WO2016136403A1 - Method for producing slurry of acrylic polymer - Google Patents

Method for producing slurry of acrylic polymer Download PDF

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Publication number
WO2016136403A1
WO2016136403A1 PCT/JP2016/053065 JP2016053065W WO2016136403A1 WO 2016136403 A1 WO2016136403 A1 WO 2016136403A1 JP 2016053065 W JP2016053065 W JP 2016053065W WO 2016136403 A1 WO2016136403 A1 WO 2016136403A1
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acrylic polymer
water
weight
fluid
organic solvent
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PCT/JP2016/053065
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French (fr)
Japanese (ja)
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服部準
篠宮寛樹
堂野宜久
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株式会社カネカ
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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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques

Definitions

  • the present invention relates to a method for producing an acrylic polymer slurry, and more particularly to a method for producing an acrylic polymer slurry using an acrylic polymer obtained by emulsion polymerization.
  • a solution composed of an acrylic polymer and a solvent that is soluble in both the polymer and water is used as a spinning dope in, for example, wet spinning or dry spinning.
  • a spinning dope for example, in Patent Document 1, a water-containing acrylic polymer obtained by precipitation polymerization in an aqueous medium and a water-containing acrylic polymer containing water are mechanically dehydrated.
  • the acrylic polymer slurry is prepared by adding a solvent for dissolving the acrylic polymer to the rate of 60% by weight or less, and water and a part of the solvent are removed by evaporation from the acrylic polymer slurry.
  • a method for producing a solution in which an acrylic polymer is dissolved is described.
  • an acrylic polymer obtained by copolymerizing a compound copolymerizable with acrylonitrile as a main component, such as methyl acrylate and vinyl acetate, dimethylformamide and water have a water content of 3 components. It is described that the mixture is made to be 2 to 10% by weight based on the weight of the two components of dimethylformamide and water, mixed slurry at a temperature of ⁇ 20 to 20 ° C., this slurry is heated and dissolved, and then spun. .
  • an acrylic polymer having acrylonitrile and a halogen-containing vinyl monomer as a copolymerization component is preferably produced by emulsion polymerization and coagulation so that coloring to yellow or brown is reduced.
  • JP-A-52-018923 Japanese Patent Publication No.42-008735
  • a water-containing acrylic polymer obtained by emulsion polymerization of acrylonitrile and a halogen-containing vinyl monomer and coagulating the slurry by dispersing it in an organic solvent or a mixed solvent of an organic solvent with reduced solubility and water.
  • the acrylic polymer slurry contains a lump of a size of several millimeters or more that is semi-dissolved, the slurry will be obstructed during transfer, for example, the pump will be blocked when the slurry is discharged by the pump, and the slurry will evaporate. Problems such as undissolved residues in the organic solvent solution of the acrylic polymer produced by degassing occur.
  • the present invention relates to a slurry of an acrylic polymer that prevents the formation of lumps having a size of several millimeters or more while using a water-containing acrylic polymer obtained by emulsion polymerization of acrylonitrile and a halogen-containing vinyl monomer and coagulation.
  • a manufacturing method is provided.
  • a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture is emulsion-polymerized in an aqueous medium and coagulated.
  • an acrylic polymer slurry containing 50 to 150 parts by weight of water and 200 to 500 parts by weight of an organic solvent c with respect to 100 parts by weight of the acrylic polymer a is used.
  • the fluid is put into a stirring tank equipped with a stirrer, and the water-containing acrylic polymer b is composed of water and an organic solvent c on the liquid surface of the fluid while the fluid is stirred and mixed with the stirrer.
  • the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added to and mixed with the fluid so as not to come into contact with the water-containing organic solvent d, the inner diameter D of the stirring tank and the liquid depth of the fluid in the stirring tank
  • the ratio H / D of the thickness H is in the range of 0.3 to 0.7
  • the stirring required power Pv per unit volume of the fluid is 1 W / m 3 or more
  • the unit volume of the hydrous acrylic polymer b per unit volume It is preferable to set the charging rate to 1000 kg / m 3 / hr or less and continuously discharge the resulting acrylic polymer slurry.
  • the acrylic polymer a contains 20 to 75% by weight of acrylonitrile, 24.95 to 80% by weight of a halogen-containing vinyl monomer, and other vinyl monomers that can be copolymerized therewith, based on the total weight of the monomer mixture. It is preferable to copolymerize a monomer mixture containing 0.05 to 5% by weight.
  • the fluid is a dispersion obtained by adding the hydrated acrylic polymer b to the hydrated organic solvent d while mixing the hydrated organic solvent d. Moreover, it is preferable that the said fluid is hold
  • the water-containing organic solvent d is preferably composed of 90 to 98% by weight of the organic solvent c and 2 to 10% by weight of water.
  • the organic solvent c is preferably at least one selected from the group consisting of dimethyl sulfoxide, N, N-dimethylacetamide and N, N-dimethylformamide.
  • the inventors of the present invention emulsion-polymerized a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture, and coagulated.
  • the obtained acrylic polymer was dispersed in a mixed solvent of an organic solvent and water to prepare a slurry, in order to solve the problem that a lump having a size of several mm or more was generated, intensive studies were made.
  • an acrylic polymer obtained by emulsion polymerization and coagulation of a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture.
  • the polymer has an aggregated particle structure with a large surface area in which a plurality of emulsion polymer particles (primary particles) having a particle size of 0.01 to 10 ⁇ m are coagulated, and the acrylic polymer having the above monomer composition dissolves in an organic solvent.
  • the surface of the acrylic polymer is dissolved in the organic solvent when the acrylic polymer comes into contact with the mixed solvent of the organic solvent and water, a lump having a size of several mm or more that is semi-dissolved is formed. I found out that it would occur. Further, it has been found that the generation of a lump having a size of several mm or more is accelerated by the heat of mixing generated when water and an organic solvent come into contact with each other. Accordingly, the water-containing acrylic system is mixed at the liquid level of the fluid while mixing the fluid containing the acrylic polymer a, the organic solvent c, and water, and the content of the organic solvent c in the liquid component is 95% by weight or less.
  • the acrylic polymer a means a dry acrylic polymer.
  • the water-containing acrylic polymer b is dried at, for example, 80 ° C. for 3 hours to obtain a dry acrylic polymer.
  • the acrylic polymer a is obtained by copolymerizing a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture. That is, the acrylic polymer a contains 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of the halogen-containing vinyl monomer with respect to the total weight of the acrylic polymer a.
  • the acrylic polymer a is easily dissolved in an organic solvent, and from the viewpoint of improving the operability when preparing a spinning dope by evaporating water from the acrylic polymer slurry, the total weight of the monomer mixture Copolymerize a monomer mixture containing 20 to 75% by weight of acrylonitrile, 24.95 to 79.95% by weight of a halogen-containing vinyl monomer, and 0.05 to 5% by weight of another vinyl monomer copolymerizable therewith.
  • a monomer mixture containing 0.05 to 5% by weight of a monomer is copolymerized.
  • the halogen-containing vinyl monomer is not particularly limited, and for example, vinyl halides typified by vinyl chloride, vinyl bromide and the like, vinylidene halides typified by vinylidene chloride, vinylidene bromide and the like can be used. .
  • the halogen-containing vinyl monomer is preferably vinyl chloride from the viewpoint of improving the tactile sensation of the acrylic fiber obtained by wet spinning of the acrylic polymer and the curl setting property by hot water.
  • the other vinyl monomers are not particularly limited as long as they are copolymerizable with acrylonitrile and halogen-containing vinyl monomers.
  • examples thereof include vinyl esters typified by vinyl acetate and vinyl butyrate, and sulfonic acid group-containing vinyl monomers. From the viewpoint of improving the dyeability of acrylic fibers obtained by wet spinning acrylic polymers, it is preferable to use sulfonic acid group-containing vinyl monomers as other vinyl monomers.
  • the sulfonic acid group-containing vinyl monomer is not particularly limited, but includes allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and sodium salts thereof. These metal salts and amine salts can be used. These other vinyl monomers can be used alone or in combination of two or more.
  • the acrylic polymer a has a median diameter (Dp50) measured by a light diffraction scattering method in an aqueous dispersion state of 0.01 to 0.3 mm from the viewpoint of slurry stability, particularly redispersibility after standing. It is preferable that the thickness is 0.05 to 0.2 mm. Further, from the viewpoint of avoiding that the acrylic polymer itself becomes an obstacle at the time of slurry transfer, the acrylic polymer a has a maximum particle size of 3 mm or less measured by a light diffraction scattering method in an aqueous dispersion state. Preferably, it is 2.5 mm or less, more preferably 2 mm or less.
  • the acrylic polymer a has a minimum particle size of 0.001 mm as measured by a light diffraction scattering method in an aqueous dispersion state. It is preferable that it is above, and it is more preferable that it is 0.005 mm or more.
  • the water-containing acrylic polymer b contains 50 to 150 parts by weight of water with respect to 100 parts by weight of the acrylic polymer a.
  • the water-containing acrylic polymer b can be obtained by emulsion-polymerizing a monomer mixture containing acrylonitrile and a halogen-containing vinyl monomer having the above-described composition in an aqueous medium, solidifying, and dehydrating.
  • the emulsion polymerization is not particularly limited, and a known method for obtaining an acrylic polymer by copolymerizing acrylonitrile with a halogen-containing vinyl monomer or another vinyl monomer can be used.
  • acrylonitrile and a halogen-containing vinyl monomer and, if necessary, other vinyl monomers such as a sulfonic acid group-containing vinyl monomer are polymerized using water, an emulsifier, a water-soluble polymerization initiator, and a polymer is obtained. Latex can be obtained.
  • a chain transfer agent and a pH adjuster that are generally used may be used as necessary.
  • the water-soluble polymerization initiator is not particularly limited, but persulfate compounds such as ammonium persulfate and potassium persulfate are suitable. It is also possible to use a redox polymerization initiator in which a persulfate compound and a sulfite are used in combination.
  • the amount of the water-soluble polymerization initiator used is 0. When the total monomer used for the polymerization is 100 parts by weight from the viewpoint of obtaining a sufficient polymerization conversion rate and preventing coloring of the acrylic polymer. The amount is preferably 01 to 1.5 parts by weight, and more preferably 0.1 to 1 part by weight.
  • a surfactant having an emulsifying ability can be used as the emulsifier.
  • the surfactant is preferably an anionic surfactant.
  • the anionic surfactant include fatty acid salts, sulfate ester salts, sulfonate salts, and phosphate ester salts.
  • a small amount of a normal nonionic surfactant may be used in combination. The amount of these surfactants to be used is 0.001 to 2 parts by weight, preferably 0.005 to 1.0 parts by weight, based on 100 parts by weight of all monomers used for polymerization.
  • An inorganic salt is added to the obtained polymer latex to solidify the polymer.
  • the inorganic salt is not particularly limited as long as it can coagulate the polymer latex, but is preferably a halide containing water-soluble alkali metal and / or alkaline earth metal.
  • sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, potassium fluoride, Sodium fluoride etc. are mentioned.
  • a water-containing acrylic polymer can be obtained by solidifying the polymer and then dehydrating it. You may wash with water before dehydration.
  • Dehydration can be performed by filtration. Washing with water and dehydration by filtration can be performed using a general apparatus. In addition, you may use as a water-containing acrylic polymer b what dried the water-containing acrylic polymer after spin-drying
  • the acrylic polymer slurry contains 50 to 150 parts by weight of water and 200 to 500 parts by weight of the organic solvent c with respect to 100 parts by weight of the acrylic polymer a. From the viewpoint of easily obtaining a spinning stock solution obtained by evaporating water from an acrylic polymer slurry and dissolving the acrylic polymer in an organic solvent, 75 to 135 parts by weight of water with respect to 100 parts by weight of the acrylic polymer a,
  • the organic solvent c is preferably contained in an amount of 250 to 500 parts by weight, more preferably 85 to 125 parts by weight of water and the organic solvent c in an amount of 250 to 500 parts by weight based on 100 parts by weight of the acrylic polymer a.
  • the slurry of the acrylic polymer contains the acrylic polymer a, the organic solvent c, and water, and while mixing the fluid in which the content of the organic solvent c in the liquid component is 95% by weight or less, In order to prevent the water-containing acrylic polymer b from coming into contact with the water-containing organic solvent d on the liquid surface, the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added and mixed in the fluid.
  • the fluid is not particularly limited as long as it contains the acrylic polymer a, the organic solvent c, and water.
  • the fluid preferably contains 50 to 150 parts by weight of water and 200 to 500 parts by weight of the organic solvent c with respect to 100 parts by weight of the acrylic polymer a.
  • the fluid is prepared, for example, by dispersing a water-containing acrylic polymer b containing 50 to 150 parts by weight of water with respect to 100 parts by weight of the acrylic polymer a in a water-containing organic solvent d. It is preferable.
  • the fluid may be an acrylic polymer slurry.
  • the water-containing organic solvent d is preferably composed of 90 to 97% by weight of organic solvent c and 3 to 10% by weight of water from the viewpoint of easy dispersion of the water-containing acrylic polymer b, and 93 to 97% by weight of organic solvent c and 3 to 3% of water. More preferably, it consists of 7% by weight.
  • the organic solvent c is not particularly limited as long as it is a good solvent for the acrylic polymer a and has water miscibility.
  • acetone, ethylene carbonate, dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), n-methylpyrrolidone (NMP) and the like can be mentioned.
  • the organic solvent c is selected from the group consisting of dimethyl sulfoxide (DMSO), N, N-dimethylacetamide (DMAc) and N, N-dimethylformamide (DMF).
  • DMSO dimethyl sulfoxide
  • DMAc dimethylacetamide
  • DMF N-dimethylformamide
  • DMF dimethylpyrrolidone
  • the water-containing acrylic polymer b While mixing the fluid, when the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added and dispersed in the fluid, the water-containing acrylic polymer b is an organic solvent on the liquid surface of the fluid. It is necessary to avoid contact with the water-containing organic solvent d containing c. When the liquid surface of the fluid comes into contact with the water-containing organic solvent d containing the organic solvent c in the water-containing acrylic polymer b, a lump having a size of several mm or more is generated.
  • a predetermined amount of the water-containing acrylic polymer b and the water-containing organic solvent d may be continuously added once, or the predetermined amount may be added in two or more times. From the viewpoint of productivity, while mixing a fluid containing an organic solvent c, water, and an acrylic polymer a, and the content of the organic solvent c in the liquid component is 95% by weight or less, And adding the water-containing acrylic polymer b and the water-containing organic solvent d to the fluid so that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d comprising water and the organic solvent c. It is preferable to repeat or continuously twice or more, and continuously discharge the resulting acrylic polymer slurry.
  • the obtained acrylic polymer slurry is continuously discharged by a pump or the like.
  • the water-containing acrylic polymer b and the water-containing organic solvent d are repeated two or more times or continuously, the water-containing acrylic polymer b is not always in contact with the water-containing organic solvent d on the liquid surface of the fluid. It is necessary to do so.
  • the water-containing acrylic polymer b and the water-containing organic solvent d may be charged simultaneously or alternately. In any case, it is necessary that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d on the liquid level of the fluid. When the hydrated acrylic polymer b and the hydrated organic solvent d are charged at the same time, it is preferable that the charged points are separated from each other.
  • the fluid is preferably maintained at a temperature of 0 ° C. or higher and 80 ° C. or lower, more preferably 10 ° C. or higher and 50 ° C. or lower.
  • the temperature of the fluid is within the above range, the water-containing acrylic polymer b is easily dispersed in the fluid without being fused, dissolved, or swollen.
  • the organic solvent c used has a large heat of dissolution in water, or when the temperature of the fluid such as the temperature of the water-containing acrylic polymer b to be charged is high, for example, a cooled water-containing organic solvent d is used. It is also possible to use it.
  • the preparation of the acrylic polymer slurry is not particularly limited, but it is preferably performed in a stirring tank equipped with a stirrer for easy mixing operation, and the acrylic polymer a is deposited in the stirring tank. From the viewpoint of suppression, it is preferable not to include a baffle. Moreover, it is preferable that a stirring tank is a jacketed stirring tank from a viewpoint of controlling the temperature in operation easily. For example, the temperature can be controlled by flowing cooling water through the jacket.
  • the shape of the stirring tank is not particularly limited, but a cylindrical shape is preferable from the viewpoint of easy stirring of the fluid.
  • the agitator may be a general uniaxial agitator, and the arrangement of the agitator in the agitation tank is a central arrangement in which the central axis of the agitator and the central axis of the agitation tank overlap.
  • shaft of a stirring tank may not overlap may be sufficient.
  • an eccentric arrangement is preferable from the viewpoint of suppressing deposition of the acrylic polymer a on the bottom surface of the stirring tank.
  • a fluid is put into a stirring tank with a jacket, or a water-containing organic solvent d is put into a stirring tank with a jacket, and a water-containing acrylic polymer b is put into the stirring tank and stirred with a stirrer. To prepare. Next, while stirring the fluid with a stirrer, in the fluid so that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d composed of water and the organic solvent c on the liquid surface of the fluid. The water-containing acrylic polymer b and the water-containing organic solvent d are respectively added to and mixed.
  • the water-containing acrylic polymer b may agglomerate and float on the liquid surface of the fluid, and it is necessary to avoid a situation in which the water-containing organic solvent d contacts the floating agglomerate.
  • each of the water-containing acrylic polymer b and the water-containing organic solvent d is continuously charged so that the water-containing acrylic polymer b is immersed in the fluid until the water-containing organic solvent d is charged.
  • the stirring state of the fluid and the charging speed of the hydrated acrylic polymer b are adjusted, and an inlet for the hydrated organic solvent d is provided in the fluid.
  • the water-containing acrylic polymer b and the water-containing organic solvent d are added simultaneously, it is preferable to add the water-containing organic solvent d to the opposite side across the place where the water-containing acrylic polymer b is added and the stirring shaft.
  • each of the water-containing acrylic polymer b and the water-containing organic solvent d is preferably continuously added, and the organic solvent c,
  • a fluid containing water and an acrylic polymer a, the content of the organic solvent c in the liquid component being 95% by weight or less is charged into a stirring tank equipped with a stirrer, and while stirring the fluid with a stirrer,
  • the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added and mixed in the fluid so that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d on the liquid surface of the fluid.
  • the ratio H / D of the inner diameter D of the agitation tank to the fluid depth H of the fluid in the agitation tank is in the range of 0.3 to 0.7, and the required power Pv for stirring per unit volume of the fluid is 1 W / m.
  • the addition rate of the combined b is less 1000Kg / m 3 / hr, and more preferably continuously discharged slurry of the acrylic polymer from the bottom of the stirred tank at a pump.
  • the value of the ratio H / D between the inner diameter D of the stirring tank and the liquid depth H of the fluid in the stirring tank indicates the mixing property of the fluid in the stirring tank.
  • the required stirring power Pv [W / m 3 ] per unit volume of the fluid is the inner diameter D [m] of the stirring tank, the liquid depth H [m] of the fluid in the stirring tank, and the stirring blade Outer diameter d [m], blade attachment angle ⁇ [degree], blade width b [m], blade number np, baffle plate conditions, stirrer speed n [1 / sec], fluid viscosity ⁇ [kg / m / Sec], from the density ⁇ [kg / m 3 ] of the fluid, described in “Stirring technology” (edited by Satake Chemical Machinery Co., Ltd., Satake Chemical Machinery Co., Ltd. (1992), pages 451 to 461, Chapter 4).
  • the liquid depth H of the fluid in the stirring tank refers to the height from the bottom of the stirring tank to the liquid level of the fluid.
  • the volume of the fluid in the agitation tank changes over time due to the introduction of the water-containing acrylic polymer b and the water-containing organic solvent d into the fluid and the continuous discharge of the acrylic polymer slurry.
  • the fluid depth H, volume, viscosity, and density of the fluid mean the fluid depth H, volume, viscosity, and density of the fluid immediately before the addition of the water-containing acrylic polymer b and the water-containing organic solvent d. .
  • liquid level H of the fluid during the manufacturing process is adjusted by adjusting the amount of the water-containing acrylic polymer b and the water-containing organic solvent d introduced into the fluid and the amount of the acrylic polymer slurry discharged. Can be held at a constant value.
  • the internal temperature of the stirring tank is preferably maintained at 0 ° C. or higher and 80 ° C. or lower, more preferably 10 ° C. or higher and 50 ° C. or lower.
  • the internal temperature of the agitation tank is within the above range, dissolution of the water-containing acrylic polymer b is suppressed and it is easy to disperse in the fluid or the water-containing organic solvent d.
  • the internal temperature of a stirring tank is equal to the temperature of a fluid.
  • the acrylic polymer slurry is preferably a metal mesh sieve having a mesh size of 3 mm or more in accordance with JIS Z-8801-1 (2006), and has no residue, and is in accordance with JIS Z-8801-1 (2006). It is more preferable that there is no residue in a metal mesh sieve having an opening of 2.5 mm or more and less than 3 mm, and a metal mesh sieve having an opening of 2.0 mm or more and less than 2.5 mm according to JIS Z-8801-1 (2006). It is more preferable that there is no residue, and it is more preferable that there is no residue with a metal net sieve having an opening of 1.5 mm or more and less than 2.0 mm according to JIS Z-8801-1 (2006).
  • the obtained acrylic polymer slurry was filtered to obtain a water-containing acrylic polymer.
  • the water content of the water-containing acrylic polymer was measured by weight change after drying at 80 ° C. for 3 hours, it was 100 parts by weight with respect to 100 parts by weight of the dry weight of the acrylic polymer. That is, the water-containing acrylic polymer obtained in Production Example 1 contained 100 parts by weight of water with respect to 100 parts by weight of the acrylic polymer.
  • the particle size of the acrylic polymer was measured by a light diffraction / scattering method in a water-dispersed state using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd., model number “LA-950”).
  • the particle diameter was 0.01 mm
  • the maximum particle diameter was 1 mm
  • the median diameter (Dp50) was 0.1 mm.
  • DMSO JIS K9702 standard, reagent grade
  • DMSO JIS K9702 standard, reagent type
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 2 in accordance with JIS Z-8801-1 (2006). No residue was observed on a 8 mm metal screen.
  • the weight of the acrylic polymer solid content is equal to the weight of the dry acrylic polymer not containing water. The same applies to the following.
  • DMSO JIS K9702 standard, reagent grade
  • DMSO JIS K9702 standard, reagent type
  • the obtained acrylic polymer slurry (fluid) had a weight of 140 kg, a liquid depth H of about 30 cm, and a H / D value of 0.54. Further, the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1100 kg / m 3 .
  • the feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 257 kg / m 3 / hr.
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 2 in accordance with JIS Z-8801-1 (2006). No residue was observed on a 8 mm metal screen.
  • Example 3 An acrylic polymer slurry (fluid) consisting of 100 parts by weight of the acrylic polymer (solid content) obtained in Example 2, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO was added to 167 g of an inner diameter D of about 8 cm. Then, it was put into a stainless steel cup (cylindrical type corresponding to a stirring tank) having a volume of 0.5 L. The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1100 kg / m 3 .
  • DMSO JIS K9702 standard, reagent grade
  • water-containing DMSO consisting of 5% by weight of water
  • the acrylic polymer slurry was discharged.
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 0.6 W / m 3 .
  • the charging rate of the water-containing acrylic polymer per unit volume of the fluid was 593 kg / m 3 / hr.
  • the hydrated DMSO was not dropped onto the hydrated acrylic polymer floating on the liquid surface in the stainless steel cup.
  • the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 22 ° C.
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
  • Example 4 An acrylic polymer slurry was prepared under the same conditions as in Example 3, except that a stainless steel cup having an inner diameter D of about 8 cm and a volume of 0.5 L was fixed in a water bath adjusted to 50 ° C.
  • the fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38.
  • the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1100 kg / m 3 .
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C.
  • the charging rate of the water-containing acrylic polymer per unit volume of the fluid was 593 kg / m 3 / hr.
  • the temperature of the water bath was almost unchanged, and the temperature of the fluid was about 50 ° C.
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
  • Example 5 A slurry of an acrylic polymer was prepared in the same manner as in Example 4 except that the addition time for adding the water-containing acrylic polymer and DMSO (JIS K9702 standard, reagent grade) was 6 minutes.
  • the fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38.
  • the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1100 kg / m 3 .
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C.
  • Example 6 Using the acrylic polymer slurry (fluid) 300g consisting of 100 parts by weight of the acrylic polymer (solid content) obtained in Example 2, 114.6 parts by weight of water and 276.7 parts by weight of DMSO, water-containing acrylic An acrylic polymer slurry was prepared in the same manner as in Example 4 except that the addition time for addition of the polymer and DMSO (JIS K9702 standard, reagent grade) was 6 minutes.
  • the fluid depth H of the fluid was about 5.4 cm, and the value of H / D was 0.68.
  • the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1100 kg / m 3 .
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 0.1 W / m 3 , and the feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 550 kg / m 3 / hr.
  • the hydrated DMSO was not dropped onto the hydrated acrylic polymer floating on the liquid surface in the stainless steel cup.
  • the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C.
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
  • Example 7 An acrylic polymer slurry was prepared in the same manner as in Example 6 except that the rotation speed of the stirrer was changed to 300 rpm.
  • the fluid depth H of the fluid was about 5.4 cm, and the value of H / D was 0.68.
  • the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1100 kg / m 3 .
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C.
  • the hydrated DMSO was not dropped onto the hydrated acrylic polymer floating on the liquid surface in the stainless steel cup.
  • the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C.
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
  • Example 8 166.0 g of water-containing DMF consisting of 95% by weight of DMF (manufactured by Nacalai Tesque Co., Ltd., reagent grade) and 5% by weight of water was put into a stainless steel cup having an inner diameter D of about 8 cm and a volume of 0.5 L.
  • a stainless steel cup was fixed in a water bath adjusted to 50 ° C., and 15 g of the water-containing acrylic polymer obtained in Production Example 1 was added to the medicine-wrapping paper at a fluid temperature of 50 ° C. while stirring the fluid at a rotation speed of 300 rpm. From the 22 g drop tube, water-containing DMF consisting of 95% by weight of DMF (manufactured by Nacalai Tesque Co., Ltd., special grade reagent) and 5% by weight of water is almost constant across the place where the water-containing acrylic polymer is charged and the stirring shaft. The mixture was stirred at a speed of 6 minutes and stirred for 5 minutes, and the resulting acrylic polymer slurry was discharged.
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent was 6 It was 5 W / m 3 .
  • the feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 536 kg / m 3 / hr.
  • the hydrous DMF was not dripped onto the hydrous acrylic polymer floating on the liquid surface in the stainless steel cup.
  • the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C.
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, 276.7 parts by weight of DMF, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
  • Example 9 An acrylic polymer slurry was prepared in the same manner as in Example 8 except that DMAc was used instead of DMF as the organic solvent.
  • the fluid depth H of the fluid was about 5.6 cm, and the value of H / D was 0.70.
  • the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1000 Kg / m 3 .
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C.
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMAc, and has an opening 1 in accordance with JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
  • the obtained polymer slurry was composed of 100 parts by weight of acrylic polymer solids, 100 parts by weight of water, and 280 parts by weight of DMSO, and a mass of several centimeters or more that did not disperse even when stirring was observed. did. Since the water-containing resin was poured into DMSO, which is a fluid whose DMSO concentration in the liquid component exceeds 95 wt%, and temperature control was not performed, extreme lumps were generated.
  • DMSO JIS K9702 standard, reagent special grade
  • DMSO JIS K9702 standard, reagent special grade
  • a jacketed stirring tank no baffle, cylindrical type
  • Stirrer one axis, eccentric about 5 cm away from the central axis of the stirring tank
  • the water-containing acrylic polymer 57Kg obtained in Production Example 1 was charged at a rate of 346Kg / hr in 10 minutes while stirring in the arrangement.
  • the inner temperature of the stirring tank was maintained at approximately 40 ° C. by controlling the temperature of the jacket.
  • the obtained acrylic polymer slurry (fluid) was pumped out from the lower part of the stirring tank with a pump at a rate of 60 L / hr, and when the liquid volume became about 50 L, the hydrous acrylic heavy polymer obtained in Production Example 1 was used. 10 kg of combined polymer is charged all at once, and 13 kg of DMSO (JIS K9702 standard, reagent special grade) is repeated four times at a time without delay. In total, 38 kg of water-containing acrylic polymer, DMSO (JIS K9702 standard, reagent special grade) ) 52.5 kg was added. In the middle of the feeding, the amount of feeding became unstable and eventually the pump could not be sucked.
  • DMSO JIS K9702 standard, reagent special grade
  • the resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 100 parts by weight of water, and 277.2 parts by weight of DMSO, and has an aperture of 2.8 mm in accordance with JIS Z-8801-1 (2006). 2 parts by weight of residue (100% by weight after washing with water and then drying at 80 ° C. for 3 hours) was observed per 100 parts by weight of the acrylic polymer solid content. A diaphragm pump was used, and a lump of about several mm was caught in the valve, and suction was impossible.
  • Comparative Example 4 A slurry of an acrylic polymer was prepared in the same manner as in Comparative Example 3 except that the addition time for addition of the hydrous acrylic polymer and DMSO (JIS K9702 standard, reagent grade) was 1.5 minutes.
  • the fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38.
  • the viscosity ⁇ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ⁇ was 1100 kg / m 3 .
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C.
  • Example 7 Except for using 400 g of an acrylic polymer slurry (fluid) consisting of 100 parts by weight of the acrylic polymer (solid content) obtained in Example 2, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, In the same manner as in Example 6, an acrylic polymer slurry was prepared.
  • the fluid depth H of the fluid was about 7.2 cm, and the H / D value was 0.9.
  • the required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C.
  • Table 1 below summarizes the results of various production conditions in Examples 3 to 9 and Comparative Examples 3 to 7 and the residue on a sieve having a mesh opening size of 1.7 mm according to JIS Z-8801.
  • Table 1 below the dry weight of the residue in a metal mesh sieve having a mesh size of 1.7 mm according to JIS Z-8801-1 (2006) is based on 100 parts by weight of the solid content of the hydrated acrylic polymer. It is shown in parts by weight.
  • the acrylic polymer slurry obtained by the production method of the present invention is prepared by evaporating and removing water to prepare a solution in which the acrylic polymer is dissolved in an organic solvent.
  • the resulting acrylic polymer is an organic solvent solution.

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Abstract

The present invention relates to a method for producing a slurry of an acrylic polymer, wherein a slurry of an acrylic polymer is obtained using a hydrated acrylic polymer b that contains 50-150 parts by weight of water per 100 parts by weight of an acrylic polymer a, which is obtained by emulsion polymerizing a monomer mixture that contains 20-75% by weight of acrylonitrile and 25-80% by weight of a halogen-containing vinyl monomer relative to the total weight of the monomer mixture in an aqueous medium and then solidifying the emulsion polymerization product, and an organic solvent c that is a good solvent for the acrylic polymer a and has water miscibility. In this method for producing a slurry of an acrylic polymer, while mixing a fluid that contains the acrylic polymer a, the organic solvent c and water such that the content of the organic solvent c in the liquid component is 95% by weight or less, the hydrated acrylic polymer b and a hydrous organic solvent d, which is composed of water and the organic solvent c, are respectively introduced into the fluid and mixed therein in such a manner that the hydrated acrylic polymer b does not come into contact with the hydrous organic solvent d in the level of the fluid.

Description

アクリル系重合体のスラリーの製造方法Method for producing slurry of acrylic polymer
　本発明は、アクリル系重合体のスラリーの製造方法に関し、詳細には、乳化重合して得られたアクリル系重合体を用いたアクリル系重合体のスラリーの製造方法に関する。 The present invention relates to a method for producing an acrylic polymer slurry, and more particularly to a method for producing an acrylic polymer slurry using an acrylic polymer obtained by emulsion polymerization.
　アクリル系重合体及び該重合体と水の双方に溶解性を有する溶剤からなる溶液は、例えば湿式紡糸や乾式紡糸における紡糸原液として用いられる。このような紡糸原液の製造について、例えば、特許文献１では、水系媒体中の析出重合により得られるアクリル系重合体及び水を含んでなる含水アクリル系重合体を機械的に脱水処理することで含水率を６０重量％以下とし、これにアクリル系重合体を溶解する溶剤を添加することによってアクリル系重合体スラリーを作製し、該アクリル系重合体スラリーから水及び溶剤の一部を蒸発除去して、アクリル系重合体を溶解した溶液を製造する方法が記載されている。また、特許文献２では、アクリロニトリルを主成分としてアクリル酸メチル、酢酸ビニルなどのこれと共重合可能な化合物を共重合したアクリル系重合体、ジメチルホルムアマイド及び水の３成分を水の含有率がジメチルホルムアマイドと水の２成分の重量に対して２～１０重量％になるようにし、－２０～２０℃の温度で混合スラリーとし、このスラリーを加熱溶解した後紡糸することが記載されている。 A solution composed of an acrylic polymer and a solvent that is soluble in both the polymer and water is used as a spinning dope in, for example, wet spinning or dry spinning. Regarding the production of such a spinning dope, for example, in Patent Document 1, a water-containing acrylic polymer obtained by precipitation polymerization in an aqueous medium and a water-containing acrylic polymer containing water are mechanically dehydrated. The acrylic polymer slurry is prepared by adding a solvent for dissolving the acrylic polymer to the rate of 60% by weight or less, and water and a part of the solvent are removed by evaporation from the acrylic polymer slurry. A method for producing a solution in which an acrylic polymer is dissolved is described. Further, in Patent Document 2, an acrylic polymer obtained by copolymerizing a compound copolymerizable with acrylonitrile as a main component, such as methyl acrylate and vinyl acetate, dimethylformamide and water have a water content of 3 components. It is described that the mixture is made to be 2 to 10% by weight based on the weight of the two components of dimethylformamide and water, mixed slurry at a temperature of −20 to 20 ° C., this slurry is heated and dissolved, and then spun. .
　一方、アクリロニトリルとハロゲン含有ビニル系モノマーを共重合成分とするアクリル系重合体は、黄色や茶色への着色が低減するように乳化重合し、凝固して製造することが好まれている。 On the other hand, an acrylic polymer having acrylonitrile and a halogen-containing vinyl monomer as a copolymerization component is preferably produced by emulsion polymerization and coagulation so that coloring to yellow or brown is reduced.
特開昭５２－０１８９２３号公報JP-A-52-018923 特公昭４２－００８７３５号公報Japanese Patent Publication No.42-008735
　しかし、アクリロニトリル及びハロゲン含有ビニル系モノマーを乳化重合し、凝固して得られた含水アクリル系重合体は、有機溶剤や、溶解性を低減させた有機溶剤と水の混合溶剤への分散でスラリーを作製する際、半溶解したような数ｍｍ以上のサイズの塊が発生しやすい問題があった。アクリル系重合体のスラリーが半溶解したような数ｍｍ以上の大きさの塊を含むと、スラリー移送時に障害、例えば、ポンプによってスラリーを排出する際にポンプが閉塞してしまうこと、スラリーの蒸発脱気により作製したアクリル系重合体の有機溶剤溶液中に溶け残りが生じてしまうこと等の障害が生じる。 However, a water-containing acrylic polymer obtained by emulsion polymerization of acrylonitrile and a halogen-containing vinyl monomer and coagulating the slurry by dispersing it in an organic solvent or a mixed solvent of an organic solvent with reduced solubility and water. When manufacturing, there was a problem that a lump of a size of several mm or more which was semi-dissolved was likely to be generated. If the acrylic polymer slurry contains a lump of a size of several millimeters or more that is semi-dissolved, the slurry will be obstructed during transfer, for example, the pump will be blocked when the slurry is discharged by the pump, and the slurry will evaporate. Problems such as undissolved residues in the organic solvent solution of the acrylic polymer produced by degassing occur.
　本発明は、アクリロニトリル及びハロゲン含有ビニル系モノマーを乳化重合し、凝固して得られた含水アクリル系重合体を用いつつ、数ｍｍ以上のサイズの塊の発生を防止したアクリル系重合体のスラリーの製造方法を提供する。 The present invention relates to a slurry of an acrylic polymer that prevents the formation of lumps having a size of several millimeters or more while using a water-containing acrylic polymer obtained by emulsion polymerization of acrylonitrile and a halogen-containing vinyl monomer and coagulation. A manufacturing method is provided.
　本発明は、単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％と、ハロゲン含有ビニル系モノマー２５～８０重量％を含む単量体混合物を水系媒体中で乳化重合し、凝固して得られたアクリル系重合体ａ１００重量部に対して、水５０～１５０重量部を含む含水アクリル系重合体ｂと、アクリル系重合体ａの良溶媒であり、かつ水混和性を有する有機溶剤ｃを用いて、アクリル系重合体ａ１００重量部に対して、水５０～１５０重量部及び有機溶剤ｃ２００～５００重量部を含むアクリル系重合体のスラリーを得るアクリル系重合体のスラリーの製造方法において、アクリル系重合体ａ、有機溶剤ｃ及び水を含み、液体成分中の有機溶剤ｃの含有量が９５重量％以下の流動体を混合しながら、上記流動体の液面において、含水アクリル系重合体ｂが水及び有機溶剤ｃからなる含水有機溶剤ｄと接触しないように、上記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合することを特徴とするアクリル系重合体のスラリーの製造方法に関する。 In the present invention, a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture is emulsion-polymerized in an aqueous medium and coagulated. A water-containing acrylic polymer b containing 50 to 150 parts by weight of water with respect to 100 parts by weight of the obtained acrylic polymer a, and an organic solvent c that is a good solvent for the acrylic polymer a and has water miscibility In the method for producing an acrylic polymer slurry, an acrylic polymer slurry containing 50 to 150 parts by weight of water and 200 to 500 parts by weight of an organic solvent c with respect to 100 parts by weight of the acrylic polymer a is used. While mixing a fluid containing an acrylic polymer a, an organic solvent c and water, and the content of the organic solvent c in the liquid component is 95% by weight or less, The water-containing acrylic polymer b and the water-containing organic solvent d are respectively added to and mixed with the fluid so that the water-acrylic polymer b does not come into contact with the water-containing organic solvent d composed of water and the organic solvent c. It relates to a method for producing an acrylic polymer slurry.
　上記流動体を攪拌機を備えた攪拌槽に投入し、該流動体を撹拌機で撹拌して混合しながら、前記流動体の液面において、含水アクリル系重合体ｂが水及び有機溶剤ｃからなる含水有機溶剤ｄと接触しないように、前記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合する際、攪拌槽の内径Ｄと攪拌槽内の流動体の液深さＨの比Ｈ／Ｄの値を０．３～０．７の範囲とし、流動体の単位体積あたり攪拌所要動力Ｐｖを１Ｗ／ｍ3以上とし、含水アクリル系重合体ｂの単位体積あたりの投入速度を１０００Ｋｇ／ｍ3／ｈｒ以下とし、得られたアクリル系重合体のスラリーを連続的に排出することが好ましい。 The fluid is put into a stirring tank equipped with a stirrer, and the water-containing acrylic polymer b is composed of water and an organic solvent c on the liquid surface of the fluid while the fluid is stirred and mixed with the stirrer. When the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added to and mixed with the fluid so as not to come into contact with the water-containing organic solvent d, the inner diameter D of the stirring tank and the liquid depth of the fluid in the stirring tank The ratio H / D of the thickness H is in the range of 0.3 to 0.7, the stirring required power Pv per unit volume of the fluid is 1 W / m 3 or more, and the unit volume of the hydrous acrylic polymer b per unit volume It is preferable to set the charging rate to 1000 kg / m 3 / hr or less and continuously discharge the resulting acrylic polymer slurry.
　アクリル系重合体ａは、単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％、ハロゲン含有ビニル系モノマー２４．９５～８０重量％、及びこれらと共重合可能な他のビニル系モノマー０．０５～５重量％を含む単量体混合物を共重合したものであることが好ましい。 The acrylic polymer a contains 20 to 75% by weight of acrylonitrile, 24.95 to 80% by weight of a halogen-containing vinyl monomer, and other vinyl monomers that can be copolymerized therewith, based on the total weight of the monomer mixture. It is preferable to copolymerize a monomer mixture containing 0.05 to 5% by weight.
　上記流動体は、含水有機溶剤ｄを混合しながら、含水有機溶剤ｄへ含水アクリル系重合体ｂを投入して分散したものであることが好ましい。また、上記流動体は０℃以上８０℃以下の温度に保持されていることが好ましい。 It is preferable that the fluid is a dispersion obtained by adding the hydrated acrylic polymer b to the hydrated organic solvent d while mixing the hydrated organic solvent d. Moreover, it is preferable that the said fluid is hold | maintained at the temperature of 0 to 80 degreeC.
　含水有機溶剤ｄは、有機溶剤ｃ９０～９８重量％及び水２～１０重量％からなることが好ましい。有機溶剤ｃは、ジメチルスルホキシド、Ｎ，Ｎ－ジメチルアセトアミド及びＮ，Ｎ－ジメチルホルムアミドからなる群から選ばれる一種以上であることが好ましい。 The water-containing organic solvent d is preferably composed of 90 to 98% by weight of the organic solvent c and 2 to 10% by weight of water. The organic solvent c is preferably at least one selected from the group consisting of dimethyl sulfoxide, N, N-dimethylacetamide and N, N-dimethylformamide.
　本発明の製造方法によると、アクリロニトリル及びハロゲン含有ビニル系モノマーを乳化重合し、凝固して得られた含水アクリル系重合体を用いつつ、数ｍｍ以上のサイズの塊の発生が抑制されたアクリル系重合体のスラリーを製造することができる。 According to the production method of the present invention, an acrylic polymer in which generation of lumps having a size of several mm or more is suppressed while using a water-containing acrylic polymer obtained by emulsion polymerization of acrylonitrile and a halogen-containing vinyl monomer and coagulation. Polymer slurries can be produced.
　本発明の発明者らは、単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％と、ハロゲン含有ビニル系モノマー２５～８０重量％を含む単量体混合物を乳化重合し、凝固して得られたアクリル系重合体を、有機溶剤と水の混合溶剤に分散してスラリーを作製する際、数ｍｍ以上のサイズの塊が発生する問題を解決するため、鋭意検討した。その結果、単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％と、ハロゲン含有ビニル系モノマー２５～８０重量％を含む単量体混合物を乳化重合し、凝固して得られたアクリル系重合体は、粒子径が０．０１～１０μｍの乳化重合粒子（一次粒子）が複数個凝固した表面積の大きい凝集粒子構造であること及び上記のモノマー組成のアクリル系重合体は有機溶剤に溶解しやすいことから、該アクリル系重合体が有機溶剤と水の混合溶剤に接触した際、該アクリル系重合体の表面が有機溶剤に溶解するため、半溶解したような数ｍｍ以上のサイズの塊が発生してしまうことを突き止めた。また、このような数ｍｍ以上のサイズの塊の発生は、水と有機溶剤が接触することによって発生する混合熱により加速されることを突き止めた。そこで、アクリル系重合体ａ、有機溶剤ｃ及び水を含み、液体成分中の有機溶剤ｃの含有量が９５重量％以下の流動体を混合しながら、上記流動体の液面において、含水アクリル系重合体ｂが水及び有機溶剤ｃからなる含水有機溶剤ｄと接触しないように、上記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合することで、数ｍｍ以上の大きいサイズの塊の発生を防止し得ることを見出した。 The inventors of the present invention emulsion-polymerized a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture, and coagulated. When the obtained acrylic polymer was dispersed in a mixed solvent of an organic solvent and water to prepare a slurry, in order to solve the problem that a lump having a size of several mm or more was generated, intensive studies were made. As a result, an acrylic polymer obtained by emulsion polymerization and coagulation of a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture. The polymer has an aggregated particle structure with a large surface area in which a plurality of emulsion polymer particles (primary particles) having a particle size of 0.01 to 10 μm are coagulated, and the acrylic polymer having the above monomer composition dissolves in an organic solvent. Since the surface of the acrylic polymer is dissolved in the organic solvent when the acrylic polymer comes into contact with the mixed solvent of the organic solvent and water, a lump having a size of several mm or more that is semi-dissolved is formed. I found out that it would occur. Further, it has been found that the generation of a lump having a size of several mm or more is accelerated by the heat of mixing generated when water and an organic solvent come into contact with each other. Accordingly, the water-containing acrylic system is mixed at the liquid level of the fluid while mixing the fluid containing the acrylic polymer a, the organic solvent c, and water, and the content of the organic solvent c in the liquid component is 95% by weight or less. By adding and mixing the water-containing acrylic polymer b and the water-containing organic solvent d into the fluid so that the polymer b does not come into contact with the water-containing organic solvent d composed of water and the organic solvent c, several mm or more It was found that the generation of large-sized lumps can be prevented.
　本発明において、アクリル系重合体ａは乾燥状態のアクリル系重合体を意味する。含水アクリル系重合体ｂを、例えば８０℃で３時間乾燥することで、乾燥状態のアクリル系重合体となる。 In the present invention, the acrylic polymer a means a dry acrylic polymer. The water-containing acrylic polymer b is dried at, for example, 80 ° C. for 3 hours to obtain a dry acrylic polymer.
　アクリル系重合体ａは、単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％と、ハロゲン含有ビニル系モノマー２５～８０重量％を含む単量体混合物を共重合したものである。すなわち、アクリル系重合体ａは、アクリル系重合体ａの全体重量に対して、アクリロニトリル２０～７５重量％、ハロゲン含有ビニル系モノマー２５～８０重量％を含む。アクリル系重合体ａは、有機溶媒に溶解しやすく、アクリル系重合体のスラリーから水を蒸発して紡糸原液を調製する際の操作性を高める観点から、単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％、ハロゲン含有ビニル系モノマー２４．９５～７９．９５重量％、及びこれらと共重合可能な他のビニル系モノマー０．０５～５重量％を含む単量体混合物を共重合したものであることが好ましく、単量体混合物の全体重量に対してアクリロニトリル２５～７０重量％、ハロゲン含有ビニル系モノマー２９．９５～７４．９５重量％、及びこれらと共重合可能な他のビニル系モノマー０．０５～５重量％を含む単量体混合物を共重合したものであることがより好ましい。 The acrylic polymer a is obtained by copolymerizing a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture. That is, the acrylic polymer a contains 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of the halogen-containing vinyl monomer with respect to the total weight of the acrylic polymer a. The acrylic polymer a is easily dissolved in an organic solvent, and from the viewpoint of improving the operability when preparing a spinning dope by evaporating water from the acrylic polymer slurry, the total weight of the monomer mixture Copolymerize a monomer mixture containing 20 to 75% by weight of acrylonitrile, 24.95 to 79.95% by weight of a halogen-containing vinyl monomer, and 0.05 to 5% by weight of another vinyl monomer copolymerizable therewith. 25 to 70% by weight of acrylonitrile, 29.95 to 74.95% by weight of halogen-containing vinyl monomers, and other vinyls copolymerizable therewith, based on the total weight of the monomer mixture More preferably, a monomer mixture containing 0.05 to 5% by weight of a monomer is copolymerized.
　上記ハロゲン含有ビニル系モノマーとしては、特に限定されず、例えば、塩化ビニル、臭化ビニルなどに代表されるハロゲン化ビニル、塩化ビニリデン、臭化ビニリデンなどに代表されるハロゲン化ビニリデンを用いることができる。アクリル系重合体を湿式紡糸して得られるアクリル系繊維の触感及び熱水によるカールセット性を向上させる観点から、上記ハロゲン含有ビニル系モノマーは塩化ビニルであることが好ましい。 The halogen-containing vinyl monomer is not particularly limited, and for example, vinyl halides typified by vinyl chloride, vinyl bromide and the like, vinylidene halides typified by vinylidene chloride, vinylidene bromide and the like can be used. . The halogen-containing vinyl monomer is preferably vinyl chloride from the viewpoint of improving the tactile sensation of the acrylic fiber obtained by wet spinning of the acrylic polymer and the curl setting property by hot water.
　上記他のビニル系モノマーは、アクリロニトリル及びハロゲン含有ビニル系モノマーと共重合可能なビニル系モノマーであればよく、特に限定されない。例えば、酢酸ビニルや酪酸ビニルに代表されるビニルエステル類、スルホン酸基含有ビニル単量体などが挙げられる。アクリル系重合体を湿式紡糸して得られるアクリル系繊維の染色性を向上させる観点から、他のビニル系モノマーとしてはスルホン酸基含有ビニル単量体を用いることが好ましい。上記スルホン酸基含有ビニル単量体としては、特に限定されないが、アリルスルホン酸、メタリルスルホン酸、スチレンスルホン酸、イソプレンスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸並びにこれらのナトリウム塩などの金属塩類及びアミン塩類などを用いることができる。これらの他のビニル系モノマーは単独もしくは２種以上組み合わせて用いることができる。 The other vinyl monomers are not particularly limited as long as they are copolymerizable with acrylonitrile and halogen-containing vinyl monomers. Examples thereof include vinyl esters typified by vinyl acetate and vinyl butyrate, and sulfonic acid group-containing vinyl monomers. From the viewpoint of improving the dyeability of acrylic fibers obtained by wet spinning acrylic polymers, it is preferable to use sulfonic acid group-containing vinyl monomers as other vinyl monomers. The sulfonic acid group-containing vinyl monomer is not particularly limited, but includes allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and sodium salts thereof. These metal salts and amine salts can be used. These other vinyl monomers can be used alone or in combination of two or more.
　アクリル系重合体ａは、スラリーの安定性、特に静置後の再分散性の観点から、水分散状態での光回折散乱法で測定したメジアン径（Ｄｐ５０）が０．０１～０．３ｍｍであることが好ましく、０．０５～０．２ｍｍであることがより好ましい。また、アクリル系重合体自体がスラリー移送時に障害となることを回避する観点から、アクリル系重合体ａは、水分散状態での光回折散乱法で測定した最大粒子径が３ｍｍ以下であることが好ましく、２．５ｍｍ以下であることがより好ましく、２ｍｍ以下であることがさらに好ましい。また、スラリーの安定性、特に静置後の再分散性、粘度増加の抑制の観点から、アクリル系重合体ａは、水分散状態での光回折散乱法で測定した最小粒子径が０．００１ｍｍ以上であることが好ましく、０．００５ｍｍ以上であることがより好ましい。 The acrylic polymer a has a median diameter (Dp50) measured by a light diffraction scattering method in an aqueous dispersion state of 0.01 to 0.3 mm from the viewpoint of slurry stability, particularly redispersibility after standing. It is preferable that the thickness is 0.05 to 0.2 mm. Further, from the viewpoint of avoiding that the acrylic polymer itself becomes an obstacle at the time of slurry transfer, the acrylic polymer a has a maximum particle size of 3 mm or less measured by a light diffraction scattering method in an aqueous dispersion state. Preferably, it is 2.5 mm or less, more preferably 2 mm or less. Further, from the viewpoint of slurry stability, particularly redispersibility after standing, and suppression of increase in viscosity, the acrylic polymer a has a minimum particle size of 0.001 mm as measured by a light diffraction scattering method in an aqueous dispersion state. It is preferable that it is above, and it is more preferable that it is 0.005 mm or more.
　含水アクリル系重合体ｂは、アクリル系重合体ａ１００重量部に対して、水を５０～１５０重量部含む。含水アクリル系重合体ｂは、上述した組成のアクリロニトリル、ハロゲン含有ビニル系モノマーを含む単量体混合物を水系媒体中で乳化重合し、凝固し、脱水することで得ることができる。 The water-containing acrylic polymer b contains 50 to 150 parts by weight of water with respect to 100 parts by weight of the acrylic polymer a. The water-containing acrylic polymer b can be obtained by emulsion-polymerizing a monomer mixture containing acrylonitrile and a halogen-containing vinyl monomer having the above-described composition in an aqueous medium, solidifying, and dehydrating.
　乳化重合は、特に限定されず、アクリロニトリルとハロゲン含有ビニル系モノマーや他のビニル系モノマーを共重合してアクリル系重合体を得る公知の方法を用いることができる。例えば、アクリロニトリル及びハロゲン含有ビニル系モノマーと、必要に応じてスルホン酸基含有ビニル系単量体などの他のビニル系モノマーを、水、乳化剤、水溶性重合開始剤を用いて重合し、重合体ラテックスを得ることができる。乳化重合において、必要に応じて、一般的に用いられる連鎖移動剤、ｐＨ調整剤を用いてもよい。 The emulsion polymerization is not particularly limited, and a known method for obtaining an acrylic polymer by copolymerizing acrylonitrile with a halogen-containing vinyl monomer or another vinyl monomer can be used. For example, acrylonitrile and a halogen-containing vinyl monomer and, if necessary, other vinyl monomers such as a sulfonic acid group-containing vinyl monomer are polymerized using water, an emulsifier, a water-soluble polymerization initiator, and a polymer is obtained. Latex can be obtained. In emulsion polymerization, a chain transfer agent and a pH adjuster that are generally used may be used as necessary.
　上記水溶性重合開始剤としては、特に限定されないが、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩化合物が好適である。また、過硫酸塩化合物と亜硫酸塩を併用したレドックス系重合開始剤を用いることも可能である。水溶性重合開始剤の使用量としては、充分な重合転化率を得ること及びアクリル系重合体の着色を防止する観点から、重合に使用する全単量体を１００重量部とした場合、０．０１～１．５重量部であることが好ましく、０．１～１重量部であることがより好ましい。 The water-soluble polymerization initiator is not particularly limited, but persulfate compounds such as ammonium persulfate and potassium persulfate are suitable. It is also possible to use a redox polymerization initiator in which a persulfate compound and a sulfite are used in combination. The amount of the water-soluble polymerization initiator used is 0. When the total monomer used for the polymerization is 100 parts by weight from the viewpoint of obtaining a sufficient polymerization conversion rate and preventing coloring of the acrylic polymer. The amount is preferably 01 to 1.5 parts by weight, and more preferably 0.1 to 1 part by weight.
　上記乳化剤としては、例えば、乳化能力を有する界面活性剤を使用することができる。上記界面活性剤は、アニオン性界面活性剤であることが好ましい。アニオン性界面活性剤としては、例えば、脂肪酸塩、硫酸エステル塩、スルホン酸塩、リン酸エステ塩等を挙げることができる。アニオン性界面活性剤の他に通常のノニオン性界面活性剤を少量併用してもよい。これら界面活性剤の使用量としては重合に使用する全単量体１００重量部に対して０．００１～２重量部、好ましくは０．００５～１．０重量部である。 As the emulsifier, for example, a surfactant having an emulsifying ability can be used. The surfactant is preferably an anionic surfactant. Examples of the anionic surfactant include fatty acid salts, sulfate ester salts, sulfonate salts, and phosphate ester salts. In addition to an anionic surfactant, a small amount of a normal nonionic surfactant may be used in combination. The amount of these surfactants to be used is 0.001 to 2 parts by weight, preferably 0.005 to 1.0 parts by weight, based on 100 parts by weight of all monomers used for polymerization.
　得られた重合体ラテックスに無機塩を添加して重合体を凝固させる。上記無機塩としては、重合体ラテックスを凝固せしめることが可能であればよく、特に限定されないが、水に可溶なアルカリ金属及び／又はアルカリ土類金属を含有するハロゲン化物であることが好ましい。例えば、塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、臭化ナトリウム、臭化カリウム、臭化カルシウム、臭化マグネシウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化カルシウム、ヨウ化マグネシウム、フッ化カリウム、フッ化ナトリウム等が挙げられる。重合体を凝固した後、脱水することで含水アクリル系重合体を得ることができる。脱水の前に、水洗してもよい。脱水は、濾過により行うことができる。水洗や、濾過による脱水は、一般的な装置を用いて行うことができる。なお、脱水後の含水アクリル系重合体を乾燥し、その後さらに水分を含有させたものを含水アクリル系重合体ｂとして用いてもよい。 An inorganic salt is added to the obtained polymer latex to solidify the polymer. The inorganic salt is not particularly limited as long as it can coagulate the polymer latex, but is preferably a halide containing water-soluble alkali metal and / or alkaline earth metal. For example, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, potassium fluoride, Sodium fluoride etc. are mentioned. A water-containing acrylic polymer can be obtained by solidifying the polymer and then dehydrating it. You may wash with water before dehydration. Dehydration can be performed by filtration. Washing with water and dehydration by filtration can be performed using a general apparatus. In addition, you may use as a water-containing acrylic polymer b what dried the water-containing acrylic polymer after spin-drying | dehydration, and also made it contain water after that.
　上記アクリル系重合体のスラリーは、アクリル系重合体ａ１００重量部に対して、水を５０～１５０重量部、有機溶剤ｃを２００～５００重量部含む。アクリル系重合体のスラリーから水を蒸発させ、アクリル系重合体を有機溶媒に溶解させた紡糸原液を得やすい観点から、アクリル系重合体ａ１００重量部に対して、水を７５～１３５重量部、有機溶剤ｃを２５０～５００重量部含むことが好ましく、アクリル系重合体ａ１００重量部に対して、水を８５～１２５重量部、有機溶剤ｃを２５０～５００重量部含むことがより好ましい。 The acrylic polymer slurry contains 50 to 150 parts by weight of water and 200 to 500 parts by weight of the organic solvent c with respect to 100 parts by weight of the acrylic polymer a. From the viewpoint of easily obtaining a spinning stock solution obtained by evaporating water from an acrylic polymer slurry and dissolving the acrylic polymer in an organic solvent, 75 to 135 parts by weight of water with respect to 100 parts by weight of the acrylic polymer a, The organic solvent c is preferably contained in an amount of 250 to 500 parts by weight, more preferably 85 to 125 parts by weight of water and the organic solvent c in an amount of 250 to 500 parts by weight based on 100 parts by weight of the acrylic polymer a.
　上記アクリル系重合体のスラリーは、アクリル系重合体ａ、有機溶剤ｃ及び水を含み、液体成分中の有機溶剤ｃの含有量が９５重量％以下の流動体を混合しながら、上記流動体の液面において、含水アクリル系重合体ｂが含水有機溶剤ｄと接触しないように、上記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合することで得られる。 The slurry of the acrylic polymer contains the acrylic polymer a, the organic solvent c, and water, and while mixing the fluid in which the content of the organic solvent c in the liquid component is 95% by weight or less, In order to prevent the water-containing acrylic polymer b from coming into contact with the water-containing organic solvent d on the liquid surface, the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added and mixed in the fluid.
　上記流動体は、アクリル系重合体ａ、有機溶剤ｃ及び水を含むものであればよく、その調製方法は特に限定されない。製造工程の最初の段階において、上記流動体は、アクリル系重合体ａ１００重量部に対して、水を５０～１５０重量部、有機溶剤ｃを２００～５００重量部含むことが好ましい。操作の簡便性から、上記流動体は、例えば、アクリル系重合体ａ１００重量部に対して水５０～１５０重量部を含む含水アクリル系重合体ｂを、含水有機溶剤ｄへ分散することで調製することが好ましい。なお、本発明において、流動体は、アクリル系重合体のスラリーであってもよい。 The fluid is not particularly limited as long as it contains the acrylic polymer a, the organic solvent c, and water. In the first stage of the production process, the fluid preferably contains 50 to 150 parts by weight of water and 200 to 500 parts by weight of the organic solvent c with respect to 100 parts by weight of the acrylic polymer a. For ease of operation, the fluid is prepared, for example, by dispersing a water-containing acrylic polymer b containing 50 to 150 parts by weight of water with respect to 100 parts by weight of the acrylic polymer a in a water-containing organic solvent d. It is preferable. In the present invention, the fluid may be an acrylic polymer slurry.
　含水有機溶剤ｄは、含水アクリル系重合体ｂを分散しやすい観点から、有機溶剤ｃ９０～９７重量％及び水３～１０重量％からなることが好ましく、有機溶剤ｃ９３～９７重量％及び水３～７重量％からなることがより好ましい。 The water-containing organic solvent d is preferably composed of 90 to 97% by weight of organic solvent c and 3 to 10% by weight of water from the viewpoint of easy dispersion of the water-containing acrylic polymer b, and 93 to 97% by weight of organic solvent c and 3 to 3% of water. More preferably, it consists of 7% by weight.
　有機溶剤ｃは、アクリル系重合体ａの良溶媒であり、かつ水混和性を有するものであればよく、特に限定されない。例えば、アセトン、エチレンカーボネート、ジメチルスルホキシド（ＤＭＳＯ）、ジメチルアセトアミド（ＤＭＡｃ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、ｎ－メチルピロリドン（ＮＭＰ）などが挙げられる。アクリル系重合体のスラリーから水を蒸発しやすい観点から、有機溶剤ｃは、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）及びＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）からなる群から選ばれる一種以上が好ましく、安全性の観点から、ジメチルスルホキシド（ＤＭＳＯ）がより好ましい。 The organic solvent c is not particularly limited as long as it is a good solvent for the acrylic polymer a and has water miscibility. For example, acetone, ethylene carbonate, dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), n-methylpyrrolidone (NMP) and the like can be mentioned. From the viewpoint of easily evaporating water from the acrylic polymer slurry, the organic solvent c is selected from the group consisting of dimethyl sulfoxide (DMSO), N, N-dimethylacetamide (DMAc) and N, N-dimethylformamide (DMF). One or more of these are preferable, and dimethyl sulfoxide (DMSO) is more preferable from the viewpoint of safety.
　上記流動体を混合しながら、上記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して分散させる際、上記流動体の液面において、含水アクリル系重合体ｂが有機溶剤ｃを含む含水有機溶剤ｄと接触しないようにする必要がある。上記流動体の液面において、含水アクリル系重合体ｂに有機溶剤ｃを含む含水有機溶剤ｄと接触すると、数ｍｍ以上の大きさの塊が発生してしまう。 While mixing the fluid, when the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added and dispersed in the fluid, the water-containing acrylic polymer b is an organic solvent on the liquid surface of the fluid. It is necessary to avoid contact with the water-containing organic solvent d containing c. When the liquid surface of the fluid comes into contact with the water-containing organic solvent d containing the organic solvent c in the water-containing acrylic polymer b, a lump having a size of several mm or more is generated.
　含水アクリル系重合体ｂと含水有機溶剤ｄは、所定の量を１回で連続的に投入してもよく、所定の量を２回以上に分けて投入してもよい。生産性の観点から、有機溶剤ｃ、水及びアクリル系重合体ａを含み、液体成分中の有機溶剤ｃの含有量が９５重量％以下の流動体を混合しながら、上記流動体の液面において、含水アクリル系重合体ｂが水及び有機溶剤ｃからなる含水有機溶剤ｄと接触しないように、上記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合する工程を２回以上繰り返しあるいは連続的に行い、得られたアクリル系重合体のスラリーを連続的に排出することが好ましい。得られたアクリル系重合体のスラリーは、ポンプなどにより連続的に排出されることが好ましい。含水アクリル系重合体ｂと含水有機溶剤ｄの投入を２回以上繰り返すあるいは連続的に行う場合は、常に、上記流動体の液面において、含水アクリル系重合体ｂが含水有機溶剤ｄと接触しないようにする必要がある。 A predetermined amount of the water-containing acrylic polymer b and the water-containing organic solvent d may be continuously added once, or the predetermined amount may be added in two or more times. From the viewpoint of productivity, while mixing a fluid containing an organic solvent c, water, and an acrylic polymer a, and the content of the organic solvent c in the liquid component is 95% by weight or less, And adding the water-containing acrylic polymer b and the water-containing organic solvent d to the fluid so that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d comprising water and the organic solvent c. It is preferable to repeat or continuously twice or more, and continuously discharge the resulting acrylic polymer slurry. It is preferable that the obtained acrylic polymer slurry is continuously discharged by a pump or the like. When the addition of the water-containing acrylic polymer b and the water-containing organic solvent d is repeated two or more times or continuously, the water-containing acrylic polymer b is not always in contact with the water-containing organic solvent d on the liquid surface of the fluid. It is necessary to do so.
　また、含水アクリル系重合体ｂと含水有機溶剤ｄの投入は、同時に行ってもよく、交互に行ってもよい。いずれの場合においても、上記流動体の液面において、含水アクリル系重合体ｂが含水有機溶剤ｄと接触しないようにする必要がある。含水アクリル系重合体ｂと含水有機溶剤ｄの投入は、同時に行う場合は、投入箇所は、互いに離れるほど好ましい。 Moreover, the water-containing acrylic polymer b and the water-containing organic solvent d may be charged simultaneously or alternately. In any case, it is necessary that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d on the liquid level of the fluid. When the hydrated acrylic polymer b and the hydrated organic solvent d are charged at the same time, it is preferable that the charged points are separated from each other.
　アクリル系重合体のスラリーの作製中において、流動体は０℃以上８０℃以下の温度に保持されていることが好ましく、１０℃以上５０℃以下の温度に保持されていることがより好ましい。流動体の温度が上記範囲内であると、含水アクリル系重合体ｂが融着、溶解、膨潤することなく、流動体中に分散しやすい。用いる有機溶剤ｃが水への溶解熱が大きい、或いは投入される含水アクリル系重合体ｂの温度が高い等の流動体の温度の上昇が見込まれる場合は、例えば、冷却した含水有機溶剤ｄを用いることも可能である。 During the production of the acrylic polymer slurry, the fluid is preferably maintained at a temperature of 0 ° C. or higher and 80 ° C. or lower, more preferably 10 ° C. or higher and 50 ° C. or lower. When the temperature of the fluid is within the above range, the water-containing acrylic polymer b is easily dispersed in the fluid without being fused, dissolved, or swollen. When the organic solvent c used has a large heat of dissolution in water, or when the temperature of the fluid such as the temperature of the water-containing acrylic polymer b to be charged is high, for example, a cooled water-containing organic solvent d is used. It is also possible to use it.
　上記アクリル系重合体のスラリーの作製は、特に限定されないが、混合操作のしやすさから、撹拌機を備えた撹拌槽で行うことが好ましく、攪拌槽内でのアクリル系重合体ａの付着堆積抑制の観点から邪魔板（バッフル）を備えないことが好ましい。また、操作中の温度を制御しやすい観点から、撹拌槽はジャケット付き撹拌槽であることが好ましい。例えば、ジャケットに冷却水を流すことで温度を制御することができる。撹拌槽の形状は特に限定されないが、流動体を撹拌しやすい観点から、円筒型であることが好ましい。また、撹拌機は一般的な一軸の撹拌機であってよく、撹拌機の撹拌槽内の配置は、撹拌機の中心軸と攪拌槽の中心軸が重なるように配置された中心配置であってもよく、撹拌機の中心軸と撹拌槽の中心軸が重ならないように配置された偏心配置であってもよい。例えば、撹拌槽底面へのアクリル系重合体ａの堆積抑制の観点から、偏心配置であることが好ましい。 The preparation of the acrylic polymer slurry is not particularly limited, but it is preferably performed in a stirring tank equipped with a stirrer for easy mixing operation, and the acrylic polymer a is deposited in the stirring tank. From the viewpoint of suppression, it is preferable not to include a baffle. Moreover, it is preferable that a stirring tank is a jacketed stirring tank from a viewpoint of controlling the temperature in operation easily. For example, the temperature can be controlled by flowing cooling water through the jacket. The shape of the stirring tank is not particularly limited, but a cylindrical shape is preferable from the viewpoint of easy stirring of the fluid. Further, the agitator may be a general uniaxial agitator, and the arrangement of the agitator in the agitation tank is a central arrangement in which the central axis of the agitator and the central axis of the agitation tank overlap. Or the eccentric arrangement | positioning arrange | positioned so that the center axis | shaft of a stirrer and the center axis | shaft of a stirring tank may not overlap may be sufficient. For example, an eccentric arrangement is preferable from the viewpoint of suppressing deposition of the acrylic polymer a on the bottom surface of the stirring tank.
　ジャケット付き撹拌槽中に流動体を投入するか、或いは、ジャケット付き撹拌槽中に含水有機溶剤ｄを投入し、そこへ含水アクリル系重合体ｂを投入して撹拌機で撹拌することで流動体を調製する。次に、上記流動体を撹拌機で撹拌しながら、上記流動体の液面において、含水アクリル系重合体ｂが水及び有機溶剤ｃからなる含水有機溶剤ｄと接触しないように、上記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合する。この混合において、含水アクリル系重合体ｂが集塊をなして流動体液面上に浮遊する場合があり、この浮遊集塊に含水有機溶剤ｄが接触する状況を回避する必要がある。この状況では、例えば流動体に含水アクリル系重合体ｂを投入混合し、少なくとも流動体液面上に含水アクリル系重合体ｂの浮遊がないことを確認した後、含水有機溶剤ｄを投入する工程を繰り返すことが挙げられる。また、含水アクリル系重合体ｂ、含水有機溶剤ｄの各々の連続的な投入であって、含水有機溶剤ｄの投入箇所に至るまでに流動体中に含水アクリル系重合体ｂが没液するように流動体の攪拌状態及び含水アクリル系重合体ｂの投入速度を調整すること、含水有機溶剤ｄの導入口を流動体中に設けること等が挙げられる。含水アクリル系重合体ｂと含水有機溶剤ｄの投入を同時に行う場合は、含水アクリル系重合体ｂの投入箇所と攪拌軸を挟んで対面側に含水有機溶剤ｄを投入することが好ましい。 A fluid is put into a stirring tank with a jacket, or a water-containing organic solvent d is put into a stirring tank with a jacket, and a water-containing acrylic polymer b is put into the stirring tank and stirred with a stirrer. To prepare. Next, while stirring the fluid with a stirrer, in the fluid so that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d composed of water and the organic solvent c on the liquid surface of the fluid. The water-containing acrylic polymer b and the water-containing organic solvent d are respectively added to and mixed. In this mixing, the water-containing acrylic polymer b may agglomerate and float on the liquid surface of the fluid, and it is necessary to avoid a situation in which the water-containing organic solvent d contacts the floating agglomerate. In this situation, for example, a step of adding and mixing the water-containing acrylic polymer b into the fluid, and confirming that the water-containing acrylic polymer b does not float on at least the fluid surface, and then adding the water-containing organic solvent d. Repeat. Further, each of the water-containing acrylic polymer b and the water-containing organic solvent d is continuously charged so that the water-containing acrylic polymer b is immersed in the fluid until the water-containing organic solvent d is charged. In addition, the stirring state of the fluid and the charging speed of the hydrated acrylic polymer b are adjusted, and an inlet for the hydrated organic solvent d is provided in the fluid. When the water-containing acrylic polymer b and the water-containing organic solvent d are added simultaneously, it is preferable to add the water-containing organic solvent d to the opposite side across the place where the water-containing acrylic polymer b is added and the stirring shaft.
　スラリー組成の変動がなく、一定速度でアクリル系重合体のスラリーを製造する生産性の観点から、含水アクリル系重合体ｂ、含水有機溶剤ｄの各々の連続的な投入が好ましく、有機溶剤ｃ、水及びアクリル系重合体ａを含み、液体成分中の有機溶剤ｃの含有量が９５重量％以下の流動体を攪拌機を備えた攪拌槽に投入し、該流動体を撹拌機で撹拌しながら、上記流動体の液面において、含水アクリル系重合体ｂが含水有機溶剤ｄと接触しないように、上記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合する際、攪拌槽の内径Ｄと攪拌槽内の流動体の液深さＨの比Ｈ／Ｄの値を０．３～０．７の範囲とし、流動体の単位体積あたり攪拌所要動力Ｐｖを１Ｗ／ｍ3以上とし、流動体単位体積あたりの含水アクリル系重合体ｂの投入速度を１０００Ｋｇ／ｍ3／ｈｒ以下とし、撹拌槽の下部からポンプにてアクリル系重合体のスラリーを連続的に排出することがより好ましい。攪拌槽の内径Ｄと攪拌槽内の流動体の液深さＨの比Ｈ／Ｄの値は、撹拌槽の流動体の混合性を示すものであり、Ｈ／Ｄの値を０．３～０．７の範囲にすることで、上記流動体の液面において、含水アクリル系重合体ｂが含水有機溶剤ｄと接触しないように制御しやすい。Ｈ／Ｄの値が０．３未満の場合、含水アクリル系重合体ｂと含水有機溶剤ｄの混合は良好となるが、撹拌翼が液面近傍となって流動体の液面において、含水アクリル系重合体ｂと含水有機溶剤ｄの接触が生じる恐れがある。一方、Ｈ／Ｄの値が０．７を上回る場合、撹拌不良箇所が生じて混合不良となる他、含水アクリル系重合体ｂが集塊をなして流動体液面上に浮遊する問題が生じる恐れがある。 From the viewpoint of productivity for producing a slurry of an acrylic polymer at a constant rate without fluctuation of the slurry composition, each of the water-containing acrylic polymer b and the water-containing organic solvent d is preferably continuously added, and the organic solvent c, A fluid containing water and an acrylic polymer a, the content of the organic solvent c in the liquid component being 95% by weight or less is charged into a stirring tank equipped with a stirrer, and while stirring the fluid with a stirrer, When the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added and mixed in the fluid so that the water-containing acrylic polymer b does not come into contact with the water-containing organic solvent d on the liquid surface of the fluid, The ratio H / D of the inner diameter D of the agitation tank to the fluid depth H of the fluid in the agitation tank is in the range of 0.3 to 0.7, and the required power Pv for stirring per unit volume of the fluid is 1 W / m. 3 above and then, water acrylic per fluid unit volume The addition rate of the combined b is less 1000Kg / m 3 / hr, and more preferably continuously discharged slurry of the acrylic polymer from the bottom of the stirred tank at a pump. The value of the ratio H / D between the inner diameter D of the stirring tank and the liquid depth H of the fluid in the stirring tank indicates the mixing property of the fluid in the stirring tank. By setting the ratio in the range of 0.7, it is easy to control the water-containing acrylic polymer b so as not to contact the water-containing organic solvent d on the liquid surface of the fluid. When the value of H / D is less than 0.3, the mixing of the water-containing acrylic polymer b and the water-containing organic solvent d is good, but the water-containing acrylic polymer is mixed with the stirring blade near the liquid surface. There is a risk of contact between the polymer b and the water-containing organic solvent d. On the other hand, when the value of H / D exceeds 0.7, there is a possibility that a stirring failure portion occurs and mixing is poor, and that the water-containing acrylic polymer b agglomerates and floats on the fluid surface. There is.
　本発明において、流動体の単位体積あたりの攪拌所要動力Ｐｖ［Ｗ／ｍ3］は、攪拌槽の内径Ｄ［ｍ］、攪拌槽内の流動体の液深さＨ［ｍ］、攪拌翼の外径ｄ［ｍ］、羽根取付角度θ［度］、羽根幅ｂ［ｍ］、羽根数ｎｐ、邪魔板条件、攪拌機の回転数ｎ［１／ｓｅｃ］、流動体の粘度μ［ｋｇ／ｍ／ｓｅｃ］、流動体の密度ρ［ｋｇ／ｍ3］より、“攪拌技術”（佐竹化学機械株式会社編、佐竹化学機械株式会社（１９９２）、４５１～４６１ページ、第４章）に記載の永田式より算出した値を示す。流動体の単位体積あたりの攪拌所要動力Ｐｖが高いほど、流動体が撹拌されやすい。攪拌槽に無邪魔板（バッフルなし）の条件では、下記の数式（１）～（７）に基づいてＰｖを算出する。本発明での流動体の単位体積あたりの攪拌所要動力Ｐｖの算出において、流動体の粘度μ［ｋｇ／ｍ／ｓｅｃ］、流動体の密度ρ［ｋｇ／ｍ3］は、それぞれ、２３℃での流動体の粘度μ［ｋｇ／ｍ／ｓｅｃ］、流動体の密度ρ［ｋｇ／ｍ3］をいう。また、攪拌槽内の流動体の液深さＨは、攪拌槽の底部から流動体の液面までの高さをいう。なお、流動体中への含水アクリル系重合体ｂ及び含水有機溶剤ｄの投入、並びにアクリル系重合体のスラリーの連続的な排出などにより、撹拌槽中の流動体の体積が経時的に変化する場合は、流動体の液深さＨ、体積、粘度及び密度は、含水アクリル系重合体ｂ及び含水有機溶剤ｄの投入する直前の流動体の液深さＨ、体積、粘度及び密度を意味する。なお、流動体中への含水アクリル系重合体ｂ及び含水有機溶剤ｄの投入量と、アクリル系重合体のスラリーの排出量を調整することで、製造工程中、流動体の液面深さＨを一定の値に保持することができる。 In the present invention, the required stirring power Pv [W / m 3 ] per unit volume of the fluid is the inner diameter D [m] of the stirring tank, the liquid depth H [m] of the fluid in the stirring tank, and the stirring blade Outer diameter d [m], blade attachment angle θ [degree], blade width b [m], blade number np, baffle plate conditions, stirrer speed n [1 / sec], fluid viscosity μ [kg / m / Sec], from the density ρ [kg / m 3 ] of the fluid, described in “Stirring technology” (edited by Satake Chemical Machinery Co., Ltd., Satake Chemical Machinery Co., Ltd. (1992), pages 451 to 461, Chapter 4). The value calculated from the Nagata formula is shown. The higher the required stirring power Pv per unit volume of the fluid, the easier the fluid is stirred. Under the condition of an innocent baffle (no baffle) in the stirring tank, Pv is calculated based on the following formulas (1) to (7). In the calculation of the stirring required power Pv per unit volume of the fluid in the present invention, the viscosity μ [kg / m / sec] of the fluid and the density ρ [kg / m 3 ] of the fluid are 23 ° C., respectively. The viscosity μ [kg / m / sec] of the fluid and the density ρ [kg / m 3 ] of the fluid. Moreover, the liquid depth H of the fluid in the stirring tank refers to the height from the bottom of the stirring tank to the liquid level of the fluid. The volume of the fluid in the agitation tank changes over time due to the introduction of the water-containing acrylic polymer b and the water-containing organic solvent d into the fluid and the continuous discharge of the acrylic polymer slurry. In this case, the fluid depth H, volume, viscosity, and density of the fluid mean the fluid depth H, volume, viscosity, and density of the fluid immediately before the addition of the water-containing acrylic polymer b and the water-containing organic solvent d. . In addition, the liquid level H of the fluid during the manufacturing process is adjusted by adjusting the amount of the water-containing acrylic polymer b and the water-containing organic solvent d introduced into the fluid and the amount of the acrylic polymer slurry discharged. Can be held at a constant value.
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-I000001
　上記アクリル系重合体の作製中において、撹拌槽の内温は、０℃以上８０℃以下に保持されることが好ましく、１０℃以上５０℃以下に保持されることがより好ましい。撹拌槽の内温が上記範囲内であると、含水アクリル系重合体ｂの溶解が抑制されるとともに流動体や含水有機溶剤ｄ中に分散しやすい。なお、撹拌槽を用いた場合、撹拌槽の内温は流動体の温度に等しい。 During the production of the acrylic polymer, the internal temperature of the stirring tank is preferably maintained at 0 ° C. or higher and 80 ° C. or lower, more preferably 10 ° C. or higher and 50 ° C. or lower. When the internal temperature of the agitation tank is within the above range, dissolution of the water-containing acrylic polymer b is suppressed and it is easy to disperse in the fluid or the water-containing organic solvent d. In addition, when a stirring tank is used, the internal temperature of a stirring tank is equal to the temperature of a fluid.
　上記アクリル系重合体のスラリーは、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き３ｍｍ以上の金属製網ふるいで残分がないことが好ましく、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き２．５ｍｍ以上３ｍｍ未満の金属製網ふるいで残分がないことがより好ましく、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き２．０ｍｍ以上２．５ｍｍ未満の金属製網ふるいで残分がないことがさらに好ましく、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．５ｍｍ以上２．０ｍｍ未満の金属製網ふるいで残分がないことがさらに好ましい。 The acrylic polymer slurry is preferably a metal mesh sieve having a mesh size of 3 mm or more in accordance with JIS Z-8801-1 (2006), and has no residue, and is in accordance with JIS Z-8801-1 (2006). It is more preferable that there is no residue in a metal mesh sieve having an opening of 2.5 mm or more and less than 3 mm, and a metal mesh sieve having an opening of 2.0 mm or more and less than 2.5 mm according to JIS Z-8801-1 (2006). It is more preferable that there is no residue, and it is more preferable that there is no residue with a metal net sieve having an opening of 1.5 mm or more and less than 2.0 mm according to JIS Z-8801-1 (2006).
　以下実施例により本発明を更に具体的に説明する。なお、本発明は下記の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example.
　＜含水アクリル系重合体の製造例１＞
　内容積２０Ｌの耐圧重合反応装置にイオン交換水１２０００ｇ、ラウリル硫酸ナトリウム５４ｇ（０．９重量部）、亜硫酸２５．８ｇ、亜硫酸水素ナトリウム１３．２ｇ、硫酸鉄０．０６ｇ、アクリロニトリル２９４ｇ（４．９重量部）、塩化ビニル３０６０ｇ（５１重量部）を投入し、窒素置換した。重合機内温を５０℃に調整し、開始剤として過硫酸アンモニウム２．１ｇ（０．０３５重量部）を投入し、重合を開始した。途中、アクリロニトリル２５２６ｇ（４２．１重量部）、スチレンスルホン酸ナトリウム１２０ｇ（２重量部）、過硫酸アンモニウム１３．８ｇ（０．２３重量部）を追加しながら、重合時間５時間１０分で重合した。その後、未反応の塩化ビニルを回収し、ラテックスを耐圧重合反応装置より払い出した。得られたアクリロニトリル５０重量％、塩化ビニル４８重量％、ｐ－スチレンスルホン酸ナトリウム２重量％からなるアクリル系重合体のラテックス１Ｋｇを８０℃に加熱、攪拌状態で２０重量％塩化ナトリウム水溶液を１００ｇ加え、これを８０～１１０℃で攪拌し、塩析凝固してアクリル系重合体スラリーを得た。得られたアクリル系重合体スラリーを濾過して含水アクリル系重合体を得た。含水アクリル系重合体の含水量を８０℃で３時間乾燥した後の重量変化で測定したところ、アクリル系重合体の乾燥重量１００重量部に対して１００重量部であった。すなわち、製造例１で得られた含水アクリル系重合体は、アクリル系重合体１００重量部に対して水を１００重量部含んでいた。アクリル系重合体の粒子径をレーザ回折／散乱式粒子径分布測定装置（株式会社堀場製作所製、型番「ＬＡ－９５０」）を用いて水分散状態での光回折散乱法で測定したところ、最小粒子径は０．０１ｍｍであり、最大粒子径は１ｍｍであり、メジアン径（Ｄｐ５０）で０．１ｍｍであった。 <Production Example 1 of Hydrous Acrylic Polymer>
In a pressure-resistant polymerization reactor with an internal volume of 20 L, ion-exchanged water 12000 g, sodium lauryl sulfate 54 g (0.9 parts by weight), sulfurous acid 25.8 g, sodium hydrogensulfite 13.2 g, iron sulfate 0.06 g, acrylonitrile 294 g (4.9) Parts by weight) and 3060 g (51 parts by weight) of vinyl chloride were added, and the atmosphere was replaced with nitrogen. The internal temperature of the polymerization machine was adjusted to 50 ° C., and 2.1 g (0.035 parts by weight) of ammonium persulfate was added as an initiator to initiate polymerization. On the way, polymerization was performed in 5 hours and 10 minutes while adding 2526 g (42.1 parts by weight) of acrylonitrile, 120 g (2 parts by weight) of sodium styrenesulfonate, and 13.8 g (0.23 parts by weight) of ammonium persulfate. Thereafter, unreacted vinyl chloride was recovered, and latex was discharged from the pressure-resistant polymerization reactor. 1 kg of the latex of an acrylic polymer composed of 50% by weight of acrylonitrile, 48% by weight of vinyl chloride and 2% by weight of sodium p-styrenesulfonate was heated to 80 ° C. and 100 g of 20% by weight aqueous sodium chloride solution was added with stirring. This was stirred at 80 to 110 ° C. and salted out and solidified to obtain an acrylic polymer slurry. The obtained acrylic polymer slurry was filtered to obtain a water-containing acrylic polymer. When the water content of the water-containing acrylic polymer was measured by weight change after drying at 80 ° C. for 3 hours, it was 100 parts by weight with respect to 100 parts by weight of the dry weight of the acrylic polymer. That is, the water-containing acrylic polymer obtained in Production Example 1 contained 100 parts by weight of water with respect to 100 parts by weight of the acrylic polymer. The particle size of the acrylic polymer was measured by a light diffraction / scattering method in a water-dispersed state using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd., model number “LA-950”). The particle diameter was 0.01 mm, the maximum particle diameter was 1 mm, and the median diameter (Dp50) was 0.1 mm.
　（実施例１）
　外径ｄが約２７ｃｍ、羽根取付角度θが３５度、羽根幅ｂが約４ｃｍの３枚羽根プロペラ翼（ｂｅ＝６ｃｍ）を備えた攪拌機（１軸、撹拌槽の中心軸より約５ｃｍ離れた偏心配置）を取りつけた内径Ｄが５６ｃｍ、容積２００Ｌのジャケット付き攪拌槽（バッフルなし、円筒型）にＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）９５重量％及び水５重量％からなる含水ＤＭＳＯを８３Ｋｇ投入し、回転数１２０ｒｐｍの攪拌機で撹拌しながら、製造例１で得られた含水アクリル系重合体５７Ｋｇを３４２Ｋｇ／ｈｒの速度にて１０分で撹拌槽中に投入した。ジャケットの温度制御により攪拌槽の内温をほぼ４０℃に維持した。得られたアクリル系重合体のスラリー（流動体）を攪拌槽下部より４０Ｌ/ｈｒの速度にてポンプで払い出しつつ、液量が約５０Ｌとなったところで、製造例１で得られた含水アクリル系重合体約１０Ｋｇを１２０Ｋｇ/ｈｒの速度で撹拌槽中に投入し、流動体の液面上に含水アクリル系重合体の浮遊がない状態を確認した後、ＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）９５重量％及び水５重量％からなる含水ＤＭＳＯ１３ｋｇを７８０Ｋｇ/ｈｒの速度で撹拌槽中に投入することを４回繰り返し、合計で含水アクリル系重合体３８Ｋｇ、含水ＤＭＳＯ５５．３Ｋｇを追加した。上記のアクリル系重合体のスラリーの製造工程において、送液は全量問題なかった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き２．８ｍｍの金属製網ふるいで残分は認められなかった。アクリル系重合体固形分の重量とは、水を含まない乾燥状態のアクリル系重合体の重量に等しい。以下においても同様である。 (Example 1)
A stirrer (one axis, about 5 cm away from the central axis of the stirring tank) having a three-blade propeller blade (be = 6 cm) having an outer diameter d of about 27 cm, a blade mounting angle θ of 35 degrees, and a blade width b of about 4 cm. 83kg of DMSO (JIS K9702 standard, reagent grade) 95% by weight DMSO (5% by weight) and DMSO (JIS K9702 standard, reagent type) is added to a jacketed stirring tank (no baffle, cylindrical type) with an inner diameter D of 56cm and a volume of 200L. Then, while stirring with a stirrer having a rotational speed of 120 rpm, 57 kg of the water-containing acrylic polymer obtained in Production Example 1 was charged into the stirring tank at a speed of 342 kg / hr in 10 minutes. The internal temperature of the stirring tank was maintained at approximately 40 ° C. by controlling the temperature of the jacket. The obtained acrylic polymer slurry (fluid) was pumped from the bottom of the stirring tank at a rate of 40 L / hr with a pump, and when the liquid volume reached about 50 L, the hydrous acrylic polymer obtained in Production Example 1 was obtained. About 10 Kg of polymer was charged into a stirring tank at a rate of 120 Kg / hr, and after confirming that there was no floating acrylic polymer on the liquid surface of the fluid, DMSO (JIS K9702 standard, reagent grade) 95 13 kg of water-containing DMSO consisting of 5% by weight and 5% by weight of water was charged into the stirring tank at a rate of 780 kg / hr four times, and 38 kg of water-containing acrylic polymer and 55.3 kg of water-containing DMSO were added in total. In the production process of the acrylic polymer slurry, there was no problem with the total amount of liquid feeding. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 2 in accordance with JIS Z-8801-1 (2006). No residue was observed on a 8 mm metal screen. The weight of the acrylic polymer solid content is equal to the weight of the dry acrylic polymer not containing water. The same applies to the following.
　（実施例２）
　外径ｄが約２７ｃｍ、羽根取付角度θが３５度、羽根幅ｂが約４ｃｍの３枚羽根プロペラ翼（ｂｅ＝６ｃｍ）を備えた攪拌機（１軸、撹拌槽の中心軸より約５ｃｍ離れた偏心配置）を取りつけた内径Ｄが５６ｃｍ、容積２００Ｌのジャケット付き攪拌槽（バッフルなし、円筒型）にＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）９５重量％及び水５重量％からなる含水ＤＭＳＯを８３Ｋｇ投入し、回転数１２０ｒｐｍの攪拌機で撹拌しながら、製造例１で得られた含水アクリル系重合体５７Ｋｇを３４２Ｋｇ/ｈｒの速度にて１０分で撹拌槽中に投入した。ジャケットの温度制御により攪拌槽の内温をほぼ４０℃に維持した。得られたアクリル系重合体のスラリー（流動体）は、重量が１４０Ｋｇであり、液深さＨが約３０ｃｍであり、Ｈ／Ｄの値が０．５４であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。上記流動体を攪拌槽下部より４０Ｌ/ｈｒの速度にてポンプで払い出しつつ、含水アクリル系重合体３８Ｋｇを１９Ｋｇ／ｈｒの速度で攪拌槽中に投入し含水アクリル系重合体の投入箇所と攪拌軸をはさんで対向側にＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）９５重量％及び水５重量％からなる含水ＤＭＳＯ５５．３Ｋｇを２５．５Ｌ／ｈｒの速度で攪拌槽中に添加した。２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１３Ｗ／ｍ3であった。流動体単位体積あたりの含水アクリル重合体の投入速度は２５７ｋｇ／ｍ3／ｈｒであった。含水ＤＭＳＯ投入口の直下に到達するまでに、含水アクリル系重合体がほぼ液中に没し、液面上に含水アクリル系重合体の浮遊がないような撹拌状態であった。上記のアクリル系重合体のスラリーの製造工程において、送液は全量問題見られなかった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き２．８ｍｍの金属製網ふるいで残分は認められなかった。 (Example 2)
A stirrer (one axis, about 5 cm away from the central axis of the stirring tank) having a three-blade propeller blade (be = 6 cm) having an outer diameter d of about 27 cm, a blade mounting angle θ of 35 degrees, and a blade width b of about 4 cm. 83kg of DMSO (JIS K9702 standard, reagent grade) 95% by weight DMSO (5% by weight) and DMSO (JIS K9702 standard, reagent type) is added to a jacketed stirring tank (no baffle, cylindrical type) with an inner diameter D of 56cm and a volume of 200L. Then, while stirring with a stirrer having a rotational speed of 120 rpm, 57 kg of the water-containing acrylic polymer obtained in Production Example 1 was charged into the stirring tank at a rate of 342 kg / hr in 10 minutes. The internal temperature of the stirring tank was maintained at approximately 40 ° C. by controlling the temperature of the jacket. The obtained acrylic polymer slurry (fluid) had a weight of 140 kg, a liquid depth H of about 30 cm, and a H / D value of 0.54. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . While discharging the above fluid from the lower part of the stirring tank with a pump at a rate of 40 L / hr, 38 kg of the water-containing acrylic polymer was put into the stirring tank at a speed of 19 kg / hr, and the location of the water-containing acrylic polymer and the stirring shaft On the opposite side, 55.3 kg of water-containing DMSO consisting of 95% by weight of DMSO (JIS K9702 standard, reagent special grade) and 5% by weight of water was added to the stirring tank at a rate of 25.5 L / hr. The required stirring power Pv per unit volume of the fluid calculated by the above-described formulas 1 to 7 under the condition of 23 ° C. and no baffle was 13 W / m 3 . The feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 257 kg / m 3 / hr. By the time it reached just below the water-containing DMSO inlet, the water-containing acrylic polymer was almost submerged in the liquid, and the water-containing acrylic polymer was in a stirred state so that there was no floating on the liquid surface. In the production process of the acrylic polymer slurry, no problem was found in the total amount of liquid fed. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 2 in accordance with JIS Z-8801-1 (2006). No residue was observed on a 8 mm metal screen.
　（実施例３）
　実施例２で得られたアクリル系重合体（固形分）１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなるアクリル系重合体のスラリー（流動体）１６７ｇを内径Ｄが約８ｃｍ、容積０．５Ｌのステンレス製カップ（撹拌槽に相当する、円筒型）へ投入した。流動体の液深さＨは約３ｃｍであり、Ｈ／Ｄの値は０．３８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。上記ステンレス製カップ中には撹拌軸に外径ｄが３．７ｃｍ、羽根取付角度θが４５度、羽根幅ｂが０．４ｃｍの４枚ピッチドパドル翼（ｂｅ＝０．８ｃｍ）を備えた攪拌機（１軸、撹拌槽の中心軸に位置する中心配置）が取り付けられていた。回転数１５０ｒｐｍの攪拌機で流動体を撹拌しながら、室温２２℃にて、上記製造例１で得られた含水アクリル系重合体１５ｇを薬包紙より、含水アクリル系重合体の投入場所と攪拌軸を挟んで対面側にＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）９５重量％及び水５重量％からなる含水ＤＭＳＯを２２ｇ滴下管より、ほぼ一定の速度にて１０分間で投入、そのまま５分間攪拌し、得られたアクリル系重合体のスラリーを排出した。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．６Ｗ／ｍ3であった。流動体単位体積あたりの含水アクリル重合体の投入速度は５９３ｋｇ／ｍ3／ｈｒであった。一連の工程において、ステンレス製カップ内の液面上に浮遊する含水アクリル系重合体に含水ＤＭＳＯが滴下されることはなかった。また、一連の工程において、ステンレス製カップ内の温度は殆ど変動なく、流動体の温度は約２２℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分は認められなかった。 (Example 3)
An acrylic polymer slurry (fluid) consisting of 100 parts by weight of the acrylic polymer (solid content) obtained in Example 2, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO was added to 167 g of an inner diameter D of about 8 cm. Then, it was put into a stainless steel cup (cylindrical type corresponding to a stirring tank) having a volume of 0.5 L. The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . In the stainless steel cup, a stirrer equipped with a four pitched paddle blade (be = 0.8 cm) having an outer diameter d of 3.7 cm, a blade mounting angle θ of 45 degrees, and a blade width b of 0.4 cm on the stirring shaft ( 1 axis, a central arrangement located on the central axis of the stirring vessel) was attached. While stirring the fluid with a stirrer having a rotational speed of 150 rpm, the water-containing acrylic polymer 15 g obtained in Production Example 1 was sandwiched from the medicine-wrapped paper at a room temperature of 22 ° C. with the stirring site of the water-containing acrylic polymer sandwiched between them. In the opposite side, DMSO (JIS K9702 standard, reagent grade) 95% by weight and water-containing DMSO consisting of 5% by weight of water was added from a 22 g dropping tube at an almost constant speed for 10 minutes and stirred for 5 minutes. The acrylic polymer slurry was discharged. The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 0.6 W / m 3 . The charging rate of the water-containing acrylic polymer per unit volume of the fluid was 593 kg / m 3 / hr. In the series of steps, the hydrated DMSO was not dropped onto the hydrated acrylic polymer floating on the liquid surface in the stainless steel cup. In the series of steps, the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 22 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
　（実施例４）
　内径Ｄが約８ｃｍ、容積０．５Ｌのステンレス製カップを５０℃に調整した水浴中に固定した以外は、実施例３と同じ条件でアクリル重合体スラリーを作製した。流動体の液深さＨが約３ｃｍ、Ｈ／Ｄの値が０．３８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．６Ｗ／ｍ3であった。流動体単位体積あたりの含水アクリル重合体の投入速度は５９３ｋｇ／ｍ3／ｈｒであった。一連の工程において水浴の温度は殆ど変動なく、流動体の温度は約５０℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分が認められなかった。 Example 4
An acrylic polymer slurry was prepared under the same conditions as in Example 3, except that a stainless steel cup having an inner diameter D of about 8 cm and a volume of 0.5 L was fixed in a water bath adjusted to 50 ° C. The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 0.6 W / m 3 . The charging rate of the water-containing acrylic polymer per unit volume of the fluid was 593 kg / m 3 / hr. In the series of steps, the temperature of the water bath was almost unchanged, and the temperature of the fluid was about 50 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
　（実施例５）
　含水アクリル系重合体及びＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）の追加添加時の投入時間を６分とした以外は、実施例４と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨが約３ｃｍ、Ｈ／Ｄの値が０．３８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．６Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は９８８ｋｇ／ｍ3／ｈｒであった。一連の工程において、ステンレス製カップ内の液面上に浮遊する含水アクリル系重合体に含水ＤＭＳＯが滴下されることはなかった。また、一連の工程において、ステンレス製カップ内の温度は殆ど変動なく、流動体の温度は約５０℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分は認められなかった。 (Example 5)
A slurry of an acrylic polymer was prepared in the same manner as in Example 4 except that the addition time for adding the water-containing acrylic polymer and DMSO (JIS K9702 standard, reagent grade) was 6 minutes. The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 .6W / m 3, input rate of the water-containing acrylic polymer per fluid unit volume was 988kg / m 3 / hr. In the series of steps, the hydrated DMSO was not dropped onto the hydrated acrylic polymer floating on the liquid surface in the stainless steel cup. In the series of steps, the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
　（実施例６）
　実施例２で得られたアクリル系重合体（固形分）１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなるアクリル系重合体のスラリー（流動体）３００ｇを用い、含水アクリル系重合体及びＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）の追加添加時の投入時間を６分とした以外は、実施例４と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨは約５．４ｃｍ、Ｈ／Ｄの値は０．６８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．１Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は５５０ｋｇ／ｍ3／ｈｒであった。一連の工程において、ステンレス製カップ内の液面上に浮遊する含水アクリル系重合体に含水ＤＭＳＯが滴下されることはなかった。また、一連の工程において、ステンレス製カップ内の温度は殆ど変動なく、流動体の温度は約５０℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分は認められなかった。 (Example 6)
Using the acrylic polymer slurry (fluid) 300g consisting of 100 parts by weight of the acrylic polymer (solid content) obtained in Example 2, 114.6 parts by weight of water and 276.7 parts by weight of DMSO, water-containing acrylic An acrylic polymer slurry was prepared in the same manner as in Example 4 except that the addition time for addition of the polymer and DMSO (JIS K9702 standard, reagent grade) was 6 minutes. The fluid depth H of the fluid was about 5.4 cm, and the value of H / D was 0.68. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 0.1 W / m 3 , and the feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 550 kg / m 3 / hr. In the series of steps, the hydrated DMSO was not dropped onto the hydrated acrylic polymer floating on the liquid surface in the stainless steel cup. In the series of steps, the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
　（実施例７）
　攪拌機の回転数を３００ｒｐｍとした以外は、実施例６と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨは約５．４ｃｍ、Ｈ／Ｄの値は０．６８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは６．８Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は５５０ｋｇ／ｍ3／ｈｒであった。一連の工程において、ステンレス製カップ内の液面上に浮遊する含水アクリル系重合体に含水ＤＭＳＯが滴下されることはなかった。また、一連の工程において、ステンレス製カップ内の温度は殆ど変動なく、流動体の温度は約５０℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分は認められなかった。 (Example 7)
An acrylic polymer slurry was prepared in the same manner as in Example 6 except that the rotation speed of the stirrer was changed to 300 rpm. The fluid depth H of the fluid was about 5.4 cm, and the value of H / D was 0.68. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent was 6 8 W / m 3 , and the feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 550 kg / m 3 / hr. In the series of steps, the hydrated DMSO was not dropped onto the hydrated acrylic polymer floating on the liquid surface in the stainless steel cup. In the series of steps, the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
　（実施例８）
　ＤＭＦ（ナカライテスク株式会社製、試薬特級）９５重量％及び水５重量％からなる含水ＤＭＦ１６６．０ｇを内径Ｄが約８ｃｍ、容積０．５Ｌのステンレス製カップへ投入した。上記ステンレス製カップ中には撹拌軸に外径ｄが３．７ｃｍ、羽根取付角度θが４５度、羽根幅ｂが０．４ｃｍの４枚ピッチドパドル翼（ｂｅ＝０．８ｃｍ）を備えた攪拌機（１軸、撹拌槽の中心軸に位置する中心配置）が取り付けられていた。回転数３００ｒｐｍの攪拌機で含水ＤＭＦを撹拌しながら、室温２２℃にて、上記製造例１で得られた含水アクリル系重合体１１４．０ｇを２０分で撹拌槽中に投入し、アクリル系重合体（固形分）１００重量部、水１１４．６重量部、ＤＭＦ２７６．７重量部からなるアクリル系重合体のスラリー（流動体）２８０ｇを作製した。流動体の液深さＨは約５．６ｃｍ、Ｈ／Ｄの値は０．７０であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１０００Ｋｇ／ｍ3であった。ステンレス製カップを５０℃に調整した水浴中に固定し、回転数３００ｒｐｍで流動体を撹拌しながら、流動体温度５０℃にて、上記製造例１で得られた含水アクリル系重合体１５ｇを薬包紙より、含水アクリル系重合体の投入場所と攪拌軸を挟んで対面側にＤＭＦ（ナカライテスク株式会社製、試薬特級）９５重量％及び水５重量％からなる含水ＤＭＦを２２ｇ滴下管より、ほぼ一定の速度にて６分間で投入、そのまま５分間攪拌し、得られたアクリル系重合体のスラリーを排出した。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは６．５Ｗ／ｍ3であった。流動体単位体積あたりの含水アクリル重合体の投入速度は５３６ｋｇ／ｍ3／ｈｒであった。一連の工程において、ステンレス製カップ内の液面上に浮遊する含水アクリル系重合体に含水ＤＭＦが滴下されることはなかった。また、一連の工程において、ステンレス製カップ内の温度は殆ど変動なく、流動体の温度は約５０℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＦ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分は認められなかった。 (Example 8)
166.0 g of water-containing DMF consisting of 95% by weight of DMF (manufactured by Nacalai Tesque Co., Ltd., reagent grade) and 5% by weight of water was put into a stainless steel cup having an inner diameter D of about 8 cm and a volume of 0.5 L. In the stainless steel cup, a stirrer equipped with a four pitched paddle blade (be = 0.8 cm) having an outer diameter d of 3.7 cm, a blade mounting angle θ of 45 degrees, and a blade width b of 0.4 cm on the stirring shaft ( 1 axis, a central arrangement located on the central axis of the stirring vessel) was attached. While stirring the water-containing DMF with a stirrer with a rotation speed of 300 rpm, 114.0 g of the water-containing acrylic polymer obtained in Production Example 1 was charged into the stirring tank at room temperature of 22 ° C. in 20 minutes. 280 g of an acrylic polymer slurry (fluid) consisting of 100 parts by weight (solid content), 114.6 parts by weight of water, and 276.7 parts by weight of DMF was prepared. The fluid depth H of the fluid was about 5.6 cm, and the value of H / D was 0.70. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1000 Kg / m 3 . A stainless steel cup was fixed in a water bath adjusted to 50 ° C., and 15 g of the water-containing acrylic polymer obtained in Production Example 1 was added to the medicine-wrapping paper at a fluid temperature of 50 ° C. while stirring the fluid at a rotation speed of 300 rpm. From the 22 g drop tube, water-containing DMF consisting of 95% by weight of DMF (manufactured by Nacalai Tesque Co., Ltd., special grade reagent) and 5% by weight of water is almost constant across the place where the water-containing acrylic polymer is charged and the stirring shaft. The mixture was stirred at a speed of 6 minutes and stirred for 5 minutes, and the resulting acrylic polymer slurry was discharged. The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent was 6 It was 5 W / m 3 . The feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 536 kg / m 3 / hr. In the series of steps, the hydrous DMF was not dripped onto the hydrous acrylic polymer floating on the liquid surface in the stainless steel cup. In the series of steps, the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, 276.7 parts by weight of DMF, and has an opening 1 according to JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
　（実施例９）
　有機溶剤としてＤＭＦに代えてＤＭＡｃを用いた以外は、実施例８と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨは約５．６ｃｍ、Ｈ／Ｄの値は０．７０であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１０００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは６．５Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は５３６ｋｇ／ｍ3／ｈｒであった。一連の工程において、ステンレス製カップ内の液面上に浮遊する含水アクリル系重合体に含水ＤＭＡｃが滴下されることはなかった。また、一連の工程において、ステンレス製カップ内の温度は殆ど変動なく、流動体の温度は約５０℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１４．６重量部、ＤＭＡｃ２７６．７重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分は認められなかった。 Example 9
An acrylic polymer slurry was prepared in the same manner as in Example 8 except that DMAc was used instead of DMF as the organic solvent. The fluid depth H of the fluid was about 5.6 cm, and the value of H / D was 0.70. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1000 Kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent was 6 0.5 W / m 3 , and the feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 536 kg / m 3 / hr. In the series of steps, the water-containing DMAc was not dripped onto the water-containing acrylic polymer floating on the liquid surface in the stainless steel cup. In the series of steps, the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 50 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 114.6 parts by weight of water, and 276.7 parts by weight of DMAc, and has an opening 1 in accordance with JIS Z-8801-1 (2006). No residue was observed on a 7 mm metal screen.
　（比較例１）
　内径約１５ｃｍ、容積３Ｌのステンレス製カップ（円筒型）に翼径４ｃｍの４枚ピッチドパドル翼を取り付けた攪拌機（１軸、撹拌槽の中心軸に位置する中心配置）を取り付けて撹拌槽とした。次いで、該撹拌槽にＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）１．４Ｋｇを投入し、攪拌機で撹拌しながら、２５℃で、製造例１で得られた含水アクリル系重合体１Ｋｇを一気に撹拌槽中に投入した。撹拌槽の内温が５０℃程度まで上昇し、一時的に混合困難となった。得られた重合体スラリーは、アクリル系重合体固形分１００重量部、水１００重量部、ＤＭＳＯ２８０重量部からなり、撹拌を続けても分散しない数ｃｍ以上の塊が認められたため、使用不能と判断した。液体成分中のＤＭＳＯ濃度が９５ｗｔ％を超える流動体であるＤＭＳＯ中に含水樹脂を一気に投入した上、温度制御も行っていないため、極端な塊の発生となった。 (Comparative Example 1)
A stirrer (one axis, central arrangement located on the central axis of the stirring tank) in which a four pitched paddle blade with a blade diameter of 4 cm was attached to a stainless steel cup (cylindrical type) having an inner diameter of about 15 cm and a volume of 3 L was used as a stirring tank. Subsequently, 1.4 kg of DMSO (JIS K9702 standard, reagent special grade) was added to the stirring tank, and 1 kg of the hydroacrylic polymer obtained in Production Example 1 was stirred at 25 ° C. in a stirring tank at 25 ° C. It was thrown into. The internal temperature of the stirring tank rose to about 50 ° C., and mixing was temporarily difficult. The obtained polymer slurry was composed of 100 parts by weight of acrylic polymer solids, 100 parts by weight of water, and 280 parts by weight of DMSO, and a mass of several centimeters or more that did not disperse even when stirring was observed. did. Since the water-containing resin was poured into DMSO, which is a fluid whose DMSO concentration in the liquid component exceeds 95 wt%, and temperature control was not performed, extreme lumps were generated.
　（比較例２）
　内径Ｄが約５６ｃｍ、容積２００Ｌのジャケット付き攪拌槽（バッフルなし、円筒型）にＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）７９Ｋｇを投入、攪拌機（１軸、撹拌槽の中心軸より約５ｃｍ離れた偏心配置）で撹拌させながら、製造例１で得られた含水アクリル系重合体５７Ｋｇを３４６Ｋｇ/ｈｒの速度にて１０分で投入した。ジャケットの温度制御により撹拌槽の内温をほぼ４０℃に維持した。得られたアクリル系重合体のスラリー（流動体）を攪拌槽下部より６０Ｌ/ｈｒの速度でポンプで払い出しつつ、液量が約５０Ｌとなったところで、製造例１で得られた含水アクリル系重合体１０Ｋｇを一気に投入し、間を置かずに、ＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）１３ｋｇを一気に投入することを４回繰り返し、合計で含水アクリル系重合体３８Ｋｇ、ＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）５２．５Ｋｇを追加した。送液は途上より送液量が不安定となり、最終的にポンプが吸引不能となった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１００重量部及びＤＭＳＯ２７７．２重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き２．８ｍｍの金属製網ふるいでアクリル系重合体固形分１００重量部あたり、２重量部の残分（水で洗浄後、８０℃で３時間乾燥した後乾燥重量）が認められた。ダイアフラムポンプを用いており、バルブにこの数ｍｍ程度の塊がかみ込んで吸引不能となっていた。 (Comparative Example 2)
DMSO (JIS K9702 standard, reagent special grade) 79 kg is introduced into a jacketed stirring tank (no baffle, cylindrical type) with an inner diameter D of about 56 cm and a volume of 200 L. Stirrer (one axis, eccentric about 5 cm away from the central axis of the stirring tank) The water-containing acrylic polymer 57Kg obtained in Production Example 1 was charged at a rate of 346Kg / hr in 10 minutes while stirring in the arrangement. The inner temperature of the stirring tank was maintained at approximately 40 ° C. by controlling the temperature of the jacket. The obtained acrylic polymer slurry (fluid) was pumped out from the lower part of the stirring tank with a pump at a rate of 60 L / hr, and when the liquid volume became about 50 L, the hydrous acrylic heavy polymer obtained in Production Example 1 was used. 10 kg of combined polymer is charged all at once, and 13 kg of DMSO (JIS K9702 standard, reagent special grade) is repeated four times at a time without delay. In total, 38 kg of water-containing acrylic polymer, DMSO (JIS K9702 standard, reagent special grade) ) 52.5 kg was added. In the middle of the feeding, the amount of feeding became unstable and eventually the pump could not be sucked. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 100 parts by weight of water, and 277.2 parts by weight of DMSO, and has an aperture of 2.8 mm in accordance with JIS Z-8801-1 (2006). 2 parts by weight of residue (100% by weight after washing with water and then drying at 80 ° C. for 3 hours) was observed per 100 parts by weight of the acrylic polymer solid content. A diaphragm pump was used, and a lump of about several mm was caught in the valve, and suction was impossible.
　（比較例３）
　投入する溶剤をＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）２１ｇとした以外は、実施例３と同じ条件でアクリル重合体スラリーを作製した。流動体の液深さＨは約３ｃｍ、Ｈ／Ｄの値は０．３８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．６Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は５９３ｋｇ／ｍ3／ｈｒであった。一連の工程において、ステンレス製カップ内の液面上に浮遊する含水アクリル系重合体にＤＭＳＯが滴下されることはなかった。また、一連の工程において、ステンレス製カップ内の温度は殆ど変動なく、流動体の温度は約２２℃であった。得られたアクリル系重合体のスラリーは、アクリル系重合体固形分１００重量部、水１１２重量部及びＤＭＳＯ２７７．３重量部からなり、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分が０．１ｇ程度認められた。含水ＤＭＳＯではなく、ＤＭＳＯを投入したことにより、塊が発生していた。 (Comparative Example 3)
An acrylic polymer slurry was produced under the same conditions as in Example 3 except that the solvent to be added was changed to 21 g of DMSO (JIS K9702 standard, reagent special grade). The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required power for stirring Pv per unit volume of the fluid calculated by Equations 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent was 1.6 W. / m 3, input rate of the water-containing acrylic polymer per fluid unit volume was 593kg / m 3 / hr. In a series of steps, DMSO was not dripped onto the water-containing acrylic polymer floating on the liquid surface in the stainless steel cup. In the series of steps, the temperature in the stainless steel cup hardly changed, and the temperature of the fluid was about 22 ° C. The resulting acrylic polymer slurry comprises 100 parts by weight of acrylic polymer solids, 112 parts by weight of water, and 277.3 parts by weight of DMSO, and has a mesh opening size of 1.7 mm in accordance with JIS Z-8801-1 (2006). About 0.1 g of residue was observed in the metal mesh sieve. Lumps were generated by adding DMSO instead of water-containing DMSO.
　（比較例４）
　含水アクリル系重合体及びＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）の追加添加時の投入時間を１．５分とした以外は、比較例３と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨは約３ｃｍ、Ｈ／Ｄの値は０．３８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．６Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は３９５２ｋｇ／ｍ3／ｈｒであった。流動体の温度は約２２℃であった。含水アクリル系重合体及びＤＭＳＯの追加添加時に、攪拌槽の液面上に浮遊する含水アクリル系重合体にＤＭＳＯが滴下される状況が認められた。得られたアクリル系重合体のスラリーは、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分が０．７ｇであり、投入された含水アクリル系重合体の固形分１００重量に対して約２重量部（水で洗浄後、８０℃で３時間乾燥した後乾燥重量）の塊の発生が確認された。含水ＤＭＳＯではなく、ＤＭＳＯを投入したこと、及び攪拌槽の液面上に浮遊する含水アクリル系重合体にＤＭＳＯが滴下されることにより、塊が多量に発生していた。 (Comparative Example 4)
A slurry of an acrylic polymer was prepared in the same manner as in Comparative Example 3 except that the addition time for addition of the hydrous acrylic polymer and DMSO (JIS K9702 standard, reagent grade) was 1.5 minutes. The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 .6W / m 3, input rate of the water-containing acrylic polymer per fluid unit volume was 3952kg / m 3 / hr. The temperature of the fluid was about 22 ° C. During the addition of the water-containing acrylic polymer and DMSO, it was observed that DMSO was dropped onto the water-containing acrylic polymer floating on the liquid surface of the stirring tank. The resulting acrylic polymer slurry was a metal mesh sieve having a mesh size of 1.7 mm according to JIS Z-8801-1 (2006), the balance being 0.7 g, and the charged acrylic polymer was charged. The formation of a lump of about 2 parts by weight (washed with water, dried at 80 ° C. for 3 hours and then dried) with respect to 100 wt. A large amount of lumps were generated by adding DMSO instead of water-containing DMSO and dropping DMSO onto the water-containing acrylic polymer floating on the liquid surface of the stirring tank.
　（比較例５）
　含水アクリル系重合体及びＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）９５重量％と水５重量％からなる含水ＤＭＳＯの追加添加時の投入時間を１．５分とした以外は、実施例３と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨは約３ｃｍ、Ｈ／Ｄの値は０．３８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．６Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は３９５２ｋｇ／ｍ3／ｈｒであった。流動体の温度は約２２℃であった。含水アクリル系重合体及び含水ＤＭＳＯの追加添加時に、攪拌槽の液面上に浮遊する含水アクリル系重合体に含水ＤＭＳＯが滴下される状況が認められた。得られたアクリル系重合体のスラリーは、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分が０．１ｇ程度認められた。 (Comparative Example 5)
Except for the addition time of 1.5 minutes for the addition of water-containing acrylic polymer and DMSO (JIS K9702 standard, reagent grade) 95% by weight and water-containing DMSO consisting of 5% by weight water, the same as in Example 3. Thus, an acrylic polymer slurry was prepared. The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required power for stirring Pv per unit volume of the fluid calculated by Equations 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent was 1.6 W. / m 3, input rate of the water-containing acrylic polymer per fluid unit volume was 3952kg / m 3 / hr. The temperature of the fluid was about 22 ° C. During the addition of the water-containing acrylic polymer and the water-containing DMSO, a situation was observed in which the water-containing DMSO was dripped into the water-containing acrylic polymer floating on the liquid surface of the stirring tank. The resulting acrylic polymer slurry was found to have a residue of about 0.1 g on a metal mesh screen having a mesh size of 1.7 mm in accordance with JIS Z-8801-1 (2006).
　（比較例６）
　含水アクリル系重合体及びＤＭＳＯ（ＪＩＳ　Ｋ９７０２規格、試薬特級）９５重量％と水５重量％からなる含水ＤＭＳＯの追加添加時の投入時間を１．５分とした以外は、実施例４と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨは約３ｃｍ、Ｈ／Ｄの値は０．３８であった。また、流動体の２３℃での粘度μは０．０３ｋｇ／ｍ／ｓｅｃ、密度ρは１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは１．６Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は３９５２ｋｇ／ｍ3／ｈｒであった。流動体の温度は約５０℃であった。含水アクリル系重合体及びＤＭＳＯ（試薬特級）の追加添加時に、攪拌槽の液面上に浮遊する含水アクリル系重合体に含水ＤＭＳＯが滴下される状況が認められた。得られたアクリル系重合体のスラリーは、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分が０．２ｇ程度であり、投入された含水アクリル系重合体の固形分１００重量に対して約０．５重量部（水で洗浄後、８０℃で３時間乾燥した後乾燥重量）の塊の発生が確認された。 (Comparative Example 6)
Except that the addition time for addition of hydrous DMSO consisting of 95% by weight of water-containing acrylic polymer and DMSO (JIS K9702 standard, reagent special grade) and 5% by weight of water was 1.5 minutes, the same as in Example 4. Thus, an acrylic polymer slurry was prepared. The fluid depth H of the fluid was about 3 cm, and the value of H / D was 0.38. Further, the viscosity μ of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ was 1100 kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 1 .6W / m 3, input rate of the water-containing acrylic polymer per fluid unit volume was 3952kg / m 3 / hr. The temperature of the fluid was about 50 ° C. During the addition of the water-containing acrylic polymer and DMSO (special reagent grade), it was observed that the water-containing DMSO was dropped onto the water-containing acrylic polymer floating on the liquid surface of the stirring tank. The resulting acrylic polymer slurry was a metal mesh sieve having a mesh size of 1.7 mm according to JIS Z-8801-1 (2006), and the remainder was about 0.2 g. Generation of a lump of about 0.5 parts by weight (washed with water, dried at 80 ° C. for 3 hours and then dried) with respect to 100% by weight of the solid content of the coalescence was confirmed.
　（比較例７）
　実施例２で得られたアクリル系重合体（固形分）１００重量部、水１１４．６重量部、ＤＭＳＯ２７６．７重量部からなるアクリル系重合体のスラリー（流動体）４００ｇを用いた以外は、実施例６と同様にしてアクリル系重合体のスラリーを作製した。流動体の液深さＨは約７．２ｃｍ、Ｈ／Ｄの値は０．９であった。また、流動体の２３℃での粘度μ＝０．０３ｋｇ／ｍ／ｓｅｃ、密度ρ＝１１００Ｋｇ／ｍ3であった。投入された含水アクリル系重合体及び含水溶剤による体積増を考慮せず、２３℃、バッフルなしの条件での上述した数式１～７にて算出した流動体単位体積あたりの攪拌所要動力Ｐｖは０．９０Ｗ／ｍ3、流動体単位体積あたりの含水アクリル重合体の投入速度は４１３ｋｇ／ｍ3／ｈｒであった。流動体の温度は約５０℃であった。含水アクリル系重合体及びＤＭＳＯ（試薬特級）の追加添加時に、攪拌槽の液面上に浮遊する含水アクリル系重合体に含水ＤＭＳＯが滴下される状況が認められた。得られたアクリル系重合体のスラリーは、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいで残分が０．２ｇ程度認められた。 (Comparative Example 7)
Except for using 400 g of an acrylic polymer slurry (fluid) consisting of 100 parts by weight of the acrylic polymer (solid content) obtained in Example 2, 114.6 parts by weight of water, and 276.7 parts by weight of DMSO, In the same manner as in Example 6, an acrylic polymer slurry was prepared. The fluid depth H of the fluid was about 7.2 cm, and the H / D value was 0.9. Further, the viscosity of the fluid at 23 ° C. was 0.03 kg / m / sec, and the density ρ = 1100 Kg / m 3 . The required stirring power Pv per unit volume of the fluid calculated by the above formulas 1 to 7 under the conditions of 23 ° C. and no baffle without considering the volume increase due to the added water-containing acrylic polymer and water-containing solvent is 0 90 W / m 3 , and the feeding rate of the water-containing acrylic polymer per unit volume of the fluid was 413 kg / m 3 / hr. The temperature of the fluid was about 50 ° C. During the addition of the water-containing acrylic polymer and DMSO (special reagent grade), it was observed that the water-containing DMSO was dropped onto the water-containing acrylic polymer floating on the liquid surface of the stirring tank. The resulting acrylic polymer slurry was found to have a residue of about 0.2 g with a metal mesh sieve having a mesh opening size of 1.7 mm in accordance with JIS Z-8801-1 (2006).
　下記表１に実施例３～９、比較例３～７における各種製造条件及びＪＩＳ　Ｚ－８８０１準拠の目開き１．７ｍｍのふるいでの残分に関する結果を纏めて示した。なお、下記表１において、ＪＩＳ　Ｚ－８８０１－１（２００６）準拠の目開き１．７ｍｍの金属製網ふるいでの残分の乾燥重量は、含水アクリル系重合体の固形分１００重量部あたりの重量部で示した。 Table 1 below summarizes the results of various production conditions in Examples 3 to 9 and Comparative Examples 3 to 7 and the residue on a sieve having a mesh opening size of 1.7 mm according to JIS Z-8801. In Table 1 below, the dry weight of the residue in a metal mesh sieve having a mesh size of 1.7 mm according to JIS Z-8801-1 (2006) is based on 100 parts by weight of the solid content of the hydrated acrylic polymer. It is shown in parts by weight.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の製造方法で得られたアクリル系重合体のスラリーは、水を蒸発除去して、アクリル系重合体が有機溶媒に溶解した溶液を調製し、得られたアクリル系重合体の有機溶媒溶液は、湿式紡糸において、紡糸原液として用いることができる。 The acrylic polymer slurry obtained by the production method of the present invention is prepared by evaporating and removing water to prepare a solution in which the acrylic polymer is dissolved in an organic solvent. The resulting acrylic polymer is an organic solvent solution. Can be used as a spinning dope in wet spinning.

Claims (7)

  1. 　単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％と、ハロゲン含有ビニル系モノマー２５～８０重量％を含む単量体混合物を水系媒体中で乳化重合し、凝固して得られたアクリル系重合体ａ１００重量部に対して、水５０～１５０重量部を含む含水アクリル系重合体ｂと、アクリル系重合体ａの良溶媒であり、かつ水混和性を有する有機溶剤ｃを用いて、アクリル系重合体ａ１００重量部に対して、水５０～１５０重量部及び有機溶剤ｃ２００～５００重量部を含むアクリル系重合体のスラリーを得るアクリル系重合体のスラリーの製造方法において、
    　有機溶剤ｃ、水及びアクリル系重合体ａを含み、液体成分中の有機溶剤ｃの含有量が９５重量％以下の流動体を混合しながら、前記流動体の液面において、含水アクリル系重合体ｂが水及び有機溶剤ｃからなる含水有機溶剤ｄと接触しないように、前記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合することを特徴とするアクリル系重合体のスラリーの製造方法。     Acrylic obtained by emulsion polymerization and coagulation of a monomer mixture containing 20 to 75% by weight of acrylonitrile and 25 to 80% by weight of a halogen-containing vinyl monomer with respect to the total weight of the monomer mixture. Water-containing acrylic polymer b containing 50 to 150 parts by weight of water with respect to 100 parts by weight of polymer a, and organic solvent c that is a good solvent for acrylic polymer a and has water miscibility, In the method for producing an acrylic polymer slurry, an acrylic polymer slurry containing 50 to 150 parts by weight of water and 200 to 500 parts by weight of an organic solvent c with respect to 100 parts by weight of the acrylic polymer a is obtained.
    A water-containing acrylic polymer is contained on the liquid surface of the fluid while mixing the fluid containing the organic solvent c, water, and the acrylic polymer a, and the content of the organic solvent c in the liquid component is 95% by weight or less. The acrylic heavy polymer is characterized in that the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added and mixed in the fluid so that b does not come into contact with the water-containing organic solvent d composed of water and the organic solvent c. A method for producing a combined slurry.
  2. 　前記流動体を攪拌機を備えた攪拌槽に投入し、該流動体を撹拌機で撹拌して混合しながら、前記流動体の液面において、含水アクリル系重合体ｂが水及び有機溶剤ｃからなる含水有機溶剤ｄと接触しないように、前記流動体中に含水アクリル系重合体ｂ及び含水有機溶剤ｄを各々投入して混合する際、攪拌槽の内径Ｄと攪拌槽内の流動体の液深さＨの比Ｈ／Ｄの値を０．３～０．７の範囲とし、流動体の単位体積あたり攪拌所要動力Ｐｖを１Ｗ／ｍ3以上とし、含水アクリル系重合体ｂの単位体積あたりの投入速度を１０００Ｋｇ／ｍ3／ｈｒ以下とし、得られたアクリル系重合体のスラリーを連続的に排出する請求項１に記載のアクリル系重合体のスラリーの製造方法。 The fluid-containing acrylic polymer b is composed of water and an organic solvent c on the liquid surface of the fluid while the fluid is put into a stirring tank equipped with a stirrer and the fluid is stirred and mixed with the stirrer. When the water-containing acrylic polymer b and the water-containing organic solvent d are respectively added to and mixed with the fluid so as not to come into contact with the water-containing organic solvent d, the inner diameter D of the stirring tank and the liquid depth of the fluid in the stirring tank The ratio H / D of the thickness H is in the range of 0.3 to 0.7, the stirring required power Pv per unit volume of the fluid is 1 W / m 3 or more, and the unit volume of the hydrous acrylic polymer b per unit volume 2. The method for producing an acrylic polymer slurry according to claim 1, wherein the charging rate is set to 1000 kg / m 3 / hr or less, and the obtained acrylic polymer slurry is continuously discharged.
  3. 　アクリル系重合体ａは、単量体混合物の全体重量に対してアクリロニトリル２０～７５重量％、ハロゲン含有ビニル系モノマー２４．９５～８０重量％、及びこれらと共重合可能な他のビニル系モノマー０．０５～５重量％を含む単量体混合物を共重合したものである請求項１又は２に記載のアクリル系重合体のスラリーの製造方法。 The acrylic polymer a contains 20 to 75% by weight of acrylonitrile, 24.95 to 80% by weight of a halogen-containing vinyl monomer, and other vinyl monomers that can be copolymerized therewith, based on the total weight of the monomer mixture. The method for producing an acrylic polymer slurry according to claim 1 or 2, wherein a monomer mixture containing 0.05 to 5% by weight is copolymerized.
  4. 　前記流動体は、水及び有機溶剤ｃからなる含水有機溶剤ｄを混合しながら、含水有機溶剤ｄへ含水アクリル系重合体ｂを投入して分散したものである請求項１～３のいずれか１項に記載のアクリル系重合体のスラリーの製造方法。 The fluid according to any one of claims 1 to 3, wherein the water-containing acrylic polymer b is added to and dispersed in the water-containing organic solvent d while mixing the water-containing organic solvent d composed of water and the organic solvent c. The manufacturing method of the slurry of the acrylic polymer as described in claim | item.
  5. 　前記流動体は０℃以上８０℃以下の温度に保持されている請求項１～４のいずれか１項に記載のアクリル系重合体のスラリーの製造方法。 The method for producing an acrylic polymer slurry according to any one of claims 1 to 4, wherein the fluid is maintained at a temperature of 0 ° C or higher and 80 ° C or lower.
  6. 　含水有機溶剤ｄは、有機溶剤ｃ９０～９８重量％及び水２～１０重量％からなる請求項１～５のいずれか１項に記載のアクリル系重合体のスラリーの製造方法。 6. The method for producing an acrylic polymer slurry according to claim 1, wherein the water-containing organic solvent d comprises 90 to 98% by weight of the organic solvent c and 2 to 10% by weight of water.
  7. 　有機溶剤ｃは、ジメチルスルホキシド、Ｎ，Ｎ－ジメチルアセトアミド及びＮ，Ｎ－ジメチルホルムアミドからなる群から選ばれる一種以上である請求項１～６のいずれか１項に記載のアクリル系重合体のスラリーの製造方法。 The acrylic polymer slurry according to any one of claims 1 to 6, wherein the organic solvent c is at least one selected from the group consisting of dimethyl sulfoxide, N, N-dimethylacetamide and N, N-dimethylformamide. Manufacturing method.
PCT/JP2016/053065 2015-02-23 2016-02-02 Method for producing slurry of acrylic polymer WO2016136403A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5143427A (en) * 1974-10-07 1976-04-14 Mitsubishi Rayon Co AKURIRONITORIRUKEIJUGOTAIKARANO BOSHOYOEKINO SEIZOHO
JPS627429A (en) * 1985-07-03 1987-01-14 Kanegafuchi Chem Ind Co Ltd Method for obtaining colloidal particle aggregate
JPS62236829A (en) * 1986-04-08 1987-10-16 Kanegafuchi Chem Ind Co Ltd Closely packed spherical body of polymer latex particle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5143427A (en) * 1974-10-07 1976-04-14 Mitsubishi Rayon Co AKURIRONITORIRUKEIJUGOTAIKARANO BOSHOYOEKINO SEIZOHO
JPS627429A (en) * 1985-07-03 1987-01-14 Kanegafuchi Chem Ind Co Ltd Method for obtaining colloidal particle aggregate
JPS62236829A (en) * 1986-04-08 1987-10-16 Kanegafuchi Chem Ind Co Ltd Closely packed spherical body of polymer latex particle

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