Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • 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
  • C08K3/32—Phosphorus-containing compounds
  • C08K2003/321—Phosphates
  • C08K2003/325—Calcium, strontium or barium phosphate

Definitions

• the present invention relates to a resin composition, and more particularly to a resin composition that is inhibited from increasing in viscosity over time during heating.
• Ethylene-vinyl alcohol copolymers (hereinafter sometimes referred to as "EVOH”) have extremely strong intermolecular forces due to hydrogen bonds between hydroxyl groups present in polymer side chains. Therefore, since it has high crystallinity and high intermolecular force even in the amorphous portion, a film using EVOH is difficult for gas molecules to pass through and exhibits excellent gas barrier properties.
• EVOH has a relatively active hydroxyl group in its molecule
• oxidation and crosslinking reactions occur in the high-temperature molten state even inside an extrusion molding machine with almost no oxygen, and it tends to increase in viscosity over time, making stable processing difficult. It tends to be difficult.
• Patent Document 1 discloses that a saponified ethylene-vinyl acetate copolymer (A) having an ethylene content of 20 to 60 mol% and a degree of saponification of 90 mol% or more, acetic acid (B ), contains magnesium acetate and/or calcium acetate (C), and the content of (B) is 0.05 parts by mass or less per 100 parts by mass of (A), and the content of (C) is metal.
• a resin composition is disclosed in which the amount is 0.001 to 0.02 parts by mass based on 100 parts by mass of (A).
• Patent Document 1 states that by using this resin composition, a molded product with excellent long-run moldability during melt molding, less fish eyes, streaks, and coloring, and excellent appearance can be obtained. It is disclosed that odor is reduced even when the molded product is made into a laminate, and the laminate has excellent interlayer adhesion even after secondary processing such as stretching or deep drawing.
• the present inventors focused on the unavoidable retention of resin due to the structure of the molding equipment, and speculated that such retention is the cause of resin deterioration. Therefore, in order to prevent the generation of such resin deterioration products, the present invention provides a resin composition in which thickening over time during heating, which causes stagnation, is suppressed, and a molded article formed by molding the resin composition. , a multilayer structure having a layer containing the resin composition, and a method for producing the resin composition.
• the present inventors have added specific nitrogen-containing compounds, alkali metal compounds, and alkaline earth metal compounds to EVOH, and have found that the content of the alkaline earth metal compounds on a metal basis It has been found that by setting the content ratio of the metal equivalent content of the alkali metal compound to the amount within a specific range, a resin composition in which thickening over time during heating is suppressed can be obtained.
• the present invention provides the following [1] to [10].
• [1] Contains EVOH (A), a nitrogen-containing compound (B), an alkali metal compound (C), and an alkaline earth metal compound (D), The content ratio (C/D) of the metal equivalent content of the alkali metal compound (C) to the metal equivalent content of the alkaline earth metal compound (D) is larger than 0.5
• the nitrogen-containing compound (B) has a resin composition in which the number of nitrogen atoms bonded to each carbon atom contained in its structure is 2 or less, and which satisfies the following (1) and/or (2). thing.
• (1) The molecular weight of the nitrogen-containing compound (B) is 280 or less.
• the nitrogen-containing compound The resin composition according to [1], wherein (B) contains a primary amino group and/or a secondary amino group.
• the resin composition of the present invention suppresses thickening over time during heating, and as a result, has excellent long-run moldability.
• x and/or y (x, y are arbitrary structures or components)" means three combinations: x only, y only, and x and y.
• X to Y (X and Y are arbitrary numbers), unless otherwise specified, it means “more than or equal to X and less than or equal to Y", and “preferably larger than X” or “preferably It also includes the meaning of "less than Y”.
• a resin composition that is an embodiment of the present invention (hereinafter referred to as "the present resin composition") comprises EVOH (A), a nitrogen-containing compound (B), an alkali metal compound (C), and an alkaline earth metal.
• Compound (D) the content ratio (C/D) of the metal equivalent content of the alkali metal compound (C) to the metal equivalent content of the alkaline earth metal compound (D) is greater than 0.5.
• the nitrogen-containing compound (B) has two or less nitrogen atoms bonded to each carbon atom contained in its structure, and satisfies the following (1) and/or (2): It is.
• the molecular weight of the nitrogen compound (B) is 280 or less (2)
• the amine equivalent defined by the following formula of the nitrogen compound (B) is less than 225 g/eq (Formula)
• Amine equivalent (g/eq) Molecular weight of nitrogen-containing compound (B)/number of primary amino groups (-NH 2 ) and secondary amino groups (-NH-) present in nitrogen-containing compound (B) Each component will be explained below.
• EVOH(A) used in this resin composition is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is non-aqueous. It is a thermoplastic resin.
• vinyl ester monomer vinyl acetate is generally used from an economical point of view.
• the copolymerization method of ethylene and vinyl ester monomer can be carried out using any known polymerization method, such as solution polymerization, suspension polymerization, emulsion polymerization, etc., and generally methanol is used as a solvent. Solution polymerization is used.
• the obtained ethylene-vinyl ester copolymer can also be saponified by a known method.
• EVOH (A) produced in this way mainly consists of ethylene structural units and vinyl alcohol structural units, and if the degree of saponification is less than 100 mol%, a small amount of vinyl ester structural units remain as unsaponified parts. This includes:
• vinyl ester monomer vinyl acetate is generally used as described above, from the economical point of view and the efficiency of treating impurities during production.
• vinyl ester monomers other than vinyl acetate include vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and versatic.
• vinyl ester monomers include aliphatic vinyl esters such as vinyl acid, and aromatic vinyl esters such as vinyl benzoate. These can be used alone or in combination of two or more.
• aliphatic vinyl esters preferably have 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms.
• the content of ethylene structural units in the EVOH (A) as measured based on ISO 14663 is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 27 to 35 mol%. If this content is too low, the gas barrier properties and melt moldability under high humidity will tend to decrease, while if it is too high, the gas barrier properties will tend to decrease.
• the content of the ethylene structural unit can be controlled by the pressure of ethylene when copolymerizing the vinyl ester monomer and ethylene.
• the saponification degree of the EVOH (A) measured based on JIS K6726 (EVOH (A) is a solution uniformly dissolved in a water/methanol solvent) is usually 90 to 100 mol%, preferably 95 ⁇ 100 mol%, particularly preferably 99 ⁇ 100 mol%. If the degree of saponification is too low, gas barrier properties tend to decrease.
• the degree of saponification can be controlled by the amount of saponification catalyst (usually an alkaline catalyst such as sodium hydroxide), temperature, time, etc. when saponifying the ethylene-vinyl ester copolymer.
• the melt flow rate (MFR) (210° C., load 2160 g) of the EVOH (A) is usually 0.5 to 100 g/10 minutes, preferably 1 to 50 g/10 minutes, particularly preferably 3 to 35 g/10 minutes. It's a minute. If the MFR is too large, film forming properties tend to become unstable, while if it is too small, the viscosity tends to become too high, making melt extrusion difficult.
• Such MFR is an indicator of the degree of polymerization of EVOH (A), and can be adjusted by the amount of polymerization initiator and the amount of solvent when copolymerizing ethylene and vinyl ester monomer.
• the EVOH (A) may further contain a structural unit derived from the comonomer shown below within a range that does not impede the effects of the present invention (for example, 10 mol% or less of the EVOH (A)). good.
• the comonomers include olefins such as propylene, 1-butene, and isobutene; 3-buten-1-ol, 3-buten-1,2-diol, 4-penten-1-ol, 5-hexene-1,2 - Derivatives such as hydroxy group-containing ⁇ -olefins such as diols and their esterification products and acylation products; Hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; Hydroxyalkyl vinylidene diacetates such as 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyryloxy-2-methylenepropane; acrylic acid, methacrylic acid , crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous)
• EVOH copolymerized with hydroxy group-containing ⁇ -olefins that is, EVOH having a hydroxyl group in the side chain
• EVOH having a hydroxyl group in the side chain is preferable because it has good secondary moldability while maintaining gas barrier properties. It is an EVOH having a primary hydroxyl group, and particularly preferably an EVOH having a 1,2-diol structure in its side chain.
• the content of structural units derived from the monomer having the primary hydroxyl group is usually 0.1 to 20 mol%, more preferably 0.5 to 15 mol%, particularly is preferably 1 to 10 mol%.
• the EVOH (A) may be one that has been "post-modified” such as urethanization, acetalization, cyanoethylation, or oxyalkylenation.
• the EVOH (A) may be a mixture of two or more types of EVOH, such as those having different degrees of saponification, those having different degrees of polymerization, and those having different copolymerization components.
• the EVOH (A) is preferably the main component of the resin composition.
• the content of the main component is 50% by mass or more of the present resin composition, preferably 70% by mass or more, more preferably 80% by mass, and even more preferably 90% by mass or more. It is particularly preferably 95% by mass or more.
• the nitrogen-containing compound (B) used in the present resin composition contains nitrogen atoms in its structure, and the number of nitrogen atoms bonded to each carbon atom contained in the structure is 2 or less, and the following: A compound that satisfies (1) and/or (2).
• the molecular weight is 280 or less
• the amine equivalent defined by the following formula is less than 225 g/eq Formula)
• Amine equivalent (g/eq) molecular weight of nitrogen-containing compound (B) / nitrogen-containing compound ( B)
• the number of primary amino groups (-NH 2 ) and secondary amino groups (-NH-) present in the nitrogen-containing compound (B) must satisfy (1) and (2) above. , particularly preferred.
• the nitrogen-containing compound (B) includes a primary amino group (-NH 2 ), a secondary amino group (-NH-), a tertiary amino group (see general formula (I) below), and a quaternary amino group (see general formula (I) below).
• An amino compound containing at least one of the following formula (see formula (II)) is preferable from the viewpoint of suppressing viscosity increase over time.
• the nitrogen-containing compound (B) is more preferably an amino compound containing a primary amino group (-NH 2 ) and/or a secondary amino group (-NH-).
• a primary amino group (-NH 2 ) and/or a secondary amino group (-NH-) there is a tendency that the effect of suppressing thickening over time can be further enhanced.
• the nitrogen-containing compound (B) has two or less nitrogen atoms bonded to each carbon atom contained in its structure. That is, all the carbon atoms contained in the nitrogen-containing compound (B) are bonded to 0, 1, or 2 nitrogen atoms, respectively.
• the number of nitrogen atoms bonded to one carbon atom is 2 or less, the effect of suppressing viscosity increase over time can be enhanced.
• the molecular weight of the nitrogen-containing compound (B) having the feature (1) above is 280 or less, preferably 230 or less, more preferably 150 or less, and even more preferably 100 or less. By having a molecular weight of 280 or less, thickening over time during heating can be suppressed with a small amount added.
• the lower limit of the molecular weight is not particularly limited, it is preferably 17 or more, more preferably 30 or more, even more preferably 40 or more, and particularly preferably 50 or more.
• the amine equivalent of the nitrogen-containing compound (B) having the feature (2) above is less than 225 g/eq, preferably 200 g/eq or less, more preferably 150 g/eq or less, and even more preferably 100 g/eq or less.
• the lower limit of the amine equivalent is not particularly limited, but the amine equivalent is preferably 10 g/eq or more, more preferably 20 g/eq or more, even more preferably 30 g/eq or more, and particularly preferably 40 g/eq or more.
• the amine equivalent When the amine equivalent is 10 g/eq or less, the compound is often not solid at around room temperature (23° C.) and tends to have poor handling properties.
• the said amine equivalent is the mass of the nitrogen-containing compound (B) containing 1 equivalent of amino groups, and can be calculated
• Amine equivalent (g/eq) molecular weight of nitrogen-containing compound (B) / number of primary amino groups (-NH 2 ) and secondary amino groups (-NH-) present in nitrogen-containing compound (B)
• the melting point of the nitrogen-containing compound (B) is not particularly limited, but is preferably 70 to 290°C, and the lower limit of the melting point is more preferably 80°C or higher, even more preferably 90°C or higher, and particularly preferably 100°C or higher.
• the upper limit of the melting point is more preferably 260°C or lower, even more preferably 230°C or lower, particularly preferably 210°C or lower, particularly preferably 190°C or lower, and most preferably 170°C or lower.
• nitrogen-containing compound (B) examples include amino acids such as inorganic amino compounds and organic amino compounds. These may be used alone or in combination of two or more.
• Examples of the inorganic amino compound include hydroxylamine, chloramine, ammonia, and the like.
• organic amino compound examples include methanolamine, ethanolamine, dimethylamine, diethylamine, isopropylamine, butylamine, ethylenediamine, propylenediamine, diethylenetriamine, 1,2-diaminopropane, 1,3-diaminopropane, triethylenetetramine, Aliphatic compounds such as tetraethylenepentamine, iminobispropylamine, hexamethylenediamine, 3-azahexane-1,6-diamine, 2-acrylamido-2-methylpropanesulfonic acid, 4,7-diazadecane-1,10-diamine, etc.
• organic amino compounds are preferable from the viewpoint of suppressing viscosity increase over time, more preferably heterocyclic aromatic amines, compounds having a urea bond, and amino acids, and even more preferably These include 2-undecylimidazole, 1-dodecylhydantoin, ethylene urea (2-imidazolidinone), and basic amino acids, and particularly preferred are ethylene urea (2-imidazolidinone) and histidine.
• the upper limit of the content of the nitrogen-containing compound (B) in the present resin composition is not particularly limited, but it may be less than 9% by mass based on the total amount of the EVOH (A) and the nitrogen-containing compound (B). Preferably, it is 8% by mass or less, more preferably 7% by mass or less, particularly preferably 5% by mass or less, particularly preferably 3% by mass or less, and 1% by mass. The following is most preferable. When the content of the nitrogen-containing compound (B) is within the above range, the effect of suppressing thickening during heating tends to be further enhanced.
• the lower limit of the content of the nitrogen-containing compound (B) is not particularly limited, but is preferably 0.000001% by mass or more based on the total amount of the EVOH (A) and the nitrogen-containing compound (B), more preferably is 0.00001% by mass or more, more preferably 0.0001% by mass or more, particularly preferably 0.001% by mass or more, particularly preferably 0.01% by mass or more, most preferably 0.1% by mass or more.
• the content of the nitrogen-containing compound (B) is within the above range, the effect of suppressing thickening during heating tends to be further enhanced.
• This resin composition contains an alkali metal compound (C).
• alkali metal of the alkali metal compound (C) include lithium, sodium, potassium, rubidium, and cesium. These can be used alone or in combination of two or more. Among these, sodium and potassium are preferred, and sodium is particularly preferred.
• alkali metal compound (C) examples include alkali metal salts and alkali metal hydroxides. Preferably, these are water-soluble. Among these, alkali metal salts are preferred from the viewpoint of dispersibility. Further, from the viewpoint of economy and dispersibility, it is preferable that the alkali metal compound (C) excludes inorganic layered compounds and double salts.
• alkali metal salts examples include inorganic salts such as carbonates, hydrogen carbonates, phosphates, borates, sulfates, and chloride salts; acetates, butyrates, propionates, enanthates, and capric salts.
• Monocarboxylic acid salts having 2 to 11 carbon atoms such as acid salts; dicarboxylic acid salts having 2 to 11 carbon atoms such as oxalate, malonate, succinate, adipate, suberate, sebatate; Monocarboxylic acid salts having 12 or more carbon atoms such as laurate, palmitate, stearate, 12-hydroxystearate, behenate, and montanate, carboxylic acid salts with polymerized terminal carboxyl groups of EVOH, etc. carboxylic acid salts, etc. These can be used alone or in combination of two or more. Among these, monocarboxylate salts having 2 to 11 carbon atoms are preferred, and acetate salts are more preferred.
• the alkali metal salt may be present in the present resin composition, for example, in the form of an alkali metal salt, or in an ionized state, or in a complex state with a resin or other ligand.
• the molecular weight of the alkali metal compound (C) is usually 20 to 10,000, preferably 20 to 1,000, particularly preferably 20 to 500.
• the content of the alkali metal compound (C) is not particularly limited, but is usually 1 to 1000 ppm, preferably 5 to 800 ppm, more preferably 10 to 700 ppm, particularly preferably It is 100 to 600 ppm.
• the content of the alkali metal compound (C) is too high, productivity tends to be impaired, and when it is too low, thermal stability tends to decrease.
• the content of the said alkali metal compound (C) is the value which totaled the metal conversion amount of all the alkali metals.
• the content of the alkali metal compound (C) can be determined, for example, by adding pure water to a solution obtained by heating and incinerating the present resin composition and treating it with hydrochloric acid, etc. to a fixed volume. It is a liquid and can be measured using an atomic absorption spectrophotometer.
• This resin composition contains an alkaline earth metal compound (D).
• alkaline earth metal of the alkaline earth metal compound (D) include beryllium, magnesium, calcium, strontium, barium, and radium. These can be used alone or in combination of two or more. Among these, magnesium and calcium are preferred in terms of market availability and economic efficiency.
• alkaline earth metal compound (D) examples include salts, oxides, and hydroxides of alkaline earth metals. Among these, alkaline earth metal oxides or alkaline earth metal salts are preferred from the viewpoint of economy and dispersibility, and alkaline earth metal salts are particularly preferred.
• the alkaline earth metal compound (D) preferably excludes layered inorganic compounds such as montmorillonite and double salts such as hydrotalcite from the viewpoint of economy and dispersibility.
• alkaline earth metal oxide examples include magnesium oxide, calcium oxide, and the like.
• alkaline earth metal salts include inorganic salts and carboxylates such as carbonates, hydrogencarbonates, phosphates, borates, sulfates, and chlorides.
• phosphates and carboxylates of alkaline earth metals are preferred because they have an excellent effect of suppressing thickening during heating.
• Such carboxylates include saturated or unsaturated carboxylates.
• the carbon number of the anion of such a carboxylate is usually 2 to 25, preferably 2 to 22 from the viewpoint of productivity, and particularly preferably 6 to 20.
• Specific carboxylates include, for example, acetate, butyrate, propionate, enanthate, caprate, laurate, palmitate, stearate, 12-hydroxystearate, behenate.
• monovalent carboxylates such as montanate, divalent carboxylates such as oxalate, malonate, succinate, adipate, suberate, sebatate, and the like. These can be used alone or in combination of two or more. In terms of commercial availability, linear saturated carboxylates are preferred, monovalent carboxylates are more preferred, and acetates are particularly preferred.
• alkaline earth metal compound (D) examples include solid (powder, fine powder, flakes, etc.), semi-solid, liquid, paste, solution, emulsion (aqueous dispersion), etc. It can be used with any properties. Among these, a powder form is preferable.
• the content of the alkaline earth metal compound (D) is not particularly limited, but is usually 0.1 to 500 ppm, preferably 0.5 to 300 ppm, more preferably 1 ⁇ 200 ppm, more preferably 2 ⁇ 150 ppm. If the content of the alkaline earth metal compound (D) is too high, the thermal stability tends to decrease, and if it is too low, the moldability of the resin composition tends to decrease. Note that when two or more of the alkaline earth metal compounds (D) are used in combination, the content of the alkaline earth metal compounds (D) is the sum of the metal equivalent amounts of all alkaline earth metals. .
• the content of the alkaline earth metal compound (D) is determined, for example, by adding pure water to a solution obtained by heating and incinerating the present resin composition and acid-treating it with hydrochloric acid or the like. It can be measured using an atomic absorption spectrophotometer using as a test solution.
• the content ratio (C/D) of the metal equivalent content of the alkali metal compound (C) to the metal equivalent content of the alkaline earth metal compound (D) is larger than 0.5.
• the content ratio (C/D) is preferably 1 or more, more preferably 2 or more, even more preferably 8 or more, and particularly preferably 15 or more.
• the upper limit of the content ratio (C/D) is not particularly limited, but is usually 10,000 or less, preferably 5,000 or less, more preferably 1,000 or less, even more preferably 300 or less, and particularly preferably 50 or less. When the content ratio (C/D) is within the above range, the thermal stability of the resin composition can be improved.
• the present resin composition further contains a boron compound in order to further enhance the effect of suppressing viscosity increase over time during heating.
• Examples of the boron compound include boric acid or a metal salt thereof, such as boric acid, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum/potassium borate, Ammonium borate (ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, tetraborate, etc.) Potassium acid, potassium pentaborate, potassium hexaborate, potassium octaborate, etc.), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, tetraborate, etc.) Copper borate, etc.), Sodium borate (sodium metaborate, sodium diborate
• the content of the boron compound is not particularly limited, but the lower limit of the content is preferably 1 ppm or more, more preferably 10 ppm or more, particularly preferably 20 ppm or more, especially in terms of boron relative to the EVOH (A). Preferably it is 50 ppm or more.
• the upper limit of the content is preferably 1000 ppm or less, more preferably 500 ppm or less, particularly preferably 300 ppm or less, particularly preferably 100 ppm or less, in terms of boron relative to the EVOH (A).
• the content can act synergistically with the nitrogen-containing compound (B) to further enhance the effect of improving long-run moldability. The reason why superior effects are obtained by using a specific amount of a boron compound is not clear, but it is presumed that the dischargeability of the resin composition is improved by adjusting the melt viscosity.
• the content of the boron compound in terms of boron can be measured using a known analytical method.
• the amount of boron can be determined by using inductively coupled plasma emission spectrometry (ICP-AES) using a fixed volume of the resin composition after wet decomposition as a test solution.
• ICP-AES inductively coupled plasma emission spectrometry
• the present resin composition contains thermoplastic resins other than the EVOH (A) (e.g., various thermoplastic resins such as polyamide, polyester, polyethylene, polypropylene, polystyrene, etc.) within a range that does not impede the effects of the present invention (e.g., (usually 30% by mass or less, preferably 20% by mass or less, particularly preferably 10% by mass or less) of the present resin composition.
• thermoplastic resins may be used alone or in combination of two or more.
• the resin composition may optionally contain plasticizers, reinforcing agents, fillers, pigments, dyes, and lubricants within a range that does not impede the effects of the invention (for example, 5% by mass or less of the resin composition).
• plasticizers for example, 5% by mass or less of the resin composition.
• antioxidant, antistatic agent, ultraviolet absorber, heat stabilizer, light stabilizer, surfactant, antibacterial agent, antistatic agent, desiccant, antiblocking agent, flame retardant, crosslinking agent, curing agent, foaming agent , a crystal nucleating agent, etc. may be contained. These may be used alone or in combination of two or more.
• the present resin composition includes the EVOH (A), the nitrogen-containing compound (B), the alkali metal compound (C), and the alkaline earth metal compound (D), and optional components that are blended as necessary. It can be obtained by mixing and preparing.
• the mixing method is not particularly limited, and a mixture of each component by dry blending can be used directly as the resin composition, but generally, after mixing by a melt mixing method, a solution mixing method, etc., pellets are formed.
• a method of preparing the present resin composition by molding it into an easy-to-handle shape is used, and a melt-mixing method is preferred from the viewpoint of productivity.
• melt-mixing method examples include a method in which each component is dry-blended and then melted and mixed.
• the mixing device for example, a known kneading device such as a kneader, an extruder, a mixing roll, a Banbury mixer, or a plastomill can be used, but it is usually industrially preferable to use a single-screw or twin-screw extruder. . Further, it is also preferable that the extruder is provided with a vent suction device, a gear pump device, a screen device, etc., as necessary.
• the melt-kneading temperature is usually in the range of 160 to 300°C, preferably 170 to 260°C, particularly preferably 180 to 240°C, as the temperature of the extruder and die. If the temperature is too low, the resin will be in an unmolten state and the processing state will tend to become unstable; if it is too high, the resin composition will thermally deteriorate and the quality of the molded product obtained will deteriorate. There is a tendency to
• the method for adjusting the amounts of the nitrogen-containing compound (B), the alkali metal compound (C), the alkaline earth metal compound (D), and any optional components added in the present resin composition There are no particular limitations on the method for adjusting the amounts of the nitrogen-containing compound (B), the alkali metal compound (C), the alkaline earth metal compound (D), and any optional components added in the present resin composition.
• a method of adjusting the amount by adding the amount, a method of preparing a masterbatch and diluting it, etc. can be used. Further, when diluting the masterbatch, any dilution method can be used, but dry blending is preferred from the viewpoint of productivity.
• an optional component such as a boron compound may be added and contained, for example, during the production of the EVOH (A), in addition to the method described above.
• the resin composition obtained in this way suppresses thickening over time during heating, and as a result has excellent long-run moldability.
• the thickening ratio is usually 1.45 or less, preferably 1.40 or less, particularly preferably 1.35 or less.
• the lower limit of the thickening ratio is better, but it is usually 1.0, preferably 0.5 or more, particularly preferably 0.1 or more.
• the thickening ratio can be calculated by the following formula from the torque value after 60 minutes and the torque value after 180 minutes of melt-kneading the resin composition.
• Thickening ratio Torque value after 180 minutes of measurement / Torque value after 60 minutes of measurement
• the present resin composition is usually molded into molded products such as films, sheets, cups, fibers, etc. by a melt molding method.
• melt molding methods include extrusion molding methods (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.), injection molding methods, and the like.
• the melt molding temperature can be selected as appropriate from the range of usually 150 to 300°C.
• the obtained molded product film, sheet, cup, fiber, etc.
• secondary processing such as uniaxial or biaxial stretching and vacuum forming.
• the molded article obtained by melt molding using the present resin composition may be a molded article consisting only of the present resin composition, or may be a molded article made of other resin sheets, films, paper, nonwoven fabric, metal foil, etc.
• the molded article may be a multilayer structure laminated with a base material.
• the multilayer structure can be produced by melt extrusion laminating a film, sheet, etc. formed using the present resin composition with another base material, or by melt extrusion laminating the present resin composition onto another base material. , a method of co-extruding the present resin composition and another base material, a method of co-extruding a film, sheet, etc. made of the present resin composition and a layer consisting of another base material using an organic titanium compound, an isocyanate compound, or a polyester compound. , a dry lamination method using a known adhesive such as a polyurethane compound, etc. can be adopted.
• ICP-AES inductively coupled plasma emission spectrometer
• Nitrogen-containing compound (B) ⁇ Nitrogen-containing compound (B1): 2-imidazolidinone (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 86, amine equivalent 43 g/eq, melting point 132°C, number of nitrogen atoms bonded to one carbon atom is 2 or less)
• Example 1 EVOH (A1) and a nitrogen-containing compound (B1) were dry blended so that (B1) was 0.1% by mass based on the total amount of (A1) and (B1) to prepare a resin composition.
• the thickening ratio was calculated from the obtained torque value after 60 minutes and the torque value after 180 minutes using the following formula.
• Thickening ratio torque value after 180 minutes of measurement/torque value after 60 minutes of measurement
• the viscosity increase suppression rate was calculated from the viscosity increase ratio of the resin composition (resin composition not containing (B)) using the following formula.
• Thickening suppression rate (%) [thickening ratio (blank) - thickening ratio (example or comparative example)] / thickening ratio (blank) x 100
• EVOH (A), a specific nitrogen-containing compound (B), an alkali metal compound (C), an alkaline earth metal compound (D) are contained, and the alkaline earth metal compound (D) is
• the resin compositions of Examples 1 to 5 in which the content ratio (C/D) of the metal equivalent content of the alkali metal compound (C) to the metal equivalent content is within a specific range do not contain the nitrogen-containing compound (B). It can be seen that the thickening over time is suppressed compared to the blank EVOH (A1) and (A2), and as a result, the long-run moldability is excellent.
• the resin composition of Comparative Example 1 in which the content ratio (C/D) of the metal equivalent content of the alkali metal compound (C) to the metal equivalent content of the alkaline earth metal compound (D) is 0.5 or less. It can be seen that the thickening ratio is higher than that of Examples 1 to 5.
• the resin composition of Comparative Example 3 in which the nitrogen-containing compound (B) is a compound having no specific molecular weight and amine equivalent, has a higher viscosity ratio than Examples 1 to 5, and has a viscosity suppressing effect. I know it's inferior. Furthermore, molded articles made of the resin compositions of Examples 1 to 5 and multilayer structures having layers containing the resin compositions of Examples 1 to 5 can also suppress thickening over time during heating. .
• the resin composition of the present invention suppresses thickening over time during heating, and as a result, has excellent long-run moldability, so it can be used in various foods, seasonings such as mayonnaise and dressing, fermented miso, etc. It is particularly useful as a packaging material for various products such as foods, oil and fat foods such as salad oil, beverages, cosmetics, and pharmaceuticals.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Priority Applications (4)

Applications Claiming Priority (4)

Related Child Applications (1)

Publications (1)

Family

ID=89706429

Family Applications (1)

Country Status (6)

Citations (4)

Family Cites Families (3)

• 2023
  • 2023-07-25 JP JP2024537734A patent/JPWO2024024768A1/ja active Pending
  • 2023-07-25 TW TW112127698A patent/TW202411334A/zh unknown
  • 2023-07-25 CN CN202380053150.6A patent/CN119630735A/zh active Pending
  • 2023-07-25 EP EP23846498.6A patent/EP4563648A4/en active Pending
  • 2023-07-25 WO PCT/JP2023/027121 patent/WO2024024768A1/ja not_active Ceased
• 2025
  • 2025-01-02 US US19/007,667 patent/US20250163243A1/en active Pending

Patent Citations (4)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events