WO2017110561A1 - エチレン-ビニルアルコール系共重合体組成物ペレット及び該エチレン-ビニルアルコール系共重合体組成物ペレットの製造方法 - Google Patents
エチレン-ビニルアルコール系共重合体組成物ペレット及び該エチレン-ビニルアルコール系共重合体組成物ペレットの製造方法 Download PDFInfo
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/726—Measuring properties of mixture, e.g. temperature or density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
- B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
- B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- 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
- C08J2329/00—Characterised by the use of homopolymers or 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Definitions
- the present invention relates to an ethylene-vinyl alcohol copolymer composition pellet in which coloring is suppressed and a method for producing the ethylene-vinyl alcohol copolymer composition pellet.
- EVOH resin An ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as “EVOH resin”) has a structure that is easy to align and is a very strong molecule due to hydrogen bonding between hydroxyl groups present in the polymer side chain. Since it has an interfacial force, it has high crystallinity and also has a high intermolecular force even in an amorphous part, so that gas molecules such as oxygen hardly pass through the EVOH resin, and films using the EVOH resin have excellent gas barrier properties. Indicates.
- EVOH resin is used by being molded into a film or sheet of food packaging material, pharmaceutical packaging material, industrial chemical packaging material, agricultural chemical packaging material, or a container such as a bottle, etc. by utilizing its excellent gas barrier property. .
- EVOH resin exhibits excellent gas barrier properties as described above, but is weak against water, wets with water, or is placed under high humidity conditions, the gas barrier properties are reduced. Therefore, when used for packaging materials for retort, etc., it is common to arrange an EVOH resin layer in an intermediate layer and sandwich it with a polyolefin resin layer or the like to form a multilayer structure. And also in EVOH resin layer, polyamide-type resin, such as nylon, is mixed with EVOH resin, and durability with respect to water is improved.
- Patent Document 1 discloses a saponified ethylene-vinyl acetate copolymer (A), the number of terminal COOH groups (x) and terminal CONRR ′ by using a terminal regulator.
- a resin composition composed of a hindered phenol compound (C) and an aliphatic carboxylic acid alkaline earth metal salt (D) has been proposed.
- Patent Document 1 describes that addition of an aliphatic carboxylic acid alkaline earth metal salt to a mixture of an EVOH resin and a polyamide-based resin improves thermal stability, suppresses the generation of gel, and enables long-run molding. Has been.
- Patent Document 2 when a resin composition obtained by mixing an EVOH resin and a polyolefin resin or a resin composition obtained by mixing an EVOH resin and a polyamide resin is heated and melted, the screw length L (mm) of the extruder is set. It describes that the ratio (L / D) of the screw outer diameter D (mm), the specific energy at the time of melt extrusion, the discharge amount per die nozzle, and the processing temperature are within a specific range. Patent Document 2 describes that, by setting the extrusion condition during heating and melting within a specific range, a gel-free pellet and an uncolored pellet can be obtained.
- Patent Document 1 has a tendency to be colored when heated and melted in an extruder, and the obtained molded product has a problem that it is difficult to apply to applications requiring transparency. Further, the technique described in Patent Document 2 cannot obtain a sufficient coloring suppression effect, and further improvement has been demanded.
- an object of the present application is to provide an ethylene-vinyl alcohol copolymer composition pellet with reduced coloring.
- the resin composition containing an EVOH resin, a polyamide-based resin, and an alkaline earth metal salt is colored after being extruded from the extruder rather than during melt kneading. I understood it. Even after extrusion from the extruder, the resin pellets remain at a high temperature.
- the inventor of the present invention pays attention to the fact that resin pellets containing EVOH resin, polyamide-based resin, and alkaline earth metal salt are likely to be colored at high temperatures, and discharge from the die of the extruder (mold of discharge port). The inventors have found that resin pellets with less coloring can be obtained by controlling the resin temperature immediately after that, and the present invention has been completed.
- the present invention has the following configurations (1) to (6).
- the mass ratio ((A) / (B)) of the ethylene-vinyl alcohol copolymer (A) and the polyamide resin (B) is 60/40 to 98/2 (1)
- the content of the alkaline earth metal salt (C) is 10 to 200 ppm in terms of metal with respect to the total amount of the ethylene-vinyl alcohol copolymer (A) and the polyamide resin (B).
- an ethylene-vinyl alcohol copolymer composition pellet with a reduced coloration having a yellow index (YI) value of 10 or less it is possible to provide an ethylene-vinyl alcohol copolymer composition pellet with a reduced coloration having a yellow index (YI) value of 10 or less. Therefore, even in a molded product requiring transparency. It can be used suitably.
- YI yellow index
- the ethylene-vinyl alcohol copolymer composition pellet of the present invention contains an ethylene-vinyl alcohol copolymer (A), a polyamide resin (B), and an alkaline earth metal salt (C).
- a yellow index (YI) value measured by a transmission method with a spectral color difference meter is 10 or less.
- the ethylene-vinyl alcohol copolymer (EVOH resin) used in the present invention is a known resin and is a water-insoluble thermoplastic resin.
- the EVOH resin is usually obtained by copolymerizing a vinyl ester monomer and ethylene to obtain an ethylene-vinyl ester copolymer, which is saponified. That is, it mainly comprises ethylene structural units and vinyl alcohol structural units, and contains a slight amount of vinyl ester structural units remaining after the saponification step.
- a known polymerization method such as a solution polymerization method may be employed.
- vinyl ester monomers examples include vinyl acetate, vinyl formate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, versatic.
- vinyl esters such as vinyl acid, and aromatic vinyl esters such as vinyl benzoate.
- aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. Ester.
- the ethylene content of the EVOH resin is determined at the time of polymerization of ethylene and a vinyl ester monomer, and does not change before and after saponification.
- the content of ethylene structural units, measured based on ISO 14663, is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 25 to 45 mol%. If the ethylene content is too low, impact resistance and workability tend to be lowered, and if it is too high, gas barrier properties and solvent resistance tend to be lowered.
- the degree of saponification of EVOH resin is usually 90 to 100 mol%, preferably 95 to 100 mol as measured by a titration method (JIS K6726) (however, EVOH resin is a solution uniformly dissolved in water / methanol solvent). %, Particularly preferably 98 to 100%. If the saponification degree is too low, the gas barrier property tends to decrease.
- the melt flow rate of EVOH resin (hereinafter sometimes referred to as MFR) is a value measured at 210 ° C. and a load of 2160 g, and usually 0.1-100 g / 10 minutes, preferably 1-50 g / 10 minutes, more preferably Is 2 to 40 g / 10 min. If this value is too high or too low, the workability tends to decrease.
- the melting point of EVOH is a value measured with a differential scanning calorimeter (DSC) at a temperature rising / falling rate of 10 ° C./min, and is usually 100 to 220 ° C., preferably 120 to 210 ° C., more preferably 140 to 200 ° C.
- DSC differential scanning calorimeter
- an ethylenically unsaturated monomer that can be copolymerized in a range that does not impair the properties required for EVOH resin (for example, less than 10 mol%) is copolymerized.
- examples of the monomer include the following.
- olefins such as propylene, 1-butene, isobutene, 2-propen-1-ol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 3,4 -Hydroxy group-containing ⁇ -olefins such as dihydroxy-1-butene and 5-hexene-1,2-diol, acylated products, and esterified products thereof.
- esterified products include 3,4-diacyloxy-1- Examples include butene, particularly 3,4-diacetoxy-1-butene.
- hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2 -Hydroxyalkylvinylidene diacetates such as methylenepropane and 1,3-dibutyronyloxy-2-methylenepropane.
- unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid or salts thereof, and mono- or dialkyl esters having 1 to 18 carbon atoms Is mentioned.
- acrylamide such as acrylamide, N-alkyl acrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, and acrylamidepropyldimethylamine or an acid salt thereof or a quaternary salt thereof.
- N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers, alkoxy Vinyl ethers such as alkyl vinyl ethers, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl halides such as vinyl bromide, vinyl silanes such as trimethoxyvinyl silane, and allyl acetate, allyl chloride, trimethyl- ( 3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid, vinyl ethylene carbonate, glycerin monoallyl ether and the like.
- EVOH obtained by copolymerizing hydroxy group-containing ⁇ -olefins, particularly EVOH having 1,2-diol in the side chain is preferably used in applications requiring secondary formability such as stretching and vacuum / pressure forming. .
- the EVOH resin used in the present invention may contain other thermoplastic resins depending on the purpose.
- the content of the other thermoplastic resin is usually less than 30% by mass with respect to the entire resin composition.
- compounding ingredients may be included depending on the purpose within a range not impairing the effects of the present invention.
- the addition amount of these compounding agents is usually less than 5% by mass with respect to the resin composition.
- Other compounding ingredients include, for example, fillers such as talc, calcium carbonate, mica, glass fiber, plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, oxygen absorbers, Waxing agent, lubricant, anti-fogging agent, anti-blocking agent, slip agent, crosslinking agent, crosslinking aid, coloring agent, flame retardant, dispersant, surfactant, drying agent, antistatic agent, antibacterial agent, curing agent, Examples include foaming agents, crystal nucleating agents, biodegradable additives, fluorescent brighteners, silane coupling agents, and the like, and any compounding agent can be used alone or in combination.
- the resin and compounding agent that can be contained means that the resin is uniformly added to the resin component (the pellet is uniformly added).
- the heat stabilizer is an organic acid such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, behenic acid, or an alkali thereof for the purpose of improving various physical properties such as heat stability during melt molding.
- Salts other than alkaline earth metal salts such as metal salts (sodium, potassium, etc.); or inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid, boric acid, or alkali metal salts thereof (sodium, potassium, etc.)
- Additives such as salts other than alkaline earth metal salts such as zinc salts may be added.
- boron compounds, acetates and phosphates including acetic acid, boric acid and salts thereof.
- the amount added is usually 0.001 to 1 part by weight, preferably 0.005 to 0.2 part by weight, particularly preferably 0.01 to 0.1 part by weight based on 100 parts by weight of the EVOH resin. Part by mass. If the amount of acetic acid added is too small, the effect of acetic acid content tends not to be obtained sufficiently, and conversely if too large, it tends to be difficult to obtain a uniform film.
- the amount added is usually 0.001 to 1 part by mass in terms of boron (analyzed by ICP emission spectrometry after ashing) with respect to 100 parts by mass of EVOH resin, preferably Is 0.002 to 0.2 parts by mass, particularly preferably 0.005 to 0.1 parts by mass. If the addition amount of the boron compound is too small, the effect of adding the boron compound may not be sufficiently obtained. Conversely, if the addition amount is too large, it tends to be difficult to obtain a uniform film.
- the addition amount of acetate and phosphate is usually in metal conversion (after ashing and analyzed by ICP emission spectrometry) with respect to 100 parts by mass of EVOH resin (A).
- the amount is 0.0005 to 0.1 parts by mass, preferably 0.001 to 0.05 parts by mass, particularly preferably 0.002 to 0.03 parts by mass. If the amount added is too small, the content effect may not be sufficiently obtained, while if too large, it tends to be difficult to obtain a uniform film.
- the method of adding acetic acid, boron compound, acetate salt and phosphate salt to EVOH resin is not particularly limited.
- a porous precipitate of EVOH resin having a water content of 20 to 80% by mass is added to an aqueous solution of the additive.
- the alkali (sodium hydroxide, potassium hydroxide, etc.) used in the conversion step is neutralized with organic acids such as acetic acid, and the remaining amount of organic acids such as acetic acid and by-product salts is washed with water.
- Such EVOH resin is usually marketed in the form of pellets and used for various melt molding.
- the shape of the pellet includes, for example, a spherical shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, etc., but is usually a spherical shape (rugby ball shape) or a cylindrical shape, and its size is convenient when used as a molding material later.
- the diameter is usually 1 to 6 mm, preferably 2 to 5 mm
- the height is usually 1 to 6 mm, preferably 2 to 5 mm
- the diameter of the bottom is usually 1 It is ⁇ 6 mm, preferably 2 to 5 mm
- the length is usually 1 to 6 mm, preferably 2 to 5 mm.
- the polyamide resin (B) used in the present invention is a known resin and is a water-insoluble thermoplastic resin.
- polyamide resins examples include polycapramide (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylauryl lactam (nylon). 12) and the like.
- copolymer polyamide resins include polyethylenediamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebamide (nylon 610).
- Polyhexamethylene dodecamide (nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 108), caprolactam / lauryl lactam copolymer (nylon 6/12), caprolactam / ⁇ -aminononanoic acid copolymer (nylon 6/9), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66), lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12/66), ethyl Diamine adipamide / hexamethylene diammonium adipate copolymer (nylon 26/66), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 66/610), ethylene ammonium adipate / hexam
- Family copolyamide amorphous polyamide, said polyamide resin methylene benzylamine, terminal modified polyamide obtained by modifying the ends with carboxyl group or an amino group such as meta-xylene diamine.
- These polyamide resins can be used alone or in combination of two or more.
- nylon 6 is preferably used from the viewpoint of retort resistance when an EVOH resin composition is used as an intermediate layer of a multilayer film.
- the polyamide-based resin (B) preferably has a melting point of usually 150 to 270 ° C., preferably 180 to 250 ° C., more preferably 200 to 230 ° C.
- the melt flow rate (MFR) is usually 0.1 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, more preferably 3 to 20 g / 10 minutes at 230 ° C. and a load of 2160 g. .
- alkaline earth metal salt (C) examples include alkaline earth metal acetates, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, behenic acid and other aliphatic carboxylates, citric acid, and the like.
- Organic acid salts such as acid salts, alkaline earth metal borates, alkaline earth metal carbonates, alkaline earth metal hydrogen carbonates, inorganic earth salts such as alkaline earth metal phosphates, etc. It is done.
- Examples of the alkaline earth metal acetate include magnesium acetate, calcium acetate, and barium acetate.
- alkaline earth metal carbonate examples include calcium carbonate, magnesium carbonate, and barium carbonate.
- alkaline earth metal hydrogen carbonate examples include calcium hydrogen carbonate, magnesium hydrogen carbonate, barium hydrogen carbonate, and the like.
- alkaline earth metal phosphate examples include calcium dihydrogen phosphate, magnesium monohydrogen phosphate, and barium hydrogen phosphate.
- the alkaline earth metal salt is preferably an organic acid salt, more preferably an aliphatic carboxylate having 1 to 6 carbon atoms, particularly acetic acid. It is preferable to use magnesium.
- the mass ratio ((A) / (B)) of the ethylene-vinyl alcohol copolymer (A) and the polyamide resin (B) is preferably 60/40 to 98/2.
- the mass ratio of the ethylene-vinyl alcohol copolymer (A) and the polyamide resin (B) is more preferably 70/30 to 95/5, still more preferably 80/20 to 90/10.
- the content of the alkaline earth metal salt (C) is 10 to 200 ppm in terms of metal with respect to the total amount of the ethylene-vinyl ester copolymer (A) and the polyamide resin (B). It is preferably 10 to 100 ppm, more preferably 10 to 50 ppm. If the content of the alkaline earth metal salt (C) is too large, gel, foaming or coloring may occur in the pellets or the moldability tends to become unstable. If it is too small, the melt viscosity tends to increase. Tend.
- an antioxidant is preferably blended.
- the thermal stability during the molding process can be improved.
- antioxidants examples include phenolic antioxidants, amine antioxidants, amino ether antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
- phenolic antioxidants examples include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4 -N-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL- ⁇ -tocopherol, steer Monocyclic phenolic compounds such as r
- amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2, Polycondensate of 6,6-tetramethylpiperidineethanol, N, N ′, N ′′, N ′′ ′′-tetrakis- [4,6-bis- ⁇ butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino ⁇ -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [ ⁇ 6- (1,1,3 -Tetramethylbutyl)
- amino ether antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1- Propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-pentyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1- Butyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,2,
- phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite , Cyclic neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl Tris (dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, di
- sulfur-based antioxidant examples include dilauryl thiodipropionate, ditridecyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate), 4,4-thiobis ( 2-tert-butyl-5-methylphenol) bis-3- (dodecylthio) propionate, dimyristyl-3,3'-thiodipropionate, lauryl-stearyl-3,3'-thiodipropionate, neopentanetetrayl And tetrakis (3-laurylthiopropionate).
- antioxidants can be used alone or in combination of two or more. Especially, it is preferable to use a phenolic antioxidant from a viewpoint of the thermal stability at the time of a shaping
- the content of the antioxidant is preferably 0.1 to 200 ppm, more preferably 1 to 100 ppm with respect to 100 parts by mass of the total amount of the EVOH resin (A) and the polyamide resin (B). More preferred is ⁇ 50 ppm.
- the content of the antioxidant is within the above range, the thermal stability during the molding process is good.
- the ethylene-vinyl alcohol copolymer composition pellets of the present invention can be blended with other additives within a range not impairing the effects of the present invention.
- other additives include plasticizers, stabilizers, fillers, colorants, lubricants, antiblocking agents, and antistatic agents.
- the ethylene-vinyl alcohol copolymer composition pellets are characterized in that the yellow index (YI) value measured by a transmission method using a spectrocolorimeter is 10 or less.
- the yellow index (YI) value is 10 or less, the transparency of the resin pellet can be ensured.
- the yellow index (YI) value is more preferably 8 or less.
- a cylindrical glass cell having a diameter of 35 mm and a height of 30 mm is filled with a pellet to prepare a measurement sample, and the sample is subjected to a transmission method using a spectrocolorimeter in accordance with JISZ-8722. Can be measured.
- the method for producing the ethylene-vinyl alcohol copolymer composition pellets of the present invention is not particularly limited.
- a method of blending the above components (A) to (C) (1) a polyamide resin (B) is added to a composition in which an ethylene-vinyl alcohol copolymer (A) and an alkaline earth metal salt (C) are blended in advance.
- a method of blending the ethylene-vinyl alcohol copolymer (A) into a composition in which the polyamide resin (B) and the alkaline earth metal salt (C) are blended in advance (3) Examples thereof include a method in which the ethylene-vinyl alcohol copolymer (A), the polyamide resin (B), and the alkaline earth metal salt (C) are blended together.
- the method (1) is preferable from the viewpoint of the physical property improving effect and productivity of the EVOH resin.
- a porous precipitate of EVOH resin having a water content of 20 to 80% by mass is contacted with an aqueous solution of an alkaline earth metal salt (C) and then dried;
- the alkaline earth metal salt (C) is contained in a uniform solution (water / alcohol solution, etc.) of EVOH resin, it is extruded into a coagulating liquid in the form of a strand, and then the obtained strand is cut into pellets and dried.
- Iii) A method in which the EVOH resin and the alkaline earth metal salt (C) are mixed together and then melt-kneaded with an extruder or the like. The method i) is preferred from the viewpoint of the physical property improving effect and productivity of the EVOH resin.
- the ethylene-vinyl alcohol copolymer composition pellet of the present invention comprises an ethylene-vinyl alcohol copolymer (A), a polyamide resin (B) and an alkaline earth metal salt (C) as described above.
- the resulting composition can be obtained by melt-kneading using a melt-kneader and adjusting the resin temperature immediately after being discharged from the melt-kneader to be lower than that of the conventional one.
- the present inventor has paid attention to the fact that coloring proceeds by contact with air in a high temperature state when melt-kneading a resin composition containing an EVOH resin, a polyamide-based resin, and an alkaline earth metal salt. This is because, in the resin composition of EVOH resin and polyamide-based resin, the alkaline earth metal salt needs to be blended for improving various physical properties. However, the resin composition is obtained by using the alkaline earth metal salt as a catalyst. It is presumed that the deterioration of the steel tends to progress.
- the present inventor pays attention to the temperature immediately after discharging from the extruder and adjusts such a temperature to be lower than the conventional one to suppress the progress of the deterioration of the resin composition of the EVOH resin and the polyamide resin. It was found that resin pellets with little coloring could be obtained, and the present invention was completed.
- melt-kneading apparatus examples include a kneader, an extruder, a mixing roll, a Banbury mixer, a kneader ruder, a blast mill, and the like. Particularly, a method using an extruder that can be continuously processed and has excellent mixing efficiency is preferable. It is.
- a twin-screw extruder particularly a twin-screw extruder having the same screw rotation direction, is sufficiently kneaded by appropriate shearing. Is preferable in that it is obtained.
- the screw effective length (L / D) of the extruder is usually 10 to 100, preferably 15 to 70, more preferably 40 to 60. If L / D is too small, melt-kneading may be insufficient and uniform dispersibility may be insufficient. On the other hand, if L / D is too large, there is a tendency to cause decomposition due to shear heat generation due to excessive shearing or excessive retention.
- the L / D of the kneading region in the screw of the extruder is generally 3 to 15, preferably 5 to 10, particularly preferably 5 to 8. When the L / D of the kneading region is in the above range, it tends to be easily adjusted to a desired temperature described later.
- the screw rotation speed is usually 100 to 1000 rpm, preferably 300 to 800 rpm, and more preferably 400 to 600 rpm. If the screw rotation number is too small, the discharge tends to become unstable. If it is too large, the resin temperature immediately after being discharged from the extruder cannot be made 268 ° C. or lower, and the pellets may be colored.
- the shape of the die is usually circular.
- the diameter is usually 1 to 10 mm, preferably 3 to 5 mm, particularly preferably 3.5 to 4.5 mm. If the diameter is too large, the strands are not stable, and thus the productivity tends to decrease. If the diameter is too small, it tends to be difficult to adjust to a desired temperature described later.
- the temperature of the composition at the time of melting in the extruder is usually 150 to 300 ° C., preferably 180 to 290 ° C., more preferably 200 to 280 ° C. If the temperature of the composition is too low, melt kneading may be insufficient and uniform resin pellets may not be obtained. On the other hand, if the temperature of the composition is too high, the resin temperature immediately after being discharged from the extruder cannot be adjusted low, and coloring may occur in the pellets. In addition, adjustment of the temperature of a composition can be normally performed by setting suitably the temperature of the cylinder in an extruder, and screw rotation speed.
- the temperature of the resin pellets (strand-like kneaded material) immediately after being discharged from a melt-kneading apparatus such as an extruder is lower than that of the prior art.
- the temperature is usually the melting point of the polyamide resin (B) +5 to 48 ° C., preferably the melting point of the polyamide resin (B) +10 to 40 ° C., particularly preferably the melting point of the polyamide resin (B). + 20-30 ° C.
- a melting point can be obtained, for example, by measuring a polyamide resin with a differential scanning calorimeter (DSC).
- the temperature of the resin pellets (strand-like kneaded material) immediately after being discharged from a melt-kneading apparatus such as an extruder is usually 268 ° C. or less, preferably 230 to 266 ° C., more preferably 240 to 266 ° C. is there.
- a melt-kneading apparatus such as an extruder
- the method for adjusting the resin temperature immediately after discharge to the above range is not particularly limited.
- the ethylene-vinyl alcohol copolymer composition pellets obtained as described above had a yellow index (YI) value of 10 or less when measured by a transmission method using a spectrocolor difference meter, and coloring was reduced.
- YI yellow index
- the specific energy (kWh / kg) at the time of melt extrusion is preferably in the range of 0.1 to 0.5. If the specific energy is less than 0.1, melt-kneading may not be sufficiently performed. Conversely, if the specific energy exceeds 0.5, the resin composition may be thermally deteriorated to cause coloration, or fish eyes may be formed on the molded product obtained from the pellets. May occur frequently. Such a value can be obtained by dividing the power value of the screw motor of the extruder by the discharge amount from the extruder.
- the ethylene-vinyl alcohol copolymer composition pellets of the present invention are formed by melt molding, for example, various types of thin containers such as films and sheets, hollow containers such as bags, cups, trays, tubes, bottles and tanks, and lid materials. It can be a thing.
- melt molding method examples include extrusion molding methods such as T-die extrusion, inflation extrusion, blow molding, melt spinning, and profile extrusion, and injection molding methods.
- the melt molding temperature is usually 190 to 250 ° C.
- the ethylene-vinyl alcohol copolymer composition pellets of the present invention can be melt-molded to form various molded products in a single layer. From the viewpoint of improvement in strength and the like, it is preferable to provide various molded products with a multilayer structure in which a thermoplastic resin layer other than the EVOH resin is laminated on the EVOH resin composition layer.
- thermoplastic resin constituting the thermoplastic resin layer other than the EVOH resin include linear low density polyethylene, low density polyethylene, Polyethylene resins such as ultra-low density polyethylene, medium density polyethylene, high density polyethylene, ethylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymer, polypropylene, propylene- ⁇ -olefin (4 carbon atoms) ⁇ 20 ⁇ -olefin) copolymer, polypropylene resin such as ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene (block and random) copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic Acid ester copolymer Polybutene, polypentene or other olefin homo- or copolymer, or Polyolefin resins in a broad sense such as those obtained by graft-modifying these ole
- a hydrophobic resin for the purpose of suppressing a decrease in gas barrier properties of the resin composition.
- a polyolefin-based resin is preferable, and a polyethylene-based resin and a polypropylene-based resin are particularly preferable.
- the EVOH resin composition layer and the other thermoplastic resin layer may each have two or more layers in the multilayer structure.
- an adhesive resin layer may be further interposed between the EVOH resin composition layer and the other thermoplastic resin layer.
- the adhesive resin layer for example, a modification containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to an olefin polymer (the above-mentioned polyolefin resin) by an addition reaction or a graft reaction. Mention may be made of olefin polymers.
- maleic anhydride graft-modified polyethylene maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block and random) copolymer, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, anhydrous
- the amount of the unsaturated carboxylic acid or anhydride thereof contained in the thermoplastic resin is usually 0.001 to 3% by mass, preferably 0.01 to 1% by mass, particularly preferably 0.03%. Is 0.5% by mass.
- thermoplastic resin layers and adhesive resin layers may contain known antioxidants, antistatic agents, plasticizers, lubricants, core materials, antiblocking agents, waxes and the like that are usually blended. .
- the multilayer structure is not particularly limited as long as it includes at least one EVOH resin composition layer according to the present invention.
- the EVOH resin composition layer of the invention is preferably an intermediate layer.
- the other thermoplastic resin layer is preferably an outer layer. That is, for example, when a multilayer structure is used as a package, another thermoplastic resin layer (particularly a hydrophobic resin layer) is a layer in contact with the inclusion and a layer in contact with the outside air.
- the layer structure of the multilayer structure is usually such that the EVOH resin composition layer of the present invention is a (a1, a2,...) And the other thermoplastic resin layers are b (b1, b2, etc. 3 to 20 layers, preferably 3 to 15 layers, particularly preferably 3 to 10 layers.
- the multilayer structure includes a mixture of an EVOH resin composition and a thermoplastic resin other than the EVOH resin, which is obtained by remelt molding an end portion or a defective product generated in the process of manufacturing the multilayer structure.
- a recycling layer can be provided.
- the layer structure of the multilayer structure is, for example, b / a / R, R / b / a, b / R / a / b, b / R / a / R / b, b / R / a / R / / b, b / R / a / R / a / R / b, and the like.
- it is industrially preferable to provide a recycling layer because a large amount of scrap generated during molding can be effectively used.
- each layer in the multilayer structure is adjusted depending on the layer configuration, application, container form, and required physical properties. For example: In addition, the following numerical value adopts the thickness of the thickest layer when there are two or more types of EVOH resin composition layer, adhesive resin layer, and other thermoplastic resin layers. To do.
- the EVOH resin composition layer of the present invention is usually 1 to 500 ⁇ m, preferably 3 to 300 ⁇ m, more preferably 5 to 200 ⁇ m.
- the other thermoplastic resin layer is usually 10 to 6000 ⁇ m, preferably 20 to 4000 ⁇ m, particularly preferably 100 to 2000 ⁇ m. If the other thermoplastic resin layer is too thin, the rigidity of the resulting molded product tends to decrease, and if the other thermoplastic resin layer is too thick, the flexibility and secondary workability of the resulting molded product decrease. Tend.
- the adhesive resin layer is usually 1 to 100 ⁇ m, preferably 2 to 50 ⁇ m, particularly preferably 5 to 40 ⁇ m.
- the thickness ratio of each layer is such that the EVOH resin composition layer / other thermoplastic resin layer thickness ratio is usually 0.005 to less than 1, preferably 0.01 to less than 1, and particularly preferably 0.02 to 0.00.
- the thickness ratio of the resin composition layer / adhesive resin layer is usually 0.2 to 100, preferably 1 to 10, and particularly preferably 1 to 5.
- the multilayer structure may be further subjected to stretching treatment by a known method.
- stretching method may be sufficient, for example, uniaxial stretching, biaxial stretching, etc. are mentioned.
- heat stretching method roll stretching method, tenter stretching method, tubular stretching method, co-injection stretch blow method, deep drawing method, vacuum forming method, pressure forming method, vacuum pressure forming method, plug assist type vacuum pressure forming method Etc.
- biaxial stretching both a simultaneous biaxial stretching method and a sequential biaxial stretching method can be employed.
- the co-injection stretch blow method either the cold parison method or the hot parison method can be employed.
- the stretching temperature is the temperature of the multilayer structure (temperature near the multilayer structure) and is usually selected from the range of about 80 to 200 ° C., preferably about 100 to 160 ° C.
- the draw ratio is usually 2 to 100 times, preferably 2 to 50 times in terms of area ratio.
- the thickness of each layer in the stretched multilayer structure is, for example, as follows.
- the EVOH resin composition layer is usually 0.1 to 200 ⁇ m, preferably 1 to 100 ⁇ m.
- the other thermoplastic resin layer is usually 1 to 1000 ⁇ m, preferably 3 to 500 ⁇ m.
- the adhesive resin layer is usually 0.1 to 50 ⁇ m, preferably 1 to 30 ⁇ m.
- the thickness ratio of each layer is such that the thickness ratio of EVOH resin composition layer / other thermoplastic resin layer is usually 0.0002 or more and less than 1, preferably 0.01 or more and less than 1, EVOH resin composition layer / adhesion
- the thickness ratio of the conductive resin layer is 0.2 to 100, preferably 1 to 10.
- the multilayer structure obtained as described above can be processed into thin containers such as films and sheets, bags and cups, hollow containers such as trays, tubes, bottles, and tanks, and containers such as lids.
- Such containers are useful as various packaging containers for general foods, seasonings such as mayonnaise and dressing, fermented foods such as miso, fats and oils such as salad oil, beverages, cosmetics, pharmaceuticals, agricultural chemicals, industrial chemicals, etc. It is.
- Example 1 Contains 35 ppm of magnesium acetate in terms of metal as the alkaline earth metal salt (C) obtained by contacting the porous precipitate of hydrous EVOH with an aqueous solution of the alkaline earth metal salt (C) and then drying.
- EVOH resin (A) (ethylene content 29 mol%, saponification degree 99.6 mol%, MFR 4.1 g / 10 min (210 ° C., load 2160 g), melting point 185.6 ° C.) 85 parts
- mass ratio (A) / (B) of EVOH resin (A) and polyamide-type resin (B) is 85/15
- the content rate of alkaline-earth metal salt (C) is EVOH resin (A). It is 30 ppm in terms of metal with respect to the total amount of the polyamide-based resin (B).
- Is C2 / C3 / C4 / C5 / C6 / C7 / C8 / C9 / C10 / C11 / C12 / C13 / C14 / C15 100/230/230/230/230/230/230/230/230/230/230/230/230/230
- the mixture was heated to / 210/210/210 to prepare ethylene-vinyl alcohol copolymer composition pellets.
- the weak kneading specification screw had two kneading areas, and the total L / D of the kneading area was 6.5.
- the temperature of the strand immediately after discharge of a die exit was measured using "IR thermometer FLIRi3" (trade name) manufactured by FLIR.
- the pellet was filled in a cylindrical glass cell having a diameter of 35 mm and a height of 30 mm, tapped three times, and then used as a sample for measuring the yellow index (YI) value.
- the yellow index (YI) value of the obtained YI value measurement sample was measured using “Spectral Color Difference Meter SE6000” (trade name) manufactured by Nippon Denshoku Industries Co., Ltd. according to JISZ-8722.
- the specific energy of the resin composition at the time of melt extrusion was calculated
- YI yellow index
- YI yellow index
- Such a normal specification screw had two kneading areas, and the total L / D of the kneading area was 10.25.
- the temperature of the strand immediately after discharge from the die outlet, the yellow index (YI) value of the molded product, and the specific energy were determined, and the results are shown in Table 1.
- Molded articles using the ethylene-vinyl alcohol copolymer composition pellets are excellent in gas barrier properties and suppressed in coloration, and are extremely useful industrially.
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Abstract
Description
(1)エチレン-ビニルアルコール系共重合体(A)、ポリアミド系樹脂(B)及びアルカリ土類金属塩(C)を含有するエチレン-ビニルアルコール系共重合体組成物ペレットであって、前記ペレットを分光色差計にて透過法により測定したイエローインデックス(YI)値が10以下であるエチレン-ビニルアルコール系共重合体組成物ペレット。
(2)前記エチレン-ビニルアルコール系共重合体(A)と前記ポリアミド系樹脂(B)の質量比((A)/(B))が、60/40~98/2である、前記(1)に記載のエチレン-ビニルアルコール系共重合体組成物ペレット。
(3)前記アルカリ土類金属塩(C)の含有割合が、前記エチレン-ビニルアルコール系共重合体(A)と前記ポリアミド系樹脂(B)の合計量に対して、金属換算で10~200ppmである、前記(1)又は(2)に記載のエチレン-ビニルアルコール系共重合体組成物ペレット。
(4)さらに酸化防止剤を含む、前記(1)~(3)のいずれか1つに記載のエチレン-ビニルアルコール系共重合体組成物ペレット。
(5)前記(1)~(4)のいずれか1つに記載のエチレン-ビニルアルコール系共重合体組成物ペレットが溶融成形されたエチレン-ビニルアルコール系共重合体組成物成形体。
(6)分光色差計にて透過法により測定したときのイエローインデックス(YI)値が10以下であるエチレン-ビニルアルコール系共重合体組成物ペレットの製造方法であって、エチレン-ビニルアルコール系共重合体(A)、ポリアミド系樹脂(B)及びアルカリ土類金属塩(C)を含有する樹脂組成物を溶融混練装置を用いて溶融混練する工程を含み、前記溶融混練装置から吐出された直後のエチレン-ビニルアルコール系共重合体組成物ストランドの温度を268℃以下とするエチレン-ビニルアルコール系共重合体組成物ペレットの製造方法。
尚、本明細書において、質量で表される全ての百分率や部は、重量で表される百分率や部と同様である。
以下に各成分について説明する。
本発明で用いるエチレン-ビニルアルコール系共重合体(EVOH樹脂)は、公知の樹脂であり、非水溶性の熱可塑性樹脂である。EVOH樹脂は、通常、ビニルエステル系単量体とエチレンを共重合してエチレン-ビニルエステル系共重合体を得、これをケン化して得られるものである。すなわち、エチレン構造単位とビニルアルコール構造単位を主とし、ケン化工程後に残存した若干量のビニルエステル構造単位を含むものである。上記共重合に際しては、溶液重合法など、公知の重合法が採用され得る。
特に延伸加工や真空・圧空成形などの二次成形性が必要な用途においてはヒドロキシ基含有α-オレフィン類を共重合したEVOH、特には1,2-ジオールを側鎖に有するEVOHが好ましく用いられる。
本発明の効果をより顕著に得るためには、添加物の分散性に優れるi)、ii)の方法、有機酸およびその塩を含有させる場合はiv)の方法を併用することが好ましい。
本発明で用いるポリアミド系樹脂(B)は、公知の樹脂であり、非水溶性の熱可塑性樹脂である。
これらのポリアミド系樹脂は1種を単独で又は2種以上を組み合わせて用いることができる。中でもEVOH樹脂組成物とし、これを多層フィルムの中間層として用いた場合の耐レトルト性の観点から、ナイロン6を用いることが好ましい。
本発明で用いるアルカリ土類金属塩(C)としては、例えば、アルカリ土類金属の酢酸塩、プロピオン酸、酪酸、ラウリル酸、ステアリン酸、オレイン酸、ベヘニン酸等の脂肪族カルボン酸塩、クエン酸塩等の有機酸塩、アルカリ土類金属のホウ酸塩、アルカリ土類金属の炭酸塩、アルカリ土類金属の炭酸水素塩、アルカリ土類金属のリン酸塩等の無機酸塩等が挙げられる。
アルカリ土類金属の酢酸塩としては、例えば、酢酸マグネシウム、酢酸カルシウム、酢酸バリウム等が挙げられる。
アルカリ土類金属の炭酸塩としては、例えば、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等が挙げられる。
アルカリ土類金属の炭酸水素塩としては、例えば、炭酸水素カルシウム、炭酸水素マグネシウム、炭酸水素バリウム等が挙げられる。
アルカリ土類金属のリン酸塩としては、例えば、リン酸二水素カルシウム、リン酸一水素マグネシウム、リン酸水素バリウム等が挙げられる。
これらのアルカリ土類金属塩は1種を単独で又は2種以上を組み合わせて含有させることができる。
中でも、EVOH樹脂の生産性の観点から、好ましくは水溶性塩である。さらに、EVOH樹脂組成物を溶融成形する際の成形性の観点から、アルカリ土類金属塩として、有機酸塩が好ましく、さらには炭素数1~6の脂肪族カルボン酸塩が好ましく、特には酢酸マグネシウムを用いることが好ましい。
その他の添加物としては、例えば、可塑剤、安定剤、フィラー、着色剤、滑剤、ブロッキング防止剤、帯電防止剤などが挙げられる。
イエローインデックス(YI)値が10以下であることで、樹脂ペレットの透明性が確保できる。イエローインデックス(YI)値は8以下であることがより好ましい。
かかる測定は、例えばペレットを直径35mm×高さ30mmの円柱型ガラス製セルに充填して測定用サンプルを作成し、かかるサンプルをJISZ-8722に準拠して分光色差計を用いて透過法にて測定することができる。
本発明のエチレン-ビニルアルコール系共重合体組成物ペレットの製造方法は、特に限定されるものではない。
上記(A)~(C)成分を配合する方法として、(1)エチレン-ビニルアルコール系共重合体(A)とアルカリ土類金属塩(C)をあらかじめ配合した組成物にポリアミド系樹脂(B)を配合する方法、(2)ポリアミド系樹脂(B)とアルカリ土類金属塩(C)をあらかじめ配合した組成物にエチレン-ビニルアルコール系共重合体(A)を配合する方法、(3)エチレン-ビニルアルコール系共重合体(A)、ポリアミド系樹脂(B)及びアルカリ土類金属塩(C)を一括して配合する方法、等が挙げられる。EVOH樹脂の物性改善効果と生産性の点で好ましくは(1)の方法である。
なお、かかる(1)の方法においては、i)含水率20~80質量%のEVOH樹脂の多孔性析出物を、アルカリ土類金属塩(C)の水溶液と接触させてから乾燥する方法;ii)EVOH樹脂の均一溶液(水/アルコール溶液等)にアルカリ土類金属塩(C)を含有させた後、凝固液中にストランド状に押し出し、次いで得られたストランドを切断してペレットとし、乾燥する方法;iii)EVOH樹脂とアルカリ土類金属塩(C)を一括して混合してから押出機等で溶融混練する方法が挙げられる。EVOH樹脂の物性改善効果と生産性の点で、好ましくはi)の方法である。
なお、組成物の温度の調整は、通常、押出機内のシリンダーの温度、及びスクリュー回転数を適宜設定することにより行うことができる。
また、押出機等の溶融混練装置から吐出された直後の樹脂ペレット(ストランド状の混練物)の温度は、通常268℃以下であり、好ましくは230~266℃、より好ましくは240~266℃である。吐出直後のペレット(ストランド)の温度をかかる範囲に調整することで、着色の発生を低減したエチレン-ビニルアルコール系共重合体組成物ペレットを得ることができる。
中でも、樹脂組成物のガスバリア性低下を抑制する目的から疎水性樹脂を用いることが好ましく、具体的にはポリオレフィン系樹脂が好ましく、特にはポリエチレン系樹脂、ポリプロピレン系樹脂が好ましい。
接着樹脂層としては、例えば、不飽和カルボン酸またはその無水物をオレフィン系重合体(上述のポリオレフィン系樹脂)に付加反応やグラフト反応等により化学的に結合させて得られるカルボキシル基を含有する変性オレフィン系重合体を挙げることができる。具体的には、無水マレイン酸グラフト変性ポリエチレン、無水マレイン酸グラフト変性ポリプロピレン、無水マレイン酸グラフト変性エチレン-プロピレン(ブロックおよびランダム)共重合体、無水マレイン酸グラフト変性エチレン-エチルアクリレート共重合体、無水マレイン酸グラフト変性エチレン-酢酸ビニル共重合体等から選ばれた1種または2種以上の混合物が好適なものとして挙げられる。このときの、熱可塑性樹脂に含有される不飽和カルボン酸又はその無水物の量は、通常0.001~3質量%であり、好ましくは0.01~1質量%、特に好ましくは0.03~0.5質量%である。変性物中の変性量が少ないと、接着性が不充分となる傾向があり、逆に多いと架橋反応を起こし、成形性が悪くなる傾向がある。
また、かかる多層構造体は、該多層構造体を製造する過程で発生する端部や不良品等を再溶融成形して得られる、EVOH樹脂組成物とEVOH樹脂以外の熱可塑性樹脂の混合物を含むリサイクル層を設けることが可能である。かかるリサイクル層をRとするとき、多層構造体の層構成は、例えばb/a/R、R/b/a、b/R/a/b、b/R/a/R/b、b/a/R/a/b、b/R/a/R/a/R/b等が挙げられる。
特にリサイクル層を設けることは、成形時に発生する多量のスクラップを有効に活用できる点で工業上好ましい。
他の熱可塑性樹脂層は通常10~6000μm、好ましくは20~4000μm、特に好ましくは100~2000μmである。他の熱可塑性樹脂層が薄すぎる場合、得られる成形物の剛性が低下する傾向があり、他の熱可塑性樹脂層が厚すぎる場合、得られる成形物の柔軟性や二次加工性が低下する傾向がある。
接着性樹脂層は通常1~100μm、好ましくは2~50μm、特に好ましくは5~40μmである。
また、各層の厚み比は、EVOH樹脂組成物層/他の熱可塑性樹脂層の厚み比が通常0.005以上1未満、好ましくは0.01以上1未満、特に好ましくは0.02~0.2であり、樹脂組成物層/接着性樹脂層の厚み比が通常0.2~100、好ましくは1~10、特に好ましくは1~5である。
なお、延伸については、公知の延伸方法でよく、例えば、一軸延伸、二軸延伸等が挙げられる。加熱延伸方法としては、ロール延伸法、テンター延伸法、チューブラー延伸法、共射出延伸ブロー法、深絞成形法、真空成形法、圧空成形法、真空圧空成形法、プラグアシスト式真空圧空成形法等のものが採用できる。二軸延伸の場合は同時二軸延伸方式、逐次二軸延伸方式のいずれの方式も採用できる。共射出延伸ブロー法の場合はコールドパリソン法、ホットパリソン法のいずれの方式も採用できる。延伸温度は、多層構造体の温度(多層構造体近傍温度)で、通常80~200℃、好ましくは100~160℃程度の範囲から選ばれる。延伸倍率は、面積比にて、通常2~100倍、好ましくは2~50倍である。
かかる容器は、一般的な食品の他、マヨネーズ、ドレッシング等の調味料、味噌等の発酵食品、サラダ油等の油脂食品、飲料、化粧品、医薬品、農薬品、工業薬品等の各種の包装容器として有用である。
尚、例中「部」、「%」とあるのは、断りのない限り質量基準を意味する。
含水EVOHの多孔性析出物を、アルカリ土類金属塩(C)の水溶液と接触させてから乾燥する方法により得られた、アルカリ土類金属塩(C)として酢酸マグネシウムを金属換算で35ppm含有するEVOH樹脂(A)(エチレン含有量29モル%、ケン化度99.6モル%、MFR4.1g/10分(210℃、荷重2160g)、融点185.6℃)を85部、ポリアミド系樹脂(B)としてナイロン6である「NOVAMID 1028EN」(商品名、三菱エンジニアリングプラスチックス株式会社製、融点220℃)を15部、及び酸化防止剤としてヒンダードフェノール系化合物(ペンタエリスリチル-テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]「Irganox1010」(商品名、チバ・ガイギー社製))を0.001部用いた。
なお、EVOH樹脂(A)とポリアミド系樹脂(B)の質量比(A)/(B)は85/15であり、アルカリ土類金属塩(C)の含有割合は、EVOH樹脂(A)とポリアミド系樹脂(B)の合計量に対して、金属換算で30ppmである。
これらを押出機に入れ、弱混練仕様スクリュー(株式会社日本製鋼所製)を用いて、窒素雰囲気下、スクリュー回転数が500rpm、ダイスの吐出口径が4.0mm、押出機のバレル温度(℃)がC2/C3/C4/C5/C6/C7/C8/C9/C10/C11/C12/C13/C14/C15=100/230/230/230/230/230/230/230/230/230/230/210/210/210となるように加熱し、エチレン-ビニルアルコール系共重合体組成物ペレットを作製した。
なお、かかる弱混練仕様スクリューとは、ニーディング領域を2か所有し、かかるニーディング領域のL/Dの総計が6.5であった。
また、ペレットを直径35mm×高さ30mmの円柱型ガラス製セルに充填し、3回タッピングしてから摺り切りイエローインデックス(YI)値測定用サンプルとした。得られたYI値測定用サンプルのイエローインデックス(YI)値を、JISZ-8722に準拠し、日本電色工業株式会社製「分光色差計 SE6000」(商品名)を用いて測定した。
また、押出機からの吐出量とスクリューモーターの電力値により溶融押出時の樹脂組成物の比エネルギーを求めた。
これらの結果を表1に示す。
実施例1において、溶融混練の条件を、スクリュー回転数を456rpm、押出機のバレルの温度(℃)をC2/C3/C4/C5/C6/C7/C8/C9/C10/C11/C12/C13/C14/C15=100/230/230/230/230/240/240/240/240/240/240/240/240/240とした以外は実施例1と同様に行い、エチレン-ビニルアルコール系共重合体組成物ペレットを作製した。
ダイス出口の吐出直後におけるストランドの温度、成形体のイエローインデックス(YI)値、比エネルギーを求め、結果を表1に示す。
実施例1において、溶融混練の条件を、押出機のバレルの温度(℃)をC2/C3/C4/C5/C6/C7/C8/C9/C10/C11/C12/C13/C14/C15=100/230/230/230/230/240/240/240/240/240/240/240/240/240とした以外は実施例1と同様に行い、エチレン-ビニルアルコール系共重合体組成物ペレットを作製した。
ダイス出口の吐出直後におけるストランドの温度、成形体のイエローインデックス(YI)値、比エネルギーを求め、結果を表1に示す。
実施例1において、スクリューとして通常仕様スクリュー(株式会社日本製鋼所製)を用いて、溶融混練の条件を、押出機のバレルの温度(℃)をC2/C3/C4/C5/C6/C7/C8/C9/C10/C11/C12/C13/C14/C15=100/230/230/230/230/240/240/240/240/240/240/240/240/240とした以外は実施例1と同様に行い、エチレン-ビニルアルコール系共重合体組成物ペレットを作製した。なお、かかる通常仕様スクリューとは、ニーディング領域を2か所有し、かかるニーディング領域のL/Dの総計が10.25であった。
ダイス出口の吐出直後におけるストランドの温度、成形体のイエローインデックス(YI)値、比エネルギーを求め、結果を表1に示す。
これにより、ダイス出口の吐出直後における樹脂温度を従来より低く調整し、特には268℃以下とすることで、着色の抑えられたエチレン-ビニルアルコール系共重合体組成物ペレットが得られることがわかった。
Claims (6)
- エチレン-ビニルアルコール系共重合体(A)、ポリアミド系樹脂(B)及びアルカリ土類金属塩(C)を含有するエチレン-ビニルアルコール系共重合体組成物ペレットであって、
前記ペレットを分光色差計にて透過法により測定したイエローインデックス(YI)値が10以下であるエチレン-ビニルアルコール系共重合体組成物ペレット。 - 前記エチレン-ビニルアルコール系共重合体(A)と前記ポリアミド系樹脂(B)の質量比((A)/(B))が、60/40~98/2である、請求項1に記載のエチレン-ビニルアルコール系共重合体組成物ペレット。
- 前記アルカリ土類金属塩(C)の含有割合が、前記エチレン-ビニルアルコール系共重合体(A)と前記ポリアミド系樹脂(B)の合計量に対して、金属換算で10~200ppmである、請求項1又は2に記載のエチレン-ビニルアルコール系共重合体組成物ペレット。
- さらに酸化防止剤を含む、請求項1~3のいずれか1項に記載のエチレン-ビニルアルコール系共重合体組成物ペレット。
- 請求項1~4のいずれか1項に記載のエチレン-ビニルアルコール系共重合体組成物ペレットが溶融成形されたエチレン-ビニルアルコール系共重合体組成物成形体。
- 分光色差計にて透過法により測定したときのイエローインデックス(YI)値が10以下であるエチレン-ビニルアルコール系共重合体組成物ペレットの製造方法であって、
エチレン-ビニルアルコール系共重合体(A)、ポリアミド系樹脂(B)及びアルカリ土類金属塩(C)を含有する樹脂組成物を溶融混練装置を用いて溶融混練する工程を含み、
前記溶融混練装置から吐出された直後のエチレン-ビニルアルコール系共重合体組成物ストランドの温度を268℃以下とするエチレン-ビニルアルコール系共重合体組成物ペレットの製造方法。
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US11091603B2 (en) * | 2017-03-06 | 2021-08-17 | Mitsubishi Chemical Corporation | Resin composition, and molding material and multilayer structure comprising same |
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TW201734120A (zh) | 2017-10-01 |
US20190010296A1 (en) | 2019-01-10 |
CN108473745A (zh) | 2018-08-31 |
EP3395889A4 (en) | 2019-08-14 |
JPWO2017110561A1 (ja) | 2018-10-11 |
JP7003407B2 (ja) | 2022-02-10 |
CN108473745B (zh) | 2022-07-08 |
TWI819997B (zh) | 2023-11-01 |
EP3395889A1 (en) | 2018-10-31 |
EP3395889B1 (en) | 2022-03-30 |
US11667761B2 (en) | 2023-06-06 |
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