Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/16—Halogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

• the present invention relates to a resin composition, a molded body, and a multilayer body.
• the present invention relates to a resin composition containing a xylylenediamine-based polyamide resin as a main component.
• Polyamide resins have excellent mechanical properties and are widely used as materials for injection-molded products such as automobiles and electrical and electronic components. They are also used as packaging materials for foods, beverages, medicines, electronic components, etc.
• polyamides obtained by polycondensation reaction of xylylenediamine and aliphatic dicarboxylic acids particularly polyamide (MXD6) obtained from metaxylylenediamine and adipic acid, are used as gas barrier materials for molded products such as films and bottles because they have low permeability to oxygen gas (Patent Document 1, etc.).
• the present invention aims to solve this problem by providing a resin composition capable of providing a molded body with excellent barrier properties, as well as a molded body and a multilayer body using the resin composition.
• the present inventors have conducted research and have found that the above problems can be solved by blending at least one chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides with a xylylenediamine-based polyamide resin. Specifically, the above problems were solved by the following means.
• a resin composition comprising a xylylenediamine-based polyamide resin and at least one chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides, the xylylenediamine-based polyamide resin comprising diamine-derived structural units and dicarboxylic acid-derived structural units, 70 mol % or more of the diamine-derived structural units being derived from xylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units being derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• ⁇ 2> The resin composition according to ⁇ 1>, containing the chloride in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the xylylenediamine-based polyamide resin.
• ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the chloride includes lithium chloride and/or magnesium chloride.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the molar ratio of metaxylylenediamine to paraxylylenediamine in the xylylenediamine is 10 to 100/90 to 0, when the total moles of metaxylylenediamine and paraxylylenediamine is 100 moles.
• ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein 70 mol% or more of the dicarboxylic acid-derived structural units are structural units derived from one or more of adipic acid, sebacic acid, and dodecanedioic acid.
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the chloride is contained in a ratio of 0.1 to 3 parts by mass per 100 parts by mass of the xylylenediamine-based polyamide resin, the chloride contains lithium chloride and/or magnesium chloride, the molar ratio of metaxylylenediamine to paraxylylenediamine in the xylylenediamine is metaxylylenediamine/paraxylylenediamine is 10 to 100/90 to 0 when the total of metaxylylenediamine and paraxylylenediamine is 100 moles, and 70 mole % or more of the dicarboxylic acid-derived structural units are structural units derived from one or more of adipic acid, sebacic acid, and dodecanedioic acid.
• ⁇ 7> A molded article formed from the resin composition according to any one of ⁇ 1> to ⁇ 6>.
• ⁇ 8> The molded article according to ⁇ 7>, which is an extrusion molded article.
• ⁇ 9> The molded article according to ⁇ 7> or ⁇ 8>, which is a film.
• ⁇ 10> The molded article according to ⁇ 9>, which is stretched.
• ⁇ 11> The molded article according to ⁇ 7>, which is an injection molded article.
• ⁇ 12> The molded article according to ⁇ 7> or ⁇ 11>, which is a hollow molded article.
• ⁇ 13> A multilayer body having the molded article according to any one of ⁇ 7> to ⁇ 12>.
• the present invention makes it possible to provide a resin composition capable of producing a molded article with excellent barrier properties, as well as a molded article and a multi-layered article using the resin composition.
• the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
• the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
• the term “film” refers to a generally flat molded body having a small thickness relative to its length and width.
• various physical properties and characteristic values are those at 23° C. unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards as of January 1, 2023, unless otherwise specified.
• the resin composition of the present embodiment comprises a xylylenediamine-based polyamide resin and at least one chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides, and is characterized in that the xylylenediamine-based polyamide resin comprises diamine-derived structural units and dicarboxylic acid-derived structural units, with 70 mol % or more of the diamine-derived structural units being derived from xylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units being derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• a resin composition or a molded article having excellent barrier properties can be obtained.
• a resin composition having excellent oxygen barrier properties and carbon dioxide gas barrier properties can be obtained.
• alkali metal ions such as lithium ions and alkaline earth metal ions such as magnesium ions are coordinated to the amide groups of the xylylenediamine-based polyamide resin, forming a pseudo-crosslinked structure and suppressing gas permeation.
• alkali metal ions and alkaline earth metal ions have polarity, they are easily dispersed in the xylylenediamine-based polyamide resin.
• chlorides makes it easier to provide alkali metal ions and alkaline earth metal ions.
• the resin composition of the present embodiment contains a xylylenediamine-based polyamide resin.
• the xylylenediamine-based polyamide resin refers to a polyamide resin that contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, in which 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 an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• the diamine-derived constituent units of the xylylenediamine-based polyamide resin are preferably derived from xylylenediamine (preferably paraxylylenediamine and/or metaxylylenediamine, more preferably metaxylylenediamine) at 75 mol % or more, more preferably 80 mol % or more, even more preferably 90 mol % or more, still more preferably 95 mol % or more, and particularly preferably 99 mol % or more.
• the dicarboxylic acid-derived constituent units of the xylylenediamine-based polyamide resin are preferably derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms at 75 mol % or more, more preferably 80 mol % or more, even more preferably 90 mol % or more, still more preferably 95 mol % or more, and particularly preferably 99 mol % or more.
• the molar ratio of metaxylylenediamine to paraxylylenediamine in the xylylenediamine is preferably metaxylylenediamine/paraxylylenediamine is 10-100/90-0, more preferably 20-100/80-0, even more preferably 40-100/60-0, even more preferably 80-100/20-0, and even more preferably 90-100/10-0.
• metaxylylenediamine/paraxylylenediamine is 10-100/90-0, more preferably 20-100/80-0, even more preferably 40-100/60-0, even more preferably 80-100/20-0, and even more preferably 90-100/10-0.
• Diamines other than metaxylylenediamine and paraxylylenediamine that can be used as raw diamine components for xylylenediamine-based polyamide resins include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine, 1,3-bis( Examples of such diamines include alicyclic diamines such as bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohex
• 70 mol % or more of the dicarboxylic acid-derived constitutional units are preferably derived from an ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• the number of carbon atoms in the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferably 6 or more, and is preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, even more preferably 13 or less, and even more preferably 12 or less.
• Examples of ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms that are preferably used as the raw dicarboxylic acid component of the xylylenediamine-based polyamide resin include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. One or more of these may be used in combination, and among these, one or more of adipic acid, sebacic acid, and dodecanedioic acid are more preferred, with adipic acid being even more preferred.
• aliphatic dicarboxylic acids such as succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid
• 50 mol % or more (preferably 70 mol % or more, more preferably 90 mol % or more) of the dicarboxylic acid-derived structural units are derived from one or more of adipic acid, sebacic acid, and dodecanedioic acid (preferably adipic acid).
• Dicarboxylic acid components other than the above-mentioned ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid, and orthophthalic 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, and can be used alone or in combination of two or more kinds.
• phthalic acid compounds such as isophthalic acid,
• the xylylenediamine-based polyamide resin is mainly composed of diamine-derived structural units and dicarboxylic acid-derived structural units, but does not completely exclude other structural units, and may, of course, contain structural units derived from lactams such as ⁇ -caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid.
• the term "main component" refers to the fact that, among the structural units constituting the xylylenediamine-based polyamide resin, the total number of diamine-derived structural units and dicarboxylic acid-derived structural units is the largest among all structural units.
• the total of the diamine-derived structural units and dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin preferably accounts for 90% by mass or more of the total structural units, more preferably accounts for 95% by mass or more, even more preferably accounts for 97% by mass or more, and even more preferably accounts for 99% by mass or more.
• the melting point of the xylylenediamine-based polyamide resin is preferably 150 to 350°C, more preferably 170 to 300°C, even more preferably 180 to 280°C, and even more preferably 180 to 260°C.
• the melting point is the one of the xylylenediamine-based polyamide resin with the greatest content.
• the glass transition temperature of the xylylenediamine-based polyamide resin is preferably 40 to 100°C, more preferably 45 to 95°C, even more preferably 50 to 95°C, and even more preferably 50 to 90°C.
• the glass transition temperature is that of the xylylenediamine-based polyamide resin with the greatest content.
• the melting point (Tm) and glass transition temperature (Tg) are values measured by differential scanning calorimetry (DSC) in accordance with ISO 11357. Specifically, they can be measured as described in paragraph 0036 of International Publication No. 2016/084475, the contents of which are incorporated herein by reference.
• DSC differential scanning calorimetry
• the lower limit of the number average molecular weight (Mn) of the xylylenediamine-based polyamide resin is preferably 6,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more, and is preferably 100,000 or less, and more preferably 50,000 or less.
• the number average molecular weight is the number average molecular weight of the mixture.
• the number average molecular weight (Mn) of xylylenediamine-based polyamide resin is measured using gel permeation chromatography (GPC) and calculated using standard polymethyl methacrylate (PMMA) equivalent values.
• GPC gel permeation chromatography
• PMMA polymethyl methacrylate
• Two columns packed with styrene-based polymers are used as the packing material, and hexafluoroisopropanol (HFIP) with a sodium trifluoroacetate concentration of 2 mmol/L is used as the solvent.
• the resin concentration is 0.02 mass%
• the column temperature is 40°C
• the flow rate is 0.3 mL/min
• measurements are made using a refractive index detector (RI).
• RI refractive index detector
• a polyamide resin produced using a biomass raw material biomass polyamide resin
• biomass polyamide resin By using a biomass polyamide resin, it is possible to reduce the environmental load.
• bio-adipic acid can be used as a biomass raw material.
• Mass balance certified (ISCC PLUS) adipic acid can also be used. Mass balance certification means that the amount of renewable raw materials or bio-raw materials used in each factory or production facility and the amount of products produced or shipped are quantified and guaranteed together with the quality.
• the content of the xylylenediamine-based polyamide resin in the resin composition of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more.
• the upper limit of the content of the xylylenediamine-based polyamide resin in the resin composition of this embodiment is an amount in which all components other than the chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides in the resin composition become xylylenediamine-based polyamide resin.
• the resin composition of the present embodiment may contain only one type of xylylenediamine-based polyamide resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
• the resin composition of the present embodiment may or may not contain a polyamide resin other than the xylylenediamine-based polyamide resin.
• the other polyamide resin may be either an aliphatic polyamide resin or a semi-aromatic polyamide resin.
• aliphatic polyamide resins include polyamide 4, polyamide 46, polyamide 410, polyamide 6, polyamide 66, polyamide 666, polyamide 610, polyamide 11, polyamide 12, and the like.
• Examples of semi-aromatic polyamide resins include polyamide 4T, polyamide 6I, polyamide 6T, polyamide 6I/6T, and polyamide 9T.
• the description in paragraph 0052 of JP-A-2023-027478 can be referred to, the contents of which are incorporated herein by reference.
• the content thereof is preferably 1 to 10 parts by mass per 100 parts by mass of the xylylenediamine-based polyamide resin.
• the resin composition of the present embodiment may be configured to be substantially free of other polyamide resins. Substantially free of other polyamide resins means that the content of other polyamide resins contained 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.
• the resin composition of the present embodiment contains at least one chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides. By containing such a chloride, a molded article having excellent barrier properties can be obtained.
• the alkali metal 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.
• 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. That is, the chloride used in this embodiment preferably contains lithium chloride and/or magnesium chloride.
• the total content of the chlorides selected from 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, and may 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, depending on the application, etc.
• the upper limit of the content of the chlorides is preferably 3 parts by mass or less, and may be 2.5 parts by mass or less, relative to 100 parts by mass of the xylylenediamine-based polyamide resin.
• the resin composition of the present embodiment may contain only one type of the chloride, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.
• the resin composition of the present embodiment may contain thermoplastic resins, fillers, additives, and the like other than those described above.
• additives include oxidation reaction accelerators, release agents, impact resistance improvers, alkalis, titanium oxide, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, coloring inhibitors, gelling inhibitors, antioxidants, heat stabilizers, light stabilizers, flame retardants, etc.
• oxidation reaction accelerators release agents, impact resistance improvers, alkalis, titanium oxide, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, coloring inhibitors, gelling inhibitors, antioxidants, heat stabilizers, light stabilizers, flame retardants, etc.
• the other additives are preferably 20.0 parts by mass or less in total, more preferably 10.0 parts by mass or less, even more preferably 5.0 parts by mass or less, and even more preferably 1.0 part by mass or less, based on 100 parts by mass of the resin composition. Only one type of the other additives may be used, or two or more types may be used in combination.
• the resin composition of the present embodiment is preferably excellent in oxygen barrier properties.
• the oxygen permeability coefficient of the stretched film formed from the resin composition of the present 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 ⁇ day ⁇ atm)) or less, and even more preferably 0.030 ((cc ⁇ mm)/(m 2 ⁇ day ⁇ atm)) or less.
• the resin composition of the present embodiment preferably has excellent carbon dioxide gas barrier properties.
• the carbon dioxide gas permeability coefficient of the stretched film formed from the resin composition of the present embodiment at 23° C. and a relative humidity of 60% is preferably 0.10 ((cc ⁇ mm)/(m 2 ⁇ day ⁇ atm)) or less, more preferably 0.09 ((cc ⁇ mm)/(m 2 ⁇ day ⁇ atm)) or less, and even more preferably 0.08 ((cc ⁇ mm)/(m 2 ⁇ day ⁇ atm)) or less.
• the oxygen permeability coefficient and the carbon dioxide permeability coefficient are measured according to the method described in the Examples below.
• Such barrier properties are achieved by blending a chloride selected from the group consisting of alkali metal chlorides and alkaline earth metal chlorides with the xylylenediamine-based polyamide resin.
• the method for producing the resin composition is not particularly specified, and a wide variety of known methods for producing thermoplastic resin compositions can be used.
• the resin composition can be produced by mixing the components in advance using various mixers such as a tumbler or a Henschel mixer, and then melt-kneading the components using a Banbury mixer, a roll, a Brabender, a single-screw extruder, a twin-screw extruder, a kneader, or the like. Chlorides can also be added in advance during resin polymerization. In this embodiment, melt-kneading using a twin-screw extruder is preferred.
• the resin composition can be produced by not mixing the components in advance, or by mixing only some of the components in advance, feeding the mixture to an extruder using a feeder, and melt-kneading the mixture. Furthermore, for example, some of the components may be mixed in advance, fed to an extruder, and melt-kneaded to obtain a masterbatch composition, which may then be mixed again with the remaining components and melt-kneaded to produce pellets.
• the molded article of the present embodiment is formed from the resin composition or pellets of the present embodiment.
• the molded body of the present embodiment may be prepared by melt-kneading the components and then directly molding the components using various molding methods, or by melt-kneading the components and pelletizing them, and then melting them again and molding them using various molding methods.
• the method for producing the molded body of the present embodiment is not particularly limited.
• One example is an extrusion molded product (for example, a film) molded by extrusion molding.
• Another example is an injection molded article molded by injection molding.
• a hollow molded article formed by blow molding is exemplified.
• the shape of the molded product in this embodiment is not particularly limited and can be appropriately selected depending on the application and purpose of the molded product.
• Examples include film-like (meaning including plate-like, plate-like, and sheet-like), cylindrical, annular, circular, elliptical, gear-like, polygonal, irregularly shaped, hollow, frame-like, box-like, and panel-like shapes, with film-like shapes being preferred.
• the fields of use of the molded article of this embodiment are not particularly specified, and it is widely used in automobile and other transport vehicle parts, general machine parts, precision machine parts, electronic and electrical equipment parts, office equipment parts, building materials and housing related parts, medical equipment, leisure sports goods, play equipment, medical supplies, everyday items such as food packaging films, defense and aerospace products, etc.
• the multilayer body of this embodiment has the molded body of this embodiment.
• layers (other layers) other than the multilayer body included in the multilayer body of this embodiment include thermoplastic resin layers such as polyester resin layers and polyolefin resin layers.
• the polyester resin is preferably a polyethylene terephthalate resin, and the polyolefin resin is more preferably a polypropylene resin or a polyethylene resin.
• the number of layers constituting the multilayer body is preferably at least 3.
• an example is a form including at least two polyester resin layers and/or polyolefin resin layers and at least one layer formed from the resin composition of the present embodiment.
• the layer formed from the resin composition of the present embodiment preferably functions as a barrier layer. More specifically, the number of layers constituting the multilayer body is more preferably 3 to 10 layers, and even more preferably 3 to 5 layers.
• the multilayer body of the present embodiment may include a gas barrier layer other than the oxygen absorbing layer, the adhesive layer, and the polyamide resin layer, a protective layer, a design layer, etc.
• a gas barrier layer other than the oxygen absorbing layer, the adhesive layer, and the polyamide resin layer, a protective layer, a design layer, etc.
• the molded article or multilayer body of the present embodiment is preferably stretched.
• the stretching may be uniaxial or biaxial.
• a film-shaped molded article may be stretched.
• it may be biaxially stretched blow molding carried out when molding a container such as a bottle.
• the lower limit is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and even more preferably 20 ⁇ m or more.
• the upper limit is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and even more preferably 35 ⁇ m or less.
• the 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.
• the upper limit is not particularly limited, but is preferably 20.0 times or less.
• the stretch ratio is preferably 1.1 times or more, more preferably 2.0 times or more, and even more preferably 4.0 times or more. There is no particular upper limit, but it is preferably 20.0 times or less.
• the multilayer body of the present embodiment is preferably used as a multilayer container.
• the shape of the multilayer container is not particularly limited, and may be, for example, a molded container such as a bottle, a cup, a tube, a tray, or Tupperware, or may be a bag-shaped container such as a pouch, a standing pouch, or a zippered storage bag.
• the items that can be stored in the multilayer container of this embodiment are not particularly limited, and examples include food, cosmetics, pharmaceuticals, toiletries, mechanical/electrical/electronic parts, oil, resins, etc., but it is particularly suitable for use as a container for storing food.
• processed seafood products, processed livestock products, rice, and liquid foods can be mentioned.
• it is suitable for preserving foods that are easily affected by oxygen.
• JP 2011-37199 A the contents of which are incorporated herein by reference.
• the food to be filled is not particularly limited, but specific examples include beverages such as vegetable juice, fruit juice, tea, coffee/coffee drinks, milk/dairy drinks, mineral water, ionic drinks, alcoholic drinks, lactic acid bacteria drinks, and soy milk; gel foods such as tofu, egg tofu, jellies, puddings, mizu yokan, mousse, yogurt, and almond tofu; seasonings such as sauce, soy sauce, ketchup, noodle soup, sauce, vinegar, mirin, dressing, jam, mayonnaise, miso, pickle base, and grated spices; salami, ham, sausage, yakitori, These include processed meat products such as meatballs, hamburgers, roast pork, and beef jerky; processed seafood products such as kamaboko, boiled shellfish, boiled fish, and chikuwa; processed rice products such as porridge, cooked rice, gomoku rice, and red rice; sauces such as meat sauce, mapo sauce, pasta sauce, curry, stew, and hayashi sauce; processed dairy
• the multilayer body and multilayer container of this embodiment may be based on the descriptions in JP 2016-198912 A, JP 2016-169027 A, and JP 60-232952 A, the contents of which are incorporated herein by reference, within the scope of the spirit of this embodiment.
• the pressure inside the reaction system was kept at normal pressure, the internal temperature was continuously raised to 240°C, and water distilled with the dropping of metaxylylenediamine was removed from the system through the partial condenser and the cooler. After the dropping of metaxylylenediamine was completed, the liquid temperature was kept at 250°C and the reaction was continued for 10 minutes. Thereafter, the pressure inside the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 260°C.
• the inside of the reactor was pressurized with nitrogen gas at 0.3 MPa, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization tank, cooled with water, and cut into pellets to obtain pellets of a molten polymerized product.
• the obtained pellets were charged at room temperature into a tumbler (rotary vacuum tank) having a jacket for heating a heat medium. While rotating the tumbler, the inside of the tank was reduced in pressure (0.5 to 10 Torr), the circulating heat medium was heated to 180°C, and the pellet temperature was raised to 170°C and maintained at that temperature for 5 hours. Thereafter, nitrogen was introduced again to return to normal pressure, and cooling was started. When the temperature of the pellets reached 70°C or less, the pellets were taken out of the tank to obtain a solid-phase polymerized product.
• the resulting polyamide resin had a melting point of 190°C and a glass transition temperature of 60°C.
• the internal pressure of the reaction system was kept at normal pressure, the internal temperature was continuously raised to 250°C, and water distilled with the dripping of para/meta-xylylenediamine was removed from the system through the partial condenser and the cooler. After the dripping of para/meta-xylylenediamine was completed, the liquid temperature was kept at 250°C and the reaction was continued for 10 minutes. Thereafter, the pressure inside the reaction system was continuously reduced to 600 Torr over 10 minutes, and the reaction was continued for 20 minutes. During this time, the reaction temperature was continuously raised to 260°C.
• the inside of the reactor was pressurized with nitrogen gas at 0.3 MPa, and the polymer was taken out as a strand from a nozzle at the bottom of the polymerization tank, and after cooling with water, it was cut into pellets to obtain pellets of a molten polymerized product.
• the obtained pellets were charged at room temperature into a tumbler (rotary vacuum tank) having a jacket for heating a heat medium. While rotating the tumbler, the inside of the tank was reduced in pressure (0.5 to 10 Torr), the circulating heat medium was heated to 190°C, and the pellet temperature was raised to 180°C and maintained at that temperature for 5 hours. Thereafter, nitrogen was again introduced to return to normal pressure, and cooling was started.
• the resulting polyamide resin (MP12) had a melting point of 216°C and a glass transition temperature of 57°C.
• MXD6 Nylon MXD6, S6007, manufactured by Mitsubishi Gas Chemical Company, Inc., had a melting point of 237°C and a glass transition temperature of 85°C.
• PA6 Polyamide 6, manufactured by Ube Industries, UBE Nylon 1022B. The melting point of polyamide 6 was 225°C and the glass transition temperature was 40°C.
• Examples 1 to 9 and Comparative Examples 1 to 4 The polyamide resins and chlorides shown in Table 1 (proportions of each component are parts by mass) were dry blended, fed to a twin-screw melt kneader (manufactured by The Japan Steel Works, Ltd., model: TEX34 ⁇ III), and melt-kneaded at a cylinder temperature of 240°C to 260°C. The mixture was then fed to a single-screw extruder with a T-die (manufactured by Plastics Engineering Research Institute, PTM-30), and melt-extruded from the die at an extrusion temperature of 250°C.
• T-die manufactured by Plastics Engineering Research Institute, PTM-30
• the resin composition in which each component was melt-kneaded was extruded to obtain unstretched films with a width of 175 mm and thicknesses of 50 ⁇ m and 180 ⁇ m.
• the 180 ⁇ m film was then cut into 90 mm squares.
• the film was stretched in both MD and TD while being heated in an air atmosphere at 100°C, so that the stretch ratio was 3.5 times in MD and 3.5 times in TD, to obtain a stretched film having a thickness of 15 ⁇ m.
• a relaxation operation was provided midway, with an MD relaxation rate of 3% and a TD relaxation rate of 3%.
• the stretching temperature was 100°C.
• heat setting was performed.
• the heat setting temperature was ⁇ 20°C of the melting point of each resin, and the heat setting time was 30 seconds.
• OTC oxygen barrier property
• OTC OTR x measured film thickness / 1000 Unit of OTR: cc/( m2 ⁇ day ⁇ atm) OTC unit cc mm/( m2 day atm) Film thickness measurement unit: ⁇ m
• the oxygen transmission rate (OTR) was measured using an oxygen transmission rate measuring device (manufactured by MOCON, product name: "OX-TRAN (registered trademark) 2/22").
• Carbon dioxide gas permeability coefficient Carbon dioxide gas barrier property
• the carbon dioxide gas permeability of the stretched film obtained above was measured in an atmosphere of 23°C and 60% relative humidity using a gas permeability measuring device in accordance with JIS K 7126-1:2006.
• the unit pressure for the carbon dioxide gas permeability and the carbon dioxide gas permeability coefficient was 1 atm, and the unit permeation time was 24 hours.
• the units of oxygen barrier property and carbon dioxide gas barrier property are cc ⁇ mm/(m 2 ⁇ day ⁇ atm).
• the molded article (film) formed from the resin composition of the present invention had excellent gas barrier properties compared to a case not containing chloride.

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