Classifications

• • 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
  • C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof

Definitions

• the present invention relates to a composition containing a vinyl alcohol polymer and a method for separating a vinyl alcohol polymer.
• PVA Vinyl alcohol polymers
• aqueous PVA solution is generally prepared by mixing PVA with water and heating, but in the case of highly hydrophobic PVA, it is usually not possible to dissolve it in water using this method, and it is known that an aqueous solution can be prepared by adding an anionic surfactant (Patent Document 1). This is due to the fact that the highly hydrophobic PVA and the anionic surfactant form a complex in water (Non-Patent Document 1).
• composition containing PVA that allows easy separation and extraction of PVA from a PVA aqueous solution once it has been prepared.
• One of the objects of the present invention is to provide a composition containing PVA that, when made into an aqueous solution, is homogeneous and from which the PVA contained in the aqueous solution can be easily separated.
• Another object of the present invention is to provide a method for separating PVA. Note that "a homogeneous aqueous solution" may mean a state in which the PVA is uniformly dissolved.
• the present invention is [1] A composition comprising a vinyl alcohol polymer (A) having a peak top retention time (RT) of 22 minutes or longer as measured by reversed-phase gradient high-performance liquid chromatography using a water-ethanol eluent, and a compound (B), wherein the compound (B) is a compound represented by formula (1); [In formula (1), X represents an oxygen atom, a group represented by the following formula (2), or a group represented by the following formula (3).
• Y represents an atomic group having 1 to 10 carbon atoms.
• Z represents one selected from the group consisting of a carboxy group, a sulfo group, a phosphate group, salts thereof, and anions thereof.
• R1 represents an acyl group or a hydrocarbon group.]
• R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a bond bonded to Y.
• composition of the present invention When the composition of the present invention is dissolved in an aqueous solution, the solution is homogeneous and the PVA contained in the aqueous solution is easily separated.
• composition of the present invention comprises a vinyl alcohol-based polymer (A) (hereinafter, may be referred to as "PVA (A)”) having a peak top retention time RT of 22 minutes or longer as measured by reversed-phase partition gradient high performance liquid chromatography using a water-ethanol eluent, and a compound (B), wherein the compound (B) is a compound represented by formula (1).
• PVA vinyl alcohol-based polymer
• X represents an oxygen atom, a group represented by the following formula (2), or a group represented by the following formula (3).
• Y represents an atomic group having 1 to 10 carbon atoms.
• Z represents one member selected from the group consisting of a carboxy group, a sulfo group, a phosphate group, salts thereof, and anions thereof.
• R1 represents an acyl group or a hydrocarbon group.
• R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a bond bonded to Y. * represents a bond.
• R 2 , R 3 or R 4 is a bond bonded to Y, X and Y form a ring structure.
• the ratio of PVA (A) to compound (B) contained in the composition is preferably 99.9:0.1 to 80:20 by mass (A):(B), but may also be 99:1 to 85:15, or 97:3 to 90:10. In some cases, it may also be preferable for (A):(B) to be 50:50 to 0.1:99.9. By being within this range, a more uniform solution can be obtained, for example, when preparing an aqueous solution with a high concentration of PVA (A), such as 30% by mass.
• the composition can be produced using any method that allows mixing of PVA (A) and compound (B).
• PVA (A) and compound (B) may be mixed directly, compound (B) may be added to a solution containing PVA (A), PVA (A) may be added to a solution containing compound (B), or the composition may be produced by mixing a solution containing PVA (A) and a solution containing compound (B).
• the composition of the present invention can be obtained by adding compound (B) to an aqueous solution of PVA (A).
• the PVA (A) contained in the composition of the present invention is a polymer having a vinyl alcohol unit as a structural unit.
• the lower limit of the ratio of the vinyl alcohol unit to the total structural units in the PVA (A) is preferably 10 mol%, more preferably 20 mol%, even more preferably 30 mol%, and even more preferably 40 mol%.
• the upper limit of the ratio of the vinyl alcohol unit is preferably 90 mol%, more preferably 80 mol%, and even more preferably 60 mol%.
• the PVA (A) may be obtained by, for example, polymerizing a vinyl ester monomer and saponifying the obtained vinyl ester polymer, and the PVA (A) may contain, for example, a vinyl ester unit in addition to the vinyl alcohol unit.
• PVA(A) has a peak top retention time (RT) of 22 minutes or more when measured by reversed-phase partition gradient high-performance liquid chromatography using a water-ethanol eluent.
• peak top means the point at which the detection intensity in the chromatogram obtained by chromatography measurement is the maximum value and is a local maximum value, and refers to the peak top derived from PVA(A).
• PVA(A) preferably has a retention time RT of more than 22 minutes.
• PVA(A) preferably has a retention time RT of 25 minutes or less, and more preferably PVA(A) with 22 minutes ⁇ RT ⁇ 25 minutes.
• the retention time RT of PVA(A) can be adjusted by introducing a modified group or adjusting the degree of saponification and the viscosity average degree of polymerization.
• the retention time RT of the PVA (A) is measured under the following measurement conditions.
• ⁇ Measurement conditions> Column: Shimpack G-ODS (4) (Shimadzu Corporation, octadecyl-modified spherical fully porous silica gel, inner diameter 4 mm ⁇ length 10 mm, particle size 5 ⁇ m) Column temperature: 45°C Eluent: a mixture of ion-exchanged water (X) and ethanol (purity 99.5%) (Y) Eluent composition at each measurement time: 0 to 5 minutes: (Y) concentration 5% by volume constant 5 to 25 minutes: (Y) concentration 5 to 100% by volume 25 to 40 minutes: (Y) concentration 100% by volume constant 40 to 41 minutes: (Y) concentration 100 to 5% by volume 41 to 55 minutes: (Y) concentration is constant at 5% by volume (The (Y) concentration between 5 and 25 minutes is gradually increased from 5% by volume to 100% by volume at a substantially constant rate.
• the lower limit of the saponification degree of PVA (A) is preferably 20 mol%, more preferably 30 mol%, even more preferably 40 mol%, and even more preferably 45 mol%.
• the upper limit of the saponification degree of PVA (A) is preferably 90 mol%, more preferably 80 mol%, even more preferably 70 mol%, even more preferably 60 mol%, and particularly preferably 55 mol%.
• the saponification degree of PVA (A) is measured by the method described in JIS K6726:1994.
• the lower limit of the viscosity average degree of polymerization of PVA(A) is preferably 100, and more preferably 200.
• the upper limit of the viscosity average degree of polymerization of PVA(A) is preferably 3500, more preferably 2000, even more preferably 1000, even more preferably 500, and particularly preferably 300.
• the viscosity average degree of polymerization of PVA(A) is measured in accordance with JIS K6726:1994.
• PVA (A) can be produced, for example, by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester monomer.
• vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate, and vinyl oleate.
• vinyl acetate is preferred from the viewpoints of availability and economy.
• the vinyl ester monomer only one type may be used, or two or more types may be used in combination.
• PVA (A) may be a polymer consisting of only monomer units derived from vinyl ester monomers, or may be a polymer consisting of only monomer units derived from vinyl acetate.
• the terminal structure of PVA (A) may be a structure derived from a polymerization initiator, a chain transfer agent, or the like other than a vinyl ester monomer.
• PVA (A) may be a polymer consisting essentially of only monomer units derived from vinyl ester monomers, or may be a polymer consisting essentially of only monomer units derived from vinyl acetate.
• the monomer units derived from vinyl ester monomers may be vinyl alcohol units and vinyl ester units.
• the lower limit of the ratio of the monomer units derived from vinyl ester monomers to the total structural units in PVA (A) is preferably, for example, 90 mol%, and may be 95 mol%, 98 mol%, 99 mol%, 99.5 mol%, or 99.9 mol%.
• the upper limit of the ratio of the monomer units derived from vinyl ester monomers may be 100 mol%.
• the terminal structure of PVA (A) may be a structure derived from a monomer other than a vinyl ester monomer.
• the PVA (A) may be a modified PVA into which units or functional groups other than units derived from vinyl ester monomers have been introduced using techniques such as copolymerization, acetalization, and esterification.
• the copolymer-modified PVA can be obtained, for example, by saponifying a vinyl ester copolymer obtained by copolymerizing a vinyl ester monomer with a monomer other than a vinyl ester monomer.
• the monomer other than the vinyl ester monomer that is copolymerized with the vinyl ester monomer can be used as long as it is copolymerizable with the vinyl ester monomer, and examples of such monomers include ⁇ -olefins such as propylene, 1-butene, isobutene, pentene, 1-hexene, 1-octene, 1-dodecene, 1-hexadecene, and 1-octadecene; methacrylic acid; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, and octadecyl (meth)
• Such monomers include amides, methacrylamide derivatives such as N-ethyl methacrylamide, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, lauryl vinyl ether, and vinyl ether stearate, allyl acetate, allyl ethers such as propyl allyl ether, butyl allyl ether, and hexyl allyl ether, monomers having an oxyalkylene group, isopropenyl acetate, and monomers having a silyl group such as vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, 3-(meth)acrylamidopropyltrimethoxysilane, and 3-(meth)acrylamidopropyl
• PVA (A) is a modified PVA in which a modifying group has been introduced by acetalization
• the modifying agent used for the introduction of the modifying group by acetalization is not particularly limited, and examples thereof include linear, branched, cyclically saturated, cyclically unsaturated, or aromatic aldehydes and aldoses having 1 to 19 carbon atoms.
• the modifying agent may be one in which one or more hydrogen atoms have been substituted with a halogen or the like.
• the modifying agents may be used alone or in combination of two or more kinds.
• the modifying agent used for introducing the modifying group by esterification is not particularly limited, and examples thereof include linear, branched, cyclic saturated, cyclic unsaturated, or aromatic carboxylic acids having 1 to 19 carbon atoms, carboxylic acid halides, vinyl esters, and carboxylic acid derivatives such as fatty acids. Specific examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, and acid chlorides thereof.
• the modifying agent may be, for example, one or more hydrogen atoms substituted with halogens or the like.
• the modifying agents may be used alone or in combination of two or more.
• PVA (A) can be produced according to a conventional method.
• methods for obtaining a vinyl ester polymer from a vinyl ester monomer include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and dispersion polymerization.
• the solution polymerization method is industrially preferred.
• a polymerization initiator may be used.
• the polymerization initiator may be selected from known initiators depending on the polymerization method. Specific examples include azo initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate, perester compounds such as t-butyl peroxyneodecanate, ⁇ -cumyl peroxyneodecanate, and t-butyl peroxydecanate, acetylcyclohexylsulfonyl peroxide, and peroxide initiators such as 2,4,4-trimethylpentyl-2-peroxyphen
• the amount of polymerization initiator may be appropriately determined depending on the type of monomer or initiator used, the desired degree of polymerization, etc., but is preferably 0.20 to 0.33% by mass based on the total mass of the vinyl ester monomer.
• a chain transfer agent may be used.
• the chain transfer agent may be selected from known chain transfer agents depending on the polymerization method. Specific examples include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; and phosphinates such as sodium phosphinate monohydrate. Among these, aldehydes and ketones are preferably used.
• the amount of the chain transfer agent is not particularly limited as long as it can be determined to the intended degree of polymerization of the vinyl ester polymer depending on the chain transfer constant of the chain transfer agent to be added.
• functional groups may be introduced using them, and an aliphatic hydrocarbon group may be introduced at the end using a chain transfer agent having an alkyl group, or an ionic functional group may be introduced at the end using a chain transfer agent having a carboxy group.
• Polymerization conditions, etc. may be appropriately determined depending on the type and amount of monomer used, the desired physical properties, the polymerization method employed, etc.
• the polymerization temperature is usually 0 to 150°C, preferably 20 to 120°C.
• the polymerization rate of the vinyl ester polymer may be, for example, 20 to 95%. From the viewpoint of improving the yield and controlling the degree of polymerization, the polymerization rate is preferably 30% or more, and more preferably 40% or more.
• the saponification reaction of the obtained vinyl ester polymer can be carried out by alcoholysis or hydrolysis using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methoxide, or an acidic catalyst such as p-toluenesulfonic acid.
• Solvents used in the saponification reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; and aromatic hydrocarbons such as benzene and toluene. These may be used alone or in combination of two or more.
• the saponification reaction is preferably carried out in the presence of sodium hydroxide, which is a basic catalyst, using methanol or a mixed solution of methanol and methyl acetate as the solvent.
• the amount of catalyst used in the saponification reaction may be appropriately determined depending on the type of catalyst used, the desired degree of saponification, etc.
• the ratio (molar ratio) of the catalyst to the vinyl ester monomer in the vinyl ester copolymer is preferably 0.0015 to 0.0095.
• Compound (B) The compound (B) contained in the composition of the present invention is a compound represented by the following formula (1).
• X represents an oxygen atom, a group represented by the following formula (2), or a group represented by the following formula (3).
• Y represents an atomic group having 1 to 10 carbon atoms.
• Z represents one member selected from the group consisting of a carboxy group, a sulfo group, a phosphate group, salts thereof, and anions thereof.
• R1 represents an acyl group or a hydrocarbon group.
• R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a bond bonded to Y. * represents a bond.
• compound (B) can improve the uniformity of the aqueous solution and the separability of the PVA by having, as X, a group containing an electron-withdrawing atom such as an oxygen atom or a nitrogen atom.
• X is preferably a group represented by the formula (2) or a group represented by the formula (3), more preferably a group represented by the formula (2).
• R 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a methyl group.
• R 3 and R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
• X is preferably a secondary amine, a tertiary amine or a quaternary amine, and more preferably a secondary amine or a tertiary amine.
• Y is an atomic group having 1 to 10 carbon atoms, preferably an atomic group having 1 to 8 carbon atoms, and more preferably an atomic group having 1 to 5 carbon atoms.
• Y may contain an atom other than carbon.
• the atom other than carbon is not particularly limited, but is preferably at least one selected from the group consisting of oxygen, nitrogen, and hydrogen.
• Y may be bonded to X to form a ring structure.
• R 2 is a bond bonded to Y
• at least one of R 3 and R 4 is a bond bonded to Y.
• Y is not bonded to X to form a ring structure.
• Y is preferably a substituted or unsubstituted hydrocarbon group.
• the hydrocarbon group represented by Y is more preferably a hydrocarbon group having 1 to 5 carbon atoms, even more preferably a group represented by -(CH 2 ) n - (n is an integer of 1 to 5), even more preferably a group represented by -(CH 2 ) n - (n is an integer of 1 to 3), and particularly preferably a methylene group (-CH 2 -) or an ethylene group (-CH 2 -CH 2 -).
• X containing an oxygen atom or a nitrogen atom, which is an electron-withdrawing atom is located in the vicinity of Z, which can further improve the uniformity of the aqueous solution and the separability of the PVA.
• a part or all of the hydrogen atoms of the hydrocarbon group represented by Y may be substituted with a substituent.
• the substituent is preferably a carboxy group, a salt of a carboxy group, or an anion of a carboxy group.
• Z is preferably a salt of a carboxy group, a salt of a sulfo group, or a salt of a phosphate group.
• Z is also preferably a carboxy group, a salt of a carboxy group, or an anion of a carboxy group, and is more preferably a salt of a carboxy group.
• Z may be an anion of a carboxy group ( -COO- ), an anion of a sulfo group ( -SO3- ) , or an anion of a phosphate group ( -HPO4- or -PO42- ).
• compound (B) may be a phosphate ester or a sulfonate ester.
• the type of salt is not particularly limited and includes alkali metal salts such as sodium, potassium, and lithium; alkaline earth metal salts such as calcium and magnesium; aluminum salts; zinc salts; ammonium salts; organic amine salts such as monoethanolamine, diethanolamine, triethanolamine (TEA), and triisopropanolamine; and basic salts such as arginine and lysine, with alkali metal salts being preferred, and sodium salts being more preferred.
• alkali metal salts such as sodium, potassium, and lithium
• alkaline earth metal salts such as calcium and magnesium
• aluminum salts such as aluminum salts
• zinc salts such as ammonium salts
• organic amine salts such as monoethanolamine, diethanolamine, triethanolamine (TEA), and triisopropanolamine
• basic salts such as arginine and lysine, with alkali metal salts being preferred, and sodium salts being more preferred.
• compound (B) which is a carboxylic acid, sulfonic acid, or phosphoric acid can be added with an alkali or an aqueous solution thereof to obtain compound (B) which is a salt thereof.
• an alkali or an aqueous solution thereof can be added to the N-long-chain acyl amino acid.
• R 1 is preferably an acyl group.
• R 1 is preferably a group represented by the following formula (4), in which R 5 represents a saturated or unsaturated hydrocarbon group having 7 to 20 carbon atoms which may have a substituent.
• R5 is preferably a saturated or unsaturated hydrocarbon group having 7 to 20 carbon atoms, more preferably a linear saturated or unsaturated hydrocarbon group having 7 to 20 carbon atoms, even more preferably a linear saturated hydrocarbon group having 7 to 20 carbon atoms, and even more preferably a linear saturated hydrocarbon group having 9 to 13 carbon atoms.
• the acyl group is preferably derived from coconut oil.
• R1 is a hydrocarbon group
• the hydrocarbon group is preferably a saturated or unsaturated hydrocarbon group having 7 to 21 carbon atoms, more preferably a linear saturated or unsaturated hydrocarbon group having 7 to 21 carbon atoms, and even more preferably a linear saturated hydrocarbon group having 7 to 21 carbon atoms.
• R1 is preferably an n-octyl group, an n-decyl group, a lauryl group, or an n-tetradecyl group.
• X in formula (1) is a group represented by formula (2) and R 1 is an acyl group.
• R 1 is a hydrocarbon group having 1 to 5 carbon atoms
• Z is a salt of a carboxy group
• R 1 is a group represented by formula (4)
• R 2 is an alkyl group having 1 to 3 carbon atoms
• R 5 is a linear saturated hydrocarbon group having 9 to 13 carbon atoms.
• compound (B) is preferably at least one selected from the group consisting of acylamino acid salts and acyllactates.
• the acylamino acid salt is preferably an N-acylamino acid salt.
• the N-acylamino acid salt preferably has an acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms.
• compound (B) is preferably at least one selected from the group consisting of phosphate salts, acylamino acid salts, acyl lactates, acyltaurate salts, soaps (higher fatty acids), alkylsulfosuccinates, acyl hydrolyzed collagen salts, and acylisethionates, more preferably at least one selected from the group consisting of acyl lactates and acylamino acid salts, even more preferably an acylamino acid salt, and even more preferably an N-acylamino acid salt.
• N-acylamino acid salts are salts of N-acylamino acids in which an acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms has been introduced into the amino group of the amino acid (hereinafter sometimes referred to as "N-long-chain acylamino acid salts").
• the amino acid residue of the N-acylamino acid salt may be any of various amino acids such as ⁇ -amino acids, ⁇ -amino acids, ⁇ -amino acids, or ⁇ -amino acids, and the amino group may be N-methyl or N-ethyl.
• amino acid residue of the N-acylamino acid salt examples include glutamic acid, aspartic acid, glycine, sarcosine, alanine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, oxyproline, ⁇ -aminopropionic acid, ⁇ -aminobutyric acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, lanthionine, ⁇ -methyllanthionine, cystathionine, dienecholic acid, phenylalanine, aminoacid, phenylalanine ...
• acids include sarcosine, ⁇ -oxyaspartic acid, ⁇ -amino- ⁇ -methylsuccinic acid, ⁇ -oxyglutamic acid, ⁇ -oxyglutamic acid, ⁇ -methylglutamic acid, ⁇ -methyleneglutamic acid, ⁇ -methyl- ⁇ -oxyglutamic acid, ⁇ -aminoadipic acid, ⁇ , ⁇ '-diaminoadipic acid, ⁇ , ⁇ '-diaminoadipic acid, ⁇ -amino- ⁇ -oxyadipic acid, ⁇ -aminopimelic acid, ⁇ -amino- ⁇ -oxypimelic acid, ⁇ -aminopimelic acid, ⁇ -aminosuberic acid, and ⁇ -aminosebacic acid, with sarcosine being preferred.
• acyl groups in the acyl lactate salts and acyl amino acid salts are preferably derived from saturated or unsaturated fatty acids having 8 to 20 carbon atoms, as described above, and may be straight-chain, branched, or cyclic.
• fatty acids include straight-chain fatty acids such as caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, and arachic acid, 2-butyl-5-methylpentanoic acid, 2-isobutyl-5-methylpentanoic acid, dimethyloctanoic acid, dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, methylundecanoic acid, dimethyldecanoic acid, 2-ethyl-3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, methyldocosanoic acid, 2-propyl-3-methylnonanoic acid, methyltridecanoic acid, dimethyldodecanoic acid, 2-butyl-3-methylnon
• the acyl group may also be derived from fatty acids obtained from natural fats and oils, and is preferably derived from a mixed fatty acid containing 80% or more of the above-mentioned saturated or unsaturated fatty acids having 8 to 20 carbon atoms.
• Examples include acyl groups derived from coconut oil fatty acid, palm oil fatty acid, linseed oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, castor oil fatty acid, olive oil fatty acid, and camellia oil fatty acid.
• acyl amino acid salts include sodium cocoyl glutamate, TEA cocoyl glutamate, potassium cocoyl glutamate, sodium lauroyl glutamate, TEA lauroyl glutamate, potassium lauroyl glutamate, sodium cocoyl sarcosine, TEA cocoyl sarcosine, potassium cocoyl sarcosine, sodium lauroyl sarcosine, TEA lauroyl sarcosine, potassium lauroyl sarcosine, sodium cocoyl aspartate, TEA cocoyl aspartate, potassium cocoyl aspartate, sodium lauroyl aspartate, TEA lauroyl aspartate, potassium lauroyl aspartate, sodium cocoyl methyl alanine, and TE cocoyl methyl alanine.
• A potassium cocoyl methyl alanine, sodium lauroyl methyl alanine, TEA lauroyl methyl alanine, potassium lauroyl methyl alanine, sodium cocoyl glycine, TEA cocoyl glycine, potassium cocoyl glycine, sodium lauroyl glycine, TEA lauroyl glycine, potassium lauroyl glycine, sodium myristoyl sarcosine, TEA myristoyl sarcosine, potassium myristoyl sarcosine, sodium lauroyl methyl- ⁇ -alanine, TEA lauroyl methyl- ⁇ -alanine, potassium lauroyl methyl- ⁇ -alanine, sodium cocoyl methyl- ⁇ -alanine, TEA cocoyl methyl- ⁇ -alanine, potassium cocoyl methyl- ⁇ -alanine, sodium lauroyl methyl- ⁇ -alanine, TEA cocoyl
• preferred acyl lactate include sodium cocoyl lactiate, TEA cocoyl lactiate, potassium cocoyl lactiate, sodium lauroyl lactiate, TEA lauroyl lactiate, potassium lauroyl lactiate, sodium stearoyl lactiate, TEA stearoyl lactiate, potassium stearoyl lactiate, sodium isostearoyl lactiate, TEA isostearoyl lactiate, potassium isostearoyl lactiate, etc.
• compound (B) is preferably at least one selected from the group consisting of acids, their salts, and their anions, each having an acid dissociation constant (pKa) in water of 0 to 6.0.
• the lower limit of pKa is preferably 0, more preferably 1.0, and even more preferably 1.5.
• the upper limit of pKa is preferably 6.0, more preferably 5.5, and even more preferably 5.0.
• composition of the present invention may contain two or more of the above-mentioned compounds (B).
• the composition of the present invention may consist of only PVA (A) and compound (B), or may further contain other components other than PVA (A) and compound (B).
• other components include polymers other than PVA (A), surfactants other than compound (B), and solvents such as water.
• optional components that may be contained in the composition for each application described below also fall under the category of other components.
• the composition may be a liquid, a slurry, or a solid such as a powder or a film.
• the lower limit of the total content of PVA (A) and compound (B) in the composition may be 1 mass%, or may be 5 mass%, 10 mass%, 20 mass%, 30 mass%, 40 mass%, 50 mass%, 60 mass%, 70 mass%, 80 mass%, 90 mass%, 95 mass%, 97 mass%, or 99 mass%.
• the upper limit of the total content of PVA (A) and compound (B) in the composition may be 100% by mass, or may be 99% by mass, 95% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, or 5% by mass.
• the composition of the present invention may be an aqueous solution containing water as another component, as described below.
• the lower limit of the total content of PVA (A), compound (B) and water in the composition is preferably 70% by mass, more preferably 80% by mass, and even more preferably 90% by mass, and may be 95% by mass, 97% by mass, 99% by mass or 99.9% by mass.
• the upper limit of the total content of PVA (A), compound (B) and water in the composition may be 100% by mass, 99.9% by mass or 99% by mass.
• the content of PVA (A) may be, for example, 1% by mass or more and 40% by mass or less, 5% by mass or more and 35% by mass or less, or 10% by mass or more and 30% by mass or less.
• composition of the present invention may consist essentially of only PVA (A) and compound (B).
• An aqueous solution containing such a composition and water, a mixture of such a composition with other components, etc. are also preferred embodiments of the present invention.
• the mixture also includes an aqueous solution, etc.
• composition of the present invention is at least one composition selected from the group consisting of an agricultural composition, an automotive composition, an aviation composition, an industrial composition, a livestock composition, a marine composition, a pharmaceutical composition, a personal care composition, a recreational composition, and a water treatment composition.
• Agricultural products refer to products and materials used in agriculture and horticulture.
• Typical agricultural product compositions include pesticide compositions, such as insecticides, fungicides, insecticides and fungicides, herbicides, rodenticides, plant growth regulators, attractants, spreaders, repellents, defoliants, fertilizers, trace element and trace nutrient agents, etc.
• the composition may contain, in addition to the PVA (A) and the compound (B), a medium such as water, and an active ingredient for imparting a desired action or function.
• active ingredients include insecticides and herbicides.
• Automotive products refer to products and materials used in the automotive industry. Examples of automotive product compositions include car wash detergents and windshield washer fluids.
• Aviation supplies refer to supplies and materials used in the aviation industry. Examples of aviation supply compositions include aircraft cleaning agents.
• Industrial products refer to products and materials used in the manufacturing industry. Examples of industrial product compositions include machine cleaners and dispersants for polymerization of vinyl compounds. As a dispersant for polymerization of vinyl compounds, a dispersant for suspension polymerization of vinyl chloride is preferred.
• Livestock products refer to products and materials used in dairy farming and livestock breeding.
• livestock product compositions include livestock barn cleaners and agricultural equipment cleaners.
• Marine products refer to supplies and materials used in fishing, the marine industry, shipbuilding, marine exploration, etc.
• Examples of marine product compositions include ship cleaning agents, ship equipment cleaning agents, and fishery processing equipment cleaning agents.
• compositions include medicines, quasi-drugs, etc.
• Personal care products refer to products that can be applied to the body of a human or non-human animal.
• body includes skin, teeth, nails, and hair.
• Examples of personal care products include cosmetics, shampoos, body washes, facial cleansers, toothpastes, etc.
• the composition may contain, in addition to the PVA (A) and the compound (B), for example, water, a thickener, a fragrance, a colorant, a dispersant, a scrubbing agent, an emulsifier, a moisturizer, a bleaching agent, etc.
• recreational products refer to products and materials used in recreation.
• Examples of recreational product compositions include foam sprays, bath additives, and pool foaming agents.
• Water treatment agents refer to agents that are added to water or liquids whose main component is water (containing 50% or more by mass of water relative to the total mass) for the purpose of preventing the growth of microorganisms, corrosion, scale, etc.
• water treatment agent compositions include water treatment agents for drinking water, industrial water treatment agents, sewage treatment agents, industrial wastewater treatment agents, pool water purification agents, etc.
• the composition when the composition is a water treatment composition, in addition to PVA (A) and compound (B), the composition may contain a medium such as water, as well as a polymer flocculant or an inorganic flocculant composed of a water-soluble (co)polymer having a water-soluble monomer as a constituent unit.
• a medium such as water
• a polymer flocculant or an inorganic flocculant composed of a water-soluble (co)polymer having a water-soluble monomer as a constituent unit.
• the composition of the present invention may be an aqueous solution further containing water.
• Such an aqueous solution is an aqueous solution in which PVA (A), which has low solubility in water and is difficult to dissolve in water by itself, is solubilized in water by the action of compound (B).
• PVA PVA
• B compound
• the aqueous solution (composition) can be separated into two phases, a transparent supernatant liquid and a resin precipitate, when the pH of the aqueous solution is adjusted to 3.0 at room temperature.
• Such an aqueous solution makes it easier to filter the PVA (A) contained in the aqueous solution.
• the mass of the resin precipitate obtained by filtration after drying the resin precipitate at 105°C for 24 hours is 70% by mass or more of the PVA (A) originally contained in the aqueous solution.
• the aqueous solution as the composition of the present invention is preferably a transparent and uniform liquid at room temperature before the operation to separate the PVA (A) contained in the aqueous solution is performed, i.e., in a state in which the PVA (A) and the compound (B) are dissolved in water.
• the pH of the aqueous solution as the composition of the present invention is preferably 4.0 to 11.0, and may be 5.0 to 10.0, 5.5 to 9.0, or 6.0 to 8.0.
• the method for separating a vinyl alcohol polymer of the present invention is a method for precipitating at least a part of PVA (A) contained in the aqueous solution (composition) by adjusting the pH of the composition, which is an aqueous solution.
• the pH of the aqueous solution it is preferable to adjust the pH of the aqueous solution to 3.0 or less to precipitate a resin precipitate containing PVA (A).
• the mass of the resin precipitate after drying the filtered resin precipitate at 105° C. for 24 hours is 70% by mass or more relative to the PVA (A) originally contained in the aqueous solution.
• the retention time RT of PVA is the retention time of the peak top measured by reversed-phase partition gradient high performance liquid chromatography using a mixture of ion-exchanged water and ethanol as an eluent. The measurement was performed under the following conditions.
• the "peak top” is the point at which the detectability in the chromatogram obtained by the chromatography measurement is the maximum and is also a local maximum.
• the (Y) concentration was gradually decreased from 100% by volume to 5% by volume at a substantially constant rate during the period from 40 to 41 minutes.
• Mobile phase flow rate 0.4mL/min
• Sample concentration 5 mg/mL
• Injection volume 5 ⁇ L Length from injection to column inlet: 900 mm Length from column outlet to nebulizer of ELSD-LTII detector: 1375 mm Pipe diameter: 0.3 mm ID
• a 50% polyvinyl acetate methanol solution was saponified by adding a NaOH methanol solution (10% by mass) to the polyvinyl acetate methanol solution so that the alkali molar ratio (moles of NaOH/moles of vinyl ester units in polyvinyl acetate) was 0.009, to obtain PVA (A) PVA2.
• the saponification degree, viscosity average polymerization degree, and retention time RT of the obtained PVA2 are shown in Table 1.
• PVA3 was obtained by adding a NaOH methanol solution (10% by mass concentration) to a methanol solution of polyvinyl acetate adjusted to 30% so that the alkali molar ratio (moles of NaOH/moles of vinyl ester units in polyvinyl acetate) was 0.0037.
• the saponification degree, viscosity average polymerization degree, and retention time RT of the obtained PVA3 are shown in Table 1.
• Example 1 To 79 parts by mass of ion-exchanged water, 20 parts by mass of PVA1 and 1 part by mass of the surfactant 1, "SOYPON SLP” (manufactured by Kawaken Fine Chemicals Co., Ltd., “SOYPON” is a registered trademark), were added, and the mixture was heated and stirred to obtain an aqueous solution, which was a composition.
• the surfactant 1 "SOYPON SLP” (manufactured by Kawaken Fine Chemicals Co., Ltd., “SOYPON” is a registered trademark)
• Example 2 To 76 parts by mass of ion-exchanged water, 20 parts by mass of PVA1 and 4 parts by mass of "AminoSurfact ACDS-L” (manufactured by Asahi Kasei Finechem Corporation, active ingredient 25%, "AminoSurfact” is a registered trademark) were added as a surfactant, and the mixture was heated and stirred to obtain an aqueous solution as a composition.
• AminoSurfact ACDS-L manufactured by Asahi Kasei Finechem Corporation, active ingredient 25%, "AminoSurfact” is a registered trademark
• Example 3 To 67.6 parts by mass of ion-exchanged water, 30 parts by mass of PVA1 and 2.4 parts by mass of the surfactant 3 "Alanon ALE” (manufactured by Kawaken Fine Chemical Co., Ltd., active ingredient 30%, “Alanon” is a registered trademark) were added, and the mixture was heated and stirred to obtain an aqueous solution which was a composition.
• Example 4 To 79 parts by mass of ion-exchanged water, 20 parts by mass of PVA2 and 1 part by mass of the surfactant 1, "SOYPON SLP” (manufactured by Kawaken Fine Chemicals Co., Ltd.), were added, and the mixture was heated and stirred to obtain an aqueous solution, which was the composition.
• aqueous solution which is a composition, was obtained in the same manner as in Example 1, except that the surfactant used was changed to Surfactant 4, "EMAL 10G” (manufactured by Kao Corporation, “EMAL” is a registered trademark).
• the aqueous solution was judged to be "A” if it immediately separated into two phases of a transparent supernatant liquid and a resin precipitate, and the resin precipitate could be filtered out, and the composition was judged to be "B” if it did not separate into a transparent supernatant liquid phase and a resin precipitate phase, and the resin precipitate could not be filtered out.
• “if the resin precipitate could be filtered out” refers to a case where the mass of the resin precipitate obtained by filtration after drying the resin precipitate at 105 ° C. for 24 hours was 70% by mass or more relative to the PVA originally contained in the composition.
• the pH of the aqueous solution was measured using a pH meter (F-51 manufactured by Horiba, Ltd.).
• Example 1 For Example 1 and Comparative Examples 1 to 5, the results of evaluating the state of the aqueous solution and the possibility of separation by adding acid are summarized in Table 3.
• the aqueous solution of Example 1 was a transparent and uniform aqueous solution, and separation of PVA was possible under weakly acidic conditions.

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• 2024
  • 2024-02-29 WO PCT/JP2024/007544 patent/WO2024181532A1/ja not_active Ceased
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