WO2010113566A1 - Stabilisateur de dispersion destiné être utilisé dans une émulsion aqueuse, et émulsion aqueuse - Google Patents

Stabilisateur de dispersion destiné être utilisé dans une émulsion aqueuse, et émulsion aqueuse Download PDF

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WO2010113566A1
WO2010113566A1 PCT/JP2010/052784 JP2010052784W WO2010113566A1 WO 2010113566 A1 WO2010113566 A1 WO 2010113566A1 JP 2010052784 W JP2010052784 W JP 2010052784W WO 2010113566 A1 WO2010113566 A1 WO 2010113566A1
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group
hydrogen atom
polyoxyalkylene
aqueous emulsion
polymerization
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Japanese (ja)
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昌人 仲前
真輔 新居
秀樹 真木
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株式会社クラレ
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • the present invention relates to a dispersion stabilizer for an aqueous emulsion containing a vinyl alcohol polymer having a specific functional group, and an aqueous emulsion.
  • an aqueous emulsion using a vinyl alcohol polymer (hereinafter sometimes abbreviated as PVA) as a dispersion stabilizer is an emulsion polymerization of monomers using only a surfactant having an emulsifying action as a dispersion stabilizer for emulsion polymerization.
  • PVA vinyl alcohol polymer
  • the emulsion has better stability, better miscibility with inorganic materials, etc., and has many advantages such as being able to impart flow characteristics suitable for various applications relatively easily. Therefore, it is widely used in various applications including adhesives and paints.
  • PVA vinyl alcohol polymer
  • the obtained aqueous emulsion has several problems, and the performance is insufficient for expanding the use and performance of the aqueous emulsion. It was.
  • Patent Document 1 discloses an aqueous emulsion containing 0.1 to 50% by weight of PVA having an average degree of polymerization of 3500 or more with respect to a polymer dispersoid as a conventionally known measure for improving initial adhesiveness.
  • the viscosity of the system is likely to increase due to the drying of the aqueous emulsion, so that the initial adhesive force is likely to be developed.
  • Patent Document 2 discloses that the dispersant has a viscosity average polymerization degree of 200 or more, a ratio Pw / Pn of weight average polymerization degree (Pw) to number average polymerization degree (Pn) of 4 or more, and GPC measurement.
  • An aqueous emulsion containing PVA having a maximum molecular weight peak position in the molecular weight distribution having a degree of polymerization of 3500 or more is disclosed. Also in this case, the thickening of the system due to drying is large and effective in developing the initial adhesive force, but workability and the like may still be a problem.
  • an adhesive obtained by adding an electrolyte such as boric acid to an aqueous emulsion as a protective colloid there is also known an adhesive obtained by adding an electrolyte such as boric acid to an aqueous emulsion as a protective colloid.
  • these products have problems such as safety of additives such as surfactants, polyalkylene glycols, and boric acid, and influence on the environment, and initial adhesiveness often fails to meet the current required level.
  • Patent Document 5 discloses an adhesive composition comprising a vinyl acetate resin emulsion using a PVA having a carboxyl group and an alkyl group having 5 to 15 carbon atoms as a protective colloid and a plasticizer.
  • Patent Document 6 discloses an adhesive composition in which an aromatic sulfonic acid alkali metal formaldehyde condensate and a plasticizer are blended with a vinyl acetate resin emulsion using PVA as a protective colloid.
  • these methods do not always have a sufficient initial adhesion level.
  • there is a problem of liberation of formaldehyde which is not preferable.
  • Patent Document 7 discloses an adhesive containing urea in a vinyl acetate resin emulsion using a copolymer of carboxyl group-modified PVA or ⁇ -olefin and an unsaturated carboxylic acid or a derivative thereof as a protective colloid, and containing a plasticizer.
  • a composition is disclosed.
  • Patent Document 8 is characterized by containing a vinyl acetate emulsion obtained by emulsion polymerization of a vinyl acetate monomer using an imidized isobutylene-maleic anhydride copolymer as a protective colloid, and a glycerin fatty acid ester.
  • a high speed adhesive composition is disclosed.
  • Patent Document 9 discloses a method for producing a modified PVA characterized by saponifying a copolymer of an unsaturated monomer containing an oxyalkylene group and vinyl acetate.
  • the oxyalkylene group in the unsaturated monomer used for the production of the modified PVA include polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups having about 1 to 50 repeating units.
  • emulsifiers for emulsion polymerization are described in many examples of uses of the modified PVA.
  • the present invention eliminates the above-mentioned problems in the prior art and produces an aqueous emulsion that has high initial adhesiveness and is capable of high-speed production, which is one of the important performances when used as an adhesive or various binders.
  • a dispersion stabilizer for aqueous emulsions suitable for use in water and an aqueous emulsion using the dispersion stabilizer as a dispersion stabilizer are provided.
  • the inventors of the present invention have various characteristics (namely, mechanical stability, chemical stability, freeze-thaw stability, miscibility with inorganic substances, etc.) that aqueous emulsions produced using conventional PVA as a protective colloid have.
  • Dispersion stabilizer for aqueous emulsion that can easily obtain an aqueous emulsion with excellent initial adhesion, which is one of the important performances when used as an adhesive or various binders, on the industrial scale. We studied earnestly.
  • POA polyoxyalkylene
  • the saponification degree is 80 to 99.99 mol%
  • the polyoxyalkylene group modification amount is 0.1 to 10 mol%
  • the polyalcohol is based on 100 parts by weight of the main chain of the vinyl alcohol polymer.
  • a dispersion stabilizer for an aqueous emulsion containing a polyoxyalkylene-modified vinyl alcohol polymer (hereinafter sometimes abbreviated as POA-modified PVA) having an oxyalkylene group content of 6 to 50 parts by weight is provided for the intended aqueous emulsion.
  • POA-modified PVA polyoxyalkylene-modified vinyl alcohol polymer having an oxyalkylene group content of 6 to 50 parts by weight
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • m and n represent the number of repeating units of each oxyalkylene unit, and 1 ⁇ m ⁇ 10 and 5 ⁇ n ⁇ 20.
  • unit 1 a unit represented by the number m of repeating units
  • unit 2 a unit represented by the number of repeating units n is referred to as unit 2.
  • the arrangement of the unit 1 and the unit 2 may be random or block.
  • the polyoxyalkylene-modified vinyl alcohol polymer was obtained by copolymerizing a macromonomer having a polyoxyalkylene group represented by the following general formula (II) with a vinyl ester and then saponifying the polymer. It is preferable that
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • m and n represent the number of repeating units of each oxyalkylene unit, and 1 ⁇ m ⁇ 10 and 5 ⁇ n ⁇ 20.
  • R3 represents a hydrogen atom or a —COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group.
  • R4 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M is as defined above.
  • X represents —O—, —CH 2 —O—, —CO—, —CO—O— or —CO—NR 5 —.
  • R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms.
  • the polyoxyalkylene-modified vinyl alcohol polymer is obtained by copolymerization of a macromonomer having a polyoxyalkylene group represented by the following general formula (III) and a vinyl ester and then saponifying. Is more preferable.
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • m and n represent the number of repeating units of each oxyalkylene unit, and 1 ⁇ m ⁇ 10 and 5 ⁇ n ⁇ 20.
  • R4 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group.
  • R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms.
  • An aqueous emulsion containing the dispersion stabilizer of the present invention and a polymer dispersoid composed of one or more unsaturated monomers selected from ethylenically unsaturated monomers and diene monomers is also included in the present invention. This is a preferred embodiment.
  • the emulsion obtained by emulsion polymerization using the dispersion stabilizer for aqueous emulsions of the present invention is excellent in initial adhesiveness as compared with the case of using a conventional dispersant.
  • the present invention is a PVA containing a POA group represented by the above general formula (I) in the side chain, the PVA has a viscosity average polymerization degree of 200 to 3,000, and a saponification degree of 80 to 99.99 mol%.
  • the POA group present in the side chain of the POA-modified PVA used in the dispersion stabilizer for aqueous emulsions has a unit 1 repeating unit number m of 1 ⁇ m ⁇ 10 and a unit 2 repeating unit number n. Needs to be 5 ⁇ n ⁇ 20. When m and n are within such ranges, excellent adhesiveness, particularly initial adhesiveness, of the aqueous emulsion using the POA-modified PVA as a dispersant is developed.
  • m is preferably 2 or more.
  • m is preferably 5 or less, and more preferably 3 or less.
  • n is preferably 8 or more.
  • n is preferably 18 or less, and more preferably 15 or less.
  • the POA group modification amount S needs to be 0.1 to 10 mol%, preferably 0.15 to 8 mol. %, More preferably 0.2 to 6 mol%.
  • the modification amount of the POA group is smaller than 0.1 mol%, the initial adhesiveness of the aqueous emulsion using the PVA as a dispersion stabilizer, which is the object of the present invention, is not expressed.
  • it exceeds 10 mol% the hydrophobicity of the PVA increases and water solubility may be lowered, which is not suitable.
  • the amount of POA group modification is represented by the molar fraction of the POA group with respect to the main chain methylene group of PVA.
  • the POA group modification amount of the POA-modified PVA is, for example, the POA-modified polyvinyl ester that is a precursor of the PVA, specifically, POA-modified polyvinyl acetate (hereinafter, polyvinyl acetate may be abbreviated as PVAc). It can be determined from proton NMR. Specifically, after re-precipitation purification of POA-modified PVAc with n-hexane / acetone three or more times, it is dried under reduced pressure at 50 ° C. for 2 days to prepare POA-modified PVAc for analysis.
  • the PVAc is dissolved in CDCl 3 and 500 MHz proton NMR (JEOL GX-500) is measured at room temperature.
  • S is calculated.
  • S (mol%) ⁇ (number of protons of ⁇ / 3n) / (number of protons of ⁇ + (number of protons of ⁇ / 3n)) ⁇ ⁇ 100 n represents the number of repeating units of unit 2.
  • the POA group content in the POA-modified PVA needs to be 6 to 50 parts by weight. Within this range, the POA-modified PVA which is the effect of the present invention is used as a dispersion stabilizer.
  • the initial adhesiveness of the aqueous emulsion is developed.
  • the content of the POA group is represented by the weight part (weight fraction) of the POA group with respect to 100 parts by weight of the main chain of PVA.
  • the content of the POA group is a value calculated using the POA group modification amount S, the number of repeating units m of unit 1, the number of repeating units n of unit 2, and the degree of saponification of POA modified PVA. Even if the above-mentioned POA group modification amount S is equivalent, the POA group content in the POA-modified PVA increases as the degree of saponification increases or as m or n increases.
  • the viscosity average polymerization degree of the PVA containing the POA group represented by the general formula (I) in the side chain needs to be 200 to 3000, preferably 250 to 2800, more preferably 300 to 2600.
  • the viscosity average degree of polymerization may be simply referred to as the degree of polymerization.
  • the degree of polymerization is less than 200, it is unsuitable because it does not have sufficient stabilizing ability as a dispersion stabilizer for aqueous emulsions, and the stability of aqueous emulsions is insufficient.
  • it is larger than 3000, it is difficult to control the viscosity of the emulsion, which is not suitable.
  • the saponification degree of the PVA containing the POA group represented by the general formula (I) in the side chain needs to be 80 to 99.99 mol%, preferably 83 to 99.5 mol%, 99 mol% is more preferable. If the degree of saponification is less than 80 mol%, the water solubility of the POA-modified PVA is lost, so that it does not function as a dispersion stabilizer and the aqueous emulsion becomes unstable. On the other hand, when the degree of saponification exceeds 99.99 mol%, the aqueous emulsion lacks stability because it does not have sufficient stabilizing ability as a dispersion stabilizer for aqueous emulsions.
  • the saponification degree of the PVA is a value that can be measured according to JIS-K6726.
  • PVA containing the POA group represented by the general formula (I) in the side chain is produced by various methods. Although it is also possible to obtain by reacting a compound having a functional group (carboxyl group, isocyanate group, etc.) capable of reacting with the POA group represented by the general formula (I) and the hydroxyl group of PVA with PVA, In general and industrially, it is obtained by copolymerizing an unsaturated monomer (macromonomer) containing a POA group represented by the general formula (I) with a vinyl ester and then saponifying it.
  • a macromonomer which has POA group what is shown by said general formula (II) is preferable.
  • R1 in the general formula (II) is a hydrogen atom
  • R2 is a hydrogen atom
  • R3 is a hydrogen atom
  • polyoxyethylene polyoxybutylene monoacrylate Polyoxyethylene polyoxybutylene monomethacrylate, polyoxyethylene polyoxybutylene monoacrylic amide, polyoxyethylene polyoxybutylene monomethacrylamide, polyoxyethylene polyoxybutylene monoallyl ether, polyoxyethylene polyoxybutylene monomethallyl
  • examples include ether and polyoxyethylene polyoxybutylene monovinyl ether.
  • polyoxyethylene polyoxybutylene monoacrylic acid amide, polyoxyethylene polyoxybutylene monomethacrylic acid amide, polyoxyethylene polyoxybutylene monovinyl ether are preferably used, polyoxyethylene polyoxybutylene monomethacrylic acid amide, Polyoxyethylene polyoxybutylene monovinyl ether is particularly preferably used.
  • R2 in the general formula (II) is an alkyl group having 1 to 8 carbon atoms
  • R1 in the general formula (II) is a hydrogen atom
  • R2 is a hydrogen atom
  • R3 is a hydrogen atom
  • the OH group at the terminal of the macromonomer exemplified in the above is substituted with an alkoxy group having 1 to 8 carbon atoms.
  • a macromonomer in which the OH group at the terminal of polyoxyethylene polyoxybutylene monomethacrylamide or polyoxyethylene polyoxybutylene monovinyl ether is substituted with a methoxy group is preferably used.
  • a macromonomer in which the OH group at the terminal of the acid amide is substituted with a methoxy group is particularly preferably used.
  • the POA-modified PVA constituting the dispersion stabilizer for an aqueous emulsion of the present invention is obtained by saponifying a copolymer of a macromonomer and a vinyl ester represented by the general formula (II), In view of the properties, it is more preferable to use a macromonomer represented by the above general formula (III) in which X is —CO—NR 5 —.
  • Examples of the macromonomer represented by the general formula (III) include polyoxyethylene polyoxybutylene monoacrylic acid amide, an unsaturated monomer in which the terminal OH group is substituted with a methoxy group, polyoxyethylene polyoxy Typical are butylene monomethacrylamide and unsaturated monomers in which the terminal OH group is substituted with a methoxy group.
  • copolymerization of a macromonomer having a POA group and a vinyl ester monomer is carried out in an alcohol solvent or without solvent, and the resulting POA modified vinyl ester system is obtained.
  • a method of saponifying the copolymer is preferred.
  • the temperature employed when copolymerizing the macromonomer having a POA group and the vinyl ester monomer is preferably from 0 to 200 ° C, more preferably from 30 to 140 ° C. When the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate.
  • polymerizes is higher than 200 degreeC, it is difficult to obtain POA modified PVA which has the POA group modification amount prescribed
  • a method for controlling the temperature employed in the copolymerization to 0 to 200 ° C. for example, by controlling the polymerization rate, the heat generated by the polymerization is balanced with the heat released from the surface of the reactor. Examples thereof include a method and a method of controlling by an external jacket using an appropriate heating medium, but the latter method is preferable from the viewpoint of safety.
  • the polymerization method used for copolymerizing the macromonomer having a POA group and the vinyl ester monomer may be any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization.
  • the polymerization method any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method can be used.
  • a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or an alcohol solvent is preferably employed, and an emulsion polymerization method is employed for the purpose of producing a copolymer having a high degree of polymerization.
  • the alcohol solvent methyl alcohol, ethyl alcohol, propyl alcohol, and the like can be used, but are not limited thereto. These solvents can be used in combination of two or more.
  • azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method.
  • the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile), etc.
  • peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, ⁇ -cumylperoxyneodecanate, t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpent
  • the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
  • the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • vinyl ester monomers vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, Examples include vinyl stearate, vinyl oleate, and vinyl benzoate. Among them, vinyl acetate is most preferable.
  • the macromonomer having a POA group and the vinyl ester monomer are copolymerized, other monomers may be copolymerized as long as the gist of the present invention is not impaired.
  • monomers that can be used include ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and its salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, and i-propyl acrylate.
  • Acrylic acid esters such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate and octadecyl acrylate; methacrylic acid and salts thereof; methyl methacrylate, methacrylic acid Methacrylic acid such as ethyl acetate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Beauty treatment Acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acryl
  • a chain transfer agent is used within the range not impairing the gist of the present invention for the purpose of adjusting the degree of polymerization of the resulting copolymer.
  • Copolymerization may be carried out in the presence of.
  • chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and halogenated hydrocarbons such as trichloroethylene and perchloroethylene. Of these, aldehydes and ketones are preferably used.
  • the addition amount of the chain transfer agent is determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target vinyl ester polymer, but is generally 0.1% relative to the vinyl ester monomer. ⁇ 10% by weight is desirable.
  • an alcoholysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as P-toluenesulfonic acid can be applied.
  • a hydrolysis reaction can be applied.
  • the solvent that can be used for this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
  • the above POA-modified PVA is used as a dispersion stabilizer, and a polymer comprising one or more unsaturated monomers selected from ethylenically unsaturated monomers or diene monomers is dispersed. It is an aqueous emulsion to make.
  • the aqueous emulsion is not particularly limited as long as it contains the POA-modified PVA as a dispersion stabilizer and the polymer as a dispersoid.
  • ethylene in the presence of POA-modified PVA is present in an aqueous medium in the sense that the initial adhesiveness, which is one of the important performances of the present invention, is fully expressed.
  • An aqueous emulsion obtained by emulsion polymerization of one or more unsaturated monomers selected from a polymerizable unsaturated monomer or a diene monomer is preferred.
  • an ordinary emulsion polymerization method in which the unsaturated monomer is added temporarily or continuously in the presence of water, a dispersion stabilizer and a polymerization initiator, and heated and stirred is used. Either can be implemented. Also, a method of continuously adding an unsaturated monomer previously mixed with a dispersion stabilizer and emulsified can be carried out.
  • the amount of the POA-modified PVA used is somewhat different depending on the polymerization degree of the POA-modified PVA, the required resin concentration of the aqueous emulsion, etc. 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the unsaturated monomer used in the synthesis of the polymer.
  • the amount of POA-modified PVA used is less than 1 part by weight, it is difficult to ensure the stability of emulsion polymerization, and when it exceeds 20 parts by weight, the viscosity of the resulting aqueous emulsion becomes too high, making it difficult to control the polymerization. At the same time, physical properties such as water resistance of the aqueous emulsion may be adversely affected.
  • the polymerization initiator used in ordinary emulsion polymerization, for example, hydrogen peroxide, persulfates, percarbonates, peroxides, etc. can be used alone, and these can be used together with oxyacids such as tartaric acid, citric acid and ascorbic acid.
  • Redox polymerization initiators in combination with carboxylic acid, oxalic acid, sulfinic acid and salts thereof, Rongalite, water-soluble iron salt and the like can be used.
  • Examples of the ethylenically unsaturated monomer and diene monomer used for the synthesis of the polymer constituting the dispersoid of the aqueous emulsion of the present invention include the following. Olefins such as ethylene, propylene and isobutylene; Halogenated olefins such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; Vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and vinyl versatate; Acrylic acid, methacrylic acid and its esters methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ⁇ -ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, dimethylaminoethyl (meth) acrylate and quaternized compounds
  • the aqueous emulsion using the dispersion stabilizer for aqueous emulsion of the present invention has characteristics desired for the aqueous emulsion by adding other protective colloids during or after the polymerization within a range not impairing the performance of the obtained aqueous emulsion. Is also effective.
  • protective colloids include conventional polyvinyl alcohol, polyacrylic acid or polymethacrylic acid and salts thereof, polyvinyl alkyl ether, copolymers of vinyl acetate and acrylic acid, methacrylic acid or maleic anhydride, and tendons thereof.
  • ком ⁇ онент such as alkyl cellulose, hydroxyalkyl cellulose, alkyl hydroxyalkyl cellulose, carboxymethyl cellulose, starch derivatives such as alkyl starch, carboxoxymethyl starch, oxidized starch, gum arabic, Examples include tragacanth rubber and polyalkylene glycol.
  • auxiliary agents such as liquid modifiers, monovalent or polyhydric alcohols, plasticizers, antifoaming agents and the like conventionally used in emulsion polymerization are added. It may be added at the time of polymerization or after polymerization.
  • anionic, nonionic, and cationic surfactants and water-soluble polymers such as PVA and hydroxyethyl cellulose can be added as long as the performance of the aqueous emulsion is not impaired.
  • the aqueous emulsion thus obtained has high initial adhesion, which is one of the important performances when used as an adhesive or various binders, and can be produced at high speed. This is considered to be because, in practical use, the interaction between specific POA groups contained in the dispersant is strengthened by concentration in the drying step, and the increase in viscosity is increased. Utilizing its characteristics, it can be used in various applications as it is or by adding conventionally known additives. For example, not only adhesives and various binders that make use of initial adhesiveness, but also paints, fiber processing agents, paper processing agents, cement admixtures, mortar primers, etc. are widely used.
  • the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was constant, polymerization was performed at 60 ° C. for 3 hours and then cooled to stop the polymerization. The total amount of comonomer solution added until the polymerization was stopped was 75 ml. The solid content concentration when the polymerization was stopped was 24.4%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C.
  • AIBN 2,2′-azobisisobutyronitrile
  • PVA1 had a polymerization degree of 1760, a saponification degree of 98.7 mol%, a POA group modification amount (S) of 0.4 mol%, and a POA group content of 10 parts by weight.
  • Production Examples 2 to 22 Charge amount of vinyl acetate and methanol, type of unsaturated monomer having POA group used during polymerization (Table 2), polymerization conditions such as addition amount, concentration of POA-modified PVAc during saponification, hydroxylation to vinyl acetate unit Various POA-modified PVA (PVA 2 to 22) were produced in the same manner as in Production Example 1 except that the saponification conditions such as the molar ratio of sodium were changed as shown in Tables 1 and 2.
  • Production Example 23 (Production of PVA23) 700 g of vinyl acetate and 300 g of methanol were charged into a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, and an initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. After cooling, the polymerization was stopped. The solid content concentration when the polymerization was stopped was 17.0%.
  • AIBN 2,2′-azobisisobutyronitrile
  • Production Examples 24-26 (Production of PVA 24-26) Various methods were used in the same manner as in Production Example 23 except that the saponification conditions such as the amount of vinyl acetate and methanol, the concentration of PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate unit were changed as shown in Table 1. Of unmodified PVA (PVA 24-26).
  • Example 1 In a 1 liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen inlet, and a squid type stirring blade, 24 g of ion-exchanged water and 24 g of PVA1 obtained in Production Example 1 were charged and dissolved at 95 ° C. did. Next, the PVA aqueous solution was cooled, purged with nitrogen, charged with 40 g of vinyl acetate while stirring at 140 rpm, heated to 60 ° C., and then polymerization was initiated in the presence of a redox initiator of hydrogen peroxide / tartaric acid. .
  • the obtained polyvinyl acetate emulsion (PVAc-1) had a solid content concentration of 46.1% and a viscosity of 5000 mPa ⁇ s (BH viscometer, 30 ° C., 20 rpm (rotor 7)).
  • the initial adhesive strength shown below was evaluated using PVAc-1. The results are shown in Table 3.
  • Example 7 A polyvinyl acetate emulsion (PVAc-27) was obtained in the same manner as in Example 1 except that 36 g of PVA1 was used in Example 1. The results are shown in Table 3.
  • Example 8 In a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen blowing port, 500 g of ion-exchanged water and 28 g of PVA2 obtained in Production Example 2 were charged and dissolved at 95 ° C. Next, 20 g of methyl methacrylate and 20 g of n-butyl acrylate were added, the temperature was raised to 65 ° C. after nitrogen substitution, and 12 g of a 1% aqueous potassium persulfate solution was added to initiate polymerization. 180 g of methyl acid and 180 g of n-butyl acrylate were continuously added.
  • the emulsion obtained by emulsion polymerization using the dispersion stabilizer for aqueous emulsions of the present invention is excellent in initial adhesiveness as compared with the case of using a conventional dispersant.
  • the aqueous emulsion obtained by using the dispersion stabilizer for aqueous emulsions of the present invention can be suitably used for various adhesives, paints, papers, fiber processing agents, etc. by taking advantage of the above characteristics, and is industrially utilized. The value is extremely great.

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un stabilisateur de dispersion destiné à être utilisé dans une émulsion aqueuse et comprenant un polymère à base d'alcool polyvinylique modifié par un polyoxyalkylène qui est un polymère contenant un groupe polyoxyalkylène représenté par la formule (I) dans une chaîne latérale, et qui a un degré de polymérisation moyen de viscosité compris entre 200 et 3000, un degré de saponification compris entre 80 et 99, 99 % en molle, et une teneur, dans le groupe polyoxyalkylène par rapport à 100 parties en poids de la chaîne principale du polymère à base d'alcool vinylique, allant de 6 à 50 parties en poids. Lors de l'utilisation du stabilisateur, on obtient également une émulsion aqueuse ayant une forte adhérence initiale qui est une de ses propriétés importantes lorsqu'elle est utilisée comme adhésif ou avec une variété de liants et qui permet une production à haut rendement. Dans la formule (I), R1 représente un atome d'hydrogène ou un groupe méthyle; R2 représente un atome d'hydrogène ou un groupe alkyle ayant 1 à 8 atomes de carbone; et m et n représentent, respectivement, le nombre de motifs de répétition d'oxyalkylène et satisfont aux formules : 1 ≤ m ≤ 10 et 5 ≤ n ≤ 20.
PCT/JP2010/052784 2009-03-31 2010-02-23 Stabilisateur de dispersion destiné être utilisé dans une émulsion aqueuse, et émulsion aqueuse WO2010113566A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014111244A (ja) * 2012-12-05 2014-06-19 Kuraray Co Ltd 高分子系界面活性剤
JPWO2016103712A1 (ja) * 2014-12-26 2017-11-02 株式会社クラレ 水性エマルジョン及びそれを用いた接着剤
CN115996961A (zh) * 2020-06-30 2023-04-21 株式会社可乐丽 改性乙烯醇系聚合物、水溶液和改性乙烯醇系聚合物的制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110872362A (zh) * 2018-08-31 2020-03-10 中国石油化工股份有限公司 醋酸乙烯-乙烯共聚乳液及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6058402A (ja) * 1983-09-07 1985-04-04 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤
JPH111505A (ja) * 1997-06-11 1999-01-06 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤
JP2004075870A (ja) * 2002-08-20 2004-03-11 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6058402A (ja) * 1983-09-07 1985-04-04 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤
JPH111505A (ja) * 1997-06-11 1999-01-06 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤
JP2004075870A (ja) * 2002-08-20 2004-03-11 Nippon Synthetic Chem Ind Co Ltd:The 分散安定剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014111244A (ja) * 2012-12-05 2014-06-19 Kuraray Co Ltd 高分子系界面活性剤
JPWO2016103712A1 (ja) * 2014-12-26 2017-11-02 株式会社クラレ 水性エマルジョン及びそれを用いた接着剤
EP3239185A4 (fr) * 2014-12-26 2018-08-15 Kuraray Co., Ltd. Émulsion aqueuse et adhésif dans lequel celle-ci est utilisée
CN115996961A (zh) * 2020-06-30 2023-04-21 株式会社可乐丽 改性乙烯醇系聚合物、水溶液和改性乙烯醇系聚合物的制造方法

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