Resin composition, molded body, and multilayer body

Abstract

Provided are a resin composition, and a molded body and a multilayer body using the resin composition. A resin composition which contains at least one type of chloride selected from the group consisting of chlorides of alkali metals and chlorides of alkaline earth metals, and which contains a xylylenediamine-based polyamide resin that contains a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, 70 mol% or more of the diamine-derived structural units are derived from xylylenediamine, and 70 mol% or more of the dicarboxylic acid-derived structural units are derived from a C4-20 [alpha], [omega]-linear aliphatic dicarboxylic acid.

Description

Technical Field

[0001] This invention relates to resin compositions, molded articles, and multilayers. In particular, it relates to resin compositions with phenylene diamine-based polyamide resins as the main component. Background Technology

[0002] Polyamide resins possess excellent mechanical properties, and are therefore widely used as materials for injection-molded products in automobiles, electrical and electronic components, etc. They are also used as packaging materials for food, beverages, pharmaceuticals, electronic components, etc. Polyamides obtained from the condensation reaction of phenylenediamine with aliphatic dicarboxylic acids, particularly polyamides (MXD6) obtained from m-phenylenediamine and adipic acid, exhibit low oxygen permeability and are therefore used as gas-barrier materials in films, bottles, and other molded products (Patent Document 1, etc.).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2017 / 073560 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] However, with recent technological innovations, there is a demand for further improvements in barrier properties. The object of this invention is to solve the above-mentioned problems and to provide: a resin composition that provides a molded article with excellent barrier properties, and molded articles and multilayers using the aforementioned resin composition.

[0008] Solution for solving the problem

[0009] Based on the above-mentioned problems, the inventors conducted research and found that the above-mentioned problems can be solved by mixing at least one of the chlorides selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides into a phenylenediamine-based polyamide resin.

[0010] Specifically, the above-mentioned problems were solved through the following solution.

[0011] <1> A resin composition comprising a phenylenediamine-based polyamide resin and comprising at least one chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides, wherein the phenylenediamine-based polyamide resin comprises structural units derived from diamines and structural units derived from dicarboxylic acids, wherein at least 70 mol% of the structural units derived from diamines are derived from phenylenediamines, and at least 70 mol% of the structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0012] <2> according to <1> The resin composition comprises, relative to 100 parts by weight of the aforementioned diphenylamine polyamide resin, the aforementioned chloride in a ratio of 0.1 to 3 parts by weight.

[0013] <3> according to <1> or <2> The resin composition wherein the aforementioned chloride comprises lithium chloride and / or magnesium chloride.

[0014] <4> according to <1> ~ <3> The resin composition according to any one of the above-mentioned phenylenediamines, wherein, for the molar ratio of m-phenylenediamine to p-phenylenediamine in the aforementioned phenylenediamine, when the total amount of m-phenylenediamine to p-phenylenediamine is set to 100 moles, the ratio of m-phenylenediamine to p-phenylenediamine is 10~100 / 90~0.

[0015] <5> according to <1> ~ <4> The resin composition according to any one of the following methods, wherein 70 mol% or more of the dicarboxylic acid-derived structural units are structural units selected from one or more of dicarboxylic acid, sebacic acid, and dodecanoic acid.

[0016] <6> according to <1> ~ <5> The resin composition according to any one of the above, wherein, relative to 100 parts by weight of the aforementioned phenylenediamine-based polyamide resin, contains the aforementioned chloride in a ratio of 0.1 to 3 parts by weight, wherein the aforementioned chloride contains lithium chloride and / or magnesium chloride, and for the molar ratio of m-phenylenediamine to p-phenylenediamine in the aforementioned phenylenediamine, when the total amount of m-phenylenediamine to p-phenylenediamine is set to 100 moles, the ratio of m-phenylenediamine to p-phenylenediamine is 10 to 100 / 90 to 0, wherein 70 mol% or more of the aforementioned dicarboxylic acid-derived structural units are structural units derived from any one or more of dicarboxylic acid, sebacic acid, and dodecanoic acid.

[0017] <7> A shaped body, which is composed of <1> ~ <6> The resin composition described in any one of the above statements is formed.

[0018] <8> according to <7> The shaped body is an extruded shaped body.

[0019] <9> according to <7> or <8> The shaped body is a thin film.

[0020] <10> according to <9> The shaped body was stretched.

[0021] <11> according to <7> The molded body is an injection molded body.

[0022] <12> according to <7> or <11> The shaped body is a hollow shaped body.

[0023] <13> A multilayer body having <7> ~ <12> The molded body as described in any one of the following.

[0024] The effects of the invention

[0025] According to the present invention, it is possible to provide: a resin composition that can provide a molded article with excellent barrier properties, and a molded article and a multilayer using the aforementioned resin composition. Detailed Implementation

[0026] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. It should be noted that the following embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0027] It should be noted that in this specification, "~" is used to encompass the values ​​listed before and after it as the lower and upper limits.

[0028] In this specification, "film" refers to a shaped body that is thin and generally flat relative to its length and width.

[0029] Unless otherwise specified, all physical property values ​​and characteristic values ​​in this specification are values ​​at 23°C.

[0030] Unless otherwise specified, the measurement methods described in the standards shown in this instruction manual may vary from year to year, and are therefore set as standards based on January 1, 2023.

[0031] The resin composition of this embodiment is characterized in that it comprises a phenylenediamine-based polyamide resin and comprises at least one chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides. The aforementioned phenylenediamine-based polyamide resin comprises structural units derived from diamines and structural units derived from dicarboxylic acids. More than 70 mol% of the aforementioned structural units derived from diamines are derived from phenylenediamine, and more than 70 mol% of the aforementioned structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0032] By configuring it in this way, resin compositions or molded articles with excellent barrier properties can be obtained. In particular, resin compositions with excellent oxygen barrier properties and carbon dioxide gas barrier properties can be obtained. It is speculated that the reason is that alkali metal ions such as lithium ions and alkaline earth metal ions such as magnesium ions are located at the amide groups of the diphenylene amine polyamide resin, forming a suspected cross-linking structure that inhibits gas permeation.

[0033] Furthermore, alkali metal ions and alkaline earth metal ions are polar, thus they are easily dispersed in diphenylene diamine-based polyamide resins. Additionally, it is speculated that the use of chlorides can readily provide alkali metal ions and alkaline earth metal ions.

[0034] <Phenylenediamine-based polyamide resin>

[0035] The resin composition of this embodiment comprises a phenylenediamine-based polyamide resin. A phenylenediamine-based polyamide resin refers to a polyamide resin that comprises structural units derived from diamines and structural units derived from dicarboxylic acids, wherein at least 70 mol% of the aforementioned structural units derived from diamines are derived from phenylenediamine, and at least 70 mol% of the aforementioned structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. In this embodiment, it is preferable to obtain a molded article that maintains the inherent strength of the phenylenediamine-based polyamide resin and exhibits excellent barrier properties.

[0036] The diamine-derived structural units of the phenylenediamine-based polyamide resin are preferably 75 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 99 mol% or more derived from phenylenediamine (preferably p-phenylenediamine and / or m-phenylenediamine, more preferably m-phenylenediamine). Furthermore, the dicarboxylic acid-derived structural units of the phenylenediamine-based polyamide resin are preferably 75 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably 99 mol% or more derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0037] In this embodiment, when the total molar ratio of m-phenylenediamine to p-phenylenediamine in diphenylenediamine is set to 100 moles, the m-phenylenediamine / p-phenylenediamine ratio is preferably 10~100 / 90~0, more preferably 20~100 / 80~0, further preferably 40~100 / 60~0, even more preferably 80~100 / 20~0, and even more preferably 90~100 / 10~0. With this configuration, a resin composition with superior processability can be obtained.

[0038] Diamines other than m-phenylenediamine and p-phenylenediamine, which can be used as raw material components in diphenylenediamine-based polyamide resins, include, but are not limited to, tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine, etc. (aliphatic diamines); 1,3-bis( Alicyclic diamines such as aminomethylcyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)naphthane, and bis(aminomethyl)tricyclodecane; and diamines with aromatic rings such as bis(4-aminophenyl)ether, p-phenylenediamine, and bis(aminomethyl)naphthalene, may be used, either one or a mixture of two or more.

[0039] Furthermore, the phenylene dimethylamine-based polyamide resin preferably has at least 70 mol% of its structural units derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. The α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms preferably has 6 or more carbon atoms, and more preferably 18 or less, more preferably 16 or less, further preferably 14 or less, even more preferably 13 or less, and even more preferably 12 or less.

[0040] The preferred dicarboxylic acid component used as a raw material for diphenylene diamine-based polyamide resins is an α,ω-linear aliphatic dicarboxylic acid with 4 to 20 carbon atoms. Examples of aliphatic dicarboxylic acids include succinic acid, glutaric acid, pimelic acid, octanoic acid, azelaic acid, adipic acid, sebacic acid, undecanoic acid, and dodecanoic acid. One type or two or more types can be used. Among these, one or more of adipic acid, sebacic acid, and dodecanoic acid are more preferred, and adipic acid is even more preferred.

[0041] As a preferred embodiment of the phenylenediamine-based polyamide resin in this embodiment, an example may be a substance derived from any one or more of adipic acid, sebacic acid, and dodecanoic acid (preferably adipic acid) with a structural unit of dicarboxylic acid being 50 mol% or more (preferably 70 mol% or more, more preferably 90 mol% or more).

[0042] Examples of dicarboxylic acid components other than the aforementioned α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid, and phthalic acid, and isomers of naphthalenedicarboxylic acid such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. One type or two or more types can be used.

[0043] It should be noted that the phenylenediamine-based polyamide resin is composed primarily of structural units derived from diamines and dicarboxylic acids, but does not completely exclude structural units other than these. It may also include structural units derived from lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. Here, "main component" refers to the structural units constituting the phenylenediamine-based polyamide resin in which the total number of structural units derived from diamines and dicarboxylic acids is the largest among all structural units. In this embodiment, the total number of structural units derived from diamines and dicarboxylic acids in the phenylenediamine-based polyamide resin preferably accounts for 90% or more by mass, more preferably 95% or more by mass, further preferably 97% or more by mass, and even more preferably 99% or more by mass.

[0044] The melting point of the phenylenediamine-based polyamide resin is preferably 150-350°C, more preferably 170-300°C, even more preferably 180-280°C, and still more preferably 180-260°C. When the resin composition of this embodiment contains two or more phenylenediamine-based polyamide resins, the melting point is set to that of the phenylenediamine-based polyamide resin with the highest content.

[0045] The glass transition temperature of the diphenylene diamine-based polyamide resin is preferably 40-100°C, more preferably 45-95°C, further preferably 50-95°C, and even more preferably 50-90°C. When the resin composition of this embodiment contains two or more diphenylene diamine-based polyamide resins, the glass transition temperature is set to that of the diphenylene diamine-based polyamide resin with the highest content.

[0046] Melting point (Tm) and glass transition temperature (Tg) are values ​​determined by differential scanning calorimetry (DSC) according to ISO 11357. Specifically, they can be determined according to the description in paragraph 0036 of International Publication No. 2016 / 084475, which is incorporated herein by reference.

[0047] As a differential scanning calorimeter, the "DSC-60" manufactured by Shimadzu Corporation was used.

[0048] The lower limit of the number-average molecular weight (Mn) of the phenylenediamine-based polyamide resin is preferably 6,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. Furthermore, it is preferably 100,000 or less, and more preferably 50,000 or less. When the resin composition of this embodiment contains two or more phenylenediamine-based polyamide resins, the number-average molecular weight of the mixture is used.

[0049] The number-average molecular weight (Mn) of the diphenylene diamine-based polyamide resin was determined by conversion of the standard polymethyl methacrylate (PMMA) value based on gel permeation chromatography (GPC). Two columns packed with styrene-based polymers were used as the column packing material. The solvent used was hexafluoroisopropanol (HFIP) at a concentration of 2 mmol / L sodium trifluoroacetate. The resin concentration was 0.02% by mass, the column temperature was 40 °C, and the flow rate was 0.3 mL / min. Measurements were performed using a refractive index detector (RI). Additionally, a standard curve was determined by dissolving six levels of PMMA in HFIP.

[0050] Phenylenediamine-based polyamide resins are also preferably polyamide resins manufactured using biomass raw materials (biomass polyamide resins). By using biomass polyamide resins, environmental impact can be reduced.

[0051] In phenylenediamine-based polyamide resins, bio-based adipic acid can be used as a biomass feedstock. Alternatively, adipic acid with ISCC Plus certification can also be used. ISCC Plus certification refers to the quantification and assurance, along with quality control, of the extent to which renewable raw materials and / or bio-based feedstocks are used in each plant and / or production facility, and of the extent to which products are produced and / or shipped in each facility.

[0052] The content of phenylenediamine-based polyamide resin in the resin composition of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more. Furthermore, the upper limit of the content of phenylenediamine-based polyamide resin in the resin composition of this embodiment is the amount in which all components except chlorides selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides constitute phenylenediamine-based polyamide resin.

[0053] The resin composition of this embodiment may contain only one type of diphenylene diamine polyamide resin, or it may contain two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0054] The resin composition of this embodiment may optionally include other polyamide resins besides diphenylene diamine polyamide resins, or may not include them.

[0055] The other polyamide resins mentioned above can be aliphatic polyamide resins or semi-aromatic polyamide resins.

[0056] Examples of aliphatic polyamide resins include polyamide 4, polyamide 46, polyamide 410, polyamide 6, polyamide 66, polyamide 666, polyamide 610, polyamide 11, and polyamide 12.

[0057] Examples of semi-aromatic polyamide resins include polyamide 4T, polyamide 6I, polyamide 6T, polyamide 6I / 6T, and polyamide 9T.

[0058] Furthermore, other polyamide resins optionally included in the resin composition of this embodiment can be found in paragraph 0052 of Japanese Patent Application Publication No. 2023-027478, and this content is incorporated into this specification.

[0059] When the resin composition of this embodiment contains other polyamide resins, the content of such resins is preferably 1 to 10 parts by weight relative to 100 parts by weight of phenylenediamine polyamide resin.

[0060] Furthermore, the resin composition of this embodiment may be substantially free of other polyamide resins. "Substantially free of other polyamide resins" means that the content of other polyamide resins in the resin composition is less than 10% by mass, preferably less than 5% by mass, more preferably less than 3% by mass, and even more preferably less than 1% by mass.

[0061] Chloride

[0062] The resin composition of this embodiment contains at least one selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides. By including such chlorides, a molded article with excellent barrier properties can be obtained.

[0063] Examples of alkali metals include lithium, sodium, potassium, rubidium, cesium, and francium, with lithium, sodium, and potassium being preferred, lithium and sodium being more preferred, and lithium being even more preferred.

[0064] Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, barium, and radium, with beryllium, magnesium, and calcium being preferred, magnesium and calcium being more preferred, and magnesium being even more preferred.

[0065] That is, the chloride used in this embodiment preferably includes lithium chloride and / or magnesium chloride.

[0066] In this embodiment, the total chloride content in the group consisting of alkali metal chlorides and alkaline earth metal chlorides is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the phenylenediamine polyamide resin. Furthermore, depending on the application, it can be 0.4 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, or 0.8 parts by mass or more. By setting it to the lower limit or above, the gas barrier properties tend to be further improved. In addition, the upper limit of the chloride content is preferably 3 parts by mass or less, or 2.5 parts by mass or less, relative to 100 parts by mass of the phenylenediamine polyamide resin. By setting it to the upper limit or below, the color deterioration of the resin composition can be effectively suppressed.

[0067] The resin composition of this embodiment may contain only one type of chloride, or it may contain two or more types. When two or more types are contained, the total amount is preferably within the range described above.

[0068] <Other Additives>

[0069] The resin composition of this embodiment may also include thermoplastic resins, fillers, additives, etc., other than those described above.

[0070] Examples of additives include oxidation reaction accelerators, release agents, impact-resistant modifiers, alkalis, titanium dioxide, hydrolysis resistance modifiers, matting agents, plasticizers, dispersants, antistatic agents, anti-coloring agents, anti-gelling agents, antioxidants, heat stabilizers, light stabilizers, and flame retardants. Detailed information on these additives can be found in paragraphs 0130-0155 of Japanese Patent No. 4894982 and paragraphs 0047-0103 of International Publication No. 2021 / 241471, which are incorporated herein by reference.

[0071] Relative to 100 parts by weight of the resin composition, the total amount of other additives is preferably 20.0 parts by weight or less, more preferably 10.0 parts by weight or less, even more preferably 5.0 parts by weight or less, and still more preferably 1.0 parts by weight or less. Only one type of other additive may be used, or two or more may be used in combination.

[0072] <Physical Properties of Resin Compositions>

[0073] The resin composition of this embodiment preferably exhibits excellent oxygen barrier properties. For example, the oxygen permeability coefficient of the stretched film formed from the resin composition of this embodiment at 23°C and 60% relative humidity is preferably 0.040 (cc·mm) / (m). 2 ·day·atm) or less, more preferably 0.035((cc·mm) / (m 2 Below 0.030 ((cc·mm) / (m) 2 The oxygen permeability coefficient of the stretched film formed from the resin composition of this embodiment at 23°C and 60% relative humidity is 0 (cc·mm) / (m). 2 Even if it is above 0.001((cc·mm) / (m) 2 The above (day·atm) also fully meets the performance requirements.

[0074] The resin composition of this embodiment preferably exhibits excellent carbon dioxide gas barrier properties. For example, the carbon dioxide gas permeability coefficient of the stretched film formed from the resin composition of this embodiment at 23°C and 60% relative humidity is preferably 0.10 (cc·mm) / (m). 2 ·day·atm)) or less, more preferably 0.09((cc·mm) / (m 2 ·day·atm)) or less, further preferably 0.08((cc·mm) / (m 2 The lower limit of the carbon dioxide gas permeability coefficient of the stretched film formed from the resin composition of this embodiment at 23°C and 60% relative humidity is 0 (cc·mm) / (m).2 Even if it is above 0.001((cc·mm) / (m) 2 The above (day·atm) also fully meets the performance requirements.

[0075] The oxygen permeability coefficient and carbon dioxide permeability coefficient were determined according to the methods described in the examples below.

[0076] Such barrier properties are achieved by blending chlorides selected from the group consisting of chlorides of alkali metals and chlorides of alkaline earth metals into the diphenylene diamine polyamide resin.

[0077] <Method for manufacturing resin composition>

[0078] In this embodiment, the method for manufacturing the resin composition is not particularly limited, and widely known methods for manufacturing thermoplastic resin compositions can be widely used. Specifically, the components can be pre-mixed using various mixers such as drum mixers and Henschel mixers, and then melt-blended using a Banbury mixer, roller mixer, Brabender mixer, single-screw extruder, twin-screw extruder, kneader, etc., to manufacture the resin composition. Alternatively, chlorides can be added pre-during resin polymerization. In this embodiment, a twin-screw extruder is preferably used for melt blending.

[0079] Alternatively, for example, the components may be fed into an extruder for melt mixing without premixing or with only a portion of the components, thereby producing a resin composition.

[0080] Alternatively, for example, a composition obtained by pre-mixing a portion of the components and feeding it to an extruder for melt blending can be used as a masterbatch, which can then be mixed again with the remaining components for melt blending to produce granules.

[0081] <molded body>

[0082] The molded body of this embodiment is formed from the resin composition or even granules of this embodiment.

[0083] For example, the molded body of this embodiment can be directly molded using various molding methods after the components are melted and mixed, or it can be melted again and molded using various molding methods after the components are melted, mixed and granulated.

[0084] The manufacturing method of the molded body in this embodiment is not particularly limited.

[0085] As an example, an extruded body (e.g., a film) formed by extrusion molding can be illustrated.

[0086] As another example, an injection-molded body formed by injection molding can be illustrated.

[0087] As another example, a hollow-formed body formed by hollow forming can be illustrated.

[0088] The shape of the molded body in this embodiment is not particularly limited and can be appropriately selected according to the use and purpose of the molded body. Examples include film shape (including plate shape, disc shape, sheet shape), cylindrical shape, ring shape, circular shape, elliptical shape, gear shape, polygonal shape, irregular shape, hollow shape, frame shape, box shape, panel shape, etc., with film shape being preferred.

[0089] The application fields of the molded articles of this embodiment are not particularly limited, and they are widely used in automobile and other transportation parts, general mechanical parts, precision mechanical parts, electronic / electrical equipment parts, OA equipment parts, building materials / residential setting related parts, medical devices, leisure and sports products, game equipment, medical products, food packaging films and other daily necessities, defense and aerospace products, etc.

[0090] <Multi-layered structure>

[0091] Next, the multilayer body of this embodiment will be described. The multilayer body of this embodiment has the molded body of this embodiment. As layers other than the multilayer body included in the multilayer body of this embodiment (other layers), thermoplastic resin layers such as polyester resin layers and polyolefin resin layers can be exemplified. Polyester resin is preferably polyethylene terephthalate resin, and polyolefin resin is more preferably polypropylene resin and polyethylene resin.

[0092] The number of layers constituting the multilayer is preferably at least three. In this embodiment, an example may be provided that includes at least two polyester resin layers and / or polyolefin resin layers, and at least one layer formed from the resin composition of this embodiment.

[0093] In the multilayer body of this embodiment, the layer formed by the resin composition of this embodiment preferably functions as a barrier layer.

[0094] More specifically, the number of layers constituting the multilayer body is more preferably 3 to 10, and even more preferably 3 to 5.

[0095] Furthermore, the multilayer body of this embodiment may include an oxygen-absorbing layer, an adhesive layer, a gas barrier layer other than a polyamide resin layer, a protective layer, and a design layer. Detailed descriptions of these layers can be found in paragraphs 0012 to 0046 of Japanese Patent Application Publication No. 2021-080025, Japanese Patent Application Publication No. 2017-114532, and Japanese Patent Application Publication No. 2016-169291, which are incorporated herein by reference.

[0096] <Stretching>

[0097] In this embodiment, the molded body or multilayer body is preferably stretched. Stretching can be uniaxial stretching or biaxial stretching. When stretching is performed, a thin film-like molded body can be stretched. Alternatively, biaxial stretch blow molding, which is performed when molding containers such as bottles, can also be used.

[0098] When the film formed from the resin composition of this embodiment is stretched, its thickness (the thickness of the stretched film) can be appropriately selected according to the application and is not particularly limited. From the viewpoints of strength, impact resistance, and barrier properties, the lower limit is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more. The upper limit is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 35 μm or less.

[0099] When the film of this embodiment is subjected to uniaxial stretching, its stretching ratio is preferably 1.1 times or more, more preferably 2.0 times or more, and even more preferably 2.5 times or more. As an upper limit, there is no particular limitation, but it is preferably 20.0 times or less.

[0100] When the film of this embodiment is biaxially stretched, its stretching ratio is preferably 1.1 times or more, more preferably 2.0 times or more, and even more preferably 4.0 times or more. As an upper limit, there is no particular limitation, but it is preferably 20.0 times or less.

[0101] Multi-layered containers

[0102] The multi-layer body in this embodiment is preferably used as a multi-layer container. The shape of the multi-layer container is not particularly limited, and it can be a shaped container such as a bottle, cup, tube, tray, or tuberware. Alternatively, it can be a bag-shaped container such as a stand-up pouch or snap-on storage bag.

[0103] There are no particular limitations on the objects that can be stored in the multi-layered container of this embodiment. Examples include food, cosmetics, pharmaceuticals, toiletries, mechanical, electrical, and electronic components, oils, and resins. In particular, it is suitable as a container for storing food.

[0104] Examples include processed aquatic products, processed livestock products, rice dishes, and liquid foods. It is particularly suitable for preserving foods that are easily affected by oxygen. For detailed information, please refer to paragraphs 0032-0035 of Japanese Patent Application Publication No. 2011-37199, which are incorporated into this specification.

[0105] There is no particular limitation on the filled food. If specific examples are shown, they may include, for example: beverages such as vegetable juice, fruit juice, tea, coffee / coffee beverages, milk-milk beverages, mineral water, ionic beverages, alcoholic beverages, lactic acid bacteria beverages, soy milk; gel-like foods such as tofu, egg tofu, jelly, pudding, agar jelly, mousse, yogurt, almond jelly; seasonings such as sauce, soy sauce, ketchup, noodle soup, dipping sauce, vinegar, mirin, dressing, jam, mayonnaise, miso, pickled vegetable base, ground spices; processed meat products such as salami, ham, sausage, yakitori, meatballs, hamburger, roast pork, beef jerky; processed aquatic products such as fish cake, boiled shellfish, boiled fish, fish sausage; processed rice products such as porridge, rice, mixed rice, red bean rice; sauce such as gravy sauce, mapo sauce; Italian sauce, curry, stew, Hayasi sauce, etc.; processed milk products such as cheese, butter, cream, curd; processed egg products such as hard-boiled eggs, onsen eggs; boiled vegetables / boiled beans; home-cooked dishes such as fried foods, steamed foods, stir-fried foods, boiled foods, grilled foods; pickled vegetables; noodles / Italian noodles such as udon, soba, spaghetti; fruit syrup pickled products, etc.

[0106] In addition, the laminate, multi-layer container, and their manufacturing methods of the present embodiment can refer to the descriptions in Japanese Patent Application Laid-Open No. 2016-198912, Japanese Patent Application Laid-Open No. 2016-169027, and Japanese Patent Application Laid-Open No. 60-232952 within the scope not departing from the gist of the present embodiment, and these contents are incorporated into the present specification.

[0107] Examples

[0108] Examples are listed below to illustrate the present invention more specifically. The materials, amounts used, ratios, treatment contents, treatment steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the protection scope of the present invention is not limited to the specific examples shown below.

[0109] When it is difficult to obtain the measuring instruments, etc. used in the examples due to production suspension, etc., other instruments with equivalent performance can be used for measurement.

[0110] 1. Raw materials

[0111] <Synthesis of MXD-10>

[0112] 60.00 mol of precisely weighed sebacic acid was added to a jacketed reaction vessel equipped with a stirrer, condenser, condenser, thermometer, dropping tank, and nitrogen inlet pipe. The vessel was then fully purged with nitrogen, and the temperature was raised to 170°C under a small nitrogen flow to dissolve the sebacic acid and create a homogeneous flow. 60 mol of m-phenylenediamine was added dropwise over 160 minutes with stirring. During this time, the reaction system was kept at atmospheric pressure, and the internal temperature was continuously raised to 240°C. Water distilled off during the addition of m-phenylenediamine was discharged from the system through the condenser and condenser. After the addition of m-phenylenediamine, the reaction was continued at 250°C for 10 minutes. Then, the internal pressure was continuously reduced to 600 Torr over 10 minutes, and the reaction continued for 20 minutes. During this time, the reaction temperature was continuously raised to 260°C. After the reaction, nitrogen gas is applied to the reaction vessel at a pressure of 0.3 MPa, and the polymer is extracted from the nozzle at the bottom of the polymerization tank in the form of a wire. After water cooling, it is cut into granules to obtain granules of the molten polymer. The obtained granules are then placed into a rotary drum mixer (rotary vacuum tank) with a jacket heated by a hot medium at room temperature. While the drum mixer is rotating, the tank is kept under reduced pressure (0.5~10 Torr), and the flowing hot medium is heated to 180°C, raising the granule temperature to 170°C, which is maintained at this temperature for 5 hours. Then, nitrogen gas is introduced again to atmospheric pressure to begin cooling. When the granule temperature reaches below 70°C, the granules are removed from the tank to obtain the solid-phase polymer.

[0113] The obtained polyamide resin has a melting point of 190℃ and a glass transition temperature of 60℃.

[0114] Synthesis of Polyamide MP12

[0115] 60.00 mol of precisely weighed dodecanoic acid was added to a jacketed reaction vessel equipped with a stirrer, condenser, condenser, thermometer, dropping tank, and nitrogen inlet pipe. The vessel was then fully purged with nitrogen, and the temperature was raised to 180°C under a small nitrogen flow to dissolve the dodecanoic acid and create a homogeneous flow. Under stirring, 60 mol of a mixture of p-phenylenediamine / m-phenylenediamine (30 mol% of the diamine component being p-phenylenediamine and 70 mol% being m-phenylenediamine) was added dropwise over 160 minutes. During this process, the reaction system was kept at atmospheric pressure, and the internal temperature was continuously raised to 250°C. Water distilled off during the dropwise addition of p-phenylenediamine / m-phenylenediamine was discharged outside the system through the condenser and condenser. After the dropwise addition of p-phenylenediamine / m-phenylenediamine was completed, the reaction was continued at 250°C for another 10 minutes. Then, the pressure inside the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction continued for another 20 minutes. During this period, the reaction temperature was continuously increased to 260°C. After the reaction was completed, a pressure of 0.3 MPa was applied to the reaction vessel with nitrogen gas, and the polymer was extracted from the nozzle at the bottom of the polymerization tank in the form of a wire. After water cooling, it was cut into granules to obtain granules of the molten polymer. The obtained granules were placed into a rotary drum mixer (rotary vacuum tank) with a jacket heated by a hot medium at room temperature. While rotating the drum mixer, the tank was kept under reduced pressure (0.5~10 Torr), and the circulating hot medium was heated to 190°C, raising the granule temperature to 180°C, which was maintained at this temperature for 5 hours. Then, nitrogen gas was introduced again to atmospheric pressure, and cooling began. When the temperature of the granules reached below 70°C, the granules were removed from the tank to obtain the solid-phase polymer.

[0116] The obtained polyamide resin (MP12) has a melting point of 216℃ and a glass transition temperature of 57℃.

[0117] MXD6: Manufactured by Mitsubishi Gas Chemical Company, Nylon MXD6, S6007, melting point 237℃, glass transition temperature 85℃.

[0118] PA6: Polyamide 6, manufactured by Ube Industries, Ltd., UBE Nylon 1022B. The melting point of polyamide 6 is 225°C and the glass transition temperature is 40°C.

[0119] MgCl2: Manufactured by Fujifilm and Koichi Chemical Co., Ltd., as a reagent.

[0120] LiCl: Manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd., as a reagent.

[0121] 2. Examples 1-9, Comparative Examples 1-4

[0122] The polyamide resin and chloride (the proportions of each component are parts by mass) shown in Table 1 were dry-mixed and fed into a twin-screw melt mixer (manufactured by Nippon Steel Corporation, model: TEX34αIII) for melt mixing at a barrel temperature of 240°C to 260°C. Then, the mixture was fed into a single-screw extruder with a T-die (manufactured by Plastics Research Institute Co., Ltd., PTM-30) for melt extrusion at an extrusion temperature of 250°C. Specifically, the resin composition formed by the melt mixing of each component was extruded to obtain an unstretched film with a width of 175 mm, a thickness of 50 μm, and a thickness of 180 μm. Next, the 180 μm film was cut into 90 mm square pieces. Then, using an intermittent biaxial stretching apparatus (tenting machine method, EX10-S5, manufactured by Toyo Seiki Co., Ltd.), heating was performed in an atmospheric atmosphere at 100°C, and stretching was carried out along MD and TD with a stretch ratio of 3.5 times on MD and 3.5 times on TD respectively, to obtain a stretched film with a thickness of 15μm. During this stretching process, a relaxation operation with a MD relaxation rate of 3% and a TD relaxation rate of 3% was set midway. The stretching temperature was set to 100°C. After stretching, heat curing was performed. The heat curing temperature was the melting point of each resin -20°C, and the heat curing time was 30 seconds.

[0123] <Oxygen permeability (OTC) (Oxygen barrier properties)>

[0124] For the unstretched and stretched films obtained above, the oxygen permeability (OTR) was measured using an oxygen permeability measuring device at 23°C and 60% relative humidity, according to ASTM D3985. The unit pressure for OTR and OTC was 1 atm, and the unit permeation time was 24 hours. It should be noted that the oxygen permeability (OTC) was calculated as follows.

[0125] OTC = OTR × Measured film thickness / 1000

[0126] The unit of OTR is cc / (m 2 ·day·atm)

[0127] The unit of OTC is cc·mm / (m) 2 ·day·atm)

[0128] The unit for measuring thin film thickness is μm.

[0129] Oxygen permeability (OTR) was measured using an oxygen permeability measuring device (manufactured by MOCON, product name: "OX-TRAN (registered trademark) 2 / 22").

[0130] <Carbon dioxide gas permeability coefficient (carbon dioxide gas barrier properties)>

[0131] For the stretched film obtained above, the carbon dioxide gas transmission rate was measured using a gas transmission rate measuring device in an atmosphere of 23°C and 60% relative humidity, according to JIS K 7126-1:2006. The unit pressure for both the carbon dioxide gas transmission rate and the carbon dioxide gas transmission coefficient was set to 1 atm, and the unit transmission time was set to 24 hours. The carbon dioxide gas transmission coefficient was calculated as follows.

[0132] Carbon dioxide gas permeability coefficient = carbon dioxide gas permeability × film thickness / 1000

[0133] The unit for carbon dioxide gas transmission rate is cc / (m). 2 ·day·atm)

[0134] The unit of carbon dioxide gas permeability coefficient is cc·mm / (m). 2 ·day·atm)

[0135] [Table 1]

[0136]

[0137] In Table 1 above, the units for oxygen barrier properties and carbon dioxide barrier properties are cc·mm / (m 2 ·day·atm).

[0138] As can be seen from the above results, the molded articles (films) formed from the resin compositions of the present invention have excellent gas barrier properties compared with those without chloride.

Claims

1. A resin composition comprising a phenylenediamine-based polyamide resin and comprising at least one chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides. The phenylenediamine-based polyamide resin comprises structural units derived from diamine and structural units derived from dicarboxylic acids, wherein more than 70 mol% of the structural units derived from diamine are derived from phenylenediamine, and more than 70 mol% of the structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

2. The resin composition according to claim 1, wherein, The chloride is contained in a ratio of 0.1 to 3 parts by weight relative to 100 parts by weight of the phenylenediamine polyamide resin.

3. The resin composition according to claim 1 or 2, wherein, The chloride comprises lithium chloride and / or magnesium chloride.

4. The resin composition according to any one of claims 1 to 3, wherein, Regarding the molar ratio of m-phenylenediamine to p-phenylenediamine in the phenylenediamine, when the total amount of m-phenylenediamine and p-phenylenediamine is set to 100 moles, the ratio of m-phenylenediamine to p-phenylenediamine is 10~100 / 90~0.

5. The resin composition according to any one of claims 1 to 4, wherein, More than 70 mol% of the structural units derived from dicarboxylic acids are structural units of any one or more of dicarboxylic acid, sebacic acid, and dodecanoic acid.

6. The resin composition according to any one of claims 1 to 5, wherein, The chloride is contained in a ratio of 0.1 to 3 parts by weight relative to 100 parts by weight of the phenylenediamine-based polyamide resin. The chloride comprises lithium chloride and / or magnesium chloride. Regarding the molar ratio of m-phenylenediamine to p-phenylenediamine in the phenylenediamine, when the total amount of m-phenylenediamine and p-phenylenediamine is set to 100 moles, the m-phenylenediamine / p-phenylenediamine ratio is 10~100 / 90~0. More than 70 mol% of the structural units derived from dicarboxylic acids are structural units of any one or more of dicarboxylic acid, sebacic acid, and dodecanoic acid.

7. A molded article formed from the resin composition according to any one of claims 1 to 6.

8. The shaped article according to claim 7 is an extruded shaped article.

9. The shaped article according to claim 7 or 8, wherein it is a film.

10. The molded article according to claim 9, which has been stretched.

11. The molded article according to claim 7, wherein it is an injection molded article.

12. The shaped body according to claim 7 or 11, wherein it is a hollow shaped body.

13. A multilayer body having the shaped body according to any one of claims 7 to 12.

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