WO2018225717A1 - Polymère à base d'alcool vinylique contenant un groupe amino à chaîne latérale - Google Patents

Polymère à base d'alcool vinylique contenant un groupe amino à chaîne latérale Download PDF

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WO2018225717A1
WO2018225717A1 PCT/JP2018/021525 JP2018021525W WO2018225717A1 WO 2018225717 A1 WO2018225717 A1 WO 2018225717A1 JP 2018021525 W JP2018021525 W JP 2018021525W WO 2018225717 A1 WO2018225717 A1 WO 2018225717A1
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group
vinyl alcohol
alcohol polymer
substituent
containing vinyl
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PCT/JP2018/021525
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English (en)
Japanese (ja)
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祐貴 立花
雄介 天野
一彦 前川
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株式会社クラレ
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Priority to JP2019523903A priority Critical patent/JP7042817B2/ja
Publication of WO2018225717A1 publication Critical patent/WO2018225717A1/fr

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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
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F16/04—Acyclic compounds
    • C08F16/06—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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • 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
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the present invention relates to a novel modified vinyl alcohol polymer having an amino group in the side chain and a method for producing the modified vinyl alcohol polymer.
  • vinyl alcohol polymers have excellent interface characteristics and strength characteristics as few crystalline water-soluble polymers, they are used in various applications such as raw materials for films and fibers. In many applications, vinyl alcohol polymers are required to be easily dissolved in water and excellent in handleability, while exhibiting high water resistance, contrary to water solubility, after reacting with a crosslinking agent. Is required.
  • the modified vinyl alcohol polymer into which such a functional group has been introduced include vinyl alcohol polymers having an amino group.
  • vinyl alcohol-vinylamine copolymers obtained by copolymerizing vinyl acetate and vinylformamide and hydrolyzing them are known as vinyl alcohol polymers having amino groups.
  • this copolymer has a problem in that the amino group function is not sufficiently exhibited due to steric hindrance of the main chain because the amino group is directly bonded to the copolymer main chain.
  • the amide group hydrolysis step requires a stricter condition than the vinyl ester saponification step in the production of a normal vinyl alcohol polymer, which causes a problem that the hue deteriorates.
  • Patent Document 1 proposes a method of introducing an amino group at a position away from the main chain in order to make the reactivity of the amino group function effectively.
  • the side chain amino group-containing vinyl alcohol polymer described in Patent Document 1 requires a deprotection step of the oxazolidinone group in the production process, and deterioration of the hue due to the process is inevitable. Therefore, the field
  • Patent Document 2 proposes a vinyl alcohol polymer having an amino group bonded to a phenyl group.
  • a compound containing sulfur is used in the production process, the problem of odor or sulfur oxide There were manufacturing problems such as the need for a removal process.
  • JP 2013-53267 A Japanese Patent Laid-Open No. 11-49913
  • the present invention has been made in order to solve the above problems, and has a good hue, excellent reactivity with a crosslinking agent, and a molded article such as a film excellent in water resistance by reaction with the crosslinking agent. It is an object of the present invention to provide a side chain amino group-containing vinyl alcohol polymer that can be obtained.
  • the present inventors have introduced a specific structure containing an amino group in the side chain of the vinyl alcohol polymer, thereby having a good hue and a crosslinking agent.
  • the inventors have found that a side chain amino group-containing vinyl alcohol polymer having excellent reactivity can be obtained, and the present invention has been completed.
  • R 1 is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or an aromatic carbon which may have a substituent.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention has an excellent reactivity with a crosslinking agent in addition to having a good hue. Therefore, it is suitably used for various uses of the vinyl alcohol-based polymer, and particularly suitably used in applications where the hue is regarded as important.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention contains 0.001 to 10 mol% of the structural unit represented by the following formula (1) with respect to the total structural units.
  • X represents a divalent aliphatic hydrocarbon group which may have a substituent, a divalent alicyclic hydrocarbon group which may have a substituent, or a substituent.
  • R 1 is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or an aromatic carbon which may have a substituent.
  • the amino group present in the repeating unit of the polymer has reactivity with various compounds such as epoxy, aldehyde, ketone, azetidine and oxazoline. Therefore, the side-chain amino group-containing vinyl alcohol polymer of the present invention can be made water resistant and produce a gel by reacting with a crosslinking agent having an amine-reactive functional group.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention since the side chain amino group-containing vinyl alcohol polymer of the present invention has no amino group directly bonded to the main chain, the steric hindrance around the amino group is small, and the reactivity of the amino group can be fully utilized. .
  • the side chain amino group-containing vinyl alcohol polymer of the present invention has a good hue, it can be suitably used even in an application field where the hue is particularly important.
  • X has a divalent aliphatic hydrocarbon group which may have a substituent, a divalent alicyclic hydrocarbon group which may have a substituent, and a substituent.
  • Examples of the divalent aliphatic hydrocarbon group which may have a substituent include an alkylene group which may have a substituent.
  • Examples of the divalent alicyclic hydrocarbon group which may have a substituent include a cycloalkylene group which may have a substituent.
  • Examples of the divalent aromatic hydrocarbon group which may have a substituent include an arylene group which may have a substituent.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.
  • the alkylene group may have a substituent.
  • substituents include a branched structure such as a methyl group and an ethyl group; a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, and a pentenyl group.
  • Alkenyl groups such as hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group; alkynyl groups such as ethynyl group, propynyl group, propargyl group, butynyl group, pentynyl group, hexynyl group, phenylethynyl group; phenyl Group, naphthyl group, anthryl group, phenanthryl group and other aryl groups; pyridyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazinyl group, oxazolyl group, thiazolyl group, pyrazolyl group, benzothiazolyl group, benzoimidazolyl group, etc.
  • Aromatic ring group methoxy , Ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, cyclohexyloxy group, heptyl Alkoxy groups such as oxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group; alkylthio groups such as methylthio group, ethylthio group, propylthio group, butylthio group; arylthio groups such as phenylthio group, naphthylthio group; tert-butyl Trisubstituted silyloxy groups such as dimethylsilyloxy group, tert-butyldiphenylsilyloxy group; acyloxy groups such as acet
  • the amino group as an example of the substituent may be a primary amino group (—NH 2 ), a secondary amino group, or a tertiary amino group.
  • the secondary amino group is a mono-substituted amino group represented by —NHR 4 (R 4 is any monovalent substituent), and R 4 includes an alkyl group, an aryl group, an acetyl group, a benzoyl group, Examples thereof include a benzenesulfonyl group and a tert-butoxycarbonyl group.
  • the secondary amino group examples include a secondary amino group in which R 4 is an alkyl group such as a methylamino group, an ethylamino group, a propylamino group, and an isopropylamino group, and a phenylamino group and a naphthylamino group.
  • R 4 is an alkyl group such as a methylamino group, an ethylamino group, a propylamino group, and an isopropylamino group, and a phenylamino group and a naphthylamino group.
  • the tertiary amino group is a disubstituted amino group represented by —NR 4 R 5 (R 4 and R 5 are any monovalent substituent), and R 5 is the same as R 4.
  • R 4 and R 5 may be the same or different from each other.
  • Specific examples of the tertiary amino group include a dimethylamino group, a diethylamino group, a dibutylamino group, an ethylmethylamino group, a diphenylamino group, a methylphenylamino group, and the like, wherein R 4 and R 5 are an alkyl group and an aryl group.
  • a tertiary amino group which is at least one selected from the group consisting of
  • cycloalkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. These cycloalkylene groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkylene group can be used.
  • arylene group examples include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and a fluorenylene group. These arylene groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkylene group can be used.
  • X in the formula (1) is a divalent aliphatic hydrocarbon group which may have a substituent or a divalent alicyclic hydrocarbon which may have a substituent from the viewpoint of reactivity. It is preferably a group, more preferably a divalent aliphatic hydrocarbon group which may have a substituent.
  • a divalent alkylene group which may have a substituent is preferably used as X, and the alkylene group may have 1 to 15 is preferable, and 1 to 10 is more preferable.
  • alkylene groups at least selected from the group consisting of a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, an isopentylene group, and a neopentylene group.
  • One type is more preferably used.
  • an cycloalkylene group which may have a substituent is suitably used as X.
  • the cycloalkylene groups at least one selected from the group consisting of a cyclopropylene group, a cyclobutylene group, and a cyclopentylene group is more preferably used.
  • R 1 has a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, or a substituent.
  • Examples of the aliphatic hydrocarbon group which may have a substituent include an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group etc. are mentioned.
  • Examples of the alicyclic hydrocarbon group which may have a substituent include a cycloalkyl group which may have a substituent.
  • Examples of the aromatic hydrocarbon group which may have a substituent include an aryl group which may have a substituent and an arylalkyl group which may have a substituent.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, Examples thereof include a tert-pentyl group, n-hexyl group, isohexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
  • alkyl groups may have a substituent, and as such a substituent, the same substituents exemplified in the description of the alkylene group can be used, and an alkyl group such as a methyl group or an ethyl group can be used. And those having a branched structure, those having an alkoxy group, and those having a hydroxyl group are preferably employed.
  • alkenyl group examples include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • These alkenyl groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkylene group can be used.
  • alkynyl group examples include ethynyl group, propynyl group, propargyl group, butynyl group, pentynyl group, hexynyl group, and phenylethynyl group.
  • These alkynyl groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkylene group can be used.
  • cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptanyl group, a cyclooctanyl group, a cyclononanyl group, a cyclodecanyl group, a cycloundecanyl group, and a cyclododecanyl group.
  • These cycloalkyl groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkylene group can be used.
  • aryl group examples include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These aryl groups may have a substituent, and as such a substituent, those similar to the substituents exemplified in the description of the alkylene group, the above-described alkyl groups, alkenyl groups, alkynyl groups, and the like are used. be able to.
  • arylalkyl group examples include benzyl group, 4-methoxybenzyl group, phenethyl group, diphenylmethyl group and the like. These arylalkyl groups may have a substituent, and as the substituent, those similar to the substituents exemplified in the description of the alkylene group can be used.
  • R 1 in Formula (1) is a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an alicyclic hydrocarbon group which may have a substituent, from the viewpoint of reactivity. It is preferably a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, and more preferably a hydrogen atom.
  • an alkyl group which may have a substituent is preferably used as R 1 , and the carbon number of the alkyl group is 1 to 15 1 to 10 is more preferable, and 1 to 5 is more preferable.
  • alkyl groups at least one selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
  • the species is more preferably used, and at least one selected from the group consisting of a methyl group and an ethyl group is particularly preferably used.
  • alicyclic hydrocarbon groups which may have a substituent a cycloalkyl group which may have a substituent is suitably used as R 1 .
  • the cycloalkyl groups at least one selected from the group consisting of a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group is more preferably used.
  • R 2 in Formula (1) is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of reactivity.
  • X and R 1 or X and R 2 may form a ring structure.
  • X and R 1 or X and R 2 may form a piperidine ring
  • X and R 1 or X and R 2 may form a pyrrolidine ring
  • X and R 1 or X and R 2 may form a piperazine ring.
  • X and R 2 form a ring structure, which X and R 2 to form a piperidine ring, which X and R 2 to form a pyrrolidine ring, X and R 2 a piperazine ring What was formed is more preferable.
  • the total carbon number of X, R 1 and R 2 is important, and the total carbon number is preferably 15 or less, more preferably 13 or less, and 11 or less. Is more preferable.
  • the total carbon number is preferably 2 or more.
  • the content of the structural unit represented by the formula (1) is 0.001 to 10 mol%, where the total structural unit is 100 mol%.
  • the content of the structural unit represented by the formula (1) is in the range of 0.001 to 10 mol%, the water resistance of the film crosslinked with the crosslinking agent is expressed.
  • the content of the structural unit represented by the formula (1) is less than 0.001 mol%, the effect of modifying the vinyl alcohol polymer by the structural unit represented by the formula (1) becomes insufficient.
  • the content of the structural unit represented by the formula (1) is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and particularly preferably 0.3 mol% or more.
  • the content of the structural unit represented by the above formula (1) is preferably 7 mol% or less, more preferably 5 mol% or less.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention may have one or more structural units represented by the formula (1).
  • the constitutional unit in the polymer means a repeating unit constituting the polymer.
  • the following vinyl alcohol units and the following vinyl ester units are also constituent units.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention preferably contains 0 to 10 mol% of a structural unit represented by the following formula (2) with respect to all structural units.
  • R 3 represents a hydrogen atom or a methyl group.
  • R 3 represents a hydrogen atom or a methyl group. From the viewpoint of facilitating the synthesis of a vinyl alcohol polymer introduced with a structural unit represented by the formula (2) [hereinafter sometimes abbreviated as “lactone ring-containing vinyl alcohol polymer”], R 3 is: A hydrogen atom is preferred.
  • the content of the structural unit represented by the formula (2) is preferably 0 to 10 mol%, with all the structural units as 100 mol%.
  • the content of the structural unit represented by the formula (2) is 10 mol% or less, the crystallinity of the vinyl alcohol polymer is less likely to be lowered, and the water resistance of the crosslinked film is less likely to be lowered. % Or less, more preferably 7 mol% or less.
  • the content of the structural unit represented by the formula (2) is more preferably 0.005 mol% or more, further preferably 0.01 mol% or more, and 0.1 mol% or more. It is particularly preferred.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention may have one or two structural units represented by the formula (2). In the case of having two types of the structural units, the total content of these structural units is preferably in the above range.
  • the content of the vinyl alcohol unit in the side chain amino group-containing vinyl alcohol polymer of the present invention is not particularly limited, but from the viewpoint of solubility in water, the total structural unit in the polymer is preferably 100 mol%, preferably 50 More preferably, it is 70 mol% or more, More preferably, it is 75 mol% or more, Most preferably, it is 80 mol% or more. Further, the content of the vinyl alcohol unit is preferably 99.95 mol% or less, more preferably 99.90 mol% or less, based on 100 mol% of all structural units in the polymer.
  • Vinyl alcohol units can be derived from vinyl ester units by hydrolysis or alcoholysis. Therefore, the vinyl ester unit may remain in the vinyl alcohol polymer depending on the conditions for converting the vinyl ester unit to the vinyl alcohol unit. Therefore, the side chain amino group-containing vinyl alcohol polymer of the present invention may contain vinyl ester units derived from the above.
  • vinyl esters of the above vinyl ester units include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, palmitic acid.
  • vinyl acid vinyl, vinyl stearate, vinyl oleate, vinyl benzoate and the like examples include vinyl acid vinyl, vinyl stearate, vinyl oleate, vinyl benzoate and the like.
  • vinyl acetate is preferable from an industrial viewpoint.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention is preferably represented by the following formula (A).
  • X, R 1 and R 2 have the same meaning as in the formula (1)
  • R 3 has the same meaning as in the formula (2)
  • a, b, c and d are Represents the content of the structural unit, a is 50 to 99.95 mol%, b is 0.05 to 30 mol%, c is 0 to 10 mol%, and d is 0.001 to 10 mol% %.
  • a is preferably 50 to 99.95 mol% with 100% by mole of all structural units in the polymer. a is more preferably 70 mol% or more, still more preferably 75 mol% or more, and particularly preferably 80 mol% or more. On the other hand, a is more preferably 99.90 mol% or less.
  • b is preferably 0.05 to 30 mol% with 100 mol% of all structural units in the polymer. “b” is more preferably 0.1 mol% or more, further preferably 0.2 mol% or more, and particularly preferably 0.5 mol% or more. On the other hand, b is more preferably 25 mol% or less, and still more preferably 20 mol% or less.
  • c is preferably 0 to 10% by mole, with 100% by mole as the total structural unit in the polymer.
  • c is more preferably 0.005 mol% or more, still more preferably 0.01 mol% or more, and particularly preferably 0.1 mol% or more.
  • c is more preferably 8 mol% or less, and even more preferably 7 mol% or less.
  • d is 0.001 to 10 mol% with 100% by mole of all structural units in the polymer.
  • d is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, and further preferably 0.3 mol% or more.
  • d is preferably 7 mol% or less, more preferably 5 mol% or less, based on 100 mol% of all structural units in the polymer.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention is a structural unit represented by the formula (1), a structural unit represented by the formula (2), a vinyl alcohol unit, and It can further have a structural unit other than the vinyl ester unit.
  • the structural unit is, for example, an unsaturated monomer that can be copolymerized with a vinyl ester and that can be converted into the structural unit represented by the formula (1), or an ethylenically unsaturated single monomer that can be copolymerized with a vinyl ester.
  • ethylenically unsaturated monomer examples include ⁇ -olefins such as ethylene, propylene, n-butene, isobutylene, and 1-hexene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, and n-propyl acrylate.
  • Acrylates such as i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and its salts Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, methacryl Meta such as octadecyl acid Rylates; acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulf
  • the side chain amino group-containing vinyl alcohol polymer of the present invention may be any of a random copolymer, a block copolymer, an alternating copolymer, and the like.
  • the viscosity average degree of polymerization of the side chain amino group-containing vinyl alcohol polymer of the present invention measured according to JIS K6726 is not particularly limited, and is preferably 100 to 5,000, more preferably 200 to 4,000. It is. When the viscosity average degree of polymerization is 100 or more, the mechanical strength of the film tends to be excellent when the film is used. When the viscosity average degree of polymerization is 5,000 or less, industrial production of the side chain amino group-containing vinyl alcohol polymer tends to be easy.
  • the production method of the side chain amino group-containing vinyl alcohol polymer of the present invention is not particularly limited.
  • a method in which an unsaturated monomer having a structural unit represented by the formula (1) and a vinyl ester are copolymerized and then the vinyl ester is hydrolyzed or alcoholically decomposed, or a structural unit represented by the formula (1) is used. After copolymerizing a convertible unsaturated monomer and a vinyl ester, the vinyl ester is hydrolyzed or alcoholically decomposed, and the structural unit convertible to the structural unit represented by the formula (1) is represented by the formula (1).
  • a method for converting to the structural unit shown, a method for introducing a reactive site into the vinyl alcohol polymer, and a method for introducing the structural unit represented by formula (1) by a post-reaction based on the reactive site are used.
  • a method using a post-reaction based on a reaction point introduced into the vinyl alcohol polymer is preferable.
  • the method include a method in which an amine compound represented by the following formula (3) is subjected to a dehydration condensation reaction with a vinyl alcohol polymer into which a carboxylic acid has been introduced.
  • vinyl alcohol polymers introduced with carboxylic acid esters vinyl alcohol polymers introduced with carboxylic acid halides, vinyl alcohol polymers introduced with carboxylic acid anhydrides, vinyl alcohol polymers introduced with lactone rings, etc.
  • a method of reacting an amine compound represented by the following formula (3) with a vinyl alcohol polymer into which a functional group having reactivity with an amine compound is introduced in particular, a method in which an amine compound represented by the following formula (3) is reacted with a vinyl alcohol polymer introduced with a structural unit represented by the following formula (2) has a relatively high reaction efficiency. is there.
  • R 3 represents a hydrogen atom or a methyl group.
  • the amine compound represented by the formula (3) is not particularly limited.
  • a compound having two or more primary amines in the molecule one in the molecule.
  • a compound having one or more primary amines, one or more secondary amines and one or more tertiary amines in the molecule At least one selected from the group consisting of a compound having two or more primary amines in the molecule and a compound having one or more primary amines and one or more secondary amines in the molecule is preferable. At least one of these is more preferred.
  • amine compounds represented by the formula (3) ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 2,2-dimethyl-1,3-propanediamine, 1,2-diamino-2-methyl Propane, 2-methyl-1,3-propanediamine, 1,2-diaminobutane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 2- Methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1-methyl-1,8-diaminooctane, 1,10-diaminodecane, 1,11 -Diaminoundecane, 1,12-diaminododecane, bis (3-aminound
  • the method for producing the lactone ring-containing vinyl alcohol polymer is not particularly limited.
  • a vinyl ester and a structural unit represented by the formula (2) [hereinafter sometimes simply referred to as “lactone ring unit”]
  • lactone ring unit examples thereof include a method including a step of copolymerizing an unsaturated monomer having a method and a method including a step of copolymerizing a vinyl ester and an unsaturated monomer which can be converted into a lactone ring unit.
  • a method including a step of copolymerizing a vinyl ester and an unsaturated monomer that can be converted into a lactone ring unit is preferable because of ease of production.
  • a vinyl ester and an unsaturated monomer that can be converted into a lactone ring unit are copolymerized, and the vinyl ester unit of the resulting copolymer is converted into a vinyl alcohol unit, while a lactone ring is converted.
  • Examples include a method of converting a unit derived from an unsaturated monomer that can be converted into a unit into a lactone ring unit.
  • a vinyl ester and a carboxylic acid derivative having an unsaturated double bond are copolymerized, and the ester bond of the vinyl ester unit of the obtained copolymer is hydrolyzed or alcoholically decomposed, and the carboxylic acid derivative portion
  • the method of condensation is simple and preferably used.
  • Examples of the carboxylic acid derivative having an unsaturated double bond include a carboxylic acid having an unsaturated bond and a salt thereof, a carboxylic acid ester having an unsaturated bond, a carboxylic acid halide having an unsaturated bond, and a carboxylic acid having an unsaturated bond.
  • An acid anhydride is preferably used, and a carboxylic acid having an unsaturated bond and a salt thereof, and a carboxylic acid ester having an unsaturated bond are more preferable.
  • Examples of the carboxylic acid having an unsaturated bond and a salt thereof and the carboxylic acid ester having an unsaturated bond include acrylic acid and a salt thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, Acrylic esters such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and its salts; methyl methacrylate, methacrylic acid Methacrylic acid esters such as ethyl, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dode
  • copolymerization step There is no particular limitation on the copolymerization method in the step of copolymerizing a vinyl ester and an unsaturated monomer that can be converted into a lactone ring unit [hereinafter sometimes simply referred to as “copolymerization step”], and bulk polymerization method
  • a solution polymerization method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method and a dispersion polymerization method can be employed.
  • preferred polymerization methods are solution polymerization, emulsion polymerization and dispersion polymerization. In the polymerization operation, any one of a batch method, a semi-batch method, and a continuous method can be employed.
  • alcohols such as methanol, ethanol and isopropanol; hydrocarbons such as hexane and heptane; water and the like are preferably used as the solvent.
  • alcohol is preferable, and methanol and ethanol are more preferable. More preferred is methanol.
  • a solvent is 1000 mass parts or less with respect to 100 mass parts of vinyl ester, and it is more preferable that it is 200 mass parts or less.
  • a solvent is 5 mass parts or more with respect to 100 mass parts of vinyl ester.
  • Examples of the polymerization initiator in the copolymerization step include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy). Azo polymerization initiators such as -2,4-dimethylvaleronitrile); peroxide polymerization initiators such as benzoyl peroxide and n-propyl peroxycarbonate, and the like. Among these, azo polymerization initiators 2,2′-azobisisobutyronitrile is more preferable.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0.001 to 10 parts by mass, more preferably 100 parts by mass with respect to a total of 100 parts by mass of unsaturated monomers that can be converted into vinyl ester and lactone ring units. Is 0.01 to 1 part by mass.
  • another monomer may be copolymerized together with the unsaturated monomer that can be converted into a vinyl ester and a lactone ring unit.
  • examples of such other monomers include those described above as monomers that provide other structural units that the vinyl alcohol unit can contain.
  • the amount of the unsaturated monomer that can be converted into the lactone ring unit may be appropriately determined according to the content of the target lactone ring unit or the type of the unsaturated monomer that can be converted into the lactone ring unit. However, based on the total number of moles of all monomers used in the copolymerization step, the unsaturated monomer that can be converted into a lactone ring unit is preferably 0.1 to 10 mol%, More preferably, it is ⁇ 7 mol%.
  • a chain transfer agent may be allowed to coexist for the purpose of adjusting the degree of polymerization of the resulting lactone ring-containing vinyl alcohol polymer.
  • chain transfer agents include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone, and cyclohexanone; mercaptans such as 2-hydroxyethanethiol and dodecyl mercaptan; trichloroethylene, perchloroethylene, and the like Among these, aldehydes and ketones are preferably used.
  • the amount of chain transfer agent used can be appropriately determined according to the chain transfer constant of the chain transfer agent used and the degree of polymerization of the desired lactone ring-containing vinyl alcohol polymer, but generally converted into vinyl ester and lactone ring units.
  • the content is preferably 0.1 to 10% by mass relative to the total mass of possible unsaturated monomers.
  • the end of the lactone ring-containing vinyl alcohol polymer, and thus the side chain amino group-containing vinyl alcohol polymer may be modified by the presence of thiols such as thiol acetic acid and mercaptopropionic acid. Good.
  • the polymerization temperature in the copolymerization step may be appropriately determined according to the type of the polymerization initiator and the properties of the target copolymer, and is preferably 0 to 100 ° C., more preferably 40 to 80 ° C.
  • the atmosphere in the copolymerization step is preferably an inert atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere.
  • the polymer after completion of the reaction can be recovered according to a known method.
  • a fractional precipitation method can be employed, and acetone, hexane, heptane, or the like can be used as a precipitant.
  • the vinyl ester unit of a copolymer of a vinyl ester and an unsaturated monomer that can be converted into a lactone ring unit is converted into a vinyl alcohol unit by hydrolysis, alcoholysis, etc.
  • a lactone ring-containing vinyl alcohol polymer can be obtained by condensing with the carboxylic acid derivative portion of the saturated monomer. Specifically, for example, by adopting a so-called saponification step in which the copolymer is brought into contact with an acidic substance or an alkaline substance, and a subsequent drying step, a part or all of the introduced carboxylic acid derivative portion is adjacent. It is converted into a lactone ring by condensation with a hydroxyl group.
  • a saponification process and a drying process can be performed according to the well-known method at the time of manufacturing polyvinyl alcohol.
  • the copolymer in the saponification step, for example, can be dissolved in a solvent containing water and / or alcohol and an acidic substance or an alkaline substance can be added.
  • a solvent such as tetrahydrofuran, dioxane, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, acetone or the like may be used in combination in order to improve the solubility of the copolymer, acidic substance or alkaline substance.
  • a saponification step in which an alkaline substance is added.
  • the reaction solution in the copolymerization step can be used as it is as the solution in the saponification step.
  • Examples of the alcohol used for dissolving the copolymer include methanol, ethanol, n-propanol, isopropanol, n-butanol, and ethylene glycol.
  • the alcohols alcohols having 1 to 4 carbon atoms are preferable, and methanol is more preferable.
  • the amount of solvent used (the total amount of solvents used) is not particularly limited, but is preferably 1 to 50 times by mass, more preferably 2 to 10 times by mass with respect to the mass of the copolymer.
  • Examples of acidic substances that can be used in the saponification step include p-toluenesulfonic acid.
  • Examples of the alkaline substance that can be used in the saponification step include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methylate.
  • the amount of the acidic substance or alkaline substance used is preferably a ratio of 0.0001 to 2 moles, and a ratio of 0.001 to 1.2 moles per mole of vinyl ester units of the copolymer. It is more preferable.
  • the reaction temperature in the saponification step is preferably 0 to 180 ° C, more preferably 20 to 80 ° C.
  • the reaction time is preferably 0.01 to 20 hours, more preferably 0.1 to 3 hours, although it depends on the reaction rate.
  • the precipitated saponified product can be recovered by a known method.
  • the lactone ring-containing vinyl alcohol polymer can be recovered by filtering the precipitated particles, washing with alcohol such as methanol, and drying.
  • the method of reacting the lactone ring-containing vinyl alcohol polymer with the amine compound represented by the formula (3) is not particularly limited, and can be selected according to the required characteristics of the target side chain amino group-containing vinyl alcohol polymer.
  • a method of mixing and reacting an amine compound represented by the formula (3) with a melted lactone ring-containing vinyl alcohol polymer; an amine compound represented by the formula (3) is dissolved, and a lactone ring is contained A method of reacting in a slurry state in a solvent in which the vinyl alcohol polymer does not dissolve; a method of impregnating a lactone ring-containing vinyl alcohol polymer with an amine compound represented by formula (3) and reacting in a solid state; A method in which a gasified amine compound is brought into contact with and reacted with a ring-containing vinyl alcohol polymer; a lactone ring-containing vinyl alcohol polymer and a solution in which all of the amine compound represented by formula (3) are uniformly dissolved A method of reacting, and the like, which are suit
  • the concentration of the lactone ring-containing vinyl alcohol polymer during the reaction is not particularly limited. 1% by mass to 50% by mass is preferable, 2% by mass to 40% by mass is more preferable, and 3% by mass to 30% by mass is more preferable.
  • the content is 1% by mass or more, it is easy to suppress a decrease in reaction rate due to the low concentration of the lactone ring-containing vinyl alcohol polymer.
  • the amount is 50% by mass or less, the stirring failure tends to be suppressed.
  • the solvent used for the reaction of the lactone ring-containing vinyl alcohol polymer with the amine compound represented by the formula (3) is not particularly limited, but water; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, alcohols such as sec-butanol and tert-butanol; aliphatic or alicyclic hydrocarbons such as n-hexane, n-pentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; chloroform, chlorobenzene and dichlorobenzene Aliphatic or aromatic halides such as: Nitriles such as acetonitrile and benzonitrile; Ethers such as diethyl ether, diphenyl ether, anisole, 1,2-dimethoxyethane, and 1,4-dioxane; Acetone and methylisopropyl , Ketones such as
  • amine compound shown by Formula (3) as a substrate and solvent.
  • alcohols, aliphatic or alicyclic hydrocarbons, aromatic hydrocarbons, ethers, ketones, and amine compounds represented by formula (3) are preferable from the viewpoint of reactivity.
  • Two or more types of solvents may be used in combination.
  • a solvent in which the lactone ring-containing vinyl alcohol polymer is not dissolved and a lactone ring-containing vinyl alcohol polymer such as N, N-dialkyllactams and sulfoxides. You may use in combination with the solvent which swells coalescence.
  • the temperature of the reaction between the lactone ring-containing vinyl alcohol polymer and the amine compound represented by the formula (3) is not particularly limited, but is preferably 20 to 150 ° C., more preferably 30 to 140 ° C. from the viewpoint of reactivity. Preferably, 40 to 130 ° C is more preferable, and 50 to 120 ° C is most preferable. Further, the reaction system may be pressurized or depressurized as necessary.
  • the method for taking out the side chain amino group-containing vinyl alcohol polymer after the reaction between the lactone ring-containing vinyl alcohol polymer and the amine compound represented by the formula (3) is not particularly limited, and can be carried out by a known method.
  • the reaction solution comprises a lactone ring-containing vinyl alcohol polymer and a side chain amino group-containing vinyl alcohol polymer. You may take out by adding and precipitating to the solvent (poor solvent) which does not melt
  • the reaction solution and the poor solvent and cutting the precipitated resin may be slurried by simultaneously mixing the reaction solution and the poor solvent and cutting the precipitated resin using a mixer, or may be taken out in a fibrous form by a wet spinning device or a dry and wet spinning device.
  • the taken out resin may be washed with an organic solvent or water that does not dissolve the resin, or may be dried with a blower dryer or the like.
  • the resin When the reaction is performed in a slurry state or a solid state in which the lactone ring-containing vinyl alcohol polymer is not dissolved, the resin may be separated by solid-liquid separation by filtration, centrifugal drainage, drying, or the like after the reaction. The separated resin may be washed with an organic solvent or water that does not dissolve the resin, or may be dried with a blower dryer or the like.
  • the gasified amine compound represented by the formula (3) is reacted with the lactone ring-containing vinyl alcohol polymer, the amine compound is replaced with a gas such as air, nitrogen, or argon after the reaction. It may be removed.
  • the side chain amino group-containing vinyl alcohol polymer obtained in the present invention is used for applications such as fibers and films whose appearance is important, it is preferable that the hue of the polymer is good.
  • the yellow index (YI) of the side chain amino group-containing vinyl alcohol polymer obtained in the present invention is preferably 50 or less.
  • the yellow index (YI) is measured according to ASTM D1925. For example, in a side-chain amino group-containing vinyl alcohol polymer, by reducing the content of carbon-carbon double bonds in the main chain, the side-chain amino group-containing vinyl alcohol polymer having a small YI and excellent hue. Coalescence can be obtained.
  • YI is more preferably 40 or less, further preferably 30 or less, and particularly preferably 20 or less. YI is usually 3 or more.
  • YI does not suppress the powder of the side chain amino group-containing vinyl alcohol polymer using a spectrocolorimeter (D65 light source, CM-A120 white calibration plate, specular reflection measurement SCE). It is obtained by measuring a sample spread on a petri dish. Specifically, it is a value measured according to the method described in the examples.
  • another functional group may be further introduced as long as an amino group is introduced into the side chain.
  • an amine compound represented by the formula (3) is added to a lactone ring-containing vinyl alcohol polymer to introduce a specific structure containing an amino group in the side chain, and has an acid, alkali, or other functional group
  • Various other functional groups can be further introduced by reacting an amine compound with a lactone ring-containing vinyl alcohol polymer.
  • introduction of carboxylic acid groups by reaction with acid compounds such as hydrochloric acid and carbonic acid introduction of carboxylic acid groups by reaction with alkali metal compounds such as sodium hydroxide and potassium hydroxide; introduction of amide groups by reaction with ammonia Introduction of an alkyl group by reaction with an alkylamine compound; introduction of an alkenyl group by reaction with an alkenylamine compound; introduction of an alkynyl group by reaction with an alkynylamine compound; introduction of an aryl group by reaction with an arylamine compound; Introduction of hydroxyl group by reaction with amine compound having silyl; Introduction of silyl group by reaction with amine compound having silyl group; Introduction of furyl group by reaction with amine compound having furyl group; With amine compound having thiol group Examples thereof include introduction of a thiol group by reaction.
  • the side chain amino group-containing vinyl alcohol polymer obtained in the present invention is a vinyl alcohol-based polymer obtained by utilizing its properties, according to a known method such as molding, spinning, or emulsification, alone or as a composition to which other components are added. It can be used for various applications in which alcohol polymers are used.
  • surfactants for various uses, paper coating agents, paper modifiers such as paper binders and pigment binders, adhesives such as wood, paper, aluminum foil and inorganic materials, nonwoven fabric binders, paints, warp glue
  • adhesives, fiber finishing agents, pastes of hydrophobic fibers such as polyester, various other films, sheets, bottles, fibers, thickeners, flocculants, soil modifiers, hydrogels and the like.
  • the side chain amino group-containing vinyl alcohol polymer obtained in the present invention has a filler, a processing stabilizer such as a copper compound, a weathering stabilizer, a coloring, within a range not impairing the effects of the present invention, depending on its use.
  • a processing stabilizer such as a copper compound, a weathering stabilizer, a coloring
  • Agent UV absorber, light stabilizer, antioxidant, antistatic agent, flame retardant, plasticizer, other thermoplastic resin, lubricant, fragrance, defoaming agent, deodorant, extender, release agent, release agent
  • Additives such as molds, reinforcing agents, fungicides, preservatives, and crystallization rate retarders can be appropriately blended as necessary.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention has a high reactivity with a water-resistant agent such as a crosslinking agent because an amino group having a high degree of freedom is introduced into the side chain. . Therefore, a vinyl alcohol polymer composition that gives a product excellent in water resistance can be obtained by blending a water-resistant agent with the side chain amino group-containing vinyl alcohol polymer of the present invention.
  • a vinyl alcohol polymer composition containing a side chain amino group-containing vinyl alcohol polymer and a water-resistant agent is a preferred embodiment of the present invention.
  • Examples of the water-proofing agent contained in the vinyl alcohol polymer composition of the present invention include zirconyl nitrate, ammonium zirconium carbonate, zirconyl chloride, zirconyl acetate, zirconyl sulfate, aluminum sulfate, aluminum nitrate, titanium lactate, titanium diisopropoxy.
  • Acid anhydrides such as bis (triethanolaminate), pyromellitic dianhydride, divinyl sulfone compounds, melamine resins, methylol melamine, methylolated bisphenol S, polyvalent vinyl compounds, polyvalent (meth) acrylate compounds, many Examples thereof include valent epoxy compounds, aldehyde compounds, polyvalent isocyanate compounds, water-soluble oxidants, polyamide polyamine epichlorohydrin resins, and the like.
  • the polyvalent (meth) acrylate compound is not particularly limited.
  • “NK Ester” (701A, A-200, A-400, A-600, A-1000, A- B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH 1G, 2G, 3G, 4G, A-PG5054E etc.) and the like.
  • the polyvalent epoxy compound is not particularly limited.
  • “Denacol” manufactured by Nagase ChemteX Corporation (EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-201, EX-211, EX-212, EX-252, EX-810, EX-811, EX- 850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-861, EX-911, EX-941, EX-920, EX-931, EX-721, EX-203, EX-711, EX-221, etc.), bisphenol A diglycidyl ether, bisphenol A di ⁇ methyl glycidyl ether, bisphenol Diol F diglycidyl ether, tetrahydroxyphenylmethane te
  • aldehyde compound examples include, but are not limited to, monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, and benzaldehyde, glyoxal, malonaldehyde, glutaraldehyde, pimelindialdehyde, suberindialdehyde, and dialdehyde.
  • monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, and benzaldehyde, glyoxal, malonaldehyde, glutaraldehyde, pimelindialdehyde, suberindialdehyde, and dialdehyde.
  • dialdehydes such as starch.
  • the polyvalent isocyanate compound is not particularly limited.
  • “Duranate” manufactured by Asahi Kasei Chemicals Corporation WB40-100, WB40-80D, WE50-100, WT30-100, WT20-100, etc.
  • Tolylene diisocyanate TDI
  • Hydrogenated TDI Trimethylolpropane-TDI adduct (eg, “DesmodurL” manufactured by Bayer); Triphenylmethane triisocyanate; Methylene (bisphenyl isocyanate) (MDI); Hydrogenated MDI; Polymerized MDI; Hexamethylene Examples include diisocyanate; xylylene diisocyanate; 4,4′-dicyclohexylmethane diisocyanate; isophorone diisocyanate. Isocyanates dispersed in water using an emulsifier can also be used.
  • the water-soluble oxidizing agent is not particularly limited, and examples thereof include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, Examples thereof include t-butyl hydroperoxide, potassium bromate, t-butyl peracetate, t-butyl perbenzoate and the like.
  • Water resistant agents may be used alone or in combination.
  • the content of the water-resistant agent is not particularly limited, but can be determined according to the type of the side chain amino group-containing vinyl alcohol polymer.
  • the amount is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer, and 0.5 parts by mass. More preferred is from 100 parts by weight to 100 parts by weight, and particularly preferred is from 1 part by weight to 80 parts by weight.
  • the vinyl alcohol polymer composition of the present invention further includes a filler, a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, Flame retardants, plasticizers, other thermoplastic resins, lubricants, fragrances, defoamers, deodorants, extenders, release agents, mold release agents, reinforcing agents, fungicides, preservatives, crystallization rate retarders Additives such as can be blended as needed.
  • a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, Flame retardants, plasticizers, other thermoplastic resins, lubricants, fragrances, defoamers, deodorants, extenders, release agents, mold release agents, reinforcing agents, fungicides, preservatives, crystallization rate retarders
  • Additives such as can be blended
  • the vinyl alcohol polymer composition of the present invention can be used for the same purpose in the same manner as a composition containing a known vinyl alcohol polymer and a water-resistant agent.
  • it is effectively used as a coating agent for inorganic materials or organic materials such as paper and various resin base materials, particularly as a surface coating agent for paper and various resin films.
  • the resin film include films of polyester, polystyrene, polyamide, polyvinyl chloride, polymethyl methacrylate, cellulose acetate, polycarbonate, polyimide, and the like.
  • the vinyl alcohol polymer composition of the present invention is very effectively used for a recording material, particularly a coating layer of a heat-sensitive recording material that cannot be heat-treated at a high temperature, particularly an overcoat layer.
  • the vinyl alcohol polymer composition of the present invention comprises an inorganic or organic adhesive or binder, a coating vehicle, a dispersant such as a pigment dispersion, a polymerization stabilizer or post-additive for a crosslinkable emulsion, a gelatin blend or a photosensitivity. It can be widely used for image forming materials such as resins, base materials for hydrogels such as bacterial cell-fixed gels or enzyme-fixed gels, and applications where water-soluble resins have been used. Furthermore, it can also be used for molded products such as films, sheets and fibers.
  • CM-8500d spectral colorimeter manufactured by Konica Minolta Co., Ltd.
  • Light source D65, CM-A120 white calibration plate, use of CM-A126 petri dish set, specular reflection measurement SCE, measurement diameter ⁇ 30 mm.
  • 5 g of the sample was added to the petri dish, and it was shaken by gently tapping the side so that the powder was not pressed down, and the powder was spread evenly. In this state, a total of 10 measurements were carried out (repeated after shaking the petri dish once each time), and the average value was taken as the YI of the resin.
  • the coating solution was cast on a 15 cm ⁇ 15 cm mold formed by bending the end of a polyethylene terephthalate film, and the solvent was sufficiently evaporated at room temperature and atmospheric pressure to obtain a film having a thickness of about 50 ⁇ m.
  • the obtained film for evaluation was immersed in boiling water for 1 hour, taken out from the water, and vacuum-dried at 40 ° C. for 12 hours, and the mass (W1) was measured.
  • Methanol was further added to the obtained methanol solution of the copolymer so that the concentration of the copolymer was 10% by mass.
  • a methanol solution of sodium hydroxide having a concentration of 10 mass% was added at a ratio of 10 mmol sodium hydroxide to 1 mol vinyl acetate unit in the copolymer for 2 hours.
  • Saponification was performed. As saponification progressed, saponified substances were precipitated in the form of particles. After neutralizing the alkali by adding methyl acetate, the obtained particulate saponified product is separated from the solution, washed thoroughly with methanol, and dried in a hot air dryer at 50 ° C. for 12 hours to obtain a copolymer. It was.
  • the lactone ring-containing vinyl into which 5 mol% of the structure in which R 3 is a hydrogen atom in formula (2) was introduced relative to the number of moles of all structural units. It was found to be an alcohol polymer. In the lactone ring-containing vinyl alcohol polymer, the ratio of the number of moles of vinyl alcohol units to the total number of moles of vinyl alcohol units and vinyl acetate units was 99 mol% or more. Further, the degree of polymerization of the obtained polymer obtained from the intrinsic viscosity [ ⁇ ] (unit: deciliter / g) measured in water at 30 ° C. by the following formula was 1500. Degree of polymerization ([ ⁇ ] ⁇ 10 3 /8.29) (1 / 0.62)
  • Example 1 100 parts by mass of the lactone ring-containing vinyl alcohol polymer obtained in Synthesis Example 1 was added to a reactor equipped with a stirrer, a reflux condenser, and a reaction substrate addition port. To this was added 567 parts by mass of methanol and 40.4 parts by mass of 1,2-diaminopropane, and the mixture was heated to 65 ° C. and stirred for 5 hours. Thereafter, the reaction solution was filtered, and the filtered resin was transferred to a reactor. After adding 1000 parts by mass of methanol and stirring at room temperature for 30 minutes, the solution was filtered. After repeating this twice, the desired side chain amino group-containing vinyl alcohol polymer was obtained by vacuum drying at 40 ° C. for 12 hours.
  • Example 2 100 parts by mass of the lactone ring-containing vinyl alcohol polymer obtained in Synthesis Example 1 was added to a reactor equipped with a stirrer and a reaction substrate addition port. To this, 300 parts by mass of methanol and 11.5 parts by mass of 3-methylaminopropylamine were mixed and heated to 60 ° C. while reducing the pressure in the reactor, and stirred until all the methanol was volatilized. After methanol volatilized, the temperature was raised to 80 ° C. and stirred for 2 hours. Then, after standing to cool to room temperature, 1000 mass parts methanol was added to the reactor, and after stirring for 30 minutes at room temperature, the solution was filtered.
  • EGDGE compound represented by formula (5) which is a waterproofing agent for the amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI and 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer Table 1 shows the evaluation results of water resistance when 9.5 parts by mass of) is used.
  • the vinyl alcohol unit was 94.5 mol%
  • the vinyl ester unit was 0.5 mol%
  • the constituent unit represented by the formula (2) was 2.5 mol%.
  • Example 3 100 parts by mass of the lactone ring-containing vinyl alcohol polymer obtained in Synthesis Example 1 and 400 parts by mass of dimethyl sulfoxide are added to a reactor equipped with a stirrer, a reflux condenser, and a reaction substrate addition port, and the concentration is 20% by mass. A solution of was prepared. To this was added 19.2 parts by mass of 3-methylaminopropylamine, the temperature was raised to 80 ° C., and the mixture was stirred for 12 hours. Thereafter, the solution was dropped into methanol to isolate the polymer, followed by vacuum drying at 40 ° C. for 12 hours to obtain a target side chain amino group-containing vinyl alcohol polymer.
  • Table 1 shows the evaluation results of the water resistance when 28.8 parts by mass () is used (25% by mass).
  • the vinyl alcohol unit was 94.5 mol%
  • the vinyl ester unit was 0.5 mol%
  • the constituent unit represented by the formula (2) was 3.0 mol%.
  • Example 4 Example 1 was the same as Example 1 except that 300 parts by mass of methanol was used, 5.6 parts by mass of 1,3-diaminopentane was used instead of 1,2-diaminopropane, and the reaction time was 3 hours. The reaction, post-treatment and analysis were performed. The amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI and EX-512 (shown by the formula (6)) as a water resistance agent with respect to 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer. Table 1 shows the evaluation results of water resistance when 2.5 parts by mass of the compound to be used is used. The vinyl alcohol unit was 94.5 mol%, the vinyl ester unit was 0.5 mol%, and the structural unit represented by the formula (2) was 4.8 mol%.
  • Example 5 In Example 1, 1,4-dioxane was used instead of methanol, 19.2 parts by mass of 3-methylaminopropylamine was used as the amine compound instead of 1,2-diaminopropane, the reaction temperature was 100 ° C., The reaction, post-treatment and analysis were performed in the same manner as in Example 1 except that the reaction time was 1 hour.
  • Table 1 shows the evaluation results of the water resistance when 14.4 parts by mass (as 25% by mass) are used.
  • the vinyl alcohol unit was 94.5 mol%
  • the vinyl ester unit was 0.5 mol%
  • the constituent unit represented by the formula (2) was 4.0 mol%.
  • Example 6 10 parts by mass of the side chain amino group-containing vinyl alcohol polymer obtained in Example 2 and 30 parts by mass of methanol were added to a reactor equipped with a stirrer, a reflux condenser, and a reaction substrate addition port, and 2N was added thereto. 6.3 parts by mass of an aqueous sodium hydroxide solution was added and stirred at 25 ° C. for 1 hour. Thereafter, the resin was collected by filtration and vacuum-dried at 40 ° C. for 12 hours to obtain a target side chain amino group-containing vinyl alcohol polymer.
  • EGDGE (compound represented by formula (5)) which is a waterproofing agent for the amount of modification of the obtained side chain amino group-containing vinyl alcohol polymer, YI and 100 parts by mass of the side chain amino group-containing vinyl alcohol polymer Table 1 shows the evaluation results of water resistance when 9.5 parts by mass of) is used.
  • the vinyl alcohol unit was 94.5 mol%
  • the vinyl ester unit was 0.5 mol%
  • the constituent unit represented by the formula (2) was not included. Further, 2.5 mol% of a sodium carboxylate group formed by opening the lactone ring was contained.
  • Example 2 According to the method of Example 1 described in JP 2013-53267 A, oxazolidinone group-containing polyvinyl acetate was synthesized, subsequently converted into oxazolidinone group-containing polyvinyl alcohol, and further derived into amino group-containing polyvinyl alcohol. 41.8 parts by mass (25 parts by mass) of the modification amount of the amino group-containing polyvinyl alcohol obtained, PAI (compound represented by the formula (4)) as a water resistance agent with respect to 100 parts by mass of YI and amino group-containing polyvinyl alcohol. Table 1 shows the evaluation results of water resistance when used as%). The vinyl alcohol unit was 97.0 mol%, and the vinyl ester unit was 0.1 mol%.
  • Example 3 In Example 1, 300 parts by mass of 1,4-dioxane was used in place of methanol, and 9.1 parts by mass of 2- (2-aminoethylamino) ethanol was used in place of 1,2-diaminopropane as the amine compound. The reaction, post-treatment and analysis were performed in the same manner as in Example 1 except that the reaction temperature was 100 ° C. and the reaction time was 4 hours.
  • Table 1 shows the evaluation results of water resistance when 36 parts by mass (as 25% by mass) is used.
  • the vinyl alcohol unit was 94.5 mol%
  • the vinyl ester unit was 0.5 mol%
  • the constituent unit represented by the formula (2) was 3.5 mol%.
  • the side chain amino group-containing vinyl alcohol polymer of the present invention has a good hue, and can be made water resistant by mixing with a water resistant agent. I understand. Therefore, the side chain amino group-containing vinyl alcohol polymer of the present invention can be used for a wide range of uses of polyvinyl alcohol.

Abstract

L'invention concerne un polymère à base d'alcool vinylique contenant un groupe amino à chaîne latérale qui contient 0,001 à 10 % en moles d'une unité structurale représentée par la formule (1) par rapport à la quantité totale d'unités structurales. Un corps moulé, tel qu'un film ayant une bonne teinte et une excellente réactivité avec un agent de réticulation, ainsi qu'une excellente résistance à l'eau due à la réaction avec un agent de réticulation, peut être obtenu à l'aide du polymère à base d'alcool vinylique contenant un groupe amino à chaîne latérale (dans la formule (1), X représente un groupe hydrocarbure aliphatique divalent qui peut avoir un substituant, un groupe hydrocarbure alicyclique divalent qui peut avoir un substituant, un groupe hydrocarbure aromatique divalent qui peut avoir un substituant, ou un groupe dans lequel au moins deux desdits groupes sont liés par l'intermédiaire d'au moins une liaison choisie dans le groupe constitué par une liaison amide, une liaison ester et une liaison éther ; R1 représente un atome d'hydrogène, un groupe hydrocarbure aliphatique qui peut avoir un substituant, un groupe hydrocarbure alicyclique qui peut avoir un substituant, un groupe hydrocarbure aromatique qui peut avoir un substituant, ou une structure formant un cycle avec X ; et R2 représente un atome d'hydrogène, un groupe méthyle ou une structure formant un cycle avec X).
PCT/JP2018/021525 2017-06-05 2018-06-05 Polymère à base d'alcool vinylique contenant un groupe amino à chaîne latérale WO2018225717A1 (fr)

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JPS49131292A (fr) * 1973-04-21 1974-12-16
JPS57118049A (en) * 1981-01-09 1982-07-22 Kuraray Co Ltd Treating agent for glass fiber
JPS5821736A (ja) * 1981-07-31 1983-02-08 Kuraray Co Ltd 感光性組成物
JP2002244242A (ja) * 2001-02-20 2002-08-30 Konica Corp 熱現像用ハロゲン化銀写真感光材料
JP2011054445A (ja) * 2009-09-02 2011-03-17 Nippon Kodoshi Corp 高イオン伝導性固体電解質及び該固体電解質を使用した電気化学システム
WO2016056574A1 (fr) * 2014-10-09 2016-04-14 株式会社クラレ Alcool polyvinylique modifié, composition de résine et film

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Publication number Priority date Publication date Assignee Title
JPH11116636A (ja) * 1997-10-20 1999-04-27 Kuraray Co Ltd アミノ基を含有するビニルアルコール系重合体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49131292A (fr) * 1973-04-21 1974-12-16
JPS57118049A (en) * 1981-01-09 1982-07-22 Kuraray Co Ltd Treating agent for glass fiber
JPS5821736A (ja) * 1981-07-31 1983-02-08 Kuraray Co Ltd 感光性組成物
JP2002244242A (ja) * 2001-02-20 2002-08-30 Konica Corp 熱現像用ハロゲン化銀写真感光材料
JP2011054445A (ja) * 2009-09-02 2011-03-17 Nippon Kodoshi Corp 高イオン伝導性固体電解質及び該固体電解質を使用した電気化学システム
WO2016056574A1 (fr) * 2014-10-09 2016-04-14 株式会社クラレ Alcool polyvinylique modifié, composition de résine et film

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