JP5679572B2 - 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 surface gloss. More specifically, optimal slipperiness is exhibited in each process such as the manufacturing process, filling process, and packaging process of the resin multilayer container, and the liquid content of the filled contents is excellent, and the contents are highly visible. The present invention relates to the improvement of a multilayer resin container.

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

  For example, JP-A-6-72424 (Patent Document 1) discloses a multilayer material including a gas barrier resin layer such as an ethylene / vinyl alcohol copolymer, an outermost layer of a polyolefin resin such as polypropylene, and an adhesive resin layer. And a multilayer bottle made by direct blow molding or the like is disclosed.

  The resin multilayer container is required to have transparency, gloss, impact resistance, and slipperiness of the container surface. For example, JP 2009-248996 A (Patent Document 2) discloses an inner layer and an outer layer, a gas barrier resin layer, an adhesive layer, and a recycling layer made of an ethylene / α-olefin copolymer polymerized using a metallocene catalyst. It is disclosed that a multi-layer plastic container provided with is used as a soft container having a balance of transparency, flexibility, rigidity, drop resistance strength and the like. On the other hand, Japanese Patent Application Laid-Open No. 11-349650 (Patent Document 3) describes a block copolymer having a polypropylene block obtained by using a specific metallocene catalyst and an ethylene / propylene copolymer block and excellent in impact resistance. A polymer is disclosed.

  In the resin multilayer container, the slipperiness on the container surface, specifically, the outermost surface and / or the innermost surface is required. 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 the container forming process line or the container alignment line in the contents filling process, even if contact between containers or between a container and a guide plate occurs, the work or production speed in the process or the next process is not affected. Slidability is required. 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, and when this is added, it exhibits good slipperiness when the container becomes hot, such as when food or other contents are filled at high temperature. become able to. These lubricants have been used in a mixture of two or more. For example, in JP 2009-214914 A (Patent Document 4), in a multilayer container filled with a non-oil content, an unsaturated aliphatic amide and a saturated aliphatic amide are blended in a polyolefin resin layer on the inner surface of the container. Is disclosed. Furthermore, JP-A-2005-307122 (Patent Document 5) discloses oleic acid amide, stearic acid amide, and erucic acid amide as slipping agents (lubricants) using oils and fats derived from natural products as raw materials.

  Furthermore, in the case of a resin multilayer container, if the surface gloss is inferior, the state of the filled contents may not be intuitively grasped, so improvement has been demanded.

JP-A-6-72424 JP 2009-248996 A JP-A-11-349650 JP 2009-214914 A 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. An object of the present invention is to provide a resin multi-layer container satisfying appropriate slipperiness between the contents and the like, and improved liquid drainage of the contents filled in the container, and having excellent surface gloss.

  As a result of intensive studies on solving the above-mentioned problems, the present inventors have determined that the surface layer (outermost layer and / or innermost layer) of a 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) a propylene / α-olefin random copolymer having a crystalline melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, (B) obtained using a metallocene catalyst. A block copolymer comprising a polymer block comprising polypropylene, a polymer block comprising an ethylene / propylene copolymer, and (C) a fatty acid amide having an unsaturated cis structure carbon double bond. A resin multilayer container provided with a layer composed of a resin composition containing as a surface layer,
The resin composition has the following (I) and (II):
(I) When the sum of (A) and (B) is 100% by mass, (B) is 0.5 to 40% by mass; and (II) with respect to the total mass part of (A) and (B) (C) is 100 to 4000 ppm;
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 (C) unsaturated cis structure carbon double bond is the following (C ₁ ), (C ₂ ) and (C ₃ ):
(C 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);
(C 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 (C 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 one formula selected from the group consisting of:

(2) The fatty acid amide having the (C) unsaturated cis-structured carbon double bond is a fatty acid amide represented by the formula (C ₁ ), and the (C ₂ ) or (C 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 (C ₂ ) is m = n + 1 or m = n−1.

(4) The said resin multilayer container whose k in the fatty acid amide represented by the formula (C ₃ ) is k = n.

(5) The fatty acid amide having the (C) unsaturated cis structure carbon double bond is a fatty acid amide represented by the above formula (C ₁ ) and the following (C ₁₁ ):
(C 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 resin multilayer container as described above, wherein (C) 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 bonds in the molecular structure.

(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 multilayer resin container as described above, wherein the 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) a propylene / α-olefin random copolymer having a crystalline melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, (B) obtained using a metallocene catalyst. A block copolymer composed of a polymer block composed of polypropylene, a polymer block composed of an ethylene / propylene copolymer, and (C) a fatty acid amide having an unsaturated cis structure carbon double bond A resin multilayer container provided with a layer made of a resin composition as a surface layer,
The resin composition has the following (I) and (II):
(I) When the sum of (A) and (B) is 100% by mass, (B) is 0.5 to 40% by mass; and (II) with respect to the total mass part of (A) and (B) (C) is 100 to 4000 ppm;
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 an excellent surface gloss.

I. Resin composition forming surface layer The resin multilayer container of the present invention was obtained by using the surface layer, specifically, one or both of the outermost layer and the innermost layer of the container using (A) a Ziegler-Natta catalyst. A propylene / α-olefin random copolymer having a crystal melting point of 125 to 165 ° C., (B) a polymer block made of polypropylene and a polymer made of ethylene / propylene copolymer, obtained using a metallocene catalyst. And (C) a resin composition containing a fatty acid amide having an unsaturated cis structure carbon double bond.

1. (A) Propylene / α-olefin random copolymer having a crystalline melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst (A) Ziegler- A propylene / α-olefin random copolymer (hereinafter, also referred to as “Ziegler catalyst random copolymer of (A)”) having a crystal melting point of 125 to 165 ° C. obtained using a Natta catalyst. This is a propylene / α-olefin random copolymer known per se obtained by using a Ziegler-Natta catalyst known as a catalyst for stereoregular polymerization of α-olefin.

  The Ziegler-Natta catalyst is well known as a catalyst for stereoregular polymerization of α-olefins, and includes transition metal compounds of Groups IV to VIII of the Periodic Table of Elements and typical metals of Groups I to II of the Periodic Table. And a third component of an electron-donating compound, which is used for polymerization of α-olefins by any polymerization method such as solvent polymerization or gas phase polymerization. Can do. Ziegler-Natta catalysts include, for example, titanium trichloride obtained by reducing titanium tetrachloride with organoaluminum, etc., treated with an electron-donating compound and further activated, and titanium tetrachloride reduced with an organoaluminum compound. Furthermore, a titanium trichloride composition obtained by treatment with various electron donors and electron acceptors, a catalyst comprising an organoaluminum compound and an aromatic carboxylic acid ester, and magnesium tetrachloride and various kinds of magnesium halide And a supported catalyst comprising the above electron donor. As the coordination metal of the Ziegler-Natta catalyst, in addition to the Group IV Ti which is the transition metal of the fourth period of the periodic table, the V of the Group Va which is the transition metal of the fourth period, the V of the fourth period Known elements such as Group VIa Cr, which is a transition metal, can be selected.

In the Ziegler catalyst random copolymer (A) in the present invention, the content of monomer units obtained from propylene in the copolymer (hereinafter sometimes referred to as “propylene content”) is 100 to 94 mass%. (Excluding 100% by mass), preferably 99.7 to 95% by mass, more preferably 99.5 to 95.5% by mass, and inclusion of monomer units obtained from the α-olefin in the copolymer The rate (hereinafter sometimes referred to as “α-olefin content”) is 0 to 6% by mass (excluding 0% by mass), preferably 0.3 to 5% by mass, more preferably 0.5 to The ratio is 4.5% by mass. Examples of the α-olefin that is a comonomer copolymerized with propylene include ethylene and / or an α-olefin having 4 to 20 carbon atoms. Specifically, ethylene, butene-1, pentene-1, hexene- 1, octene-1, 4-methylpentene-1, and the like. Two or more α-olefins can be used in combination. When the α-olefin content is within the above range, practically good rigidity can be maintained. A particularly preferred copolymer is a propylene / ethylene random copolymer having an ethylene content of 0.3 to 5% by mass, particularly 0.5 to 4.5% by mass. If the α-olefin content is too high, the temperature of the crystal melting point becomes low, and the required strength may not be obtained, or the fluidity of the polymer may be lowered. Therefore, the Ziegler catalyst random copolymer (A) in the present invention does not substantially contain a copolymer belonging to a so-called elastomer region. The propylene content and the α-olefin content can be measured using ¹³ C-NMR (nuclear magnetic resonance spectrum). Specifically, it can be measured with a 270 MHz apparatus of FT-NMR manufactured by JEOL Ltd.

The Ziegler catalyst random copolymer (A) usually has a density of about 0.880 to 0.930 g / cm ³ , preferably about 0.885 to 0.925 g / cm ³ , and MFR (temperature 190 ° C., load) 21.18N) is 0.5 to 100 g / 10 min, preferably about 1 to 50 g / 10 min. If the MFR exceeds the above range, the impact strength tends to be insufficient, and if the MFR is below the above range, the moldability may be poor. Further, the polydispersity (Mw / Mn), which is an index of molecular weight distribution, is usually 1.2 to 5, preferably 1.5 to 4.5, more preferably 2 to 4 in terms of moldability. It is effective in terms of improvement. The density and MFR are measured according to JIS K6922-2, and the polydispersity (Mw / Mn) is measured according to JIS K7252.

[Crystal melting point]
The crystal melting point (Tm) of the Ziegler catalyst random copolymer (A) in the present invention is in the range of 125 to 165 ° C, preferably 127 to 163 ° C, more preferably 130 to 161 ° C. In accordance with JIS K7121, the crystal melting point was measured by using a differential scanning calorimeter (DSC) to raise the temperature of the sample to 200 ° C., hold it for 5 minutes, and then drop the temperature to 40 ° C. at 10 ° C./min. This was determined as the maximum melting peak temperature when the temperature was raised to 200 ° C. at 10 ° C./min after being converted to 1 min. The crystal melting point can be adjusted by increasing or decreasing the content of the copolymerization monomer. When the crystal melting point of the Ziegler catalyst random copolymer of (A) is too low, the required strength cannot be obtained, the melt moldability is lowered, or the surface gloss and slipperiness of the resulting resin multilayer container are deteriorated. Sometimes. When the crystal melting point is too high, for example, the moldability by direct blow molding deteriorates. The random propylene / α-olefin copolymer belonging to the so-called elastomer region has a crystal melting point of usually less than 125 ° C., and is not substantially contained in the Ziegler catalyst random copolymer of (A) in the present invention.

  It can be confirmed by the following method that the resin composition in the present invention contains the Ziegler catalyst random copolymer (A). That is, a resin pellet is cut with a glass to a thickness of 100 μm to form a sample, which is laid on a scanning electron microscope SEM, and equipped with an energy dispersive X-ray detector as an analyzer that distributes the generated fluorescent X-ray energy. Qualitative analysis is performed using a scanning electron microscope (manufactured by Hitachi, Ltd., FE-SEM-EDX, S-800, detector Kevex) to detect a trace amount of catalyst element species remaining in the specimen. Group IVa Ti (titanium), which is the transition metal of the fourth period of the periodic table, Group Va, V (vanadium) of the group Va, which is the transition metal of the fourth period, or Group VIa, which is the transition metal of the fourth period By confirming the appearance peak corresponding to the energy of Cr (chromium), it can be determined that the polyolefin is polymerized using a Ziegler-Natta catalyst. 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.

  As the Ziegler catalyst random copolymer (A) in the present invention, a synthetic product can be used, but a commercially available product may be used. As a commercial item, there is a brand name Nobren (registered trademark) manufactured by Japan Polyethylene Corporation.

  The content of the (A) Ziegler catalyst random copolymer in the resin composition is not particularly limited, but is usually 60 to 99.5 mass when the total of (A) and (B) is 100 mass%. %, Preferably 62 to 99% by mass, more preferably 65 to 98% by mass. If the content of the Ziegler catalyst random copolymer (A) in the resin composition is too small, the surface gloss may be poor, and if the content is too large, the slipperiness may be lowered.

2. (B) A block copolymer comprising a polymer block comprising polypropylene and a polymer block comprising an ethylene / propylene copolymer, obtained using a metallocene catalyst. (A), (B ) And (C) a resin multilayer container having as a surface a layer composed of a resin composition comprising (B) a block of a polymer composed of polypropylene obtained by using a metallocene catalyst in the resin composition. The block of the polymer composed of an ethylene / propylene copolymer and the block copolymer composed of 0.5 to 40% by mass when the total of (A) and (B) is 100% by mass. It is characterized by that.

  (B) A block copolymer comprising a polymer block made of polypropylene and a polymer block made of an ethylene / propylene copolymer, obtained using a metallocene catalyst (hereinafter referred to as “metallocene of (B)”. The catalyst block copolymer "may be referred to as a polymer block made of polypropylene (hereinafter also referred to as" PP block ") and a polymer block made of ethylene / propylene copolymer (hereinafter referred to as" PP block "). Is a block copolymer obtained by using a metallocene catalyst, each of which is bonded to one or more blocks, and maintains the rigidity of the polypropylene while maintaining the rigidity of the ethylene / propylene copolymer. A block copolymer known per se that exhibits high rigidity and impact resistance in a well-balanced manner with improved impact resistance by coalescence. A.

  The method for producing the metallocene catalyst block copolymer (B) is not particularly limited. For example, the first-stage polymerization described in JP-A No. 11-349650 mentioned above is performed on a polymer made of polypropylene. As the block polymerization, a two-stage polymerization method in which a polymer block made of an ethylene / propylene copolymer is polymerized can be adopted.

  That is, a PP block which is one block constituting the metallocene catalyst block copolymer of (B) is produced by the first stage polymerization (first stage polymerization) at the time of preparing the block copolymer using a metallocene catalyst. To do. The PP block is a propylene homopolymer or a random copolymer of propylene and an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms other than propylene. Examples of the α-olefin in the random copolymer include ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like. The content of these α-olefin units in the random copolymer is 10% by mass or less, preferably 0 to 5% by mass. Further, usually, the polymerization temperature and the polymerization time are selected so that the amount of the polymer obtained in the first stage is 50 to 95% by mass of the total polymer production amount.

  Next, in the presence of the polymer produced by the first stage polymerization, copolymerization of ethylene and propylene is performed as the second stage polymerization to produce an EP block copolymer. The EP block copolymer is a copolymer composed of 10 to 80% by mass of ethylene units, preferably 25 to 75% by mass, and 90 to 20% by mass, preferably 75 to 25% by mass of propylene units. Is a polymer comprising an ethylene / propylene random copolymer. So-called ethylene / propylene rubber can be preferably used as an EP block copolymer. Usually, the polymerization temperature and the polymerization time are selected so that the amount of the polymer obtained by the second-stage polymerization is 5 to 50% by mass of the total polymer production amount.

The metallocene catalyst generally includes a metallocene, that is, a transition metal component composed of a complex composed of two substituted or unsubstituted cyclopentadienyl rings and various transition metals, an organoaluminum component, particularly an aluminoxane, and the like. Is a general term for a catalyst consisting of 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.

  In the present invention, the metallocene catalyst described in JP-A No. 11-349650 is preferable. That is, the Cp is a substituted cyclopentadienyl ring, and the cyclopentadienyl ring includes A bridged azulene-type metallocene catalyst obtained by crosslinking and condensing two azulene skeletons that condense with each other can be used. In the bridged azulene-type metallocene catalyst, a clay mineral can also be used as a promoter. The metallocene catalyst block copolymer (B) in the present invention is synthesized by polymerization in an organic solvent, in a liquid monomer or in a gas phase method in the presence of the metallocene catalyst. Any method that satisfies the above conditions can be used for the purpose of the present invention.

  The polymerization temperature is usually 0 to 100 ° C, preferably 20 to 90 ° C. Hydrogen is preferred as the molecular weight regulator. After the polymerization in the first stage and the second stage, copolymerization of propylene and other α-olefin, homopolymerization of ethylene, or copolymerization of ethylene and other α-olefin as further polymerization in the third stage and after. Can also be done.

The metallocene catalyst block copolymer (B) in the present invention usually has a density of about 0.880 to 0.930 g / cm ³ , preferably about 0.885 to 0.925 g / cm ³ , and MFR (temperature 190 C., load 21.18 N) is 0.5 to 100 g / 10 min, preferably about 1 to 50 g / 10 min. If the MFR exceeds the above range, the impact strength tends to be insufficient, and if the MFR is below the above range, the moldability may be poor. The crystal melting point (Tm) of the metallocene catalyst block copolymer (B) is in the range of 80 to 120 ° C, preferably 85 to 115 ° C, more preferably 90 to 110 ° C. The crystalline melting point is measured using DSC. The crystal melting point can be adjusted by increasing or decreasing the content of the copolymerization monomer. When the crystal melting point of the metallocene catalyst block copolymer (B) is too low, the required strength of the resulting resin multilayer container cannot be obtained, the melt moldability is reduced, or the surface gloss of the resin multilayer container is reduced. And slipperiness may deteriorate. If the crystal melting point is too high, the formability deteriorates.

  In the metallocene catalyst block copolymer (B) in the present invention, a reinforcing material such as talc, calcium carbonate, titanium oxide, carbon black, mica, or the like is added to 10 parts by mass of the block copolymer, if necessary. -60 mass parts can be mix | blended. In addition, additives such as antioxidants, photodegradation inhibitors, antistatic agents, or nucleating agents can be used.

  In addition, other elastomers can be blended to improve low temperature impact resistance, elongation properties and moldability. Examples of the other elastomer include ethylene / α-olefin random copolymer rubber and styrene-containing thermoplastic elastomer, and the other elastomer is 0 with respect to 100 parts by mass of the metallocene catalyst block copolymer of (B). .5 to 50 parts by mass, preferably 1 to 40 parts by mass.

  The ethylene / α-olefin random copolymer rubber is a random copolymer of ethylene and an α-olefin having 4 or more carbon atoms. As the α-olefin, 1-butene, 1-pentene, 1-hexene, 1 -Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like can be mentioned, among which 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Octene is preferred. The content rate of an alpha olefin unit is 15-70 mass%, Preferably it is 20-55 mass%. If the content of the α-olefin unit is too lower than the above range, the low-temperature impact strength is inferior. On the other hand, if the content is too high, not only the elongation characteristics and moldability are lowered, but also the shape of this elastomer is difficult to hold in a pellet form. The handling during production may be significantly reduced.

  The styrene-containing thermoplastic elastomer is an elastomer containing 5 to 60% by mass, preferably 10 to 30% by mass of a polystyrene part. Specific examples of the styrene-containing thermoplastic elastomer include styrene / ethylene / butylene / styrene block copolymer (SEBS). The SEBS used in the present invention preferably contains polystyrene units in an amount of 10 to 40% by mass. Along with SEBS, SBR, SBS, SIS and SIS hydrogenated products can also be used.

  As the elastomer component, the above-described ethylene / α-olefin random copolymer rubber or styrene-containing thermoplastic elastomer may be used alone or in appropriate combination.

  The presence of the metallocene catalyst block copolymer (B) 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, and is made of Zr (zirconium) or Hf (hafnium). ) To confirm the existence 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.

  A synthetic product can be used as the metallocene catalyst block copolymer (B), but it can also be selected from commercially available products. Examples of commercially available products include Kernel (registered trademark) manufactured by Nippon Polyethylene Corporation.

  The content of the metallocene catalyst block copolymer (B) in the resin composition is 0.5 to 40% by mass when the total of (A) and (B) is 100% by mass, preferably It is 1-38 mass%, More preferably, it is 2-35 mass%. If the content of the metallocene catalyst block copolymer (B) in the resin composition is too small, the surface gloss of the resulting resin multilayer container may be lowered. On the other hand, if the content is too large, it will be obtained. In some cases, the slipperiness of the resin multilayer container is deteriorated, and the surface gloss is further lowered.

3. (C) Fatty acid amide having an unsaturated cis-structured carbon double bond The resin composition containing (A), (B), and (C) in the present invention contains (C) unsaturated The fatty acid amide having a cis structure carbon double bond is contained in an amount of 100 to 4000 ppm based on the total mass part of (A) and (B).
(C) A fatty acid amide having an unsaturated cis-structured carbon double bond (hereinafter sometimes referred to as “(C) unsaturated fatty acid amide”) functions as a lubricant. The unsaturated fatty acid amide of (C) is an unsaturated fatty acid amide having at least one carbon double bond in the molecular structure of the fatty acid amide, and all of the carbon double bonds are carbon bis having an unsaturated cis structure. It is an unsaturated aliphatic amide that is a heavy bond. 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 deteriorates and the surface gloss deteriorates.

  The content of unsaturated fatty acid amide (C) is preferably 105 to 3900 ppm, more preferably 110 to 3800 ppm, still more preferably 115 to 3700 ppm, and particularly preferably 120 to 3600 ppm. When the content of the unsaturated fatty acid amide of (C) is too small, the slipping property of the resulting resin multi-layer container is insufficient, and during the manufacture of the container, during transportation or during filling of the contents, adjacent containers or Due to contact with the devices, there is a risk of generating defective products, stopping the production line, or failure of the devices. Also, if the slipperiness of the innermost layer of the resulting resin multilayer container is insufficient, the filling of the contents may not be performed smoothly, or the liquid drainage of the contents may be insufficient when used by consumers. is there. When there is too much content of unsaturated fatty acid amide of (C), the surface glossiness of the resin multilayer container obtained will become small, and the stickiness during conveyance operation will increase. When the unsaturated fatty acid amide (C) is a mixture of fatty acid amides having two or more types of unsaturated cis structure carbon double bonds as described later, the total content of fatty acid amides is included in the above range. Need to be.

  (C) 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.

  (C) The fatty acid amide having an unsaturated cis structure carbon double bond may be an unsaturated fatty acid amide having a plurality of unsaturated cis structure 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 (C) most preferably used in the present invention is an unsaturated cis structure carbon dioxygen having 1 to 4 bonds of unsaturated cis structure carbon bonds in the molecular structure. It is a fatty acid amide having a heavy bond.

Examples of the (C) fatty acid amide having an unsaturated cis structure carbon double bond having one unsaturated cis structure carbon double bond include the following formulas (C ₁ ) to (C ₃ ):
(C 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);
(C 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 (C 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 of the formula of _{C 1),} there may be referred to as "formula _{(C 1)} fatty acid amide of the" further may be simply referred to as a "formula _{(C 1)". (C} 2) The same applies to the fatty acid amide represented by the formula (C ₃ ).)

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

Formula (C 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)
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 (C ₂ ): H ₂ N—CO — (— CH ₂ —) _{m− 2} —CH═CH — (— CH ₂ —) _m —CH ₃ (where m is in the range of 6 ≦ m ≦ 10) integer)
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 _{(C 3): H 2 N} -CO - (- CH 2 -) k + 4 -CH = CH - (- CH 2 -) k -CH 3 ( however, k is in the range of 6 ≦ k ≦ 10 integer)
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 ]

(C) The fatty acid amide having an unsaturated cis-structured carbon double bond includes the fatty acid amide of the above formula (C ₁ ) to the formula (C ₃ ), or the unsaturated of 2 to 4 bonds in the molecular structure. If one type of unsaturated fatty acid amide selected from fatty acid amides having a cis structure carbon double bond is used, the desired effect can be obtained, but two or more types of (C) unsaturated cis structure carbons can be obtained. Mixtures of fatty acid amides having double bonds may be used. The mixture of fatty acid amides preferably contains the fatty acid amide of the above formula (C ₁ ).

Therefore, a preferred mixture of (C) fatty acid amides having an unsaturated cis structure carbon double bond is represented by the above formula (C ₁ ) fatty acid amide and the above formula (C ₂ ) or (C ₃ ). A mixture with at least one fatty acid amide. The proportion of the fatty acid amide of the formula (C ₁ ) in the mixture is 0.05 to 99.95% by mass, preferably 0.1 to 99.9% by mass, more preferably 0.15 to 99.85% by mass. It is. Therefore, the ratio of the fatty acid amide of the formula (C ₂ ) or the fatty acid amide of the formula (C ₃ ) is 99.95 to 0.05% by mass, preferably 99.9 to 0.1% by mass, Preferably it is 99.85-0.15 mass%.

In particular, (C) a mixture of fatty acid amides having an unsaturated cis-structured carbon double bond is a fatty acid amide of the above formula (C 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 (C 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 (C ₁ ) corresponds to cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (n = 7 ) And
Formula _{(C 2)} is, cis-6,7-tetradecenoamide _{[H 2 N-CO - (-} CH 2 -) 4 -CH = CH - (- CH 2 -) 6 -CH 3 ] (m = 6 = n -1) or cis-8,9-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₆ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ] (m = 8 = (equivalent to n + 1) is preferably used.

In addition, (C) a mixture of fatty acid amides having an unsaturated cis-structured carbon double bond is a fatty acid amide of the above formula (C 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 (C 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 (C 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 (C 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, (C) a mixture of fatty acid amides having an unsaturated cis structure carbon double bond is a mixture of two or more compounds belonging to the fatty acid amide of the above formula (C ₁ ) and having different values of n. be able to. That is, (C 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 (C 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)).

Specifically, for example, cis-9,10-octadecenoamide [H ₂ N—CO — (— CH ₂ —) ₇ —CH═CH — (— CH ₂ —) ₇ —CH ₃ ] (corresponding to n = 7) ) And cis-10, 11-eicosenoamide [H ₂ N—CO — (— CH ₂ —) ₈ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ] (corresponding to j = 8) Etc. can be preferably used.

Furthermore, (C) a 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, alone or in other (C) It can also be used as a mixture with a fatty acid amide having an unsaturated cis structure carbon double bond. As the other (C) fatty acid amide having an unsaturated cis structure carbon double bond, the fatty acid amides of the above formulas (C ₁ ) to (C ₃ ) are preferably used, and in particular, the fatty acid amide of the formula (C 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 -) and 4 -CH _3], a mixture of cis-9,10-octadecenoamide of the formula _{(C 1)} and It can be preferably used.

4). (C) Method for Producing Fatty Acid Amide Having Unsaturated cis-Structure Carbon Double Bond The unsaturated fatty acid amide (C) 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 _{(C 2), i.e., (C 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, and may be obtained as a synthetic product.

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 ) As a starting material. ((Formula a) illustrates a compound having a hydroxyl terminal.)

(Formula _{a) CH 3 O-CO -} (- CH 2 -) m-1 -OH

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 to give an ionic intermediate of formula (b).

(Formula b) [CH ₃ O—CO — (— CH ₂ —) _m−1 -PPh ₃ ] ⁺ + Br ⁻

The ionic intermediate (formula b) is reacted with decyl aldehyde, and the PPh ₃ group is terminated with an alkyl group having an unsaturated cis-structured carbon double bond. , ω structure compound.

(Formula _{c) CH 3 O-CO -} (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3

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, to synthesize a fatty acid amide having an unsaturated cis structure carbon double bond represented by the following (formula d), that is, a fatty acid amide of (C ₂ ).

(Wherein _{d) H 2 N-CO -} (- CH 2 -) m-2 -CH = CH - (- CH 2 -) m -CH 3

  By changing 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 is obtained using this synthetic route. Can do.

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 with a concentration gradient of 100% by mass (initial development) to 40% by mass of ethyl acetate and hexane, and isomers of unsaturated cis structure and unsaturated trans structure are obtained. To separate. At that time, using a proton ¹ H-NMR nuclear magnetic resonance apparatus, identification according to the chemical shift value is performed based on a standard substance made by Aldorich for the fraction solution at each chromatography development time. Identify the fluid. The fraction solution is dried under reduced pressure to recover the desired fatty acid amide having an unsaturated cis structure carbon double bond.

5. Other compounding agents The resin composition in this invention can contain various additives, such as a heat stabilizer, a light stabilizer, a coloring pigment, an inorganic filler, as another compounding agent as needed. In addition, the resin composition of the present invention may be used as an other compounding agent within the range not impairing the object of the present invention, as desired, such as 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.

  Other lubricants can also be used as various additives. 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.

  The content in the case of containing a saturated fatty acid amide is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably based on the total amount of the unsaturated fatty acid amide of the formula (C) and the saturated fatty acid amide. Is 6 mass% or less, and the lower limit of the content is about 0.5 mass%, and if it is 1 mass%, a sufficient effect can be realized.

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 above resin composition, that is, a layer made of the resin composition containing the above (A), (B), and (C), as the outermost layer of the container. Or it can be provided in one or both of the innermost layers.

  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 the contact between adjacent 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 and used by consumers. There are some effects such as excellent drainage of the contents.

  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 for forming the barrier layer include ethylene / vinyl alcohol copolymers or partially saponified products of ethylene / vinyl acetate copolymers (hereinafter sometimes collectively referred to as “EVOH”). Can be mentioned. 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, an aromatic polyamide (MXD6) formed from metaxylylenediamine and adipic acid, a vinylidene chloride copolymer, or 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%, has 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., load 21.18 N) of 6 g / 10 min or less, preferably 5 g / 10 min or less, more preferably 4 g / 10 minutes or less.

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 resin used for 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, poly An acrylic imide etc. can be mentioned.

  If desired, the resin used for the adhesive layer can contain various additives such as inorganic fillers, plasticizers, heat stabilizers, light stabilizers, and dyes.

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 is provided with a layer made of the resin composition containing the above (A), (B), and (C) as a surface layer, and preferably a surface layer as a layer structure. , A resin multilayer container including 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 / recovery 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% (thickness ratio) with respect to the total thickness.

  The surface layer is preferably 55 to 85% (thickness ratio), more preferably 60 to 80% (thickness ratio). The collection layer is usually 5 to 30% (thickness ratio), preferably 10 to 25% (thickness ratio), more preferably 15 to 25% (thickness ratio). The barrier layer is usually 1 to 10% (thickness ratio), preferably 2 to 8% (thickness ratio), more preferably 3 to 6% (thickness ratio). The adhesive layer is generally 0.005 to 2% (thickness ratio) in total, preferably 0.007 to 1.5% (thickness ratio), more preferably 0.008 to 1.2% (thickness ratio). ).

  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% (thickness ratio), preferably 15 to 75% ( (Thickness ratio), more preferably 20 to 70% (thickness ratio), particularly preferably 25 to 65% (thickness ratio).

  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 made of the resin composition containing the above (A), (B), and (C). 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 sealing material having a two-layer structure (aluminum / LDPE) including low density polyethylene (LDPE) is used, and the LDPE side of the sealing material is connected to the opening of the container. Place on the part and heat weld to 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.

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

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, that is, resin multilayer containers formed by direct blow molding are more preferable.

  Therefore, the resin multilayer container of the present invention can be used for various shapes of containers by blow molding (including stretch blow molding), injection molding, folding and bonding of a film or sheet, vacuum forming and / or pressure forming of a sheet. It can be manufactured by molding. 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 bottle-shaped container is manufactured by blow molding, it is preferable to manufacture a cylindrical (pipe-shaped) multi-layer parison 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 die orifice, not only a circular shape but also a flat shape can be used. 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. In general, 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 thermoplastic 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 and forming into a container shape, the upper part (head or bag part) of the unnecessary container mouth is cut off 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 bottle, 6 to 7.5 times for a heat resistant bottle, and 7 to 8 times for a large bottle.

  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 K7121.

[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.

[Alpha-olefin content]
The α-olefin content (% by mass) in the Ziegler catalyst random copolymer of (A) was determined by using a 270 MHz apparatus of FT-NMR manufactured by JEOL Ltd., and ¹³ C-NMR (nuclear magnetic resonance spectrum). It measured using.

[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. 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 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.

[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, from the body portion 20 to 100 mm above the bottom of the container, the normal direction (T direction) to the bottom surface when standing the container is 60 mm, and the direction parallel to the bottom surface when standing the container (L direction) A sample of 80 mm was cut out. 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 mass of the multilayer container was 20 g.

(1) Surface layer (outermost layer and innermost layer):
(A) Propylene / α-olefin random copolymer having a crystalline melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst: trade name NOBREN (registered trademark) manufactured by Nippon Polyethylene Co., Ltd. 905 g / cm ³ , MFR (temperature 190 ° C., load 21.18 N) 3.5 g / 10 min, crystal melting point 132 ° C., polydispersity (Mw / Mn) = 3, α-olefin content = 4 mass%] 90 A block copolymer consisting of a polymer block composed of polypropylene and a polymer block composed of an ethylene / propylene copolymer, obtained by using a metallocene catalyst, and a mass copolymer (B): Nippon Polyethylene Co., Ltd. Ltd. the trade name kernel (registered trademark) [density 0.905 g ^/ cm 3, MFR (temperature 190 ° C., load 21.18 N) 3.5 g / 10 min, crystallinity Point 97 ° C.] 10 wt%
[However, the mass% of (A) and (B) is a value when the total of (A) and (B) is 100 mass%. The same applies below. ],
And
(C) 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] (99.8 wt%; unsaturated fatty acid amides of the formula _{(C 1))} and 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 ] (0.2 mass% ) Mixture (C) was blended to 130 ppm with respect to the total mass part of (A) and (B). [Thus, the total content (ppm) of (C) is expressed as the ratio of (A) and (B) to the total parts by mass. The same applies to the following examples and comparative examples. ]

(2) Barrier layer: trade name EVAL (registered trademark) manufactured by Kuraray Co., Ltd. [an ethylene / vinyl alcohol copolymer having an ethylene content of 44 mol%. Density 1.140 g / cm ³ , MFR (190 ° C., load 21.18 N) 1.7 g / 10 min, crystal melting point 165 ° C.]

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

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

  The thickness ratio of the layers (1) to (4) was 75: 4: 20: 1. Table 1 shows the results of measuring the surface sliding friction coefficient (hereinafter referred to as “sliding friction”) and surface gloss of the molded container.

[Example 2]
(C) Fatty acid amides having an unsaturated cis structure carbon double bond are converted into cis-9,10-octadecenoamide [formula (C ₁ )] (99.0% by mass) 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 (C ₂ )] (1.0% by mass) (C) The multilayer container was molded in the same manner as in Example 1 except that the content was changed to 1, and blended to 1500 ppm. Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

Example 3
(C) Fatty acid amides having an unsaturated cis structure carbon double bond are converted into cis-9,10-octadecenoamide [formula (C ₁ )] (85.0 mass%) and cis-10,11-eicosenoamide [H ₂ N In the mixture (C) of —CO — (— CH ₂ —) ₈ —CH═CH — (— CH ₂ —) ₈ —CH ₃ ; unsaturated fatty acid amide of formula (C ₁₁ )] (15.0 mass%) change, except the changes was blended so that 350 ppm, in the same manner as in example 1, were molded multilayer container. Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

Example 4
(C) Fatty acid amides having an unsaturated cis structure carbon double bond are converted into cis-9,10-octadecenoamide [formula (C ₁ )] (98.0% by mass) and cis-13,14-docosenoamide [H ₂ N _{-CO - (- CH 2 -)} 11 -CH = CH - (- CH 2 -) 7 -CH 3; mixture of formula _{(C 3)} of the unsaturated fatty acid amide] (2.0 wt%) to (C) A multilayer container was formed in the same manner as in Example 1 except that the change was made so as to be 3500 ppm. Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

Example 5
(C) Fatty acid amides having unsaturated cis-structured carbon double bonds are converted into cis-13,14-docosenoamide [formula (C ₃ )] (98.0% by mass) and cis-9,10-octadecenoamide [formula (C ₁ )] A multilayer container was molded in the same manner as in Example 4 except that the mixture (C) was changed to (2.0% by mass). Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

Example 6
(C) Fatty acid amides having unsaturated cis-structured carbon double bonds are converted into cis-9,10-octadecenoamide [formula (C ₁ )] (95.0 mass%) and cis-13,14-docosenoamide [formula (C ₃ )] (3.0% by mass) of the mixture (C), and further containing a saturated fatty acid amide, behenic acid amide, at a rate of 2.0% by mass, the unsaturated fatty acid amide and the saturated fatty acid amide. A multilayer container was molded in the same manner as in Example 4 except for the change in which the total content with amide was 1000 ppm. Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

Example 7
(C) Fatty acid amides having an unsaturated cis structure carbon double bond are converted into cis-9,10-octadecenoamide [formula (C ₁ )] (92.0 mass%) and cis-13,14-docosenoamide [formula (C ₃ )] (3.0% by mass) of the mixture (C), and further containing a fatty acid amide, stearic acid amide, at a rate of 5.0% by mass, the unsaturated fatty acid amide and the saturated fatty acid amide A multilayer container was molded in the same manner as in Example 4 except for the change in which the total content with amide was 1000 ppm. Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

[Comparative Example 1]
(C) The fatty acid amide having an unsaturated cis structure carbon double bond corresponds to trans-9,10-octadecenoamide [corresponding to the trans structure of the unsaturated fatty acid amide of the formula (C ₁ ). ] A multilayer container was molded in the same manner as in Example 4 except that it was changed to (single use). Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

[Comparative Example 2]
trans-9,10-octadecenoamide [corresponds to the trans structure of the unsaturated fatty acid amide of the formula (C ₁ ). ] (Single use) 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, A multilayer container was molded in the same manner as in Comparative Example 1 except that the blending was performed so that the total content with the saturated fatty acid amide was 3000 ppm. Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

  From the results in Table 1, (A), (B), and (C) a resin multilayer container comprising as a surface layer a layer made of a resin composition containing a fatty acid amide having an unsaturated cis structure carbon double bond, When the total of (I), (A) and (B) is 100% by mass, (B) is 0.5 to 40% by mass; and (II) (A) and (B ), The resin multilayer containers of Examples 1 to 7 satisfying (C) of 100 to 4000 ppm have a surface sliding friction coefficient of 0.22 to 0.38 and surface slippage. The glossiness of the surface gloss was 42 to 52%, the gloss was good, and the slipperiness and the surface gloss were improved in a well-balanced manner.

  On the other hand, instead of the fatty acid amide having an unsaturated cis structure carbon double bond (C), the resin multilayer containers of Comparative Examples 1 and 2 containing a fatty acid amide having an unsaturated trans structure carbon double bond are: The surface friction coefficient was as large as 0.44 or 0.43, there was a sticky feeling, and the slipperiness was insufficient.

Example 8
The surface layer was changed to (A) 97% by mass and (B) 3% by mass, and (C) a fatty acid amide having an unsaturated cis structure carbon double bond was blended to 400 ppm, A multilayer container was formed in the same manner as in Example 2. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2.

Example 9
A multilayer container was molded in the same manner as in Example 8 except that the surface layer was changed to (A) 70% by mass and (B) 30% by mass. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2.

[Example 10]
For the surface layer, the Ziegler catalyst random copolymer of (A) having a crystal melting point of 132 ° C. and an α-olefin content of 4% by mass has a crystal melting point of 160 ° C. and an α-olefin (ethylene) content of 1% by mass. A multilayer container was molded in the same manner as in Example 3 except that the propylene / ethylene random copolymer was changed. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2.

[Comparative Example 3]
Except for the change in which the surface layer was changed to (A) 50% by mass and (B) 50% by mass, and (C) the fatty acid amide having an unsaturated cis-structured carbon double bond was blended to be 5000 ppm. In the same manner as in No. 2, a multilayer container was molded. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2.

[Comparative Example 4]
A surface layer is (B) 100 mass% [(A) is not contained. A multilayer container was molded in the same manner as in Comparative Example 3 except that (C) a fatty acid amide having an unsaturated cis structure carbon double bond was added to 4000 ppm. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2.

[Comparative Example 5]
A surface layer is (A) 100 mass% [(B) is not contained. The multilayer container was molded in the same manner as in Comparative Example 3 except that (C) a fatty acid amide having an unsaturated cis structure carbon double bond was blended to 80 ppm. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2.

  From the results of Table 2, (A), (B), and (C) a multilayer container made of a resin comprising a layer made of a resin composition containing a fatty acid amide having an unsaturated cis structure carbon double bond as a surface layer. When the total of (I), (A) and (B) is 100% by mass, (B) is 0.5 to 40% by mass; and (II) (A) and (B ), The resin multilayer containers of Examples 8 to 10 satisfying (C) of 100 to 4000 ppm have a surface sliding friction coefficient of 0.34 to 0.38 and surface slippage. It was found that the glossiness of the surface gloss was 49 to 51%, the gloss was good, and the slipperiness and the surface gloss were improved in a well-balanced manner.

  On the other hand, the surface layer (outermost layer and innermost layer) contains a large amount of (B), and the resin multilayer container of Comparative Example 3 made of a resin composition containing a large amount of (C) has a surface gloss. It was found that the gloss value was 35% and the gloss was not good. Furthermore, the resin multilayer container of Comparative Example 4 in which the surface layers (outermost layer and innermost layer) are made of a resin composition not containing (A) has a gloss value of 36%, and gloss is not good, and The surface friction coefficient was as large as 0.53, there was a feeling of stickiness, and the slipperiness was insufficient. Furthermore, the surface layer (outermost layer and innermost layer) does not contain (B), and the resin multilayer container of Comparative Example 5 having a small content of (C) has a large surface sliding friction coefficient of 0.41, There was a sticky feeling and the slipperiness was insufficient.

The present invention includes (A) a propylene / α-olefin random copolymer having a crystalline melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, and (B) a polypropylene obtained using a metallocene catalyst. A resin composition comprising: a polymer block comprising: a polymer block comprising an ethylene / propylene copolymer; a block copolymer comprising: (C) 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 resin composition has the following (I) and (II):
(I) When the sum of (A) and (B) is 100% by mass, (B) is 0.5 to 40% by mass; and (II) with respect to the total mass part of (A) and (B) (C) is 100 to 4000 ppm;
By satisfying the above requirements, the resin multilayer container can exhibit slipperiness according to various environmental temperatures in the steps of bottle molding, filling, transferring, and packaging of the contents. It is possible to provide a resin multi-layer container with improved liquid drainage of the contents and excellent surface gloss, so the productivity is high and the reliability during transportation and storage is high. And since the resin multilayer container with which the user's satisfaction improved can be provided, industrial applicability is high.

Claims (14)

(A) A propylene / α-olefin random copolymer having a crystalline melting point of 125 to 165 ° C., obtained using a Ziegler-Natta catalyst, and (B) a polymer comprising polypropylene, obtained using a metallocene catalyst. And a block comprising a block of a polymer comprising an ethylene / propylene copolymer, and (C) a layer comprising a resin composition containing a fatty acid amide having an unsaturated cis structure carbon double bond A multi-layer container made of resin as a surface layer,
The resin composition has the following (I) and (II):
(I) When the sum of (A) and (B) is 100% by mass, (B) is 0.5 to 40% by mass; and (II) with respect to the total mass part of (A) and (B) (C) is 100 to 4000 ppm;
Satisfying the above-mentioned resin multilayer container. The (C) fatty acid amide having an unsaturated cis structure carbon double bond is represented by the following (C ₁ ), (C ₂ ) and (C ₃ ):
(C 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);
(C 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 (C 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 one formula selected from the group consisting of: The fatty acid amide having the (C) unsaturated cis structure carbon double bond is represented by the fatty acid amide represented by the formula (C ₁ ) and the formula (C ₂ ) or (C 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 (C 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 (C ₃ ) is k = n. The fatty acid amide having the (C) unsaturated cis structure carbon double bond is the fatty acid amide represented by the above formula (C ₁ ) and the following (C ₁₁ ):
(C 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 fatty acid amide having the (C) unsaturated cis structure carbon double bond contains a compound having 2 to 4 bonds of unsaturated cis structure carbon bonds in the molecular structure. A multilayer resin container as described in 1.   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, wherein the surface layer is one or both of an outermost layer and an innermost layer.   The resin multilayer container according to claim 1, further comprising a barrier layer.   The resin multilayer container according to claim 10, wherein the barrier layer is an ethylene / vinyl alcohol copolymer or polyglycolic acid.   The resin multilayer container according to claim 1, further comprising a recovery layer.   The resin multilayer container according to any one of claims 1 to 12, wherein the resin multilayer container includes a surface layer, a barrier layer, an adhesive layer, and a recovery layer.   The resin multilayer container according to any one of claims 1 to 13, wherein the resin multilayer container is composed of an outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer.