WO2021261568A1 - Dust scattering inhibitor - Google Patents

Dust scattering inhibitor Download PDF

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Publication number
WO2021261568A1
WO2021261568A1 PCT/JP2021/024014 JP2021024014W WO2021261568A1 WO 2021261568 A1 WO2021261568 A1 WO 2021261568A1 JP 2021024014 W JP2021024014 W JP 2021024014W WO 2021261568 A1 WO2021261568 A1 WO 2021261568A1
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WO
WIPO (PCT)
Prior art keywords
mass
emulsion
less
deposit
parts
Prior art date
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PCT/JP2021/024014
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French (fr)
Japanese (ja)
Inventor
和也 渡邉
貫治 中尾
和歩 林
Original Assignee
株式会社日本触媒
石原ケミカル株式会社
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Application filed by 株式会社日本触媒, 石原ケミカル株式会社 filed Critical 株式会社日本触媒
Priority to BR112022026010A priority Critical patent/BR112022026010A2/en
Priority to AU2021296105A priority patent/AU2021296105A1/en
Publication of WO2021261568A1 publication Critical patent/WO2021261568A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G3/00—Storing bulk material or loose, i.e. disorderly, articles
    • B65G3/02—Storing bulk material or loose, i.e. disorderly, articles in the open air
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/22—Materials not provided for elsewhere for dust-laying or dust-absorbing

Definitions

  • the present invention relates to a novel agent, particularly a dust scattering inhibitor and the like.
  • Minerals and earth and sand in ironworks and quarries are deposited in the open air, for example, they are stored as open-stacked sediments, but there is a problem that dust is scattered from the sediments and pollutes the neighborhood.
  • chemicals such as water and an aqueous solution of calcium chloride have been sprayed.
  • Patent Document 1 discloses that a surfactant is used to prevent dust scattering of minerals.
  • An object of the present invention is to provide a novel agent (particularly, a dust scattering inhibitor).
  • the present inventor has found that the scattering of dust can be suppressed by using an emulsion of an acid group-containing polymer. Further, the present inventor has also found that, according to one aspect, the scattering of dust can be suppressed even after being exposed to a high temperature environment, and further research has been carried out to complete the present invention.
  • a dust scattering inhibitor containing an emulsion of an acid group-containing polymer.
  • a coagulant for open-stacked deposits containing an emulsion of acid group-containing polymers.
  • the agent according to [1] or [2], wherein the dust or deposit is a raw material for steelmaking.
  • a deposit of sedimentary components which contains an emulsion of an acid group-containing polymer.
  • a method for producing a sediment in which an emulsion of an acid group-containing polymer is sprayed on a sediment component.
  • the sediment components that is, the powders of the constituent components of the sediment are easily bundled with each other to increase the cohesiveness, and as a result, the sediment is wet and spread (adhered) to the transport equipment such as a belt conveyor. ) Can be suppressed and the handling of sediments can be improved. As a result, it is possible to facilitate the movement of sediment in a transport facility such as a belt conveyor.
  • the elution property into water is low, it is possible to efficiently suppress dust scattering even when exposed to rain.
  • the amount of water used can be reduced, so that the suppression of dust scattering can be efficiently suppressed. It can be realized.
  • the present invention it is possible to provide a novel coagulant for open-stacked sediments. According to such an agent, since the powder of the sedimentary component can be easily bundled, the collapse of the sediment can be suppressed and the sediment can be efficiently transported even in the step of transporting the sediment before and after the open stacking.
  • the agent of the present invention contains an emulsion of an acid group-containing polymer.
  • the agent of the present invention can be used for various purposes, for example, as a dust scattering inhibitor and a coagulant for open-stacked sediments.
  • emulsion of acid group-containing polymer An emulsion of an acid group-containing polymer (hereinafter, simply referred to as “emulsion (A)”) is usually an acid group-containing polymer or polymer particles in an emulsion state dispersed in a solvent.
  • the acid group-containing polymer In the acid group-containing polymer (hereinafter, simply referred to as "polymer (B)"), examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the acid group may be one or more, and may have a different kind of acid group.
  • the polymerization component of the polymer (B), that is, the monomer component usually contains an acid group-containing monomer.
  • the polymer (B) may be a polymer having a structural unit derived from an acid group-containing monomer.
  • the acid group-containing monomer may have one or more acid groups, or may have a different kind of acid group.
  • the acid group-containing monomer examples include a carboxylic acid group-containing monomer [for example, an unsaturated monocarboxylic acid (for example, an aliphatic unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, and crotonic acid), and an unsaturated dicarboxylic acid (for example, malein).
  • a carboxylic acid group-containing monomer for example, an unsaturated monocarboxylic acid (for example, an aliphatic unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, and crotonic acid), and an unsaturated dicarboxylic acid (for example, malein).
  • Acids aliphatic unsaturated dicarboxylic acids such as fumaric acid), acid anhydrides (eg, maleic anhydride, itaconic anhydride)], sulfonic acid group-containing monomers [eg, vinyl-based monomers (eg, vinyl sulfonic acid), styrene System monomer (eg, styrene sulfonic acid)], phosphate group-containing monomer ⁇ eg, phosphate mono to triester [eg, mono (2-methacryloyloxyethyl) phosphate, mono (2-acryloyloxyethyl) phosphate, 2- (Meta) acryloyloxypropyl phosphate] ⁇ and the like.
  • the acid group-containing monomer may be anionized.
  • the acid group-containing monomer may be used alone or in combination of two or more.
  • At least a carboxylic acid group-containing monomer from the viewpoint of suppressing dust scattering and coagulation of sediments.
  • the polymerization component of the polymer (B) may contain a monomer other than the acid group-containing monomer.
  • the polymer (B) may have structural units derived from other monomers.
  • the other monomer is not particularly limited, but is, for example, an aliphatic (meth) acrylate ⁇ for example, C such as an alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like. 1-20 alkyl (meth) acrylic], alkoxyalkyl (meth) acrylate [eg, C 1-12 alkoxy C 1-12 alkyl methacrylate such as 2-methoxyethyl (meth) acrylate] ⁇ , alicyclic (meth) acrylate.
  • C aliphatic (meth) acrylate
  • C such as an alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like. 1-20 alkyl (meth) acrylic], alkoxyalkyl (meth
  • cycloalkyl (meth) acrylate for example, C 4-20 cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate], crosslinked cyclic (meth) acrylate [for example, isobornyl (meth) acrylate, adamantyl (meth). ) Acrylate] ⁇ , hydroxyl group-containing (meth) acrylate ⁇ for example, hydroxyalkyl (meth) acrylate [for example, hydroxy C 2-10 alkyl (meth) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
  • styrene-based monomers eg, styrene, vinyltoluene, ⁇ -methylstyrene, ethylvinylbenzene, chloromethylstyrene
  • (meth) acrylamide-based monomers eg, (meth) acrylamide, N-monomethyl (meth) Acrylate (meth) acrylic acid such as acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide
  • polyalkylene glycol chain-containing monomer for example, polyethylene glycol (meth) acrylic ester, and polyalkylene glycol.
  • n may be preferably 10 to 100, more preferably 20 to 80, still more preferably 40 to 60, particularly preferably 45 to 55 or the like.
  • the hydrocarbon group of R 2 includes, for example, a linear alkyl group (for example, a hexyl group, a heptyl group, an octyl group, a nonyl group, a dodecyl group, an octadecyl group) and a branched alkyl group (for example, for example.
  • a linear alkyl group for example, a hexyl group, a heptyl group, an octyl group, a nonyl group, a dodecyl group, an octadecyl group
  • a branched alkyl group for example, for example.
  • the hydrocarbon group may be partially substituted. Further, the carbon number of R 2 may be preferably 8 to 30, more preferably 12 to 20, particularly preferably 16 to 20, and the like.
  • the polymer (B) may contain at least an acid group-containing polymer as a polymerization component and an aliphatic (meth) acrylate as another monomer.
  • the proportion of the acid group-containing monomer in the entire monomer component of the polymer (B) is, for example, 5 from the viewpoint of suppressing dust scattering and coagulation of sediments. It may be mass% or more, preferably 15% by mass or more, more preferably 25% by mass or more, or a relatively high proportion (for example, 50% by mass or more).
  • the upper limit of the ratio of the acid group-containing monomer in the entire monomer component (a) may be, for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less.
  • An appropriate range (for example, not limited to 5 to 99% by mass, and other upper limit values and lower limit values may be combined) may be set by appropriately combining these upper limit values and lower limit values.
  • the proportion of the acid group-containing monomer in the entire monomer component (a) is, for example, 5 mol% or more (for example, 10 mol% or more), preferably 15 mol%, from the viewpoint of suppressing dust scattering and coagulation of deposits. It may be more than (for example, 20 mol% or more), more preferably 25 mol% or more (for example, 30 mol% or more), and a relatively high ratio (for example, 35 mol% or more, 40 mol% or more, 45). It may be mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 75 mol% or more, etc.).
  • the upper limit of the proportion of the acid group-containing monomer in the entire monomer component (a) is, for example, 99 mol% or less (for example, 95 mol% or less), preferably 90 mol% or less (for example, 85 mol% or less). It may be preferably 80 mol% or less (for example, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less) and the like.
  • An appropriate range may be set by appropriately combining these upper limit values and lower limit values (for example, not limited to 5 to 99 mol%, but other upper limit values and lower limit values may be combined).
  • the proportion of other monomers in the entire monomer component (a) is not particularly limited, but is, for example, 0.1% by mass or more (for example, 0.5% by mass or more), preferably 1% by mass or more (for example, 1. 5% by mass or more), more preferably 2% by mass or more (for example, 2.5% by mass or more), and a relatively high proportion (for example, 3% by mass or more, 5% by mass or more, 10% by mass or more).
  • 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more) and the like may be used.
  • the upper limit of the ratio of other monomers in the entire monomer component (a) is, for example, 80% by mass or less (for example, 70% by mass or less), preferably 60% by mass or less (for example, 50% by mass or less), more preferably. May be 45% by mass or less (for example, 40% by mass or less).
  • An appropriate range may be set by appropriately combining these upper limit values and lower limit values (for example, not limited to 5 to 60% by mass, but other upper limit values and lower limit values may be combined).
  • the proportion of the aliphatic (meth) acrylate in the entire monomer component (a) is, for example, 10% by mass or more (for example, 13% by mass). % Or more), preferably 15% by mass or more (for example, 18% by mass or more), more preferably 20% by mass or more (for example, 23% by mass or more), and a relatively high proportion (for example, 25% by mass). % Or more, 28% by mass or more, 30% by mass or more, 33% by mass or more, 35% by mass or more, 38% by mass or more, 40% by mass or more, etc.).
  • the upper limit of the aliphatic (meth) acrylate ratio in the entire monomer component (a) is, for example, 80% by mass or less (for example, 70% by mass or less), preferably 60% by mass or less (for example, 50% by mass or less). ), More preferably 45% by mass or less (for example, 40% by mass or less) and the like.
  • the proportion of the other monomer (b) in the entire monomer component (a) is, for example, 0.1% by mass or more (for example,). It may be 0.5% by mass or more, preferably 1% by mass or more (for example, 5% by mass or more), more preferably 10% by mass or more (for example, 15% by mass or more), and a relatively high proportion (for example, 15% by mass or more). For example, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, etc.) may be used.
  • the upper limit of the ratio of the other monomer (b) in the entire monomer component (a) is, for example, 80% by mass or less (for example, 70% by mass or less), preferably 60% by mass or less (for example, 50%). It may be (% by mass or less), more preferably 45% by mass or less (for example, 40% by mass or less) and the like.
  • the glass transition temperature of the polymer (B) is, for example, ⁇ 40 ° C. or higher, preferably ⁇ 30 ° C. or higher, more preferably ⁇ 20 ° C. or higher, particularly preferably ⁇ 10 ° C. or higher, from the viewpoint of film-forming property. You may.
  • the upper limit of the glass transition temperature of the polymer (B) may be, for example, 80 ° C. or lower, preferably 75 ° C. or lower, more preferably 65 ° C. or lower, particularly preferably 50 ° C. or lower.
  • the weight average molecular weight of the polymer (B) may be, for example, 1 million or more, preferably 3 million or more, and more preferably 5 million or more from the viewpoint of cohesive force, cohesive force and the like.
  • the upper limit of the weight average molecular weight of the polymer (B) may be, for example, 50 million or less from the viewpoint of cohesive force, cohesive force and the like.
  • the weight average molecular weight is measured using, for example, gel permeation chromatography [for example, manufactured by Toso Co., Ltd., product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L are used in series] ( It may be measured by a molecular weight measuring device (DLS-8000 manufactured by Otsuka Denshi Co., Ltd.) by a static light scattering method.
  • a molecular weight measuring device DLS-8000 manufactured by Otsuka Denshi Co., Ltd.
  • the acid value of the emulsion (A) is, for example, 40 mg KOH / g or more (for example, 45 mg KOH / g or more), preferably 50 mg KOH / g or more (for example, 50 mg KOH / g or more) from the viewpoint of suppressing dust scattering and coagulation of deposits. 55 mg KOH / g or higher), more preferably 60 mg KOH / g or higher (eg, 65 mg KOH / g or higher), particularly preferably 70 mg KOH / g or higher (eg, 75 mg KOH / g or higher, 80 mg KOH / g or higher, 85 mg KOH).
  • the upper limit of the acid value of the emulsion (A) is, for example, 500 mg KOH / g or less (for example, 450 mg KOH / g or less), preferably 400 mg KOH / g or less (for example, 350 mg KOH / g or less), more preferably. May be 300 mg KOH / g or less (for example, 280 mg KOH / g or less).
  • the acid value of the emulsion (A) for example, the acid value (mgKOH / g) per 1 g of the resin solid content may be measured by an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.).
  • the viscosity of the emulsion (A) is, for example, 10,000 mPa ⁇ s or less, preferably 5,000 mPa ⁇ s or less, more preferably 2,000 mPa ⁇ s or less, and particularly preferably 1, from the viewpoint of the dispersability of the emulsion. It may be 500 mPa ⁇ s or less. Further, the lower limit of the viscosity of the emulsion (A) may be, for example, 10 mPa ⁇ s or more.
  • a BM viscometer manufactured by Toki Sangyo Co., Ltd., product number: TVB-10M
  • TVB-10M BM viscometer
  • the average particle size of the emulsion particles may be, for example, 30 nm or more, preferably 50 nm or more, from the viewpoint of the viscosity of the emulsion, the impregnation property with respect to the deposit, and the like.
  • the upper limit of the average particle size of the emulsion particles may be, for example, 3,000 nm or less, preferably 1,000 nm or less.
  • the average particle size of the emulsion particles is the volume average particles measured using a particle size distribution measuring device [Particle Sizing Systems, trade name: NICOMP Model 380] by a dynamic light scattering method. It may be a diameter.
  • the solid content (nonvolatile content) of the polymer (B) in the emulsion (A) is, for example, 0.5% by mass or more (for example, 1% by mass or more) from the viewpoint of suppressing dust scattering and coagulation of deposits. It may be preferably 3% by mass or more (for example, 5% by mass or more), more preferably 10% by mass or more (for example, 13% by mass or more, 15% by mass or more, 17% by mass or more, 20% by mass or more) or the like. From the viewpoint of handleability and the like, for example, it may be 60% by mass or less, preferably 50% by mass or less.
  • non-volatile content of the polymer (B) in the emulsion (A) for example, 1 g of the emulsion (A) was weighed and dried in a hot air dryer at a temperature of 110 ° C. for 1 hour, and the obtained residue was used as the non-volatile content.
  • [Non-volatile content (mass%) in emulsion (A)] ([mass of residue] ⁇ [emulsion (A) 1 g]) ⁇ 100 Can be calculated based on.
  • the emulsion (A) may contain a solvent other than the polymer (B).
  • the solvent include water and an aqueous solvent such as a solvent containing water [for example, a mixed solvent of water and an alcohol (for example, C 1-4 alcohol such as methanol and ethanol)].
  • the solvent may be used alone or in combination of two or more.
  • the emulsion (A) preferably contains water as a solvent, and is preferably an aqueous dispersion.
  • the method for producing the emulsion (A) is not particularly limited, but for example, it may be produced by emulsion polymerization of the monomer component which is the raw material of the polymer (B) in a solvent.
  • the solvent examples include water and an aqueous solvent such as a solvent containing water [for example, a mixed solvent of water and an alcohol (for example, C 1-4 alcohol such as methanol and ethanol)].
  • a solvent containing water for example, a mixed solvent of water and an alcohol (for example, C 1-4 alcohol such as methanol and ethanol)
  • the solvent may be used alone or in combination of two or more.
  • the method for emulsion-polymerizing the monomer component is not particularly limited, but for example, a method of polymerizing by dropping the monomer component into a solvent containing an emulsifier, a method of dropping a monomer component emulsified with an emulsifier in advance into the solvent, or the like.
  • a method of polymerizing and the like can be mentioned.
  • the amount of the solvent may be appropriately set in consideration of the amount of non-volatile content contained in the obtained emulsion and the like.
  • the emulsifier is not particularly limited, and for example, an anionic emulsifier (for example, an alkyl sulfonate salt such as ammonium dodecyl sulfate or sodium dodecyl sulfate; an alkyl sulfonate salt such as ammonium dodecyl sulfonate or sodium dodecyl sulfonate; ammonium dodecylbenzene sulfonate, sodium dodecyl).
  • an anionic emulsifier for example, an alkyl sulfonate salt such as ammonium dodecyl sulfate or sodium dodecyl sulfate; an alkyl sulfonate salt such as ammonium dodecyl sulfonate or sodium dodecyl sulfonate; ammonium dodecylbenzene sulfonate, sodium dodecyl.
  • Alkylaryl sulfonate salts such as naphthalene sulfonate; polyoxyethylene alkyl sulphate salt; polyoxyethylene alkyl aryl sulphate salt; polyoxyethylene alkyl ether sulfate; dialkyl sulfosuccinate; aryl sulfonic acid-formalin condensate; ammonium laurylate, sodium
  • Nonionic emulsifiers eg, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acids, etc.
  • cationic emulsifiers eg, dialkyldimethylammonium salt, ester-type dialkylammonium
  • Acrylic acid-based water-soluble polymers hydroxyethyl (meth) acrylic acid-based water-soluble polymers; hydroxypropyl (meth) acrylic acid-based water-soluble polymers; polyvinylpyrrolidone, etc.) and the like.
  • One type or two or more types of emulsifiers may be used.
  • the amount of the emulsifier to be used may be appropriately set according to the type of emulsifier and the like, and is not particularly limited, but is, for example, 0.1 part by mass or more, preferably 0.5 part by mass with respect to 100 parts by mass of the monomer component (a). It may be 20 parts by mass or less, preferably 15 parts by mass or less.
  • the polymerization may be carried out in the presence of a polymerization initiator.
  • a polymerization initiator examples include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (2,2-azobis).
  • 2-Diaminopropane) Hydrochloride azo compounds such as 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; peroxides Examples thereof include peroxides such as hydrogen, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
  • the polymerization initiator may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be appropriately set according to the type of the polymerization initiator and the like, and is not particularly limited, but is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the monomer component (a). May be 0.1 parts by mass or more, and may be, for example, 2 parts by mass or less, preferably 1 part by mass or less.
  • the method of adding the polymerization initiator is not particularly limited, and examples thereof include batch charging, split charging, and continuous dropping.
  • a reducing agent for example, sodium hydrogen sulfite
  • a decomposition agent for the polymerization initiator for example, a transition metal salt such as ferrous sulfate
  • a chain transfer agent for example, a thiol group
  • the atmosphere at the time of polymerization is not particularly limited, but may be an inert gas such as nitrogen gas from the viewpoint of polymerization efficiency and the like.
  • the polymerization temperature is not particularly limited, but may be, for example, 50 to 100 ° C, preferably 60 to 95 ° C.
  • the polymerization temperature may be constant or may be changed during the polymerization reaction.
  • the polymerization time is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is, for example, 1 hour or more (for example, 1 to 24 hours), preferably 2 to 12 hours (for example, 2 to 9 hours). It may be about time).
  • the agent of the present invention particularly the dust scattering inhibitor and the coagulant for the piled up deposits, usually contains an emulsion (A) which is an emulsion of the above-mentioned polymer (B).
  • deposit (C1) By spraying or mixing the agent of the present invention on a deposit containing dust (hereinafter, deposit (C1)), the scattering of dust can be suppressed.
  • the deposit (C1) may be a dust-only deposit or a deposit containing at least dust, for example, a deposit containing lumps other than dust.
  • the agent of the present invention can be coagulated by spraying or mixing the piled up deposits (hereinafter referred to as deposits (C2)).
  • the deposit (C2) may be the same as the deposit (C1) described above.
  • the amount of dust contained in the deposit depends on the type of dust and the like, but may be, for example, 0.1 part by mass or more, 10 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of the deposit. May be.
  • the amount of dust contained in the deposit may be, for example, 30 parts by mass or less, 10 parts by mass or less, and 1 part by mass or less with respect to 100 parts by mass of the deposit.
  • the amount of dust contained in the deposit may be, for example, 0.1 part by mass or more, 10 parts by mass or more, and 30 parts by mass with respect to 100 parts by mass of the deposit.
  • the amount of dust contained in the deposit may be, for example, 0.1 part by mass or more and 30 parts by mass or more with respect to 100 parts by mass of the deposit. It may be 10 parts by mass or less, 30 parts by mass or less, or 1 part by mass or less.
  • the particle size of the dust depends on the type of dust, but may be, for example, 5,000 ⁇ m or less, preferably 1,000 ⁇ m or less.
  • the type of deposit (C1) or deposit (C2) is not particularly limited, but is, for example, minerals (for example, iron ore, copper ore, nickel ore, other metal ores, slag, limestone, etc.), carbonaceous substances (, etc.). For example, coal, coke, etc.), soil, sand, earth and sand, etc. may be mentioned. Further, the deposit (C1) or the deposit (C2) may be, for example, an iron-making raw material such as iron ore, slag, limestone, coal, or coke. Further, the deposit (C1) or the deposit (C2) may be basic. The deposit (C1) or the deposit (C2) may be one kind or two or more kinds.
  • Typical examples of the deposit (C1) or the deposit (C2) include a pile of iron ore, a pile of coal, and the like.
  • a pile of iron ore may usually be formed solely of iron ore.
  • the deposit (C1) is preferably piled up in the open.
  • the height of the deposit (C1) or the deposit (C2), that is, the maximum height may be, for example, 5 m or more, preferably 10 m or more.
  • the width of the deposit (C1) or the deposit (C2), that is, the maximum width may be, for example, 5 m or more, preferably 30 m or more.
  • the weight of the deposit (C1) or the deposit (C2) depends on the type of the deposit, but for example, in the case of iron ore, it may be about several thousand to 10,000 tons.
  • the deposit (C1) or the deposit (C2) has a particle size of, for example, 15 mm or more (for example, 10 mm or more), preferably 5 mm or more (for example, 3 mm or more), more preferably, although it depends on the type of the deposit. May contain sedimentary components such as 1 mm or more.
  • the sediment (C1) or the deposit (C2) may have a water content or a water absorption rate of, for example, 0.01% by mass or more, preferably 5% by mass or more with respect to the total amount of the sediment. Further, the sediment (C1) or the deposit (C2) may have a water content of, for example, 50% by mass or less, preferably 30% by mass or less, and more preferably 10% by mass or less with respect to the total amount of the sediment. The water content may be, for example, the ratio of water released after heating at 105 ° C. for 2 hours to the total amount of sediment.
  • the proportion of the polymer (B) is, for example, 0. 01 parts by mass or more (for example, more than 0.05 parts by mass, 0.06 parts by mass or more, 0.07 parts or more), preferably 0.08 parts by mass or more (for example, 0.09 parts by mass or more), more preferably.
  • 0.1 parts by mass or more for example, 0.11 parts by mass or more, 0.12 parts by mass or more, 0.13 parts by mass or more, 0.14 parts by mass or more
  • particularly preferably 0.15 parts by mass or more for example, It may be used so as to be 0.16 parts by mass or more, 0.17 parts by mass or more, 0.18 parts by mass or more, 0.19 parts by mass or more, and a relatively high ratio (for example, 0.2 parts by mass).
  • Parts or more, 0.3 parts by mass or more, 0.4 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, 0.7 parts by mass or more, 0.8 parts by mass or more, 0.9 parts by mass As mentioned above, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 7 parts by mass or more, 10 parts by mass or more, etc. may be used.
  • the proportion of the polymer (B) is, for example, 30 parts by mass or less with respect to 100 parts by mass of the deposit (C1) or the deposit (C2) from the viewpoint of cost, environmental load and the like. (Preferably 25 parts by mass or less), preferably 20 parts by mass or less (for example, 10 parts by mass or less), more preferably 5 parts by mass or less (for example, 3 parts by mass or less, 1 part by mass or less) and the like. You may use it.
  • the present invention also includes a deposit (hereinafter, deposit (D)) containing an emulsion (A) which is an emulsion of the polymer (B).
  • the deposit (D) may be a sedimentary component, i.e., a deposit of a constituent of the deposit.
  • the deposit (D) may be a piled up in the open, or may be a deposit in the transportation process before and after the open up.
  • the type and size of the sediment (D) or the sedimentary component of the deposit (D) may be the same as that of the above-exemplified sediment (C1) or sediment (C2).
  • the proportion of the polymer (B) in the entire deposit (D) is, for example, 0.01% by mass or more (for example, more than 0.05% by mass, 0.06% by mass or more, 0.07% by mass or more), preferably. Is 0.08% by mass or more (for example, 0.09% by mass or more), more preferably 0.1% by mass or more (for example, 0.11% by mass or more, 0.12% by mass or more, 0.13% by mass or more). , 0.14% by mass or more), particularly preferably 0.15% by mass or more (for example, 0.16% by mass or more, 0.17% by mass or more, 0.18% by mass or more, 0.19% by mass or more) and the like.
  • the upper limit of the proportion of the polymer (B) in the entire deposit (D) is, for example, 30% by mass or less (for example, 25% by mass or less), preferably 20% by mass or less (for example, 10% by mass or less). , More preferably 5% by mass or less (for example, 3% by mass or less, 1% by mass or less) and the like.
  • the deposit (D) can be obtained by spraying or mixing the emulsion (A), which is an emulsion of the polymer (B), with the sediment component, that is, the constituent component of the deposit. That is, the present invention also includes a method for producing a sediment, in which the emulsion (A) of the polymer (B) is sprayed on a sediment component, that is, a constituent component of the sediment.
  • the method of spraying the emulsion (A) on the deposited component is not particularly limited, but for example, various (drop) spraying devices such as a sprinkler, a spray, a shower nozzle, a vinyl chloride pipe, and a sprinkler may be used.
  • various (drop) spraying devices such as a sprinkler, a spray, a shower nozzle, a vinyl chloride pipe, and a sprinkler may be used.
  • a rod-shaped spray may be used from the discharge port, or a fine shower ring may be preferably used from the viewpoint of increasing the adhesion efficiency to the deposit and enhancing the dust suppressing effect. Further, it may be mixed with a base at the time of spraying and sprayed.
  • the timing of spraying the emulsion (A) on the sedimentary components may be any timing, and the deposits before and before the field stacking may be sprayed during the transportation of the belt conveyor, or during the field stacking work. It may also be sprayed on the sediment after being piled up in the open.
  • the agent is preferably in the form of containing water (for example, an emulsion (A) containing water, a water-diluted solution of the emulsion (A), etc.).
  • water for example, an emulsion (A) containing water, a water-diluted solution of the emulsion (A), etc.
  • spraying it is preferable to spray the emulsion (A) containing water or the water-diluted solution of the emulsion (A).
  • the solid content of the emulsion (A) in the emulsion (A) (or agent), that is, the concentration of the solid content of the emulsion (A) and the emulsifier can be efficiently sprayed, dust scattering is suppressed, and the coagulation property of the deposit is satisfied.
  • the solid content concentration in the emulsion (A) (or agent) is, for example, 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, from the viewpoint of efficient spraying. May be good.
  • the solid content concentration in the emulsion (A) (or agent) may be a relatively high concentration (for example, 40% by mass or more) or a relatively low concentration (for example, 20% by mass or less). May be good.
  • the emulsion (A) (or agent) having a relatively high solid content concentration may be diluted with water or the like and sprayed.
  • the viscosity of the emulsion (A) (or agent) is, for example, 0 mPa ⁇ s or more, preferably 20 mPa ⁇ s or more, more preferably 30 mPa, from the viewpoints of efficient spraying, suppression of dust scattering, coagulation of deposits, and the like. -It may be s or more.
  • the viscosity of the emulsion (A) (or agent) is, for example, 5,000 mPa ⁇ s or less, preferably 2,000 mPa ⁇ s or less, more preferably 1,000 mPa ⁇ s or less, from the viewpoint of efficient spraying. And so on.
  • the viscosity of the emulsion (A) (or agent) may be measured at 25 ° C. at a rotation speed of 30 rpm using, for example, a BM viscometer (manufactured by Toki Sangyo Co., Ltd., product number: TVB-10M).
  • the emulsion (A) may be sprayed so that the ratio of the polymer (B) to the sediment component is in the same range as the ratio to the above-exemplified deposit (C1) or deposit (C2).
  • Example 1 A sample was prepared by diluting a polycarboxylic acid-based emulsion WR-517 (solid content 30%, acid value 245 mg KOH / g, manufactured by Nippon Catalyst Co., Ltd.) with deionized water so as to have a solid content of 5%. To 110 parts of Brazilian Carajás iron ore having a water content of 10% and sieved with a mesh opening of 1 mm, 10 parts of a sample adjusted to have a solid content of 5% was added and subjected to the above evaluation.
  • WR-517 solid content 30%, acid value 245 mg KOH / g, manufactured by Nippon Catalyst Co., Ltd.
  • Example 2 The procedure was the same as in Example 1 except for the solid content adjustment.
  • Example 5 The same procedure as in Example 1 was carried out except that the Brazilian Carajás iron ore having a water content of 10% was classified by a sieve having an opening of 5 mm and the solid content was adjusted.
  • Example 6 The same procedure as in Example 1 was carried out except that the polycarboxylic acid emulsion WR-650 (solid content 30%, acid value 255 mg KOH / g, manufactured by Nippon Shokubai Co., Ltd.) was used at a solid content of 30%.
  • Example 7 Polycarboxylic acid emulsion WR-517-A (Nippon Shokubai Co., Ltd. solid content 30%, acid value 275 mg KOH / g)
  • Example 8 Polycarboxylic acid emulsion WR-517-B (Nippon Shokubai Co., Ltd. solid content 30%, acid value 120 mg KOH / g)
  • Example 9 Polycarboxylic acid emulsion WR-517-C (Nippon Shokubai Co., Ltd. solid content 30%, acid value 145 mg KOH / g)
  • Example 10 Polycarboxylic acid emulsion WR-517-D (Nippon Shokubai Co., Ltd. solid content 30%, acid value 115 mg KOH / g)
  • Tables 1 and 2 show a summary of these results.

Abstract

The present invention provides a novel agent.　A dust scattering inhibitor according to the present invention contains an emulsion of an acid group-containing polymer.

Description

粉塵飛散抑制剤Dust scattering inhibitor
　本発明は、新規な剤、特に、粉塵飛散抑制剤等に関する。 The present invention relates to a novel agent, particularly a dust scattering inhibitor and the like.
　製鉄所や採石場等における鉱物や土砂は、野外に堆積、例えば、野積みされた堆積物として保管されているが、堆積物から粉塵が飛散し、近隣を汚染するという問題がある。
　従来、このような粉塵飛散抑制には、水や塩化カルシウム水溶液等の薬剤の散布が行われてきた。 Minerals and earth and sand in ironworks and quarries are deposited in the open air, for example, they are stored as open-stacked sediments, but there is a problem that dust is scattered from the sediments and pollutes the neighborhood.
Conventionally, in order to suppress such dust scattering, chemicals such as water and an aqueous solution of calcium chloride have been sprayed.
　このような中、特許文献１には、界面活性剤を、鉱物の粉塵飛散防止に使用することが開示されている。 Under such circumstances, Patent Document 1 discloses that a surfactant is used to prevent dust scattering of minerals.
特開昭５７－９８５７９号公報Japanese Unexamined Patent Publication No. 57-98579
　本発明の目的は、新規な剤（特に、粉塵飛散抑制剤）を提供することにある。 An object of the present invention is to provide a novel agent (particularly, a dust scattering inhibitor).
　本発明者は、上記課題を解決するために鋭意研究を重ねた結果、酸基含有ポリマーのエマルションを使用することにより、粉塵の飛散を抑制しうることなどを見出した。
　また、本発明者は、その中でも一態様によれば、高温環境下に曝された後にも粉塵の飛散を抑制しうることなども見出し、さらに研究を重ねて本発明を完成した。 As a result of diligent research to solve the above problems, the present inventor has found that the scattering of dust can be suppressed by using an emulsion of an acid group-containing polymer.
Further, the present inventor has also found that, according to one aspect, the scattering of dust can be suppressed even after being exposed to a high temperature environment, and further research has been carried out to complete the present invention.
　すなわち、本発明は、以下の発明等に関する。
［１］
　酸基含有ポリマーのエマルションを含有する、粉塵飛散抑制剤。
［２］
　酸基含有ポリマーのエマルションを含有する、野積みされた堆積物用の凝固剤。
［３］
　粉塵又は堆積物が、製鉄原料である、［１］又は［２］記載の剤。
［４］
　堆積成分の堆積物であって、酸基含有ポリマーのエマルションを含有する堆積物。
［５］
　酸基含有ポリマーのエマルションを堆積成分に散布する、堆積物の製造方法。
［６］
　堆積物が野積みされた製鉄原料である、［４］記載の堆積物又は［５］記載の製造方法。
［７］
　エマルションの酸価が１１０ｍｇ　ＫＯＨ／ｇ以上である［１］～［６］のいずれかに記載の剤、堆積物、又は製造方法。
［８］
　酸基が、カルボン酸基、スルホン酸基及びリン酸基から選択される１種以上である［１］～［７］のいずれかに記載の剤、堆積物、又は製造方法。
［９］
　酸基含有ポリマーのエマルションを用いた、粉塵の飛散抑制方法。
［１０］
　酸基含有ポリマーのエマルションを用いた、野積みされた堆積物の凝固方法。 That is, the present invention relates to the following inventions and the like.
[1]
A dust scattering inhibitor containing an emulsion of an acid group-containing polymer.
[2]
A coagulant for open-stacked deposits containing an emulsion of acid group-containing polymers.
[3]
The agent according to [1] or [2], wherein the dust or deposit is a raw material for steelmaking.
[4]
A deposit of sedimentary components, which contains an emulsion of an acid group-containing polymer.
[5]
A method for producing a sediment, in which an emulsion of an acid group-containing polymer is sprayed on a sediment component.
[6]
The deposit according to [4] or the production method according to [5], wherein the deposit is a raw material for steelmaking piled up in the open.
[7]
The agent, deposit, or production method according to any one of [1] to [6], wherein the acid value of the emulsion is 110 mg KOH / g or more.
[8]
The agent, deposit, or production method according to any one of [1] to [7], wherein the acid group is one or more selected from a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
[9]
A method for suppressing dust scattering using an emulsion of an acid group-containing polymer.
[10]
A method for coagulating open-stacked sediments using an emulsion of an acid group-containing polymer.
　本発明によれば、新規な剤（特に、粉塵飛散抑制剤）を提供できる。 According to the present invention, it is possible to provide a novel agent (particularly, a dust scattering inhibitor).
　本発明の他の態様によれば、高温環境下に曝された後にも粉塵の飛散を抑制しうるため、夏場等においても粉塵の飛散抑制効果を奏しうる。 According to another aspect of the present invention, since it is possible to suppress the scattering of dust even after being exposed to a high temperature environment, it is possible to exert the effect of suppressing the scattering of dust even in the summer or the like.
　本発明の他の態様によれば、堆積成分すなわち、堆積物の構成成分の粉末同士を纏わりやすく凝集性を高めるため、結果として堆積物がベルトコンベア等の搬送設備へ濡れ広がる事（付着する事）を抑制し、堆積物のハンドリング性を向上しうる。
　その結果、ベルトコンベア等の搬送設備での堆積物の移動を容易にしうる。 According to another aspect of the present invention, the sediment components, that is, the powders of the constituent components of the sediment are easily bundled with each other to increase the cohesiveness, and as a result, the sediment is wet and spread (adhered) to the transport equipment such as a belt conveyor. ) Can be suppressed and the handling of sediments can be improved.
As a result, it is possible to facilitate the movement of sediment in a transport facility such as a belt conveyor.
　本発明の他の態様によれば、水への溶出性が低いため、雨に曝された場合にも粉塵飛散抑制を効率良く実現しうる。 According to another aspect of the present invention, since the elution property into water is low, it is possible to efficiently suppress dust scattering even when exposed to rain.
　また、従来、堆積物の粉塵飛散抑制には、大量の水を繰り返し散布していたが、本発明の他の態様によれば、水の使用量を低減しうるため、粉塵飛散抑制を効率良く実現しうる。 Further, conventionally, a large amount of water has been repeatedly sprayed to suppress the scattering of dust in the sediment, but according to another aspect of the present invention, the amount of water used can be reduced, so that the suppression of dust scattering can be efficiently suppressed. It can be realized.
　本発明の他の態様によれば、野積みされた堆積物用の新規な凝固剤を提供できる。このような剤によれば、堆積成分の粉末を纏わりやすくしうるため、野積みさせる前後に堆積物を輸送する工程においても、堆積物の崩れを抑制し、堆積物を効率良く輸送しうる。 According to another aspect of the present invention, it is possible to provide a novel coagulant for open-stacked sediments. According to such an agent, since the powder of the sedimentary component can be easily bundled, the collapse of the sediment can be suppressed and the sediment can be efficiently transported even in the step of transporting the sediment before and after the open stacking.
　本発明の剤は、酸基含有ポリマーのエマルションを含有する。本発明の剤は、種々の用途に使用することができ、例えば、粉塵飛散抑制剤、野積みされた堆積物用の凝固剤として使用することができる。 The agent of the present invention contains an emulsion of an acid group-containing polymer. The agent of the present invention can be used for various purposes, for example, as a dust scattering inhibitor and a coagulant for open-stacked sediments.
［酸基含有ポリマーのエマルション］
　酸基含有ポリマーのエマルション（以下、単に、「エマルション（Ａ）」という）は、通常、エマルション状態にある酸基含有ポリマー又はポリマー粒子が溶媒中に分散したものである。 [Emulsion of acid group-containing polymer]
An emulsion of an acid group-containing polymer (hereinafter, simply referred to as "emulsion (A)") is usually an acid group-containing polymer or polymer particles in an emulsion state dispersed in a solvent.
（酸基含有ポリマー）
　酸基含有ポリマー（以下、単に、「ポリマー（Ｂ）」という）において、酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基などが挙げられる。酸基は、１つ又は２つ以上であってよく、異種の酸基を有していてもよい。
　また、ポリマー（Ｂ）の重合成分すなわち、モノマー成分は、通常、酸基含有モノマーを含む。換言すれば、ポリマー（Ｂ）は、酸基含有モノマー由来の構造単位を有するポリマーであってもよい。酸基含有モノマーは、酸基を１つ又は２以上有していてもよく、異種の酸基を有していてもよい。 (Acid group-containing polymer)
In the acid group-containing polymer (hereinafter, simply referred to as "polymer (B)"), examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. The acid group may be one or more, and may have a different kind of acid group.
Further, the polymerization component of the polymer (B), that is, the monomer component usually contains an acid group-containing monomer. In other words, the polymer (B) may be a polymer having a structural unit derived from an acid group-containing monomer. The acid group-containing monomer may have one or more acid groups, or may have a different kind of acid group.
　酸基含有モノマーとしては、カルボン酸基含有モノマー［例えば、不飽和モノカルボン酸（例えば、アクリル酸、メタクリル酸、クロトン酸等の脂肪族不飽和モノカルボン酸）、不飽和ジカルボン酸（例えば、マレイン酸、フマル酸等の脂肪族不飽和ジカルボン酸）、酸無水物（例えば、無水マレイン酸、無水イタコン酸）］、スルホン酸基含有モノマー［例えば、ビニル系モノマー（例えば、ビニルスルホン酸）、スチレン系モノマー（例えば、スチレンスルホン酸）］、リン酸基含有モノマー｛例えば、リン酸モノ乃至トリエステル［例えば、モノ（２－メタクリロイルオキシエチル）ホスフェート、モノ（２－アクリロイルオキシエチル）ホスフェート、２－（メタ）アクリロイルオキシプロピルホスフェート］｝等が挙げられる。
　なお、酸基含有モノマーは、アニオン化されていてもよい。 Examples of the acid group-containing monomer include a carboxylic acid group-containing monomer [for example, an unsaturated monocarboxylic acid (for example, an aliphatic unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, and crotonic acid), and an unsaturated dicarboxylic acid (for example, malein). Acids, aliphatic unsaturated dicarboxylic acids such as fumaric acid), acid anhydrides (eg, maleic anhydride, itaconic anhydride)], sulfonic acid group-containing monomers [eg, vinyl-based monomers (eg, vinyl sulfonic acid), styrene System monomer (eg, styrene sulfonic acid)], phosphate group-containing monomer {eg, phosphate mono to triester [eg, mono (2-methacryloyloxyethyl) phosphate, mono (2-acryloyloxyethyl) phosphate, 2- (Meta) acryloyloxypropyl phosphate]} and the like.
The acid group-containing monomer may be anionized.
　酸基含有モノマーは、単独で又は２種以上組み合わせて使用してもよい。 The acid group-containing monomer may be used alone or in combination of two or more.
　これらのうち、粉塵飛散抑制や堆積物の凝固性等の観点から、少なくともカルボン酸基含有モノマーを含むことが好ましい。 Of these, it is preferable to contain at least a carboxylic acid group-containing monomer from the viewpoint of suppressing dust scattering and coagulation of sediments.
　ポリマー（Ｂ）の重合成分は、酸基含有モノマー以外の他のモノマーを含んでいてもよい。換言すれば、ポリマー（Ｂ）は、他のモノマー由来の構造単位を有していてもよい。 The polymerization component of the polymer (B) may contain a monomer other than the acid group-containing monomer. In other words, the polymer (B) may have structural units derived from other monomers.
　他のモノマーとしては、特に限定されないが、例えば、脂肪族（メタ）アクリレート｛例えば、アルキル（メタ）アクリレート［例えば、メチル（メタ）アクリート、エチル（メタ）アクリート、ブチル（メタ）アクリート等のＣ１－２０アルキル（メタ）アクリート］、アルコキシアルキル（メタ）アクリレート［例えば、２－メトキシエチル（メタ）アクリレート等のＣ１－１２アルコキシＣ１－１２アルキルメタクリレート］｝、脂環式（メタ）アクリレート｛例えば、シクロアルキル（メタ）アクリレート［例えば、シクロヘキシル（メタ）アクリレート等のＣ４－２０シクロアルキル（メタ）アクリレート］、架橋環式（メタ）アクリレート［例えば、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート］｝、水酸基含有（メタ）アクリレート｛例えば、ヒドロキシアルキル（メタ）アクリレート［例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシＣ２－１０アルキル（メタ）アクリレート］｝、スチレン系モノマー（例えば、スチレン、ビニルトルエン、α－メチルスチレン、エチルビニルベンゼン、クロロメチルスチレン）、（メタ）アクリルアミド系モノマー［例えば、（メタ）アクリルアミド、Ｎ－モノメチル（メタ）アクリルアミド、Ｎ－モノエチル（メタ）アクリルアミド、Ｎ　，Ｎ－ジメチル（メタ）アクリルアミド］、ポリアルキレングリコール鎖含有モノマー［例えば、ポリエチレングリコール（メタ）アクリルエステルなどの（メタ）アクリル酸とポリアルキレングリコールとのモノエステル］、加水分解性基が結合したシリル基含有モノマー［例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－（メタ）アクリロイルプロピルトリメトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、アリルトリエトキシシラン］、エポキシ基含有モノマー　［例えば、（メタ）アクリル酸グリシジル、アリルグリシジルエーテル］、オキサゾリン基含有モノマー（例えば、２－イソプロペニル－２－オキサゾリン、２－ビニルオキサゾリン）、アジリジン基含有モノマー［例えば、（メタ）アクリル酸－２－アジリジニルエチル、（メタ）アクリロイルアジリジン］、ハロゲン原子含有モノマー（例えば、フッ化ビニル、フッ化ビニリデン、塩化ビニル、塩化ビニリデン）、酢酸ビニル、（メタ）アクリロニトリル等が挙げられる。 The other monomer is not particularly limited, but is, for example, an aliphatic (meth) acrylate {for example, C such as an alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like. 1-20 alkyl (meth) acrylic], alkoxyalkyl (meth) acrylate [eg, C 1-12 alkoxy C 1-12 alkyl methacrylate such as 2-methoxyethyl (meth) acrylate]}, alicyclic (meth) acrylate. {For example, cycloalkyl (meth) acrylate [for example, C 4-20 cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate], crosslinked cyclic (meth) acrylate [for example, isobornyl (meth) acrylate, adamantyl (meth). ) Acrylate]}, hydroxyl group-containing (meth) acrylate {for example, hydroxyalkyl (meth) acrylate [for example, hydroxy C 2-10 alkyl (meth) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. ) Acrylate]}, styrene-based monomers (eg, styrene, vinyltoluene, α-methylstyrene, ethylvinylbenzene, chloromethylstyrene), (meth) acrylamide-based monomers [eg, (meth) acrylamide, N-monomethyl (meth) Acrylate (meth) acrylic acid such as acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide], polyalkylene glycol chain-containing monomer [for example, polyethylene glycol (meth) acrylic ester, and polyalkylene glycol. Monoester], silyl group-containing monomers with hydrolyzable groups [eg, vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloylpropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, allyltri Ethoxysilane], epoxy group-containing monomers [eg, glycidyl (meth) acrylate, allyl glycidyl ether], oxazoline group-containing monomers (eg, 2-isopropenyl-2-oxazoline, 2-vinyloxazoline), azilysin group-containing monomers [ For example, (meth) acrylate-2-aziridinylethyl, (meth) acryloyl aziridin], halogen atom-containing monomers (eg, vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride). N), vinyl acetate, (meth) acrylonitrile and the like.
　また、他のモノマーは、側鎖に、下記式（Ｉ）
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ１は、メチレン基、エチレン基、プロピレン基及びブチレン基からなる群より選択される１種以上であり、ｎは、１０～３００であり、Ｘは、直接結合、－Ｃ（＝Ｏ）－、又は－Ｃ（＝Ｏ）ＮＨ－であり、Ｒ２は、炭素数６～３０の炭化水素基を示す。）で表される基を有するモノマー（以下、単に、「他のモノマー（ｂ）」という。）であってもよい。 In addition, other monomers have the following formula (I) in the side chain.
Figure JPOXMLDOC01-appb-C000001
 (In the formula, R 1 is one or more selected from the group consisting of a methylene group, an ethylene group, a propylene group and a butylene group, n is 10 to 300, X is a direct bond, -C ( = O)-or -C (= O) NH-, where R 2 represents a hydrocarbon group having 6 to 30 carbon atoms) and a monomer having a group represented by (hereinafter, simply "another". It may be a monomer (b) ”).
　上記式（Ｉ）において、ｎは、好ましくは１０～１００、より好ましくは２０～８０、さらに好ましくは４０～６０、特に好ましくは４５～５５等であってもよい。 In the above formula (I), n may be preferably 10 to 100, more preferably 20 to 80, still more preferably 40 to 60, particularly preferably 45 to 55 or the like.
　上記式（Ｉ）において、Ｒ２の炭化水素基としては、例えば、直鎖アルキル基（例えば、ヘキシル基、ヘプチル基、オクチル基、ノニル基、ドデシル基、オクタデシル基）、分岐アルキル基（例えば、３－メチルヘキシル基、４ ，４－ジエチルオクチル基）、環状アルキル基（例えば、シクロオクチル基、コレスタニル基、ラノスタニル基）、アリール基（例えば、フェニル基、ナフチル基、アントリル基）、アルキルアリール基（例えば、ノニルフェニル基、ドデシルフェニル基）等が挙げられる。なお、炭化水素基は、一部が置換されていてもよい。
　また、Ｒ２の炭素数は、好ましくは８～３０、より好ましくは１２～２０、特に好ましくは１６～２０等であってもよい。 In the above formula (I), the hydrocarbon group of R 2 includes, for example, a linear alkyl group (for example, a hexyl group, a heptyl group, an octyl group, a nonyl group, a dodecyl group, an octadecyl group) and a branched alkyl group (for example, for example. 3-Methylhexyl group, 4,4-diethyloctyl group), cyclic alkyl group (eg cyclooctyl group, cholestanyl group, lanostenyl group), aryl group (eg phenyl group, naphthyl group, anthryl group), alkylaryl group (For example, nonylphenyl group, dodecylphenyl group) and the like can be mentioned. The hydrocarbon group may be partially substituted.
Further, the carbon number of R 2 may be preferably 8 to 30, more preferably 12 to 20, particularly preferably 16 to 20, and the like.
　他のモノマーは、単独で又は２種以上組み合わせて使用してもよい。 Other monomers may be used alone or in combination of two or more.
　ポリマー（Ｂ）は、重合成分として、特に、酸基含有ポリマーと、他のモノマーとして脂肪族（メタ）アクリレートを少なくとも含むものであってもよい。 The polymer (B) may contain at least an acid group-containing polymer as a polymerization component and an aliphatic (meth) acrylate as another monomer.
　ポリマー（Ｂ）のモノマー成分（以下、単に、「モノマー成分（a）」という。）全体において、酸基含有モノマーの割合は、粉塵飛散抑制や堆積物の凝固性等の観点から、例えば、５質量％以上、好ましくは１５質量％以上、さらに好ましくは２５質量％以上等であってもよく、比較的高割合（例えば、５０質量％以上）等であってもよい。 The proportion of the acid group-containing monomer in the entire monomer component of the polymer (B) (hereinafter, simply referred to as “monomer component (a)”) is, for example, 5 from the viewpoint of suppressing dust scattering and coagulation of sediments. It may be mass% or more, preferably 15% by mass or more, more preferably 25% by mass or more, or a relatively high proportion (for example, 50% by mass or more).
　モノマー成分（ａ）全体において、酸基含有モノマーの割合の上限値は、例えば、９９質量％以下、好ましくは９０質量％以下、より好ましくは８０質量％以下等であってもよい。 The upper limit of the ratio of the acid group-containing monomer in the entire monomer component (a) may be, for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less.
　なお、これらの上限値と下限値とを適宜組み合わせて適当な範囲（例えば、５～９９質量％に限らず、他の上限値と下限値を組み合わせても良い）を設定してもよい。 An appropriate range (for example, not limited to 5 to 99% by mass, and other upper limit values and lower limit values may be combined) may be set by appropriately combining these upper limit values and lower limit values.
　モノマー成分（a）全体において、酸基含有モノマーの割合は、粉塵飛散抑制や堆積物の凝固性等の観点から、例えば、５モル％以上（例えば、１０モル％以上）、好ましくは１５モル％以上（例えば、２０モル％以上）、さらに好ましくは２５モル％以上（例えば、３０モル％以上）等であってもよく、比較的高割合（例えば、３５モル％以上、４０モル％以上、４５モル％以上、５０モル％以上、５５モル％以上、６０モル％以上、６５モル％以上、７５モル％以上等）等であってもよい。 The proportion of the acid group-containing monomer in the entire monomer component (a) is, for example, 5 mol% or more (for example, 10 mol% or more), preferably 15 mol%, from the viewpoint of suppressing dust scattering and coagulation of deposits. It may be more than (for example, 20 mol% or more), more preferably 25 mol% or more (for example, 30 mol% or more), and a relatively high ratio (for example, 35 mol% or more, 40 mol% or more, 45). It may be mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 75 mol% or more, etc.).
　モノマー成分（ａ）全体において、酸基含有モノマーの割合の上限値は、例えば、９９モル％以下（例えば、９５モル％以下）、好ましくは９０モル％以下（例えば、８５モル％以下）、より好ましくは８０モル％以下（例えば、７５モル％以下、７０モル％以下、６５モル％以下、６０モル％以下）等であってもよい。 The upper limit of the proportion of the acid group-containing monomer in the entire monomer component (a) is, for example, 99 mol% or less (for example, 95 mol% or less), preferably 90 mol% or less (for example, 85 mol% or less). It may be preferably 80 mol% or less (for example, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less) and the like.
　なお、これらの上限値と下限値とを適宜組み合わせて適当な範囲（例えば、５～９９モル％に限らず、他の上限値と下限値を組み合わせても良い）を設定してもよい。 An appropriate range may be set by appropriately combining these upper limit values and lower limit values (for example, not limited to 5 to 99 mol%, but other upper limit values and lower limit values may be combined).
　モノマー成分（a）全体において、他のモノマーの割合は、特に限定されないが、例えば、０．１質量％以上（例えば、０．５質量％以上）、好ましくは１質量％以上（例えば、１．５質量％以上）、さらに好ましくは２質量％以上（例えば、２．５質量％以上）等であってもよく、比較的高割合（例えば、３質量％以上、５質量％以上、１０質量％以上、１５質量％以上、２０質量％以上、２５質量％以上、３０質量％以上、３５質量％以上、４０質量％以上、４５質量％以上）等であってもよい。 The proportion of other monomers in the entire monomer component (a) is not particularly limited, but is, for example, 0.1% by mass or more (for example, 0.5% by mass or more), preferably 1% by mass or more (for example, 1. 5% by mass or more), more preferably 2% by mass or more (for example, 2.5% by mass or more), and a relatively high proportion (for example, 3% by mass or more, 5% by mass or more, 10% by mass or more). As mentioned above, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more) and the like may be used.
　モノマー成分（ａ）全体において、他のモノマーの割合の上限値は、例えば、８０質量％以下（例えば、７０質量％以下）、好ましくは６０質量％以下（例えば、５０質量％以下）、より好ましくは４５質量％以下（例えば、４０質量％以下）等であってもよい。 The upper limit of the ratio of other monomers in the entire monomer component (a) is, for example, 80% by mass or less (for example, 70% by mass or less), preferably 60% by mass or less (for example, 50% by mass or less), more preferably. May be 45% by mass or less (for example, 40% by mass or less).
　なお、これらの上限値と下限値とを適宜組み合わせて適当な範囲（例えば、５～６０質量％に限らず、他の上限値と下限値を組み合わせても良い）を設定してもよい。 An appropriate range may be set by appropriately combining these upper limit values and lower limit values (for example, not limited to 5 to 60% by mass, but other upper limit values and lower limit values may be combined).
　特に、重合成分が、他のモノマーとして脂肪族（メタ）アクリレートを含有する場合、モノマー成分（ａ）全体において、脂肪族（メタ）アクリレートの割合は、例えば、１０質量％以上（例えば、１３質量％以上）、好ましくは１５質量％以上（例えば、１８質量％以上）、さらに好ましくは２０質量％以上（例えば、２３質量％以上）等であってもよく、比較的高割合（例えば、２５質量％以上、２８質量％以上、３０質量％以上、３３質量％以上、３５質量％以上、３８質量％以上、４０質量％以上等）であってもよい。
　また、モノマー成分（ａ）全体において、脂肪族（メタ）アクリレート割合の上限値は、例えば、８０質量％以下（例えば、７０質量％以下）、好ましくは６０質量％以下（例えば、５０質量％以下）、より好ましくは４５質量％以下（例えば、４０質量％以下）等であってもよい。 In particular, when the polymerization component contains an aliphatic (meth) acrylate as another monomer, the proportion of the aliphatic (meth) acrylate in the entire monomer component (a) is, for example, 10% by mass or more (for example, 13% by mass). % Or more), preferably 15% by mass or more (for example, 18% by mass or more), more preferably 20% by mass or more (for example, 23% by mass or more), and a relatively high proportion (for example, 25% by mass). % Or more, 28% by mass or more, 30% by mass or more, 33% by mass or more, 35% by mass or more, 38% by mass or more, 40% by mass or more, etc.).
Further, the upper limit of the aliphatic (meth) acrylate ratio in the entire monomer component (a) is, for example, 80% by mass or less (for example, 70% by mass or less), preferably 60% by mass or less (for example, 50% by mass or less). ), More preferably 45% by mass or less (for example, 40% by mass or less) and the like.
　また、重合成分が、他のモノマーとして他のモノマー（ｂ）を含有する場合、モノマー成分（ａ）全体において、他のモノマー（ｂ）の割合は、例えば、０．１質量％以上（例えば、０．５質量％以上）、好ましくは１質量％以上（例えば、５質量％以上）、さらに好ましくは１０質量％以上（例えば、１５質量％以上）等であってもよく、比較的高割合（例えば、２０質量％以上、２５質量％以上、３０質量％以上、３５質量％以上、４０質量％以上等）であってもよい。
　また、単量体成分（ａ）全体において、他のモノマー（ｂ）の割合の上限値は、例えば、８０質量％以下（例えば、７０質量％以下）、好ましくは６０質量％以下（例えば、５０質量％以下）、より好ましくは４５質量％以下（例えば、４０質量％以下）等であってもよい。 When the polymerization component contains another monomer (b) as another monomer, the proportion of the other monomer (b) in the entire monomer component (a) is, for example, 0.1% by mass or more (for example,). It may be 0.5% by mass or more, preferably 1% by mass or more (for example, 5% by mass or more), more preferably 10% by mass or more (for example, 15% by mass or more), and a relatively high proportion (for example, 15% by mass or more). For example, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, etc.) may be used.
Further, the upper limit of the ratio of the other monomer (b) in the entire monomer component (a) is, for example, 80% by mass or less (for example, 70% by mass or less), preferably 60% by mass or less (for example, 50%). It may be (% by mass or less), more preferably 45% by mass or less (for example, 40% by mass or less) and the like.
　ポリマー（Ｂ）のガラス転移温度は、造膜性等の観点から、例えば、－４０℃以上、好ましくは－３０℃以上、より好ましくは－２０℃以上、特に好ましくは－１０℃以上等であってもよい。
　また、ポリマー（Ｂ）のガラス転移温度の上限値は、例えば、８０℃以下、好ましくは７５℃以下、より好ましくは６５℃以下、特に好ましくは５０℃以下等であってもよい。 The glass transition temperature of the polymer (B) is, for example, −40 ° C. or higher, preferably −30 ° C. or higher, more preferably −20 ° C. or higher, particularly preferably −10 ° C. or higher, from the viewpoint of film-forming property. You may.
The upper limit of the glass transition temperature of the polymer (B) may be, for example, 80 ° C. or lower, preferably 75 ° C. or lower, more preferably 65 ° C. or lower, particularly preferably 50 ° C. or lower.
　なお、ガラス転移温度は、ポリマーを構成するモノマー成分に使用されているモノマーの単独重合体のガラス転移温度を用いて、
式（Ｉ）：　１／Ｔｇ＝Σ（Ｗｍ／Ｔｇｍ）／１００　　　　　　　　（Ｉ）
〔式中、Ｗｍは重合体を構成するモノマー成分における単量体ｍの含有率(質量％)、Ｔｇｍはモノマーｍの単独重合体のガラス転移温度（絶対温度：Ｋ）を示す〕
で表されるフォックス（Ｆｏｘ）の式に基づいて求められた温度であってもよい。 The glass transition temperature is determined by using the glass transition temperature of the homopolymer of the monomer used as the monomer component constituting the polymer.
Equation (I): 1 / Tg = Σ (Wm / Tgm) / 100 (I)
[In the formula, Wm indicates the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm indicates the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m].
The temperature may be determined based on the Fox equation represented by.
　ポリマー（Ｂ）の重量平均分子量は、凝集力、凝結力等の観点から、例えば、１００万以上、好ましくは３００万以上、さらに好ましくは５００万以上であってもよい。
　ポリマー（Ｂ）の重量平均分子量の上限値は、凝集力、凝結力等の観点から、例えば、５０００万以下等であってもよい。 The weight average molecular weight of the polymer (B) may be, for example, 1 million or more, preferably 3 million or more, and more preferably 5 million or more from the viewpoint of cohesive force, cohesive force and the like.
The upper limit of the weight average molecular weight of the polymer (B) may be, for example, 50 million or less from the viewpoint of cohesive force, cohesive force and the like.
　重量平均分子量は、例えば、ゲルパーミエイションクロマトグラフィー〔例えば、東ソー（株）製、品番：ＨＬＣ－８１２０ＧＰＣ、カラム：ＴＳＫｇｅｌ　Ｇ－５０００ＨＸＬとＴＳＫｇｅｌ　ＧＭＨＸＬ－Ｌとを直列に使用〕を用いて測定（ポリスチレン換算）してもよいし、静的光散乱法による分子量測定器（大塚電子製　ＤＬＳ－８０００）によって測定してもよい。 The weight average molecular weight is measured using, for example, gel permeation chromatography [for example, manufactured by Toso Co., Ltd., product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L are used in series] ( It may be measured by a molecular weight measuring device (DLS-8000 manufactured by Otsuka Denshi Co., Ltd.) by a static light scattering method.
（エマルション）
　エマルション（Ａ）の酸価は、粉塵飛散抑制や堆積物の凝固性等の観点から、例えば、４０ｍｇ ＫＯＨ／ｇ以上（例えば、４５ｍｇ ＫＯＨ／ｇ以上）、好ましくは５０ｍｇ ＫＯＨ／ｇ以上（例えば、５５ｍｇ ＫＯＨ／ｇ以上）、より好ましくは６０ｍｇ ＫＯＨ／ｇ以上（例えば、６５ｍｇ ＫＯＨ／ｇ以上）、特に好ましくは７０ｍｇ ＫＯＨ／ｇ以上（例えば、７５ｍｇ ＫＯＨ／ｇ以上、８０ｍｇ ＫＯＨ／ｇ以上、８５ｍｇ ＫＯＨ／ｇ以上、９０ｍｇ ＫＯＨ／ｇ以上、９５ｍｇ ＫＯＨ／ｇ以上、１００ｍｇ ＫＯＨ／ｇ以上、１０５ｍｇ ＫＯＨ／ｇ以上、１１０ｍｇ ＫＯＨ／ｇ以上、１１５ｍｇ ＫＯＨ／ｇ以上）等であってもよい。
　また、エマルション（Ａ）の酸価の上限値は、例えば、５００ｍｇ ＫＯＨ／ｇ以下（例えば、４５０ｍｇ ＫＯＨ／ｇ以下）、好ましくは４００ｍｇ ＫＯＨ／ｇ以下（例えば、３５０ｍｇ ＫＯＨ／ｇ以下）、より好ましくは３００ｍｇ ＫＯＨ／ｇ以下（例えば、２８０ｍｇ ＫＯＨ／ｇ以下）等であってもよい。 (Emulsion)
The acid value of the emulsion (A) is, for example, 40 mg KOH / g or more (for example, 45 mg KOH / g or more), preferably 50 mg KOH / g or more (for example, 50 mg KOH / g or more) from the viewpoint of suppressing dust scattering and coagulation of deposits. 55 mg KOH / g or higher), more preferably 60 mg KOH / g or higher (eg, 65 mg KOH / g or higher), particularly preferably 70 mg KOH / g or higher (eg, 75 mg KOH / g or higher, 80 mg KOH / g or higher, 85 mg KOH). / G or more, 90 mg KOH / g or more, 95 mg KOH / g or more, 100 mg KOH / g or more, 105 mg KOH / g or more, 110 mg KOH / g or more, 115 mg KOH / g or more) and the like.
The upper limit of the acid value of the emulsion (A) is, for example, 500 mg KOH / g or less (for example, 450 mg KOH / g or less), preferably 400 mg KOH / g or less (for example, 350 mg KOH / g or less), more preferably. May be 300 mg KOH / g or less (for example, 280 mg KOH / g or less).
　エマルション（Ａ）の酸価は、例えば、自動滴定装置（商品名：ＣＯＭ－５５５、平沼産業社製）によって樹脂固形分１ｇ当たりの酸価（ｍｇＫＯＨ／ｇ）を測定してもよい。 For the acid value of the emulsion (A), for example, the acid value (mgKOH / g) per 1 g of the resin solid content may be measured by an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.).
　エマルション（Ａ）の粘度は、エマルションの散布性等の観点から、例えば、１０，０００ｍＰａ・ｓ以下、好ましくは５，０００ｍＰａ・ｓ以下、さらに好ましくは２，０００ｍＰａ・ｓ以下、特に好ましくは１，５００ｍＰａ・ｓ以下であってもよい。
　また、エマルション（Ａ）の粘度の下限値は、例えば、１０ｍＰａ・ｓ以上等であってもよい。 The viscosity of the emulsion (A) is, for example, 10,000 mPa · s or less, preferably 5,000 mPa · s or less, more preferably 2,000 mPa · s or less, and particularly preferably 1, from the viewpoint of the dispersability of the emulsion. It may be 500 mPa · s or less.
Further, the lower limit of the viscosity of the emulsion (A) may be, for example, 10 mPa · s or more.
　エマルション（Ａ）の粘度は、例えば、ＢＭ粘度計（東機産業製、品番：ＴＶＢ－１０Ｍ）を用い、回転速度３０ｒｐｍでの２５℃における粘度を測定してもよい。 For the viscosity of the emulsion (A), for example, a BM viscometer (manufactured by Toki Sangyo Co., Ltd., product number: TVB-10M) may be used to measure the viscosity at 25 ° C. at a rotation speed of 30 rpm.
　エマルション粒子の平均粒子径は、エマルションの粘度、堆積物に対する含浸性などの観点から、例えば、３０ｎｍ以上、好ましくは５０ｎｍ以上等であってもよい。
　また、エマルション粒子の平均粒子径の上限値は、例えば、３，０００ｎｍ以下、好ましくは１，０００ｎｍ以下等であってもよい。 The average particle size of the emulsion particles may be, for example, 30 nm or more, preferably 50 nm or more, from the viewpoint of the viscosity of the emulsion, the impregnation property with respect to the deposit, and the like.
The upper limit of the average particle size of the emulsion particles may be, for example, 3,000 nm or less, preferably 1,000 nm or less.
　なお、エマルション粒子の平均粒子径は、動的光散乱法による粒度分布測定器〔パーティクル・サイジング・システムズ（Ｐａｒｔｉｃｌｅ　Ｓｉｚｉｎｇ　Ｓｙｓｔｅｍｓ）社製、商品名：ＮＩＣＯＭＰ　Ｍｏｄｅｌ　３８０〕を用いて測定された体積平均粒子径であってよい。 The average particle size of the emulsion particles is the volume average particles measured using a particle size distribution measuring device [Particle Sizing Systems, trade name: NICOMP Model 380] by a dynamic light scattering method. It may be a diameter.
　エマルション（Ａ）におけるポリマー（Ｂ）の固形分（不揮発分）量は、粉塵飛散抑制や堆積物の凝固性等の観点から、例えば、０．５質量％以上（例えば、１質量％以上）、好ましくは３質量％以上（例えば、５質量％以上）、より好ましくは１０質量％以上（例えば、１３質量％以上、１５質量％以上、１７質量％以上、２０質量％以上）等であってよく、取り扱い性等の観点から、例えば、６０質量％以下、好ましくは５０質量％以下等であってもよい。 The solid content (nonvolatile content) of the polymer (B) in the emulsion (A) is, for example, 0.5% by mass or more (for example, 1% by mass or more) from the viewpoint of suppressing dust scattering and coagulation of deposits. It may be preferably 3% by mass or more (for example, 5% by mass or more), more preferably 10% by mass or more (for example, 13% by mass or more, 15% by mass or more, 17% by mass or more, 20% by mass or more) or the like. From the viewpoint of handleability and the like, for example, it may be 60% by mass or less, preferably 50% by mass or less.
　なお、エマルション（Ａ）におけるポリマー（Ｂ）の不揮発分量は、例えば、エマルション（Ａ）１ｇを秤量し、熱風乾燥機で１１０℃の温度で１時間乾燥させ、得られた残渣を不揮発分とし、
式：〔エマルション（Ａ）における不揮発分量（質量％）〕＝（〔残渣の質量〕÷〔エマルション（Ａ）１ｇ〕）×１００
に基づいて求めることができる。 As for the non-volatile content of the polymer (B) in the emulsion (A), for example, 1 g of the emulsion (A) was weighed and dried in a hot air dryer at a temperature of 110 ° C. for 1 hour, and the obtained residue was used as the non-volatile content.
Formula: [Non-volatile content (mass%) in emulsion (A)] = ([mass of residue] ÷ [emulsion (A) 1 g]) × 100
Can be calculated based on.
　エマルション（Ａ）は、前記のように、ポリマー（Ｂ）以外に溶媒を含有していてもよい。溶媒としては、例えば、水、水を含む溶媒［例えば、水とアルコール（例えば、メタノール、エタノール等のＣ１－４アルコール）の混合溶媒］等の水性溶媒が挙げられる。
　溶媒は、１種又は２種以上を組み合わせて使用してもよい。
　エマルション（Ａ）は溶媒に水を含むことが好ましく、水性分散体であることが好ましい。 As described above, the emulsion (A) may contain a solvent other than the polymer (B). Examples of the solvent include water and an aqueous solvent such as a solvent containing water [for example, a mixed solvent of water and an alcohol (for example, C 1-4 alcohol such as methanol and ethanol)].
The solvent may be used alone or in combination of two or more.
The emulsion (A) preferably contains water as a solvent, and is preferably an aqueous dispersion.
［エマルションの製造方法］
　エマルション（Ａ）の製造方法は、特に限定されないが、例えば、溶媒中で、ポリマー（Ｂ）の原料であるモノマー成分を乳化重合することにより製造してもよい。 [Emulsion manufacturing method]
The method for producing the emulsion (A) is not particularly limited, but for example, it may be produced by emulsion polymerization of the monomer component which is the raw material of the polymer (B) in a solvent.
　溶媒としては、例えば、水、水を含む溶媒［例えば、水とアルコール（例えば、メタノール、エタノール等のＣ１－４アルコール）の混合溶媒］等の水性溶媒が挙げられる。
　溶媒は、１種又は２種以上を組み合わせて使用してもよい。 Examples of the solvent include water and an aqueous solvent such as a solvent containing water [for example, a mixed solvent of water and an alcohol (for example, C 1-4 alcohol such as methanol and ethanol)].
The solvent may be used alone or in combination of two or more.
　モノマー成分を乳化重合させる方法としては、特に限定されないが、例えば、乳化剤を含む溶媒に、モノマー成分を滴下などして重合する方法、予め乳化剤によって乳化させておいたモノマー成分を溶媒に滴下などして重合する方法等が挙げられる。 The method for emulsion-polymerizing the monomer component is not particularly limited, but for example, a method of polymerizing by dropping the monomer component into a solvent containing an emulsifier, a method of dropping a monomer component emulsified with an emulsifier in advance into the solvent, or the like. A method of polymerizing and the like can be mentioned.
　なお、溶媒の量は、得られるエマルションに含まれる不揮発分量等を考慮して適宜設定すればよい。 The amount of the solvent may be appropriately set in consideration of the amount of non-volatile content contained in the obtained emulsion and the like.
　乳化剤としては、特に限定されないが、例えば、アニオン性乳化剤（例えば、アンモニウムドデシルサルフェート、ナトリウムドデシルサルフェートなどのアルキルサルフェート塩；アンモニウムドデシルスルホネート、ナトリウムドデシルスルホネートなどのアルキルスルホネート塩；アンモニウムドデシルベンゼンスルホネート、ナトリウムドデシルナフタレンスルホネートなどのアルキルアリールスルホネート塩；ポリオキシエチレンアルキルサルフェート塩；ポリオキシエチレンアルキルアリールサルフェート塩；ポリオキシエチレンアルキルエーテル硫酸塩；ジアルキルスルホコハク酸塩；アリールスルホン酸－ホルマリン縮合物；アンモニウムラウリレート、ナトリウムステアリレートなどの脂肪酸塩等）、ノニオン性乳化剤（例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリエチレングリコールとポリプロピレングリコールとの縮合体、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸モノグリセライド、エチレンオキサイドと脂肪族アミンとの縮合体等）、カチオン性乳化剤（例えば、ジアルキルジメチルアンモニウム塩、エステル型ジアルキルアンモニウム塩、アミド型ジアルキルアンモニウム塩、ジアルキルイミダゾリニウム塩等）、両性乳化剤（例えば、アルキルジメチルアミノ酢酸ベタイン、アルキルジメチルアミンオキサイド、アルキルカルボキシメチルヒドロキシエチルイミダゾリニウムベタイン、アルキルアミドプロピルベタイン、アルキルヒドロキシスルホベタイン等）、高分子乳化剤（例えば、ポリビニルアルコールおよびその変性物；（メタ）アクリル酸系水溶性高分子；ヒドロキシエチル（メタ）アクリル酸系水溶性高分子；ヒドロキシプロピル（メタ）アクリル酸系水溶性高分子；ポリビニルピロリドン等）等が挙げられる。
　乳化剤は、１種又は２種以上を使用してもよい。 The emulsifier is not particularly limited, and for example, an anionic emulsifier (for example, an alkyl sulfonate salt such as ammonium dodecyl sulfate or sodium dodecyl sulfate; an alkyl sulfonate salt such as ammonium dodecyl sulfonate or sodium dodecyl sulfonate; ammonium dodecylbenzene sulfonate, sodium dodecyl). Alkylaryl sulfonate salts such as naphthalene sulfonate; polyoxyethylene alkyl sulphate salt; polyoxyethylene alkyl aryl sulphate salt; polyoxyethylene alkyl ether sulfate; dialkyl sulfosuccinate; aryl sulfonic acid-formalin condensate; ammonium laurylate, sodium Nonionic emulsifiers (eg, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acids, etc.) Monoglyceride, condensates of ethylene oxide and aliphatic amines, etc.), cationic emulsifiers (eg, dialkyldimethylammonium salt, ester-type dialkylammonium salt, amide-type dialkylammonium salt, dialkylimidazolinium salt, etc.), amphoteric emulsifiers (eg, dialkylimidazolinium salt, etc.) , Alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethyl imidazolinium betaine, alkylamide propylbetaine, alkylhydroxysulfobetaine, etc.), high molecular weight emulsifiers (eg, polyvinyl alcohol and its modifications; (meth). Acrylic acid-based water-soluble polymers; hydroxyethyl (meth) acrylic acid-based water-soluble polymers; hydroxypropyl (meth) acrylic acid-based water-soluble polymers; polyvinylpyrrolidone, etc.) and the like.
One type or two or more types of emulsifiers may be used.
　乳化剤の使用量は、乳化剤の種類等に応じて適宜設定すればよく、特に限定されないが、モノマー成分（a）１００質量部に対して、例えば、０．１質量部以上、好ましくは０．５質量部以上等であってよく、例えば、２０質量部以下、好ましくは１５質量部以下等であってもよい。 The amount of the emulsifier to be used may be appropriately set according to the type of emulsifier and the like, and is not particularly limited, but is, for example, 0.1 part by mass or more, preferably 0.5 part by mass with respect to 100 parts by mass of the monomer component (a). It may be 20 parts by mass or less, preferably 15 parts by mass or less.
　重合は、重合開始剤の存在下で行ってもよい。
　重合開始剤としては、例えば、アゾビスイソブチロニトリル、２，２－アゾビス（２－ メチルブチロニトリル）、２，２－アゾビス（２，４－ジメチルバレロニトリル）、２， ２－アゾビス（２―ジアミノプロパン）ハイドロクロライド、４，４－アゾビス（４－シ アノ吉草酸）、２，２－アゾビス（２－メチルプロピオンアミジン）などのアゾ化合物；過硫酸カリウムなどの過硫酸塩；過酸化水素、ベンゾイルパーオキサイド、パラクロロベンゾイルパーオキサイド、ラウロイルパーオキサイド、過酸化アンモニウムなどの過酸化物などが挙げられる。
　重合開始剤は、１種又は２種以上を組み合わせて使用してもよい。 The polymerization may be carried out in the presence of a polymerization initiator.
Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (2,2-azobis). 2-Diaminopropane) Hydrochloride, azo compounds such as 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; peroxides Examples thereof include peroxides such as hydrogen, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
The polymerization initiator may be used alone or in combination of two or more.
　重合開始剤の使用量は、重合開始剤の種類等に応じて適宜設定すればよく、特に限定されないが、モノマー成分（a）１００質量部に対して、例えば、０．０５質量部以上、好ましくは０．１質量部以上等であってよく、例えば、２質量部以下、好ましくは１質量部以下等であってもよい。 The amount of the polymerization initiator used may be appropriately set according to the type of the polymerization initiator and the like, and is not particularly limited, but is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the monomer component (a). May be 0.1 parts by mass or more, and may be, for example, 2 parts by mass or less, preferably 1 part by mass or less.
　重合開始剤の添加方法は、特に限定されないが、例えば、一括仕込み、分割仕込み、連続滴下などが挙げられる。 The method of adding the polymerization initiator is not particularly limited, and examples thereof include batch charging, split charging, and continuous dropping.
　なお、重合反応は、必要に応じて、還元剤（例えば、亜硫酸水素ナトリウム）、重合開始剤の分解剤（例えば、硫酸第一鉄などの遷移金属塩）、連鎖移動剤［例えば、チオール基を有する化合物（例えば、ｔｅｒｔ－ドデシルメルカプタン）］、ｐＨ緩衝剤、キレート剤等の存在下で行ってもよい。 In the polymerization reaction, if necessary, a reducing agent (for example, sodium hydrogen sulfite), a decomposition agent for the polymerization initiator (for example, a transition metal salt such as ferrous sulfate), and a chain transfer agent [for example, a thiol group may be used. It may be carried out in the presence of a compound having (for example, tert-dodecyl mercaptan)], a pH buffer, a chelating agent and the like.
　重合の際の雰囲気は、特に限定されないが、重合効率などの観点から、窒素ガスなどの不活性ガスであってもよい。 The atmosphere at the time of polymerization is not particularly limited, but may be an inert gas such as nitrogen gas from the viewpoint of polymerization efficiency and the like.
　重合温度は、特に限定されないが、例えば、５０～１００℃、好ましくは６０～９５℃であってもよい。重合温度は、一定であってもよく、重合反応の途中で変化させてもよい。 The polymerization temperature is not particularly limited, but may be, for example, 50 to 100 ° C, preferably 60 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.
　重合時間は、特に限定されず、重合反応の進行状況に応じて適宜設定すればよいが、例えば、１時間以上（例えば、１～２４時間）、好ましくは２～１２時間（例えば、２～９時間）程度であってもよい。 The polymerization time is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is, for example, 1 hour or more (for example, 1 to 24 hours), preferably 2 to 12 hours (for example, 2 to 9 hours). It may be about time).
[剤]
　本発明の剤、特に、粉塵飛散抑制剤、野積みされた堆積物用の凝固剤は、通常、上述したポリマー（Ｂ）のエマルションであるエマルション（Ａ）を含有する。
　本発明の剤を、粉塵を含む堆積物（以下、堆積物（Ｃ１））に散布もしくは混合等することにより、粉塵の飛散を抑制しうる。堆積物（Ｃ１）は、粉塵のみの堆積物であってもよいし、粉塵を少なくとも含む堆積物、例えば、粉塵以外の塊も含む堆積物であってもよい。
　また、本発明の剤を、野積みされた堆積物（以下、堆積物（Ｃ２））に散布もしくは混合等をすることにより、野積みされた堆積物を凝固させうる。堆積物（Ｃ２）は、上記した堆積物（Ｃ１）と同様のものであってもよい。
　堆積物に含まれる粉塵の量は、粉塵の種類等にもよるが、堆積物１００質量部に対し、例えば、０．１質量部以上であってもよく、１０質量部以上、３０質量部以上であってもよい。
　堆積物に含まれる粉塵の量は、堆積物１００質量部に対し、例えば、３０質量部以下であってもよく、１０質量部以下、１質量部以下であってもよい。
　製鉄原料として石炭が用いられる場合は、堆積物に含まれる粉塵の量は、堆積物１００質量部に対し、例えば、０．１質量部以上であってもよく、１０質量部以上、３０質量部以上であってもよく、５０質量部以下であってもよく、４０質量部以下であってもよく、３０質量部以下であってもよく、１０質量部以下、１質量部以下であってもよい。
　製鉄原料として鉄鉱石が用いられる場合は、堆積物に含まれる粉塵の量は、堆積物１００質量部に対し、例えば、０．１質量部以上であってもよく、１０質量部以上、３０質量部以上であってもよく、３０質量部以下であってもよく、１０質量部以下、１質量部以下であってもよい。 [Agent]
The agent of the present invention, particularly the dust scattering inhibitor and the coagulant for the piled up deposits, usually contains an emulsion (A) which is an emulsion of the above-mentioned polymer (B).
By spraying or mixing the agent of the present invention on a deposit containing dust (hereinafter, deposit (C1)), the scattering of dust can be suppressed. The deposit (C1) may be a dust-only deposit or a deposit containing at least dust, for example, a deposit containing lumps other than dust.
In addition, the agent of the present invention can be coagulated by spraying or mixing the piled up deposits (hereinafter referred to as deposits (C2)). The deposit (C2) may be the same as the deposit (C1) described above.
The amount of dust contained in the deposit depends on the type of dust and the like, but may be, for example, 0.1 part by mass or more, 10 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of the deposit. May be.
The amount of dust contained in the deposit may be, for example, 30 parts by mass or less, 10 parts by mass or less, and 1 part by mass or less with respect to 100 parts by mass of the deposit.
When coal is used as a raw material for iron making, the amount of dust contained in the deposit may be, for example, 0.1 part by mass or more, 10 parts by mass or more, and 30 parts by mass with respect to 100 parts by mass of the deposit. It may be more than or equal to 50 parts by mass, may be 40 parts by mass or less, may be 30 parts by mass or less, may be 10 parts by mass or less, and may be 1 part by mass or less. good.
When iron ore is used as a raw material for iron making, the amount of dust contained in the deposit may be, for example, 0.1 part by mass or more and 30 parts by mass or more with respect to 100 parts by mass of the deposit. It may be 10 parts by mass or less, 30 parts by mass or less, or 1 part by mass or less.
　粉塵の粒径としては、粉塵の種類にもよるが、例えば、５，０００μｍ以下、好ましくは１，０００μｍ以下等であってもよい。 The particle size of the dust depends on the type of dust, but may be, for example, 5,000 μm or less, preferably 1,000 μm or less.
　堆積物（Ｃ１）又は堆積物（Ｃ２）の種類としては、特に限定されないが、例えば、鉱物（例えば、鉄鉱石、銅鉱石、ニッケル鉱石、その他金属鉱石、スラグ、石灰石等）、炭素質物質（例えば、石炭、コークス等）、土、砂、土砂等が挙げられる。また、堆積物（Ｃ１）又は堆積物（Ｃ２）は、例えば、鉄鉱石、スラグ、石灰石、石炭、コークス等の製鉄原料であってもよい。また、堆積物（Ｃ１）又は堆積物（Ｃ２）は、塩基性であってもよい。
　堆積物（Ｃ１）又は堆積物（Ｃ２）は、１種又は２種以上であってもよい。
　堆積物（Ｃ１）又は堆積物（Ｃ２）としては、代表的には、例えば、鉄鉱石の山、石炭の山等が挙げられる。例えば、鉄鉱石の山は、通常、鉄鉱石のみで形成されていてよい。
　なお、堆積物（Ｃ１）は、野積みされた物が好ましい。 The type of deposit (C1) or deposit (C2) is not particularly limited, but is, for example, minerals (for example, iron ore, copper ore, nickel ore, other metal ores, slag, limestone, etc.), carbonaceous substances (, etc.). For example, coal, coke, etc.), soil, sand, earth and sand, etc. may be mentioned. Further, the deposit (C1) or the deposit (C2) may be, for example, an iron-making raw material such as iron ore, slag, limestone, coal, or coke. Further, the deposit (C1) or the deposit (C2) may be basic.
The deposit (C1) or the deposit (C2) may be one kind or two or more kinds.
Typical examples of the deposit (C1) or the deposit (C2) include a pile of iron ore, a pile of coal, and the like. For example, a pile of iron ore may usually be formed solely of iron ore.
The deposit (C1) is preferably piled up in the open.
　堆積物（Ｃ１）又は堆積物（Ｃ２）の高さ、すなわち、最大高さは、例えば、５ｍ以上、好ましくは１０ｍ以上であってもよい。 The height of the deposit (C1) or the deposit (C2), that is, the maximum height may be, for example, 5 m or more, preferably 10 m or more.
　堆積物（Ｃ１）又は堆積物（Ｃ２）の幅、すなわち、最大幅は、例えば、５ｍ以上、好ましくは３０ｍ以上であってもよい。 The width of the deposit (C1) or the deposit (C2), that is, the maximum width may be, for example, 5 m or more, preferably 30 m or more.
　堆積物（Ｃ１）又は堆積物（Ｃ２）の重さは、堆積物の種類にもよるが、例えば、鉄鉱石の場合、数千ｔ～１万ｔ程度であってもよい。 The weight of the deposit (C1) or the deposit (C2) depends on the type of the deposit, but for example, in the case of iron ore, it may be about several thousand to 10,000 tons.
　堆積物（Ｃ１）又は堆積物（Ｃ２）は、堆積物の種類にもよるが、粒径が、例えば、１５ｍｍ以上（例えば、１０ｍｍ以上）、好ましくは５ｍｍ以上（例えば、３ｍｍ以上）、より好ましくは１ｍｍ以上等の堆積成分を含んでいてもよい。 The deposit (C1) or the deposit (C2) has a particle size of, for example, 15 mm or more (for example, 10 mm or more), preferably 5 mm or more (for example, 3 mm or more), more preferably, although it depends on the type of the deposit. May contain sedimentary components such as 1 mm or more.
　堆積物（Ｃ１）又は堆積物（Ｃ２）は、堆積物全量に対する含水率、又は、吸水率が、例えば、０．０１質量％以上、好ましくは５質量％以上であってもよい。
　また、堆積物（Ｃ１）又は堆積物（Ｃ２）は、堆積物全量に対する含水率が、例えば、５０質量％以下、好ましくは３０質量％以下、より好ましくは１０質量％以下であってもよい。
　なお、含水率は、堆積物全量に対して、例えば、１０５℃で２時間加熱後に放出される水の割合であってよい。 The sediment (C1) or the deposit (C2) may have a water content or a water absorption rate of, for example, 0.01% by mass or more, preferably 5% by mass or more with respect to the total amount of the sediment.
Further, the sediment (C1) or the deposit (C2) may have a water content of, for example, 50% by mass or less, preferably 30% by mass or less, and more preferably 10% by mass or less with respect to the total amount of the sediment.
The water content may be, for example, the ratio of water released after heating at 105 ° C. for 2 hours to the total amount of sediment.
　本発明の剤は、ポリマー（Ｂ）の割合が、粉塵飛散抑制や堆積物の凝固性等の観点から、堆積物（Ｃ１）又は堆積物（Ｃ２）１００質量部に対して、例えば、０．０１質量部以上（例えば、０．０５質量部超、０．０６質量部以上、０．０７部以上）、好ましくは０．０８質量部以上（例えば、０．０９質量部以上）、より好ましくは０．１質量部以上（例えば、０．１１質量部以上、０．１２質量部以上、０．１３質量部以上、０．１４質量部以上）、特に好ましくは０．１５質量部以上（例えば、０．１６質量部以上、０．１７質量部以上、０．１８質量部以上、０．１９質量部以上）等となるように使用してもよく、比較的高い割合（例えば、０．２質量部以上、０．３質量部以上、０．４質量部以上、０．５質量部以上、０．６質量部以上、０．７質量部以上、０．８質量部以上、０．９質量部以上、１質量部以上、２質量部以上、３質量部以上、４質量部以上、５質量部以上、７質量部以上、１０質量部以上等）となるように使用してもよい。 In the agent of the present invention, the proportion of the polymer (B) is, for example, 0. 01 parts by mass or more (for example, more than 0.05 parts by mass, 0.06 parts by mass or more, 0.07 parts or more), preferably 0.08 parts by mass or more (for example, 0.09 parts by mass or more), more preferably. 0.1 parts by mass or more (for example, 0.11 parts by mass or more, 0.12 parts by mass or more, 0.13 parts by mass or more, 0.14 parts by mass or more), particularly preferably 0.15 parts by mass or more (for example, It may be used so as to be 0.16 parts by mass or more, 0.17 parts by mass or more, 0.18 parts by mass or more, 0.19 parts by mass or more, and a relatively high ratio (for example, 0.2 parts by mass). Parts or more, 0.3 parts by mass or more, 0.4 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, 0.7 parts by mass or more, 0.8 parts by mass or more, 0.9 parts by mass As mentioned above, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 7 parts by mass or more, 10 parts by mass or more, etc.) may be used.
　また、本発明の剤は、ポリマー（Ｂ）の割合が、コスト、環境負荷等の観点から、堆積物（Ｃ１）又は堆積物（Ｃ２）１００質量部に対して、例えば、３０質量部以下、（好ましくは、２５質量部以下）、好ましくは２０質量部以下（例えば、１０質量部以下）、より好ましくは５質量部以下（例えば、３質量部以下、１質量部以下）等となるように使用してもよい。 Further, in the agent of the present invention, the proportion of the polymer (B) is, for example, 30 parts by mass or less with respect to 100 parts by mass of the deposit (C1) or the deposit (C2) from the viewpoint of cost, environmental load and the like. (Preferably 25 parts by mass or less), preferably 20 parts by mass or less (for example, 10 parts by mass or less), more preferably 5 parts by mass or less (for example, 3 parts by mass or less, 1 part by mass or less) and the like. You may use it.
[堆積物]
　本発明は、ポリマー（Ｂ）のエマルションであるエマルション（Ａ）を含有する堆積物（以下、堆積物（Ｄ））も包含する。堆積物（Ｄ）は、堆積成分、すなわち、堆積物の構成成分の堆積物であってよい。
　堆積物（Ｄ）は、野積みされた物であってもよいし、野積み前後の輸送工程における物であってもよい。
　堆積物（Ｄ）、又は、堆積物（Ｄ）の堆積成分の種類や大きさは、上記例示の堆積物（Ｃ１）又は堆積物（Ｃ２）と同様のものであってよい。 [Sediment]
The present invention also includes a deposit (hereinafter, deposit (D)) containing an emulsion (A) which is an emulsion of the polymer (B). The deposit (D) may be a sedimentary component, i.e., a deposit of a constituent of the deposit.
The deposit (D) may be a piled up in the open, or may be a deposit in the transportation process before and after the open up.
The type and size of the sediment (D) or the sedimentary component of the deposit (D) may be the same as that of the above-exemplified sediment (C1) or sediment (C2).
　堆積物（Ｄ）全体において、ポリマー（Ｂ）の割合は、例えば、０．０１質量％以上（例えば、０．０５質量％超、０．０６質量％以上、０．０７質量％以上）、好ましくは０．０８質量％以上（例えば、０．０９質量％以上）、より好ましくは０．１質量％以上（例えば、０．１１質量％以上、０．１２質量％以上、０．１３質量％以上、０．１４質量％以上）、特に好ましくは０．１５質量％以上（例えば、０．１６質量％以上、０．１７質量％以上、０．１８質量％以上、０．１９質量％以上）等となるように使用してもよく、比較的高い割合（例えば、０．２質量％以上、０．３質量％以上、０．４質量％以上、０．５質量％以上、０．６質量％以上、０．７質量％以上、０．８質量％以上、０．９質量％以上、１質量％以上、２質量％以上、３質量％以上、４質量％以上、５質量％以上、７質量％以上、１０質量％以上等）等であってもよい。 The proportion of the polymer (B) in the entire deposit (D) is, for example, 0.01% by mass or more (for example, more than 0.05% by mass, 0.06% by mass or more, 0.07% by mass or more), preferably. Is 0.08% by mass or more (for example, 0.09% by mass or more), more preferably 0.1% by mass or more (for example, 0.11% by mass or more, 0.12% by mass or more, 0.13% by mass or more). , 0.14% by mass or more), particularly preferably 0.15% by mass or more (for example, 0.16% by mass or more, 0.17% by mass or more, 0.18% by mass or more, 0.19% by mass or more) and the like. It may be used in a relatively high proportion (for example, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass). 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 7% by mass % Or more, 10% by mass or more, etc.).
　また、堆積物（Ｄ）全体において、ポリマー（Ｂ）の割合の上限値は、例えば、３０質量％以下（例えば、２５質量％以下）、好ましくは２０質量％以下（例えば、１０質量％以下）、より好ましくは５質量％以下（例えば、３質量％以下、１質量％以下）等であってもよい。 Further, the upper limit of the proportion of the polymer (B) in the entire deposit (D) is, for example, 30% by mass or less (for example, 25% by mass or less), preferably 20% by mass or less (for example, 10% by mass or less). , More preferably 5% by mass or less (for example, 3% by mass or less, 1% by mass or less) and the like.
[堆積物の製造方法]
　上記堆積物（Ｄ）は、ポリマー（Ｂ）のエマルションであるエマルション（Ａ）を堆積成分、すなわち、堆積物の構成成分に散布もしくは混合等することにより、得ることができる。すなわち、本発明は、ポリマー（Ｂ）のエマルション（Ａ）を堆積成分、すなわち堆積物の構成成分に散布する、堆積物の製造方法も包含する。 [Manufacturing method of sediment]
The deposit (D) can be obtained by spraying or mixing the emulsion (A), which is an emulsion of the polymer (B), with the sediment component, that is, the constituent component of the deposit. That is, the present invention also includes a method for producing a sediment, in which the emulsion (A) of the polymer (B) is sprayed on a sediment component, that is, a constituent component of the sediment.
　エマルション（Ａ）を堆積成分に散布する方法としては、特に限定されないが、例えば、散水車、スプレー、シャワーノズル、塩化ビニルパイプ、スプリンクラー等の各種（滴下）散布装置を使用してもよい。 The method of spraying the emulsion (A) on the deposited component is not particularly limited, but for example, various (drop) spraying devices such as a sprinkler, a spray, a shower nozzle, a vinyl chloride pipe, and a sprinkler may be used.
　散布方法としては、吐出口から棒状に散布（ベタ掛け）してもよく、堆積物に対する付着効率が高まり、粉塵抑制効果が高まる等の観点から、細かいシャワーリングを好適に使用してもよい。
　また、散布時に塩基と混合して、散布してもよい。 As a spraying method, a rod-shaped spray (solid) may be used from the discharge port, or a fine shower ring may be preferably used from the viewpoint of increasing the adhesion efficiency to the deposit and enhancing the dust suppressing effect.
Further, it may be mixed with a base at the time of spraying and sprayed.
　エマルション（Ａ）を堆積成分に散布するタイミングとしては、如何なるタイミングでも良く、野積み前および、野積み前の堆積物をベルトコンベア輸送中に散布してもよいし、野積み作業中でもよい。また野積み後の堆積物に散布しても良い。 The timing of spraying the emulsion (A) on the sedimentary components may be any timing, and the deposits before and before the field stacking may be sprayed during the transportation of the belt conveyor, or during the field stacking work. It may also be sprayed on the sediment after being piled up in the open.
　剤は、水を含む形態（例えば、水を含むエマルション（Ａ）、エマルション（Ａ）の水希釈液等）であるのが好ましい。例えば、散布においては、水を含むエマルション（Ａ）又はエマルション（Ａ）の水希釈液を散布することが好ましい。
　エマルション（Ａ）（又は剤）におけるエマルション（Ａ）の固形分、すなわちエマルション（Ａ）及び乳化剤の固形分の濃度は、効率良く散布できることや、粉塵飛散抑制、堆積物の凝固性等の観点から、例えば、０．０１質量％以上、好ましくは０．１質量％以上、より好ましくは１質量％以上等であってもよい。
　また、エマルション（Ａ）（又は剤）における固形分濃度は、効率良く散布できる等の観点から、例えば、５０質量％以下、好ましくは４０質量％以下、より好ましくは３０質量％以下等であってもよい。
　エマルション（Ａ）（又は剤）における固形分濃度は、比較的高い濃度（例えば、４０質量％以上等）であってもよいし、比較的低い濃度（例えば、２０質量％以下等）であってもよい。なお、散布においては、比較的高い固形分濃度のエマルション（Ａ）（又は剤）を、水等によって希釈して散布してもよい。 The agent is preferably in the form of containing water (for example, an emulsion (A) containing water, a water-diluted solution of the emulsion (A), etc.). For example, in spraying, it is preferable to spray the emulsion (A) containing water or the water-diluted solution of the emulsion (A).
The solid content of the emulsion (A) in the emulsion (A) (or agent), that is, the concentration of the solid content of the emulsion (A) and the emulsifier can be efficiently sprayed, dust scattering is suppressed, and the coagulation property of the deposit is satisfied. For example, it may be 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more.
The solid content concentration in the emulsion (A) (or agent) is, for example, 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, from the viewpoint of efficient spraying. May be good.
The solid content concentration in the emulsion (A) (or agent) may be a relatively high concentration (for example, 40% by mass or more) or a relatively low concentration (for example, 20% by mass or less). May be good. In spraying, the emulsion (A) (or agent) having a relatively high solid content concentration may be diluted with water or the like and sprayed.
　エマルション（Ａ）（又は剤）の粘度は、効率良く散布できることや、粉塵飛散抑制、堆積物の凝固性等の観点から、例えば、０ｍＰａ・ｓ以上、好ましくは２０ｍＰａ・ｓ以上、より好ましくは３０ｍＰａ・ｓ以上等であってもよい。
　また、エマルション（Ａ）（又は剤）の粘度は、効率良く散布できる等の観点から、例えば、５，０００ｍＰａ・ｓ以下、好ましくは２，０００ｍＰａ・ｓ以下、より好ましくは１，０００ｍＰａ・ｓ以下等であってもよい。 The viscosity of the emulsion (A) (or agent) is, for example, 0 mPa · s or more, preferably 20 mPa · s or more, more preferably 30 mPa, from the viewpoints of efficient spraying, suppression of dust scattering, coagulation of deposits, and the like. -It may be s or more.
The viscosity of the emulsion (A) (or agent) is, for example, 5,000 mPa · s or less, preferably 2,000 mPa · s or less, more preferably 1,000 mPa · s or less, from the viewpoint of efficient spraying. And so on.
　なお、エマルション（Ａ）（又は剤）の粘度は、例えば、ＢＭ粘度計（東機産業製、品番：ＴＶＢ－１０Ｍ）を用い、回転速度３０ｒｐｍでの２５℃における粘度を測定してもよい。 The viscosity of the emulsion (A) (or agent) may be measured at 25 ° C. at a rotation speed of 30 rpm using, for example, a BM viscometer (manufactured by Toki Sangyo Co., Ltd., product number: TVB-10M).
　エマルション（Ａ）の散布は、堆積成分に対するポリマー（Ｂ）の割合が、上記例示の堆積物（Ｃ１）又は堆積物（Ｃ２）に対する割合と同様の範囲となるように行ってもよい。 The emulsion (A) may be sprayed so that the ratio of the polymer (B) to the sediment component is in the same range as the ratio to the above-exemplified deposit (C1) or deposit (C2).
　本発明は上述した各実施形態に限定されるものではなく、種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明に含まれる。 The present invention is not limited to the above-described embodiments, and various modifications can be made, and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the present invention. ..
　次に本発明を実施例に基づいてさらに詳細に説明するが、本発明は、かかる実施例のみに限定されるものではない。なお、以下の実施例において、「部」及び「％」は断りのない限り、それぞれ「質量部」及び「質量％」を意味する。 Next, the present invention will be described in more detail based on Examples, but the present invention is not limited to such Examples. In the following examples, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.
〔粉塵抑制〕
　含水率１０％のブラジル産カラジャス鉄鉱石１１０部を使って高さ３～１０ｃｍ、幅５～１５ｃｍの山を作り、当該鉄鉱石の山に対して、各試料１０部の溶液を霧吹きで散布した。試料を塗布した山に対して、扇風機（松下精工株式会社製 F-C301H）の「強」で送風し、重量変化量(飛散量)を測定した。 [Dust control]
Using 110 parts of Brazilian Carajás iron ore with a water content of 10%, a mountain with a height of 3 to 10 cm and a width of 5 to 15 cm was made, and a solution of 10 parts of each sample was sprayed on the mountain of iron ore. .. A fan (F-C301H manufactured by Matsushita Seiko Co., Ltd.) was used to blow air to the mountain to which the sample was applied, and the amount of weight change (scattering amount) was measured.
　初期粉塵飛散量
　鉄鉱石に試料を散布した直後に試験し、以下基準で評価した。
（評価基準）
◎：重量損失が０．６％未満
○：重量損失が０．６～３％未満
△：重量損失が３～１０％未満
×：重量損失が１０％以上 Initial dust scattering amount The test was conducted immediately after the sample was sprayed on the iron ore, and the evaluation was made according to the following criteria.
(Evaluation criteria)
⊚: Weight loss is less than 0.6% ○: Weight loss is less than 0.6 to 3% Δ: Weight loss is less than 3 to 10% ×: Weight loss is 10% or more
　５０℃で２４時間乾燥後の粉塵飛散量
　鉄鉱石に試料を散布し、５０℃で２４時間乾燥後のサンプルを試験し、以下基準で評価した。
（評価基準）
◎：重量損失が０．６％未満
○：重量損失が０．６～３％未満
△：重量損失が３～１０％未満
×：重量損失が１０％以上 Amount of dust scattered after drying at 50 ° C. for 24 hours The sample was sprayed on iron ore, and the sample after drying at 50 ° C. for 24 hours was tested and evaluated according to the following criteria.
(Evaluation criteria)
⊚: Weight loss is less than 0.6% ○: Weight loss is less than 0.6 to 3% Δ: Weight loss is less than 3 to 10% ×: Weight loss is 10% or more
〔鉄鉱石粉末指触〕
　上記粉塵抑制で作成した５０℃で２４時間乾燥後の各試料を指触し、以下基準で評価した。
（評価基準）
○：鉄鉱石粉末が纏り硬い
△：鉄鉱石粉末が纏っているが簡単に崩れてばらける
×：鉄鉱石粉末が纏っていない [Iron ore powder touch]
Each sample after drying at 50 ° C. for 24 hours prepared by controlling dust was touched and evaluated according to the following criteria.
(Evaluation criteria)
○: Iron ore powder is covered and hard △: Iron ore powder is covered but easily crumbles and disintegrates ×: Iron ore powder is not covered
〔溶出試験〕
　含水率１０％のブラジル産カラジャス鉄鉱石１００部に対して、各試料を１０部添加して、よく掻き混ぜた（試料の固形重量をＷ０とする）。１５０℃で１時間乾燥し初期重量(Ｗ１)を測定した。初期重量を測定した各試料に対して、脱イオン水２００部で洗浄し、ろ紙（ＡＤＶＡＮＴＥＣ社製円形定性ろ紙Ｎｏ１３１　目開き３μｍ）でろ過して含水した試料を回収し、さらに１５０℃２時間で乾燥後の重量（Ｗ２）を測定した。
　以下の式で算出した値を溶出量Ｗ（％）として、評価した。
　　　　　　　　　Ｗ＝{（Ｗ１－Ｗ２）／Ｗ０}×１００ [Elution test]
To 100 parts of Brazilian Carajás iron ore having a water content of 10%, 10 parts of each sample was added and stirred well (the solid weight of the sample is W0). The product was dried at 150 ° C. for 1 hour and the initial weight (W1) was measured. Each sample whose initial weight was measured was washed with 200 parts of deionized water, filtered through a filter paper (ADVANTEC circular qualitative filter paper No131, opening 3 μm) to collect the water-containing sample, and further at 150 ° C. for 2 hours. The weight (W2) after drying was measured.
The value calculated by the following formula was evaluated as the elution amount W (%).
W = {(W1-W2) / W0} × 100
（評価基準）
○：溶出率が１０％未満
△：溶出率が１０％以上３０％未満
×：溶出率が３０％以上 (Evaluation criteria)
◯: Elution rate is less than 10% Δ: Elution rate is 10% or more and less than 30% ×: Elution rate is 30% or more
（実施例１）
　ポリカルボン酸系エマルションＷＲ－５１７（株式会社日本触媒製　固形分３０％、酸価２４５ｍｇ ＫＯＨ／ｇ）を固形分５％になるように脱イオン水で希釈して試料を調製した。目開き１ｍｍの篩に掛けた含水率１０％のブラジル産カラジャス鉄鉱石１１０部に、上記固形分５％に調整した試料を１０部添加して上記評価に供した。 (Example 1)
A sample was prepared by diluting a polycarboxylic acid-based emulsion WR-517 (solid content 30%, acid value 245 mg KOH / g, manufactured by Nippon Catalyst Co., Ltd.) with deionized water so as to have a solid content of 5%. To 110 parts of Brazilian Carajás iron ore having a water content of 10% and sieved with a mesh opening of 1 mm, 10 parts of a sample adjusted to have a solid content of 5% was added and subjected to the above evaluation.
（実施例２～４）
　固形分調整以外は実施例１と同様に行った。 (Examples 2 to 4)
The procedure was the same as in Example 1 except for the solid content adjustment.
（実施例５）
　含水率１０％のブラジル産カラジャス鉄鉱石を目開き５ｍｍの篩で分級したことと、固形分調整以外は、実施例１と同様に行った。 (Example 5)
The same procedure as in Example 1 was carried out except that the Brazilian Carajás iron ore having a water content of 10% was classified by a sieve having an opening of 5 mm and the solid content was adjusted.
（実施例６）
　ポリカルボン酸系エマルションＷＲ－６５０（株式会社日本触媒製　固形分３０％、酸価２５５ｍｇ ＫＯＨ／ｇ）を固形分３０％で用いた以外は実施例１と同様に行った。 (Example 6)
The same procedure as in Example 1 was carried out except that the polycarboxylic acid emulsion WR-650 (solid content 30%, acid value 255 mg KOH / g, manufactured by Nippon Shokubai Co., Ltd.) was used at a solid content of 30%.
（実施例７～１０）
　以下のポリカルボン酸系エマルションを固形分３０％で用いた以外は実施例１と同様に行った。
実施例７：ポリカルボン酸系エマルションＷＲ－５１７－Ａ（株式会社日本触媒製　固形分３０％、酸価２７５ｍｇ ＫＯＨ／ｇ）
実施例８：ポリカルボン酸系エマルションＷＲ－５１７－Ｂ（株式会社日本触媒製　固形分３０％、酸価１２０ｍｇ ＫＯＨ／ｇ）
実施例９：ポリカルボン酸系エマルションＷＲ－５１７－Ｃ（株式会社日本触媒製　固形分３０％、酸価１４５ｍｇ ＫＯＨ／ｇ）
実施例１０：ポリカルボン酸系エマルションＷＲ－５１７－Ｄ（株式会社日本触媒製　固形分３０％、酸価１１５ｍｇ ＫＯＨ／ｇ） (Examples 7 to 10)
The same procedure as in Example 1 was carried out except that the following polycarboxylic acid emulsion was used with a solid content of 30%.
Example 7: Polycarboxylic acid emulsion WR-517-A (Nippon Shokubai Co., Ltd. solid content 30%, acid value 275 mg KOH / g)
Example 8: Polycarboxylic acid emulsion WR-517-B (Nippon Shokubai Co., Ltd. solid content 30%, acid value 120 mg KOH / g)
Example 9: Polycarboxylic acid emulsion WR-517-C (Nippon Shokubai Co., Ltd. solid content 30%, acid value 145 mg KOH / g)
Example 10: Polycarboxylic acid emulsion WR-517-D (Nippon Shokubai Co., Ltd. solid content 30%, acid value 115 mg KOH / g)
（比較例１）
　含水率１０％のブラジル産カラジャス鉄鉱石に試料を何も用いず評価に供した。 (Comparative Example 1)
Brazilian Carajás iron ore with a water content of 10% was evaluated without using any samples.
（比較例２）
　含水率１０％のブラジル産カラジャス鉄鉱石１１０部に脱イオン水１０部を添加して評価に供した。 (Comparative Example 2)
10 parts of deionized water was added to 110 parts of Brazilian Carajás iron ore having a water content of 10% and used for evaluation.
（比較例３）
　ＰＥＧ１０００（株式会社ＡＤＥＫＡ製　Ｍｗ１０００のポリエチレグリコール）を脱イオン水で溶解させ固形分３０％に調整し、含水率１０％のブラジル産カラジャス鉄鉱石１１０部に対して１０部添加して評価に供した。 (Comparative Example 3)
PEG1000 (polyethyleglycol of Mw1000 manufactured by ADEKA Corporation) was dissolved in deionized water to adjust the solid content to 30%, and 10 parts were added to 110 parts of Brazilian Carajas iron ore having a water content of 10% for evaluation. ..
（比較例４）
　塩化カルシウム（林純薬工業製　一級試薬）を脱イオン水で溶解させ固形分５％に調整し、含水率１０％のブラジル産カラジャス鉄鉱石１１０部に対して１０部添加して評価に供した。 (Comparative Example 4)
Calcium chloride (a first-class reagent manufactured by Hayashi Junyaku Kogyo) was dissolved in deionized water to adjust the solid content to 5%, and 10 parts were added to 110 parts of Brazilian Carajas iron ore with a water content of 10% for evaluation. ..
（比較例５～８）
　塩化カルシウムの固形分調整以外は比較例４と同様に行った。 (Comparative Examples 5 to 8)
The procedure was the same as in Comparative Example 4 except that the solid content of calcium chloride was adjusted.
　これらの結果等をまとめたものを表１及び表２に示す。 Tables 1 and 2 show a summary of these results.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１に示すように、実施例では、初期の粉塵飛散量と高温環境下に曝された後の粉塵飛散量を抑制できた。また、実施例では、高温環境下に曝された後の方が、初期より粉塵飛散量を抑制できた。
　また、実施例では、鉄鉱石粉末が纏わりやすく、崩れにくかった。
　さらに、実施例では、水中への試料の溶出量が少なかった。 As shown in Table 1, in the examples, it was possible to suppress the initial amount of dust scattering and the amount of dust scattered after being exposed to a high temperature environment. Further, in the examples, the amount of dust scattered could be suppressed from the initial stage after being exposed to a high temperature environment.
Further, in the examples, the iron ore powder was easy to cling to and did not easily collapse.
Furthermore, in the examples, the amount of the sample eluted in water was small.
　本発明によれば、粉塵飛散抑制用などとして有用な剤等を提供できる。 According to the present invention, it is possible to provide an agent or the like useful for suppressing dust scattering.

Claims (8)

  1. 　酸基含有ポリマーのエマルションを含有する、粉塵飛散抑制剤。 A dust scattering inhibitor containing an emulsion of an acid group-containing polymer.
  2. 　酸基含有ポリマーのエマルションを含有する、野積みされた堆積物用の凝固剤。 A coagulant for open-stacked sediments containing an emulsion of acid group-containing polymers.
  3. 　粉塵又は堆積物が、製鉄原料である、請求項１又は２記載の剤。 The agent according to claim 1 or 2, wherein the dust or deposit is a raw material for steelmaking.
  4. 　堆積成分の堆積物であって、酸基含有ポリマーのエマルションを含有する堆積物。 Sediment of sedimentary components, which contains an emulsion of an acid group-containing polymer.
  5. 　酸基含有ポリマーのエマルションを堆積成分に散布する、堆積物の製造方法。 A method for producing sediments, in which an emulsion of an acid group-containing polymer is sprayed on the sedimentary components.
  6. 　堆積物が野積みされた製鉄原料である、請求項４記載の堆積物又は請求項５記載の製造方法。 The deposit according to claim 4 or the production method according to claim 5, wherein the deposit is a raw material for steelmaking that is piled up in the open.
  7. 　エマルションの酸価が１１０ｍｇ ＫＯＨ／ｇ以上である請求項１～６のいずれかに記載の剤、堆積物、又は製造方法。 The agent, deposit, or production method according to any one of claims 1 to 6, wherein the acid value of the emulsion is 110 mgKOH / g or more.
  8. 　酸基が、カルボン酸基、スルホン酸基及びリン酸基から選択される１種以上である請求項１～７のいずれかに記載の剤、堆積物、又は製造方法。 The agent, deposit, or production method according to any one of claims 1 to 7, wherein the acid group is at least one selected from a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
PCT/JP2021/024014 2020-06-25 2021-06-24 Dust scattering inhibitor WO2021261568A1 (en)

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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5247587A (en) * 1975-10-14 1977-04-15 Mitsui Petrochem Ind Ltd Scattering inhibitor for pulverulent bodies
JPS5278786A (en) * 1975-12-26 1977-07-02 Nippon Zeon Co Ltd Scattering preventive
JPS53115684A (en) * 1977-03-19 1978-10-09 Mitsui Petrochem Ind Ltd Powdery body scattering preventive agent
JPS5413481A (en) * 1977-07-02 1979-01-31 Mitsui Petrochem Ind Ltd Powder scattering inhibitor
JPS5543133A (en) * 1978-09-20 1980-03-26 Nippon Steel Corp Coating for deposit stored in open air
JPS6143679A (en) * 1984-08-07 1986-03-03 Kurita Water Ind Ltd Agent for suppressing increase of water-content of material stored in open-air
JPS62146804A (en) * 1985-12-20 1987-06-30 Sumitomo Metal Ind Ltd Treatment for open freighting coal accumulation
JPS62240376A (en) * 1986-04-10 1987-10-21 Idemitsu Petrochem Co Ltd Coat dust scattering inhibitor
JPS62285963A (en) * 1986-06-05 1987-12-11 Nippon Steel Corp Paint for use in coating open-air stored cargo and coating method
JPH04347161A (en) * 1991-05-24 1992-12-02 Tetsugen:Kk Film-forming type dustproof and deodorizing agent
JP2001031955A (en) * 1999-07-19 2001-02-06 Daicel Chem Ind Ltd Surface-treating agent for deposited particulate substance and method for preventing flowing powder
JP2003001219A (en) * 2001-06-22 2003-01-07 Kurita Water Ind Ltd Scattering preventive agent for deposit in incineration plant
JP2011094007A (en) * 2009-10-29 2011-05-12 Eco-Bond Co Ltd Dust preventive and dust preventing method
WO2012132521A1 (en) * 2011-03-25 2012-10-04 栗田工業株式会社 Method for modifying slurry of coal and/or iron ore
JP2019090004A (en) * 2017-11-14 2019-06-13 東洋インキＳｃホールディングス株式会社 Coating agent for preventing scattering of outdoor deposit

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5247587A (en) * 1975-10-14 1977-04-15 Mitsui Petrochem Ind Ltd Scattering inhibitor for pulverulent bodies
JPS5278786A (en) * 1975-12-26 1977-07-02 Nippon Zeon Co Ltd Scattering preventive
JPS53115684A (en) * 1977-03-19 1978-10-09 Mitsui Petrochem Ind Ltd Powdery body scattering preventive agent
JPS5413481A (en) * 1977-07-02 1979-01-31 Mitsui Petrochem Ind Ltd Powder scattering inhibitor
JPS5543133A (en) * 1978-09-20 1980-03-26 Nippon Steel Corp Coating for deposit stored in open air
JPS6143679A (en) * 1984-08-07 1986-03-03 Kurita Water Ind Ltd Agent for suppressing increase of water-content of material stored in open-air
JPS62146804A (en) * 1985-12-20 1987-06-30 Sumitomo Metal Ind Ltd Treatment for open freighting coal accumulation
JPS62240376A (en) * 1986-04-10 1987-10-21 Idemitsu Petrochem Co Ltd Coat dust scattering inhibitor
JPS62285963A (en) * 1986-06-05 1987-12-11 Nippon Steel Corp Paint for use in coating open-air stored cargo and coating method
JPH04347161A (en) * 1991-05-24 1992-12-02 Tetsugen:Kk Film-forming type dustproof and deodorizing agent
JP2001031955A (en) * 1999-07-19 2001-02-06 Daicel Chem Ind Ltd Surface-treating agent for deposited particulate substance and method for preventing flowing powder
JP2003001219A (en) * 2001-06-22 2003-01-07 Kurita Water Ind Ltd Scattering preventive agent for deposit in incineration plant
JP2011094007A (en) * 2009-10-29 2011-05-12 Eco-Bond Co Ltd Dust preventive and dust preventing method
WO2012132521A1 (en) * 2011-03-25 2012-10-04 栗田工業株式会社 Method for modifying slurry of coal and/or iron ore
JP2019090004A (en) * 2017-11-14 2019-06-13 東洋インキＳｃホールディングス株式会社 Coating agent for preventing scattering of outdoor deposit

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