WO2020213046A1 - エチレン-ビニルアルコール共重合体及びその製造方法 - Google Patents
エチレン-ビニルアルコール共重合体及びその製造方法 Download PDFInfo
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- WO2020213046A1 WO2020213046A1 PCT/JP2019/016214 JP2019016214W WO2020213046A1 WO 2020213046 A1 WO2020213046 A1 WO 2020213046A1 JP 2019016214 W JP2019016214 W JP 2019016214W WO 2020213046 A1 WO2020213046 A1 WO 2020213046A1
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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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
-
- 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
- C08F18/00—Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
- C08F18/08—Vinyl acetate
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/46—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals
- C08F4/463—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from sodium or potassium
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/30—Applications used for thermoforming
Definitions
- the present invention relates to an ethylene-vinyl alcohol copolymer, a resin composition and a molded product containing the same, and a method for producing the same.
- Ethylene-vinyl alcohol copolymer (hereinafter, may be abbreviated as "EVOH”) has excellent gas barrier properties and melt moldability. Therefore, films, sheets, pipes, and tubes can be obtained by various melt molding methods. , Molded into bottles, etc., and widely used as packaging materials in the food and industrial fields where gas barrier properties are required. In order to stably produce a packaging material having uniform performance and quality such as gas barrier properties, mechanical properties, and appearance, it is preferable that the melt viscosity of EVOH changes little with time.
- EVOH-containing resin compositions have been proposed.
- Patent Document 1 describes a resin composition containing EVOH, a boron compound, sodium acetate and magnesium acetate. Then, according to the resin composition, it is described that the long-running property at the time of melt molding is improved.
- Patent Document 2 describes a resin composition containing EVOH and a conjugated polyene compound.
- Patent Document 3 describes a resin composition containing EVOH, a specific carboxylic acid metal salt, and a hindered phenolic antioxidant. It is described that the resin composition is excellent in thermal stability and the formation of an oxidizing gel at a high temperature is suppressed.
- Patent Document 4 describes a resin composition containing EVOH and a specific unsaturated aldehyde. Then, according to the resin composition, it is described that the generation of defects such as fish eyes and gel due to melt molding is suppressed, and the long-run property at the time of melt molding is improved.
- the above EVOH-containing resin composition has a certain effect on suppressing gel formation and controlling the melt viscosity of the resin staying in the extruder for a long time, it has been found that the viscosity stability at the initial stage of melting is insufficient. .. Therefore, the resin temperature and pressure are not constant, the resin discharge amount during melt molding is uneven, and the melt molding process is still unstable, and various performances such as gas barrier properties and mechanical properties of the obtained molded product vary. It could occur. In addition, it may be colored under high temperature (for example, 80 ° C.) and alkaline conditions.
- an object of the present invention is to provide EVOH which is excellent in viscosity stability at the initial stage of melting, can stabilize the melt molding process, and is also excellent in coloring resistance under high temperature (for example, 80 ° C.) and alkaline conditions. It is in.
- the present invention is as follows.
- the total content of the structure (I) and the structure (II) is 0.002 to 0.020 mol% with respect to all the monomer units, and the structure (I) and the structure (II) are contained.
- the molar ratio R [I / (I + II)] of the structure (I) to the total of is satisfied with the following formula (1), EVOH;
- Y is a hydrogen atom or a methyl group.
- [3] A resin composition containing the EVOH of [1] or [2] and 100 to 400 ppm of metal ions; [4] The resin composition of [3] containing 50 to 400 ppm of carboxylic acid; [5] Mold containing EVOH according to [1] or [2]; [6] Mold containing the resin composition of [3] or [4]; [7] A copolymerization step of copolymerizing ethylene and vinyl ester in a solution using an azonitrile-based compound containing an alkoxy group as a polymerization initiator to obtain an ethylene-vinyl ester copolymer solution, and in the solution.
- the EVOH of the present invention is excellent in viscosity stability at the initial stage of melting, can stabilize the melt molding process, and is also excellent in coloring resistance under high temperature (for example, 80 ° C.) and alkaline conditions.
- the EVOH of the present invention has an ethylene unit content of 15 to 60 mol% and a saponification degree of 85 mol% or more, and the molecule and structure in which the copolymer contains the following structure (I) at the end. It contains a molecule containing (II), and the total content of the structure (I) and the structure (II) is 0.002 to 0.020 mol% with respect to all the monomer units, and the structure (I) and the structure
- the molar ratio R [I / (I + II)] of the structure (I) to the total of (II) satisfies the following formula (1).
- Y is a hydrogen atom or a methyl group.
- the EVOH of the present invention has an ethylene unit and a vinyl alcohol unit as main structural units.
- the EVOH contains a vinyl ester unit as an optional component.
- the EVOH of the present invention contains a molecule having a structure (I) at the end and a molecule having a structure (II) at the end.
- the total content of the structure (I) and the structure (II) with respect to all the monomer units in the EVOH is 0.002 to 0.020 mol%. As a result, the viscosity stability of the EVOH at the initial stage of melting is improved.
- the obtained molded product may be colored under alkaline conditions, or appearance abnormalities such as foaming may occur during melt molding at a high temperature.
- the total content is preferably 0.012 mol% or less.
- the monomer unit in the ethylene-vinyl alcohol copolymer means an ethylene unit, a vinyl alcohol unit, a vinyl ester unit, and other monomer units copolymerized as needed.
- the total monomer unit means the total amount of moles of each monomer unit.
- the unit including the terminal structure represented by the structure (I) or the structure (II) is also included in the monomer unit for calculation.
- the molar ratio R [I / (I + II)] of the structure (I) to the sum of the structures (I) and the structure (II) must satisfy the following formula (1), and the following formula (2) ) Is preferably satisfied.
- Et is the ethylene unit content (mol%).
- the right side of the formula (1) and the formula (2) is the molar ratio R [I / (I + II)] of the structure (I) to the sum of the structures (I) and the structure (II) in the EVOH. Is the sum of the molar ratios of ethylene units (ethylene units / total monomer units) to all the monomer units in the EVOH.
- Equations (1) and (2) indicate that the sum needs to be larger than a certain value, and that when Et is small, the molar ratio R needs to be a large value.
- both the structure (I) and the structure (II) are structures derived from the polymerization initiator used in the polymerization step.
- the structure (I) contains a cyclic ester structure formed by the reaction of the nitrile group derived from the polymerization initiator with the hydroxyl group in the same molecule, and the structure (II) is before such a reaction occurs. ..
- a large value on the right side of the formulas (1) and (2) means that the proportion of the nitrile group derived from the polymerization initiator converted into the cyclic ester structure is high, and the formula (2) is expressed in the formula (2). , Means that the ratio is even higher.
- the molar ratio R [I / (I + II)] of the structure (I) to the total of the structures (I) and the structure (II) is 0 in the EVOH of the present invention. It is preferably .5 or more, and more preferably 0.6 or more. On the other hand, the molar ratio R [I / (I + II)] is preferably 0.99 or less.
- the ethylene unit content of EVOH of the present invention (that is, the ratio of the number of moles of ethylene units to the total number of moles of all monomer units in EVOH) is in the range of 15 to 60 mol%.
- the lower limit of the ethylene unit content of EVOH is preferably 20 mol%, more preferably 23 mol%.
- the upper limit of the ethylene unit content of EVOH is preferably 55 mol%, more preferably 50 mol%. If the ethylene unit content of EVOH is less than 15 mol%, the gas barrier property under high humidity may be lowered, and the melt moldability may also be deteriorated. On the contrary, if the ethylene unit content of EVOH exceeds 60 mol%, sufficient gas barrier properties may not be obtained.
- the ethylene unit content and saponification degree of EVOH are determined by a nuclear magnetic resonance (NMR) method.
- the saponification degree of EVOH (that is, the ratio of the number of moles of vinyl alcohol units to the total number of moles of vinyl alcohol units and vinyl ester units in EVOH) is 85 mol% or more.
- the lower limit of the saponification degree of EVOH is preferably 95 mol%, more preferably 99 mol%.
- the upper limit of the saponification degree of EVOH is preferably 100 mol%, more preferably 99.99 mol%. If the saponification degree of EVOH is less than 85 mol%, sufficient gas barrier properties may not be obtained, and further, thermal stability may be insufficient.
- the lower limit of the melt flow rate (temperature 210 ° C., load 2160 g, hereinafter sometimes abbreviated as "MFR") based on EVOH JIS K 7210: 2014 is usually 0.1 g / 10 minutes, and the upper limit is usually 50 g. / 10 minutes.
- EVOH can contain monomer units other than ethylene units, vinyl alcohol units and vinyl ester units as copolymerization units as long as the effects of the present invention are not impaired.
- the monomer include ⁇ -olefins such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene and 1-octene; and non-olefins such as itaconic acid, methacrylic acid, acrylic acid and maleic acid.
- vinyl silane compounds such as vinyl silane compounds; unsaturated sulfonic acids or salts thereof; unsaturated thiols; vinyl pyrrolidones and the like.
- the content of the monomer unit other than the ethylene unit, the vinyl alcohol unit and the vinyl ester unit in the EVOH is usually 5 mol% or less, preferably 2 mol% or less, and more preferably 1 mol% or less.
- the resin composition containing EVOH is a preferred embodiment of the present invention.
- the content of EVOH in the resin composition is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. When the content of EVOH is within this range, the melt moldability of the resin composition of the present invention is improved, and the gas barrier property and oil resistance of the obtained molded product are also excellent.
- the resin contained in the resin composition may be substantially composed of only EVOH, or may be composed of only EVOH.
- the resin composition of the present invention further contains metal ions.
- the interlayer adhesiveness when formed into a multi-layer molded product, that is, a multi-layer structure becomes excellent.
- the reason for improving the interlayer adhesiveness is not clear, but when a molecule having a functional group capable of reacting with the hydroxy group of EVOH is contained in the layer adjacent to the layer made of the resin composition, both are subjected to metal ions. It is considered that the bond formation reaction of is accelerated. Further, by controlling the content ratio of the metal ion and the carboxylic acid described later, the melt moldability and coloring resistance of the resin composition of the present invention can be improved.
- the lower limit of the content thereof is preferably 100 ppm, more preferably 150 ppm.
- the upper limit of the metal ion content is preferably 400 ppm, more preferably 350 ppm. If the metal ion content is less than 100 ppm, the interlayer adhesiveness of the obtained multilayer structure may be insufficient. On the other hand, if the content of the metal ion is larger than 400 ppm, the coloring resistance may be insufficient.
- the metal ion examples include alkali metal ion, alkaline earth metal ion, and other transition metal ion, and these may be composed of one or more kinds. Of these, alkali metal ions are preferable. From the viewpoint that the resin composition can be easily produced and the interlayer adhesiveness of the multilayer structure can be further improved, it is preferable that the metal ions consist only of alkali metal ions.
- alkali metal ion examples include lithium, sodium, potassium, rubidium, and cesium ions, and sodium or potassium ions are preferable from the viewpoint of industrial availability.
- alkali metal salt that gives alkali metal ions include aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, and metal complexes. Of these, sodium acetate, potassium acetate, sodium phosphate, and potassium phosphate are more preferable because they are easily available.
- alkaline earth metal ions as metal ions.
- the metal ions contain alkaline earth metal ions, for example, thermal deterioration of EVOH when the trim is recovered and reused is suppressed, and the generation of gel and lumps in the obtained molded product may be suppressed.
- the alkaline earth metal ion include beryllium, magnesium, calcium, strontium, and barium ions, but magnesium or calcium ions are preferable from the viewpoint of industrial availability.
- alkaline earth metal salt that gives alkaline earth metal ions include aliphatic carboxylates, aromatic carboxylates, carbonates, hydrochlorides, nitrates, sulfates, phosphates, and metal complexes. ..
- the resin composition of the present invention preferably further contains a carboxylic acid.
- a carboxylic acid the melt moldability of the resin composition of the present invention and the coloring resistance at high temperatures can be improved.
- the pKa of the carboxylic acid is in the range of 3.5 to 5.5 because the pH buffering capacity of the obtained resin composition is enhanced and the coloring resistance to acidic substances and basic substances may be improved. More preferred.
- the lower limit of the content is preferably 50 ppm, more preferably 100 ppm.
- the upper limit of the carboxylic acid content is preferably 400 ppm, more preferably 350 ppm. If the content of the carboxylic acid is less than 50 ppm, the coloring resistance due to high temperature may be insufficient. On the other hand, if the content of the carboxylic acid is larger than 400 ppm, the melt moldability may be insufficient or the odor may become a problem.
- the content of the carboxylic acid in the resin composition is calculated by titrating an extract obtained by extracting 10 g of the resin composition with 50 ml of pure water at 95 ° C. for 8 hours. Here, the content of the carboxylic acid salt present in the extract is not taken into consideration as the content of the carboxylic acid in the resin composition.
- the carboxylic acid examples include a monovalent carboxylic acid and a polyvalent carboxylic acid, and these may be composed of one or more kinds.
- the melt moldability of the obtained resin composition and the coloring resistance at a high temperature may be further 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 further 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.
- PKa 4.88
- carboxylic acids may have substituents such as hydroxyl groups, amino groups and halogen atoms as long as pKa is in the range of 3.5 to 5.5.
- acetic acid is preferable because it is highly safe and easy to handle.
- a polyvalent carboxylic acid is a compound having two or more carboxyl groups in the molecule.
- the pKa of at least one carboxyl group is preferably in the range of 3.5 to 5.5.
- the resin composition of the present invention may further 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, cross-linking agents, desiccants, antioxidants, antioxidants, oxygen absorbers, plasticizers, lubricants, heat stabilizers (melt stable). Agents), processing aids, surfactants, deodorants, antistatic agents, UV absorbers, antifogging agents, flame retardants, pigments, dyes, fillers, fillers, reinforcing agents such as various fibers.
- the lower limit of the content is usually 1 ppm in terms of phosphoric acid root.
- the upper limit of the content is usually 200 ppm in terms of phosphate root. If a phosphoric acid compound is contained in this range, the thermal stability of the resin composition of the present invention may be improved. In particular, it may be possible to suppress the generation and coloring of gel-like lumps during melt molding for a long period of time.
- the phosphoric acid compound for example, various acids such as phosphoric acid and phosphorous acid and salts thereof can be used.
- the phosphate may be in the form of a first phosphate, a second phosphate, or a third phosphate.
- Examples of cation species of phosphate include alkali metals and alkaline earth metals.
- Specific examples of the phosphoric acid compound include 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 is usually 5 ppm in terms of boron element.
- the upper limit of the content is usually 1000 ppm in terms of boron element. If a boron compound is contained in this range, the thermal stability of the resin composition of the present invention during melt molding can be improved, and the generation of gel-like lumps may be suppressed. In some cases, the mechanical properties of the obtained molded product can be improved. It is speculated that these effects are due to the occurrence of chelate interactions between EVOH and the boron compound.
- the boron compound include boric acid, borate ester, borate, and boron hydride.
- examples of boric acid include orthoboric acid (H 3 BO 3 ), metaboric acid, and tetraboric acid, and examples of boric acid ester include trimethyl borate and triethyl borate, and boric acid.
- examples of the salt include the alkali metal salt of boric acid, the alkaline earth metal salt, and borax.
- thermoplastic resins other than EVOH include various polyolefins (polyethylene, polypropylene, poly1-butene, poly4-methyl-1-pentene, ethylene-propylene copolymer, ethylene and ⁇ -olefin having 4 or more carbon atoms.
- Copolymers polyolefins and maleic anhydride copolymers, ethylene-vinyl ester copolymers, ethylene-acrylic acid ester copolymers, or modified polyolefins graft-modified with unsaturated carboxylic acids or derivatives thereof, etc.) , Various polyamides (Nylon 6, Nylon 6.6, Nylon 6/66 copolymer, Nylon 11, Nylon 12, Polymethoxylylen adipamide, etc.), Various polyesters (Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, etc.) , Polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate and modified polyvinyl alcohol resin.
- 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 product containing EVOH of the present invention is a preferred embodiment of the present invention. At this time, it is more preferable to use the resin composition as the EVOH.
- the EVOH may be a molded product having a single-layer structure, or may be a molded product having a multi-layer structure of two or more types together with various other substrates, that is, a multi-layer structure.
- Examples of the molding method include extrusion molding, thermoforming, malformed molding, hollow molding, rotary molding, and injection molding.
- the molded product of the present invention has a wide variety of uses, and examples thereof include films, sheets, containers, bottles, tanks, pipes, hoses, and the like.
- films, sheets, pipes and hoses can be molded by extrusion molding
- container shapes can be molded by injection molding
- hollow containers such as bottles and tanks can be molded by hollow molding or rotary molding.
- the hollow molding include extrusion hollow molding in which a parison is formed by extrusion molding and then blown to perform molding, and injection hollow molding in which a preform is molded by injection molding and then blown to perform molding.
- a method of molding 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-shaped packaging material are preferably used.
- the molded product is a multilayer structure including a layer made of the resin composition of the present invention.
- the multilayer structure is obtained by laminating a layer made of the resin composition of the present invention and another layer.
- the layer structure of the multilayer structure if the layer made of a resin other than the resin composition of the present invention is the x layer, the resin composition layer of the present invention is the y layer, and the adhesive resin layer is the z layer, for example, 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 / Examples include x and the like.
- the types may be the same or different.
- a layer using a recovery resin made of scrap such as trim generated during molding may be separately provided, or the recovery resin may be mixed with a layer made of another resin.
- the thickness ratio of the y layer to the total layer thickness is usually 2 to 20% from the viewpoint of moldability and cost.
- thermoplastic resin As the resin used for the x layer, a thermoplastic resin is preferable from the viewpoint of workability and the like.
- thermoplastic resin include various polyolefins (polyethylene, polypropylene, poly1-butene, poly4-methyl-1-pentene, ethylene-propylene copolymer, and copolymers of ethylene and ⁇ -olefin having 4 or more carbon atoms.
- Polyolefin and maleic anhydride copolymer ethylene-vinyl ester copolymer, ethylene-acrylic acid ester copolymer, or modified polyolefin obtained by graft-modifying these with unsaturated carboxylic acid or a derivative thereof
- various polyamides Nylon 6, Nylon 6.6, Nylon 6/66 copolymer, Nylon 11, Nylon 12, Polymethoxylylene adipamide, etc.
- Various polyesters Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, etc.
- Polychloride examples thereof include vinyl, polyvinylidene chloride, polystyrene, polyacrylonitrile, polyurethane, polycarbonate, polyacetal, polyacrylate and modified polyvinyl alcohol resin.
- the thermoplastic resin layer may be unstretched, or may be uniaxially or biaxially stretched or rolled.
- polyolefin is preferable in terms of moisture resistance, mechanical properties, economy and heat sealability
- polyamide and polyester are preferable in terms of mechanical properties and heat resistance.
- the adhesive resin used for the z layer need only be able to bond between the layers, and for example, polyurethane-based or polyester-based one-component or two-component curable adhesives and carboxylic acid-modified polyolefins are suitable.
- the carboxylic acid-modified polyolefin is a polyolefin-based copolymer containing an unsaturated carboxylic acid or an anhydride thereof (maleic anhydride or the like) as a copolymerization component; or an unsaturated carboxylic acid or an anhydride thereof is grafted onto the polyolefin. Means the graft copolymer obtained from the above.
- Examples of the method for obtaining the multilayer structure include coextrusion molding, coextrusion hollow molding, coinjection molding, extrusion laminating, coextrusion laminating, dry laminating, solution coating and the like.
- the multilayer structure obtained by such a method is further subjected to secondary processing molding after reheating within the range below the melting point of EVOH by methods such as vacuum pressure air depth drawing molding, blow molding, and press molding. ,
- the desired molded body structure may be obtained.
- the multilayer structure is stretched by a roll stretching method, a pantograph stretching method, an inflation stretching method, or the like after reheating in a range below the melting point of EVOH and then uniaxially or biaxially stretched. You can also get it.
- the method for producing EVOH of the present invention comprises (i) a copolymerization step of copolymerizing ethylene and vinyl ester to obtain an ethylene-vinyl ester copolymer, and (ii) an alkali catalyst of the ethylene-vinyl ester copolymer. It comprises a saponification step of saponifying below to obtain an ethylene-vinyl alcohol copolymer.
- an ethylene-vinyl ester copolymer solution is obtained by copolymerizing ethylene and vinyl ester in a solution using an azonitrile-based compound containing an alkoxy group as a polymerization initiator.
- a copolymerization step of obtaining an ethylene-vinyl alcohol copolymer by saponifying the ethylene-vinyl ester copolymer in the solution under an alkali catalyst is included, and the ethylene-vinyl ester copolymer is obtained in the saponification step.
- the EVOH production method in which 1.2 mol or more of an alkali catalyst is used for 1 mol of the vinyl ester component contained in the copolymer and the solution is irradiated with ultrasonic waves or microwaves is extremely preferable.
- saponification step of saponification it is also preferable to include (iii) a granulation step of obtaining a hydrous pellet by a granulation operation, and (iv) a drying step of drying the hydrous pellet to obtain EVOH.
- ⁇ (I) Copolymerization step In the copolymerization step, in addition to the step of copolymerizing ethylene and vinyl ester, a polymerization inhibitor is added as necessary, and then unreacted ethylene and unreacted vinyl ester are removed to remove ethylene-vinyl ester copolymer weight. It also includes the step of obtaining a coalesced solution.
- the copolymerization method of ethylene and vinyl ester include known methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization, and the solution polymerization method is preferable.
- the vinyl ester an aliphatic vinyl ester such as vinyl acetate, vinyl propionate and vinyl pivalate is preferable, and vinyl acetate is more preferable.
- other monomers copolymerizable with ethylene and vinyl ester may be copolymerized in a small amount as long as the effect of the present invention is not impaired.
- the polymerization temperature is preferably 20 to 90 ° C, 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%, based on the charged vinyl ester.
- the resin content in the reaction solution after the polymerization is usually 5 to 85% by mass.
- an azonitrile-based compound containing an alkoxy group is used as a polymerization initiator.
- the alkoxy group-containing azonitrile-based compound preferably used in the present invention include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (4-ethoxy-). 2,4-Dimethylvaleronitrile) and the like, with 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) being preferred.
- the azonitrile-based compounds containing these alkoxy groups are unlikely to undergo abnormal decomposition due to contact with a metal, and have a high decomposition rate at low temperatures.
- ethylene and vinyl ester can be copolymerized safely, efficiently and economically.
- an azonitrile-based compound containing an alkoxy group is used as a polymerization initiator, and ethylene and vinyl ester are copolymerized in the solution to obtain an ethylene-vinyl ester copolymer solution. Is preferable.
- an alkali catalyst is added to the ethylene-vinyl ester copolymer solution, and the ethylene-vinyl ester copolymer in the solution is saponified to obtain an ethylene-vinyl alcohol copolymer.
- the saponification step can be carried out by either a continuous method or a batch method.
- the alkali catalyst include sodium hydroxide, potassium hydroxide, and alkali metal alcoholate.
- an alkali catalyst is added to 1 mol of the vinyl ester component contained in the ethylene-vinyl ester copolymer. It is extremely preferable to use 2 mol or more and to irradiate the solution with ultrasonic waves or microwaves.
- the alkali catalyst it is more preferable to use 2 mol or more of the alkali catalyst with respect to 1 mol of the vinyl ester component.
- an irradiation method There are no particular restrictions on the irradiation device and irradiation location used.
- the wavelength and intensity of the ultrasonic waves or microwaves to be irradiated are not particularly limited.
- the irradiation time is also not particularly limited, and ultrasonic waves or microwaves may be irradiated at least for a part of the time during the saponification reaction.
- a method of irradiating the reaction solution with ultrasonic waves for the last 15 to 60 minutes of the saponification reaction at an output of 80 W and a frequency of 40 kHz using an ultrasonic cleaner US CLEANER USK-2R.
- the output is set to 800 W using a microwave irradiation device (Multiwave 3000 type manufactured by Antonio Par), and the frequency is 2450 MHz.
- a method of irradiating the reaction solution with microwaves at (2.45 GHz) for 2 hours is adopted.
- an acid such as acetic acid to neutralize the remaining alkaline catalyst.
- the reaction solution obtained in the saponification step is extruded into a low-temperature poor solvent to precipitate or solidify the copolymer, and immediately after that or after further cooling and solidifying, the copolymer is cut to contain water.
- a method of obtaining pellets (2) a method of contacting the reaction solution obtained in the saponification step with water vapor to prepare a hydrous resin composition in advance, and then cutting the reaction solution to obtain a hydrous pellet, (3) a reaction solution obtained in the saponification step It can be carried out by a method of adding water to precipitate a copolymer and then crushing the copolymer to obtain hydrous pellets.
- the water content of the water-containing pellet is usually 50 to 200 parts by mass with respect to 100 parts by mass of EVOH.
- the hydrous pellets obtained in the granulation step are preferably subjected to a drying step to be EVOH dried pellets.
- the water content in the dry pellet is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, and 0.3 part by mass with respect to 100 parts by mass of EVOH for the purpose of preventing the generation of voids during molding. Less than a part is more preferable.
- Examples of the drying method include static drying and fluid drying, which may be used alone or in combination of two or more.
- the drying step may be performed by either a continuous method or a batch method, and when a plurality of drying methods are combined, a continuous method or a batch method can be freely selected for each drying method. It is preferable that the drying step is performed in a low oxygen concentration or anoxic state because deterioration of EVOH due to oxygen during drying can be reduced.
- the contents of the structure (I) and the structure (II) are the amount of the polymerization initiator used, the temperature and time until the addition of the polymerization initiator, the polymerization temperature, the polymerization time, the polymerization rate, and the type of the polymerization solvent in the copolymerization step. It can be controlled by adjusting the amount and the amount, adjusting the amount of the alkali catalyst in the saponification step, and irradiating with ultrasonic waves or microwaves. In addition, the contents of the structure (I) and the structure (II) may change in the granulation step and the drying step.
- a method for producing a resin composition by containing each component such as a metal ion or a carboxylic acid in EVOH of the present invention for example, a method of mixing the pellets together with each component and melt-kneading the pellets is prepared. Examples thereof include a method of mixing each component, a method of immersing the pellet in a solution containing each component, and the like.
- the pellets both hydrous pellets and dry pellets can be used.
- the EVOH of the present invention is excellent in viscosity stability at the initial stage of melting, it is possible to stably produce molded bodies such as pellets, films, sheets and containers.
- Ethylene unit content and saponification degree of EVOH Dimethyl sulfoxide (DMSO-d 6 ) containing tetramethylsilane (TMS) as an internal standard and trifluoroacetic acid (TFA) as an additive was used in each example and comparison.
- the dried pellets obtained in the example were melted and measured at 80 ° C. using 1 H-NMR (manufactured by Nippon Denshi Co., Ltd .: “GX-500”) at 500 MHz, in ethylene units, vinyl alcohol units, and vinyl ester units.
- the ethylene unit content and saponification degree were determined from the peak intensity ratio.
- Carboxylic acid content 10 g of dried pellets and 50 mL of pure water obtained in each Example and Comparative Example were placed in a 100 mL Erlenmeyer flask with a stopper, and after mounting a reflux condenser and heating at 95 ° C. for 8 hours, It was cooled to 20 ° C. The obtained extract was titrated with a 0.02 mol / L sodium hydroxide aqueous solution using phenolphthalein as an indicator to quantify the carboxylic acid.
- Example 1 The methanol solution of the ethylene-vinyl acetate copolymer obtained in Synthesis Example 1 was charged into a saponification reactor, and a 2 mol / L methanol solution of sodium hydroxide (NaOH) was added to water for the vinyl ester component in the copolymer. The solution was added so that the molar ratio of sodium oxide (NaOH / vinyl ester unit) was 3, and methanol was further added to adjust the copolymer concentration to 5% by mass. The temperature of this solution was raised to 60 ° C., and a saponification reaction was carried out for 3 hours with stirring.
- NaOH sodium hydroxide
- a reaction was carried out using an ultrasonic cleaner "US CLEANER USK-2R" at an output of 80 W and a frequency of 40 kHz while irradiating the reaction solution with ultrasonic waves via the reactor. Then, acetic acid and water were added to stop the saponification reaction, and EVOH was precipitated. The precipitated EVOH was recovered and finely crushed to obtain hydrous pellets, washed with an aqueous acetic acid solution and ion-exchanged water, and further immersed in an aqueous solution containing sodium acetate and acetic acid. The aqueous solution and the hydrous pellet were separated and deliquescented, and then placed in a hot air dryer and dried at 80 ° C.
- the resin composition of the present invention as a dry pellet.
- the obtained dried pellets were used for the above analysis and evaluation.
- the concentrations of sodium acetate and acetic acid in the aqueous solution were adjusted to obtain resin compositions having sodium and acetic acid contents of 180 ppm and 300 ppm, respectively.
- Example 2 A 2 mol / L methanol solution of sodium hydroxide was added so that the molar ratio of sodium hydroxide (NaOH / vinyl ester unit) to the vinyl ester component in the copolymer was 1.5, and the saponification reaction. Dry pellets were produced by the same operation as in Example 1 except that the irradiation with ultrasonic waves was performed for the last 15 minutes, and analysis and evaluation were performed.
- Examples 3 to 5 Dry pellets were produced by the same procedure as in Example 1 except that the methanol solution of the ethylene-vinyl acetate copolymer obtained in the synthetic examples shown in Table 1 was used, and analysis and evaluation were performed.
- Example 6 Drying was carried out in the same manner as in Example 1 except that potassium acetate was used instead of sodium acetate and the concentration of each component of the dipping aqueous solution was adjusted so that the contents of potassium and acetic acid were 300 ppm and 300 ppm, respectively. Pellets were produced and analyzed and evaluated.
- Example 7 The methanol solution of the ethylene-vinyl acetate copolymer obtained in Synthesis Example 1 was charged into a polytetrafluoride ethylene resin reactor, and a 2 mol / L methanol solution of sodium hydroxide was added to the vinyl ester component in the copolymer. It was added so that the molar ratio of sodium hydroxide to sodium hydroxide (NaOH / vinyl ester unit) was 3, and further methanol was added to adjust the copolymer concentration to 5%. The obtained solution was allowed to stand in a microwave irradiation device (Multiwave 3000 type manufactured by Antonio Par), sealed, and stirring was started.
- a microwave irradiation device Multiwave 3000 type manufactured by Antonio Par
- the output was set to 800 W, the temperature was raised until the temperature reached 60 ° C., and then the temperature was maintained for 2 hours.
- the frequency of the microwave irradiated to the reaction solution was 2450 MHz (2.45 GHz).
- the reactor was taken out from the microwave irradiation device, allowed to cool at room temperature, acetic acid and water were added to stop the saponification reaction, and EVOH was precipitated.
- the precipitated EVOH was recovered and finely crushed to obtain hydrous pellets, washed with an aqueous acetic acid solution and ion-exchanged water, and further immersed in an aqueous solution containing sodium acetate and acetic acid.
- the aqueous solution and the hydrous pellet were separated and deliquescented, and then placed in a hot air dryer and dried at 80 ° C. for 3 hours and then at 110 ° C. for 35 hours to obtain the resin composition of the present invention as a dry pellet.
- the obtained dried pellets were used for the above analysis and evaluation.
- the concentrations of sodium acetate and acetic acid in the aqueous solution were adjusted to obtain resin compositions having sodium and acetic acid contents of 180 ppm and 300 ppm, respectively.
- Example 2 Dry pellets were produced by the same operation as in Example 1 except that the methanol solution of the ethylene-vinyl acetate copolymer obtained in Synthesis Example 5 was used, and analysis and evaluation were performed.
- Comparative Example 3 Dry pellets were produced by the same operation as in Comparative Example 1 except that the methanol solution of the ethylene-vinyl acetate copolymer obtained in Synthesis Example 5 was used, and analysis and evaluation were performed.
- Table 1 shows the contents of the structures (I) and (II) in each of the resin compositions obtained in Examples and Comparative Examples, their ratios, and the evaluation results.
- the resin composition of the present invention having a total content of the structure (I) and the structure (II) of 0.002 to 0.020 mol% and satisfying the above formula (1) has a viscosity stability at the initial stage of melting. It was excellent. In addition, these resin compositions were also excellent in appearance characteristics after melt molding. On the other hand, each resin composition of the comparative example had a large change in viscosity at the initial stage of melting, and the melt molding process was unstable.
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Abstract
Description
[1]エチレン単位含有量が15~60モル%、けん化度が85モル%以上であるEVOHであって、前記共重合体が末端に下記の構造(I)を含有する分子及び構造(II)を含有する分子を含み、全単量体単位に対する、構造(I)及び構造(II)の合計含有量が0.002~0.020モル%であり、かつ構造(I)及び構造(II)の合計に対する、構造(I)のモル比R[I/(I+II)]が下記式(1)を満たす、EVOH;
0.8<R+Et/100 (1)
[式(1)中、Etは前記エチレン単位含有量(モル%)である。]
[2]下記式(2)を満たす、[1]のEVOH;
0.9<R+Et/100 (2)
[式(2)中、R及びEtは式(1)と同じである。]
[3][1]又は[2]のEVOH及び金属イオン100~400ppmを含有する、樹脂組成物;
[4]カルボン酸50~400ppmを含有する、[3]の樹脂組成物;
[5][1]又は[2]のEVOHを含む成形体;
[6][3]又は[4]の樹脂組成物を含む成形体;
[7]アルコキシ基を含有するアゾニトリル系化合物を重合開始剤として用いて、溶液中でエチレンとビニルエステルとを共重合してエチレン-ビニルエステル共重合体溶液を得る共重合工程と、前記溶液中のエチレン-ビニルエステル共重合体をアルカリ触媒下でけん化してEVOHを得るけん化工程とを含み、前記けん化工程において、エチレン-ビニルエステル共重合体に含まれるビニルエステル成分1モルに対してアルカリ触媒を1.2モル以上使用するとともに、超音波又はマイクロ波を前記溶液に照射する、[1]又は[2]のEVOHの製造方法である。
本発明のEVOHは、エチレン単位含有量が15~60モル%、けん化度が85モル%以上であるものであって、前記共重合体が末端に下記の構造(I)を含有する分子及び構造(II)を含有する分子を含み、全単量体単位に対する、構造(I)及び構造(II)の合計含有量が0.002~0.020モル%であり、かつ構造(I)及び構造(II)の合計に対する、構造(I)のモル比R[I/(I+II)]が下記式(1)を満たすものである。
0.8<R+Et/100 (1)
0.9<R+Et/100 (2)
[式(1)及び式(2)中、Etは前記エチレン単位含有量(モル%)である。]
本発明の樹脂組成物が金属イオンをさらに含有することが好ましい。本発明の樹脂組成物が金属イオンを含有すると、多層の成形体、すなわち多層構造体とした時の層間接着性が優れたものとなる。層間接着性が向上する理由は定かでないが、前記樹脂組成物からなる層と隣接する層中に、EVOHのヒドロキシ基と反応し得る官能基を有する分子が含まれる場合には、金属イオンによって両者の結合生成反応が加速されると考えられる。また、金属イオンと後述するカルボン酸との含有比率を制御すると、本発明の樹脂組成物の溶融成形性や着色耐性も改善できる。
本発明の樹脂組成物はカルボン酸をさらに含有することが好ましい。本発明の樹脂組成物がカルボン酸を含有すると、本発明の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は、本発明の効果を損なわない範囲でその他の成分をさらに含有していてもよい。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が挙げられる。
本発明のEVOHを含む成形体が本発明の好適な実施態様である。このとき、前記EVOHとして、前記樹脂組成物を用いることがより好適である。前記EVOH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、射出成形が挙げられる。本発明の成形体の用途は多岐に亘り、例えばフィルム、シート、容器、ボトル、タンク、パイプ、ホース等が挙げられる。
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、その種類は同じでも異なってもよい。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よいし、回収樹脂を他の樹脂からなる層に混合してもよい。多層構造体の各層の厚さ構成は、成形性及びコスト等の観点から、全層厚さに対するy層の厚さ比が通常2~20%である。
本発明のEVOHの製造方法は、(i)エチレンとビニルエステルとを共重合してエチレン-ビニルエステル共重合体を得る共重合工程、及び(ii)前記エチレン-ビニルエステル共重合体をアルカリ触媒下でけん化してエチレン-ビニルアルコール共重合体を得るけん化工程を含む。とりわけ、前記EVOHを簡便に製造する観点からは、アルコキシ基を含有するアゾニトリル系化合物を重合開始剤として用いて、溶液中でエチレンとビニルエステルとを共重合してエチレン-ビニルエステル共重合体溶液を得る共重合工程と、前記溶液中のエチレン-ビニルエステル共重合体をアルカリ触媒下でけん化してエチレン-ビニルアルコール共重合体を得るけん化工程とを含み、前記けん化工程において、エチレン-ビニルエステル共重合体に含まれるビニルエステル成分1モルに対してアルカリ触媒を1.2モル以上使用するとともに、超音波又はマイクロ波を前記溶液に照射する、前記EVOHの製造方法が極めて好ましい。
共重合工程は、エチレンとビニルエステルとを共重合させる工程に加え、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も含む。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、溶液重合方法が好適である。ビニルエステルとしては、酢酸ビニル、プロピオン酸ビニル及びピバリン酸ビニル等の脂肪族ビニルエステルが好ましく、酢酸ビニルがより好ましい。なお、エチレン及びビニルエステルと共重合し得る他の単量体を、本発明の効果を損なわない範囲で少量共重合してもよい。重合温度は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。重合後の反応液中の樹脂含有量は、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、溶液中のエチレン-ビニルエステル共重合体をけん化することによりエチレン-ビニルアルコール共重合体を得る。けん化工程は連続式、回分式のいずれの方式でも行うことができる。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。式(1)を満たすようモル比R[I/(I+II)]を制御するには、けん化工程において、エチレン-ビニルエステル共重合体に含まれるビニルエステル成分1モルに対してアルカリ触媒を1.2モル以上使用するとともに、超音波又はマイクロ波を前記溶液に照射することが極めて好ましい。
造粒工程は、例えば、(1)けん化工程で得られた反応液を低温の貧溶媒中に押出して共重合体を析出又は凝固させ、その直後に又はさらに冷却固化させた後に切断して含水ペレットを得る方法、(2)けん化工程で得られた反応液を水蒸気と接触させて予め含水樹脂組成物としてから切断して含水ペレットを得る方法、(3)けん化工程で得られた反応液に水を加えて共重合体を析出させた後に当該共重合体を砕いて含水ペレットを得る方法により行うことができる。含水ペレットの含水量は、通常EVOH100質量部に対して、50~200質量部である。
造粒工程で得られた含水ペレットは、乾燥工程に付してEVOHの乾燥ペレットとすることが好ましい。乾燥ペレット中の含水率は、成形加工時のボイドの発生を防ぐ目的から、EVOH100質量部に対して、1.0質量部以下が好ましく、0.5質量部以下がより好ましく、0.3質量部以下がさらに好ましい。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、これら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。乾燥工程は連続式、バッチ式いずれの方法で行ってもよく、複数の乾燥方法を組み合わせて行う場合は、各乾燥方法について連続式、バッチ式を自由に選択できる。なお、乾燥工程を低酸素濃度或いは無酸素状態で行うと、乾燥中における酸素によるEVOHの劣化を低減できる点で好ましい。
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)を含む重ジメチルスルホキシド(DMSO-d6)に、各実施例及び比較例で得られた乾燥ペレットを溶解し、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。
内部標準物質としてTMSを含むDMSO-d6に各実施例及び比較例で得られた乾燥ペレットを溶解し、500MHzの1H-NMR(日本電子株式会社製:「GX-500」)を用いて45℃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と構造(I)及び構造(II)が有するメトキシ基のメチル水素又はエトキシ基のメチレン水素のピーク強度比より構造(I)及び構造(II)の含有量を求めた。なお、構造(I)及び構造(II)が有するメトキシ基のメチル水素のピークは、それぞれ3.07ppm、3.09ppm付近に検出された。
各実施例及び比較例で得られた乾燥ペレット0.5gを、テフロン(登録商標)製圧力容器に入れ、濃硝酸5mLを加えて室温で30分間静置し、次いで蓋をして150℃で10分間、次いで180℃で5分間加熱することで湿式分解を行い、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を用いて、ICP発光分光分析装置により各金属イオンの含有量を定量した。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できる。
各実施例及び比較例で得られた乾燥ペレット10gと純水50mLを共栓付き100mL三角フラスコに入れ、還流冷却器を取り付けて95℃で8時間加熱した後、20℃まで冷却した。得られた抽出液を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し、カルボン酸を定量した。
各実施例及び比較例で得られた乾燥ペレット60gを、ラボプラストミル(二軸異方向)を用いて100rpm、230℃で混練したときのトルク変化を測定した。混練開始から1~5分後までの間のトルクの平均値TIと、混練開始から5~20分後までの間でのトルクの最大値TMとの比率(TM/TI)を下記のA~Dの基準で評価し(数字が小さい方が粘度安定性に優れる)、粘度安定性の指標とした。
A :1.10未満
B :1.10以上1.25未満
C :1.25以上1.40未満
D :1.40以上
各実施例及び比較例で得られた乾燥ペレット10gを、加熱圧縮プレス装置で220℃、6分間加熱溶融させて、厚み3mmの円盤状試験片を複数作製した。得られた試験片を0.1モル/Lの水酸化ナトリウム水溶液100gに浸漬し、試験片が入った容器の蓋をして80℃で1週間静置した。試験片を取り出し、その着色度合いを別途80℃で純水に1週間浸漬した別の試験片と目視で比較して下記のA~Dの基準で評価し、アルカリ条件下における着色耐性の指標とした。
A:目視ではほとんど区別できない
B:わずかに着色している
C:やや着色(淡黄色)している
D:かなり着色(黄色)している
容量250Lの加圧反応槽を用いて、以下の原料及び条件で重合を行うことにより、エチレン-酢酸ビニル共重合体を得た。
・酢酸ビニル:83.0kg
・メタノール:26.6kg
・重合開始剤: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℃
・重合槽のエチレン圧力:3.6MPa
重合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24モル%のエチレン-酢酸ビニル共重合体のメタノール溶液を得た。
・酢酸ビニル:102.0kg
・メタノール:17.7kg
・重合開始剤: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
・重合槽のエチレン圧力:2.9MPa
重合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%のエチレン-酢酸ビニル共重合体のメタノール溶液を得た。
・酢酸ビニル:85.2kg
・メタノール:32.3kg
・重合開始剤: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
・重合槽のエチレン圧力:2.9MPa
重合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%のエチレン-酢酸ビニル共重合体のメタノール溶液を得た。
・酢酸ビニル:76.7kg
・メタノール:11.0kg
・重合開始剤: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
・重合槽のエチレン圧力:5.5MPa
重合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%のエチレン-酢酸ビニル共重合体のメタノール溶液を得た。
・酢酸ビニル:83.0kg
・メタノール:20.8kg
・重合開始剤: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:1450mL、連続供給量:4360mL/hr
・重合槽のエチレン圧力:3.8MPa
合成例1で得られたエチレン-酢酸ビニル共重合体のメタノール溶液をケン化反応器に仕込み、水酸化ナトリウム(NaOH)の2モル/Lメタノール溶液を、共重合体中のビニルエステル成分に対する水酸化ナトリウムのモル比(NaOH/ビニルエステル単位)が3となるように添加し、さらにメタノールを加えて共重合体濃度が5質量%になるように調整した。この溶液を60℃に昇温し、攪拌しながら3時間けん化反応を行った。この際、最後の1時間は超音波洗浄器「US CLEANER USK-2R」を用いて、出力80W、周波数40kHzで、超音波を反応器を介して反応液に照射しながら反応を行った。その後、酢酸と水を添加してけん化反応を停止させるとともに、EVOHを析出させた。析出したEVOHを回収し、細かく砕いて含水ペレットを得た後、酢酸水溶液及びイオン交換水を用いて洗浄し、さらに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110℃で35時間乾燥を行って、本発明の樹脂組成物を乾燥ペレットとして得た。得られた乾燥ペレットを用いて、上記した分析及び評価を行った。なお、浸漬処理において、水溶液の酢酸ナトリウム及び酢酸の濃度を調節することで、ナトリウム及び酢酸の含有量がそれぞれ180ppm、300ppmの樹脂組成物を得た。
水酸化ナトリウムの2モル/Lメタノール溶液を、共重合体中のビニルエステル成分に対する水酸化ナトリウムのモル比(NaOH/ビニルエステル単位)が1.5となるように添加したこと、及びけん化反応の最後の15分間に超音波の照射を行っ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。
表1に記載された合成例で得られたエチレン-酢酸ビニル共重合体のメタノール溶液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。
酢酸ナトリウムの代わりに酢酸カリウムを使用し、カリウム及び酢酸の含有量がそれぞれ300ppm、300ppmとなるように浸漬処理用水溶液の各成分の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。
合成例1で得られたエチレン-酢酸ビニル共重合体のメタノール溶液をポリ四フッ化エチレン樹脂製反応器に仕込み、水酸化ナトリウムの2モル/Lメタノール溶液を、共重合体中のビニルエステル成分に対する水酸化ナトリウムのモル比(NaOH/ビニルエステル単位)が3となるように添加し、さらにメタノールを加えて共重合体濃度が5%になるように調整した。得られた溶液をマイクロ波照射装置(Anton Paar社製、Multiwave3000型)内に静置して密閉し、攪拌を開始した。出力を800Wとし、温度が60℃になるまで昇温させ、その後2時間保持した。ここで反応液に照射したマイクロ波の周波数は2450MHz(2.45GHz)であった。その後、反応器をマイクロ波照射装置から取り出して、室温下で放冷後、酢酸と水を添加してけん化反応を停止させるとともに、EVOHを析出させた。析出したEVOHを回収し、細かく砕いて含水ペレットを得た後、酢酸水溶液及びイオン交換水を用いて洗浄し、さらに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110℃で35時間乾燥を行って、本発明の樹脂組成物を乾燥ペレットとして得た。得られた乾燥ペレットを用いて、上記した分析及び評価を行った。なお、浸漬処理において、水溶液の酢酸ナトリウム及び酢酸の濃度を調節することで、ナトリウム及び酢酸の含有量がそれぞれ180ppm、300ppmの樹脂組成物を得た。
水酸化ナトリウムの2モル/Lメタノール溶液を、共重合体中のビニルエステル成分に対する水酸化ナトリウムのモル比(NaOH/ビニルエステル単位)が0.8となるように添加したこと及び超音波の照射を行わなかっ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。
合成例5で得られたエチレン-酢酸ビニル共重合体のメタノール溶液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。
合成例5で得られたエチレン-酢酸ビニル共重合体のメタノール溶液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。
Claims (7)
- エチレン単位含有量が15~60モル%、けん化度が85モル%以上であるエチレン-ビニルアルコール共重合体であって、
前記共重合体が末端に下記の構造(I)を含有する分子及び構造(II)を含有する分子を含み、全単量体単位に対する、構造(I)及び構造(II)の合計含有量が0.002~0.020モル%であり、かつ
構造(I)及び構造(II)の合計に対する、構造(I)のモル比R[I/(I+II)]が下記式(1)を満たす、エチレン-ビニルアルコール共重合体。
0.8<R+Et/100 (1)
[式(1)中、Etは前記エチレン単位含有量(モル%)である。] - 下記式(2)を満たす、請求項1に記載のエチレン-ビニルアルコール共重合体。
0.9<R+Et/100 (2)
[式(2)中、R及びEtは式(1)と同じである。] - 請求項1又は2に記載のエチレン-ビニルアルコール共重合体及び金属イオン100~400ppmを含有する、樹脂組成物。
- カルボン酸50~400ppmを含有する、請求項3に記載の樹脂組成物。
- 請求項1又は2に記載のエチレン-ビニルアルコール共重合体を含む成形体。
- 請求項3又は4に記載の樹脂組成物を含む成形体。
- アルコキシ基を含有するアゾニトリル系化合物を重合開始剤として用いて、溶液中でエチレンとビニルエステルとを共重合してエチレン-ビニルエステル共重合体溶液を得る共重合工程と、前記溶液中のエチレン-ビニルエステル共重合体をアルカリ触媒下でけん化してエチレン-ビニルアルコール共重合体を得るけん化工程とを含み、
前記けん化工程において、エチレン-ビニルエステル共重合体に含まれるビニルエステル成分1モルに対してアルカリ触媒を1.2モル以上使用するとともに、超音波又はマイクロ波を前記溶液に照射する、請求項1又は2に記載のエチレン-ビニルアルコール共重合体の製造方法。
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WO2013146961A1 (ja) | 2012-03-28 | 2013-10-03 | 株式会社クラレ | エチレン-ビニルアルコール共重合体含有樹脂組成物 |
JP2016029159A (ja) * | 2014-07-11 | 2016-03-03 | 株式会社クラレ | 樹脂組成物、多層構造体、多層シート、ブロー成形容器及び熱成形容器 |
CN105879850A (zh) * | 2016-06-21 | 2016-08-24 | 黄万忠 | 以石榴皮为原料制备重金属吸附剂的方法 |
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US20220195159A1 (en) | 2022-06-23 |
KR20210154976A (ko) | 2021-12-21 |
EP3957658A1 (en) | 2022-02-23 |
TW202039594A (zh) | 2020-11-01 |
SG11202111292YA (en) | 2021-11-29 |
JPWO2020213046A1 (ja) | 2021-05-06 |
JP6733059B1 (ja) | 2020-07-29 |
EP3957658A4 (en) | 2022-12-14 |
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