WO2023120705A1 - Procédé de production d'un copolymère d'éthylène-alcool vinylique modifié et composition de résine le comprenant - Google Patents

Procédé de production d'un copolymère d'éthylène-alcool vinylique modifié et composition de résine le comprenant Download PDF

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WO2023120705A1
WO2023120705A1 PCT/JP2022/047645 JP2022047645W WO2023120705A1 WO 2023120705 A1 WO2023120705 A1 WO 2023120705A1 JP 2022047645 W JP2022047645 W JP 2022047645W WO 2023120705 A1 WO2023120705 A1 WO 2023120705A1
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vinyl alcohol
alcohol copolymer
ethylene
evoh
epoxy compound
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PCT/JP2022/047645
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English (en)
Japanese (ja)
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利孝 染宮
靖 森原
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株式会社クラレ
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Priority to JP2023526509A priority Critical patent/JP7318153B1/ja
Publication of WO2023120705A1 publication Critical patent/WO2023120705A1/fr
Priority to JP2023117618A priority patent/JP2023139112A/ja

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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
    • C08F216/12—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 ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • 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
    • C08F8/08—Epoxidation
    • 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
    • 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
    • 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
    • C08L29/10—Homopolymers or copolymers of unsaturated ethers

Definitions

  • the present invention relates to a method for producing a modified ethylene-vinyl alcohol copolymer. Moreover, it is related with the manufacturing method of the resin composition containing the said copolymer. Furthermore, it relates to a method for producing mixed pellets containing pellets of the copolymer. The present invention also relates to a resin composition containing a modified ethylene-vinyl alcohol copolymer.
  • Ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) has excellent transparency and gas barrier properties, but has the drawback of lacking stretchability and bending resistance.
  • EVOH Ethylene-vinyl alcohol copolymer
  • a method of blending EVOH with a flexible resin such as an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer is known.
  • this method has the drawback that the transparency is greatly reduced.
  • Patent Document 1 EVOH and a monovalent epoxy compound having a molecular weight of 500 or less are melt-kneaded in an extruder in the presence of a catalyst containing ions of metals belonging to groups 3 to 12 of the periodic table. A method for producing modified EVOH containing 0.3 to 40 mol % of structural unit (I) is described. The modified EVOH is said to be excellent in barrier properties, transparency, stretchability and bending resistance.
  • a catalyst solution was prepared by dissolving equimolar amounts of zinc acetylacetonate monohydrate and trifluoromethanesulfonic acid in 1,2-dimethoxyethane, and this catalyst solution and a monovalent epoxy compound were dissolved. is fed to the extruder and more structural units (I) can be introduced into the EVOH than when no catalyst solution is added. It also describes that deterioration of the thermal stability of the resulting modified EVOH can be suppressed by using trisodium ethylenediaminetetraacetate trihydrate as a catalyst deactivator.
  • the modified EVOH thus obtained contained 120-150 ppm (1.9-2.3 ⁇ mol/g) of zinc ions as catalyst residues.
  • Patent Document 2 also describes a resin composition containing a modified EVOH containing 0.3 to 40 mol% of the structural unit (I) and a thermoplastic resin other than that. It describes an example of a resin composition containing the modified EVOH and unmodified EVOH and an example of a resin composition containing the modified EVOH and polyolefin.
  • the modified EVOH described in Patent Document 1 tends to be colored, and when melt-kneaded for a long period of time, torque fluctuations are large, and there is a problem in melt stability.
  • the present invention was made in order to solve such problems, and an object of the present invention is to provide a method for producing a modified EVOH that is excellent in barrier properties, stretchability, etc., and is also excellent in melt stability. is. It is also an object of the present invention to provide a method of making resin compositions containing such modified EVOH and other resins. It is also an object of the present invention to provide a method for producing mixed pellets containing such modified EVOH pellets and other resin pellets. It is also an object of the present invention to provide resin compositions containing such modified EVOH.
  • the above problem is solved by using a catalyst solution (D), which is an acetone solution containing zinc ions (F) and sulfonate ions, to prepare an ethylene-vinyl alcohol copolymer (A) and a monovalent epoxy compound having 2 to 8 carbon atoms (
  • the solution is provided by providing a method for producing a modified ethylene-vinyl alcohol copolymer (C), in which B) is reacted by melt-kneading in an extruder.
  • the ethylene-vinyl alcohol copolymer (A), the monofunctional epoxy compound (B), and the catalyst solution (D) are introduced into an extruder and melt-kneaded in the extruder to obtain It is preferable to react the ethylene-vinyl alcohol copolymer (A) with the monovalent epoxy compound (B). At this time, it is preferable to add a mixture of the monovalent epoxy compound (B) and the catalyst solution (D) to the molten ethylene-vinyl alcohol copolymer (A).
  • the ethylene-vinyl alcohol copolymer (A) is impregnated with the catalyst solution (D), introduced into an extruder, and melt-kneaded with the monovalent epoxy compound (B) in the extruder. Therefore, it is also preferable to react the ethylene-vinyl alcohol copolymer (A) with the monovalent epoxy compound (B).
  • the ethylene-vinyl alcohol copolymer (A) preferably has an ethylene content of 5 to 55 mol% and a degree of saponification of 90 mol% or more. It is also preferable to melt-knead 1 to 50 parts by mass of the monofunctional epoxy compound (B) with 100 parts by mass of the ethylene-vinyl alcohol copolymer (A). It is also preferable to use zinc ions (F) in an amount of 0.05 to 1.0 ⁇ mol/g in terms of number of moles relative to the mass of the ethylene-vinyl alcohol copolymer (A).
  • a preferred embodiment is to melt-knead the ethylene-vinyl alcohol copolymer (A) and the monovalent epoxy compound (B), then add the catalyst deactivator (E) and further melt-knead.
  • the catalyst deactivator (E) is preferably a chelating agent. It is also preferred that the catalyst deactivator (E) is a metal salt. It is also preferable that the ratio (E/F) of the number of moles of the catalyst deactivator (E) to the number of moles of zinc ions (F) contained in the catalyst solution (D) is 1.5-40.
  • the ethylene-vinyl alcohol copolymer (A) and the monovalent epoxy compound (B) are melt-kneaded, and after removing the unreacted monovalent epoxy compound (B), the catalyst deactivator (E) is added. is also preferred.
  • the modified ethylene-vinyl alcohol copolymer (C) obtained in the above production method preferably contains 0.3 to 40 mol% of the structural unit (I) represented by the following formula (I).
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an alicyclic carbonized group having 3 to 6 carbon atoms. represents a hydrogen group or a phenyl group, and the aliphatic hydrocarbon group, alicyclic hydrocarbon group and phenyl group may have a hydroxyl group, an alkoxy group, a carboxyl group or a halogen atom, and R 3 and R 4 are may be combined).
  • a method for producing a resin composition comprising a step of melt-kneading the modified ethylene-vinyl alcohol copolymer (C) obtained by the production method and an unmodified ethylene-vinyl alcohol copolymer or polyolefin is the method of the present invention. This is the preferred embodiment. Further, a step of pelletizing the modified ethylene-vinyl alcohol copolymer (C) obtained by the above production method, pellets of the obtained modified ethylene-vinyl alcohol copolymer (C), and unmodified ethylene-vinyl alcohol A method of making mixed pellets comprising dry blending with copolymer or polyolefin pellets is also a preferred embodiment of the present invention.
  • the above object includes a modified ethylene-vinyl alcohol copolymer (C) containing 2 to 40 mol% of structural units (I) represented by the following formula (I) and zinc ions (F), and zinc ions (The problem is also solved by providing a resin composition in which the content of F) is 0.05 to 1.0 ⁇ mol/g.
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an alicyclic carbonized group having 3 to 6 carbon atoms. represents a hydrogen group or a phenyl group, and the aliphatic hydrocarbon group, alicyclic hydrocarbon group and phenyl group may have a hydroxyl group, an alkoxy group, a carboxyl group or a halogen atom, and R 3 and R 4 are may be combined).
  • the resin composition further contains an alkali metal ion (G), and the molar ratio (G/F) of the alkali metal ion (G) to the zinc ion (F) is 5 to 80. .
  • the method for producing a modified EVOH of the present invention it is possible to produce a modified EVOH that is excellent in barrier properties, stretchability, etc., and also excellent in melt stability. Moreover, according to the method for producing a resin composition of the present invention, a resin composition containing modified EVOH and other resins can be produced. Further, according to the method for producing mixed pellets of the present invention, mixed pellets containing modified EVOH pellets and other resin pellets can be produced. Furthermore, the resin composition of the present invention contains a low amount of catalyst residue while containing a highly modified EVOH. Therefore, it has excellent barrier properties, stretchability, and the like, and also has excellent melt stability and is less likely to be colored.
  • the modified EVOH (C) produced by the method of the present invention is a reaction product of EVOH (A) and a monovalent epoxy compound (B), and preferably contains the following structural unit (I).
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group having 3 to 6 carbon atoms. or a phenyl group, and the aliphatic hydrocarbon group, alicyclic hydrocarbon group and phenyl group may have a hydroxyl group, an alkoxy group, a carboxyl group or a halogen atom, and R 3 and R 4 are bonded You may have
  • the aliphatic hydrocarbon group includes an alkyl group and an alkenyl group.
  • a cycloalkyl group and a cycloalkenyl group are mentioned as an alicyclic hydrocarbon group.
  • both R 1 and R 2 are hydrogen atoms. In a further preferred embodiment, both R 1 and R 2 are hydrogen atoms, and one of R 3 and R 4 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms and the other is hydrogen is an atom. Preferably, said aliphatic hydrocarbon group is an alkyl or alkenyl group. From the viewpoint of emphasizing gas barrier properties when the modified EVOH (C) is used as a barrier material, it is more preferable that one of R 3 and R 4 is a methyl group or an ethyl group and the other is a hydrogen atom. preferable.
  • both R 1 and R 2 are hydrogen atoms, and one of R 3 and R 4 is (CH 2 ). It is also preferred that a substituent represented by i OH (where i is an integer of 1 to 6) and the other is a hydrogen atom.
  • i in the substituent represented by (CH 2 ) i OH is preferably an integer of 1 to 4, more preferably 1 or 2. It is preferably 1, more preferably 1.
  • the amount of the structural unit (I) contained in the modified EVOH (C) is preferably 0.3 to 40 mol%.
  • the lower limit of the amount of structural unit (I) is more preferably 0.5 mol % or more, still more preferably 1 mol % or more, and particularly preferably 2 mol % or more.
  • the upper limit of the amount of structural unit (I) is more preferably 20 mol % or less, still more preferably 15 mol % or less, and particularly preferably 10 mol % or less.
  • the ethylene content of the modified EVOH (C) is preferably 5-55 mol%.
  • the lower limit of the ethylene content of the modified EVOH (C) is more preferably 10 mol% or more, more preferably 20 mol. % or more, more preferably 25 mol % or more, and particularly preferably 31 mol % or more.
  • the upper limit of the ethylene content of the modified EVOH (C) is more preferably 50 mol% or less, more preferably 45 mol% or less. be.
  • the degree of saponification of modified EVOH (C) means the degree of saponification of EVOH (A) described later.
  • the monomeric units other than the structural unit (I) and ethylene units that constitute the modified EVOH (C) are mainly vinyl alcohol units.
  • This vinyl alcohol unit is usually a vinyl alcohol unit that did not react with the monovalent epoxy compound (B) among the vinyl alcohol units contained in the raw material EVOH (A).
  • unsaponified vinyl acetate units that may be contained in EVOH (A) are usually contained as they are in modified EVOH (C).
  • the content of vinyl alcohol units is preferably 40 to 80 mol %.
  • the lower limit of the vinyl alcohol unit content of the modified EVOH (C) is more preferably 45 mol % or more, and more preferably 50 mol % or more.
  • the upper limit of the vinyl alcohol unit content of the modified EVOH (C) is more preferably 75 mol % or less. and more preferably 70 mol % or less.
  • Modified EVOH (C) is a random copolymer containing these monomer units. Furthermore, other monomeric units may be included within the range that does not hinder the object of the present invention, but monomeric units other than structural unit (I), ethylene units, vinyl alcohol units and vinyl acetate units The content of is preferably 5 mol% or less, more preferably 3 mol% or less, further preferably 2 mol% or less, and may be 1 mol% or less, substantially Other monomeric units may not be included. Other monomer units include those exemplified as copolymerizable monomers described later in EVOH (A).
  • a preferred melt flow rate (MFR) (190° C., under 2160 g load) of the modified EVOH (C) is 0.1 to 30 g/10 min, more preferably 0.3 to 25 g/10 min, more preferably is 0.5 to 20 g/10 minutes. However, if the melting point is around 190°C or above 190°C, it is measured at multiple temperatures above the melting point under a load of 2160 g. Expressed as a value extrapolated to 190°C.
  • the present invention relates to a method for producing the modified EVOH (C).
  • an ethylene-vinyl alcohol copolymer (A) and a monovalent epoxy compound ( B) is melt-kneaded in an extruder to produce a modified ethylene-vinyl alcohol copolymer (C).
  • EVOH (A) used in the present invention is preferably obtained by saponifying an ethylene-vinyl ester copolymer.
  • Vinyl acetate is a typical vinyl ester used in the production of EVOH, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used.
  • Monomers copolymerizable with ethylene and vinyl esters such as alkenes such as propylene, butylene, pentene, and hexene; 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1 -butene, 3,4-diacyloxy-1-butene, 3-acyloxy-4-methyl-1-butene, 4-acyloxy-2-methyl-1-butene, 4-acyloxy-3-methyl-1-butene, 3 , 4-diacyloxy-2-methyl-1-butene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-acyloxy-1-hexene, 5-acyloxy -1-hexene, 6-acyloxy-1-hexene, 5,6-diacyloxy-1-hexene, 1,3-diacetoxy-2-methylenepropane and other alkenes having an ester group or
  • the ethylene content of EVOH (A) used in the present invention is preferably 5 to 55 mol%.
  • the lower limit of the ethylene content of the EVOH (A) is more preferably 10 mol% or more, more preferably 20 mol%. or more, particularly preferably 25 mol % or more, more preferably 31 mol % or more.
  • the upper limit of the ethylene content of the EVOH (A) is more preferably 50 mol% or less, more preferably 45 mol% or less. .
  • the melt moldability may deteriorate, and if it exceeds 55 mol %, the gas barrier properties may be insufficient.
  • the EVOH (A) is a blend of two or more EVOHs with different ethylene contents, the average value calculated from the blending mass ratio is taken as the ethylene content.
  • the degree of saponification of the vinyl ester component of EVOH (A) used in the present invention is preferably 90 mol% or more.
  • the degree of saponification of the vinyl ester component is more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 99 mol% or more. If the degree of saponification is less than 90 mol%, the gas barrier properties of the modified EVOH (C), especially at high humidity, may be lowered, and the thermal stability may be insufficient, resulting in gels and grains in the molded product. may become more likely to occur.
  • the EVOH (A) is a blend of two or more EVOHs with different degrees of saponification
  • the average value calculated from the blending mass ratio is taken as the degree of saponification.
  • the ethylene content and saponification degree of EVOH (A) can be obtained by nuclear magnetic resonance (NMR) method.
  • EVOH blended with a boron compound can also be used as EVOH (A) within a range that does not hinder the object of the present invention.
  • boron compounds include boric acids, borate esters, borates, and boron hydrides.
  • boric acids include orthoboric acid, metaboric acid, and tetraboric acid.
  • boric acid esters include triethyl borate and trimethyl borate.
  • Examples include alkali metal salts of acids, alkaline earth metal salts, borax, and the like.
  • orthoboric acid hereinafter sometimes simply referred to as boric acid is preferred.
  • the content of the boron compound is preferably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of boron element.
  • the boron compound By blending the boron compound within this range, it is possible to obtain EVOH with suppressed torque fluctuation during heating and melting. If it is less than 20 ppm, such effect is small, and if it exceeds 2000 ppm, gelation tends to occur, resulting in poor moldability.
  • EVOH (A) containing a phosphoric acid compound may also be used as EVOH (A). In some cases, this can stabilize the quality (coloration, etc.) of the resin.
  • the phosphoric acid compound used in the present invention is not particularly limited, and various acids such as phosphoric acid and phosphorous acid, salts thereof, and the like can be used.
  • the phosphate may be contained in any form of primary phosphate, secondary phosphate, and tertiary phosphate, but primary phosphate is preferred.
  • the cationic species is not particularly limited, it is preferably an alkali metal salt. Among these, sodium dihydrogen phosphate and potassium dihydrogen phosphate are preferred.
  • the phosphate deactivates the catalyst. Smaller amounts are preferred. Therefore, the content of the phosphate compound in EVOH (A) is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less in terms of phosphate radicals. A suitable lower limit when blending a phosphoric acid compound is 5 ppm or more.
  • the EVOH (A) and the monofunctional epoxy compound (B) are melt-kneaded in an extruder using the catalyst solution (D). During the reaction, EVOH is exposed to heating conditions. At this time, if EVOH (A) contains an excessive amount of alkali metal salt and/or alkaline earth metal salt, the catalyst is deactivated, so the addition amount thereof is preferably small. Therefore, it is preferable that the alkali metal salt contained in EVOH (A) is 50 ppm or less in terms of metal element.
  • the alkali metal salt contained in EVOH (A) is 30 ppm or less, more preferably 20 ppm or less, in terms of metal element.
  • the alkaline earth metal salt contained in EVOH (A) is preferably 20 ppm or less, more preferably 10 ppm or less, in terms of metal element.
  • the intrinsic viscosity of EVOH (A) used in the present invention is preferably 0.06 L/g or more.
  • the intrinsic viscosity of EVOH (A) is more preferably in the range of 0.07 to 0.2 L/g, still more preferably 0.075 to 0.15 L/g, particularly preferably 0.080 to 0.080. 12 L/g. If the intrinsic viscosity of EVOH (A) is less than 0.06 L/g, stretchability and flex resistance may deteriorate. Further, when the intrinsic viscosity of EVOH (A) exceeds 0.2 L/g, there is a possibility that gels and lumps are likely to occur in molded articles made of modified EVOH (C).
  • the EVOH (A) used in the present invention preferably has a melt flow rate (MFR) (190° C., under 2160 g load) of 0.1 to 30 g/10 min, more preferably 0.3 to 25 g/10 min. , more preferably 0.5 to 20 g/10 minutes. However, if the melting point is around 190°C or above 190°C, it is measured at multiple temperatures above the melting point under a load of 2160 g. Expressed as a value extrapolated to 190°C. A mixture of two or more EVOHs having different MFRs can also be used.
  • MFR melt flow rate
  • the monovalent epoxy compound (B) used in the present invention must be a monovalent epoxy compound. That is, it must be an epoxy compound having only one epoxy group in the molecule. The effects of the present invention cannot be obtained when a polyvalent epoxy compound having a divalent or higher valence is used. However, in the manufacturing process of the monovalent epoxy compound, a very small amount of the polyepoxy compound may be contained. A monovalent epoxy compound containing a very small amount of polyepoxy compound can be used as the monovalent epoxy compound (B) in the present invention as long as it does not impair the effects of the present invention.
  • the number of carbon atoms of the monovalent epoxy compound (B) used in the present invention is 2-8. Specifically, compounds represented by the following formulas (II) to (IV) are preferably used.
  • R 5 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or a phenyl group.
  • R 6 and R 7 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 3 to 5 carbon atoms.
  • i represents an integer of 1-6.
  • the number of carbon atoms in the monovalent epoxy compound is preferably 2-6, more preferably 2-4.
  • the monofunctional epoxy compound is more preferably epoxyethane, epoxypropane, 1,2-epoxybutane and glycidol, and more preferably epoxypropane and 1,2-epoxybutane. .
  • a modified EVOH (C) is obtained by reacting the above EVOH (A) with the above monovalent epoxy compound (B).
  • a suitable mixing ratio of EVOH (A) and monovalent epoxy compound (B) is 1 to 50 parts by mass of (B) per 100 parts by mass of (A), more preferably (A) 2 to 40 parts by mass of (B) per 100 parts by mass, and particularly preferably 5 to 35 parts by mass of (B) per 100 parts by mass of (A).
  • the catalyst solution (D) used when reacting EVOH (A) and the monovalent epoxy compound (B) is an acetone solution containing zinc ions (F) and sulfonate ions. By melt-kneading using such a catalyst solution, the EVOH (A) and the monovalent epoxy compound (B) can be efficiently reacted.
  • the catalyst solution (D) used in the present invention contains zinc ions (F).
  • the most important thing as a metal ion used in the catalyst solution (D) is to have moderate Lewis acidity, and zinc ion (F) is used from this point.
  • zinc ions (F) By using zinc ions (F), the catalytic activity is high and the thermal stability of the resulting modified EVOH (C) is excellent.
  • the amount of zinc ions (F) added is preferably 0.05 to 1.0 ⁇ mol/g in terms of the number of moles of zinc ions (F) with respect to the mass of EVOH (A). If the amount of zinc ions (F) is too large, when the resulting modified EVOH (C) is melt-kneaded over a long period of time, the torque fluctuates greatly, resulting in a problem of melt stability. Moreover, the resulting modified EVOH (C) may be colored.
  • the number of moles of zinc ions (F) is more preferably 0.9 ⁇ mol/g or less.
  • the amount of zinc ions (F) is too small, the effect of adding the catalyst (D) may not be sufficiently exhibited, and it is more preferably 0.1 ⁇ mol/g or more, and still more preferably 0.2 ⁇ mol/g. /g or more, more preferably 0.35 ⁇ mol/g or more.
  • the catalyst solution (D) contains sulfonate ions in addition to zinc ions (F).
  • the sulfonate ion acts as a counter ion for the zinc ion (F), and improves the Lewis acidity of the zinc ion (F), thereby improving the catalytic activity.
  • the sulfonate ion does not react with the hydroxyl group or epoxy group of EVOH, and is thermally stable as an anion species itself.
  • the sulfonate ion is exemplified by methanesulfonate ion, ethanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion, etc. Trifluoromethanesulfonate ion is most suitable.
  • a catalyst solution is used in which equimolar amounts of zinc acetylacetonate monohydrate and trifluoromethanesulfonic acid are dissolved in 1,2-dimethoxyethane. That is, the number of moles of sulfonate ions contained in the catalyst solution was one times the number of moles of zinc ions (F). In contrast, in the present invention, the number of moles of sulfonate ions contained in the catalyst solution (D) is preferably 1.2 to 4 times the number of moles of zinc ions (F).
  • the Lewis acidity of the zinc ions (F) is improved, and the reaction can proceed smoothly with a smaller amount of catalyst.
  • the number of moles of sulfonate ions to the number of moles of zinc ions (F) is more preferably 1.5 times or more, more preferably 1.8 times or more. Also, it is more preferably 3 times or less, more preferably 2.5 times or less. It is optimal that the amount is substantially doubled, and at this time, divalent zinc ions and monovalent sulfonate ions can form a salt in just the right amount. Since neither the zinc ion (F) nor the sulfonate ion are volatilized, the ratio of both here is maintained at the same value even in the modified EVOH composition.
  • the solvent for dissolving zinc ions (F) and sulfonate ions is acetone.
  • Patent Document 1 it is said that it is preferable to use an ether-based solvent, and an example using a catalyst solution obtained by dissolving zinc acetylacetonate monohydrate and trifluoromethanesulfonic acid in 1,2-dimethoxyethane was used. is described.
  • 1,2-dimethoxyethane is used as the solvent, the resulting modified EVOH (C) is likely to be colored, and when the modified EVOH (C) is melt-kneaded for a long time, torque fluctuations are large and melting occurs. It also had problems with stability.
  • the ignition point of 1,2-dimethoxyethane is 202° C., which is close to the melt-kneading temperature, and poses a danger during production.
  • the reaction can proceed with a smaller amount of catalyst, and the amount of zinc ions (F) contained in the resulting modified EVOH (C) can be reduced. This can improve the problems of coloration and melt stability.
  • the ignition point of acetone is 540° C., which greatly reduces the danger during production.
  • the catalyst solution (D) may contain a small amount of solvent other than acetone. Such other solvent can be dissolved in acetone and does not interfere with the present invention, and is exemplified by methanol and the like. Its content is usually 20% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the catalyst solution (D) which is an acetone solution containing zinc ions (F) and sulfonate ions, is used to prepare EVOH (A) and a monovalent epoxy compound (B). are reacted by melt-kneading in an extruder.
  • the following two methods are exemplified.
  • EVOH (A), a monovalent epoxy compound (B), and a catalyst solution (D) are introduced into an extruder and melt-kneaded in the extruder to obtain EVOH (A) and
  • a modified EVOH (C) is obtained by reacting it with a monovalent epoxy compound (B).
  • EVOH (A) is impregnated with a catalyst solution (D), introduced into an extruder, and melt-kneaded with a monofunctional epoxy compound (B) in the extruder to obtain EVOH (A ) and a monovalent epoxy compound (B) to obtain a modified EVOH (C).
  • a method for impregnating EVOH (A) with the catalyst solution (D) a method of contacting pellets of EVOH (A) with the catalyst solution (D) and then drying is preferably mentioned. In this case, the dry pellets thus obtained are introduced into an extruder.
  • the extruder used for reacting the EVOH (A) and the monovalent epoxy compound (B) in the extruder is not particularly limited, but may be a single screw extruder, a twin screw extruder or a multi-screw extruder with two or more screws. is used, and the temperature in the extruder is set to 180 to 250° C., and the EVOH (A) and the monofunctional epoxy compound (B) are preferably reacted. When the temperature inside the extruder exceeds 250°C, EVOH may deteriorate, and the temperature is more preferably 230°C or less. On the other hand, if the temperature is less than 180°C, the reaction between EVOH (A) and the monofunctional epoxy compound (B) may not proceed sufficiently, and the temperature is more preferably 190°C or higher.
  • twin-screw extruder or a multi-screw extruder When using a twin-screw extruder or a multi-screw extruder with two or more screws, it is easy to increase the pressure in the reaction section by changing the screw configuration, and the EVOH (A) and the monofunctional epoxy compound (B) reaction can be carried out efficiently.
  • a single-screw extruder it is possible to increase the pressure in the reaction section by connecting two or more extruders and arranging a valve in the resin flow path between them.
  • two or more twin-screw extruders or multi-screw extruders having two or more screws may be connected to manufacture.
  • the reactivity between the EVOH (A) and the monovalent epoxy compound (B) is increased by pressurizing the extruder under pressure, and the monovalent epoxy compound is It is possible to remarkably suppress volatilization of (B) out of the system.
  • the method of mixing the EVOH (A) and the monofunctional epoxy compound (B) during the reaction in the extruder is not particularly limited. Suitable examples include a method of spraying, a method of feeding EVOH (A) to an extruder, and a method of contacting the monofunctional epoxy compound (B) in the extruder. Among these, from the viewpoint of suppressing volatilization of the monovalent epoxy compound (B) to the outside of the system, after feeding EVOH (A) to the extruder, the monovalent epoxy compound (B ) is preferred.
  • the position at which the monovalent epoxy compound (B) is added into the extruder is also arbitrary, but from the viewpoint of the reactivity between the EVOH (A) and the monovalent epoxy compound (B), the molten EVOH (A) It is preferable to add the monohydric epoxy compound (B).
  • the step of adding the monovalent epoxy compound (B) it is preferable to press-fit the monovalent epoxy compound (B) under pressure. At this time, if the pressure is insufficient, problems such as a decrease in the reaction rate and variations in the ejection amount occur.
  • the required pressure varies greatly depending on the boiling point of the monofunctional epoxy compound (B) and the extrusion temperature, but is usually preferably in the range of 0.5-30 MPa, more preferably in the range of 1-20 MPa. The same is true when adding a mixture of the monovalent epoxy compound (B) and the catalyst solution (D).
  • the position at which the catalyst solution (D) is introduced into the extruder is not particularly limited, but it is preferable to add it at a position where the EVOH (A) is completely melted so that it can be blended uniformly. It is preferably added at the same location as or near the location where the monofunctional epoxy compound (B) is added.
  • EVOH (A) and monovalent epoxy compound (B) are melt-kneaded in an extruder in the presence of zinc ions (F) as a catalyst, and EVOH (A) and monovalent epoxy compound After (B) is melt-kneaded, the catalyst deactivator (E) is preferably added and further melt-kneaded. If the catalyst is not deactivated, the resulting modified EVOH (C) may have poor thermal stability, which may cause problems in use depending on the application.
  • the catalyst deactivator (E) used is not particularly limited as long as it reduces the action of the zinc ion (F) acting as a catalyst as a Lewis acid.
  • Metal salts such as alkali metal salts are preferably used. Deactivation of catalysts containing anions of sulfonic acids, which are strong acids, requires the use of alkali metal salts of the anions of acids weaker than the sulfonic acids. This is because the counter ion of the zinc ion (F) constituting the catalyst is exchanged with an anion of a weak acid, resulting in a decrease in the Lewis acidity of the zinc ion (F).
  • the cationic species of the alkali metal salt used for the catalyst deactivator (E) is not particularly limited, and suitable examples include sodium salt, potassium salt and lithium salt.
  • the anion species is also not particularly limited, and carboxylates, phosphates and phosphonates are exemplified as suitable ones.
  • Suitable chelating agents used as the catalyst deactivator (E) include oxycarboxylates, aminocarboxylates, aminophosphonates, and the like.
  • examples of the oxycarboxylate include disodium citrate, disodium tartrate, disodium malate, and the like.
  • Aminocarboxylic acid salts include trisodium nitrilotriacetate, disodium ethylenediaminetetraacetic acid, trisodium ethylenediaminetetraacetate, tripotassium ethylenediaminetetraacetate, trisodium diethylenetriaminepentaacetic acid, trisodium 1,2-cyclohexanediaminetetraacetate, ethylenediamine diacetic acid.
  • Monosodium acetate, monosodium N-(hydroxyethyl)iminodiacetate and the like are exemplified.
  • aminophosphonates include hexasodium nitrilotrismethylenephosphonate, octasodium ethylenediaminetetra(methylenephosphonate), and the like.
  • polyaminopolycarboxylic acids are preferred, and alkali metal salts of ethylenediaminetetraacetic acid are most suitable in terms of performance and cost.
  • chelating agents such as alkali metal salts of ethylenediaminetetraacetic acid may corrode metals that make up kneading equipment. This time, it was clarified that the reaction between EVOH (A) and monovalent epoxy compound (B) proceeds smoothly even if the amount of zinc ion (F) used as a catalyst is reduced. From the viewpoint of preventing corrosion of the catalyst, it is preferable to use an alkali metal salt of a monocarboxylic acid as the catalyst deactivator (E).
  • the number of carbon atoms in the monocarboxylic acid is preferably 2 to 18, more preferably 6 or less, even more preferably 4 or less. Specifically, acetic acid, propionic acid, and lactic acid are preferred examples.
  • Alkali metal is preferably sodium or potassium.
  • the amount of the catalyst deactivator (E) added is not particularly limited, but the ratio (E/F) of the number of moles of the catalyst deactivator (E) to the number of moles of zinc ions (F) is 1.5 to 40. It is preferable to If the ratio (E/F) is less than 1.5, the zinc ions (F) may not be sufficiently deactivated, and in the case of melt-kneading for a long time, torque fluctuations are large and melt stability is affected. may have problems.
  • the ratio (E/F) is more preferably 2 or more, more preferably 2.5 or more.
  • the ratio (E/F) exceeds 40, the resulting modified EVOH (C) may be colored and the production cost may increase. It is preferably 20 or less.
  • the method of introducing the catalyst deactivator (E) into the extruder is not particularly limited. It is preferable to introduce Considering the solubility of the catalyst deactivator (E) and the influence on the surrounding environment, it is preferable to add it as an aqueous solution.
  • the position at which the catalyst deactivator (E) is added to the extruder may be after the EVOH (A) and the monovalent epoxy compound (B) are melt-kneaded in the presence of the zinc ions (F).
  • the EVOH (A) and the monovalent epoxy compound (B) are melt-kneaded in the presence of zinc ions (F), and after removing the unreacted monovalent epoxy compound (B), the catalyst deactivator (E ) is preferably added.
  • the vent is because water will be mixed in the monovalent epoxy compound (B) that is removed and recovered for use by e.g., and the separation operation is troublesome. It is also preferable to remove moisture by venting or the like after adding the aqueous solution of the catalyst deactivator (E).
  • the resin composition obtained by the production method of the present invention includes a modified EVOH (C) containing 0.3 to 40 mol% of the structural unit (I) represented by the formula (I) and zinc ions.
  • (F) is preferably contained, and the content of zinc ion (F) is more preferably 0.05 to 1.0 ⁇ mol/g.
  • the zinc ions (F) in the modified EVOH composition are contained as catalyst residues when the catalyst solution (D) is used in the production method described above.
  • the content of zinc ions (F) in the modified EVOH composition of the present invention is more preferably 0.05 to 1.0 ⁇ mol/g.
  • the zinc ion (F) content is more preferably 0.9 ⁇ mol/g or less.
  • the reaction between EVOH (A) and the monovalent epoxy compound (B) is promoted.
  • the content of zinc ions (F) is more preferably 0.1 ⁇ mol/g or more, still more preferably 0.2 ⁇ mol/g or more, and particularly preferably 0.35 ⁇ mol/g or more.
  • the modified EVOH composition of the present invention contains an alkali metal ion (G), and the molar ratio (G/F) of the alkali metal ion (G) to the zinc ion (F) is 5 to 80. preferable.
  • the alkali metal ions are mainly contained as residues when the catalyst deactivator (E) is used in the production method described above.
  • said alkali metal ions (G) are sodium ions and/or potassium ions.
  • the molar ratio (G/F) is 5 or more, the catalyst can be effectively deactivated, and even when melt-kneaded for a long time, the torque fluctuation is small and the melt stability is excellent. It becomes a resin composition.
  • the molar ratio (G/F) is more preferably 6 or more. On the other hand, if the molar ratio (G/F) exceeds 80, the resin composition may turn yellow.
  • the molar ratio (G/F) is more preferably 60 or less, and even more preferably 40 or less.
  • the modified EVOH composition of the present invention at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acid compounds and phosphoric acid compounds is added by reacting EVOH (A) with epoxy compound (B). It can also be added after the modified EVOH (C) is obtained.
  • EVOH is optionally selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acids and phosphoric acid compounds. At least one of the However, as described above, the addition of the various compounds shown above may cause coloration, viscosity reduction, etc.
  • the modified EVOH composition of the present invention can be obtained without causing problems such as coloring and viscosity reduction.
  • additives can be added to the modified EVOH composition of the present invention as necessary.
  • additives include antioxidants, plasticizers, heat stabilizers, UV absorbers, antistatic agents, lubricants, colorants, fillers, or other polymeric compounds, which may be They can be blended as long as the effects of the present invention are not impaired.
  • the total content of polymer compounds other than modified EVOH (C) and various additives may be 10% by mass or less, 5% by mass or less, or 1% by mass or less. .
  • the modified EVOH composition of the present invention preferably has an oxygen transmission rate of 100 cc ⁇ 20 ⁇ m/m 2 ⁇ day ⁇ atm or less at 20° C. and 65% RH.
  • the upper limit of the oxygen transmission rate is more preferably 50 cc ⁇ 20 ⁇ m/m 2 ⁇ day ⁇ atm or less, further preferably 20 cc ⁇ 20 ⁇ m/m 2 ⁇ day ⁇ atm or less, and 10 cc ⁇ 20 ⁇ m/m 2 ⁇ It is particularly preferable that it is day ⁇ atm or less. Since it is a resin having such a low oxygen transmission rate, the modified EVOH composition of the present invention is suitably used as a barrier material, and is particularly suitably used as a food packaging container.
  • the modified EVOH composition of the present invention is preferably molded into various molded articles such as films, sheets, containers, pipes, hoses, and fibers by melt molding. These moldings can be pulverized and molded again for the purpose of reuse. It is also possible to uniaxially or biaxially stretch films, sheets, fibers and the like. Extrusion molding, melt spinning, injection molding, injection blow molding, and the like can be used as the melt molding method.
  • the melting temperature varies depending on the melting point of the modified EVOH (C) and the like, but is preferably about 120 to 270°C.
  • the modified EVOH composition of the present invention is preferably used as an extruded product.
  • the method for producing the extruded article is not particularly limited, but preferred examples include film extrusion casting, sheet extrusion casting, pipe extrusion, hose extrusion, profile extrusion, extrusion blow molding, and inflation extrusion. . It is also possible to subject the extruded products obtained by these molding methods to secondary processing such as uniaxial or biaxial stretching or thermoforming.
  • the modified EVOH composition of the present invention can also be put into practical use as a single-layer molding. From the viewpoint of effectively utilizing the modified EVOH composition of the present invention, which is excellent in barrier properties, impact resistance, and flex resistance, films and extrusion blow-molded products (preferably bottles, etc.), flexible packaging containers (preferably flexible tubes or flexible pouches, etc.), pipes, hoses and deformed moldings.
  • a stretched film is particularly preferable from the viewpoint of taking advantage of the property of the modified EVOH composition of the present invention, which is excellent in stretchability. Among them, a stretched film obtained by stretching twice or more in at least one direction is preferable. Furthermore, it is also preferable to use the stretched film as a heat-shrinkable film.
  • the modified EVOH composition of the present invention can be practically used as a single-layer molded product, but it is also preferable to use it as a multilayer structure containing at least one layer made of the modified EVOH composition.
  • the layer structure of the multilayer structure the modified EVOH composition of the present invention, which is often used as a barrier material, is Barrier, the adhesive resin is Ad, the resin other than the barrier material is R, and the scrap recovery layer is Reg.
  • resins other than the modified EVOH composition When resins other than the modified EVOH composition are provided on both sides of the layer composed of the modified EVOH composition, they may be of different types or may be the same. Additionally, the recovered resin may be blended with resins other than the modified EVOH composition. Each layer may be a single layer, or in some cases may be multiple layers.
  • a resin composition comprising a modified EVOH (C) containing 0.3 to 40 mol% of the structural unit (I) represented by the formula (I) and an unmodified EVOH or a polyolefin, wherein the modified EVOH
  • a resin composition containing 0.05 to 1.0 ⁇ mol/g of zinc ions (F) relative to the mass of (C) is also a preferred embodiment of the present invention.
  • This resin composition can be produced by melt-kneading modified EVOH (C) and unmodified EVOH or polyolefin.
  • unmodified EVOH means EVOH containing no structural unit (I).
  • the blending ratio of modified EVOH (C) and unmodified EVOH or polyolefin is not particularly limited, it preferably contains 1 to 99% by mass of modified EVOH (C) and 1 to 99% by mass of unmodified EVOH or polyolefin. .
  • modified EVOH (C) modified EVOH
  • unmodified EVOH the same EVOH (A) as the raw material of the modified EVOH (C) can be used. It is appropriately selected depending on the application.
  • the resin composition preferably consists of 1 to 50% by mass of modified EVOH (C) and 50 to 99% by mass of unmodified EVOH. That is, it is preferable that the unmodified EVOH is the main component and the modified EVOH (C) is the secondary component. By doing so, flexibility and secondary workability can be imparted to the resin composition without significantly impairing the gas barrier properties and transparency inherent in the unmodified EVOH.
  • the modified EVOH (C) is economically advantageous because the manufacturing cost is higher than that of the unmodified EVOH. More preferably, the content of modified EVOH (C) is 5% by mass or more, and more preferably 10% by mass or more.
  • the content of unmodified EVOH is more preferably 95% by mass or less, more preferably 90% by mass or less.
  • the content of modified EVOH (C) is more preferably 40% by mass or less, more preferably 30% by mass or less.
  • the content of unmodified EVOH is more preferably 60% by mass or more, more preferably 70% by mass or more.
  • polyolefin is highly useful because of its excellent mechanical properties and workability and low cost, but its barrier properties are low. By blending the modified EVOH (C) with this, it is possible to improve the barrier property without significantly deteriorating the impact resistance, fatigue resistance, workability, and the like.
  • the polyolefin used here is not particularly limited. For example, polypropylene, polyethylene, ethylene-propylene copolymer and ethylene-vinyl acetate copolymer are preferably used, and polyethylene and polypropylene are particularly preferably used.
  • the resin composition preferably consists of 10 to 60% by mass of modified EVOH (C) and 40 to 90% by mass of polyolefin. That is, the resin composition preferably contains about half or more of the polyolefin. By doing so, it is possible to impart barrier properties to the resin composition without significantly impairing the inherent mechanical properties and workability of the polyolefin.
  • modified EVOH (C) is much more expensive to manufacture than polyolefins, so the blending ratio is economically advantageous. More preferably, the modified EVOH (C) content is 20% by mass or more, and the polyolefin content is 80% by mass or less. On the other hand, the content of modified EVOH (C) is more preferably 50% by mass or less, and the content of polyolefin is more preferably 50% by mass or more.
  • the mixed pellets are obtained by a step of pelletizing the modified EVOH (C) obtained by the production method of the present invention, and a step of dry blending the obtained modified EVOH (C) pellets and unmodified EVOH or polyolefin pellets. It can be manufactured by a manufacturing method including: According to such a mixed pellet, a molded product of the resin composition can be easily obtained simply by introducing it into a kneading apparatus and melt-molding it.
  • the resin composition obtained by the production method of the present invention and its use have been described above.
  • the resin composition thus obtained contains a novel resin composition containing a highly modified EVOH with a low catalyst residue content. That is, another aspect of the present invention is a modified ethylene-vinyl alcohol copolymer (C) containing 2 to 40 mol% of a structural unit (I) represented by the following formula (I) and a zinc ion (F). and a zinc ion (F) content of 0.05 to 1.0 ⁇ mol/g.
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an alicyclic carbonized group having 3 to 6 carbon atoms. represents a hydrogen group or a phenyl group, and the aliphatic hydrocarbon group, alicyclic hydrocarbon group and phenyl group may have a hydroxyl group, an alkoxy group, a carboxyl group or a halogen atom, and R 3 and R 4 are may be combined).
  • the method for producing this resin composition is not particularly limited.
  • the content of the structural unit (I) is 2 mol % or more, the above descriptions of the resin composition obtained by the production method of the present invention and its use apply.
  • Example 1 Ethylene content 32 mol%, degree of saponification 99.6 mol%, water-containing pellets made of ethylene-vinyl alcohol copolymer having an intrinsic viscosity of 0.0882 L / g (water content: 130% (dry base): 57% (wet 100 parts by mass of Base)) was immersed in 370 parts by mass of an aqueous solution containing 0.1 g/L of acetic acid and 0.044 g/L of potassium dihydrogen phosphate at 25° C. for 6 hours with stirring. The obtained pellets were dried at 105° C. for 20 hours to obtain dry EVOH pellets.
  • the dry EVOH pellets have a potassium content of 8 ppm (converted to metal element), an acetic acid content of 53 ppm, a phosphate compound content of 20 ppm (converted to phosphate radical), and an alkaline earth metal salt (Mg salt or Ca salt). The content was 0 ppm. Moreover, the MFR of the dried pellets was 8 g/10 minutes (190° C., under 2160 g load).
  • the EVOH pellets thus obtained were used as EVOH (A).
  • Epoxypropane was used as the monovalent epoxy compound (B).
  • a solution containing 3.3% by mass of zinc trifluoromethanesulfonate, 0.6% by mass of methanol, and 96.0% by mass of acetone was used as the catalyst solution (D).
  • Barrel C1 was cooled with water, barrels C2 to C15 were set at 200° C., and operated at a screw speed of 250 rpm.
  • the above EVOH (A) pellets were added from the resin feed port of C1 at a rate of 11 kg / hr, the internal pressure of the vent 1 was reduced to 60 mmHg, and epoxy propane was added from the injection port 1 of C8 at a rate of 1.5 kg / hr.
  • the catalyst solution (D) was mixed and then fed so that the catalyst solution (D) was added at a rate of 0.07 kg/hr (pressure during feeding: 3 MPa).
  • an 8.2% by mass aqueous solution of ethylenediaminetetraacetic acid trisodium trihydrate (EDTA) as a catalyst deactivator (E) was added to C13. It was added from injection port 2 at a rate of 0.11 kg/hr.
  • the mixing ratio of the monovalent epoxy compound (B) in the melt-kneading operation was 13.6 parts by mass with respect to 100 parts by mass of EVOH (A).
  • Catalyst solution (D) was added at 0.57 ⁇ mol/g in moles of zinc ions (F) relative to the mass of EVOH (A).
  • the molar ratio (E/F) of the catalyst deactivator (E) to the zinc ions (F) contained in the catalyst solution (D) was 3.5.
  • the vent 3 was evacuated to an internal pressure of 20 mmHg to remove moisture and obtain modified EVOH (C).
  • the resulting modified EVOH (C) had an MFR of 7 g/10 min (190°C, under a load of 2160 g) and a melting point of 132°C.
  • the content of zinc ions is 35 ppm (0.54 ⁇ mol/g)
  • the content of alkali metal ions (G) is 138 ppm (5.9 ⁇ mol/g) in terms of metal elements [sodium: 130 ppm (5.7 ⁇ mol/g ), potassium: 8 ppm (0.2 ⁇ mol/g)].
  • the alkaline earth metal salt (Mg salt or Ca salt) content was 0 ppm.
  • the alkaline earth metal salt content was 0 ppm also in other examples and comparative examples of the present application.
  • the molar ratio (G/F) of alkali metal ions (G) to zinc ions (F) was 10.9.
  • the number of moles of sulfonate ions contained is twice the number of moles of zinc ions (F), and this is the same for Examples 2-11.
  • the chemical structure of the modified EVOH (C) modified with epoxypropane thus obtained was determined by performing NMR measurement after trifluoroacetylating the modified EVOH (C) according to the procedure described in Patent Document 1. .
  • the modified EVOH (C) had an ethylene content of 32 mol% and a structural unit (I) content of 5.5 mol%.
  • a multi-layer sheet (ionomer resin layer/adhesive resin layer /modified EVOH (C) layer/adhesive resin layer/ionomer resin layer).
  • the composition of the sheet consists of two outermost layers of ionomer resin (“Himilan 1652” manufactured by Mitsui DuPont Polychemicals) each having a thickness of 250 ⁇ m, an adhesive resin (“Admer NF500” manufactured by Mitsui Chemicals) each having a thickness of 30 ⁇ m, and a modified EVOH (C ) layer is 90 ⁇ m.
  • the multi-layer sheet thus obtained was subjected to simultaneous biaxial stretching at 60° C. at a stretching ratio of 4 ⁇ 4 times using a pantograph type biaxial stretching apparatus manufactured by Toyo Seiki Co., Ltd.
  • the film appearance after stretching was evaluated according to the following evaluation criteria.
  • Judgment Criteria A: No unevenness and local uneven thickness.
  • C Slight nonuniformity and slight local unevenness in thickness, but bearable for practical use.
  • D Significant unevenness and large local uneven thickness.
  • E The film was torn.
  • the stretched film of this example had neither unevenness nor local unevenness in thickness, and was graded as A.
  • the minimum value Tmin correlates with the degree of decomposition of the resin under high temperature shear, and the smaller ⁇ T, the higher the long-term operational stability during melt molding of the resin.
  • ⁇ T of the modified EVOH (C) obtained in this example was 0.3 (kgf ⁇ m).
  • the peeling interface is the interface between the modified EVOH (C) layer and the adhesive resin layer.
  • the yellowness index (YI) of the obtained resin composition pellets was measured using a spectrophotometer ("LabScan XE Sensor" manufactured by HunterLab) and judged according to the following criteria. was evaluated as A.
  • the YI value is an index representing the yellowness of an object, and the higher the YI value, the stronger the yellowness, while the lower the YI value, the weaker the yellowness and less coloring.
  • the manufacturing method of the modified EVOH (C) is summarized in Table 1, the composition is summarized in Table 2, and the film and resin evaluation results are summarized in Table 3.
  • Example 2 As raw material EVOH pellets, EVOH with an ethylene content of 44 mol%, a degree of saponification of 99.8 mol%, an intrinsic viscosity of 0.096 L/g, and an MFR of 5 g/10 minutes (190°C, under a load of 2160 g) ⁇ acetic acid content of 53 ppm , a sodium content of 1 ppm (converted to metal element), a potassium content of 8 ppm (converted to metal element), and a phosphoric acid compound content of 20 ppm (converted to phosphate radical) ⁇ were placed in a polyethylene bag. Subsequently, 395 g of the same catalyst solution (D) as in Example 1 was added to the EVOH in the bag.
  • D the same catalyst solution
  • the EVOH to which the catalyst solution was added as described above was heated at 50° C. for 10 hours with the mouth of the bag closed while occasionally shaking to impregnate the EVOH with the catalyst solution (D).
  • the obtained EVOH was vacuum-dried at 30° C. to obtain EVOH pellets containing zinc ions (F) and sulfonate ions.
  • EVOH a pellet mixture obtained by dry blending 10 parts by mass of EVOH pellets containing zinc ions and sulfonate ions with 90 parts by mass of the raw material EVOH pellets was used. Also, 1,2-epoxybutane was used as the monovalent epoxy compound (B).
  • Barrel C1 was water-cooled, barrels C2-C3 were set at 200° C., and barrels C4-C15 were set at 220° C., and the operation was performed at a screw speed of 200 rpm.
  • the pellet mixture was fed as EVOH (A) at a rate of 11 kg / hr, the internal pressure of the vent 1 was reduced to 60 mmHg, and epoxybutane was fed from the injection port 1 of C8 at a rate of 2.5 kg / hr.
  • the vent 2 was evacuated to an internal pressure of 200 mmHg to remove unreacted epoxybutane, and an 8.2% by mass aqueous solution of trisodium ethylenediaminetetraacetate trihydrate was added at a rate of 0.14 kg/hr from the injection port 2 of C13. .
  • the mixing ratio of the monovalent epoxy compound (B) in the melt-kneading operation was 22.7 parts by mass with respect to 100 parts by mass of EVOH (A).
  • Zinc ions (F) were added at 0.78 ⁇ mol/g in moles relative to the mass of EVOH (A).
  • the molar ratio (E/F) of the catalyst deactivator (E) to the zinc ions (F) was 3.3.
  • the vent 3 was evacuated to an internal pressure of 20 mmHg to remove moisture and obtain modified EVOH (C).
  • the modified EVOH (C) had an MFR of 5 g/10 minutes (190°C, under a load of 2160 g) and a melting point of 109°C.
  • the zinc ion (F) content is 46 ppm (0.70 ⁇ mol/g)
  • the alkali metal salt content is 168 ppm (7.1 ⁇ mol/g) in terms of metal element [sodium: 160 ppm (6.9 ⁇ mol/g ), potassium: 8 ppm (0.2 ⁇ mol/g)].
  • the chemical structure of the modified EVOH (C) modified with epoxybutane obtained in this manner was obtained by trifluoroacetylation of the modified EVOH (C) according to the procedure described in Patent Document 1 and then performing NMR measurement. rice field.
  • the modified EVOH (C) prepared in Example 2 had an ethylene content of 44 mol % and a structural unit (I) content of 7.0 mol %.
  • Example 3 As raw material EVOH pellets, EVOH ⁇ Using pellets with an acetic acid content of 53 ppm, a sodium content of 11 ppm (converted to metal element), a potassium content of 8 ppm (converted to metal element), and a phosphoric acid compound content of 20 ppm (converted to phosphate group) ⁇ , a catalyst deactivator (E) A modified EVOH (C) was obtained in the same manner as in Example 2, except that the addition rate of the solution was changed to 0.15 kg/hr. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 4 A modified EVOH (C) was obtained in the same manner as in Example 1, except that the addition rate of the catalyst solution (D) was changed to 0.11 kg/hr. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 5 A modified EVOH (C) was obtained in the same manner as in Example 1, except that the addition rate of the catalyst solution (D) was changed to 0.04 kg/hr. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 6 A modified EVOH (C) was obtained in the same manner as in Example 1, except that the addition rate of the catalyst deactivator (E) solution was changed to 0.22 kg/hr. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 7 Example 1 was repeated except that the addition rate of the catalyst solution (D) was changed to 0.04 kg/hr and the addition rate of the catalyst deactivator (E) solution was changed to 0.32 kg/hr. to obtain modified EVOH (C). Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 8 Ethylene content 32 mol%, degree of saponification 99.6 mol%, water-containing pellets made of ethylene-vinyl alcohol copolymer having an intrinsic viscosity of 0.0882 L / g (water content: 130% (dry base): 57% (wet Base))) was immersed and stirred in 370 parts by mass of an aqueous solution containing 0.1 g/L of acetic acid and 0.88 g/L of potassium dihydrogen phosphate at 25°C for 6 hours. The obtained pellets were dried at 105° C. for 20 hours to obtain dry EVOH pellets.
  • the dry EVOH pellets have a potassium content of 160 ppm (converted to metal element), an acetic acid content of 53 ppm, a phosphate compound content of 400 ppm (converted to phosphate radical), and an alkaline earth metal salt (Mg salt or Ca salt). The content was 0 ppm.
  • Modified EVOH (C) was obtained in the same manner as in Example 1, except that the dried EVOH pellets thus obtained were used as EVOH (A). Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 9 Ethylene content 32 mol%, degree of saponification 99.6 mol%, water-containing pellets made of ethylene-vinyl alcohol copolymer having an intrinsic viscosity of 0.0882 L / g (water content: 130% (dry base): 57% (wet 100 parts by mass of Base)) was immersed in 370 parts by mass of an aqueous solution containing 0.1 g/L of acetic acid and 0.022 g/L of potassium dihydrogen phosphate at 25° C. for 6 hours while stirring. The obtained pellets were dried at 105° C. for 20 hours to obtain dry EVOH pellets.
  • the dry EVOH pellets have a potassium content of 4 ppm (converted to metal element), an acetic acid content of 53 ppm, a phosphate compound content of 10 ppm (converted to phosphate radical), and an alkaline earth metal salt (Mg salt or Ca salt). The content was 0 ppm.
  • the dry EVOH pellets thus obtained were used as EVOH (A), the addition rate of the catalyst solution (D) was changed to 0.11 kg/hr, and the addition rate of the catalyst deactivator (E) solution was changed to 0.08 kg/hr.
  • a modified EVOH (C) was obtained in the same manner as in Example 1, except that it was changed. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 10 A modified EVOH (C) was obtained in the same manner as in Example 1, except that the addition rate of the catalyst solution (D) was changed to 0.01 kg/hr. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 11 Modified EVOH (C) was obtained in the same manner as in Example 1, except that the catalyst deactivator (E) was changed to a 4.9% by mass aqueous solution of sodium acetate. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Comparative example 1 28 parts by mass of zinc acetylacetonate monohydrate was mixed with 957 parts by mass of 1,2-dimethoxyethane to obtain a mixed solution. 15 parts by mass of trifluoromethanesulfonic acid was added to the obtained mixture while stirring to obtain a catalyst solution (D).
  • the catalyst solution (D) contains 1 mol of trifluoromethanesulfonic acid per 1 mol of zinc acetylacetonate monohydrate.
  • a modified EVOH (C) was obtained in the same manner as in Example 1, except that the catalyst solution (D) was added at a rate of 0.22 kg/hr. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3. Although the amount of zinc ions (F) contained in modified EVOH (C) was three times or more that of Example 1, the content of structural units (I) was the same as in Example 1. From this, it can be seen that a large amount of zinc ions (F) were required as compared with the examples. The number of moles of sulfonate ions contained in modified EVOH (C) was one times the number of moles of zinc ions (F).
  • Comparative example 2 5 kg of the same raw material pellets as in Example 2 were placed in a polyethylene bag. Subsequently, a catalyst solution (D) prepared by dissolving 27.44 g (0.125 mol) of zinc acetate dihydrate and 15 g (0.1 mol) of trifluoromethanesulfonic acid in 500 g of water was added to the EVOH in the bag. The EVOH to which the catalyst solution had been added as described above was heated at 90° C. for 5 hours with the mouth of the bag closed while occasionally shaking to impregnate the EVOH with the catalyst solution (D). The obtained EVOH was vacuum-dried at 90° C. to obtain EVOH pellets containing zinc ions (F) and sulfonate ions.
  • D catalyst solution prepared by dissolving 27.44 g (0.125 mol) of zinc acetate dihydrate and 15 g (0.1 mol) of trifluoromethanesulfonic acid in 500 g of water was added to the EVOH
  • EVOH (A) a pellet mixture obtained by dry blending 10 parts by mass of EVOH pellets containing zinc ions and sulfonate ions with 90 parts by mass of the raw material EVOH pellets was used.
  • a modified EVOH (C) was obtained in the same manner as in Example 2 except that the EVOH (A) thus obtained was used.
  • Using the modified EVOH (C) thus obtained a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • the number of moles of sulfonate ions contained in modified EVOH (C) was 0.8 times the number of moles of zinc ions (F).
  • Comparative example 3 In Example 1, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1 using dry EVOH pellets before being fed into the extruder. The results are summarized in Tables 1-3.
  • the flex resistance was measured by bending 25 times, 30 times, 35 times, 40 times, 50 times, 60 times, 80 times and 100 times.
  • Comparative example 4 In Example 2, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1 using raw EVOH pellets before being impregnated with the catalyst solution (D). The results are summarized in Tables 1-3. The flex resistance was measured in the same manner as in Comparative Example 3.
  • Comparative example 5 A modified EVOH (C) was obtained in the same manner as in Example 1, except that the feeding of the catalyst solution (D) and the catalyst deactivator (E) was stopped. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 2 instead of using a pellet mixture obtained by dry-blending EVOH pellets containing zinc ions and sulfonate ions with raw EVOH pellets, only raw EVOH pellets were used, and the feed of the catalyst deactivator (E) was stopped.
  • Modified EVOH (C) was obtained in the same manner as in Example 1 except that Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Comparative example 7 A modified EVOH (C) was obtained in the same manner as in Comparative Example 1, except that the catalyst solution (D) was added at a rate of 0.06 kg/hr. Using the modified EVOH (C) thus obtained, a single layer film and a multilayer film were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1-3.
  • Example 12 Provide of resin composition pellets Ethylene content 32 mol%, saponification degree 99.9 mol%, melt flow rate (190 ° C., under 2160 g load) 1.6 g / 10 minutes, melting point 183 ° C. Unmodified EVOH 80 parts by mass , and 20 parts by mass of the modified EVOH (C) obtained in Example 1 were dry-blended to obtain mixed pellets. Using a 30mm ⁇ twin-screw extruder (Japan Steel Works, Ltd.
  • the mixed pellets are extruded and pelletized under the conditions of a barrel temperature of 200 ° C., a screw rotation speed of 300 rpm, and an extruded resin amount of 25 kg / hour. After that, hot air drying was performed at 80° C. for 16 hours to obtain resin composition pellets.
  • the phosphoric acid compound content (in terms of phosphate root), acetic acid content and Na ion content (in terms of metal element) of the obtained resin composition were measured and found to be 40 ppm, 250 ppm and 160 ppm, respectively.
  • the melt flow rate of the resin composition (190° C., under 2160 g load) was 1.9 g/10 minutes.
  • Example 1(a) a monolayer film having a thickness of 25 ⁇ m was obtained in the same manner as in Example 1(a). Using the obtained single-layer film, the oxygen transmission rate was measured in the same manner as in Example 1 (b). showed sex.
  • Young's modulus was 180 kgf/mm 2 .
  • the monolayer film was conditioned in an atmosphere of 23° C. and 50% RH for 7 days, and then cut into strips with a width of 15 mm. Using this film sample, the tensile strength at yield and tensile elongation at break were measured with an Autograph AGS-H manufactured by Shimadzu Corporation under the conditions of a chuck interval of 50 mm and a tensile speed of 500 mm/min. Ten samples were measured, and the average value was obtained. The tensile strength at yield and tensile elongation at break were 6.5 kgf/mm 2 and 310%, respectively.

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Abstract

L'invention concerne un procédé de production d'un copolymère d'éthylène-alcool vinylique modifié (C), le procédé comprenant la réaction d'un copolymère d'éthylène-alcool vinylique (A) et d'un composé époxy monovalent en C2-8 (B) par malaxage à l'état fondu dans une extrudeuse à l'aide d'une solution de catalyseur (D) qui est une solution d'acétone contenant des ions zinc (F) et des ions sulfonate. Dans ce procédé, il est préférable d'utiliser 0,05-1,0 μmol/g d'ions zinc (F) en termes de nombre de moles par rapport à la masse du copolymère éthylène-alcool vinylique (A). De plus, il est préférable d'ajouter un mélange du composé époxy monovalent (B) et de la solution de catalyseur (D) au copolymère d'éthylène-alcool vinylique fondu (A). Il est ainsi fourni un procédé de production d'EVOH modifié ayant une stabilité à l'état fondu exceptionnelle ainsi que des propriétés de barrière exceptionnelles, une aptitude à l'étirage, et analogues.
PCT/JP2022/047645 2021-12-24 2022-12-23 Procédé de production d'un copolymère d'éthylène-alcool vinylique modifié et composition de résine le comprenant WO2023120705A1 (fr)

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JP2023117618A JP2023139112A (ja) 2021-12-24 2023-07-19 変性エチレン－ビニルアルコール共重合体の製造方法及びそれを含む樹脂組成物

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002092643A1 (fr) * 2001-05-14 2002-11-21 Kuraray Co., Ltd. Copolymere ethylene-alcool de vinyle modifie et methode de production du copolymere
JP2004160755A (ja) * 2002-11-11 2004-06-10 Kuraray Co Ltd 変性エチレン−ビニルアルコール共重合体からなる表面層を有する多層構造体
WO2011125739A1 (fr) * 2010-03-31 2011-10-13 株式会社クラレ Structure multicouche, stratifié et procédés de production de ceux-ci
WO2012165441A1 (fr) * 2011-05-31 2012-12-06 株式会社クラレ Revêtement intérieur pour pneumatiques, son procédé de fabrication et pneumatique
WO2014024912A1 (fr) * 2012-08-09 2014-02-13 株式会社クラレ Copolymère éthylène-(alcool vinylique) modifié, son procédé de fabrication, et son utilisation
JP2015083665A (ja) * 2013-09-20 2015-04-30 日本合成化学工業株式会社 エチレンービニルアルコール共重合体組成物、並びにこれを用いた積層体及びその二次成形品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002092643A1 (fr) * 2001-05-14 2002-11-21 Kuraray Co., Ltd. Copolymere ethylene-alcool de vinyle modifie et methode de production du copolymere
JP2004160755A (ja) * 2002-11-11 2004-06-10 Kuraray Co Ltd 変性エチレン−ビニルアルコール共重合体からなる表面層を有する多層構造体
WO2011125739A1 (fr) * 2010-03-31 2011-10-13 株式会社クラレ Structure multicouche, stratifié et procédés de production de ceux-ci
WO2012165441A1 (fr) * 2011-05-31 2012-12-06 株式会社クラレ Revêtement intérieur pour pneumatiques, son procédé de fabrication et pneumatique
WO2014024912A1 (fr) * 2012-08-09 2014-02-13 株式会社クラレ Copolymère éthylène-(alcool vinylique) modifié, son procédé de fabrication, et son utilisation
JP2015083665A (ja) * 2013-09-20 2015-04-30 日本合成化学工業株式会社 エチレンービニルアルコール共重合体組成物、並びにこれを用いた積層体及びその二次成形品

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