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WO2020138126A1 - Composition de résine réticulable et produit durci de cette dernière - Google Patents

Composition de résine réticulable et produit durci de cette dernière Download PDF

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Publication number
WO2020138126A1
WO2020138126A1 PCT/JP2019/050725 JP2019050725W WO2020138126A1 WO 2020138126 A1 WO2020138126 A1 WO 2020138126A1 JP 2019050725 W JP2019050725 W JP 2019050725W WO 2020138126 A1 WO2020138126 A1 WO 2020138126A1
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Prior art keywords
group
resin composition
mass
crosslinkable resin
cured product
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PCT/JP2019/050725
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English (en)
Japanese (ja)
Inventor
祐貴 立花
一彦 前川
雄介 天野
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Kuraray Co Ltd
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Kuraray Co Ltd
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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a crosslinkable resin composition and a cured product using the same, and more particularly to a crosslinkable resin composition that can provide a material having excellent water absorption and a cured product using the same.
  • a cross-linked polymer obtained by introducing a cross-linking structure into a water-soluble polymer such as polyvinyl alcohol or poly(meth)acrylic acid is a water-absorbing polymer that is insoluble in water but can retain water to a high degree.
  • Water-absorbent polymers are used as materials that make up a wide range of products such as disposable diapers, agricultural materials, ground improvement materials, and contact lenses. In these products, the water-absorbent polymer is required to have both sufficient water absorbency and the property of being moldable into a desired shape.
  • water-absorbent polymers a cross-linked product of anionic electrolyte polymer such as poly(meth)acrylic acid expresses extremely high water absorption, but it is hard and brittle, and it is pointed out that moldability is poor.
  • non-electrolyte polymers such as polyvinyl alcohol are rich in flexibility and toughness and have good film-forming properties, so that they can be formed into films and fibers, but they are inferior in water absorption compared to electrolyte polymers. It has been pointed out. That is, it has been difficult to achieve both high water absorption and high moldability by using each of the electrolyte polymer and the non-electrolyte polymer alone.
  • Patent Document 1 discloses a radical initiator which is a water-soluble peroxide is added to a mixed aqueous solution of polyvinyl alcohol and polyacrylic acid, and cross-linked through heating and drying to give a predetermined shape such as a coating, a film, or a fiber.
  • Patent Document 2 discloses a hydrogel that is crosslinked by irradiating a mixed aqueous solution of polyvinyl alcohol and poly(meth)acrylic acid with radiation such as an electron beam or ⁇ -ray.
  • Patent Document 3 discloses a hydrous gel in which a mixed aqueous solution of polyvinyl alcohol and poly(meth)acrylic acid is freeze-thawed and crosslinked.
  • JP-A-1-92226 Japanese Patent Laid-Open No. 2018-9096 JP-A-5-230313
  • the present invention is intended to solve the above problems, and its object is to provide a material having both excellent water absorption and molding processability, and more simply having the water absorption. It is intended to provide a crosslinkable resin composition that can be obtained and a cured product using the same.
  • the present invention provides a crosslinkable resin composition containing a modified vinyl alcohol polymer containing a vinyl alcohol unit and a structural unit represented by the following formula (I), and an anionic polyelectrolyte:
  • X is a carbon-carbon bond or a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may be branched
  • Y is a hydrogen atom or an optionally branched carbon atom. It is a divalent saturated hydrocarbon group of the numbers 1 to 6 and Z is a hydrogen atom or a methyl group).
  • Y in formula (I) is a hydrogen atom.
  • X in formula (I) is a carbon-carbon bond.
  • the modified vinyl alcohol-based polymer contains the structural unit represented by the formula (I) in a proportion of 0.01 to 3 mol %.
  • the anionic polyelectrolyte is a polymer having in the side chain at least one group selected from the group consisting of a carboxylic acid group or a salt thereof and a sulfonic acid group or a salt thereof.
  • the anionic polyelectrolyte is poly(meth)acrylic acid.
  • the crosslinkable resin composition of the present invention further contains a crosslinking agent.
  • the present invention is also a cured product containing a crosslinked product of the above-mentioned crosslinkable resin composition.
  • the water absorption capacity of the cured product is 5 times or more.
  • the elution rate of the cured product is 40% or less.
  • the present invention is also a method for producing a cured product, which comprises a step of crosslinking the crosslinkable resin composition by irradiating the crosslinkable resin composition with an active energy ray.
  • the present invention is also a method for producing a cured product, which comprises a step of crosslinking the crosslinkable composition by heating the crosslinkable resin composition.
  • the present invention is also a water absorbent product containing the above cured product.
  • the present invention it is possible to easily obtain a cured product that has been crosslinked and made water resistant by using an energy ray or a crosslinking agent without requiring a complicated crosslinking operation. Further, according to the present invention, the crosslinking density can be easily controlled during the crosslinking, and the physical properties (for example, water absorption and water resistance) of the obtained cured product can be improved and the physical properties can be controlled arbitrarily.
  • the crosslinkable resin composition of the present invention contains a modified vinyl alcohol polymer and an anionic polyelectrolyte.
  • the crosslinkable resin composition of the present invention is a composition that can be crosslinked by application of an active energy ray such as irradiation with a crosslinking agent or UV light described below, and has a property of forming a cured product.
  • modified vinyl alcohol polymer contains a vinyl alcohol unit and a structural unit represented by the following formula (I).
  • the side chain olefin present in the formula (I) is highly reactive and can be easily crosslinked in the presence of a predetermined crosslinking agent or by application of energy rays.
  • the modified vinyl alcohol-based polymer has the property of being water-resistant and capable of forming a gel by crosslinking.
  • X is a carbon-carbon bond or an optionally branched divalent saturated hydrocarbon group having 1 to 10 carbon atoms.
  • X is a carbon-carbon bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, which may be branched, from the viewpoint that appropriate modified water-soluble polymer itself can be imparted with water solubility. It is preferable that it is a carbon-carbon bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms which may be branched, and most preferably a carbon-carbon bond.
  • the divalent saturated hydrocarbon group is preferably at least one selected from the group consisting of alkylene groups and cycloalkylene groups.
  • the optionally branched divalent saturated hydrocarbon group having 1 to 10 carbon atoms is selected from the group consisting of a branched or linear alkylene group having 1 to 10 carbon atoms and a cycloalkylene group. Is preferably at least one kind.
  • the alkylene group 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 and a nonylene group.
  • These alkylene groups may have an alkyl group such as a methyl group and an ethyl group as a branched structure.
  • cycloalkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group and a cyclononylene group.
  • These cycloalkylene groups may have an alkyl group such as a methyl group and an ethyl group as a branched structure.
  • Examples of the optionally branched alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene.
  • Y is a hydrogen atom or an optionally branched saturated hydrocarbon group having 1 to 6 carbon atoms.
  • Y is preferably a hydrogen atom or an optionally branched saturated hydrocarbon group having 1 to 5 carbon atoms from the viewpoint that appropriate water solubility and reactivity can be imparted to the modified vinyl alcohol polymer itself.
  • a hydrogen atom or an optionally branched saturated hydrocarbon group having 1 to 2 carbon atoms is more preferable, and a hydrogen atom is still more preferable.
  • the saturated hydrocarbon group is preferably at least one selected from the group consisting of an alkyl group and a cycloalkyl group.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group and hexyl group.
  • at least one alkyl group selected from methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group and neopentyl group is preferable.
  • At least one alkyl group selected from the group consisting of a methyl group and an ethyl group is preferably used.
  • the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group and the like.
  • at least one cycloalkyl group selected from the group consisting of a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group is preferably used.
  • Z is a hydrogen atom or a methyl group.
  • Z is preferably a hydrogen atom from the viewpoint that suitable modified water-soluble polymer itself can be imparted with appropriate water solubility.
  • the content of the structural unit of the formula (I) in the modified vinyl alcohol-based polymer is preferably 0.01 mol% or more, and preferably 0.05 when the total structural unit of the polymer is 100 mol %. It is at least mol%, more preferably at least 0.1 mol%, and even more preferably at least 0.3 mol%. Further, the content of the structural unit of the formula (I) is preferably 3 mol% or less, and preferably 2.5 mol% or less, when all the structural units of the polymer are 100 mol%. It is preferably 2 mol% or less, and more preferably 1.5 mol% or less.
  • the content of the constituent unit of the above formula (I) is within these ranges, the water resistance of the cured product crosslinked in the presence of a predetermined crosslinking agent or the application of active energy rays is likely to be exhibited.
  • the content of the constituent unit of the above formula (I) is less than 0.01 mol %, the effect of modifying the vinyl alcohol polymer by the constituent unit of the formula (I) may not be sufficiently exhibited.
  • the content of the constituent unit of the above formula (I) exceeds 3 mol %, the crystallinity of the vinyl alcohol polymer due to the constituent unit of the formula (I) begins to decrease and the water resistance of the cured product decreases, resulting in hydrophobization.
  • the modified polyvinyl alcohol-based polymer may include one or more structural units represented by formula (I). When two or more constituent units are contained, the total content of these two or more constituent units preferably satisfies the above range.
  • substitutional unit used in the present specification refers to a repeating unit constituting a polymer. For example, a vinyl alcohol unit and a vinyl ester unit described later are also constituent units.
  • the content of the vinyl alcohol unit in the modified vinyl alcohol-based polymer is not particularly limited, but when all the constituent units in the polymer are 100 mol% from the viewpoint of being able to impart appropriate solubility in water. , Preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 75 mol% or more, still more preferably 80 mol% or more. Further, the content of the vinyl alcohol unit is preferably 99.99 mol% or less, more preferably 99.90 mol% or less, when the total constitutional units in the polymer are 100 mol%.
  • the vinyl alcohol unit can be derived from the vinyl ester unit by hydrolysis or alcoholysis. Therefore, the vinyl ester unit may remain in the modified vinyl alcohol-based polymer depending on the conditions for converting the vinyl ester unit to the vinyl alcohol unit. Therefore, the modified vinyl alcohol-based polymer may contain a vinyl ester unit other than the constitutional unit represented by the above formula (I).
  • vinyl ester of the vinyl ester unit examples include vinyl formate, vinyl acetate, vinyl prilopionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versaticate, vinyl caproate, vinyl caprylate, vinyl laurate, palmitin.
  • vinyl acetate, vinyl stearate, vinyl oleate, and vinyl benzoate examples include vinyl acetate, vinyl stearate, vinyl oleate, and vinyl benzoate. Of these, vinyl acetate is preferable from the industrial viewpoint.
  • the modified vinyl alcohol polymer may further contain a structural unit other than the structural unit represented by the formula (I), the vinyl alcohol unit and the vinyl ester unit as long as the effects of the present invention can be obtained.
  • the constituent unit is, for example, an unsaturated monomer copolymerizable with a vinyl ester and convertible into a constituent unit represented by the formula (I), or an ethylenically unsaturated monomer copolymerizable with a vinyl ester. It is a structural unit derived from a polymer or the like.
  • 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, n-propyl acrylate, Acrylic acid esters 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-ethylhe
  • the arrangement order of the structural unit represented by the formula (I), the vinyl alcohol unit, and any other structural unit in the modified vinyl alcohol-based polymer is not particularly limited, and the modified polyvinyl alcohol-based polymer is a random copolymer. It may be a block copolymer, an alternating copolymer, or the like.
  • the modified vinyl alcohol-based polymer preferably has a predetermined viscosity average degree of polymerization according to JIS K6726.
  • the modified vinyl alcohol-based polymer according to JIS K6726 has a viscosity average degree of polymerization of preferably 100 to 5,000, more preferably 200 to 4,000. If the viscosity average degree of polymerization is less than 100, the mechanical strength of the film may decrease when the film is formed. When the viscosity average degree of polymerization exceeds 5,000, industrial production of the modified vinyl alcohol polymer may be difficult.
  • the method for producing the modified vinyl alcohol-based polymer is not particularly limited.
  • a transesterification reaction of a vinyl alcohol-based polymer and an ester compound represented by the following formula (II) (hereinafter referred to as ester compound (II))
  • ester compound (II) The method of doing is simple.
  • X, Y and Z are the same as those defined in the above formula (I), and R is a saturated hydrocarbon group having 1 to 5 carbon atoms.
  • the vinyl alcohol polymer and the ester compound (II) are mixed with a transesterification reaction catalyst to transesterify the vinyl alcohol unit of the vinyl alcohol polymer and the ester compound (II).
  • the method can be adopted as a preferred embodiment.
  • the alcohol represented by ROH R is the same as defined in the above formula (II)
  • ROH is the same as defined in the above formula (II)
  • the reaction between the vinyl alcohol polymer and the ester compound (II) is promoted.
  • the alcohol represented by ROH is preferably a compound having a low boiling point, the carbon number of R is 1 to 5, preferably 1 to 3, and more preferably 1. ..
  • the saturated hydrocarbon group at least one selected from the group consisting of an alkyl group and a cycloalkyl group is suitable.
  • the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group and the like.
  • At least one alkyl group selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group is preferably used, and a methyl group is more preferably used.
  • the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and the like.
  • at least one cycloalkyl group selected from the group consisting of a cyclopropyl group, a cyclobutyl group and a cyclopentyl group is preferably used.
  • X, Y and Z in the formula (II) those exemplified in the above formula (I) are preferably used.
  • ester compound (II) examples include methyl methacrylate, methyl acrylate, methyl crotone, methyl 3-methyl-3-butenoate, methyl 4-pentenoate, methyl 2-methyl-4-pentenoate, and 5-hexene.
  • methyl methacrylate, methyl acrylate, methyl 4-pentenoate, methyl 2-methyl-4-pentenoate, methyl 5-hexenoate, and 3,3-dimethyl-methyl ester are preferred because the transesterification reaction proceeds easily.
  • At least one selected from the group consisting of methyl 4-pentenoate, methyl 7-octenoate, methyl trans-3-pentenoate and methyl trans-4-pentenoate is preferable, and it is excellent in water solubility and energy reactivity.
  • the transesterification reaction catalyst is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic carboxylic acids such as acetic acid, propionic acid, phthalic acid and benzoic acid; methylsulfonic acid, benzenesulfonic acid, p- Organic sulfonic acids such as toluene sulfonic acid and trifluoromethane sulfonic acid; Organic phosphoric acids such as diethyl phosphate and phenyl phosphate; Hydroxylation of alkali metal or alkaline earth metal such as sodium hydroxide, potassium hydroxide and magnesium hydroxide Compounds; carbonates and hydrogen carbonates of alkali metals or alkaline earth metals such as sodium hydrogen carbonate, potassium carbonate, calcium hydrogen carbonate; trilithium phosphate, potassium dihydrogen phosphate, sodium pyrophosphate, alkali metal such as calcium metaphosphate Or alkaline earth
  • Triethylamine tri-n-butylamine, N-methyl-N-ethylaniline, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, etc.
  • Nitrogen-containing aromatic heterocyclic compounds such as pyridine, picoline, quinoline, imidazole, pyrimidine, N,N-dimethylaminopyridine; Cadmium compounds such as cadmium chloride, cadmium oxide, cadmium acetate; Tin chloride, tin oxide , Tin acetate, tin octoate, tributyltin, acetylacetone tin (IV) chloride and other tin compounds; lead chloride, lead oxide, lead carbonate, lead tetraacetate and other lead compounds; aluminum chloride, aluminum oxide, aluminum acetate, Aluminum compounds such as aluminum alkoxide; zinc chloride, zinc bromide, zinc iodide, zinc oxide, zinc acetate, zinc trifluoroacetate, zinc stearate, zinc nitrate, zinc carbonate, zinc sulfate, zinc acetylacetone (II), trifluor Zinc (II) methanesulf
  • molybdenum compounds such as molybdenum chloride, molybdenum oxide, molybdenum acetate, acetylacetone molybdenum (VI) dioxide
  • manganese compounds such as manganese chloride,
  • Hafnium-based compounds such as hafnium (IV) methanesulfonate; lanthanum chloride, Lanthanum compounds such as lanthanum oxide, lanthanum acetate, lanthanum nitrate, lanthanum alkoxide, acetylacetone lanthanum (III) and lanthanum (III) trifluoromethanesulfonate; germanium compounds such as germanium chloride and germanium oxide; enzymes such as lipase; It is preferably used.
  • the amount of the transesterification reaction catalyst added is not particularly limited, but is preferably 0.01 part by mass to 30 parts by mass with respect to 100 parts by mass of the vinyl alcohol polymer. If the amount of the transesterification reaction catalyst added is less than 0.01 part by mass, the reaction rate may be lowered. When the amount of the transesterification reaction catalyst added exceeds 30 parts by mass, it becomes difficult to remove the catalyst residue, and the hue and thermal stability of the resulting modified vinyl alcohol-based polymer may decrease.
  • the addition amount of the ester compound (II) is not particularly limited, and is preferably 0.1 part by mass to 1000 parts by mass, more preferably 5 parts by mass to 500 parts by mass with respect to 100 parts by mass of the vinyl alcohol polymer. .. If the amount added is less than 0.1 parts by mass, the reaction rate may decrease. If the addition amount exceeds 1000 parts by mass, it may be difficult to remove the ester compound remaining after the reaction.
  • the transesterification reaction may be carried out in a state in which the vinyl alcohol-based polymer, the ester compound (II) and the transesterification reaction catalyst are mixed, and for example, the molten vinyl alcohol-based polymer is mixed with the ester compound (II) and the ester compound (II).
  • Method of mixing and reacting transesterification reaction catalyst Method of dissolving ester compound (II) and transesterification catalyst and reacting in slurry state in solvent in which vinyl alcohol polymer is not dissolved; Vinyl alcohol system And the like, in which the polymer, the ester compound (II) and the transesterification reaction catalyst are all uniformly dissolved in the solution.
  • the concentration of the vinyl alcohol polymer during the reaction is not particularly limited, but it is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 40% by mass. It is a mass%, and more preferably 3 mass% to 30 mass%. If the concentration is less than 1% by mass, it may be too dilute to reduce the reaction rate, and if the concentration exceeds 50% by mass, poor stirring may occur in the reaction system.
  • the solvent used in the transesterification reaction is not particularly limited, and examples thereof include water; alcohols such as methanol, ethanol, propanol and butanol; aliphatic or alicyclic hydrocarbons such as n-hexane, n-pentane and cyclohexane; benzene.
  • Aromatic hydrocarbons such as toluene; aliphatic or aromatic halides such as chloroform, chlorobenzene and dichlorobenzene; nitriles such as acetonitrile and benzonitrile; diethyl ether, diphenyl ether, anisole, 1,2-dimethoxyethane, 1 , Ethers such as 4-dioxane; ketones such as acetone, methyl isopropyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and ethyl propionate; N-alkyl lactams such as N-methyl-2-pyrrolidone; N , N-dimethylformamide, N,N-dimethylacetamide and other N,N-dialkylamides; dimethyl sulfoxide and other sulfoxides; sulfolane and other sulfolanes; Of these, aprotic polar solvents
  • the reaction temperature in the transesterification reaction is not particularly limited, but in order to properly remove the alcohol desorbed from the ester compound (II) to the outside of the reaction system, it is preferably the boiling point of the alcohol or higher. From such a viewpoint, 20° C. to 200° C. is preferable, 30° C. to 180° C. is more preferable, 40° C. to 170° C. is further preferable, and 50° C. to 150° C. is further more preferable.
  • the reaction system may be depressurized if necessary in order to lower the boiling point of the alcohol desorbed from the ester compound.
  • the pressure in the reaction system is preferably 5 kPa to 99 kPa, more preferably 8 kPa to 97 kPa, and further preferably 10 kPa to 95 kPa.
  • the anionic polyelectrolyte is a natural or synthetic polymer and is, for example, a thermoplastic resin having a predetermined functional group in the side chain, a polysaccharide, a polypeptide, or a salt thereof.
  • the functional group that may be contained in the anionic polyelectrolyte include a carboxylic acid group or a salt thereof (carboxylate group), a sulfonic acid or a salt thereof (sulfonate group), and a combination thereof. ..
  • anionic polyelectrolyte examples include heat of poly(meth)acrylic acid, polystyrene sulfonic acid, maleic acid-based copolymer, itaconic acid-based copolymer, 2-acrylamido-2-methylpropanesulfonic acid copolymer, and the like.
  • Plastic resins polysaccharides such as carboxymethyl cellulose, sodium dextran sulfate, alginic acid, hyaluronic acid, heparin, heparan sulfate, chondroitin sulfate, cellouronic acid; polypeptides such as polyaspartic acid, polyglutamic acid, cellouronic acid; and salts thereof; and A combination thereof can be mentioned.
  • Poly(meth)acrylic acid is preferable because it can be made highly resistant to water together with the modified vinyl alcohol polymer.
  • the mixing ratio of the modified vinyl alcohol polymer and the anionic polyelectrolyte is not particularly limited, but is preferably 1/99 to 99/1, and more preferably based on the mass. It is 10/90 to 90/10, and more preferably 20/80 to 80/20.
  • the resin composition obtained does not require a complicated crosslinking operation, and the presence of a predetermined crosslinking agent is present.
  • a crosslinked structure can be easily formed underneath or by applying an active energy ray.
  • the crosslinkable resin composition of the present invention may contain a crosslinking agent known in the art.
  • the cross-linking agent preferably includes a compound having two or more thiol groups in one molecule, a compound having two or more amino groups in one molecule, and the like.
  • Examples of the compound having two or more thiol groups in one molecule include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5 -Pentanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, 2,3-dihydroxy-1,4-butanedithiol, ethylene bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate) , 1,4-butanediol bis(thioglycolate), 2,2'-thiodiethanethiol, 3,6-dioxa-1,8-octanedithiol (DODT), 3,7-dithia-1,9- Nonanedithiol, 1,4-benzenedithiol, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tri
  • Examples of the compound having two or more amino groups in one molecule include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 2,2-dimethyl-1,3-propanediamine, 1, 2-diamino-2-methylpropane, 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-
  • the content of the cross-linking agent is not particularly limited, but is, for example, preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the modified vinyl alcohol polymer. It is a mass part. If the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linked structure is not sufficiently formed in the resin composition, and there is a possibility that the obtained cured product may not have satisfactory water resistance. When the content of the cross-linking agent exceeds 20 parts by mass, the cross-linking in the obtained cured product does not proceed further, and the productivity may be rather lowered.
  • the crosslinkable resin composition of the present invention may contain a photopolymerization initiator known in the art in place of the above crosslinker.
  • the photopolymerization initiator is not particularly limited, but is, for example, a propiophenone compound such as 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone; 4′-phenoxy-2,2- Dichloroacetophenone, 4'-t-butyl-2,2,2-trichloroacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-1-(4 '-Dodecylphenyl)-1-propanone, 1-[4'-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-4' -Acetophenone compounds such as methylthio-2-morpholinopropiophenone; benzo
  • the photopolymerization initiator is not particularly limited, but is, for example, preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass with respect to 100 parts by mass of the modified vinyl alcohol polymer. It is a department.
  • the content of the photopolymerization initiator is less than 0.1 parts by mass, for example, even if the resin composition is irradiated with UV light, a crosslinked structure is not sufficiently formed, and the resulting cured product has satisfactory water resistance. May not be achieved.
  • the content of the photopolymerization initiator is more than 10 parts by mass, the crosslinking in the obtained cured product does not proceed further, and the productivity may rather be lost.
  • the crosslinkable resin composition of the present invention may contain other additives known in the art.
  • additives include fillers, processing stabilizers, weather resistance stabilizers, colorants, UV light absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, plasticizers. , Lubricants, fragrances, defoamers, deodorants, release agents, mold release agents, reinforcing agents, fungicides, preservatives, crystallization rate retarders, and other water-soluble resins, and combinations thereof.
  • the content of the above-mentioned other additives is not particularly limited, and an amount that does not impair the efficiency of the present invention can be arbitrarily set by those skilled in the art.
  • cured material of this invention contains the crosslinked body of the said crosslinkable resin composition.
  • the crosslinked product of the crosslinkable resin composition is represented by the above formula (I) in which the modified vinyl alcohol-based polymer and the anionic polyelectrolyte contained in the crosslinkable resin composition constitute the modified vinyl alcohol-based polymer. It is chemically or physically integrated by crosslinking based on the constitutional unit.
  • the cured product of the present invention has excellent water resistance.
  • the degree of such water resistance can be evaluated by, for example, measuring the elution rate of the obtained crosslinked product.
  • the dissolution rate can be calculated according to
  • the cured product of the present invention preferably has an elution rate of 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and most preferably 25% by mass or less.
  • elution rate 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and most preferably 25% by mass or less.
  • the cured product of the present invention has excellent water absorption.
  • the degree of such water absorption can be evaluated, for example, by measuring the water absorption capacity of the obtained crosslinked product.
  • the cured product of the present invention preferably has a water absorption capacity of 5 times or more, more preferably 7 times or more, still more preferably 10 times or more.
  • the upper limit of the water absorption capacity of the cured product of the present invention is not particularly limited, but is, for example, 2000 times or less and 1000 times or less. Since the cured product of the present invention satisfies the water absorption capacity in the above range, it is understood that the constituents have the ability to absorb a large amount of water when immersed in the water.
  • the cured product of the present invention can be produced, for example, as follows using the above crosslinkable resin composition.
  • crosslinkable resin composition contains a photopolymerization initiator together with the modified polyvinyl alcohol-based polymer and the anionic polyelectrolyte will be described.
  • the crosslinkable resin composition is irradiated with ⁇ -rays, ⁇ -rays, electron beams, i-rays, active energy rays such as UV rays, and particularly preferably UV rays.
  • the irradiation conditions of UV light are not necessarily limited because they vary depending on the amount of the crosslinkable resin composition used and the content of the contents thereof, and appropriate irradiation conditions (for example, irradiation intensity and irradiation time) can be determined by those skilled in the art. It can be appropriately selected. Irradiation of the UV light to the crosslinkable resin composition may be performed continuously or intermittently.
  • the modified vinyl alcohol-based polymer and the anionic polyelectrolyte contained in the composition constitute the modified vinyl alcohol-based polymer and have the above formula (I).
  • Crosslinking based on the constitutional unit represented by is chemically or physically integrated to form a predetermined crosslinked body. In this way, the cured product of the present invention can be obtained.
  • crosslinkable resin composition contains a crosslinker together with the modified vinyl alcohol polymer and the anionic polyelectrolyte will be described.
  • the crosslinkable resin composition is heated.
  • the heating conditions are not necessarily limited because they vary depending on the amount of the crosslinkable resin composition used, the content of those contents, etc., and appropriate heating conditions (for example, heating temperature and heating time) are appropriately selected by those skilled in the art. obtain.
  • the heating of the crosslinkable resin composition may be performed continuously or intermittently.
  • the modified polyvinyl alcohol-based polymer and the anionic polyelectrolyte contained in the composition are structural units represented by the above formula (I) that constitute the modified polyvinyl alcohol-based polymer. Based on the cross-linking, they are chemically or physically integrated to form a predetermined cross-linked product. In this way, the cured product of the present invention can be obtained.
  • the cured product of the present invention is not particularly limited, but by utilizing its excellent water absorption and water resistance, hygiene products (for example, diapers and sanitary products), medical-related products (for example, dressing materials for wound protection), agriculture/ Gardening materials (eg soil water retention agent, seedling sheet, seed coating material), food packaging materials (eg freshness retention film, dew condensation prevention sheet, barrier coating material), pet related products (eg pet sheet, cat sand), electricity It can be used as a material for forming various industrial products such as related materials (for example, water-stopping materials for communication cables, building materials (for example, wallpaper for preventing dew condensation)).
  • related materials for example, water-stopping materials for communication cables, building materials (for example, wallpaper for preventing dew condensation)
  • modified PVOH-2 obtained in this synthesis example are shown in Table 1.
  • modified PVOH-5 modified polyvinyl alcohol polymer
  • Example 1 To 1 part by mass of a polyacrylic acid aqueous solution (168-07375, 25% aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.), 1.5 parts by mass of ion-exchanged water was added, and they were mixed sufficiently until they became uniform. Next, 2.5 parts by mass of a 10% aqueous solution of modified PVOH-1 obtained in Synthesis Example 1 was added and mixed until uniform to obtain a mixed solution containing modified PVOH-1 and polyacrylic acid. To the resulting mixed solution, 5 parts by mass of ion-exchanged water was added to prepare a 5% by mass aqueous solution, and 2-hydroxy-4′-(2-hydroxyethoxy)-2 as a photopolymerization initiator was added thereto.
  • a polyacrylic acid aqueous solution 168-07375, 25% aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
  • HEMP -Methylpropiophenone
  • Example 2 2.25 parts by mass of ion-exchanged water was added to 0.25 parts by mass of polymethacrylic acid (00578-50 manufactured by Wako Pure Chemical Industries, Ltd.), and they were mixed sufficiently until they were completely dissolved. Next, 2.5 parts by mass of a 10% aqueous solution of modified PVOH-2 obtained in Synthesis Example 2 was added and mixed until uniform to obtain a mixed solution containing modified PVOH-2 and polymethacrylic acid. 0.005 parts by mass of HEMP as a photopolymerization initiator was added to the obtained mixed liquid and stirred until completely dissolved to prepare an aqueous solution (E2) which is a crosslinkable resin composition.
  • E2 aqueous solution
  • this aqueous solution (E2) was transferred to a petri dish having a diameter of 3 cm and a thickness of 1 cm, and UV light was irradiated from above the petri dish at an intensity of 3000 mJ/cm 2 to obtain a crosslinked gel (SE2).
  • the evaluation results of the obtained crosslinked gel (SE2) are shown in Table 2.
  • Example 3 To 1 part by mass of an aqueous polyacrylic acid solution (168-07375, 25% aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.), 1.4 parts by mass of ion-exchanged water was added, and 0.11 parts by mass of 8N KOH aqueous solution was added, Mix well until uniform. Next, 2.5 parts by mass of a 10% aqueous solution of modified PVOH-3 obtained in Synthesis Example 3 was added and mixed until uniform to obtain a mixed solution containing modified PVOH-3 and polyacrylic acid.
  • an aqueous polyacrylic acid solution 168-07375, 25% aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 4 To 0.2 parts by mass of sodium alginate (manufactured by Wako Pure Chemical Industries, 191-09965), 1.8 parts by mass of ion-exchanged water was added, and they were sufficiently mixed until completely dissolved. Next, 3 parts by mass of a 10% aqueous solution of modified PVOH-4 obtained in Synthesis Example 4 was added and mixed until uniform to obtain a mixed solution containing modified PVOH-4 and alginic acid. 0.005 parts by mass of HEMP was added to the obtained mixed liquid and stirred until completely dissolved to prepare an aqueous solution (E4) which is a crosslinkable resin composition.
  • E4 a crosslinkable resin composition
  • a crosslinked gel (SE4) was obtained in the same manner as in Example 1 except that this aqueous solution (E4) was used and the intensity of the irradiated UV light was changed to 3000 mJ/cm 2 .
  • Table 2 shows the evaluation results of the obtained crosslinked gel (SE4).
  • Example 5 To 1.4 parts by mass of an aqueous polyacrylic acid solution (168-07375, Wako Pure Chemical Industries, 25% aqueous solution), 3.0 parts by mass of ion-exchanged water was added, and 0.154 parts by mass of 8N KOH aqueous solution was added. And mixed well until uniform. Next, 1.5 parts by mass of a 10% aqueous solution of modified PVOH-2 obtained in Synthesis Example 2 was added and mixed until uniform to obtain an aqueous solution containing modified PVOH-2 and polyacrylic acid.
  • aqueous polyacrylic acid solution 168-07375, Wako Pure Chemical Industries, 25% aqueous solution
  • Example 6 1.4 parts by mass of ion-exchanged water was added to 1 part by mass of a polyacrylic acid aqueous solution (manufactured by Wako Pure Chemical Industries, 168-07375, 25% aqueous solution), and 0.055 parts by mass of an 8N KOH aqueous solution was added. , Mixed well until uniform. Next, 2.5 parts by mass of a 10% aqueous solution of modified PVOH-2 obtained in Synthesis Example 2 was added and mixed until uniform to obtain a mixed solution containing modified PVOH-2 and polyacrylic acid.
  • a polyacrylic acid aqueous solution manufactured by Wako Pure Chemical Industries, 168-07375, 25% aqueous solution
  • 8N KOH aqueous solution 8N KOH aqueous solution
  • Example 7 To 0.2 parts by mass of an aqueous solution of polyacrylic acid (168-07375, Wako Pure Chemical Industries, 25% aqueous solution), 0.28 parts by mass of ion-exchanged water was added, and 0.022 parts by mass of 8N KOH aqueous solution was added. And mixed well until uniform. Next, 4.5 parts by mass of a 10% aqueous solution of modified PVOH-3 obtained in Synthesis Example 3 was added and mixed until uniform to obtain a mixed solution containing modified PVOH-3 and polyacrylic acid.
  • polyacrylic acid 168-07375, Wako Pure Chemical Industries, 25% aqueous solution
  • 8N KOH aqueous solution 8N KOH aqueous solution
  • aqueous solution (E7) which is a crosslinkable resin composition was prepared.
  • a crosslinked film (SE7) was obtained in the same manner as in Example 1 except that this aqueous solution (E7) was used and the intensity of the irradiated UV light was changed to 1500 mJ/cm 2 .
  • Table 2 shows the evaluation results of the obtained crosslinked film (SE7).
  • Example 8 To 1.4 parts by mass of an aqueous polyacrylic acid solution (168-07375, Wako Pure Chemical Industries, 25% aqueous solution), 3.0 parts by mass of ion-exchanged water was added, and 0.154 parts by mass of 8N KOH aqueous solution was added. And mixed well until uniform. Next, 1.5 parts by mass of a 10% aqueous solution of modified PVOH-5 obtained in Synthesis Example 5 was added and mixed until uniform to obtain a mixed solution containing modified PVOH-5 and polyacrylic acid.
  • aqueous polyacrylic acid solution 168-07375, Wako Pure Chemical Industries, 25% aqueous solution
  • Comparative Example 1 1.4 parts by mass of ion-exchanged water was added to 1 part by mass of a polyacrylic acid aqueous solution (manufactured by Wako Pure Chemical Industries, 168-07375, 25% aqueous solution), and 0.11 parts by mass of an 8N KOH aqueous solution was added to obtain a uniform mixture. Mix well until Next, 2.5 parts by mass of a 10% aqueous solution of PVOH-6 obtained in Synthesis Example 6 was added and mixed until uniform to obtain a mixed solution containing PVOH-6 and polyacrylic acid.
  • a polyacrylic acid aqueous solution manufactured by Wako Pure Chemical Industries, 168-07375, 25% aqueous solution
  • Comparative example 2 In the same manner as in Comparative Example 1, a mixed solution containing PVOH-6 and polyacrylic acid was obtained. A predetermined amount of ion-exchanged water is added to the obtained mixed liquid to prepare a 5% by mass aqueous solution, and 0.01 part by mass of DODT as a crosslinking agent is added thereto, and the mixture is stirred until completely dissolved to obtain a resin composition. To prepare an aqueous solution (C2). Then, a film (SC2) was obtained in the same manner as in Example 5 except that this aqueous solution (C2) was used. Table 2 shows the evaluation results of the obtained film (SC2).
  • Comparative example 3 In the same manner as in Comparative Example 1, a mixed solution containing PVOH-6 and polyacrylic acid was obtained. 0.005 parts by mass of HEMP as an initiator was added to the obtained mixed liquid and stirred until completely dissolved to prepare an aqueous solution (C3) which is a resin composition. Next, this aqueous solution (C3) was transferred to a petri dish having a diameter of 3 cm and a thickness of 1 cm, and UV light was irradiated from above the petri dish at an intensity of 3000 mJ/cm 2 to try to prepare a crosslinked gel. However, the aqueous solution (C3) remained as an aqueous solution without cross-linking gelation. The evaluation results are shown in Table 2.
  • aqueous solution (C4) which was a resin composition from a mixed solution containing PVOH-6 in the same manner as in Comparative Example 1 except that the aqueous solution of polyacrylic acid was not contained and PVOH-2 was used instead of PVOH-1. was produced. Then, a film (SC4) was obtained in the same manner as in Comparative Example 1 except that this aqueous solution (C4) was used and the intensity of the irradiated UV light was changed to 3000 mJ/cm 2 . Table 2 shows the evaluation results of the obtained film (SC4).
  • aqueous solution (C5) which is a resin composition was prepared from a mixed solution containing polyacrylic acid in the same manner as in Comparative Example 1 except that PVOH-6 was not included. Then, this aqueous solution (C5) was transferred to a petri dish having a diameter of 3 cm and a thickness of 1 cm, and UV light was irradiated from above the petri dish at an intensity of 3000 mJ/cm 2 to try to prepare a crosslinked gel. However, the aqueous solution (C5) remained as an aqueous solution without being crosslinked. The evaluation results are shown in Table 2.
  • each of the crosslinkable resin compositions (E1) to (E8) prepared in Examples 1 to 8 was converted into a crosslinked film or gel by irradiation with UV light or addition of a crosslinking agent. It could be molded.
  • the resin compositions (C1) to (C3) and (C5) of Comparative Examples 1 to 3 and 5 in which the modified polyvinyl alcohol-based polymer was not used the crosslinking itself was difficult and the film was made water resistant. Or could not be gelled from an aqueous solution.
  • a material for forming various industrial products as a resin molding field, a healthcare product field, a medical product field, an agricultural/horticultural field, a food/distribution field, a pet-related product field, an electrical field, and a construction field. It is useful in fields.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Une composition de résine réticulable selon la présente invention contient: un polymère d'alcool vinylique modifié contenant une unité alcool vinylique et une unité structurale représentée par la formule (I); et un électrolyte polymère anionique. [Dans la formule (I), X représente une liaison carbone-carbone ou un groupe hydrocarboné saturé divalent ayant éventuellement une structure ramifiée comprenant de 1 à 6 atomes de carbone, Y représente un atome d'hydrogène ou un groupe hydrocarboné saturé ayant éventuellement une structure ramifiée comprenant de 1 à 6 atomes de carbone, et Z représente un atome d'hydrogène ou un groupe méthyle.
PCT/JP2019/050725 2018-12-28 2019-12-24 Composition de résine réticulable et produit durci de cette dernière Ceased WO2020138126A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02138307A (ja) * 1988-07-12 1990-05-28 Dynic Corp 皮膜状高吸水性シートおよびその製造方法
JP2007092052A (ja) * 2005-08-31 2007-04-12 Tohcello Co Ltd ガスバリア性膜、ガスバリア性積層体及びその製造方法
JP2017066366A (ja) * 2015-10-01 2017-04-06 コリア アトミック エナジー リサーチ インスティテュートＫｏｒｅａ Ａｔｏｍｉｃ Ｅｎｅｒｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ 放射線架橋型ポリビニルアルコールを含むイオン性高分子膜及びその製造方法
WO2018124014A1 (fr) * 2016-12-28 2018-07-05 株式会社クラレ Polymère d'alcool vinylique contenant une oléfine à chaîne latérale, et procédé de production de ce dernier
WO2018181735A1 (fr) * 2017-03-30 2018-10-04 株式会社クラレ Papier de base de papier anti-adhésif et son procédé de production, et papier anti-adhésif
JP2020023634A (ja) * 2018-08-08 2020-02-13 株式会社クラレ 水性インク用組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02138307A (ja) * 1988-07-12 1990-05-28 Dynic Corp 皮膜状高吸水性シートおよびその製造方法
JP2007092052A (ja) * 2005-08-31 2007-04-12 Tohcello Co Ltd ガスバリア性膜、ガスバリア性積層体及びその製造方法
JP2017066366A (ja) * 2015-10-01 2017-04-06 コリア アトミック エナジー リサーチ インスティテュートＫｏｒｅａ Ａｔｏｍｉｃ Ｅｎｅｒｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ 放射線架橋型ポリビニルアルコールを含むイオン性高分子膜及びその製造方法
WO2018124014A1 (fr) * 2016-12-28 2018-07-05 株式会社クラレ Polymère d'alcool vinylique contenant une oléfine à chaîne latérale, et procédé de production de ce dernier
WO2018181735A1 (fr) * 2017-03-30 2018-10-04 株式会社クラレ Papier de base de papier anti-adhésif et son procédé de production, et papier anti-adhésif
JP2020023634A (ja) * 2018-08-08 2020-02-13 株式会社クラレ 水性インク用組成物

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