene, (B) 15% by mass of high-density polyethylene, and (C) 30% by mass of metallocene-catalyzed ethylene-based polyolefin. A multilayer container was molded in the same manner as in Example 2 except that the total content of fatty acid amides having a heavy bond was changed to 400 ppm. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 11]
(D) Fatty acid amide having an unsaturated cis-structured carbon double bond is converted to 95.0% by mass of cis-9,10-octadecenoamide [formula (D ₁ )] and cis-13,14-docosenoamide [formula (D ₃ )] A multilayer container was molded in the same manner as in Example 10 except that the mixture was changed to a mixture with 5.0% by mass. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 12]
Except that the surface layer was changed to (A) 41% by mass of low-density polyethylene, (B) 49% by mass of high-density polyethylene, and (C) 10% by mass of metallocene-catalyzed ethylene-based polyolefin, the same as in Example 10. A multilayer container was formed. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Example 13]
(D) Fatty acid amide having an unsaturated cis-structured carbon double bond is converted to 95.0% by mass of cis-9,10-octadecenoamide [formula (D ₁ )] and cis-13,14-docosenoamide [formula (D ₃ )] A multilayer container was molded in the same manner as in Example 12 except that the mixture was changed to a mixture with 5.0% by mass. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Comparative Example 3]
Except that the surface layer was changed to (A) 45% by mass of low-density polyethylene, (B) 10% by mass of high-density polyethylene, and (C) 45% by mass of metallocene-catalyzed ethylene-based polyolefin, the same as in Example 13 A multilayer container was formed. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Comparative Example 4]
Except that the surface layer was changed to (A) 65% by mass of low density polyethylene, (B) 30% by mass of high density polyethylene, and (C) 5% by mass of metallocene-catalyzed ethylene-based polyolefin, the same as in Comparative Example 3 A multilayer container was formed. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Comparative Example 5]
The surface layer was changed to (A) 65% by mass of low-density polyethylene and (B) 35% by mass of high-density polyethylene [(C) metallocene-catalyzed ethylene-based polyolefin was not used. And (D) a fatty acid amide having an unsaturated cis structure carbon double bond, cis-9,10-octadecenoamide [formula (D ₁ )] 98.0% by mass, cis-13,14-docosenoamide [Formula (D ₃ )] A multilayer container was molded in the same manner as in Comparative Example 4 except that the mixture was changed to a mixture with 2.0% by mass and the total content of fatty acid amide was changed to 90 ppm. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Comparative Example 6]
The surface layer was changed to (A) 100% by mass of low-density polyethylene [(B) high-density polyethylene and (C) metallocene-catalyzed ethylene-based polyolefin were not used. In addition, a multilayer container was molded in the same manner as in Comparative Example 5 except that (D) the total content of the fatty acid amide having an unsaturated cis structure carbon double bond was changed to 350 ppm. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

[Comparative Example 7]
ULTRAZEX made by Prime Polymer Co., Ltd., which is an ethylene-based polyolefin obtained by polymerizing the surface layer in the presence of (A) 55% by mass of low-density polyethylene, (B) 25% by mass of high-density polyethylene, and Ziegler-Natta catalyst. (Registered trademark) 1520L [density 0.913 kg / m ³ , MFR (temperature 190 ° C., load 21.18 N) 2.3 g / 10 min, crystal melting point = 115 ° C., polydispersity (Mw / Mn) = 2] 20 [(C) Metallocene-catalyzed ethylene-based polyolefin was not used. And (D) the multilayer container was molded in the same manner as in Comparative Example 5 except that the total content of the fatty acid amide having an unsaturated cis structure carbon double bond was changed to 390 ppm. Table 2 shows the results of measuring the sliding friction, puncture strength, and surface gloss of the molded container.

  From the results in Table 2, (A) low-density polyethylene, (B) high-density polyethylene, (C) an ethylene-based polyolefin obtained using a metallocene catalyst, and (D) a fatty acid having an unsaturated cis structure carbon double bond A resin multilayer container including a layer made of a resin composition containing an amide as a surface layer, wherein the resin composition has a total of (I) (A), (B) and (C) of 100% by mass Example 10 wherein (C) is 8-40% by weight; and (II) (D) is 100-4000 ppm relative to the total weight of (A), (B) and (C). The resin multi-layer container of ˜13 has a surface sliding friction coefficient of 0.28 to 0.35, good surface slidability, puncture strength of 30 to 43 N, excellent puncture resistance, and surface Gloss was 42-49, and it was found that gloss was good.

  In contrast, the resin multilayer container of Comparative Example 3 whose surface layer (the innermost layer and the outermost layer) is made of a resin composition containing a large amount of ethylene-based polyolefin obtained by using (C) a metallocene catalyst (45% by mass). The surface sliding friction coefficient was as large as 0.49, and there was a sticky feeling, and the puncture strength was as small as 22 N, and the puncture resistance was insufficient. Further, the resin multilayer container of Comparative Example 4 whose surface layer (innermost layer and outermost layer) is made of a resin composition containing only 5% by mass of ethylene-based polyolefin obtained by using (C) a metallocene catalyst, The puncture strength was as low as 29N, the puncture resistance was insufficient, the surface gloss was as low as 36, and the gloss was not good. Furthermore, the surface layer (the innermost layer and the outermost layer) does not contain an ethylene-based polyolefin obtained by using the (C) metallocene catalyst, and the content of unsaturated fatty acid amide is as small as 90 ppm. Both the container and the container of Comparative Example 6 not containing (C) the ethylene-based polyolefin obtained using the metallocene catalyst and (B) the high-density polyethylene have a surface sliding friction coefficient of 0.42 or 0.00. It was as large as 41 and had a sticky feeling, and the puncture strength was as small as 29N or 23N, and the puncture resistance was insufficient. And the surface layer (the innermost layer and the outermost layer) is replaced with (C) an ethylene-based polyolefin obtained by using a metallocene catalyst, and a resin composition containing an ethylene-based polyolefin obtained by using a Ziegler-Natta catalyst. The resin multilayer container of Comparative Example 7 has a puncture strength as small as 28N and lacks puncture resistance.

The present invention provides (A) low-density polyethylene, (B) high-density polyethylene, (C) an ethylene-based polyolefin obtained using a metallocene catalyst, and (D) a fatty acid amide having an unsaturated cis-structured carbon double bond. A resin multilayer container having as a surface layer a layer composed of a resin composition containing the resin composition,
I: When the total of (A), (B) and (C) is 100% by mass, (C) is 8 to 40% by mass,
II: By the resin multilayer container containing 100 to 4000 ppm of (D) with respect to the total mass of (A), (B) and (C), from the molding and transfer of the container, Can exhibit slipperiness that suits various process lines and environmental conditions in each process of filling and packaging, improves the liquid drainage of the contents filled in the container, and has high puncture resistance, Since it is possible to provide a multi-layer resin container having excellent surface gloss, it is possible to provide a container with high productivity and high reliability during transportation and storage, and the industrial applicability is high.

Claims (13)

(A) Low-density polyethylene, (B) high-density polyethylene, (C) an ethylene-based polyolefin obtained using a metallocene catalyst, and (D) a fatty acid amide having an unsaturated cis structure carbon double bond It is a resin multilayer container provided with a layer made of a material as a surface layer,
The surface layer is the outermost layer, or both the outermost layer and the innermost layer;
The resin composition has the following I and II:
(I) When the total of (A), (B) and (C) is 100 mass%, (A) is 40-60 mass%, (B) is 12-50 mass%, (C) is 8 -40 mass%; and (II) (D) is 100-4000 ppm with respect to the total mass of (A), (B) and (C);
Satisfying the above-mentioned resin multilayer container. The (D) fatty acid amide having an unsaturated cis structure carbon double bond is represented by the following (D ₁ ), (D ₂ ) and (D ₃ ):
_{(D 1) H 2 N-} CO - (- CH 2 -) n -CH = CH - (- CH 2 -) n -CH 3 ( where, n is in the range of 6 ≦ n ≦ 10 integer);
_{(D 2) H 2 N-} CO - (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3 ( however, m is an integer in the range of 6 ≦ m ≦ 10) And (D ₃ ) H ₂ N—CO — (— CH ₂ —) _{k + 4} —CH═CH — (— CH ₂ —) _k —CH ₃ (where k is an integer in the range of 6 ≦ k ≦ 10); ;
The resin multilayer container according to claim 1, comprising at least one fatty acid amide represented by a formula selected from the group consisting of: The fatty acid amide having the (D) unsaturated cis structure carbon double bond is represented by the fatty acid amide represented by the formula (D ₁ ) and the formula (D ₂ ) or (D ₃ ). The resin multilayer container according to claim 2, which is a mixture with at least one fatty acid amide. The resin multilayer container according to claim 3, wherein m in the fatty acid amide represented by the formula (D ₂ ) is m = n + 1 or m = n−1. The resin multilayer container according to claim 3, wherein k in the fatty acid amide represented by the formula (D ₃ ) is k = n. The fatty acid amide having the (D) unsaturated cis structure carbon double bond is the fatty acid amide represented by the above formula (D ₁ ) and the following (D ₁₁ ):
(D ₁₁ ) H ₂ N—CO — (— CH ₂ —) _j —CH═CH — (— CH ₂ —) _j —CH ₃ (where j is an integer in the range of 6 ≦ j ≦ 10, j ≠ n);
The resin multilayer container according to claim 2, which is a mixture with a fatty acid amide represented by the formula: The resin product according to claim 1, wherein the (D) fatty acid amide having an unsaturated cis structure carbon double bond contains a compound having 2 to 4 bonds of unsaturated cis structure carbon double bonds in the molecular structure. Multi-layer container. The resin multilayer container according to any one of claims 1 to 7, wherein the resin composition further contains a saturated fatty acid amide. The resin multilayer container according to any one of claims 1 to 8, further comprising a barrier layer. The resin multilayer container according to claim 9, wherein the barrier layer is an ethylene vinyl alcohol copolymer or polyglycolic acid. The process of collect | recovering material from the collection | recovery goods of the resin multilayer container of any one of Claims 1 thru | or 10, or the process of manufacturing the resin multilayer container of any one of Claims 1 thru | or 10 Recovering the material at:
Forming a recovery layer containing the recovered material as a main component;
The resinous multilayer container further comprises the recovery layer,
Manufacturing method of resin multilayer container. The process of collect | recovering material from the collection | recovery goods of the resin multilayer container of any one of Claims 1 thru | or 8, The process of manufacturing the resin multilayer container of any one of Claims 1 thru | or 8 Recovering the material at:
Forming a recovery layer containing the recovered material as a main component;
Resin multilayer container of the can, the surface layer, the barrier layer, adhesive layer, and is intended to include the recovery layer,
Manufacturing method of resin multilayer container. The process of collect | recovering material from the collection | recovery goods of the resin multilayer container of any one of Claims 1 thru | or 8, The process of manufacturing the resin multilayer container of any one of Claims 1 thru | or 8 Recovering the material at:
Forming a recovery layer containing the recovered material as a main component;
Resin multilayer container of the can, consisting of the outermost layer / adhesive layer / barrier layer / adhesive layer / the recovery layer / the innermost layer,
Manufacturing method of resin multilayer container.