WO2019130989A1 - エチレン-ビニルアルコール共重合体含有樹脂組成物、並びにそれからなる成形体及び包装材料 - Google Patents
エチレン-ビニルアルコール共重合体含有樹脂組成物、並びにそれからなる成形体及び包装材料 Download PDFInfo
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- WO2019130989A1 WO2019130989A1 PCT/JP2018/044240 JP2018044240W WO2019130989A1 WO 2019130989 A1 WO2019130989 A1 WO 2019130989A1 JP 2018044240 W JP2018044240 W JP 2018044240W WO 2019130989 A1 WO2019130989 A1 WO 2019130989A1
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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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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides 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
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/02—Wrappers or flexible covers
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- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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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
- 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
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
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- 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
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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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- 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
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Definitions
- the present invention relates to a resin composition containing an ethylene-vinyl alcohol copolymer as a main component, and a molded article and a packaging material using the resin composition.
- Ethylene-vinyl alcohol copolymer (hereinafter referred to as "EVOH”) has excellent gas barrier properties and melt moldability, so it can be molded into films, sheets, pipes, tubes, bottles, etc. by various melt molding methods. It is widely used as a packaging material in food and industrial fields where gas barrier properties are required. And in order to improve productivity in recent years, high-speed melt formability in high temperature compared with before is calculated
- melt molding at high temperature defects such as voids caused by low molecular weight volatile components inherent in the resin or generated by decomposition of the resin become problems. In particular, when a film is produced at a high temperature, voids are easily generated at the end of the film, which is one of the factors that lower the productivity.
- the moisture content of the EVOH resin composition is preferably 1.0% or less for the purpose of preventing molding problems such as generation of voids during melt molding, and excessive decomposition during melt molding is For the purpose of suppressing, it is described that 60 ⁇ mol / g or less of the alkaline earth metal ion in the EVOH resin composition is preferable.
- the demand for the quality of packaging materials is becoming severe, and there is a need for further improvement of the quality of flexible packaging materials, particularly in the food field.
- the present invention has been made based on the above circumstances, and an object thereof is to suppress the generation of voids even when melt molding is performed at high temperature, and a resin composition suitably used for high-speed melt molding process at high temperature To provide goods.
- the inventors of the present invention have found that, in a resin composition containing EVOH manufactured using an azonitrile-based polymerization initiator, the amount of nitrogen element derived from the polymerization initiator is It is found that generation of voids can be suppressed at the time of performing melt molding at high temperature when the ratio of the amount of nitrogen element is in a specific range before and after performing a reprecipitation operation within a specific range, leading to the present invention
- the invention made in order to solve the above-mentioned subject is as follows.
- the content is 20 to 60 mol%
- the degree of saponification is 85 mol% or more
- the amount of nitrogen element (NI) derived from the polymerization initiator is 5 to 60 ppm
- the following operation relative to the amount of nitrogen element (NI) A resin composition, wherein the ratio (NF / NI) of the amount of elemental nitrogen (NF) contained in the dried solid obtained by (X) is in the range of 0.65 to 0.99.
- the resin composition of the present invention can suppress the generation of voids even when melt molding is performed at high temperature, and is suitably used for high-speed melt molding process at high temperature.
- the resin composition of the present invention can be provided economically, it can be used for the production of various packaging materials.
- the illustrated material may be used individually by 1 type, and may use 2 or more types together.
- the resin composition of the present invention contains, as a main component, an ethylene-vinyl alcohol copolymer (A) (hereinafter sometimes abbreviated as EVOH (A)) produced using an azonitrile type polymerization initiator. .
- the nitrogen element amount (NI) derived from the polymerization initiator in the resin composition is 5 to 60 ppm, and the nitrogen element contained in the dried solid obtained by the following operation (X) with respect to the nitrogen element amount (NI)
- the ratio (NF / NI) of the amount (NF) needs to be 0.65 to 0.99.
- the coloring of the molded body obtained can be improved by satisfying the conditions described above for the elemental nitrogen content (NI) and the elemental nitrogen content (NF). .
- NI elemental nitrogen content
- NF elemental nitrogen content
- the ratio (NF / NI) is preferably in the range of 0.75 to 0.95.
- the elemental nitrogen content can be quantified by a trace total nitrogen analyzer.
- the amount of nitrogen element derived from the component is separately quantified, and the amount is measured with a trace total nitrogen analyzer. The net amount of nitrogen element derived from the polymerization initiator is calculated by subtracting from the measured amount.
- EVOH (A) is a main component of the resin composition of the present invention.
- EVOH (A) is a copolymer having an ethylene unit and a vinyl alcohol unit as main structural units.
- EVOH (A) also contains a vinyl ester unit as an optional component.
- EVOH (A) is usually obtained by polymerizing ethylene and a vinyl ester, and saponifying the resulting ethylene-vinyl ester copolymer.
- the ethylene unit content of EVOH (A) (that is, the ratio of the number of ethylene units to the total number of monomer units in EVOH (A)) needs to be 20 to 60 mol%. 22 mol% is preferable and 24 mol% of the minimum of ethylene unit content of EVOH (A) is more preferable. On the other hand, 55 mol% is preferable and 50 mol% of the upper limit of ethylene unit content of EVOH (A) is more preferable. If the ethylene unit content of EVOH (A) is less than 20 mol%, the gas barrier properties under high humidity may be lowered, and the melt moldability may also be deteriorated. Conversely, if the ethylene unit content of EVOH (A) exceeds 60 mol%, sufficient gas barrier properties may not be obtained.
- the degree of saponification of EVOH (A) (that is, the ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in EVOH (A)) needs to be 85 mol% or more. 95 mol% is preferable and, as for the minimum of the degree of saponification of EVOH (A), 99 mol% is more preferable. On the other hand, 100 mol% is preferable and 99.99 mol% of the upper limit of the saponification degree of EVOH (A) is more preferable. If the degree of saponification of EVOH (A) is less than 85 mol%, sufficient gas barrier properties may not be obtained, and the heat stability may be insufficient.
- EVOH (A) consists of a mixture of 2 or more types of EVOH in which ethylene unit content differs
- an average value computed from mixed mass ratio be ethylene unit content of EVOH (A).
- the difference in ethylene unit content between EVOHs having the ethylene unit content farthest apart be 30 mol% or less. 20 mol% or less is more preferable, and, as for the difference of ethylene unit content, 15 mol% or less is more preferable.
- the average value calculated from the mixed mass ratio is taken as the degree of saponification of EVOH (A).
- the difference between the degree of saponification between the most distant EVOHs is preferably 7% or less, more preferably 5% or less.
- the ethylene unit content is 24 mol% or more and less than 34 mol%, and saponification Containing EVOH (A-1) having an acidity of 99 mol% or more, and EVOH (A-2) having an ethylene unit content of 34 mol% or more and less than 50 mol% and having a degree of saponification of 99 mol% or more; It is also possible to use one having a mass ratio (A-1 / A-2) of EVOH (A-1) to EVOH (A-2) of 60/40 to 90/10 as the EVOH (A).
- the ethylene unit content and the degree of saponification of EVOH (A) can be determined by nuclear magnetic resonance (NMR) method.
- melt flow rate according to JIS K 7210: 2014 of EVOH (A) (hereinafter simply referred to as “MFR”; temperature 210 ° C., load 2160 g) is usually 0.1 g / 10 min, and the upper limit is , Usually 50 g / 10 min.
- EVOH (A) can contain, as copolymerized units, monomer units other than ethylene units, vinyl alcohol units and vinyl ester units, as long as the object of the present invention is not inhibited.
- the monomer include ⁇ -olefins such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene and 1-octene; itaconic acid, methacrylic acid, acrylic acid, and maleic acid Etc., unsaturated carboxylic acids thereof, their salts, their partial or complete esters, their nitriles, their amides, their anhydrides; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyl Vinylsilane compounds such as trimethoxysilane; unsaturated sulfonic acids or salts thereof; unsaturated thiols; vinylpyrrolidones.
- Contents of ethylene units, vinyl alcohol units and other monomer units other than vinyl ester units in EVOH (A) ie, the total number of other monomer units relative to the total number of monomer units in EVOH (A)
- the ratio of the numbers is usually 5 mol% or less, preferably 2 mol% or less, and more preferably 1 mol% or less.
- the resin composition contains EVOH (A) as the main component means that the content of EVOH (A) in the resin composition is 70% by mass or more, and 80% by mass or more Preferably, it is 90% by mass or more.
- EVOH (A) is the main component of the resin composition, the melt moldability of the obtained resin composition is improved, and the gas barrier properties, oil resistance, and the like of the molded article obtained therefrom become excellent.
- the resin composition of the present invention preferably further contains a metal ion (B).
- the resin composition of the present invention is excellent in interlayer adhesion when formed into a multilayer structure by containing the metal ion (B).
- the reason why the metal ion (B) improves the interlayer adhesion is not clear, but the molecule contained in the layer adjacent to the EVOH (A) has a functional group capable of reacting with the hydroxyl group of the EVOH (A). It is considered that this bond formation reaction is accelerated by the metal ion (B).
- the melt moldability and coloring tolerance of the resin composition obtained can be improved by controlling the content ratio with the carboxylic acid (C) mentioned later.
- 100 ppm is preferable and, as for the minimum of content of the metal ion (B) in the said resin composition, 150 ppm is more preferable.
- 400 ppm is preferable and, as for the upper limit of content of the metal ion (B) in the said resin composition, 350 ppm is more preferable. If the content of the metal ion (B) in the resin composition is less than 100 ppm, the interlayer adhesion of the resulting multilayer structure may be insufficient. On the other hand, when the content of the metal ion (B) in the resin composition is more than 400 ppm, the coloring resistance may be insufficient.
- the metal ion (B) examples include alkali metal ions, alkaline earth metal ions, other transition metal ions, and the like, and these may be made of one or more kinds. Among them, it is preferable to contain an alkali metal ion. It is more preferable that the metal ion (B) consists only of an alkali metal ion from the viewpoint that the resin composition can be easily produced and that the interlayer adhesion of the multilayer structure can be further improved.
- alkali metal ion examples include lithium, sodium, potassium, rubidium and cesium ions, but from the viewpoint of industrial availability, sodium or potassium ions are preferable.
- alkali metal salt which gives an alkali metal ion
- aliphatic carboxylates of lithium, sodium and potassium aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates and metal complexes
- sodium acetate, potassium acetate, sodium phosphate and potassium phosphate are more preferable in terms of easy availability.
- the metal ion (B) comprises an alkaline earth metal ion.
- the metal ion (B) contains an alkaline earth metal ion, the thermal deterioration of the EVOH (A) when the trim is reused is suppressed, and the generation of gel and lumps of the resulting molded body may be suppressed. is there.
- alkaline earth metal ion examples include ions of beryllium, magnesium, calcium, strontium and barium, but in terms of industrial availability, ions of magnesium or calcium are preferable.
- alkaline earth metal salts that give alkaline earth metal ions include aliphatic carboxylates of magnesium and calcium, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates and metal complexes. It can be mentioned.
- the resin composition of the present invention preferably further contains a carboxylic acid (C).
- a carboxylic acid (C) By containing the carboxylic acid (C), the resin composition of the present invention can improve the melt moldability of the obtained resin composition and the coloring resistance at high temperature.
- the pKa of the carboxylic acid (C) is in the range of 3.5 to 5.5, since the pH buffering capacity of the resulting resin composition may be enhanced and the coloring resistance to acidic substances and basic substances may be improved. It is more preferable that
- the content of the carboxylic acid (C) in the resin composition is less than 50 ppm, the color resistance at high temperatures may be insufficient.
- the content of the carboxylic acid (C) in the resin composition is more than 400 ppm, the melt moldability may be insufficient or the odor may be a problem.
- the content of the carboxylic acid salt is not considered as the content of the carboxylic acid (C) in the resin composition.
- carboxylic acid (C) monovalent carboxylic acid and polyvalent carboxylic acid can be mentioned, and these may consist of 1 type or multiple types.
- carboxylic acid (C) the melt-moldability of the obtained resin composition and the color resistance at high temperatures may be particularly improved.
- the polyvalent carboxylic acid may have three or more carboxyl groups. In this case, the coloring resistance of the resin composition of the present invention may be more effectively improved.
- a monovalent carboxylic acid is a compound having one carboxyl group in the molecule.
- the pKa of the monovalent carboxylic acid is preferably in the range of 3.5 to 5.5.
- These carboxylic acids may have a substituent such as a hydroxyl group, an amino group or a halogen atom.
- acetic acid is preferable because it is highly safe and easy to handle.
- the polyvalent carboxylic acid is a compound having two or more carboxyl groups in the molecule.
- polyvalent carboxylic acids having a pKa of at least one carboxyl group in the range of 3.5 to 5.5 are preferred.
- the resin composition of the present invention may contain other components as long as the effects of the present invention are not impaired.
- Other components include, for example, phosphoric acid compounds, boron compounds, thermoplastic resins other than EVOH (A), crosslinking agents, drying agents, oxidation accelerators, antioxidants, oxygen absorbers, plasticizers, lubricants, thermal stabilizers (Melting stabilizer), processing aids, surfactants, deodorizing agents, antistatic agents, UV absorbers, antifogging agents, flame retardants, pigments, dyes, fillers, fillers, reinforcing agents such as various fibers, etc.
- the lower limit of the content thereof in the resin composition is preferably 1 ppm, more preferably 10 ppm in terms of phosphoric acid.
- the upper limit of the content in the resin composition is preferably 200 ppm, more preferably 100 ppm, in terms of phosphoric acid.
- the phosphate may be in any form of primary phosphate, secondary phosphate or tertiary phosphate.
- the cationic species of the phosphate is also not particularly limited, but the cationic species is preferably an alkali metal or an alkaline earth metal. Among them, it is preferable to add a phosphoric acid compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.
- the lower limit of the content thereof in the resin composition is preferably 5 ppm in terms of boron element, and more preferably 10 ppm.
- the upper limit of the content in the resin composition is preferably 1,000 ppm in terms of boron element, and more preferably 500 ppm.
- boric acid includes, for example, orthoboric acid (H 3 BO 3 ), metaboric acid, and tetraboric acid
- boric acid esters include, for example, trimethyl borate and triethyl borate
- boric acid salt examples include alkali metal salts of the above-mentioned boric acids, alkaline earth metal salts, borax and the like. Among these, orthoboric acid is preferred.
- thermoplastic resins other than EVOH (A) for example, various polyolefins (polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene-propylene copolymer, ethylene and ⁇ -containing 4 or more carbon atoms can be used.
- the content of the thermoplastic resin in the resin composition is usually less than 30% by mass, preferably less than 20% by mass, and more preferably less than 10% by mass.
- a molded article containing the resin composition of the present invention is a preferred embodiment of the present invention.
- the resin composition may be a molded body having a single-layer structure, or may be a molded body of two or more multilayer structures, that is, a multilayer structure, along with other various substrates.
- a molding method for example, extrusion molding, thermoforming, profile forming, hollow molding, rotational molding, and injection molding are exemplified.
- the applications of the molded body of the present invention are various, and films, sheets, containers, bottles, tanks, pipes, hoses and the like are suitable.
- a film, a sheet, a pipe, a hose or the like may be extrusion molded by extrusion molding
- a container shape may be injection molded
- a hollow container such as a bottle or tank may be hollow molded or rotational molded. It can be molded.
- the hollow molding includes, for example, extrusion hollow molding in which a parison is molded by extrusion molding and blow molding the parison, and injection hollow molding in which a preform is molded by injection molding and blow molding thereof.
- a method of forming a packaging material such as a multilayer film by extrusion molding, and a method of thermoforming a multilayer sheet formed by extrusion molding into a container-like packaging material are suitably used.
- the said molded object is a multilayer structure containing the layer which consists of a resin composition of this invention.
- the said multilayer structure is obtained by laminating
- the layer configuration of the multilayer structure for example, when the layer composed of a resin other than the resin composition of the present invention is x layer, the resin composition layer of the present invention is y layer, and the adhesive resin layer is z layer, for example y, x / y / x, x / z / y, x / z / y / z / x, x / y / x / y / x, x / z / y / z / x / z / y / z / x etc.
- the types may be the same or different.
- each layer of the multilayer structure is not particularly limited, but the thickness ratio of the y layer to the total layer thickness is usually 2 to 20% from the viewpoint of formability and cost.
- the resin used for the x layer is preferably a thermoplastic resin from the viewpoint of processability and the like.
- the thermoplastic resin for example, various polyolefins (polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene-propylene copolymer, copolymer of ethylene and ⁇ -olefin having 4 or more carbon atoms) , Copolymers of polyolefin and maleic anhydride, ethylene-vinyl ester copolymers, ethylene-acrylic acid ester copolymers, or modified polyolefins obtained by graft-modifying these with unsaturated carboxylic acids or derivatives thereof), various polyamides (Nylon 6, nylon 6, 6 nylon 6/66 copolymer, nylon 11, nylon 12, polymethaxylylene adipamide etc), various polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate etc), polychlorinated Vinyl, poly Flu
- the thermoplastic resin layer may be unstretched, or may be uniaxially or biaxially stretched or rolled.
- thermoplastic resins polyolefin is preferable in terms of moisture resistance, mechanical properties, economy, heat sealability and the like, and polyamide and polyester are preferred in terms of mechanical properties, heat resistance and the like.
- the adhesive resin used in the z layer is not particularly limited as long as it can bond the respective layers, and a polyurethane-based or polyester-based one-component or two-component curable adhesive, carboxylic acid-modified polyolefin, etc. Is preferably used.
- the carboxylic acid-modified polyolefin is a polyolefin copolymer containing unsaturated carboxylic acid or its anhydride (maleic anhydride etc.) as a copolymer component; or graft obtained by grafting unsaturated carboxylic acid or its anhydride onto polyolefin It is a copolymer.
- Examples of the method for obtaining the multilayer structure of the present invention include coextrusion molding, coextrusion hollow molding, coinjection molding, extrusion lamination, coextrusion lamination, dry lamination, solution coating and the like.
- the multilayer structure obtained by such a method is further subjected to secondary processing after reheating within the range of the melting point of EVOH (A) by a method such as vacuum pressure deep drawing, blow molding, press molding, etc. It may be molded to have a desired molded body structure.
- the multilayer structure is uniaxially or biaxially stretched after reheating in the range of the melting point of EVOH (A) or less by a method such as roll stretching method, pantograph stretching method, inflation stretching method, etc. It is also possible to obtain a structure.
- EVOH (A) is produced using an azonitrile-based polymerization initiator, and the amount of nitrogen element (NI) derived from the polymerization initiator is 5 to 60 ppm, A resin composition is obtained in which the ratio (NF / NI) of the nitrogen element amount (NF) contained in the dried solid obtained by the following operation (X) to the element amount (NI) is 0.65 to 0.99 It is not particularly limited as long as it is a method.
- a copolymerization step (I) for obtaining ethylene-vinyl ester copolymer by copolymerizing ethylene and vinyl ester using an azonitrile type polymerization initiator ethylene-vinyl ester copolymer Saponification step (II) to obtain EVOH (A) by saponification
- resin composition including EVOH (A) by drying the water-containing pellets Drying step (IV) to obtain the product ethylene-vinyl ester copolymer by copolymerizing ethylene and vinyl ester using an azonitrile type polymerization initiator, ethylene-vinyl ester copolymer Saponification step (II) to obtain EVOH (A) by saponification
- granulation step (III) to obtain water-containing pellets of EVOH (A) by granulation operation
- the copolymerization step (I) As a method of controlling the nitrogen element amount (NI) and ratio (NF / NI) derived from the polymerization initiator, in the copolymerization step (I), type and amount of the polymerization initiator, temperature until addition and Adjusting the time, polymerization temperature, polymerization time, polymerization rate, type and amount of polymerization solvent, etc. In the saponification step (II), appropriately adjust the type and amount of alkali catalyst, reaction temperature, reaction time, etc.
- the paste concentration and temperature at which the paste of EVOH (A) is deposited, the composition and temperature of the coagulation bath, and immersing the water-containing pellet of EVOH (A) in the subsequent steps can be appropriately adjusted.
- the ratio (NF / NI) can be increased by immersing the water-containing pellet in an alcohol solvent such as methanol. At this time, the alcohol concentration is increased, the immersion temperature is increased, the immersion time is increased, the number of immersions is increased, agitation is performed during immersion, ultrasonic treatment is performed during immersion, or the like.
- the ratio (NF / NI) can be more effectively increased.
- each component such as metal ion (B) and carboxylic acid (C) into the resin composition of the present invention
- a method of incorporating each component such as metal ion (B) and carboxylic acid (C) into the resin composition of the present invention for example, a method of mixing the above-mentioned pellet together with each component and melt-kneading, The method of mixing each component, the method of making the said pellet immerse in the solution in which each component is contained, etc. are mentioned. At this time, both water-containing pellets and dry pellets can be used as the pellets.
- ⁇ Copolymerization step (I)> in addition to the step of copolymerization of ethylene and vinyl ester, a polymerization inhibitor is optionally added, and then unreacted ethylene and unreacted vinyl ester are removed to give ethylene-vinyl ester co-weight Including the step of obtaining a combined solution.
- the copolymerization method of ethylene and vinyl ester include known methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization.
- Typical vinyl esters used for polymerization include vinyl acetate, but other aliphatic vinyl esters such as vinyl propionate and vinyl pivalate can also be used.
- the polymerization temperature is preferably 20 to 90 ° C., and more preferably 40 to 70 ° C.
- the polymerization time is usually 2 to 15 hours.
- the polymerization rate is preferably 10 to 90%, more preferably 30 to 80%, with respect to the charged vinyl ester.
- the resin content in the solution after polymerization is usually 5 to 85% by mass.
- the azonitrile type polymerization initiator can control the 10-hour half-life temperature and the solubility in a solvent by the molecular skeleton.
- the process can be performed safely and stably.
- azonitrile type polymerization initiators examples include 4,4′-azobis (4-cyanovaleric acid), 1,1′-azobis (cyclohexane-1-carbonitrile), and 2,2′-azobis (2-methylbutyl). , 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvalero) Nitrile etc. can be mentioned.
- 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2 , 4-Dimethylvaleronitrile) can be preferably used.
- an alkali catalyst is added to the ethylene-vinyl ester copolymer solution to saponify the copolymer in the solution to obtain EVOH (A).
- the saponification method may be either continuous or batch.
- the alkali catalyst include sodium hydroxide, potassium hydroxide and alkali metal alcoholates.
- it is generally carried out to add an acid such as acetic acid to neutralize the remaining alkali catalyst.
- ⁇ Granulation process (III)> As the operation of granulation, for example, (1) a method of extruding a solution of EVOH (A) into a low temperature poor solvent to precipitate or coagulate, and cooling or solidifying immediately after cooling, (2) EVOH (A) The solution of (iii) is brought into contact with steam, and cut in advance as a water-containing resin composition of EVOH (A).
- the water content of the water-containing pellet of EVOH (A) obtained by these methods is preferably 50 to 200 parts by mass, and 70 to 150 parts by mass with respect to 100 parts by mass of EVOH (A). It is more preferable that It is also generally performed that the obtained water-containing pellet is subjected to washing treatment with a solvent, additive treatment, and the like, as necessary.
- the water-containing pellet of EVOH (A) obtained in the granulation step is preferably dried to obtain a dry pellet of EVOH (A).
- the content of water in the dry pellet is preferably 1.0 part by mass or less with respect to 100 parts by mass of EVOH (A), for the purpose of preventing forming problems such as generation of voids during forming processing.
- the content is more preferably 5 parts by mass or less, still more preferably 0.3 parts by mass or less.
- a method of drying the water-containing pellet for example, stationary drying or fluid drying can be mentioned. These drying methods may be used alone or in combination of two or more.
- the drying process may be carried out by either a continuous system or a batch system, and in the case of combining a plurality of drying systems, a continuous system or a batch system can be freely selected for each drying system. It is also preferable to carry out the drying at a low oxygen concentration or in the absence of oxygen from the viewpoint of reducing the deterioration of the resin composition due to the oxygen during the drying.
- the resin composition of the present invention can suppress the generation of voids even when melt molding is performed at high temperature, it is suitably used for a high-speed melt molding process at high temperature. Also, the resin composition of the present invention can be provided economically. Therefore, the resin composition of the present invention is formed into a film, a sheet, a container, etc., and is suitably used as various packaging materials.
- the packaging material which has a molded object containing the resin composition of this invention is a more preferable embodiment of this invention.
- Ethylene unit content and degree of saponification of EVOH (A) The dried pellet was dissolved in dimethyl sulfoxide (DMSO-d 6 ) containing tetramethylsilane (TMS) as an internal standard substance and trifluoroacetic acid (TFA) as an additive. It melts and it measures at 80 ° C using 1 H-NMR (made by Nippon Denshi Co., Ltd .: "GX-500”) of 500 MHz, According to the peak intensity ratio of an ethylene unit, a vinyl alcohol unit, and a vinyl ester unit, ethylene unit content is included. The amount and degree of saponification were determined.
- DMSO-d 6 dimethyl sulfoxide
- TMS tetramethylsilane
- TSA trifluoroacetic acid
- Amount of elemental nitrogen (NF) contained in the dried solid obtained by operation (X) A solution formed by dissolving 5 g of dry pellets in 100 g of 1,1,1,3,3,3-hexafluoro-2-propanol is dropped into 1000 g of methanol (20 ° C.) under stirring to form a precipitate. Separated. From the dried solid obtained by drying this precipitate at 100 ° C for 24 hours, 20 mg is weighed, and the nitrogen element is determined by a trace nitrogen / sulfur analyzer (using “TS-2100H type” manufactured by Mitsubishi Chemical Analytech Co., Ltd.) The amount of elemental nitrogen (NF) in the dried solid was determined.
- Void evaluation A dry pellet was formed into a film under the following conditions to obtain a 30 cm wide single layer film. With respect to a single layer film obtained one hour after the start of film formation, the void generation state was visually confirmed and evaluated based on the criteria of A to D below, to be an index of void evaluation.
- the YI value is an index showing the yellowness (yellowness) of the object, and the higher the YI value, the stronger the yellowness, while the lower the YI value, the weaker the yellowness and the less coloring.
- the YI range of the roll end face is determined by comparing the hue of the roll end face for 200 m of the single layer film obtained in (6) with the hue of the prepared disk-like sample. It is used as an index of color tolerance by evaluating it on the basis.
- LLDPE linear low density polyethylene
- adhesive resin Densilicate resin
- the extruder and extrusion conditions, and the die used were as follows.
- LLDPE Single screw extruder (Plastic Engineering Research Institute Ltd.
- Die Coat hanger die for 300 mm width 3 types and 5 layers (Plastic Engineering Research Institute Co., Ltd.)
- Synthesis Example 1 The ethylene-vinyl acetate copolymer was polymerized under the following raw materials and conditions using a 250 L pressure reaction tank. ⁇ Vinyl acetate: 83.0 kg ⁇ Methanol: 26.6 kg -Initial supply of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (2.5 g / L in methanol): 362 mL, continuous supply: 1120 mL / hr Polymerization temperature: 60 ° C. -Polymerization tank ethylene pressure: 3.6MPa When the polymerization rate of vinyl acetate reached about 40%, sorbic acid was added and the polymerization was stopped by cooling.
- the reaction tank is opened to deethyleneize, and then the reaction liquid is supplied to a purge tower, and unreacted vinyl acetate is removed from the tower top by introduction of methanol vapor from the lower portion of the tower, and the ethylene-vinyl acetate copolymer Methanol solution was obtained.
- This solution is charged into a saponification reactor, sodium hydroxide / methanol solution (80 g / L) is added so that the molar ratio of sodium hydroxide to vinyl ester units in the copolymer is 0.7, and methanol is added. To adjust the copolymer concentration to 15%. The temperature of this solution was raised to 60 ° C., and a saponification reaction was allowed to occur for about 4 hours while blowing nitrogen gas into the reactor.
- the saponification reaction was stopped by adding acetic acid and water to obtain an EVOH suspension.
- the suspension was drained by a centrifugal drainer and then dried at 60 ° C. for 24 hours to obtain a crude dry of EVOH having an ethylene unit content of 32 mol% and a degree of saponification of 99.9 mol%.
- Synthesis Example 2 A crude EVOH having an ethylene unit content of 24 mol% and a degree of saponification of 99.9 mol% by the same operation as in Synthesis Example 1 except that the polymerization conditions of the ethylene-vinyl acetate copolymer were changed as follows: A dry product was obtained. ⁇ Vinyl acetate: 102.0 kg ⁇ Methanol: 17.7 kg -Initial supply of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (2.5 g / L in methanol): 280 mL, continuous supply: 850 mL / hr Polymerization temperature: 60 ° C. -Polymerization tank ethylene pressure: 2.9MPa
- Synthesis Example 3 A crude dry product of EVOH having an ethylene unit content of 27 mol% and a degree of saponification of 99.9 mol% by the same operation as in Synthesis Example 1 except that the conditions for polymerization of the ethylene-vinyl acetate copolymer were changed to the following I got ⁇ Vinyl acetate: 85.2 kg ⁇ Methanol: 32.3 kg ⁇
- Synthesis Example 4 A crude dry product of EVOH having an ethylene unit content of 44 mol% and a degree of saponification of 99.9 mol% by the same operation as in Synthesis Example 1 except that the conditions for polymerization of the ethylene-vinyl acetate copolymer were changed to the following I got ⁇ Vinyl acetate: 76.7 kg ⁇ Methanol: 11.0 kg ⁇
- Synthesis Example 5 A crude dry product of EVOH having an ethylene unit content of 32 mol% and a degree of saponification of 99.9 mol% by the same operation as in Synthesis Example 1 except that the conditions for polymerization of the ethylene-vinyl acetate copolymer were changed to the following I got ⁇ Vinyl acetate: 105.0 kg ⁇ Methanol: 38.3 kg -Initial supply of 2,2'-azobis (2,4-dimethyl valeronitrile) (10.0 g / L solution in methanol): 2440 mL, continuous supply: none-Polymerization temperature: 60 ° C -Polymerization tank ethylene pressure: 3.7MPa
- Synthesis Example 6 The same operation as in Synthesis Example 5 except that the concentration of a methanol solution of 2,2'-azobis (2,4-dimethylvaleronitrile) was 20.0 g / L and the solution was used after storage at 51 ° C for 10 hours As a result, a crude dried product of EVOH having an ethylene unit content of 32 mol% and a degree of saponification of 99.9 mol% was obtained.
- Example 3 When repeating the procedure of immersion and washing in methanol at 50 ° C. for 1 hour while repeating washing three times, dry pellets are manufactured and analyzed and evaluated in the same manner as in Example 1 except that ultrasonic waves are applied. Did.
- Example 9 A dry pellet was produced by the same operation as Example 1 except that the crude dried product of EVOH obtained in the above Synthesis Example 5 was used, and analysis and evaluation were performed.
- Example 10 A dry pellet was manufactured by the same operation as Example 2 except that the crude dried product of EVOH obtained in the above Synthesis Example 5 was used, and analysis and evaluation were performed.
- Example 11 A dry pellet was manufactured by the same operation as Example 1 except that the crude dried product of EVOH obtained in the above Synthesis Example 6 was used, and analysis and evaluation were performed.
- Example 12 to 16 The dry pellet is manufactured and analyzed and evaluated in the same manner as in Example 1 except that the type and concentration of each component of the aqueous solution for immersion treatment are adjusted so that the content of the components will be as described in Table 1. went.
- Comparative Example 1 The dried pellet was manufactured, analyzed and evaluated in the same manner as in Example 1 except that the operation of immersion in 50 ° C. methanol for 1 hour while stirring and washing was not repeated three times.
- Comparative Example 6 A dry pellet was manufactured by the same operation as Comparative Example 1 except that the crude dried product of EVOH obtained in the above Synthesis Example 5 was used, and analysis and evaluation were performed.
- Comparative Example 7 The dried pellet was manufactured by the same operation as Example 2 except that the crude dried product of EVOH obtained in the above Synthesis Example 6 was used, and analysis and evaluation were performed.
- Comparative Example 8 A dry pellet was manufactured by the same operation as Comparative Example 1 except that the crude dried product of EVOH obtained in the above Synthesis Example 6 was used, and analysis and evaluation were performed.
Abstract
Description
操作(X):5gの樹脂組成物を100gの1,1,1,3,3,3-ヘキサフルオロ-2-プロパノールに溶解させた溶液を、攪拌下にある1000gのメタノールに滴下して、生成した沈殿を分離した後乾燥して乾燥固形物を得る。
(2) 前記比率(NF/NI)が0.75~0.95である、(1)に記載の樹脂組成物。
(3) さらに金属イオン(B)を100~400ppm含有する、(1)または(2)に記載の樹脂組成物。
(4) さらにカルボン酸(C)を50~400ppm含有する、(1)~(3)のいずれかに記載の樹脂組成物。
(5) (1)~(4)のいずれかに記載の樹脂組成物を含む成形体。
(6) 多層構造体である、(5)に記載の成形体。
(7) (5)または(6)に記載の成形体を有する包装材料。
本発明の樹脂組成物は、アゾニトリル系重合開始剤を用いて製造されるエチレン-ビニルアルコール共重合体(A)(以下、EVOH(A)と略記することがある。)を主成分として含有する。前記樹脂組成物中の前記重合開始剤に由来する窒素元素量(NI)が5~60ppmであり、窒素元素量(NI)に対する、下記操作(X)により得られる乾燥固形物に含まれる窒素元素量(NF)の比率(NF/NI)が0.65~0.99である必要がある。
操作(X):5gの樹脂組成物を100gの1,1,1,3,3,3-ヘキサフルオロ-2-プロパノールに溶解させた溶液を、攪拌下にある1000gのメタノールに滴下して、生成した沈殿を分離した後乾燥して乾燥固形物を得る。
EVOH(A)は、本発明の樹脂組成物の主成分である。EVOH(A)は、主構造単位として、エチレン単位及びビニルアルコール単位を有する共重合体である。またEVOH(A)は、任意成分としてビニルエステル単位を含有する。EVOH(A)は、通常、エチレンとビニルエステルとを重合し、得られるエチレン-ビニルエステル共重合体をけん化して得られる。
本発明の樹脂組成物が、さらに金属イオン(B)を含有することが好ましい。本発明の樹脂組成物は金属イオン(B)を含有することで、多層構造体とした時の層間接着性に優れる。金属イオン(B)が層間接着性を向上させる理由は明らかではないが、EVOH(A)と隣接する層に含まれる分子が、EVOH(A)のヒドロキシ基と反応し得る官能基を有する場合には、この結合生成反応が金属イオン(B)によって加速されることが考えられる。また、後述するカルボン酸(C)との含有比率を制御することで、得られる樹脂組成物の溶融成形性や着色耐性を改善できる。
本発明の樹脂組成物が、さらにカルボン酸(C)を含有することが好ましい。本発明の樹脂組成物はカルボン酸(C)を含有することで、得られる樹脂組成物の溶融成形性や高温下での着色耐性を改善できる。特に、得られる樹脂組成物のpH緩衝能力が高まり、酸性物質や塩基性物質に対する着色耐性を改善できる場合がある点から、カルボン酸(C)のpKaが3.5~5.5の範囲にあることがより好ましい。
本発明の樹脂組成物には、本発明の効果を損なわない範囲でその他の成分を含有してもよい。その他の成分としては、例えばリン酸化合物、ホウ素化合物、EVOH(A)以外の熱可塑性樹脂、架橋剤、乾燥剤、酸化促進剤、酸化防止剤、酸素吸収剤、可塑剤、滑剤、熱安定剤(溶融安定剤)、加工助剤、界面活性剤、脱臭剤、帯電防止剤、紫外線吸収剤、防曇剤、難燃剤、顔料、染料、フィラー、充填剤、各種繊維等の補強剤等が挙げられる。
リン酸化合物を含有する場合、樹脂組成物中のその含有量の下限は、リン酸根換算で1ppmが好ましく、10ppmがより好ましい。一方、樹脂組成物中の前記含有量の上限は、リン酸根換算で200ppmが好ましく、100ppmがより好ましい。この範囲でリン酸化合物を含有することで、樹脂組成物の熱安定性を改善できる。特に、長時間にわたって溶融成形を行う際のゲル状ブツの発生や着色を抑制できる場合がある。
ホウ素化合物を含有する場合、樹脂組成物中のその含有量の下限は、ホウ素元素換算で5ppmが好ましく、10ppmがより好ましい。一方、樹脂組成物中の前記含有量の上限は、ホウ素元素換算で1,000ppmが好ましく、500ppmがより好ましい。この範囲でホウ素化合物を含有することで、樹脂組成物の溶融成形時の熱安定性を向上でき、ゲル状ブツの発生が抑制できる場合がある。また、得られる成形体の機械的性質が向上する場合もある。これらの効果は、EVOH(A)とホウ素化合物との間にキレート相互作用が発生することに起因すると推測される。
本発明の樹脂組成物を含む成形体が本発明の好適な実施態様である。前記樹脂組成物は、単層構造の成形体とすることもできるし、他の各種基材と共に2種以上の多層構造の成形体、すなわち多層構造体とすることもできる。成形方法としては、例えば押出成形、熱成形、異形成形、中空成形、回転成形、射出成形が例示される。本発明の成形体の用途は多岐にわたり、フィルム、シート、容器、ボトル、タンク、パイプ、ホース等が好適である。
前記成形体が本発明の樹脂組成物からなる層を含む多層構造体であることが好ましい。当該多層構造体は、本発明の樹脂組成物からなる層と他の層とを積層して得られる。当該多層構造体の層構成としては、本発明の樹脂組成物以外の樹脂からなる層をx層、本発明の樹脂組成物層をy層、接着性樹脂層をz層とすると、例えばx/y、x/y/x、x/z/y、x/z/y/z/x、x/y/x/y/x、x/z/y/z/x/z/y/z/x等が挙げられる。複数のx層、y層、z層を設ける場合は、その種類は同じであっても異なっていてもよい。また、成形時に発生するトリム等のスクラップからなる回収樹脂を用いた層を別途設けてもよいし、回収樹脂を他の樹脂からなる層にブレンドしてもよい。当該多層構造体の各層の厚さ構成は、特に限定されるものではないが、成形性及びコスト等の観点から、全層厚さに対するy層の厚さ比は通常2~20%である。
本発明の樹脂組成物の製造方法としては、アゾニトリル系重合開始剤を用いてEVOH(A)の製造を行い、前記重合開始剤に由来する窒素元素量(NI)が5~60ppmであり、窒素元素量(NI)に対する、下記操作(X)により得られる乾燥固形物に含まれる窒素元素量(NF)の比率(NF/NI)が0.65~0.99である樹脂組成物が得られる方法であれば特に限定されない。
操作(X):5gの樹脂組成物を100gの1,1,1,3,3,3-ヘキサフルオロ-2-プロパノールに溶解させた溶液を、攪拌下にある1000gのメタノールに滴下して、生成した沈殿を分離した後乾燥して乾燥固形物を得る。
共重合工程は、エチレンとビニルエステルとの共重合の工程に加え、必要に応じて重合禁止剤を添加し、それに続いて未反応エチレン、未反応ビニルエステルを除去してエチレン-ビニルエステル共重合体溶液を得る工程を含む。エチレンとビニルエステルとの共重合方法としては、例えば溶液重合、懸濁重合、乳化重合、バルク重合などの公知の方法が挙げられる。重合に用いられる代表的なビニルエステルとして酢酸ビニルが挙げられるが、その他の脂肪族ビニルエステル、例えばプロピオン酸ビニルやピバリン酸ビニルも使用できる。他にも、共重合し得る単量体を少量共重合させることができる。重合温度としては、20~90℃が好ましく、40~70℃がより好ましい。重合時間は、通常2~15時間である。重合率は、仕込みのビニルエステルに対して10~90%が好ましく、30~80%がより好ましい。重合後の溶液中の樹脂分は、通常5~85質量%である。
次に、エチレン-ビニルエステル共重合体溶液にアルカリ触媒を添加し、溶液中の共重合体をけん化してEVOH(A)を得る。けん化方法は、連続式、回分式のいずれも可能である。アルカリ触媒としては、例えば水酸化ナトリウム、水酸化カリウム、アルカリ金属アルコラートが挙げられる。また、けん化工程の後に、酢酸等の酸を添加して残存するアルカリ触媒を中和することも一般に行われる。
造粒の操作としては、例えば、(1)EVOH(A)の溶液を低温の貧溶媒中に押出して析出又は凝固させ、冷却固化させた後又は直後にカットする方法、(2)EVOH(A)の溶液を水蒸気と接触させて予めEVOH(A)の含水樹脂組成物としてカットする方法が挙げられる。これらの方法により得られたEVOH(A)の含水ペレット中の水の含有量は、EVOH(A)100質量部に対して、50~200質量部であることが好ましく、70~150質量部であることがより好ましい。得られた含水ペレットに対し、必要に応じて溶媒による洗浄処理や添加剤処理などを行うことも一般に行われる。
造粒工程で得られたEVOH(A)の含水ペレットは、乾燥することでEVOH(A)の乾燥ペレットとすることが好ましい。乾燥ペレット中の水の含有量は、成形加工時のボイドの発生といった成形トラブルを防ぐ目的から、EVOH(A)100質量部に対して、1.0質量部以下であることが好ましく、0.5質量部以下であることがより好ましく、0.3質量部以下であることがさらに好ましい。含水ペレットの乾燥方法としては、例えば静置乾燥や流動乾燥が挙げられる。これらの乾燥方法は単独で用いてもよいし、複数を組み合わせて用いてもよい。乾燥処理は連続式、バッチ式いずれの方法で行っても良く、複数の乾燥方式を組み合わせて行う場合は、各乾燥方式について連続式、バッチ式を自由に選択できる。乾燥を低酸素濃度或いは無酸素状態で行うことも、乾燥中の酸素による樹脂組成物の劣化を低減できる点で好ましい。
乾燥ペレットを、内部標準物質としてテトラメチルシラン(TMS)、添加剤としてトリフルオロ酢酸(TFA)を含むジメチルスルホキシド(DMSO-d6)に溶解し、500MHzの1H-NMR(日本電子株式会社製:「GX-500」)を用いて80℃で測定し、エチレン単位、ビニルアルコール単位、ビニルエステル単位のピーク強度比より、エチレン単位含有量及びけん化度を求めた。
乾燥ペレット約20mgを秤量し、微量窒素・硫黄分析装置(三菱ケミカルアナリテック社製「TS-2100H型」を使用)により窒素元素を定量し、乾燥ペレット(樹脂組成物)中の窒素元素量(NI)を求めた。
乾燥ペレット5gを100gの1,1,1,3,3,3-ヘキサフルオロ-2-プロパノールに溶解させた溶液を、攪拌下にある1000gのメタノール(20℃)に滴下して、生成した沈殿を分離した。この沈殿を100℃で24時間乾燥して得られた乾燥固形物から20mgを秤量し、微量窒素・硫黄分析装置(三菱ケミカルアナリテック社製「TS-2100H型」を使用)により窒素元素を定量し、乾燥固形物中の窒素元素量(NF)を求めた。
乾燥ペレット0.5gをテフロン(登録商標)製圧力容器に入れ、ここに濃硝酸5mLを加えて室温で30分間分解させた。分解後に蓋をし、湿式分解装置により150℃で10分間、次いで180℃で5分間加熱することでさらに分解を行い、その後、室温まで冷却した。得られた処理液を50mLのメスフラスコに移し純水でメスアップした溶液について、ICP発光分光分析装置により各金属イオンを定量した。なお、リン酸化合物、ホウ素化合物の含有量も同様の方法で定量することができる。
乾燥ペレット10gと純水50mLを共栓付き100mL三角フラスコに投入し、冷却コンデンサーを付け、95℃で8時間撹拌した。得られた抽出液を20℃まで冷却した後、フェノールフタレインを指示薬として、0.02モル/Lの水酸化ナトリウム水溶液で滴定することにより、カルボン酸(C)を定量した。
乾燥ペレットを以下の条件で製膜して幅30cmの単層フィルムを得た。製膜開始から1時間後に得られた単層フィルムについて、ボイド発生状況を目視で確認し、下記のA~Dの基準で評価することでボイド評価の指標とした。
<製膜条件>
押出機:東洋精機製作所社製20mm押出機「D2020」
スクリュー:フルフライトスクリュー、L/D=20、圧縮比=2.0
押出温度:供給部/圧縮部/計量部/ダイ=180/280/280/280℃
スクリュー回転数:20rpm
引取りロール温度:80℃
引取りロール速度:フィルム厚みが20μmとなるように調節
<評価>
A:ボイドは観察されない、または端部から1cm以内の領域にボイドが散見されたが、それより内側にボイドが観察されなかった
B:端部から1cmを超えて2cm以内の領域にボイドが散見されたが、それより内側にボイドが確認されなかった
C:端部から2cmを超えて4cm以内の領域にボイドが散見されたが、それより内側にボイドが確認されなかった
D:端部から4cmより内側にボイドが確認された
各実施例及び比較例で得た乾燥ペレット10gを用いて、加熱圧縮プレス装置にて220℃で6分間加熱溶融させて、厚み3mmの円盤状サンプルを作製した。この円盤状サンプルを複数作成し、YI(イエローインデックス)がそれぞれ10、15、20となる円盤状サンプルを用意した。なお、YIは、乾燥ペレットを製造する際の120℃で行う乾燥時間を変更することにより調整した。円盤状サンプルのYIは、HunterLab社製「LabScan XE Sensor」を用いて測定した。なお、YI値は対象物の黄色度(黄色み)を表す指標であり、YI値が高いほど黄色度が強く、一方、YI値が低いほど黄色度が弱く、着色が少ないことを表している。
次に、(6)で得た単層フィルム200m分のロール端面の色相と、上記用意した円盤状サンプルの色相とを比較することでロール端面のYI範囲を判定し、下記のA~Cの基準で評価することで着色耐性の指標とした。
A :10未満
B :10以上15未満
C :15以上
乾燥ペレット、直鎖状低密度ポリエチレン(日本ポリエチレン社製ノバテックLL-UF943。以下LLDPEと略記する。)及び接着性樹脂(デュポン社製バイネルCXA417E107質量部とLLDPE93質量部の混合物。以下Adと略記する。)を用い、3種5層の多層フィルム(LLDPE/Ad/EVOH/Ad/LLDPE=50μm/10μm/10μm/10μm/50μm)を製膜した。押出機及び押出条件、使用したダイは下記の通りとした。
押出機:
EVOH:単軸押出機(東洋精機株式会社 ラボ機ME型CO-EXT)
口径20mmφ、L/D20、フルフライトスクリュー
供給部/圧縮部/計量部/ダイ=175/210/220/220℃
LLDPE:単軸押出機(株式会社プラスチック工学研究所 GT-32-A)
口径32mmφ、L/D28、フルフライトスクリュー
供給部/圧縮部/計量部/ダイ=150/200/210/220℃
Ad:単軸押出機(株式会社テクノベル SZW20GT-20MG-STD)
口径20mmφ、L/D20、フルフライトスクリュー
供給部/圧縮部/計量部/ダイ=150/200/220/220℃
ダイ:300mm幅3種5層用コートハンガーダイ(プラスチック工学研究所社製)
A :500g/15mm以上
B :300g/15mm以上500g/15mm未満
C :300g/15mm未満
250Lの加圧反応槽を用いて以下の原料及び条件でエチレン-酢酸ビニル共重合体を重合した。
・酢酸ビニル:83.0kg
・メタノール:26.6kg
・2,2′-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)(2.5g/Lメタノール溶液)初期供給量:362mL、連続供給量:1120mL/hr
・重合温度:60℃
・重合槽エチレン圧力:3.6MPa
酢酸ビニルの重合率が約40%となったところでソルビン酸を添加して冷却して重合を停止した。次いで、反応槽を開放して脱エチレンした後に反応液を追出塔に供給し、塔下部からのメタノール蒸気の導入により未反応酢酸ビニルを塔頂より除去して、エチレン-酢酸ビニル共重合体のメタノール溶液を得た。この溶液をケン化反応器に仕込み、水酸化ナトリウム/メタノール溶液(80g/L)を、共重合体中のビニルエステル単位に対する水酸化ナトリウムのモル比が0.7となるように添加し、メタノールを加えて共重合体濃度が15%になるように調整した。この溶液を60℃に昇温し、反応器内に窒素ガスを吹き込みながら約4時間けん化反応させた。その後、酢酸と水を添加してけん化反応を停止させ、EVOH懸濁液を得た。この懸濁液を遠心脱液機により脱液し、次いで60℃で24時間乾燥させることでエチレン単位含有量32モル%、けん化度99.9モル%のEVOHの粗乾燥物を得た。
前記エチレン-酢酸ビニル共重合体の重合時の条件を下記のとおり変更した以外は、合成例1と同様の操作により、エチレン単位含有量24モル%、けん化度99.9モル%のEVOHの粗乾燥物を得た。
・酢酸ビニル:102.0kg
・メタノール:17.7kg
・2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)(2.5g/Lメタノール溶液)初期供給量:280mL、連続供給量:850mL/hr
・重合温度:60℃
・重合槽エチレン圧力:2.9MPa
前記エチレン-酢酸ビニル共重合体の重合時における条件を下記に変更した以外は合成例1と同様の操作により、エチレン単位含有量27モル%、けん化度99.9モル%のEVOHの粗乾燥物を得た。
・酢酸ビニル:85.2kg
・メタノール:32.3kg
・2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)(2.5g/Lメタノール溶液)初期供給量:310mL、連続供給量:950mL/hr
・重合温度:60℃
・重合槽エチレン圧力:2.9MPa
前記エチレン-酢酸ビニル共重合体の重合時における条件を下記に変更した以外は合成例1と同様の操作により、エチレン単位含有量44モル%、けん化度99.9モル%のEVOHの粗乾燥物を得た。
・酢酸ビニル:76.7kg
・メタノール:11.0kg
・2,2′-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)(2.5g/Lメタノール溶液)初期供給量:510mL、連続供給量:1570mL/hr
・重合温度:60℃
・重合槽エチレン圧力:5.5MPa
前記エチレン-酢酸ビニル共重合体の重合時における条件を下記に変更した以外は合成例1と同様の操作により、エチレン単位含有量32モル%、けん化度99.9モル%のEVOHの粗乾燥物を得た。
・酢酸ビニル:105.0kg
・メタノール:38.3kg
・2,2’-アゾビス(2,4-ジメチルバレロニトリル)(10.0g/Lメタノール溶液)初期供給量:2440mL、連続供給量:なし
・重合温度:60℃
・重合槽エチレン圧力:3.7MPa
2,2’-アゾビス(2,4-ジメチルバレロニトリル)のメタノール溶液の濃度を20.0g/Lとし、当該溶液を51℃で10時間保存した後に使用した以外は合成例5と同様の操作により、エチレン単位含有量32モル%、けん化度99.9モル%のEVOHの粗乾燥物を得た。
上記合成例1で得られたEVOHの粗乾燥物を、固形分40質量%となるように水/メタノール=40/60(質量比)の混合溶媒に入れ、60℃で6時間攪拌して溶解させ、直径4mmのノズルより、0℃に調整した水/メタノール=90/10(質量比)の析出浴中に連続的に押出してストランド状に析出させた。このストランドをペレタイザーに導入して多孔質の含水ペレットを得た。この含水ペレットを50℃のメタノールに1時間、攪拌しながら浸漬させて洗浄する操作を3度繰り返し、次いで酢酸水溶液及びイオン交換水を用いて洗浄した後、酢酸ナトリウム及び酢酸を含む水溶液で浸漬処理を行った。この水溶液と含水ペレットを分離して脱液した後、熱風乾燥機に入れて80℃で3時間、次いで120℃で40時間乾燥を行って、水分率0.1%以下の乾燥ペレット(樹脂組成物)を得た。この乾燥ペレットを用いて、上記の分析及び評価を行った。なお、浸漬処理用水溶液の各成分の濃度を調節することにより、各成分の含有量が表1に記載の通りとなるように樹脂組成物を調製した。
50℃のメタノールに1時間、攪拌しながら浸漬させて洗浄する操作を3度繰り返す代わりに、30℃の水/メタノール=50/50(質量比)の混合溶媒に10分間、攪拌せずに浸漬させて洗浄する操作を1度のみ行った以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
50℃のメタノールに1時間、攪拌しながら浸漬させて洗浄する操作を3度繰り返す際に、超音波を当てたこと以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例2で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=55/45(質量比)の混合溶媒を用いた以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例2で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=55/45(質量比)の混合溶媒を用いた以外は実施例2と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例3で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=50/50(質量比)の混合溶媒を用いた以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例3で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=50/50(質量比)の混合溶媒を用いた以外は実施例2と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例4で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=25/75(質量比)の混合溶媒を用いた以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例5で得られたEVOHの粗乾燥物を使用した以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例5で得られたEVOHの粗乾燥物を使用した以外は実施例2と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例6で得られたEVOHの粗乾燥物を使用した以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
成分の含有量が表1に記載の通りとなるように浸漬処理用水溶液の各成分の種類及び濃度を調節した以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
50℃のメタノールに1時間、攪拌しながら浸漬させて洗浄する操作を3度繰り返す操作を行わなかった以外は実施例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例2で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=55/45(質量比)の混合溶媒を用いた以外は比較例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例3で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=50/50(質量比)の混合溶媒を用いた以外は比較例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例4で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=25/75(質量比)の混合溶媒を用いた以外は実施例2と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例4で得られたEVOHの粗乾燥物を使用し、溶解させる溶媒として水/メタノール=25/75(質量比)の混合溶媒を用いた以外は比較例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例5で得られたEVOHの粗乾燥物を使用した以外は比較例1と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
上記合成例6で得られたEVOHの粗乾燥物を使用した以外は実施例2と同様の操作により、乾燥ペレットを製造して分析及び評価を行った。
Claims (7)
- アゾニトリル系重合開始剤を用いて製造されるエチレン-ビニルアルコール共重合体(A)を主成分として含有する樹脂組成物であって、
エチレン-ビニルアルコール共重合体(A)のエチレン単位含有量が20~60モル%、けん化度が85モル%以上であり、
前記重合開始剤に由来する窒素元素量(NI)が5~60ppmであり、かつ
窒素元素量(NI)に対する、下記操作(X)により得られる乾燥固形物に含まれる窒素元素量(NF)の比率(NF/NI)が0.65~0.99である、樹脂組成物。
操作(X):5gの樹脂組成物を100gの1,1,1,3,3,3-ヘキサフルオロ-2-プロパノールに溶解させた溶液を、攪拌下にある1000gのメタノールに滴下して、生成した沈殿を分離した後乾燥して乾燥固形物を得る。 - 比率(NF/NI)が0.75~0.95である、請求項1に記載の樹脂組成物。
- さらに金属イオン(B)を100~400ppm含有する、請求項1または2に記載の樹脂組成物。
- さらにカルボン酸(C)を50~400ppm含有する、請求項1~3のいずれかに記載の樹脂組成物。
- 請求項1~4のいずれかに記載の樹脂組成物を含む成形体。
- 多層構造体である、請求項5に記載の成形体。
- 請求項5または6に記載の成形体を有する包装材料。
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US16/958,501 US20210061975A1 (en) | 2017-12-27 | 2018-11-30 | Resin composition including ethylene/vinyl alcohol copolymer, and molded object and packaging material both comprising same |
JP2019562893A JP7084944B2 (ja) | 2017-12-27 | 2018-11-30 | エチレン-ビニルアルコール共重合体含有樹脂組成物、並びにそれからなる成形体及び包装材料 |
CN201880090393.6A CN111742010B (zh) | 2017-12-27 | 2018-11-30 | 含有乙烯-乙烯醇共聚物的树脂组合物和包含其的成形体和包装材料 |
SG11202005638PA SG11202005638PA (en) | 2017-12-27 | 2018-11-30 | Resin composition including ethylene/vinyl alcohol copolymer, and molded object and packaging material both comprising same |
EP18897810.0A EP3733766A4 (en) | 2017-12-27 | 2018-11-30 | RESIN COMPOSITION COMPRISING AN ETHYLENE / VINYL ALCOHOL COPOLYMER AND MOLDED OBJECT AND PACKAGING MATERIAL COMPRISING IT BOTH |
KR1020207021733A KR102550270B1 (ko) | 2017-12-27 | 2018-11-30 | 에틸렌-비닐알코올 공중합체 함유 수지 조성물, 및 이로 이루어지는 성형체 및 포장 재료 |
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CN111742010A (zh) | 2020-10-02 |
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