JP5824244B2 - Resin multilayer container with collection layer - Google Patents

Description

  The present invention relates to a resin multilayer container, and more particularly to a resin multilayer container including a recovery layer, and more particularly to a resin multilayer container including a recovery layer and having improved slipperiness and surface gloss of the container surface layer.

  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 the multilayer plastic container provided with a soft container having a balance of transparency, flexibility, rigidity, drop-proof 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. 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 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.

  In the resin multilayer container, the resin multilayer is further provided with a recovery layer for the purpose of improving the adhesive strength between the layers, improving the strength of the resin multilayer container, and contributing to effective use of resources and reduction of environmental load. A resin multilayer container including a container, that is, a surface layer, a barrier layer, an adhesive layer, and a recovery layer is known. The recovery layer is a layer containing, as a main component, unnecessary parts and burrs that are generated during the manufacture of the container, recovered products such as containers out of product specifications, and other materials generated in the manufacturing process of the container. For example, Japanese Patent Laid-Open No. 5-8355 (Patent Document 6) discloses that a multilayer plastic container whose outermost surface layer is a propylene homopolymer is provided with a layer in which a scrap resin is singly or blended with a polyolefin resin. Yes. Japanese Unexamined Patent Publication No. 2003-191930 (Patent Document 7) discloses a multilayer container having a base resin layer, a barrier resin layer, an adhesive resin layer, and a recovery resin layer.

  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. A resin multilayer container having a recovery layer is still insufficient in that it has both excellent slipperiness and excellent surface gloss, and improvement has been demanded.

JP-A-6-72424 JP 2009-248996 A JP-A-11-349650 JP 2009-214914 A JP-A-2005-307122 JP-A-5-8355 JP 2003-191930 A

  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. Providing a resin multilayer container having a proper slipperiness between the contents and the like and an improved liquid drainage of the contents filled in the container and having a recovery layer having an excellent surface gloss is there.

  As a result of intensive studies on solving the above-mentioned problems, the inventors of the present invention have obtained a recovery layer using (A) a Ziegler-Natta catalyst, and has a crystalline melting point of 125 to 165 ° C. An olefin random copolymer, (B) a block copolymer obtained by using a metallocene catalyst, a polymer block comprising polypropylene, and a polymer block comprising an ethylene / propylene copolymer, and ( C) The present invention has been completed by finding that the problem can be solved by using a resin multilayer container containing a fatty acid amide having an unsaturated cis-structured carbon double bond.

That is, according to the present invention, a resin multilayer container including at least a surface layer and a recovery layer,
The recovery layer was obtained using (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 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. The above-mentioned resin multilayer container is provided.

  Moreover, according to this invention, the resin multilayer containers of the following (1)-(16) are provided as an embodiment.

(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 a 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) k in fatty acid amide represented by the formula (C ₃₎ is said of the resin multilayer container 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 above-mentioned resin multilayer container, 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 double bonds in the molecular structure.

(7) The said resin multilayer container in which a collection | recovery layer contains saturated fatty acid amide further.

(8) The said resin multilayer container in which a collection | recovery layer contains one or both of adhesive resin or barrier resin further.

(9) The said resin multilayer container in which adhesive resin contains acid-modified polyolefin.

(10) barrier resin, wherein the resin multilayer container is ethylene-vinyl alcohol copolymer or polyglycolic acid.

(11) The resin multilayer container as described above, wherein the resin multilayer container includes a surface layer, a barrier layer, an adhesive layer, and a recovery layer.

(12) The said resin multilayer container which a resin multilayer container consists of outermost layer / adhesive layer / barrier layer / adhesive layer / collection layer / innermost layer.

(13) The said resin multilayer container in which an adhesive layer contains acid-modified polyolefin.

(14) The said resin multilayer container in which a barrier layer contains an ethylene-vinyl alcohol copolymer or polyglycolic acid.

(15) A surface layer was obtained using (A) a propylene / α-olefin random copolymer having a crystal melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, and (B) 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. And the content of (C) is said resin multilayer container which is 100-4000 ppm with respect to the total mass part of (A) and (B).

(16) The said resin multilayer container shape | molded by direct blow molding.

  According to the present invention, a propylene resin container having at least a surface layer and a recovery layer, wherein the recovery layer is obtained using (A) a Ziegler-Natta catalyst and has a crystal melting point of 125 to 165 ° C. .Alpha.-Olefin Random Copolymer, (B) A block copolymer obtained by using a metallocene catalyst and comprising a polymer block comprising polypropylene and a polymer block comprising ethylene / propylene copolymer. And (C) the resin multilayer container characterized by containing a fatty acid amide having an unsaturated cis-structured carbon double bond, having excellent slipperiness and surface gloss, and low environmental impact There exists an effect that this resin multilayer container can be provided.

I. Recovery Layer The resin multilayer container of the present invention is a resin multilayer container having at least a surface layer and a recovery layer, and the recovery layer is obtained using (A) a Ziegler-Natta catalyst and has a crystalline melting point of 125-125. A propylene / α-olefin random copolymer at 165 ° C., (B) a polymer block made of polypropylene and a polymer block made of ethylene / propylene copolymer, obtained using a metallocene catalyst. And (C) a fatty acid amide having an unsaturated cis structure carbon double bond. That is, the resin multilayer container of the present invention is a resin multilayer container that has an essential requirement to have a recovery layer, and that the recovery layer has a specific composition.

1. Recovery Layer The recovery layer in the resin multilayer container of the present invention is synonymous with a recovery layer commonly used in the industry to increase the strength of the resin multilayer container and increase the recyclability of resources. That is, the recovery layer of the resin multi-layer container of the present invention is manufactured at the material recovered from the resin multi-layer container of the present invention itself (burrs and unnecessary parts of the product container, the adjustment stage before product molding, and the product molding end stage. A layer containing a material recovered as a main component in the process of manufacturing the resin multilayer container of the present invention. 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, a layer containing as a main component a resin collected by cutting away a portion other than the bag portion of the blow molded container, a parison before molding, and materials and raw materials forming each layer of the resin multilayer container But you can.

Therefore, the composition of the recovery layer of the resin multilayer container of the present invention can be adjusted by the composition of each layer constituting the surface multilayer and other resin multilayer containers and the thickness of each layer. When the resin multilayer container further includes a barrier layer and / or an adhesive layer, the recovery layer of the resin multilayer container is included in the barrier resin and / or the adhesive layer contained in the barrier layer. An adhesive resin, that is, one or both of a barrier resin and an adhesive resin is contained. For example, when the resin multilayer container includes a barrier layer containing an ethylene / vinyl alcohol copolymer or polyglycolic acid, the collection layer contains the ethylene / vinyl alcohol copolymer or polyglycolic acid, The composition of the collection layer also varies depending on the composition and thickness of the barrier layer and / or adhesive layer.

  The resin multilayer container according to the present invention is a propylene / α-olefin random copolymer in which the recovery layer is obtained using (A) a Ziegler-Natta catalyst and has a crystalline melting point of 125 to 165 ° C., (B) A block copolymer composed of a polymer block composed of polypropylene, a polymer block composed of an ethylene / propylene copolymer, and (C) an unsaturated cis structure carbon double obtained using a metallocene catalyst It contains an aliphatic amide having a bond.

2. (A) Propylene / α-olefin random copolymer having a crystalline melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst (A) Ziegler contained in the recovery layer of the resin multilayer container of the present invention A propylene / α-olefin random copolymer (hereinafter, also referred to as “(A) Ziegler catalyst random copolymer”) having a crystal melting point of 125 to 165 ° C. obtained using a Natta catalyst. And 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 recovery layer in the resin multilayer container of 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 an 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 pellet may be a raw material resin composition of the recovery layer or a recovery layer cut out from the resin multilayer container, or may be a layer on the surface of the recovery layer where the layers of the resin multilayer container are separated.

  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 recovery layer is not particularly limited, but is usually 60 to 99.5% by mass when the total of (A) and (B) is 100% by mass. The ratio of the Ziegler catalyst random copolymer (A) in the surface layer and the thickness of the surface layer in the resin multilayer container is preferably 62 to 99% by mass, more preferably 65 to 98% by mass. Furthermore, it can be adjusted by the ratio of the material recovered from the resin multilayer container itself and the material recovered in the process of manufacturing the resin multilayer container. When the content of the Ziegler catalyst random copolymer (A) in the recovery layer is too small, the melt viscosity of the resin in the blow molding extrusion described later becomes small, and the handling property of the direct blow bubbles deteriorates. Problems may occur and the surface gloss of the container may be poor. If the content of the Ziegler catalyst random copolymer (A) in the recovery layer is too large, the slipping property may be lowered.

3. (B) A block copolymer composed of a polymer block composed of polypropylene and a polymer block composed of an ethylene / propylene copolymer, obtained using a metallocene catalyst. Recovery of the resin multilayer container of the present invention A block copolymer (hereinafter referred to as “a block of a polymer block made of polypropylene and a polymer block made of an ethylene / propylene copolymer” obtained using the (B) metallocene catalyst contained in the layer. The (B) metallocene catalyst block copolymer ”is sometimes referred to as a polymer block composed of polypropylene (hereinafter sometimes referred to as“ PP block ”) and a polymer composed of an ethylene / propylene copolymer. Of the metallocene (hereinafter sometimes referred to as “EP block”), each of which is a combination of one or more blocks. A block copolymer obtained by using a catalyst, which maintains the rigidity of polypropylene and exhibits high rigidity and impact resistance in a well-balanced manner with improved impact resistance by ethylene / propylene copolymer. It is a known block copolymer.

  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, the polymerization temperature and the polymerization time are usually selected so that the amount of the polymer obtained by the first stage polymerization 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. 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 recovery layer 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 pellet may be a raw material resin composition of the recovery layer or a recovery layer cut out from the resin multilayer container, or may be a layer on the surface of the recovery layer where the layers of the resin multilayer container are separated.

  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 recovery layer is not particularly limited, but preferably 0.5 to 40 mass when the total of (A) and (B) is 100 mass%. %, More preferably 1 to 38% by mass, still more preferably 2 to 35% by mass. The content of the metallocene catalyst block copolymer (B) in the recovery layer is mainly the ratio of the content of the metallocene catalyst block copolymer (B) in the surface layer or the thickness of the surface layer in the resin multilayer container, The ratio can be adjusted by the ratio of the material recovered from the resin multilayer container itself and the material recovered in the process of manufacturing the resin multilayer container. If the content of the metallocene catalyst block copolymer (B) in the recovery layer is too small, the slipping property of the resulting resin multilayer container may be deteriorated or the rigidity may be insufficient. If the content of the metallocene catalyst block copolymer (B) in the recovery layer is too large, drawdown may occur when the container is molded, or melt fracture may occur in the parison used for blow molding. In addition, the surface gloss of the resulting resin multilayer container may be reduced, and the slipperiness may be deteriorated.

4). (C) Fatty acid amide having unsaturated cis-structured carbon double bond (C) Fatty acid amide having unsaturated cis-structured carbon double bond contained in the recovery layer of the resin multilayer container of the present invention [hereinafter referred to as “(C ) Unsaturated fatty acid amide. ] 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 becomes insufficient, or the unsaturated fatty acid amide having the trans structure is obtained from the resin multilayer container obtained. In some cases, it may be deposited on the surface, resulting in deterioration of the slidability of the resulting resin multilayer container or reduction in surface gloss.

  The content of the unsaturated fatty acid amide (C) in the recovery layer of the resin multilayer container of the present invention is not particularly limited, but is preferably 100 to 4000 ppm with respect to the total mass part of (A) and (B). More preferably, it is 105-3800 ppm, More preferably, it can be set as the range of 110-3600 ppm. The content of the unsaturated fatty acid amide (C) in the recovery layer is mainly the ratio of the content of the unsaturated fatty acid amide (C) in the surface layer and the thickness of the surface layer in the resin multilayer container, and further the resin multilayer container It can be adjusted by the ratio of the material recovered from itself and the material recovered in the process of manufacturing the resin multilayer container. If the content of the unsaturated fatty acid amide (C) in the recovery layer is too small, the resulting resin multilayer container is insufficiently slippery, and the container is produced during the production, transportation or filling of the contents. Contact or collision with each other or devices may cause defective products, production line stoppage, device failure, and the like. In addition, the slipperiness of the innermost layer of the resulting resin multilayer container is insufficient, so that the contents may not be filled smoothly, or the contents may not be sufficiently drained when used by consumers. There is. When the content of the unsaturated fatty acid amide (C) is too large, the surface gloss of the resulting resin multilayer container may be reduced, or the stickiness during the carrying operation may be increased. 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. It is preferred that

  (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, (C) the fatty acid amide having an unsaturated cis structure carbon double bond most preferably used in the present invention is an unsaturated cis structure having 1 to 4 bonds of unsaturated cis structure carbon double bonds in the molecular structure. It is a fatty acid amide having a carbon double 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 ratio of the fatty acid amide of the formula (C ₁ ) in the mixture is usually 0.05 to 99.95% by mass, preferably 0.1 to 99.9% by mass, more preferably 0.15 to 99.85% by mass. % Range. Therefore, the ratio of the fatty acid amide that is a mixture of the above formula (C ₂ ), formula (C ₃ ), or formula (C ₂ ) and formula (C 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 99.85 to 0.15% by 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. Examples of the other (C) unsaturated cis structure fatty acid amide having a carbon-carbon double bond, fatty acid amides of the formula _{(C 1) ~ (C 3} ) are preferably used, in particular, fatty acids 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.

5. (C) Method for Producing Fatty Acid Amide Having Unsaturated cis-Structure Carbon Double Bond Commercially available products may be used as unsaturated fatty acid amide (C) contained in the recovery layer of the resin multilayer container of the present invention. However, when a commercial product is a mixture or contains impurities, a desired unsaturated fatty acid amide may be obtained by separation 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 ):
(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
In represented by unsaturated cis structure fatty acid amide having a carbon-carbon double bond, i.e., to synthesize a fatty acid amide of formula (C _2).

  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.

6). Other compounding agents The collection layer of the resin multilayer container of the present invention contains various additives such as a heat stabilizer, a light stabilizer, a coloring pigment, and an inorganic filler as other compounding agents as necessary. be able to.

  Further, the recovery layer of the resin multilayer container of the present invention, as other compounding agents, within a range not impairing the object of the present invention, if desired, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, Other polymers such as ethylene / methyl acrylate copolymer, and acid-modified polyolefins known as adhesive resins such as maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene can be contained. The content of these various additives, other polymers and acid-modified polyolefin is usually 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less in the recovery layer. It can be adjusted by the composition of each layer constituting the multilayer container, the thickness of each layer, and the amount of the other compounding agent further blended in the material forming the recovery layer.

  As various additives, a saturated fatty acid amide known as a lubricant can be used. By using the saturated fatty acid amide in combination, effects such as further improvement of the slipperiness and surface gloss of the resulting resin multilayer container 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 amount of the unsaturated fatty acid amide of the formula (C) and the saturated fatty acid amide. More preferably, the ratio is 6% by mass or less, and the lower limit of the content ratio 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 (C) and the saturated fatty acid amide in the recovery layer is in the range of 100 to 4000 ppm with respect to the total mass part of (A) and (B). It is preferable.

II. Resin multilayer container The resin multilayer container of the present invention is a resin multilayer container including at least a surface layer and a recovery layer having the above-described specific composition. As the surface layer in the resin multilayer container, there are an outermost layer and an innermost layer, the resin multilayer container of the present invention has two layers, three layers, four layers, five layers or the like provided with a recovery layer having a specific composition. The resin multilayer container having the above multilayer structure is included. Since the collection layer is rarely employed as the surface layer, the resin multilayer container of the present invention usually has a three-layer, four-layer, five-layer or more multilayer structure including the collection layer having the above-mentioned specific composition. This is a resin multilayer container. The resin multilayer container of the present invention may include a barrier layer and / or an adhesive layer in addition to the surface layer and the recovery layer. Therefore, the resin multilayer container of the present invention includes a surface layer, a barrier layer, and an adhesive layer. And a recovery layer.

1. Surface Layer The surface layer of the resin multilayer container of the present invention is not particularly limited, but the surface layer of the resin multilayer container, specifically, the outermost layer and the innermost layer of the container are one of the components forming the recovery layer. In particular, when the thickness of the surface layer of the resin multilayer container occupies a majority of the thickness of the resin multilayer container, the composition of the recovery layer is largely determined by the composition of the surface layer, so the composition of the surface layer is adjusted. As a result, the composition of the recovery layer can be adjusted.

  Therefore, the resin composition forming the surface layer is obtained by using (A) a propylene / α-olefin random copolymer having a crystal melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, and (B) a metallocene catalyst. A block copolymer comprising a polymer block comprising polypropylene, a polymer block comprising an ethylene / propylene copolymer, and (C) an unsaturated cis structure carbon double bond obtained by using It preferably contains a fatty acid amide. The content of the unsaturated fatty acid amide (C) in the resin composition forming the surface layer is preferably 100 to 4000 ppm, more preferably 105 to 3900 ppm, based on the total mass part of (A) and (B). More preferably, it is 110-3800 ppm, Most preferably, it is 115-3700 ppm, Most preferably, it can be set as the range of 120-3600 ppm. If the content of the unsaturated fatty acid amide (C) in the resin composition forming the surface layer is too small, the resulting multi-layered resin container is insufficiently slidable, and the container is being manufactured, transported, or During filling, contact with or collision with containers or devices may cause defective products, production line stoppage, device failure, and the like. In addition, the slipperiness of the innermost layer of the resulting resin multilayer container is insufficient, so that the contents may not be filled smoothly, or the contents may not be sufficiently drained when used by consumers. There is. When the content of the unsaturated fatty acid amide (C) is too large, the surface gloss of the resulting resin multilayer container may be reduced, or the stickiness during the carrying operation may be increased. When the unsaturated fatty acid amide of (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 amount of the mixture is included in the above range. Is preferred.

  The resin composition forming the surface layer is (C) a fatty acid having an unsaturated trans structure carbon double bond having a trans structure carbon double bond instead of the fatty acid amide having an unsaturated cis structure carbon double bond. If it contains an amide, the uniform blending of the resin material may be insufficient, or the unsaturated fatty acid amide having the trans structure may be deposited on the surface of the resin multilayer container to be obtained. The sliding property of the resin multilayer container may be deteriorated, and the surface gloss may be reduced.

  The resin composition forming the surface layer is (A) a propylene / α-olefin random copolymer having a crystal melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, and (B) a metallocene catalyst. A block copolymer comprising a polymer block comprising polypropylene and a polymer block comprising ethylene / propylene copolymer, and (C) a fatty acid amide having an unsaturated cis structure carbon double bond 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 (A), (B) and (C). , One or both of the outermost layer and the innermost layer of the container can be provided.

  By arranging the layer composed of the resin composition in the outermost layer of the resin multilayer container, the slipperiness of the outer surface of the container is improved, so during the manufacture of the container, during transportation or during filling of the contents, It has the effect of preventing the occurrence of defective products, the stop of the production line, the failure of the device, etc. due to the contact or collision between containers or devices, and the surface gloss is also excellent.

  By arranging the layer composed of the resin composition 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 used by consumers. There is an effect that the liquid drainage of the contents is sometimes excellent.

  By arranging the layer composed of the resin composition in the outermost layer and the innermost layer of the resin multilayer container, the effects of both the case where the resin composition is arranged in the outermost layer and the case of the innermost layer are realized. can do.

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, a metal foil, a barrier resin layer, or the like on which a metal or an inorganic oxide is deposited can be used depending on the type of container. Since the collection layer of the resin multilayer container of the present invention contains a component that forms the barrier layer, it is preferable to use a barrier layer formed from a barrier resin.

  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. Moreover, since it is excellent in not only oxygen gas barrier property but carbon dioxide gas barrier property, polyglycolic acid can be used as barrier property resin. Furthermore, a barrier layer can also be formed from an aromatic polyamide (MXD6) formed from metaxylylenediamine and adipic acid, a vinylidene chloride copolymer, or the like.

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 The resin multilayer container of the present invention preferably has an adhesive layer interposed between the layers in order to increase the delamination strength of the layers constituting the multilayer container. The adhesive layer may be provided between all layers of each layer constituting the multilayer container, or may be provided between some layers of each layer, but it is preferable to provide adhesive layers on both sides of the barrier layer.

  The adhesive layer is preferably formed from an adhesive resin 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 resin 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, A polyacrylimide etc. can be mentioned. Since the recovery layer of the resin multilayer container of the present invention contains the adhesive resin, the acid-modified polyolefin is considered in consideration of the compatibility with the aforementioned (A), (B) and (C). Is preferred.

  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). Multilayer container The resin multilayer container of the present invention is a resin multilayer container including at least a surface layer and a recovery layer, and preferably a resin multilayer container including a surface layer, a barrier layer, an adhesive layer, and a recovery layer as a layer configuration. It is. More specifically, a resin multilayer container having an adhesive layer on both sides of the barrier layer and having a layer configuration of outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer is more preferable.

  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 resin multilayer container having at least a surface layer and a recovery layer, and the recovery layer contains the above (A), (B) and (C). It is a container with excellent slipperiness. In particular, one or both of the outermost layer and the innermost layer as the surface layer contain the above-mentioned (A), (B), and (C) in the same manner as the recovery layer. The slipperiness of the surface and / or inner surface can be made excellent. 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 resin multilayer container having at least a surface layer and a recovery layer, and the recovery layer contains the above (A), (B) and (C). It is a container with excellent surface gloss. 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 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, 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, 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 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 multilayer parison by the coextrusion method using a tubular die, using the number of extruders corresponding to the type of resin, while developing the resin corresponding to each layer such as the surface layer and the recovery layer in a tubular shape, The molten resin is merged in the die passage so as to be 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.

  In addition, as mentioned above, a 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 fat 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 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 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 a multilayer die, the following (1) to (4) materials are used, and the layer configuration is the outermost layer / adhesive layer / barrier layer / adhesive layer / recovery layer / innermost layer The parison was extruded, and a multi-layer resin multi-layer container (hereinafter referred to as “multi-layer container”) having an internal volume of 500 cm ³ was molded by a rotary direct blow molding machine. The mass of the multilayer container was 20 g. The thickness ratio of the layers formed from the materials (1) to (4) was 75: 4: 1: 20.

(1) Materials for forming surface layers (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 ; unsaturated fatty acid amide of formula (C ₁ )] 99.8% 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 ] with 0.2 wt% The mixture (C) was blended so as to be 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) Material for forming the barrier layer: Trade name EVAL (registered trademark) manufactured by Kuraray Co., Ltd. [EVOH having an ethylene content of 44 mol%. 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) Material for forming the adhesive layer: maleic anhydride-modified polyethylene manufactured by Mitsubishi Chemical Corporation, trade name Modic (registered trademark)

(4) Material for forming the recovery layer: Resin (recovery) obtained by cutting the container head (bag part) generated when direct-blow molding the multilayer container manufactured according to this example and then crushing it with a crusher Resin). In addition, a resin obtained by pulverizing a non-product container manufactured on a trial basis before the actual production with a crusher was also used as the recovered resin. This recovered resin contains the above (A), (B) and (C), and the EVOH and maleic anhydride-modified polyethylene, and the total content (ppm) of (C) It was about 115 ppm with respect to the total mass part, and about 130 ppm with respect to the total mass part of (A) and (B).

  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%) A multilayer container was molded in the same manner as in Example 1 except that the change was made so that the content was 350 ppm. 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%) 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). Note that (C) fatty acid amide having an unsaturated cis structure carbon double bond was not contained in the collection layer of the multilayer container. 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. Note that (C) fatty acid amide having an unsaturated cis structure carbon double bond was not contained in the collection layer of the multilayer container. Table 1 shows the results of measuring the sliding friction and surface gloss of the molded container.

  From the result of Table 1, it is a resin multilayer container provided with a surface layer, a barrier layer, an adhesive layer, and a recovery layer, and the recovery layer is (A), (B), and (C) an unsaturated cis structure carbon double bond The resin multilayer containers of Examples 1 to 7 containing a fatty acid amide having a surface friction coefficient of 0.22 to 0.38, good surface slipperiness, and a gloss value of surface gloss It was found that the gloss was good at 42 to 52%, and the slipperiness and 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]
A surface layer is (B) 100 mass% [(A) is not contained. A multilayer container was molded in the same manner as in Example 2 except that (C) a fatty acid amide having an unsaturated cis structure carbon double bond was mixed to 4000 ppm. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2. In addition, the Ziegler catalyst random copolymer of (A) was not contained in the collection layer of the multilayer container.

[Comparative Example 4]
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. The recovery layer of the multilayer container did not contain the metallocene catalyst block copolymer (B).

[Comparative Example 5]
Comparative Example, except for changing the surface layer to (A) 50% by mass and (B) 50% by mass, and (C) blending the fatty acid amide having an unsaturated cis structure carbon double bond to 5000 ppm In the same manner as in No. 3, a multilayer container was formed. The results of measuring the sliding friction and surface gloss of the molded container are shown in Table 2.

  From the results in Table 2, it is a resin multilayer container including a surface layer, a barrier layer, an adhesive layer, and a recovery layer, and the recovery layer is (A), (B), and (C) an unsaturated cis structure carbon double bond The resin multilayer containers of Examples 8 to 10 containing a fatty acid amide having a surface friction coefficient of 0.34 to 0.38, good surface slipperiness, and a gloss value of surface gloss It was found that the gloss was good at 49 to 51%, and the slipperiness and surface gloss were improved in a well-balanced manner.

  On the other hand, the resin multilayer container of Comparative Example 3 in which the recovery layer does not contain (A) has a gloss value of 36% in surface gloss, is not glossy, and has a surface sliding friction coefficient of 0.53. It was large and had a sticky feeling, and slipperiness was insufficient. Furthermore, the resin multilayer container of Comparative Example 4 in which the recovery layer did not contain (B) had a large surface sliding friction coefficient of 0.41, had a solid feeling, and lacked sliding properties. In addition, as a material for forming the surface layer (outermost layer and innermost layer), the total content of (C) is as large as 5000 ppm with respect to the total mass part of (A) and (B), and (B) When the total content of (A) and (B) is 100% by mass, the resin multilayer container of Comparative Example 5 manufactured using a resin composition exceeding 40% by mass has a surface sliding friction coefficient. Although the surface slipperiness was good at 0.24, it was found that the gloss value of the surface gloss was 35% and the gloss was not good.

  The present invention is a resin multilayer container comprising at least a surface layer and a recovery layer, wherein the recovery layer is obtained using (A) a Ziegler-Natta catalyst and has a crystalline melting point of 125 to 165 ° C. -Olefin random copolymer, (B) a copolymer obtained by using a metallocene catalyst, a polymer block comprising polypropylene, and a polymer block comprising an ethylene / propylene copolymer, and ( C) By providing the above-mentioned resin multilayer container containing a fatty acid amide having an unsaturated cis-structured carbon double bond, it is possible to provide a resin multilayer container that is excellent in slipperiness and surface gloss and has a small environmental load. This enables efficient use of resources, high productivity, high reliability during transportation and storage, and excellent container usability. High availability of the above.

Claims (17)

A resin multilayer container having at least a surface layer and a recovery layer,
The surface layer has an outermost layer and an innermost layer;
The recovery layer was obtained using (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 metallocene catalyst. contains a block polymer of polypropylene, a block polymer comprising ethylene-propylene copolymer, a block copolymer comprising, and (C) unsaturated cis structure fatty acid amide having a carbon-carbon double bond ,
The outermost layer was obtained using (A) a propylene / α-olefin random copolymer having a crystal melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, and (B) 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. ,
The content of (C) in the outermost layer is 100 to 4000 ppm with respect to the total mass part of (A) and (B),
The content of (A) in the outermost layer is 60 to 99.5% by mass when the total of (A) and (B) is 100% by mass.
Tree fat-made multi-layer container. A resin multilayer container having at least a surface layer and a recovery layer,
The surface layer has an outermost layer and an innermost layer;
The recovery layer was obtained using (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 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. ,
The innermost layer was obtained using (A) a propylene / α-olefin random copolymer having a crystal melting point of 125 to 165 ° C. obtained using a Ziegler-Natta catalyst, and (B) 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. ,
The content of (C) in the innermost layer is 100 to 4000 ppm with respect to the total mass part of (A) and (B),
The content of (A) in the innermost layer is 60 to 99.5% by mass when the total of (A) and (B) is 100% by mass.
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 ( however, 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); ;
Resin multilayer container according to claim 1 or claim 2 containing at least one fatty acid amide of the formula which are 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 3 , which is a mixture with at least one fatty acid amide. The resin multilayer container according to claim 4 , 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 4 , 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 3 , which is a mixture with a fatty acid amide represented by the formula: Wherein the (C) unsaturated cis structure fatty acid amide having a carbon double bond, either one of claims 1 to 7 containing in its molecular structure unsaturated cis structure carbon double bond of two bonds to 4 coupled with compound The resin multilayer container according to Item 1. The resin multilayer container according to any one of claims 1 to 8 , wherein the recovery layer further contains a saturated fatty acid amide. The resin multilayer container according to any one of claims 1 to 9 , wherein the recovery layer further contains one or both of an adhesive resin and a barrier resin. The resin multilayer container according to claim 10 , wherein the adhesive resin contains an acid-modified polyolefin. The resin multilayer container according to claim 10 or 11 , wherein the barrier resin is an ethylene / vinyl alcohol copolymer or polyglycolic acid.
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 12, wherein the resin multilayer container is composed of an outermost layer / adhesive layer / barrier layer / adhesive layer / collection layer / innermost layer. The resin multilayer container according to claim 13 or 14 , wherein the adhesive layer contains an acid-modified polyolefin. The resin multilayer container according to any one of claims 13 to 15 , wherein the barrier layer contains an ethylene / vinyl alcohol copolymer or polyglycolic acid. The resin multilayer container according to any one of claims 13 to 16, which is formed by direct blow molding.