WO2014003112A1 - Method for producing alkali detergent composition for steel plate - Google Patents

Method for producing alkali detergent composition for steel plate Download PDF

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Publication number
WO2014003112A1
WO2014003112A1 PCT/JP2013/067637 JP2013067637W WO2014003112A1 WO 2014003112 A1 WO2014003112 A1 WO 2014003112A1 JP 2013067637 W JP2013067637 W JP 2013067637W WO 2014003112 A1 WO2014003112 A1 WO 2014003112A1
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agent
carbon atoms
detergent composition
weight
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PCT/JP2013/067637
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French (fr)
Japanese (ja)
Inventor
弘子 池内
土井　康広
Original Assignee
花王株式会社
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Priority to CN201380020586.1A priority Critical patent/CN104245912B/en
Publication of WO2014003112A1 publication Critical patent/WO2014003112A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to a method for producing an alkaline detergent composition for a steel sheet used for cleaning oil stains, iron powder, and the like adhering to a steel sheet (steel strip) made of iron, aluminum, copper or the like.
  • Degreasing and cleaning of the steel sheet surface is necessary as a pretreatment for performing surface treatment such as plating and painting along with pickling, and is a very large factor that determines the quality of products.
  • the dirt adhering to the steel sheet surface include oil dirt such as rolling oil and rust preventive oil adhering during cold rolling, and solid dirt such as iron powder.
  • rolling oil suitable for improving mill cleanliness and productivity has come to be used, and a cleaning agent having excellent cleaning properties for rolling oil is required.
  • the cleaning agent is required to have fluidity even at a high concentration and to have excellent storage stability.
  • the cleaning agent is also required to have low foaming and excellent workability.
  • JP-A-7-41975 alcohols, surfactants, fatty acids, chelating agents, etc., which are usually poorly soluble at a high alkali concentration, can be blended, and the high detergency, foam suppression,
  • the alkali agent is 10 to 35% by weight on the basis of Na 2 O
  • the aliphatic compound having 2 to 6 polar groups in one molecule is 0.1 to
  • a high-concentration one-component alkaline detergent composition characterized by containing 20% by weight is disclosed.
  • Japanese Patent Application Laid-Open No. 2011-117043 discloses that a steel plate can be cleaned and removed with high cleaning efficiency while suppressing slippage of the steel plate on a roll at a low cleaning temperature of 40 to 60 ° C., and foaming is prevented.
  • an alkaline detergent composition for steel sheet that can be suppressed an alkaline agent, two types of polyoxyalkylene alkyl ethers in which oxyalkylene is bonded to a secondary alcohol having 9 to 15 carbon atoms, An alkaline detergent composition for steel sheet containing a chelating agent and water is disclosed.
  • Japanese Patent Application Laid-Open No. 2001-316693 has an object to provide a liquid alkaline detergent composition that has excellent detergency, does not foam during washing, can be stably stored in a concentrated state, and does not adversely affect the global environment.
  • a liquid alkaline detergent composition comprising an alkali agent and a polyoxyethylene amino ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms is disclosed.
  • a component containing an alkaline agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F) is mixed with a stirring blade.
  • a method for producing an alkaline detergent composition for a steel sheet comprising the step (1) of introducing into a stirring tank having a step and the step (2) of mixing the components by rotating the stirring blade, wherein the step (1)
  • the proportion of the component introduced into the stirring tank in the above is as follows: alkaline agent (A) 34 wt% or more and 45 wt% or less, chelating agent (B) 0.5 wt% or more and 12 wt% or less, nonionic surfactant ( C) 0.1 wt% or more and 8 wt% or less, slurrying agent (D) 0.4 wt% or more and 4.5 wt% or less, dispersant (E) 0.05 wt% or more and 2.0 wt% or less
  • the dispersant (E) is composed of compounds represented by the following general formulas (1) to (5) A dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 ⁇ m are dispersed in a
  • R 1 is a hydrocarbon group having 1 to 4 carbon atoms
  • R 2 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms
  • R 3 is a hydrogen atom or a methyl group.
  • R 4 is a hydrocarbon group having 1 to 6 carbon atoms
  • a 1 O is an alkyleneoxy group having 2 or 3 carbon atoms
  • m is an average added mole number of A 1 O of 0 or more. 3 or less
  • the total number of carbon atoms of (A 1 O) m is 0 or more and 6 or less.
  • R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms.
  • R 6 is a hydrogen atom or a methyl group.
  • R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
  • a 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the average value of the total of n1, n2, n3 and n4 is 0.5 or more and 8 or less.
  • the present invention is for a steel sheet containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F).
  • A alkali agent
  • B a chelating agent
  • C nonionic surfactant
  • D a slurrying agent
  • E dispersing agent
  • F water
  • An alkaline detergent composition wherein the proportion of each component is from 34% to 45% by weight of the alkali agent (A), 0.5% to 12% by weight of the chelating agent (B), a nonionic interface Activator (C) 0.1 wt% to 8 wt%, Slurrant (D) 0.4 wt% to 4.5 wt%, Dispersant (E) 0.05 wt% to 2.0 wt% % Or less, and the dispersant (E) is at least one selected from the group consisting of compounds represented by the general formulas (1) to (5), and the alkaline detergent composition for steel sheet, Oil droplets of the nonionic surfactant (C) having a particle size of less than 50 ⁇ m are dispersed in the phase containing water (F). A dispersion, a steel sheet for an alkaline detergent composition.
  • JP-A-7-41975 and JP-A-111-117043 concentrated detergents are produced.
  • the blended raw materials are used as a line mixer.
  • a step of stirring with an apparatus having a high shearing force such as a homomixer and a homogenizer is required.
  • the liquid alkaline detergent composition disclosed in JP-A-2001-316693 can be stably stored, but if the shearing force during stirring of the raw material containing polyoxyethylene amino ether, which is an oil component, is low, the oil component is reduced. It became difficult to reduce the particle size, and the stability tended to decrease. Therefore, there is a demand for a method of producing a concentrated detergent composition having excellent storage stability by using a stirring device having a stirring blade having a low shearing force instead of a stirring device having a high shearing force.
  • a component containing an alkaline agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F) is mixed with a stirring blade.
  • a method for producing an alkaline detergent composition for a steel sheet comprising the step (1) of introducing into a stirring tank having a step and the step (2) of mixing the components by rotating the stirring blade, wherein the step (1)
  • the proportion of the component introduced into the stirring tank in the above is as follows: alkaline agent (A) 34 wt% or more and 45 wt% or less, chelating agent (B) 0.5 wt% or more and 12 wt% or less, nonionic surfactant ( C) 0.1 wt% or more and 8 wt% or less, slurrying agent (D) 0.4 wt% or more and 4.5 wt% or less, dispersant (E) 0.05 wt% or more and 2.0 wt% or less
  • the dispersant (E) comprises the compounds represented by the general formulas (1) to (5).
  • the present invention is for a steel sheet containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F).
  • A alkali agent
  • B a chelating agent
  • C nonionic surfactant
  • D a slurrying agent
  • E dispersing agent
  • F water
  • An alkaline detergent composition wherein the proportion of each component is from 34% to 45% by weight of the alkali agent (A), 0.5% to 12% by weight of the chelating agent (B), a nonionic interface Activator (C) 0.1 wt% to 8 wt%, Slurrant (D) 0.4 wt% to 4.5 wt%, Dispersant (E) 0.05 wt% to 2.0 wt% % Or less, and the dispersant (E) is at least one selected from the group consisting of compounds represented by the general formulas (1) to (5), and the alkaline detergent composition for steel sheet, Oil droplets of the nonionic surfactant (C) having a particle size of less than 50 ⁇ m are dispersed in the phase containing water (F).
  • a concentrated detergent composition having excellent storage stability in a stirring tank having a stirring blade. Further, according to the present invention, a concentrated detergent composition having excellent storage stability can be provided.
  • the nonionic surfactant forms oil droplets.
  • the oil droplet particle size decreases and storage stability improves, but when the shear force is weak, there are oil droplets with large particle size, and there are chelating agents and slurry agents. Even with time, the oil droplets coalesce with each other to form larger oil droplets and finally separate from the water phase as the oil phase.
  • a dispersant is formed at the interface between oil droplets and water together with a chelating agent and a slurrying agent.
  • the oil droplets are adsorbed and the interfacial tension of the oil droplets is lowered, and the oil droplets are easily broken.
  • the oil droplets are easily dispersed even with low shearing force stirring, and the particle size of the oil droplets is small.
  • the oil droplets are stabilized by a chelating agent, a slurrying agent and a dispersing agent, and the storage stability of the cleaning composition is improved. That is, when stirring at a high shear force, a detergent composition having excellent stability can be obtained without a specific dispersant, but in the case of a low shear force, stability can be obtained by adding a specific dispersant. An excellent cleaning composition is obtained.
  • the manufacturing method of this embodiment is a component containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E), and water (F).
  • A alkali agent
  • B a chelating agent
  • C nonionic surfactant
  • D a slurrying agent
  • E dispersing agent
  • F water
  • any water-soluble alkaline agent can be used in order to ensure the removal of oil stains.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal silicates such as sodium orthosilicate, sodium metasilicate and sodium sesquisilicate
  • alkali metal phosphorus such as trisodium phosphate.
  • An alkali metal carbonate such as an acid salt, disodium carbonate, sodium hydrogen carbonate or dipotassium carbonate, an alkali metal borate such as sodium borate, or the like can be used.
  • Two or more water-soluble alkaline agents may be combined.
  • alkali metal hydroxides and alkali metal silicates preferred are alkali metal hydroxides.
  • sodium hydroxide, potassium hydroxide, sodium orthosilicate and sodium metasilicate are preferable, and sodium hydroxide or potassium hydroxide is more preferable.
  • the blending amount of the alkaline agent (A) is 34% by weight or more and 45% by weight or less.
  • the blending amount of the alkaline agent (A) is preferably 35% by weight or more, and more preferably 37% by weight or more, from the viewpoint of the storage stability of the cleaning agent.
  • the blending amount of the alkaline agent (A) is preferably 42% by weight or less, and more preferably 40% by weight or less, from the viewpoint of suppressing the viscosity increase of the cleaning agent.
  • the blending amount of the alkaline agent (A) corresponds to the content of the alkaline agent in the alkaline detergent composition for steel sheet.
  • ⁇ Chelating agent (B)> The chelating agent (B) used in this embodiment improves the storage stability by reducing the particle size of oil droplets (hereinafter also simply referred to as “oil droplets”) such as a nonionic surfactant (C), It is also presumed that it acts on iron soap and other soils to chelate iron ions and the like, making it easier to dissolve the soil using fatty acid sodium soap and improving the detergency of oil.
  • oil droplets such as a nonionic surfactant (C)
  • Examples of the chelating agent (B) include aldonic acids such as gluconic acid, glucoheptonic acid, glyceric acid, tetronic acid, pentonic acid, hexonic acid and heptonic acid, or alkali metal salts thereof or lower amine salts having 1 to 4 carbon atoms; Alkali metal salt or lower amine salt of aminocarboxylic acid such as acetic acid, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, tetraethylenetetraminehexaacetic acid; alkali metal salt or lower amine salt of citric acid, malic acid or the like or oxycarboxylic acid thereof; amino Phosphonic acids such as trimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid or alkali metal salts or lower amine salts thereof; Ethanolamine, can be used
  • aldonic acid or a salt thereof is preferable, and an alkali metal salt or a lower amine salt is preferable.
  • alkali metal salts or lower amine salts of gluconic acid and glucoheptonic acid are preferable, and gluconate is more preferable.
  • the alkali metal salt is preferably a sodium salt from the viewpoint of improving detergency.
  • Chelating agent (B) should just use at least 1 type, and can be used in combination of 2 or more type. For example, a combination of an alkali metal salt of gluconic acid and an alkali metal salt of ethylenediaminetetraacetic acid can be used.
  • the compounding amount of the chelating agent (B) is 0.5% by weight or more and 12% by weight or less.
  • the blending amount of the chelating agent (B) is preferably 1% by weight or more, more preferably 3% by weight or more, and more preferably 5% by weight or more from the viewpoint of reducing the particle size of the oil droplets of the nonionic surfactant (C). Is more preferable, and 6% by weight or more is even more preferable.
  • the blending amount of the chelating agent (B) is preferably 10% by weight or less, and preferably 8% by weight or less from the viewpoint of reducing the particle size of the oil droplets of the nonionic surfactant (C).
  • the compounding amount of the chelating agent (B) corresponds to the content of the chelating agent in the alkaline detergent composition for steel sheet.
  • Nonionic surfactant (C) used in the present embodiment those generally used for alkaline detergents can be used. However, the nonionic surfactant (C) does not include a compound belonging to the dispersant (E).
  • the nonionic surfactant (C) used in the present embodiment include a compound having a structure in which an alkylene oxide is added to a monohydric alcohol having a hydrocarbon group having 8 or more carbon atoms, and having 8 or more carbon atoms.
  • a compound having a structure in which an alkylene oxide is added to a monovalent or divalent amine having a hydrocarbon group can be used.
  • polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkenylamine can be used.
  • the nonionic surfactant (C) is at least one selected from a compound represented by the following general formula (7) and a compound represented by the following general formula (8) from the viewpoint of oil detergency. It is preferable.
  • R 8 represents a hydrocarbon group having 8 to 18 carbon atoms
  • a 3 O represents an alkyleneoxy group having 2 to 4 carbon atoms
  • o represents an average addition of A 3 O.
  • the number of moles is 2 or more and 20 or less.
  • R 9 represents a hydrocarbon group having 8 to 18 carbon atoms
  • a 4 O represents an alkyleneoxy group having 2 to 4 carbon atoms
  • p and q are averages of A 4 O, respectively. The number of added moles is shown, and p + q is 2 or more and 20 or less.
  • R 8 may be a linear or branched aliphatic hydrocarbon group having 8 to 18 carbon atoms from the viewpoint of oil detergency.
  • the aliphatic hydrocarbon group include saturated (alkyl group) and unsaturated (alkenyl group).
  • the carbon number of R 8 is preferably 14 or less, and more preferably 12 or less, from the viewpoint of oil detergency.
  • Specific examples of the compound represented by the general formula (7) include polyoxyalkylene alkyl ether and polyoxyalkylene alkenyl ether.
  • the alkyleneoxy group represented by A 3 O is an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group. From the viewpoint of storage stability of the cleaning agent, an ethyleneoxy group and / or propylene An oxy group is preferable, and one having both an ethyleneoxy group and a propyleneoxy group is more preferable.
  • the average addition mole number o of the alkyleneoxy group represented by A 3 O is 2 or more, and preferably 4 or more, from the viewpoint of oil detergency.
  • the average added mole number o of the alkyleneoxy group represented by A 3 O in the general formula (7) is 20 or less, and preferably 16 or less, from the viewpoint of oil detergency.
  • R 9 is a linear or branched aliphatic hydrocarbon group having 8 to 18 carbon atoms from the viewpoint of oil detergency.
  • the aliphatic hydrocarbon group include saturated (alkyl group) and unsaturated (alkenyl group).
  • the number of carbon atoms in R 9 is preferably 12 or more, more preferably 16 or more, from the viewpoint of oil detergency.
  • Specific examples of the compound represented by the general formula (8) include polyoxyethylene alkylamine and polyoxyethylene alkenylamine.
  • At least one kind of nonionic surfactant (C) may be used, and two or more kinds may be used in combination.
  • the alkyleneoxy group represented by A 4 O is an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, and is preferably an ethyleneoxy group and / or a propyleneoxy group from the viewpoint of detergency.
  • An ethyleneoxy group is more preferable.
  • the average added mole numbers p and q of the alkyleneoxy group in the general formula (8) are 2 or more, preferably 5 or more, and more preferably 8 or more. From the viewpoint of oil detergency, the average added mole numbers p and q of the alkyleneoxy group in the general formula (8) are 20 or less, more preferably 12 or less.
  • the nonionic surfactant (C) is more preferably the general formula (7) than the general formula (8) from the viewpoint of the storage stability of the cleaning agent.
  • the blending amount of the nonionic surfactant (C) is 0.1% by weight or more and 8% by weight or less. In the present embodiment, the blending amount of the nonionic surfactant (C) is preferably 0.5% by weight or more, and more preferably 0.8% by weight or more from the viewpoint of oil detergency. The blending amount of the nonionic surfactant (C) is preferably 5% by weight or less, more preferably 3% by weight or less from the viewpoint of storage stability and cost of the cleaning agent. The compounding amount of the nonionic surfactant (C) corresponds to the content of the nonionic surfactant in the alkaline detergent composition for steel sheet.
  • the slurrying agent (D) can be blended with a water-soluble polymer carboxylic acid.
  • the cleaning composition containing at least one kind of the water-soluble polymer carboxylic acid can improve the storage stability of the cleaning composition in a liquid or slurry state even at a high concentration.
  • the cleaning composition containing water-soluble polymer carboxylic acid is diluted with water, it maintains the dispersion of the iron powder released in the steel plate cleaning process and makes it difficult to adhere to the steel plate. It contributes to the improvement.
  • Water-soluble polymer carboxylic acid is a polymer containing at least one carboxylic acid, such as acrylic acid homopolymer, acrylic acid-maleic acid copolymer, ⁇ -hydroxyacrylic acid homopolymer, C5 olefin-maleic acid Copolymers, isobutylene-maleic acid copolymers, and alkali metal salts or amine salts such as sodium salts thereof can be used.
  • carboxylic acid such as acrylic acid homopolymer, acrylic acid-maleic acid copolymer, ⁇ -hydroxyacrylic acid homopolymer, C5 olefin-maleic acid Copolymers, isobutylene-maleic acid copolymers, and alkali metal salts or amine salts such as sodium salts thereof can be used.
  • the water-soluble polymeric carboxylic acids from the viewpoint of improving the storage stability of the detergent composition, one or more selected from acrylic acid homopolymers and acrylic acid-maleic acid copolymers are preferable.
  • the weight average molecular weight (MW) of the water-soluble polymer carboxylic acid is 1,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 20,000, still more preferably 5,000 to 10,000.
  • the form of polymerization in the case of a copolymer may be block or random. Two or more water-soluble polymer carboxylic acids may be combined.
  • a weight average molecular weight is measured by the method as described in an Example.
  • the blending amount of the slurrying agent (D) is 0.4 wt% or more and 4.5 wt% or less.
  • the blending amount of the slurry agent (D) is preferably 1% by weight or more, and more preferably 1.2% by weight or more from the viewpoint of storage stability of the cleaning agent.
  • the blending amount of the slurry agent (D) is preferably 3% by weight or less, more preferably 2% by weight or less from the viewpoint of appropriately controlling the viscosity of the detergent composition and ensuring the piping transportation of the detergent composition. .
  • the blending amount of the slurry agent (D) corresponds to the content of the slurry agent in the alkaline detergent composition for steel sheet.
  • the weight ratio of the slurry agent (D) to the nonionic surfactant (C) [slurry agent (D) / nonionic surfactant (C)] is 0.1% from the viewpoint of storage stability of the cleaning agent.
  • the above is preferable, and 1 or more is more preferable.
  • the weight ratio of the slurry agent (D) to the nonionic surfactant (C) [slurry agent (D) / nonionic surfactant (C)] is 50 or less from the viewpoint of the storage stability of the cleaning agent.
  • 15 or less is more preferable, 5 or less is further preferable, and 2 or less is still more preferable.
  • Dispersant (E) at least one selected from the compounds represented by the general formulas (1) to (5) is used.
  • Dispersant (E) is a stable flow that is obtained by finely dispersing a nonionic surfactant or the like that is hardly soluble in an alkaline aqueous solution in a high-concentration alkaline aqueous solution evenly using a stirring device having a low shearing force stirring blade. This makes it possible to prepare a detergent composition containing alkali at a high concentration. Further, the dispersant (E) stabilizes the cleaning composition, but does not adversely affect the antifoaming performance of the cleaning agent.
  • R 1 is a hydrocarbon group having 1 to 4 carbon atoms.
  • the number of carbon atoms of R 1 is preferably 1 or more and 3 or less from the viewpoint of storage stability of the cleaning agent.
  • R 2 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
  • the number of carbon atoms of R 2 is preferably 1 or more and 2 or less from the viewpoint of storage stability of the cleaning agent.
  • R 3 is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of storage stability of the cleaning agent.
  • the compound represented by the general formula (1) is N-alkylmonoalkanolamine or N, N-dialkylmonoalkanolamine, specifically, N-methylethanolamine, N-ethylethanolamine, Nn -Butylethanolamine, N-isobutylethanolamine, N-tert-butylethanolamine, N-methylisopropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-methylethylethanolamine and N, N-dimethylisopropanolamine or the like can be used.
  • N-ethylethanolamine and N, N-dimethylethanolamine are preferable from the viewpoint of storage stability of the detergent, and N-ethylethanolamine is more preferable.
  • R 4 is a hydrocarbon group having 1 to 6 carbon atoms.
  • the aliphatic hydrocarbon group for R 4 include saturated (alkyl group) and unsaturated (alkenyl group), and saturated is preferable from the viewpoint of storage stability of the detergent.
  • the aliphatic hydrocarbon group includes straight and branched chains, and is preferably a straight chain from the viewpoint of the storage stability of the detergent.
  • the number of carbon atoms in R 4 is preferably 2 or more, and more preferably 3 or more, from the viewpoint of storage stability of the cleaning agent.
  • the number of carbon atoms of R 4 is preferably 5 or less, and more preferably 4 or less, from the viewpoint of storage stability of the cleaning agent.
  • the alkyleneoxy group has 2 or 3 carbon atoms, and 2 is preferable from the viewpoint of storage stability of the cleaning agent.
  • the average added mole number m of the alkyleneoxy group is 0 or more and 3 or less.
  • the average added mole number m of the alkyleneoxy group is preferably 1 or more, and preferably 2 or less, from the viewpoint of storage stability of the cleaning agent.
  • the total number of carbon atoms of the alkyleneoxy group is 0 or more and 6 or less.
  • the total number of carbon atoms of the alkyleneoxy group is preferably 2 or more from the viewpoint of the storage stability of the detergent.
  • the total number of carbon atoms of the alkyleneoxy group is preferably 4 or less from the viewpoint of the storage stability of the detergent.
  • primary alcohols having 1 to 6 carbon atoms As the compound represented by the general formula (2), primary alcohols having 1 to 6 carbon atoms, ethylene oxide adducts thereof, and propylene oxide adducts thereof can be used.
  • Specific examples of primary alcohols having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, and n-hexanol.
  • primary alcohols having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, and n-hexanol.
  • an alkylene glycol monoalkyl ether which is an average of 1 to 3 mol adduct of these ethylene oxides and an average of 1 to 3 mol adducts of these propylene oxides can be used.
  • Specific examples include methyl glycol, methyl triglycol, isopropyl glycol, isopropyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, isobutyl triglycol, hexyl glycol, methyl propylene glycol, methyl propylene Diglycol and allyl glycol can be used.
  • R 5 is a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms.
  • 1,2-diol having 2 to 4 carbon atoms in total can be used. Specifically, ethylene glycol, propylene glycol, and butylene glycol can be used.
  • R 6 is a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint of storage stability of the detergent.
  • N- ( ⁇ -aminoether) ethanolamine and N- ( ⁇ -aminoether) isopropanolamine can be used as the compound represented by the general formula (4).
  • N- ( ⁇ -aminoether) isopropanolamine is preferable from the viewpoint of storage stability of the cleaning agent.
  • R 7 is — (A 2 O) n1 —H or a compound represented by the general formula (6), and A 2 O is an alkyleneoxy group having 2 or 3 carbon atoms. Yes, 2 carbon atoms are preferred.
  • n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added.
  • the average value of the total of n1, n2, n3 and n4 in the compound represented by the general formula (5) is 0.5 or more and 8.0 or less, and preferably 1.0 or more from the viewpoint of the storage stability of the cleaning agent. 1.5 or more is more preferable, and 5.0 or less is preferable, 3.5 or less is more preferable, and 2.5 or less is more preferable.
  • a compound obtained by adding ethylene oxide and / or propylene oxide to one or more compounds selected from glycerin and diglycerin can be used.
  • a compound obtained by adding ethylene oxide and / or propylene oxide to glycerin is preferable.
  • the compound represented by the general formula (1) and the compound represented by the general formula (4) are preferable from the viewpoint of the storage stability of the cleaning agent.
  • N-ethylethanolamine and N- ( ⁇ -aminoether) isopropanolamine are preferable from the viewpoint of the storage stability of the cleaning agent, and N-ethylethanolamine is more preferable from the viewpoint of the cleanability of the steel sheet.
  • the blending amount of the dispersant (E) is 0.05% by weight or more and 2.0% by weight or less.
  • the blending amount of the dispersant (E) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and still more preferably 0.4% by weight or more, from the viewpoint of the storage stability of the detergent composition. .
  • the blending amount of the dispersant (E) is preferably 1.8% by weight or less, more preferably 1.5% by weight or less, more preferably 1.0% by weight from the viewpoint of the storage stability of the detergent composition and the blending cost of the detergent. % Or less is even more preferable.
  • the compounding quantity of a dispersing agent (E) is corresponded to content of the dispersing agent in the alkaline cleaning composition for steel plates.
  • the weight ratio of the dispersant (E) to the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is preferably 0.1 or more from the viewpoint of the storage stability of the cleaning agent. 0.4 or more is more preferable.
  • the weight ratio of the dispersant (E) to the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is 4.0 or less from the viewpoint of the storage stability of the cleaning agent. Preferably, 2.0 or less is more preferable, and 1.5 or less is more preferable.
  • the blending amount of water (F) is the total amount of alkali agent (A), chelating agent (B), nonionic surfactant (C), slurrying agent (D), dispersing agent (E) and other components.
  • the blending amount of water (F) may be the balance of the total amount of alkaline agent (A), chelating agent (B), nonionic surfactant (C), slurrying agent (D), and dispersing agent (E).
  • it is preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 60% by weight or less, and even more preferably 55% by weight or less.
  • the alkaline detergent composition for a steel sheet includes an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F).
  • alkali agent (A) a chelating agent
  • C a nonionic surfactant
  • D a slurrying agent
  • E dispersing agent
  • G water
  • Other components such as an antifoaming agent (G) can be contained.
  • the antifoaming agent (G) from the viewpoint of storage stability of the cleaning composition, it is preferable to use a primary alcohol having 8 or more carbon atoms, more preferably a primary alcohol having 10 to 22 carbon atoms, A primary alcohol of 12 or more and 20 or less is more preferable.
  • a primary alcohol having 8 or more carbon atoms more preferably a primary alcohol having 10 to 22 carbon atoms
  • a primary alcohol of 12 or more and 20 or less is more preferable.
  • decanol, lauryl alcohol, tridecanol, myristyl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, and the like can be used.
  • the blending amount of the antifoaming agent (G) is preferably 0.1% by weight or more, and more preferably 0.3% by weight or more from the viewpoint of further improving the storage stability of the cleaning composition.
  • the blending amount of the antifoaming agent (G) is preferably 1% by weight or less, and more preferably 0.7% by weight or less from the viewpoint of storage stability of the cleaning composition.
  • the compounding quantity of an antifoamer (G) is corresponded to content of the antifoamer in the said process (1).
  • step (1) it is preferable to prepare a chelating agent aqueous solution by mixing the chelating agent (B) and water (F).
  • the nonionic surfactant (C), the slurrying agent (D), the dispersing agent (E), and if necessary, the antifoaming agent (G) to the chelating agent aqueous solution and mixing them.
  • an alkaline agent (A) it is preferable to add an alkaline agent (A) to these liquid mixture.
  • a stirring device having a stirring blade with low shearing force can be used as the stirring device.
  • the peripheral speed of rotation of the stirring blade is preferably 0.45 m / s or more, more preferably 0.48 m / s or more, still more preferably 0.52 m / s or more, from the viewpoint of the storage stability of the cleaning composition. 0.75 m / s or more is even more preferable.
  • the peripheral speed of rotation of the stirring blade is preferably 1.20 m / s or less, more preferably 1.10 m / s or less, and 0.90 m / s from the viewpoint of preventing deterioration of the storage stability of the detergent due to entrainment of bubbles. The following is more preferable.
  • the amount of electric power when rotating the stirring blade is preferably 3.5 kw / kg or more, more preferably 6.0 kw / kg or more, and 6.5 kw / kg or more from the viewpoint of storage stability of the cleaning composition. Further, from the viewpoint of preventing the storage stability of the cleaning agent from being lowered due to entrainment of foam, it is preferably 20 kw / kg or less, more preferably 18 kw / kg or less, and even more preferably 17 kw / kg or less.
  • the type of the stirring blade is not particularly limited, and for example, stirring blades known in the art such as paddle blades, propeller blades, anchor blades, and the like can be used. From the viewpoint of uniform dispersion, the stirring blade is preferably a paddle blade. The number of blades can be selected as appropriate. In order to improve the stirring shear force, a baffle plate may be installed in the stirring tank.
  • the stirring time is preferably 30 minutes or more, more preferably 60 minutes or more, and still more preferably 100 minutes or more, from the viewpoint of the storage stability of the cleaning composition.
  • the stirring time is preferably 300 minutes or less, more preferably 200 minutes or less, and even more preferably 150 minutes or less from the viewpoint of the production efficiency of the cleaning composition.
  • the temperature of the alkaline detergent composition for steel plate during stirring is not particularly limited, and may be room temperature, for example.
  • the temperature of the alkaline detergent composition for steel plate during stirring is preferably 5 ° C or higher, more preferably 10 ° C or higher, and further preferably 20 ° C or higher, from the viewpoint of storage stability of the cleaning composition.
  • the temperature of the alkaline detergent composition for steel plate during stirring is preferably 50 ° C. or less from the viewpoint of storage stability of the detergent composition.
  • the alkaline detergent composition for steel sheet obtained in the step (2) is a dispersion in which oil droplets having a particle diameter of less than 50 ⁇ m are dispersed in a phase containing water.
  • the particle diameter of the oil droplet is preferably 45 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 35 ⁇ m or less, still more preferably 30 ⁇ m or less, and even more preferably 25 ⁇ m or less.
  • the particle diameter of the oil droplet is preferably 10 ⁇ m or more, and more preferably 12 ⁇ m or more.
  • the step (3) of further storing the alkaline detergent composition for steel sheet at 10 ° C. or more and 50 ° C. or less for 7 days or more, and water and the stored alkaline detergent composition for steel sheet are mixed It is preferable to have a step (4) of obtaining a water-diluted cleaning liquid (hereinafter also referred to as a second steel sheet alkaline cleaning composition) used for cleaning the steel sheet.
  • the dilution factor is preferably 12 to 40 times, more preferably 15 to 30 times, from the viewpoint of the cleanability of the steel sheet.
  • the storage temperature of the steel sheet alkaline detergent composition is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, from the viewpoint of storage stability. Moreover, 50 degreeC or less is preferable from a viewpoint of storage stability, and, as for the storage temperature of the alkaline cleaning composition for steel plates obtained with the manufacturing method of this embodiment, 40 degrees C or less is more preferable.
  • the said alkaline cleaning composition for steel plates is excellent in storage stability, it is suitable for storing for 7 days or more in the step (3), and more suitable for storing for 30 days or more.
  • storage for 300 days or less is preferable, storage for 200 days or less is more preferable, and storage for 150 days or less is more preferable.
  • the content of the alkaline agent (A) in the second alkaline detergent composition for steel sheet obtained in the step (4) is preferably 0.1% by weight or more, and 0.5% by weight from the viewpoint of the steel sheet detergency. % Or more is more preferable. Further, the content of the alkali agent (A) in the second steel sheet alkaline cleaning composition obtained in the step (4) is preferably 20% by weight or less, preferably 10% by weight or less, from the viewpoint of the cleanability of the steel sheet. Is more preferable, and 8 weight% or less is still more preferable.
  • the second alkaline detergent composition for steel sheet obtained in the step (4) comprises a cold rolling process for cold rolling a steel sheet in the presence of rolling oil, and a detergent for removing the rolling oil adhering to the rolled steel sheet.
  • cleaning process in the manufacturing method of the cold-rolled steel plate which has a washing
  • cold rolled steel sheets can be produced by the same method as in the prior art.
  • the cold rolling step is a processing step for cold rolling a steel sheet in the presence of rolling oil at a steel mill or the like.
  • the rolling oil is cleaned and removed using the second alkaline cleaning composition for steel sheet by continuous cleaning, that is, immersion cleaning, spray cleaning, brush cleaning, electrolytic cleaning, and the like.
  • the second alkaline cleaning composition for steel sheet is particularly alkaline cleaning agent when the cleaning process is immersion and electrolytic cleaning, and the rolled steel sheet is passed through a roll into an alkaline immersion cleaning tank and an alkaline electrolytic cleaning tank. Can be suitably used.
  • the second steel sheet alkaline detergent composition obtained by the production method of the present embodiment can be used as an alkaline detergent at a washing temperature of 40 to 80 ° C. in the washing step.
  • the balance of emulsification is improved, the detergency against dirt adhering to the steel plate is good, and the antifoaming property is good, and slippage on the roll in dipping / electrolytic washing can be suppressed.
  • the present invention further discloses the following production method, composition, or application regarding the above-described embodiment.
  • Components containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E), and water (F) are mixed with a stirring blade.
  • a step (1) of introducing the mixture into a stirring tank having a step, and a step (2) of mixing the components by rotating the stirring blade A method for producing an alkaline detergent composition for steel sheet, comprising:
  • the ratio of the components to be introduced into the stirring tank is Alkaline agent (A) is 34% by weight or more, preferably 35% by weight or more, more preferably 37% by weight or more, 45% by weight or less, preferably 42% by weight or less, more preferably 40% by weight or less, Chelating agent (B) 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, still more preferably 6% by weight or more, and 12% by weight or less.
  • Alkaline agent (A) is 34% by weight or more, preferably 35% by weight or more, more preferably 37% by weight or more, 45% by weight or less, preferably 42% by weight or less, more preferably 40% by weight or less
  • Nonionic surfactant (C) is 0.1 wt% or more, preferably 0.5 wt% or more, more preferably 0.8 wt% or more, 8 wt% or less, and preferably 5 wt% or less.
  • Slurry agent (D) is 0.4 wt% or more, preferably 1 wt% or more, more preferably 1.2 wt% or more, 4.5 wt% or less, preferably 3 wt% or less, 2 wt% % Or less is more preferable.
  • the dispersant (E) is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.4% by weight or more, and 2.0% by weight or less.
  • the dispersant (E) is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (5), [In the general formula (1), R 1 is a hydrocarbon group having 1 or more carbon atoms and 4 or less, preferably 3 or less, and R 2 is a hydrogen atom or 1 or more carbon atoms and 3 or less, A hydrocarbon group of 2 or less is preferred, and R 3 is preferably a hydrogen atom, a methyl group or a hydrogen atom.
  • R 4 has 1 or more carbon atoms, preferably 2 or more, more preferably 3 or more, 6 or less, preferably 5 or less, more preferably 4 or less, A 1 O is an alkyleneoxy group having 2 or 3 carbon atoms, m is an average added mole number of A 1 O of 0 or more, preferably 1 or more, 3 or less, and preferably 2 or less, (A 1 O) m The total number of carbon atoms is 0 or more, preferably 2 or more, 6 or less, and 4 or less.
  • R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms.
  • R 6 is a hydrogen atom or a methyl group.
  • R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
  • a 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, preferably 2;
  • n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the total of n1, n2, n3 and n4
  • the average value is 0.5 or more, preferably 1.0 or more, more preferably 1.5 or more and 8 or less, preferably 5.0 or less, more preferably 3.5 or less, still more preferably 2.5 or less. is there.
  • the steel sheet alkaline detergent composition is a dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 ⁇ m are dispersed in a phase containing water (F).
  • the stirring blade is preferably at least 3.5 kw / kg, more preferably at least 6.0 kw / kg, preferably at most 20 kw / kg, more preferably at most 18 kw / kg, even more preferably Is a method for producing an alkaline detergent composition for steel sheet according to the above ⁇ 1>, wherein each component is mixed by rotating at an electric energy of 17 kw / kg or less.
  • R 8 preferably has 8 or more carbon atoms, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less, and A 3 O has 2 to 4 carbon atoms.
  • An alkyleneoxy group is preferable, and o is an average added mole number of A 3 O, preferably 2 or more, more preferably 4 or more, preferably 20 or less, and more preferably 16 or less.
  • R 9 preferably has 8 or more carbon atoms, more preferably 12 or more, still more preferably 16 or more, and more preferably 18 or less, and A 4 O has 2 to 4 carbon atoms.
  • An alkyleneoxy group is preferable, an ethyleneoxy group is more preferable, p and q each represent an average added mole number of A 4 O, p + q is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and 20 or less Is preferable, and 12 or less is more preferable.
  • ⁇ 4> The method for producing an alkaline detergent composition for a steel sheet according to any one of ⁇ 1> to ⁇ 3>, wherein the slurry agent (D) is a water-soluble polymer carboxylic acid.
  • the weight ratio of the slurry agent (D) and the nonionic surfactant (C), and the slurry agent (D) / nonionic surfactant (C) is preferably 0.1 or more, and preferably 1 or more. Is more preferably 50 or less, more preferably 15 or less, still more preferably 5 or less, and even more preferably 2 or less of the alkaline detergent composition for steel sheet according to any one of the above ⁇ 1> to ⁇ 4> Production method.
  • the proportion of water (F) is preferably 45% by weight or more, more preferably 50% by weight or more, preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 60% by weight or less, 55
  • the dispersant (E) is (1 ') Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, senandary butanol, tertiary butanol, n-pentanol and n-hexanol, methyl glycol, methyl triglycol, isopropyl glycol, isopropyldi Glycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, isobutyl triglycol, hexyl glycol, methyl propylene glycol, methyl propylene diglycol, allyl glycol, (2 ′) ethylene glycol, propylene glycol, butylene glycol, (3 ′) N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N-is
  • the weight ratio of the dispersant (E) to the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is preferably 0.1 or more, and 0.4 or more. More preferably, 4.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less, the method for producing an alkaline detergent composition for steel sheet according to any one of the above ⁇ 1> to ⁇ 7> .
  • the weight average molecular weight (MW) of the slurry agent (D) is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 20,000,
  • the content of the antifoaming agent (G) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, preferably 1% by weight or less, more preferably 0.7% by weight or less.
  • ⁇ 12> Further, a step (3) of storing the alkaline detergent composition for a steel sheet obtained by the production method according to any one of ⁇ 1> to ⁇ 11> at 10 ° C. or more and 50 ° C.
  • the stirring blade has a peripheral speed of 0.45 m / s or more, preferably 0.48 m / s or more, more preferably 0.52 m / s or more, and further 0.75 m / s or more.
  • the time for rotating and mixing each component is preferably 30 minutes or more and 60 minutes or more
  • Alkaline detergent for steel sheet containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F)
  • Alkaline agent (A) is 34% by weight or more, preferably 35% by weight or more, more preferably 37% by weight or more, 45% by weight or less, preferably 42% by weight or less, more preferably 40% by weight or less
  • Chelating agent (B) 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, still more preferably 6% by weight or more, and 12% by weight or less.
  • the nonionic surfactant (C) is 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 0.8% by weight or more, 8% by weight or less, and 5% by weight or less.
  • Slurry agent (D) is 0.4 wt% or more, preferably 1 wt% or more, more preferably 1.2 wt% or more, 4.5 wt% or less, preferably 3 wt% or less, 2 wt% % Or less is more preferable
  • the dispersant (E) is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.4% by weight or more, and 2.0% by weight or less.
  • the dispersant (E) is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (5), [In the general formula (1), R 1 is a hydrocarbon group having 1 or more carbon atoms and 4 or less, preferably 3 or less, and R 2 is a hydrogen atom or 1 or more carbon atoms and 3 or less, A hydrocarbon group of 2 or less is preferred, and R 3 is preferably a hydrogen atom, a methyl group or a hydrogen atom.
  • R 4 has 1 or more carbon atoms, preferably 2 or more, more preferably 3 or more, 6 or less, preferably 5 or less, more preferably 4 or less, A 1 O is an alkyleneoxy group having 2 or 3 carbon atoms, m is an average added mole number of A 1 O of 0 or more, preferably 1 or more, 3 or less, and preferably 2 or less, (A 1 O) m The total number of carbon atoms is 0 or more, preferably 2 or more, 6 or less, and 4 or less.
  • R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms.
  • R 6 is a hydrogen atom or a methyl group.
  • R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
  • a 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, preferably 2;
  • n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the total of n1, n2, n3 and n4
  • the average value is 0.5 or more, preferably 1.0 or more, more preferably 1.5 or more and 8 or less, preferably 5.0 or less, more preferably 3.5 or less, still more preferably 2.5 or less. is there.
  • the steel sheet alkaline detergent composition is a dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 ⁇ m are dispersed in a phase containing water (F).
  • Composition ⁇ 16> The steel sheet according to ⁇ 15>, wherein the nonionic surfactant (C) is at least one selected from the group consisting of compounds represented by the following general formulas (7) and (8).
  • Alkaline detergent composition [In the general formula (7), R 8 preferably has 8 or more carbon atoms, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less, and A 3 O has 2 to 4 carbon atoms.
  • An alkyleneoxy group is preferable, and o is an average added mole number of A 3 O, preferably 2 or more, more preferably 4 or more, preferably 20 or less, and more preferably 16 or less.
  • R 9 preferably has 8 or more carbon atoms, more preferably 12 or more, still more preferably 16 or more, and more preferably 18 or less, and A 4 O has 2 to 4 carbon atoms.
  • An alkyleneoxy group is preferable, an ethyleneoxy group is more preferable, p and q each represent an average added mole number of A 4 O, p + q is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and 20 or less Is preferable, and 12 or less is more preferable.
  • p + q is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and 20 or less Is preferable, and 12 or less is more preferable.
  • the weight ratio of the slurry agent (D) and the nonionic surfactant (C), and the slurry agent (D) / nonionic surfactant (C) is preferably 0.1 or more, and preferably 1 or more. Is more preferably 50 or less, more preferably 15 or less, still more preferably 5 or less, and even more preferably 2 or less, and the alkaline detergent composition for steel sheet according to any one of the above items ⁇ 14> to ⁇ 17>.
  • the proportion of water (F) is preferably 45% by weight or more, more preferably 50% by weight or more, preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 60% by weight or less,
  • the dispersant (E) is (1 ') Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, senandary butanol, tertiary butanol, n-pentanol and n-hexanol, methyl glycol, methyl triglycol, isopropyl glycol, isopropyldi Glycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, isobutyl triglycol, hexyl glycol, methyl propylene glycol, methyl propylene diglycol, allyl glycol, (2 ′) ethylene glycol, propylene glycol, butylene glycol, (3 ′) N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N-is
  • the weight ratio of the dispersant (E) and the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is preferably 0.1 or more, and 0.4 or more. More preferably, 4.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less, the alkaline detergent composition for steel sheet according to any one of ⁇ 15> to ⁇ 20>.
  • the weight average molecular weight (MW) of the slurry agent (D) is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 20,000, The alkaline cleaner composition for steel sheets according to any one of the above ⁇ 15> to ⁇ 21>, further preferably 5,000 to 10,000.
  • the content of the antifoaming agent (G) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, preferably 1% by weight or less, more preferably 0.7% by weight or less,
  • Step (1) As a chelating agent, 60.0 g (10.0 wt%) of sodium gluconate and 88.6 g (14.8 wt%) of water are put into a glass beaker (inner diameter 80.5 mm) having a capacity of 500 ml, An aqueous chelating agent solution was prepared.
  • Step (2) The mixture is stirred for 40 minutes at 530 rpm with a stirrer having a stirring blade (four pitched paddles, diameter: 80 mm, blade height is 200 ml of beaker) to obtain an alkaline cleaning composition for steel sheet. It was.
  • the peripheral speed is 0.71 m / s.
  • Examples 2 to 55, Examples 2-1 to 2-12, Comparative Examples 1 to 32, Comparative Examples 2-1 to 2-5> Prepared in the same manner as in Example 1 except that the components and amounts shown in Tables 1 to 7 were used.
  • the unit of the amount described in Tables 1 to 7 is% by weight.
  • acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, and then extracted, and an average addition mole number of PO adduct of glycerin with 1 mol (glycerin A) Got.
  • acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 2 mol glycerin PO adduct (glycerin B) Got.
  • acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 3 mol glycerin PO adduct (glycerin C).
  • acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 7 mol glycerin PO adduct (glycerin D) Got.
  • acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 12 mol glycerin PO adduct (glycerin K) Got.
  • acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, and then extracted, and the glycerin PO adduct (glycerin L) having an average addition mole number of 24 mol. Got.
  • ⁇ Dispersant Production Example 12> The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 396.5 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an EO adduct of glycerin having an average addition mole number of 9 mol (glycerin M). Got.
  • ⁇ Dispersant Production Example 13> The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 88.1 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, 581.0 g of propylene oxide was charged.
  • ⁇ Dispersant Production Example 16> The autoclave was charged with 166.2 g of diglycerin and 2.0 g of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 88.1 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, 116.2 g of propylene oxide was then charged.
  • ⁇ Evaluation method> ⁇ Weight average molecular weight> The weight average molecular weight was measured in terms of standard polyethylene by gel permeation chromatography.
  • Measurement condition Gel filtration chromatograph SC-8020 series build-up system manufactured by Tosoh Corporation Column: G2000HXL + G4000HXL Detector: UV220nm Carrier: Tetrahydrofuran 1mL / min Column temperature: 38 ° C ⁇ Particle size of oil droplet> About 0.03 ml (one drop with a Pasteur pipette) of the alkaline detergent composition for each steel plate was dropped on a slide glass, and a photograph was taken at 200 times magnification using an optical microscope (manufactured by NIKON).
  • the diameter of the oil droplet with the largest particle size was measured with a ruler to obtain the maximum particle size.
  • the maximum particle size is less than 50 ⁇ m, the storage stability is excellent.
  • Tables 1 to 7 when separation or precipitation was observed and the particle size was not measured, “-” was indicated.
  • ⁇ State> The alkaline detergent composition for each steel plate was placed in a transparent polypropylene bottle having a capacity of 500 ml and stored at room temperature (20 ° C. to 25 ° C.) for 24 hours, and the appearance of the alkaline detergent composition for each steel plate was visually observed. And the presence or absence of upper layer separation, thickening, solidification, etc. was evaluated. When no abnormality was found, “OK” was set. When an abnormality was found, the state (separation, bubbles, precipitation, etc.) is shown in Tables 1 to 7.
  • ⁇ Electricity> The outlet of the motor of the stirrer was connected to a voltage detector and measured. The electric energy (kw / kg) was calculated by the effective voltage (V) ⁇ the effective current (A) ⁇ the power factor (PF) displayed by the voltage detector.
  • the evaluation results are shown in Tables 1-7.
  • the numerical values in the table are the content (% by weight) of each component in the cleaning agent, the D / C weight ratio is the weight ratio of the slurrying agent (D) / nonionic surfactant (C) content, E / C weight ratio shows weight ratio of content of a dispersing agent (E) and nonionic surfactant (C).
  • Examples 56 to 59, Comparative Examples 33 to 35> The mixture was prepared in the same manner as in Example 1 except that the components and amounts shown in Table 8 were used.
  • the unit of the blending amount shown in Table 7 is% by weight. This mixture was stirred with a stirring device having a stirring blade (four pitched paddles, diameter: 80 mm, blade height 200 ml position of beaker) under the stirring conditions shown in Table 7 to obtain an alkaline detergent composition for steel sheet. It was.
  • Step (1) As a chelating agent, 50.4 g (6.3% by weight) of sodium gluconate and 78.7 g (9.8% by weight) of water are put into a glass tall beaker (inner diameter 92.6 mm) having a capacity of 1000 ml. A chelating agent aqueous solution was prepared. Subsequently, 8.0 g (1.0% by weight) of polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether as a nonionic surfactant, and isotridecyl alcohol as an antifoaming agent 4.
  • Step (2) This mixture was stirred at 630 rpm for 120 minutes with a stirrer having a stirring blade (4 pitched paddles, diameter: 80 mm, blade height 300 ml of beaker) to obtain an alkaline cleaning composition for steel sheet. It was. The peripheral speed is 0.84 m / s.
  • Step (1) As a chelating agent, 126.0 g (6.3 wt%) of sodium gluconate and 196.8 g (9.8 wt%) of water are put in a glass beaker (inner diameter 130 mm) having a capacity of 2000 ml and chelated. An aqueous agent solution was prepared. Subsequently, 20.0 g (1.0% by weight) of polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether as a nonionic surfactant, and isotridecyl alcohol 10.
  • Step (2) This mixture was stirred at 770 rpm for 120 minutes with a stirrer having a stirring blade (4 pitched paddles, diameter: 80 mm, blade height 750 ml position of beaker) to obtain an alkaline cleaning composition for steel sheet. It was. The peripheral speed is 1.03 m / s.
  • a chelating agent 126.0 g (6.3% by weight) of sodium gluconate and 196.8 g (9.8% by weight) of water were placed in a glass beaker having a capacity of 2000 ml to prepare an aqueous chelating agent solution. Next, 60.0 g of sodium polyacrylate (solid content 42%) as a slurrying agent was stirred and mixed, and 1579.2 g (NaOH) of 48% sodium hydroxide as an alkaline agent was further mixed.
  • nonionic surfactant polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether 20.0 g (1.0 wt%), antifoaming agent
  • polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether 20.0 g (1.0 wt%), antifoaming agent As a steel plate, 10.0 g (0.5% by weight) of isotridecyl alcohol and 8.0 g (0.4% by weight) of ethylethanolamine as a dispersing agent are added and stirred uniformly with high shear force (homomixer: 10,000 rpm). An alkaline detergent composition was obtained.
  • ⁇ Evaluation method> ⁇ Particle size of oil droplet> The maximum particle size was measured by the same method as the measurement of the particle size of the oil droplet of Example 1. When the maximum particle size is less than 50 ⁇ m, the storage stability is excellent.
  • the steel sheet alkaline detergent composition was placed in a gallusac type specific gravity bottle defined in JIS R 3503, and the specific gravity was measured at 30 ° C. by the method of JIS K 0061.
  • the alkaline detergent composition for a steel sheet involves air bubbles during preparation, the storage stability tends to decrease.
  • the specific gravity of the alkaline detergent composition for steel sheet decreases, so it is desirable that the specific gravity does not decrease.
  • the evaluation results are shown in Table 8.
  • the numerical values in the table are the content (% by weight) of each component in the cleaning agent, the D / C weight ratio is the weight ratio of the slurrying agent (D) / nonionic surfactant (C) content, E / C weight ratio shows weight ratio of content of a dispersing agent (E) and nonionic surfactant (C).
  • the target particle size can be obtained if the peripheral speed during stirring is produced at 1.03 m / s.
  • the entrainment of air bubbles is large, the specific gravity is decreased, and the stability is improved. I can't get it.
  • the alkaline detergent composition for steel sheet according to the example can suppress the entrainment of bubbles even when the peripheral speed during stirring is increased, and can produce a stable alkaline detergent composition for steel sheet.
  • the peripheral speed was higher than that in Example 60 and Comparative Example 36, the amount of power was small. This is because a vortex is formed by stirring and the stirring blade is exposed on the liquid surface.
  • Step 3 The alkaline detergent composition for steel plate of Example 59 and the alkaline detergent composition for steel plate of Reference Example 2 were stored at 30 ° C. for 30 days.
  • Step 4 After the storage, the alkaline detergent composition for steel plate of Example 59 and the alkaline detergent composition for steel plate of Reference Example 2 were stirred and further diluted 25 times with water, respectively, for the second steel plate. An alkaline detergent composition was prepared.
  • the amount of adhered oil remaining on the surface of the steel sheet after the cleaning test (the amount of remaining adhered oil) was measured using a steel sheet adhered oil amount measuring device EMIA-111 (manufactured by Horiba, Ltd.).
  • the measured value is an average value of five measurements. It represents that the smaller the amount of residual adhered oil, the better the cleaning performance of the steel sheet.
  • the amount of residual adhered oil when washed with the second alkaline detergent composition for steel sheet prepared from the alkaline detergent composition for steel sheet of Example 59 was 15.7 mg / m 2 .
  • the amount of residual adhered oil when washed with the second alkaline detergent composition for steel sheet prepared from the alkaline detergent composition for steel sheet is equivalent to 14.1 mg / m 2 , both of which are excellent cleaning for steel sheet Had sex.

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Abstract

A method for producing an alkali detergent composition for a steel plate, said method comprising step (1) for introducing components including an alkaline agent, a chelating agent, a nonionic surfactant, a slurrying agent, a dispersing agent and water into a stirring tank that is equipped with stirring blades, and step (2) for mixing these components by rotating the stirring blades, wherein: in step (1), the aforesaid components are introduced into the stirring tank at the following ratio, i.e., 34-45 wt% of the alkaline agent, 0.5-12 wt% of the chelating agent, 0.1-8 wt% of the nonionic surfactant, 0.4-4.5 wt% of the slurrying agent, and 0.05-2.0 wt% of the dispersing agent; and the dispersing agent is at least one member selected from the group consisting of compounds represented by general formulae (1) to (5). According to the method of the present invention for producing an alkali detergent composition for a steel plate, a method for producing a concentrated detergent composition with high storage stability in a stirring tank, said tank being equipped with stirring blades, and a concentrated detergent composition with high storage stability can be provided.

Description

鋼板用アルカリ洗浄剤組成物の製造方法Method for producing alkaline detergent composition for steel sheet
　本発明は、鉄、アルミニウム、銅等からなる鋼板（鋼帯）に付着した油汚れ及び鉄粉等を洗浄する際に用いられる、鋼板用アルカリ洗浄剤組成物の製造方法に関する。 The present invention relates to a method for producing an alkaline detergent composition for a steel sheet used for cleaning oil stains, iron powder, and the like adhering to a steel sheet (steel strip) made of iron, aluminum, copper or the like.
　鋼板表面の脱脂洗浄は、酸洗と共にメッキ、塗装等の表面処理を行う前処理として必要であり、製品の良否を決定付ける非常に大きな因子である。鋼板表面に付着している汚れとしては、冷間圧延時に付着する圧延油、防錆油などの油汚れや、鉄粉等の固体汚れ等が挙げられている。特に、近年の鋼板の冷間圧延においては、ミル清浄性や生産性向上に適した圧延油が用いられるようになり、圧延油に対する優れた洗浄性を有する洗浄剤が求められている。 Degreasing and cleaning of the steel sheet surface is necessary as a pretreatment for performing surface treatment such as plating and painting along with pickling, and is a very large factor that determines the quality of products. Examples of the dirt adhering to the steel sheet surface include oil dirt such as rolling oil and rust preventive oil adhering during cold rolling, and solid dirt such as iron powder. In particular, in cold rolling of steel sheets in recent years, rolling oil suitable for improving mill cleanliness and productivity has come to be used, and a cleaning agent having excellent cleaning properties for rolling oil is required.
　一方、前記洗浄剤には、高濃度でも流動性があり、保存安定性に優れることが求められる。また、前記洗浄剤には、泡立ちが小さく作業性に優れることも求められている。 On the other hand, the cleaning agent is required to have fluidity even at a high concentration and to have excellent storage stability. The cleaning agent is also required to have low foaming and excellent workability.
　特開平７－４１９７５号公報には、高アルカリ濃度において通常難溶性のアルコール、界面活性剤、脂肪酸、キレート剤等を配合させることができ、洗浄剤に要求される高洗浄性、抑泡性、低ＣＯＤ、低コストを満足することを目的として、アルカリ剤をＮａ２Ｏ基準で１０～３５重量％、及び一分子中に２～６個の極性基を有する脂肪族系化合物を０．１～２０重量％含有することを特徴とする高濃度一液型アルカリ洗浄剤組成物が開示されている。 In JP-A-7-41975, alcohols, surfactants, fatty acids, chelating agents, etc., which are usually poorly soluble at a high alkali concentration, can be blended, and the high detergency, foam suppression, For the purpose of satisfying low COD and low cost, the alkali agent is 10 to 35% by weight on the basis of Na 2 O, and the aliphatic compound having 2 to 6 polar groups in one molecule is 0.1 to A high-concentration one-component alkaline detergent composition characterized by containing 20% by weight is disclosed.
　特開２０１１－１１７０４３号公報には、４０～６０℃の低温の洗浄温度において、ロール上で鋼板の滑りを抑えながら、洗浄効率よく、鋼板の汚れを洗浄除去することができ、かつ、泡立ちを抑えることができる、鋼板用アルカリ洗浄剤組成物を提供することを目的として、アルカリ剤と、炭素数が９～１５の２級アルコールにオキシアルキレンが結合した２種のポリオキシアルキレンアルキルエーテルと、キレート剤と、水とを含有する鋼板用アルカリ洗浄剤組成物が開示されている。 Japanese Patent Application Laid-Open No. 2011-117043 discloses that a steel plate can be cleaned and removed with high cleaning efficiency while suppressing slippage of the steel plate on a roll at a low cleaning temperature of 40 to 60 ° C., and foaming is prevented. For the purpose of providing an alkaline detergent composition for steel sheet that can be suppressed, an alkaline agent, two types of polyoxyalkylene alkyl ethers in which oxyalkylene is bonded to a secondary alcohol having 9 to 15 carbon atoms, An alkaline detergent composition for steel sheet containing a chelating agent and water is disclosed.
　特開２００１－３１６６９３号公報には、洗浄性に優れ、洗浄時に発泡せず、濃厚状態で安定に保管でき、かつ地球環境に悪影響を及ぼさない液状アルカリ性洗浄剤組成物を提供することを目的として、アルカリ剤と、炭素数１０～２０の直鎖又は分岐鎖のアルキル基又はアルケニル基を有するポリオキシエチレンアミノエーテルとを含むことを特徴とする液状アルカリ性洗浄剤組成物が開示されている。 Japanese Patent Application Laid-Open No. 2001-316693 has an object to provide a liquid alkaline detergent composition that has excellent detergency, does not foam during washing, can be stably stored in a concentrated state, and does not adversely affect the global environment. A liquid alkaline detergent composition comprising an alkali agent and a polyoxyethylene amino ether having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms is disclosed.
　本発明は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含む成分を、攪拌翼を有する攪拌槽に導入する工程（１）、及び前記攪拌翼を回転させて各成分を混合する工程（２）を有する鋼板用アルカリ洗浄剤組成物の製造方法であって、前記工程（１）において前記攪拌槽に導入する前記成分の割合が、アルカリ剤（Ａ）３４重量％以上４５重量％以下、キレート剤（Ｂ）０．５重量％以上１２重量％以下、非イオン性界面活性剤（Ｃ）０．１重量％以上８重量％以下、スラリー化剤（Ｄ）０．４重量％以上４．５重量％以下、分散剤（Ｅ）０．０５重量％以上２．０重量％以下であり、前記分散剤（Ｅ）が、下記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物の製造方法である。
Figure JPOXMLDOC01-appb-C000017
 〔前記一般式（１）中、Ｒ１は炭素数１以上４以下の炭化水素基、Ｒ２は水素原子又は炭素数１以上３以下の炭化水素基、Ｒ３は水素原子又はメチル基である。〕
Figure JPOXMLDOC01-appb-C000018
 〔前記一般式（２）中、Ｒ４は炭素数１以上６以下の炭化水素基、Ａ１Ｏは炭素数２又は３のアルキレンオキシ基、ｍはＡ１Ｏの平均付加モル数で０以上３以下、（Ａ１Ｏ）ｍの総炭素数は０以上６以下である。〕
Figure JPOXMLDOC01-appb-C000019
 〔前記一般式（３）中、Ｒ５は水素原子又は炭素数１又は２の炭化水素基である。〕
Figure JPOXMLDOC01-appb-C000020
 〔前記一般式（４）中、Ｒ６は水素原子又はメチル基である。〕
Figure JPOXMLDOC01-appb-C000021
 〔前記一般式（５）中、Ｒ７は－（Ａ２Ｏ）ｎ３－Ｈ、又は下記一般式（６）で表される化合物であり、
Figure JPOXMLDOC01-appb-C000022
 Ａ２Ｏは炭素数２又は３のアルキレンオキシ基、ｎ１、ｎ２、ｎ３及びｎ４は、それぞれＡ２Ｏの付加モル数を示す整数であり、ｎ１、ｎ２、ｎ３及びｎ４の合計の平均値は０．５以上８以下である。〕 In the present invention, a component containing an alkaline agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F) is mixed with a stirring blade. A method for producing an alkaline detergent composition for a steel sheet, comprising the step (1) of introducing into a stirring tank having a step and the step (2) of mixing the components by rotating the stirring blade, wherein the step (1) The proportion of the component introduced into the stirring tank in the above is as follows: alkaline agent (A) 34 wt% or more and 45 wt% or less, chelating agent (B) 0.5 wt% or more and 12 wt% or less, nonionic surfactant ( C) 0.1 wt% or more and 8 wt% or less, slurrying agent (D) 0.4 wt% or more and 4.5 wt% or less, dispersant (E) 0.05 wt% or more and 2.0 wt% or less And the dispersant (E) is composed of compounds represented by the following general formulas (1) to (5) A dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 μm are dispersed in a phase containing water (F). It is a manufacturing method of the alkaline cleaning composition for steel plates which is a body.
Figure JPOXMLDOC01-appb-C000017
 [In the general formula (1), R 1 is a hydrocarbon group having 1 to 4 carbon atoms, R 2 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group. . ]
Figure JPOXMLDOC01-appb-C000018
 [In the general formula (2), R 4 is a hydrocarbon group having 1 to 6 carbon atoms, A 1 O is an alkyleneoxy group having 2 or 3 carbon atoms, and m is an average added mole number of A 1 O of 0 or more. 3 or less, and the total number of carbon atoms of (A 1 O) m is 0 or more and 6 or less. ]
Figure JPOXMLDOC01-appb-C000019
 [In the general formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. ]
Figure JPOXMLDOC01-appb-C000020
 [In the general formula (4), R 6 is a hydrogen atom or a methyl group. ]
Figure JPOXMLDOC01-appb-C000021
 [In the general formula (5), R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
Figure JPOXMLDOC01-appb-C000022
 A 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the average value of the total of n1, n2, n3 and n4 is 0.5 or more and 8 or less. ]
　さらに、本発明は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含有する鋼板用アルカリ洗浄剤組成物であって、前記各成分の割合が、アルカリ剤（Ａ）３４重量％以上４５重量％以下、キレート剤（Ｂ）０．５重量％以上１２重量％以下、非イオン性界面活性剤（Ｃ）０．１重量％以上８重量％以下、スラリー化剤（Ｄ）０．４重量％以上４．５重量％以下、分散剤（Ｅ）０．０５重量％以上２．０重量％以下であり、前記分散剤（Ｅ）が、前記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物である。 Furthermore, the present invention is for a steel sheet containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F). An alkaline detergent composition, wherein the proportion of each component is from 34% to 45% by weight of the alkali agent (A), 0.5% to 12% by weight of the chelating agent (B), a nonionic interface Activator (C) 0.1 wt% to 8 wt%, Slurrant (D) 0.4 wt% to 4.5 wt%, Dispersant (E) 0.05 wt% to 2.0 wt% % Or less, and the dispersant (E) is at least one selected from the group consisting of compounds represented by the general formulas (1) to (5), and the alkaline detergent composition for steel sheet, Oil droplets of the nonionic surfactant (C) having a particle size of less than 50 μm are dispersed in the phase containing water (F). A dispersion, a steel sheet for an alkaline detergent composition.
発明の詳細な説明Detailed Description of the Invention
　特開平７－４１９７５号公報及び特開２０１１－１１７０４３号公報では濃縮型の洗浄剤を製造しているが、保存安定性に優れる洗浄剤組成物を得るためには、配合された原料をラインミキサー、ホモミキサー及びホモジナイザー等の高剪断力を有する装置で攪拌する工程が必要であった。また、特開２００１－３１６６９３号公報の液状アルカリ性洗浄剤組成物は安定に保管できるものであるが、油分であるポリオキシエチレンアミノエーテルを含む原料の攪拌時の剪断力が低いと、油分を小粒径化することは困難となり、安定性が低下する傾向があった。そこで、高剪断力の攪拌装置ではなく、剪断力の低い攪拌翼を有する攪拌装置で、保存安定性の優れる濃縮型の洗浄剤組成物を製造する方法が望まれる。 In JP-A-7-41975 and JP-A-111-117043, concentrated detergents are produced. In order to obtain a detergent composition having excellent storage stability, the blended raw materials are used as a line mixer. In addition, a step of stirring with an apparatus having a high shearing force such as a homomixer and a homogenizer is required. Further, the liquid alkaline detergent composition disclosed in JP-A-2001-316693 can be stably stored, but if the shearing force during stirring of the raw material containing polyoxyethylene amino ether, which is an oil component, is low, the oil component is reduced. It became difficult to reduce the particle size, and the stability tended to decrease. Therefore, there is a demand for a method of producing a concentrated detergent composition having excellent storage stability by using a stirring device having a stirring blade having a low shearing force instead of a stirring device having a high shearing force.
　本発明の課題は、攪拌翼を有する攪拌槽で、保存安定性に優れる濃縮型の洗浄剤組成物の製造方法を提供することである。また、本発明の課題は、保存安定性に優れる濃縮型の洗浄剤組成物を提供することである。 An object of the present invention is to provide a method for producing a concentrated cleaning composition having excellent storage stability in a stirring tank having a stirring blade. Another object of the present invention is to provide a concentrated detergent composition having excellent storage stability.
　本発明は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含む成分を、攪拌翼を有する攪拌槽に導入する工程（１）、及び前記攪拌翼を回転させて各成分を混合する工程（２）を有する鋼板用アルカリ洗浄剤組成物の製造方法であって、前記工程（１）において前記攪拌槽に導入する前記成分の割合が、アルカリ剤（Ａ）３４重量％以上４５重量％以下、キレート剤（Ｂ）０．５重量％以上１２重量％以下、非イオン性界面活性剤（Ｃ）０．１重量％以上８重量％以下、スラリー化剤（Ｄ）０．４重量％以上４．５重量％以下、分散剤（Ｅ）０．０５重量％以上２．０重量％以下であり、前記分散剤（Ｅ）が、前記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物の製造方法である。 In the present invention, a component containing an alkaline agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F) is mixed with a stirring blade. A method for producing an alkaline detergent composition for a steel sheet, comprising the step (1) of introducing into a stirring tank having a step and the step (2) of mixing the components by rotating the stirring blade, wherein the step (1) The proportion of the component introduced into the stirring tank in the above is as follows: alkaline agent (A) 34 wt% or more and 45 wt% or less, chelating agent (B) 0.5 wt% or more and 12 wt% or less, nonionic surfactant ( C) 0.1 wt% or more and 8 wt% or less, slurrying agent (D) 0.4 wt% or more and 4.5 wt% or less, dispersant (E) 0.05 wt% or more and 2.0 wt% or less And the dispersant (E) comprises the compounds represented by the general formulas (1) to (5). A dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 μm are dispersed in a phase containing water (F). It is a manufacturing method of the alkaline cleaning composition for steel plates which is a body.
　さらに、本発明は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含有する鋼板用アルカリ洗浄剤組成物であって、前記各成分の割合が、アルカリ剤（Ａ）３４重量％以上４５重量％以下、キレート剤（Ｂ）０．５重量％以上１２重量％以下、非イオン性界面活性剤（Ｃ）０．１重量％以上８重量％以下、スラリー化剤（Ｄ）０．４重量％以上４．５重量％以下、分散剤（Ｅ）０．０５重量％以上２．０重量％以下であり、前記分散剤（Ｅ）が、前記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物、及びその鋼板用アルカリ洗浄剤組成物の鋼板の洗浄剤としての使用である。 Furthermore, the present invention is for a steel sheet containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F). An alkaline detergent composition, wherein the proportion of each component is from 34% to 45% by weight of the alkali agent (A), 0.5% to 12% by weight of the chelating agent (B), a nonionic interface Activator (C) 0.1 wt% to 8 wt%, Slurrant (D) 0.4 wt% to 4.5 wt%, Dispersant (E) 0.05 wt% to 2.0 wt% % Or less, and the dispersant (E) is at least one selected from the group consisting of compounds represented by the general formulas (1) to (5), and the alkaline detergent composition for steel sheet, Oil droplets of the nonionic surfactant (C) having a particle size of less than 50 μm are dispersed in the phase containing water (F). A dispersion, a use as a cleaning agent for steel of the steel sheet for an alkaline detergent composition, and a steel sheet for an alkaline detergent composition.
　本発明によれば、攪拌翼を有する攪拌槽で、保存安定性に優れる濃縮型の洗浄剤組成物の製造方法を提供することができる。また、本発明によれば、保存安定性に優れる濃縮型の洗浄剤組成物を提供することができる。 According to the present invention, it is possible to provide a method for producing a concentrated detergent composition having excellent storage stability in a stirring tank having a stirring blade. Further, according to the present invention, a concentrated detergent composition having excellent storage stability can be provided.
　本発明の効果の発現機構は定かでないが、以下のように推定される。 Although the manifestation mechanism of the effect of the present invention is not clear, it is estimated as follows.
　洗浄剤組成物の原料を配合すると、アルカリ剤が多量に存在するため水がアルカリ剤と相互作用をして、非イオン界面活性剤は水に溶解できなくなる。その結果、非イオン界面活性剤は油滴を形成する。高剪断力で攪拌すると油滴の粒子径が小さくなり保存安定性が向上するが、剪断力が弱いと油滴の粒子径が大きいものが存在することになり、キレート剤やスラリー化剤が存在しても時間の経過と共に油滴が互いに合一し、さらに大きな油滴を生じ、最後には油相として水相と分離してしまう。 When the raw material of the cleaning composition is blended, a large amount of alkaline agent is present, so that water interacts with the alkaline agent, and the nonionic surfactant cannot be dissolved in water. As a result, the nonionic surfactant forms oil droplets. When stirring with high shear force, the oil droplet particle size decreases and storage stability improves, but when the shear force is weak, there are oil droplets with large particle size, and there are chelating agents and slurry agents. Even with time, the oil droplets coalesce with each other to form larger oil droplets and finally separate from the water phase as the oil phase.
　一方、本発明のように、水酸基と比較的短いアルキル基とを有する適度な分子サイズの特定の化合物を分散剤として用いるとキレート剤及びスラリー化剤と共に油滴と水との界面に分散剤が吸着し、油滴の界面張力が低下して油滴が壊れやすくなり、低剪断力の攪拌でも油滴の分散が容易になり、油滴の粒子径が小さいものなる。いったん粒子径が小さくなった油滴はキレート剤、スラリー化剤及び分散剤によって安定化され、洗浄剤組成物の保存安定性が向上すると推定される。すなわち、高剪断力で攪拌する場合には特定の分散剤が無くても安定性に優れた洗浄剤組成物が得られるが、低剪断力の場合は特定の分散剤を配合することで安定性に優れた洗浄剤組成物が得られる。 On the other hand, when a specific compound having an appropriate molecular size having a hydroxyl group and a relatively short alkyl group is used as a dispersant as in the present invention, a dispersant is formed at the interface between oil droplets and water together with a chelating agent and a slurrying agent. The oil droplets are adsorbed and the interfacial tension of the oil droplets is lowered, and the oil droplets are easily broken. The oil droplets are easily dispersed even with low shearing force stirring, and the particle size of the oil droplets is small. It is presumed that once the particle size is reduced, the oil droplets are stabilized by a chelating agent, a slurrying agent and a dispersing agent, and the storage stability of the cleaning composition is improved. That is, when stirring at a high shear force, a detergent composition having excellent stability can be obtained without a specific dispersant, but in the case of a low shear force, stability can be obtained by adding a specific dispersant. An excellent cleaning composition is obtained.
　以下、本発明の一実施形態について説明する。 Hereinafter, an embodiment of the present invention will be described.
　本実施形態の製造方法は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含む成分を、攪拌翼を有する攪拌槽に導入する工程（１）、及び前記攪拌翼を回転させて各成分を混合する工程（２）を有する。 The manufacturing method of this embodiment is a component containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E), and water (F). Are introduced into a stirring vessel having a stirring blade, and a step (2) of mixing the components by rotating the stirring blade.
＜工程（１）について＞
＜原料成分＞
＜アルカリ剤（Ａ）＞
　本実施形態で用いられるアルカリ剤（Ａ）は、油汚れの除去性を確保するため、水溶性のアルカリ剤であればいずれのものも使用できる。具体例としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、オルソ珪酸ナトリウム、メタ珪酸ナトリウム、セスキ珪酸ナトリウム等のアルカリ金属の珪酸塩、リン酸三ナトリウム等のアルカリ金属のリン酸塩、炭酸二ナトリウム、炭酸水素ナトリウム、炭酸二カリウム等のアルカリ金属の炭酸塩、ホウ酸ナトリウム等のアルカリ金属のホウ酸塩等を用いることができる。二種以上の水溶性アルカリ剤を組み合わせてもよい。洗浄性を高める観点から、好ましくはアルカリ金属の水酸化物及びアルカリ金属の珪酸塩であり、より好ましくはアルカリ金属の水酸化物である。これらの中でも、好ましくは水酸化ナトリウム、水酸化カリウム、オルソ珪酸ナトリウム及びメタ珪酸ナトリウムであり、より好ましくは水酸化ナトリウム又は水酸化カリウムである。 <About step (1)>
<Raw ingredient>
<Alkaline agent (A)>
As the alkaline agent (A) used in the present embodiment, any water-soluble alkaline agent can be used in order to ensure the removal of oil stains. Specific examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal silicates such as sodium orthosilicate, sodium metasilicate and sodium sesquisilicate, and alkali metal phosphorus such as trisodium phosphate. An alkali metal carbonate such as an acid salt, disodium carbonate, sodium hydrogen carbonate or dipotassium carbonate, an alkali metal borate such as sodium borate, or the like can be used. Two or more water-soluble alkaline agents may be combined. From the viewpoint of enhancing the detergency, preferred are alkali metal hydroxides and alkali metal silicates, and more preferred are alkali metal hydroxides. Of these, sodium hydroxide, potassium hydroxide, sodium orthosilicate and sodium metasilicate are preferable, and sodium hydroxide or potassium hydroxide is more preferable.
　本実施形態において、アルカリ剤（Ａ）の配合量は、３４重量％以上４５重量％以下である。アルカリ剤（Ａ）の配合量は、洗浄剤の保存安定性の観点から、３５重量％以上が好ましく、３７重量％以上がより好ましい。アルカリ剤（Ａ）の配合量は、洗浄剤の粘度上昇抑制の観点から、４２重量％以下が好ましく、４０重量％以下がより好ましい。アルカリ剤（Ａ）の配合量は、鋼板用アルカリ洗浄剤組成物におけるアルカリ剤の含有量に相当する。 In this embodiment, the blending amount of the alkaline agent (A) is 34% by weight or more and 45% by weight or less. The blending amount of the alkaline agent (A) is preferably 35% by weight or more, and more preferably 37% by weight or more, from the viewpoint of the storage stability of the cleaning agent. The blending amount of the alkaline agent (A) is preferably 42% by weight or less, and more preferably 40% by weight or less, from the viewpoint of suppressing the viscosity increase of the cleaning agent. The blending amount of the alkaline agent (A) corresponds to the content of the alkaline agent in the alkaline detergent composition for steel sheet.
＜キレート剤（Ｂ）＞
　本実施形態で用いられるキレート剤（Ｂ）は、非イオン性界面活性剤（Ｃ）等の油滴（以下、単に「油滴」ともいう）の粒子径を小さくし保存安定性を向上させ、また鉄石けん等の汚れに作用して鉄イオン等をキレートし、脂肪酸ナトリウム石けんにして汚れを溶解し易くして、油の洗浄性を向上させると推定される。キレート剤（Ｂ）としては、グルコン酸、グルコヘプトン酸、グリセリン酸、テトロン酸、ペントン酸、ヘキソン酸、ヘプトン酸等のアルドン酸又はそのアルカリ金属塩若しくは炭素数１～４の低級アミン塩；ニトリロ三酢酸、エチレンジアミン四酢酸、エチレンジアミン二酢酸、テトラエチレンテトラミン六酢酸等のアミノカルボン酸のアルカリ金属塩若しくは低級アミン塩；クエン酸、リンゴ酸等又はそのオキシカルボン酸のアルカリ金属塩若しくは低級アミン塩；アミノトリメチレンホスホン酸、ヒドロキシエチリデンジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸等のホスホン酸又はそのアルカリ金属塩若しくは低級アミン塩；その他、前記のモノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン塩を用いることができる。これらの中でも、油の洗浄性の観点から、アルドン酸又はその塩が好ましく、アルカリ金属塩又は低級アミン塩が好ましい。なかでも、油の洗浄性の観点から、グルコン酸、グルコヘプトン酸のアルカリ金属塩若しくは低級アミン塩が好ましく、グルコン酸塩がより好ましい。アルカリ金属塩は、洗浄性を高める観点から、ナトリウム塩が好ましい。キレート剤（Ｂ）は少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。例えば、グルコン酸のアルカリ金属塩とエチレンジアミン四酢酸のアルカリ金属塩の組み合わせを用いることができる。 <Chelating agent (B)>
The chelating agent (B) used in this embodiment improves the storage stability by reducing the particle size of oil droplets (hereinafter also simply referred to as “oil droplets”) such as a nonionic surfactant (C), It is also presumed that it acts on iron soap and other soils to chelate iron ions and the like, making it easier to dissolve the soil using fatty acid sodium soap and improving the detergency of oil. Examples of the chelating agent (B) include aldonic acids such as gluconic acid, glucoheptonic acid, glyceric acid, tetronic acid, pentonic acid, hexonic acid and heptonic acid, or alkali metal salts thereof or lower amine salts having 1 to 4 carbon atoms; Alkali metal salt or lower amine salt of aminocarboxylic acid such as acetic acid, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, tetraethylenetetraminehexaacetic acid; alkali metal salt or lower amine salt of citric acid, malic acid or the like or oxycarboxylic acid thereof; amino Phosphonic acids such as trimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid or alkali metal salts or lower amine salts thereof; Ethanolamine, can be used alkanolamine salts such as triethanolamine. Among these, from the viewpoint of oil detergency, aldonic acid or a salt thereof is preferable, and an alkali metal salt or a lower amine salt is preferable. Among these, from the viewpoint of oil detergency, alkali metal salts or lower amine salts of gluconic acid and glucoheptonic acid are preferable, and gluconate is more preferable. The alkali metal salt is preferably a sodium salt from the viewpoint of improving detergency. Chelating agent (B) should just use at least 1 type, and can be used in combination of 2 or more type. For example, a combination of an alkali metal salt of gluconic acid and an alkali metal salt of ethylenediaminetetraacetic acid can be used.
　本実施形態において、キレート剤（Ｂ）の配合量は、０．５重量％以上１２重量％以下である。キレート剤（Ｂ）の配合量は、非イオン性界面活性剤（Ｃ）の油滴の粒子径を小さくする観点から、１重量％以上が好ましく、３重量％以上がより好ましく、５重量％以上が更に好ましく、６重量％以上がより更に好ましい。キレート剤（Ｂ）の配合量は、非イオン性界面活性剤（Ｃ）の油滴の粒子径を小さくする観点から、１０重量％以下が好ましく、８重量％以下が好ましい。当該配合量が０．５重量％以上で油滴の微細化ができ、洗浄剤は安定であり、１２重量％以下ではキレート剤の溶解が容易である。キレート剤（Ｂ）の配合量は、鋼板用アルカリ洗浄剤組成物におけるキレート剤の含有量に相当する。 In this embodiment, the compounding amount of the chelating agent (B) is 0.5% by weight or more and 12% by weight or less. The blending amount of the chelating agent (B) is preferably 1% by weight or more, more preferably 3% by weight or more, and more preferably 5% by weight or more from the viewpoint of reducing the particle size of the oil droplets of the nonionic surfactant (C). Is more preferable, and 6% by weight or more is even more preferable. The blending amount of the chelating agent (B) is preferably 10% by weight or less, and preferably 8% by weight or less from the viewpoint of reducing the particle size of the oil droplets of the nonionic surfactant (C). If the blending amount is 0.5% by weight or more, the oil droplets can be made finer, the cleaning agent is stable, and if it is 12% by weight or less, the chelating agent is easily dissolved. The compounding amount of the chelating agent (B) corresponds to the content of the chelating agent in the alkaline detergent composition for steel sheet.
＜非イオン性界面活性剤（Ｃ）＞
　本実施形態で用いられる非イオン性界面活性剤（Ｃ）は、アルカリ洗浄剤に一般に用いられているものが使用できる。ただし、非イオン性界面活性剤（Ｃ）は分散剤（Ｅ）に属する化合物は含まない。本実施形態で用いられる非イオン性界面活性剤（Ｃ）としては、例えば、炭素数が８以上の炭化水素基を有する１価アルコールにアルキレンオキシドを付加した構造の化合物、炭素数が８以上の炭化水素基を有する１価又は２価のアミンにアルキレンオキシドを付加した構造の化合物を用いることができる。具体例としてはポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルケニルアミンを用いることができる。 <Nonionic surfactant (C)>
As the nonionic surfactant (C) used in the present embodiment, those generally used for alkaline detergents can be used. However, the nonionic surfactant (C) does not include a compound belonging to the dispersant (E). Examples of the nonionic surfactant (C) used in the present embodiment include a compound having a structure in which an alkylene oxide is added to a monohydric alcohol having a hydrocarbon group having 8 or more carbon atoms, and having 8 or more carbon atoms. A compound having a structure in which an alkylene oxide is added to a monovalent or divalent amine having a hydrocarbon group can be used. As specific examples, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylamine, and polyoxyethylene alkenylamine can be used.
　非イオン性界面活性剤（Ｃ）は、油の洗浄性の観点から、下記一般式（７）で示される化合物及び下記一般式（８）で示される化合物から選ばれるいずれか少なくとも１種を用いることが好ましい。 The nonionic surfactant (C) is at least one selected from a compound represented by the following general formula (7) and a compound represented by the following general formula (8) from the viewpoint of oil detergency. It is preferable.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
〔前記一般式（７）中、Ｒ８は炭素数８以上１８以下の炭化水素基を示し、Ａ３Ｏは炭素数２以上４以下のアルキレンオキシ基を示し、ｏはＡ３Ｏの平均付加モル数で２以上２０以下である。〕 [In the general formula (7), R 8 represents a hydrocarbon group having 8 to 18 carbon atoms, A 3 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and o represents an average addition of A 3 O. The number of moles is 2 or more and 20 or less. ]
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
〔前記一般式（８）中、Ｒ９は炭素数８以上１８以下の炭化水素基を示し、Ａ４Ｏは炭素数２以上４以下のアルキレンオキシ基、ｐ及びｑはそれぞれＡ４Ｏの平均付加モル数を示し、ｐ＋ｑが２以上２０以下である。〕 [In the general formula (8), R 9 represents a hydrocarbon group having 8 to 18 carbon atoms, A 4 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and p and q are averages of A 4 O, respectively. The number of added moles is shown, and p + q is 2 or more and 20 or less. ]
　前記一般式（７）中、Ｒ８は、油の洗浄性の観点から、炭素数８以上１８以下の直鎖又は分岐鎖の脂肪族炭化水素基が挙げられる。当該脂肪族炭化水素基としては、飽和（アルキル基）及び不飽和（アルケニル基）が挙げられる。Ｒ８の炭素数は、油の洗浄性の観点から、１４以下が好ましく、１２以下がより好ましい。前記一般式（７）で示される化合物の具体例としてはポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテルが挙げられる。 In the general formula (7), R 8 may be a linear or branched aliphatic hydrocarbon group having 8 to 18 carbon atoms from the viewpoint of oil detergency. Examples of the aliphatic hydrocarbon group include saturated (alkyl group) and unsaturated (alkenyl group). The carbon number of R 8 is preferably 14 or less, and more preferably 12 or less, from the viewpoint of oil detergency. Specific examples of the compound represented by the general formula (7) include polyoxyalkylene alkyl ether and polyoxyalkylene alkenyl ether.
　前記一般式（７）中、Ａ３Ｏで示されるアルキレンオキシ基は、エチレンオキシ基、プロピレンオキシ基、ブチレンオキシ基であり、洗浄剤の保存安定性の観点から、エチレンオキシ基及び／又はプロピレンオキシ基が好ましく、エチレンオキシ基とプロピレンオキシ基を両方有するものがより好ましい。 In the general formula (7), the alkyleneoxy group represented by A 3 O is an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group. From the viewpoint of storage stability of the cleaning agent, an ethyleneoxy group and / or propylene An oxy group is preferable, and one having both an ethyleneoxy group and a propyleneoxy group is more preferable.
　前記一般式（７）中、Ａ３Ｏで示されるアルキレンオキシ基の平均付加モル数ｏは、油の洗浄性の観点から、２以上であり、４以上が好ましい。前記一般式（７）中のＡ３Ｏで示されるアルキレンオキシ基の平均付加モル数ｏは、油の洗浄性の観点から、２０以下であり、１６以下が好ましい。 In the general formula (7), the average addition mole number o of the alkyleneoxy group represented by A 3 O is 2 or more, and preferably 4 or more, from the viewpoint of oil detergency. The average added mole number o of the alkyleneoxy group represented by A 3 O in the general formula (7) is 20 or less, and preferably 16 or less, from the viewpoint of oil detergency.
　前記一般式（８）中、Ｒ９は、油の洗浄性の観点から、炭素数８以上１８以下の直鎖又は分岐鎖の脂肪族炭化水素基が挙げられる。当該脂肪族炭化水素基としては、飽和（アルキル基）及び不飽和（アルケニル基）が挙げられる。Ｒ９の炭素数は、油の洗浄性の観点から、１２以上が好ましく、１６以上がより好ましい。前記一般式（８）で示される化合物の具体例としてはポリオキシエチレンアルキルアミン、ポリオキシエチレンアルケニルアミンが挙げられる。 In the general formula (8), R 9 is a linear or branched aliphatic hydrocarbon group having 8 to 18 carbon atoms from the viewpoint of oil detergency. Examples of the aliphatic hydrocarbon group include saturated (alkyl group) and unsaturated (alkenyl group). The number of carbon atoms in R 9 is preferably 12 or more, more preferably 16 or more, from the viewpoint of oil detergency. Specific examples of the compound represented by the general formula (8) include polyoxyethylene alkylamine and polyoxyethylene alkenylamine.
　非イオン性界面活性剤（Ｃ）は少なくとも１種を用いればよく、２種以上を組み合わせて用いることができる。 At least one kind of nonionic surfactant (C) may be used, and two or more kinds may be used in combination.
　前記一般式（８）中、Ａ４Ｏで示されるアルキレンオキシ基は、エチレンオキシ基、プロピレンオキシ基、ブチレンオキシ基であり、洗浄性の観点から、エチレンオキシ基及び／又はプロピレンオキシ基が好ましく、エチレンオキシ基がより好ましい。 In the general formula (8), the alkyleneoxy group represented by A 4 O is an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, and is preferably an ethyleneoxy group and / or a propyleneoxy group from the viewpoint of detergency. An ethyleneoxy group is more preferable.
　前記一般式（８）中のアルキレンオキシ基の平均付加モル数ｐ及びｑは、油の洗浄性の観点から、ｐ＋ｑが２以上であり、５以上が好ましく、８以上がより好ましい。前記一般式（８）中のアルキレンオキシ基の平均付加モル数ｐ及びｑは、油の洗浄性の観点から、ｐ＋ｑが２０以下であり、１２以下がより好ましい。非イオン性界面活性剤（Ｃ）は、洗浄剤の保存安定性の観点から、一般式（８）よりも一般式（７）のほうが好ましい。 From the viewpoint of oil detergency, the average added mole numbers p and q of the alkyleneoxy group in the general formula (8) are 2 or more, preferably 5 or more, and more preferably 8 or more. From the viewpoint of oil detergency, the average added mole numbers p and q of the alkyleneoxy group in the general formula (8) are 20 or less, more preferably 12 or less. The nonionic surfactant (C) is more preferably the general formula (7) than the general formula (8) from the viewpoint of the storage stability of the cleaning agent.
　本実施形態において、非イオン性界面活性剤（Ｃ）の配合量は、０．１重量％以上８重量％以下である。本実施形態において、非イオン性界面活性剤（Ｃ）の配合量は、油の洗浄性の観点から、０．５重量％以上が好ましく、０．８重量％以上がより好ましい。前記非イオン性界面活性剤（Ｃ）の配合量は、洗浄剤の保存安定性及びコストの観点から、５重量％以下が好ましく、３重量％以下がより好ましい。非イオン性界面活性剤（Ｃ）の配合量は、鋼板用アルカリ洗浄剤組成物における非イオン性界面活性剤の含有量に相当する。 In this embodiment, the blending amount of the nonionic surfactant (C) is 0.1% by weight or more and 8% by weight or less. In the present embodiment, the blending amount of the nonionic surfactant (C) is preferably 0.5% by weight or more, and more preferably 0.8% by weight or more from the viewpoint of oil detergency. The blending amount of the nonionic surfactant (C) is preferably 5% by weight or less, more preferably 3% by weight or less from the viewpoint of storage stability and cost of the cleaning agent. The compounding amount of the nonionic surfactant (C) corresponds to the content of the nonionic surfactant in the alkaline detergent composition for steel sheet.
＜スラリー化剤（Ｄ）＞
　本実施形態において、スラリー化剤（Ｄ）は、水溶性高分子カルボン酸を配合することができる。当該水溶性高分子カルボン酸の少なくとも１種を含む洗浄剤組成物は、高濃度においても液体状又はスラリー状で洗浄剤組成物の保存安定性を向上させることができる。また水溶性高分子カルボン酸が配合された洗浄剤組成物を水で希釈した場合には、鋼板の洗浄工程で遊離した鉄粉の分散を維持し、鋼板に付着させ難くすることにより、洗浄性の向上にも寄与する。 <Slurry agent (D)>
In this embodiment, the slurrying agent (D) can be blended with a water-soluble polymer carboxylic acid. The cleaning composition containing at least one kind of the water-soluble polymer carboxylic acid can improve the storage stability of the cleaning composition in a liquid or slurry state even at a high concentration. In addition, when the cleaning composition containing water-soluble polymer carboxylic acid is diluted with water, it maintains the dispersion of the iron powder released in the steel plate cleaning process and makes it difficult to adhere to the steel plate. It contributes to the improvement.
　水溶性高分子カルボン酸として、少なくともひとつ以上のカルボン酸を含む高分子であり、例えば、アクリル酸ホモポリマー、アクリル酸－マレイン酸共重合体、α－ヒドロキシアクリル酸ホモポリマー、Ｃ５オレフィン－マレイン酸共重合体、イソブチレン－マレイン酸共重合体、及びこれらのナトリウム塩等のアルカリ金属塩もしくはアミン塩等を用いることができる。水溶性高分子カルボン酸の中でも、洗浄剤組成物の保存安定性を向上する観点から、アクリル酸ホモポリマー及びアクリル酸－マレイン酸共重合体から選ばれる１種以上であることが好ましい。水溶性高分子カルボン酸は、洗浄剤中で溶解するものが好ましい。本明細書において、水溶性とは水１００ｇに対して１ｇ以上溶解するものをいう。 Water-soluble polymer carboxylic acid is a polymer containing at least one carboxylic acid, such as acrylic acid homopolymer, acrylic acid-maleic acid copolymer, α-hydroxyacrylic acid homopolymer, C5 olefin-maleic acid Copolymers, isobutylene-maleic acid copolymers, and alkali metal salts or amine salts such as sodium salts thereof can be used. Among the water-soluble polymeric carboxylic acids, from the viewpoint of improving the storage stability of the detergent composition, one or more selected from acrylic acid homopolymers and acrylic acid-maleic acid copolymers are preferable. The water-soluble polymer carboxylic acid is preferably one that dissolves in the cleaning agent. In the present specification, water-soluble means that 1 g or more dissolves in 100 g of water.
　水溶性高分子カルボン酸の重量平均分子量（ＭＷ）は１，０００～１００，０００、好ましくは３，０００～５０，０００、より好ましくは５，０００～２０，０００、更に好ましくは５，０００～１０，０００である。共重合体の場合の重合形態はブロックでもランダムでもよい。２種以上の水溶性高分子カルボン酸を組み合わせても良い。なお、本明細書において、重量平均分子量は、実施例に記載の方法により測定する。 The weight average molecular weight (MW) of the water-soluble polymer carboxylic acid is 1,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 20,000, still more preferably 5,000 to 10,000. The form of polymerization in the case of a copolymer may be block or random. Two or more water-soluble polymer carboxylic acids may be combined. In addition, in this specification, a weight average molecular weight is measured by the method as described in an Example.
　本実施形態において、スラリー化剤（Ｄ）の配合量は、０．４重量％以上４．５重量％以下である。スラリー化剤（Ｄ）の配合量は、洗浄剤の保存安定性の観点から、１重量％以上が好ましく、１．２重量％以上がより好ましい。スラリー化剤（Ｄ）の配合量は、洗浄剤組成物の粘度を適度に制御でき、洗浄剤組成物の配管輸送を確保する観点から、３重量％以下が好ましく、２重量％以下がより好ましい。スラリー化剤（Ｄ）の配合量は、鋼板用アルカリ洗浄剤組成物におけるスラリー化剤の含有量に相当する。 In this embodiment, the blending amount of the slurrying agent (D) is 0.4 wt% or more and 4.5 wt% or less. The blending amount of the slurry agent (D) is preferably 1% by weight or more, and more preferably 1.2% by weight or more from the viewpoint of storage stability of the cleaning agent. The blending amount of the slurry agent (D) is preferably 3% by weight or less, more preferably 2% by weight or less from the viewpoint of appropriately controlling the viscosity of the detergent composition and ensuring the piping transportation of the detergent composition. . The blending amount of the slurry agent (D) corresponds to the content of the slurry agent in the alkaline detergent composition for steel sheet.
　スラリー化剤（Ｄ）と非イオン界面活性剤（Ｃ）の重量比〔スラリー化剤（Ｄ）／非イオン界面活性剤（Ｃ）〕は、洗浄剤の保存安定性の観点から、０．１以上が好ましく、１以上がより好ましい。スラリー化剤（Ｄ）と非イオン界面活性剤（Ｃ）の重量比〔スラリー化剤（Ｄ）／非イオン界面活性剤（Ｃ）〕は、洗浄剤の保存安定性の観点から、５０以下が好ましく、１５以下がより好ましく、５以下が更に好ましく、２以下がより更に好ましい。 The weight ratio of the slurry agent (D) to the nonionic surfactant (C) [slurry agent (D) / nonionic surfactant (C)] is 0.1% from the viewpoint of storage stability of the cleaning agent. The above is preferable, and 1 or more is more preferable. The weight ratio of the slurry agent (D) to the nonionic surfactant (C) [slurry agent (D) / nonionic surfactant (C)] is 50 or less from the viewpoint of the storage stability of the cleaning agent. Preferably, 15 or less is more preferable, 5 or less is further preferable, and 2 or less is still more preferable.
＜分散剤（Ｅ）＞
　本実施形態において、分散剤（Ｅ）としては、前記一般式（１）～（５）で示される化合物から選ばれる少なくともいずれか１種以上が用いられる。 <Dispersant (E)>
In this embodiment, as the dispersant (E), at least one selected from the compounds represented by the general formulas (1) to (5) is used.
　分散剤（Ｅ）は、剪断力の低い攪拌翼を有する攪拌装置を用いてもアルカリ水溶液に難溶性の非イオン界面活性剤などを高濃度アルカリ水溶液中で微細化し均一に分散させ、安定な流動性を有する高濃度でアルカリを含有する洗浄剤組成物の調製を可能とする。さらに、分散剤（Ｅ）は、洗浄剤組成物を安定化する一方で、洗浄剤の抑泡性能に対して悪影響を与えない。 Dispersant (E) is a stable flow that is obtained by finely dispersing a nonionic surfactant or the like that is hardly soluble in an alkaline aqueous solution in a high-concentration alkaline aqueous solution evenly using a stirring device having a low shearing force stirring blade. This makes it possible to prepare a detergent composition containing alkali at a high concentration. Further, the dispersant (E) stabilizes the cleaning composition, but does not adversely affect the antifoaming performance of the cleaning agent.
　前記一般式（１）中、Ｒ１は炭素数１以上４以下の炭化水素基である。Ｒ１の炭素数は、洗浄剤の保存安定性の観点から、１以上３以下が好ましい。 In the general formula (1), R 1 is a hydrocarbon group having 1 to 4 carbon atoms. The number of carbon atoms of R 1 is preferably 1 or more and 3 or less from the viewpoint of storage stability of the cleaning agent.
　前記一般式（１）中、Ｒ２は水素原子又は炭素数１以上３以下の炭化水素基である。Ｒ２の炭素数は、洗浄剤の保存安定性の観点から、１以上２以下が好ましい。 In the general formula (1), R 2 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. The number of carbon atoms of R 2 is preferably 1 or more and 2 or less from the viewpoint of storage stability of the cleaning agent.
　前記一般式（１）中、Ｒ３は水素原子又はメチル基であり、洗浄剤の保存安定性の観点から、水素原子が好ましい。 In the general formula (1), R 3 is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of storage stability of the cleaning agent.
　前記一般式（１）で示される化合物として、Ｎ－アルキルモノアルカノールアミン又はＮ，Ｎ－ジアルキルモノアルカノールアミンであり、具体的には、Ｎ－メチルエタノールアミン、Ｎ－エチルエタノールアミン、Ｎ－ｎ－ブチルエタノールアミン、Ｎ－イソブチルエタノールアミン、Ｎ－タシャリーブチルエタノールアミン、Ｎ－メチルイソプロパノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、Ｎ，Ｎ－メチルエチルエタノールアミン及びＮ，Ｎ－ジメチルイソプロパノールアミン等を用いることができる。これらの中でも、洗浄剤の保存安定性の観点からＮ－エチルエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミンが好ましく、Ｎ－エチルエタノールアミンがより好ましい。 The compound represented by the general formula (1) is N-alkylmonoalkanolamine or N, N-dialkylmonoalkanolamine, specifically, N-methylethanolamine, N-ethylethanolamine, Nn -Butylethanolamine, N-isobutylethanolamine, N-tert-butylethanolamine, N-methylisopropanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-methylethylethanolamine and N, N-dimethylisopropanolamine or the like can be used. Among these, N-ethylethanolamine and N, N-dimethylethanolamine are preferable from the viewpoint of storage stability of the detergent, and N-ethylethanolamine is more preferable.
　前記一般式（２）中、Ｒ４は炭素数１以上６以下の炭化水素基である。Ｒ４の脂肪族炭化水素基としては、飽和（アルキル基）及び不飽和（アルケニル基）が挙げられ、洗浄剤の保存安定性の観点から、飽和が好ましい。また、Ｒ４の炭素数が３以上の場合、脂肪族炭化水素基は直鎖と分岐鎖が挙げられ、洗浄剤の保存安定性の観点から、直鎖が好ましい。Ｒ４の炭素数は、洗浄剤の保存安定性の観点から、２以上が好ましく、３以上がより好ましい。Ｒ４の炭素数は、洗浄剤の保存安定性の観点から、５以下が好ましく、４以下がより好ましい。 In the general formula (2), R 4 is a hydrocarbon group having 1 to 6 carbon atoms. Examples of the aliphatic hydrocarbon group for R 4 include saturated (alkyl group) and unsaturated (alkenyl group), and saturated is preferable from the viewpoint of storage stability of the detergent. In addition, when R 4 has 3 or more carbon atoms, the aliphatic hydrocarbon group includes straight and branched chains, and is preferably a straight chain from the viewpoint of the storage stability of the detergent. The number of carbon atoms in R 4 is preferably 2 or more, and more preferably 3 or more, from the viewpoint of storage stability of the cleaning agent. The number of carbon atoms of R 4 is preferably 5 or less, and more preferably 4 or less, from the viewpoint of storage stability of the cleaning agent.
　前記一般式（２）中、アルキレンオキシ基の炭素数は２又は３であり、洗浄剤の保存安定性の観点から、２が好ましい。 In the general formula (2), the alkyleneoxy group has 2 or 3 carbon atoms, and 2 is preferable from the viewpoint of storage stability of the cleaning agent.
　前記一般式（２）中、アルキレンオキシ基の平均付加モル数ｍは０以上３以下である。アルキレンオキシ基の平均付加モル数ｍは、洗浄剤の保存安定性の観点から、１以上が好ましく、２以下が好ましい。 In the general formula (2), the average added mole number m of the alkyleneoxy group is 0 or more and 3 or less. The average added mole number m of the alkyleneoxy group is preferably 1 or more, and preferably 2 or less, from the viewpoint of storage stability of the cleaning agent.
　前記一般式（２）中、アルキレンオキシ基の総炭素数は０以上６以下である。アルキレンオキシ基の総炭素数は、洗浄剤の保存安定性の観点から、２以上が好ましい。アルキレンオキシ基の総炭素数は、洗浄剤の保存安定性の観点から、４以下が好ましい。 In the general formula (2), the total number of carbon atoms of the alkyleneoxy group is 0 or more and 6 or less. The total number of carbon atoms of the alkyleneoxy group is preferably 2 or more from the viewpoint of the storage stability of the detergent. The total number of carbon atoms of the alkyleneoxy group is preferably 4 or less from the viewpoint of the storage stability of the detergent.
　前記一般式（２）で示される化合物として、炭素数１以上６以下の１級アルコール、これらのエチレンオキサイド付加物及びこれらのプロピレンオキサイド付加物を用いることができる。炭素数１以上６以下の１級アルコールの具体例としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、セカンダリーブタノール、ターシャリーブタノール、ｎ－ペンタノール及びｎ－ヘキサノール等を用いることができる。また、これらのエチレンオキサイドの平均１以上３モル付加物及びこれらのプロピレンオキサイドの平均１以上３モル付加物であるアルキレングリコールモノアルキルエーテルを用いることができる。具体例としては、メチルグリコール、メチルトリグリコール、イソプロピルグリコール、イソプロピルジグリコール、ブチルグリコール、ブチルジグリコール、ブチルトリグリコール、イソブチルグリコール、イソブチルジグリコール、イソブチルトリグリコール、ヘキシルグリコール、メチルプロピレングリコール、メチルプロピレンジグリコール、アリルグリコールを用いることができる。 As the compound represented by the general formula (2), primary alcohols having 1 to 6 carbon atoms, ethylene oxide adducts thereof, and propylene oxide adducts thereof can be used. Specific examples of primary alcohols having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, and n-hexanol. Can be used. Further, an alkylene glycol monoalkyl ether which is an average of 1 to 3 mol adduct of these ethylene oxides and an average of 1 to 3 mol adducts of these propylene oxides can be used. Specific examples include methyl glycol, methyl triglycol, isopropyl glycol, isopropyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, isobutyl triglycol, hexyl glycol, methyl propylene glycol, methyl propylene Diglycol and allyl glycol can be used.
　前記一般式（３）中、Ｒ５は水素原子又は炭素数１又は２の炭化水素基である。前記一般式（３）で示される化合物として、全炭素数が２以上４以下の１，２－ジオールを用いることができる。具体的には、エチレングリコール、プロピレングリコール及びブチレングリコールを用いることができる。 In the general formula (3), R 5 is a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. As the compound represented by the general formula (3), 1,2-diol having 2 to 4 carbon atoms in total can be used. Specifically, ethylene glycol, propylene glycol, and butylene glycol can be used.
　前記一般式（４）中、Ｒ６は水素原子又はメチル基であり、洗浄剤の保存安定性の観点から、メチル基が好ましい。前記一般式（４）で示される化合物として、Ｎ－（β－アミノエーテル）エタノールアミン及びＮ－（β－アミノエーテル）イソプロパノールアミンを用いることができる。これらの中でも、洗浄剤の保存安定性の観点からＮ－（β－アミノエーテル）イソプロパノールアミンが好ましい。 In the general formula (4), R 6 is a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint of storage stability of the detergent. As the compound represented by the general formula (4), N- (β-aminoether) ethanolamine and N- (β-aminoether) isopropanolamine can be used. Among these, N- (β-aminoether) isopropanolamine is preferable from the viewpoint of storage stability of the cleaning agent.
　前記一般式（５）中、Ｒ７は－（Ａ２Ｏ）ｎ１－Ｈ、又は前記一般式（６）で表される化合物であり、Ａ２Ｏは炭素数２又は３のアルキレンオキシ基であり、炭素数２が好ましい。ｎ１、ｎ２、ｎ３及びｎ４は、それぞれＡ２Ｏの付加モル数を示す整数である。一般式（５）で表される化合物におけるｎ１、ｎ２、ｎ３及びｎ４の合計の平均値は０．５以上８．０以下であり、洗浄剤の保存安定性の観点から１．０以上が好ましく、１．５以上がより好まく、そして、５．０以下が好ましく、３．５以下がより好ましく、２．５以下が更に好ましい。 In the general formula (5), R 7 is — (A 2 O) n1 —H or a compound represented by the general formula (6), and A 2 O is an alkyleneoxy group having 2 or 3 carbon atoms. Yes, 2 carbon atoms are preferred. n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added. The average value of the total of n1, n2, n3 and n4 in the compound represented by the general formula (5) is 0.5 or more and 8.0 or less, and preferably 1.0 or more from the viewpoint of the storage stability of the cleaning agent. 1.5 or more is more preferable, and 5.0 or less is preferable, 3.5 or less is more preferable, and 2.5 or less is more preferable.
　前記一般式（５）で表される化合物として、グリセリン及びジグリセリンから選ばれる１種以上の化合物、にエチレンオキサイド及び／又はプロピレンオキサイドを付加した化合物を用いることができる。洗浄剤の保存安定性の観点からグリセリンにエチレンオキサイド及び／又はプロピレンオキサイド付加した化合物が好ましい。 As the compound represented by the general formula (5), a compound obtained by adding ethylene oxide and / or propylene oxide to one or more compounds selected from glycerin and diglycerin can be used. From the viewpoint of storage stability of the cleaning agent, a compound obtained by adding ethylene oxide and / or propylene oxide to glycerin is preferable.
　分散剤（Ｅ）の中でも、洗浄剤の保存安定性の観点から一般式（１）で表される化合物及び一般式（４）で表される化合物が好ましい。具体的には、洗浄剤の保存安定性の観点からＮ－エチルエタノールアミン及びＮ－（β－アミノエーテル）イソプロパノールアミンが好ましく、鋼板の洗浄性の観点からＮ－エチルエタノールアミンがより好ましい。 Among the dispersants (E), the compound represented by the general formula (1) and the compound represented by the general formula (4) are preferable from the viewpoint of the storage stability of the cleaning agent. Specifically, N-ethylethanolamine and N- (β-aminoether) isopropanolamine are preferable from the viewpoint of the storage stability of the cleaning agent, and N-ethylethanolamine is more preferable from the viewpoint of the cleanability of the steel sheet.
　本実施形態において、分散剤（Ｅ）の配合量は、０．０５重量％以上２．０重量％以下である。分散剤（Ｅ）の配合量は、洗浄剤組成物の保存安定性の観点から、０．１重量％以上が好ましく、０．３重量％以上がより好ましく、０．４重量％以上が更に好ましい。分散剤（Ｅ）の配合量は、洗浄剤組成物の保存安定性と洗浄剤の配合コストの観点から、１．８重量％以下が好ましく１．５重量％以下が更に好ましく、１．０重量％以下がより更に好ましい。分散剤（Ｅ）の配合量は、鋼板用アルカリ洗浄剤組成物における分散剤の含有量に相当する。 In this embodiment, the blending amount of the dispersant (E) is 0.05% by weight or more and 2.0% by weight or less. The blending amount of the dispersant (E) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and still more preferably 0.4% by weight or more, from the viewpoint of the storage stability of the detergent composition. . The blending amount of the dispersant (E) is preferably 1.8% by weight or less, more preferably 1.5% by weight or less, more preferably 1.0% by weight from the viewpoint of the storage stability of the detergent composition and the blending cost of the detergent. % Or less is even more preferable. The compounding quantity of a dispersing agent (E) is corresponded to content of the dispersing agent in the alkaline cleaning composition for steel plates.
　分散剤（Ｅ）と非イオン界面活性剤（Ｃ）の重量比〔分散剤（Ｅ）／非イオン界面活性剤（Ｃ）〕は、洗浄剤の保存安定性の観点から０．１以上が好ましく、０．４以上がより好ましい。分散剤（Ｅ）と非イオン界面活性剤（Ｃ）の重量比〔分散剤（Ｅ）／非イオン界面活性剤（Ｃ）〕は、洗浄剤の保存安定性の観点から、４．０以下が好ましく、２．０以下がより好ましく、１．５以下が更に好ましい。 The weight ratio of the dispersant (E) to the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is preferably 0.1 or more from the viewpoint of the storage stability of the cleaning agent. 0.4 or more is more preferable. The weight ratio of the dispersant (E) to the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is 4.0 or less from the viewpoint of the storage stability of the cleaning agent. Preferably, 2.0 or less is more preferable, and 1.5 or less is more preferable.
＜水（Ｆ）＞
　本実施形態において、水（Ｆ）は、工業用水、水道水及び脱イオン水等を用いることができる。水（Ｆ）の配合量は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及びその他の成分の合計量の残部でよいが、洗浄剤組成物の保存安定性の観点から、４５重量％以上が好ましく、５０重量％以上がより好ましい。水（Ｆ）の配合量は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）の合計量の残部でよいが、洗浄剤組成物の保存安定性の観点から、７０重量％以下が好ましく、６５重量％以下がより好ましく、６０重量％以下が更に好ましく、５５重量％以下がより更に好ましい。 <Water (F)>
In this embodiment, industrial water, tap water, deionized water, etc. can be used for water (F). The blending amount of water (F) is the total amount of alkali agent (A), chelating agent (B), nonionic surfactant (C), slurrying agent (D), dispersing agent (E) and other components. However, from the viewpoint of the storage stability of the cleaning composition, it is preferably 45% by weight or more, more preferably 50% by weight or more. The blending amount of water (F) may be the balance of the total amount of alkaline agent (A), chelating agent (B), nonionic surfactant (C), slurrying agent (D), and dispersing agent (E). However, from the viewpoint of the storage stability of the cleaning composition, it is preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 60% by weight or less, and even more preferably 55% by weight or less.
＜その他の成分＞
　鋼板用アルカリ洗浄剤組成物は、アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）以外に、消泡剤（Ｇ）等の他の成分を含有することができる。 <Other ingredients>
The alkaline detergent composition for a steel sheet includes an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F). Other components such as an antifoaming agent (G) can be contained.
　消泡剤（Ｇ）として、洗浄剤組成物の保存安定性の観点から、炭素数８以上の１級アルコールを用いることが好ましく、炭素数１０以上２２以下の１級アルコールがより好ましく、炭素数１２以上２０以下の１級アルコールがより好ましい。具体的には、デカノール、ラウリルアルコール、トリデカノール、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール及びイソステアリルアルコール等を用いることができる。 As the antifoaming agent (G), from the viewpoint of storage stability of the cleaning composition, it is preferable to use a primary alcohol having 8 or more carbon atoms, more preferably a primary alcohol having 10 to 22 carbon atoms, A primary alcohol of 12 or more and 20 or less is more preferable. Specifically, decanol, lauryl alcohol, tridecanol, myristyl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, and the like can be used.
　消泡剤（Ｇ）の配合量は、洗浄剤組成物の保存安定性をより高める観点から、０．１重量％以上が好ましく、０．３重量％以上がより好ましい。消泡剤（Ｇ）の配合量は、洗浄剤組成物の保存安定性の観点から、１重量％以下が好ましく、０．７重量％以下がより好ましい。消泡剤（Ｇ）の配合量は、前記工程（１）における消泡剤の含有量に相当する。 The blending amount of the antifoaming agent (G) is preferably 0.1% by weight or more, and more preferably 0.3% by weight or more from the viewpoint of further improving the storage stability of the cleaning composition. The blending amount of the antifoaming agent (G) is preferably 1% by weight or less, and more preferably 0.7% by weight or less from the viewpoint of storage stability of the cleaning composition. The compounding quantity of an antifoamer (G) is corresponded to content of the antifoamer in the said process (1).
　前記工程（１）では、キレート剤（Ｂ）と水（Ｆ）とを混合し、キレート剤水溶液を調製することが好ましい。次いで、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）、更に要すれば消泡剤（Ｇ）をキレート剤水溶液に添加して混合することが好ましい。そして、これらの混合液にアルカリ剤（Ａ）を添加することが好ましい。
＜工程（２）について＞ In the step (1), it is preferable to prepare a chelating agent aqueous solution by mixing the chelating agent (B) and water (F). Next, it is preferable to add the nonionic surfactant (C), the slurrying agent (D), the dispersing agent (E), and if necessary, the antifoaming agent (G) to the chelating agent aqueous solution and mixing them. And it is preferable to add an alkaline agent (A) to these liquid mixture.
<About step (2)>
　前記工程（２）では、攪拌装置として、剪断力の低い攪拌翼を有する攪拌装置を用いることができる。攪拌翼の回転の周速は、洗浄剤組成物の保存安定性の観点から、０．４５ｍ／ｓ以上が好ましく、０．４８ｍ／ｓ以上がより好ましく、０．５２ｍ／ｓ以上が更に好ましく、０．７５ｍ／ｓ以上がより更に好ましい。攪拌翼の回転の周速は、泡の巻込みによる洗浄剤の保存安定性の低下を防ぐ観点から１．２０ｍ／ｓ以下が好ましく、１．１０ｍ／ｓ以下がより好ましく、０．９０ｍ／ｓ以下が更に好ましい。また、攪拌翼を回転させる際の電力量は、洗浄剤組成物保存安定性の観点から、３．５ｋｗ／ｋｇ以上が好ましく、６．０ｋｗ／ｋｇ以上がより好ましく、６．５ｋｗ／ｋｇ以上が更に好ましく、そして、泡の巻込みによる洗浄剤の保存安定性の低下を防ぐ観点から、２０ｋｗ／ｋｇ以下が好ましく、１８ｋｗ／ｋｇ以下がより好ましく、１７ｋｗ／ｋｇ以下が更に好ましい。 In the step (2), a stirring device having a stirring blade with low shearing force can be used as the stirring device. The peripheral speed of rotation of the stirring blade is preferably 0.45 m / s or more, more preferably 0.48 m / s or more, still more preferably 0.52 m / s or more, from the viewpoint of the storage stability of the cleaning composition. 0.75 m / s or more is even more preferable. The peripheral speed of rotation of the stirring blade is preferably 1.20 m / s or less, more preferably 1.10 m / s or less, and 0.90 m / s from the viewpoint of preventing deterioration of the storage stability of the detergent due to entrainment of bubbles. The following is more preferable. In addition, the amount of electric power when rotating the stirring blade is preferably 3.5 kw / kg or more, more preferably 6.0 kw / kg or more, and 6.5 kw / kg or more from the viewpoint of storage stability of the cleaning composition. Further, from the viewpoint of preventing the storage stability of the cleaning agent from being lowered due to entrainment of foam, it is preferably 20 kw / kg or less, more preferably 18 kw / kg or less, and even more preferably 17 kw / kg or less.
　攪拌翼の種類は特に限定されず、例えば、パドル翼、プロペラ翼、アンカー翼等の当分野において知られている攪拌翼を使用することができる。均一に分散する観点から攪拌翼はパドル翼が好ましい。翼枚数は適宜選択することが可能である。また攪拌剪断力を向上させるために、攪拌槽内に邪魔板を設置してもよい。 The type of the stirring blade is not particularly limited, and for example, stirring blades known in the art such as paddle blades, propeller blades, anchor blades, and the like can be used. From the viewpoint of uniform dispersion, the stirring blade is preferably a paddle blade. The number of blades can be selected as appropriate. In order to improve the stirring shear force, a baffle plate may be installed in the stirring tank.
　前記工程（２）において、攪拌時間は、洗浄剤組成物の保存安定性の観点から、３０分間以上が好ましく、６０分間以上がより好ましく、１００分間以上が更に好ましい。攪拌時間は、洗浄剤組成物の生産効率の観点から、３００分間以下が好ましく、２００分間以下がより好ましく、１５０分間以下が更に好ましい。 In the step (2), the stirring time is preferably 30 minutes or more, more preferably 60 minutes or more, and still more preferably 100 minutes or more, from the viewpoint of the storage stability of the cleaning composition. The stirring time is preferably 300 minutes or less, more preferably 200 minutes or less, and even more preferably 150 minutes or less from the viewpoint of the production efficiency of the cleaning composition.
　前記工程（２）において、攪拌時の鋼板用アルカリ洗浄剤組成物の温度は、特に限定はないが、例えば、室温で良い。具体的には、攪拌時の鋼板用アルカリ洗浄剤組成物の温度は、洗浄剤組成物の保存安定性の観点から、５℃以上が好ましく、１０℃以上がより好ましく、２０℃以上が更に好ましい。また、攪拌時の鋼板用アルカリ洗浄剤組成物の温度は、洗浄剤組成物の保存安定性の観点から、５０℃以下が好ましい。アルカリ剤（Ａ）の配合の際に中和熱により温度上昇が生じるが、前記温度以下に制御するのが好ましい。 In the step (2), the temperature of the alkaline detergent composition for steel plate during stirring is not particularly limited, and may be room temperature, for example. Specifically, the temperature of the alkaline detergent composition for steel plate during stirring is preferably 5 ° C or higher, more preferably 10 ° C or higher, and further preferably 20 ° C or higher, from the viewpoint of storage stability of the cleaning composition. . In addition, the temperature of the alkaline detergent composition for steel plate during stirring is preferably 50 ° C. or less from the viewpoint of storage stability of the detergent composition. When the alkali agent (A) is blended, the temperature rises due to heat of neutralization.
　前記工程（２）で得られる鋼板用アルカリ洗浄剤組成物は、水を含む相に粒子径が５０μｍ未満の油滴が分散した分散体である。洗浄剤組成物の保存安定性の観点から、当該油滴の粒子径が４５μｍ以下が好ましく、４０μｍ以下がより好ましく、３５μｍ以下が更に好ましく、３０μｍ以下がより更に好ましく、２５μｍ以下がより更に好ましい。また、鋼板用アルカリ洗浄剤組成物の生産効率の観点から、当該油滴の粒子径は１０μｍ以上が好ましく、１２μm以上がより好ましい。 The alkaline detergent composition for steel sheet obtained in the step (2) is a dispersion in which oil droplets having a particle diameter of less than 50 μm are dispersed in a phase containing water. From the viewpoint of storage stability of the cleaning composition, the particle diameter of the oil droplet is preferably 45 μm or less, more preferably 40 μm or less, still more preferably 35 μm or less, still more preferably 30 μm or less, and even more preferably 25 μm or less. Further, from the viewpoint of production efficiency of the alkaline detergent composition for steel sheet, the particle diameter of the oil droplet is preferably 10 μm or more, and more preferably 12 μm or more.
　本実施形態では、さらに前記鋼板用アルカリ洗浄剤組成物を１０℃以上５０℃以下で７日以上保存する工程（３）、及び水と前記保存した鋼板用アルカリ洗浄剤組成物とを混合し、鋼板の洗浄に使用する、水希釈の洗浄液（以下、第２の鋼板用アルカリ洗浄剤組成物ともいう）を得る工程（４）を有することが好ましい。希釈倍率は、鋼板の洗浄性の観点から、１２～４０倍が好ましく、１５～３０倍がより好ましい。 In this embodiment, the step (3) of further storing the alkaline detergent composition for steel sheet at 10 ° C. or more and 50 ° C. or less for 7 days or more, and water and the stored alkaline detergent composition for steel sheet are mixed, It is preferable to have a step (4) of obtaining a water-diluted cleaning liquid (hereinafter also referred to as a second steel sheet alkaline cleaning composition) used for cleaning the steel sheet. The dilution factor is preferably 12 to 40 times, more preferably 15 to 30 times, from the viewpoint of the cleanability of the steel sheet.
　前記工程（３）において、前記鋼板用アルカリ洗浄剤組成物の保存温度は、保存安定性の観点から、１０℃以上が好ましく、２０℃以上がより好ましい。また、本実施形態の製造方法で得られる鋼板用アルカリ洗浄剤組成物の保存温度は、保存安定性の観点から、５０℃以下が好ましく、４０℃以下がより好ましい。 In the step (3), the storage temperature of the steel sheet alkaline detergent composition is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, from the viewpoint of storage stability. Moreover, 50 degreeC or less is preferable from a viewpoint of storage stability, and, as for the storage temperature of the alkaline cleaning composition for steel plates obtained with the manufacturing method of this embodiment, 40 degrees C or less is more preferable.
　また、前記鋼板用アルカリ洗浄剤組成物は保存安定性に優れるため、前記工程（３）において７日以上保存する場合に好適であり、３０日以上保存する場合により好適である。アルカリ剤（Ａ）の沈降を抑制するため、保存中に攪拌することが好ましい。攪拌は、保存中に断続的または連続的にあるいは使用前に行うことができる。また、保存安定性の観点から、３００日以下の保存が好ましく、２００日以下の保存がより好ましく、１５０日以下の保存がより好ましい。 Moreover, since the said alkaline cleaning composition for steel plates is excellent in storage stability, it is suitable for storing for 7 days or more in the step (3), and more suitable for storing for 30 days or more. In order to suppress sedimentation of the alkaline agent (A), it is preferable to stir during storage. Agitation can be done intermittently or continuously during storage or prior to use. In addition, from the viewpoint of storage stability, storage for 300 days or less is preferable, storage for 200 days or less is more preferable, and storage for 150 days or less is more preferable.
　前記工程（４）で得られる第２の鋼板用アルカリ洗浄剤組成物のアルカリ剤（Ａ）の含有量は、鋼板の洗浄性の観点から、０．１重量％以上が好ましく、０．５重量％以上がより好ましい。また、前記工程（４）で得られる第２の鋼板用アルカリ洗浄剤組成物のアルカリ剤（Ａ）の含有量は、鋼板の洗浄性の観点から、２０重量％以下が好ましく、１０重量％以下がより好ましく、８重量％以下が更に好ましい。 The content of the alkaline agent (A) in the second alkaline detergent composition for steel sheet obtained in the step (4) is preferably 0.1% by weight or more, and 0.5% by weight from the viewpoint of the steel sheet detergency. % Or more is more preferable. Further, the content of the alkali agent (A) in the second steel sheet alkaline cleaning composition obtained in the step (4) is preferably 20% by weight or less, preferably 10% by weight or less, from the viewpoint of the cleanability of the steel sheet. Is more preferable, and 8 weight% or less is still more preferable.
　前記工程（４）で得られる第２の鋼板用アルカリ洗浄剤組成物は、鋼板を圧延油の存在下で冷間圧延する冷間圧延工程と、圧延された鋼板に付着する圧延油を洗浄剤により洗浄する洗浄工程とを有する冷間圧延鋼板の製造方法における前記洗浄工程において、アルカリ洗浄剤として用いることができる。前記洗浄工程において、第２の鋼板用アルカリ洗浄剤組成物をアルカリ洗浄剤として用いた場合でも、それ以外は従来と同様の方法により、冷間圧延鋼板を製造することができる。 The second alkaline detergent composition for steel sheet obtained in the step (4) comprises a cold rolling process for cold rolling a steel sheet in the presence of rolling oil, and a detergent for removing the rolling oil adhering to the rolled steel sheet. In the said washing | cleaning process in the manufacturing method of the cold-rolled steel plate which has a washing | cleaning process wash | cleaned by (1), it can use as an alkali cleaning agent. Even in the case where the second alkaline cleaning composition for steel sheet is used as the alkaline cleaning agent in the cleaning step, cold rolled steel sheets can be produced by the same method as in the prior art.
　前記冷間圧延工程は、製鉄所等において鋼板を圧延油の存在下で冷間圧延する加工処理工程である。前記洗浄工程では、連続洗浄、即ち浸漬洗浄、スプレー洗浄、ブラシ洗浄、電解洗浄等により、第２の鋼板用アルカリ洗浄剤組成物を用いて圧延油を洗浄除去する。第２の鋼板用アルカリ洗浄剤組成物は、特に、洗浄工程が浸漬ならびに電解洗浄であり、圧延された鋼板を、アルカリ浸漬洗浄槽ならびにアルカリ電解洗浄槽内にロールにより通過させる場合にアルカリ洗浄剤として好適に使用することができる。 The cold rolling step is a processing step for cold rolling a steel sheet in the presence of rolling oil at a steel mill or the like. In the cleaning step, the rolling oil is cleaned and removed using the second alkaline cleaning composition for steel sheet by continuous cleaning, that is, immersion cleaning, spray cleaning, brush cleaning, electrolytic cleaning, and the like. The second alkaline cleaning composition for steel sheet is particularly alkaline cleaning agent when the cleaning process is immersion and electrolytic cleaning, and the rolled steel sheet is passed through a roll into an alkaline immersion cleaning tank and an alkaline electrolytic cleaning tank. Can be suitably used.
　本実施形態の製造方法で得られる第２の鋼板用アルカリ洗浄剤組成物は、前記洗浄工程における洗浄温度が４０～８０℃でアルカリ洗浄剤として用いることができ、低温においても洗浄剤の浸透と乳化のバランスがよくなり、鋼板に付着する汚れに対する洗浄性がよく、また抑泡性がよく、浸漬・電解洗浄におけるロール上の滑りを抑制できる。 The second steel sheet alkaline detergent composition obtained by the production method of the present embodiment can be used as an alkaline detergent at a washing temperature of 40 to 80 ° C. in the washing step. The balance of emulsification is improved, the detergency against dirt adhering to the steel plate is good, and the antifoaming property is good, and slippage on the roll in dipping / electrolytic washing can be suppressed.
　上述した実施形態に関し、本発明はさらに以下の製造方法、組成物、或いは用途を開示する。
＜１＞アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含む成分を、攪拌翼を有する攪拌槽に導入する工程（１）、及び
　前記攪拌翼を回転させて各成分を混合する工程（２）
を有する鋼板用アルカリ洗浄剤組成物の製造方法であって、
　前記工程（１）において前記攪拌槽に導入する前記成分の割合が、
アルカリ剤（Ａ）３４重量％以上であり、３５重量％以上が好ましく、３７重量％以上がより好ましく、４５重量％以下であり、４２重量％以下が好ましく、４０重量％以下がより好ましく、
キレート剤（Ｂ）０．５重量％以上であり、１重量％以上が好ましく、３重量％以上がより好ましく、５重量％以上が更に好ましく、６重量％以上がより更に好ましく、１２重量％以下であり、１０重量％以下が好ましく、８重量％以下が好ましく、
非イオン性界面活性剤（Ｃ）０．１重量％以上であり、０．５重量％以上が好ましく、０．８重量％以上がより好ましく、８重量％以下であり、５重量％以下が好ましく、３重量％以下がより好ましく、
スラリー化剤（Ｄ）０．４重量％以上であり、１重量％以上が好ましく、１．２重量％以上がより好ましく、４．５重量％以下であり、３重量％以下が好ましく、２重量％以下がより好ましく、
分散剤（Ｅ）０．０５重量％以上であり、０．１重量％以上が好ましく、０．３重量％以上がより好ましく、０．４重量％以上が更に好ましく、２．０重量％以下であり、１．８重量％以下が好ましく１．５重量％以下が更に好ましく、１．０重量％以下がより更に好ましく、
　前記分散剤（Ｅ）が、下記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、
Figure JPOXMLDOC01-appb-C000025
 〔前記一般式（１）中、Ｒ１は炭素数１以上であり、４以下であり、３以下が好ましい炭化水素基、Ｒ２は水素原子又は炭素数１以上であり、３以下であり、２以下が好ましい炭化水素基、Ｒ３は水素原子又はメチル基、水素原子が好ましい。〕
Figure JPOXMLDOC01-appb-C000026
 〔前記一般式（２）中、Ｒ４は炭素数１以上であり、２以上が好ましく、３以上がより好ましく、６以下であり、５以下が好ましく、４以下がより好ましい炭化水素基、Ａ１Ｏは炭素数２又は３のアルキレンオキシ基、ｍはＡ１Ｏの平均付加モル数で０以上であり、１以上が好ましく、３以下であり、２以下が好ましく、（Ａ１Ｏ）ｍの総炭素数は０以上であり、２以上が好ましく、６以下であり、４以下が好ましい。〕
Figure JPOXMLDOC01-appb-C000027
 〔前記一般式（３）中、Ｒ５は水素原子又は炭素数１又は２の炭化水素基である。〕
Figure JPOXMLDOC01-appb-C000028
 〔前記一般式（４）中、Ｒ６は水素原子又はメチル基である。〕
Figure JPOXMLDOC01-appb-C000029
 〔前記一般式（５）中、Ｒ７は－（Ａ２Ｏ）ｎ３－Ｈ、又は下記一般式（６）で表される化合物であり、
Figure JPOXMLDOC01-appb-C000030
 Ａ２Ｏは炭素数２又は３、好ましくは２のアルキレンオキシ基、ｎ１、ｎ２、ｎ３及びｎ４は、それぞれＡ２Ｏの付加モル数を示す整数であり、ｎ１、ｎ２、ｎ３及びｎ４の合計の平均値は０．５以上、好ましくは１．０以上、より好ましくは１．５以上、８以下、好ましくは５．０以下、より好ましくは３．５以下、更に好ましくは２．５以下である。〕
　前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物の製造方法。
＜２＞前記工程（２）において、前記攪拌翼を好ましくは３．５ｋｗ／ｋｇ以上、より好ましくは６．０ｋｗ／ｋｇ以上、好ましくは２０ｋｗ／ｋｇ以下、より好ましくは１８ｋｗ／ｋｇ以下、更に好ましくは１７ｋｗ／ｋｇ以下の電力量で回転させて各成分を混合する、前記＜１＞に記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜３＞前記非イオン性界面活性剤（Ｃ）が、下記一般式（７）及び（８）で表される化合物からなる群より選ばれる１種以上である、前記＜１＞又は＜２＞に記載の鋼板用アルカリ洗浄剤組成物の製造方法。
Figure JPOXMLDOC01-appb-C000031
 〔前記一般式（７）中、Ｒ８は炭素数８以上が好ましく、１８以下が好ましく、１４以下がより好ましく、１２以下が更に好ましい炭化水素基、Ａ３Ｏは炭素数２以上４以下のアルキレンオキシ基が好ましく、ｏはＡ３Ｏの平均付加モル数で２以上が好ましく、４以上がより好ましく、２０以下が好ましく、１６以下がより好ましい。〕
Figure JPOXMLDOC01-appb-C000032
 〔前記一般式（８）中、Ｒ９は炭素数８以上が好ましく、１２以上がより好ましく、１６以上が更に好ましく、１８以下が好ましい炭化水素基、Ａ４Ｏは炭素数２以上４以下のアルキレンオキシ基が好ましく、エチレンオキシ基がより好ましく、ｐ及びｑはそれぞれＡ４Ｏの平均付加モル数を表し、ｐ＋ｑが２以上が好ましく、５以上がより好ましく、８以上が更に好ましく、２０以下が好ましく、１２以下がより好ましい。〕
＜４＞前記スラリー化剤（Ｄ）が水溶性高分子カルボン酸である、前記＜１＞～＜３＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜５＞前記スラリー化剤（Ｄ）と前記非イオン界面活性剤（Ｃ）の重量比、スラリー化剤（Ｄ）／非イオン界面活性剤（Ｃ）が、０．１以上が好ましく、１以上がより好ましく、５０以下が好ましく、１５以下がより好ましく、５以下が更に好ましく、２以下がより更に好ましい、前記＜１＞～＜４＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜６＞前記水（Ｆ）の割合が４５重量％以上が好ましく、５０重量％以上がより好ましく、７０重量％以下が好ましく、６５重量％以下がより好ましく、６０重量％以下が更に好ましく、５５重量％以下がより更に好ましい、前記＜１＞～＜５＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜７＞前記分散剤（Ｅ）が、
（１’）メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、セナンダリーブタノール、ターシャリーブタノール、ｎ－ペンタノール及びｎ－ヘキサノール、メチルグリコール、メチルトリグリコール、イソプロピルグリコール、イソプロピルジグリコール、ブチルグリコール、ブチルジグリコール、ブチルトリグリコール、イソブチルグリコール、イソブチルジグリコール、イソブチルトリグリコール、ヘキシルグリコール、メチルプロピレングリコール、メチルプロピレンジグリコール、アリルグリコール、
（２’）エチレングリコール、プロピレングリコール、ブチレングリコール、
（３’）Ｎ－メチルエタノールアミン、Ｎ－エチルエタノールアミン、Ｎ－ｎ－ブチルエタノールアミン、Ｎ－イソブチルエタノールアミン、Ｎ－タシャリーブチルエタノールアミン、Ｎ－メチルイソプロパノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、Ｎ，Ｎ－メチルエチルエタノールアミン、Ｎ，Ｎ－ジメチルイソプロパノールアミン、
（４’）Ｎ－（β－アミノエーテル）エタノールアミン及びＮ－（β－アミノエーテル）イソプロパノールアミン、
（５’）グリセリン及びジグリセリンから選ばれる１種以上の化合物、にエチレンオキサイド及び／又はプロピレンオキサイドを付加した化合物
からなる群より選ばれる１種以上である、前記＜１＞～＜６＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜８＞分散剤（Ｅ）と非イオン界面活性剤（Ｃ）の重量比〔分散剤（Ｅ）／非イオン界面活性剤（Ｃ）〕が、０．１以上が好ましく、０．４以上がより好ましく、４．０以下が好ましく、２．０以下がより好ましく、１．５以下が更に好ましい、前記＜１＞～＜７＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜９＞スラリー化剤（Ｄ）の重量平均分子量（ＭＷ）が、好ましくは１，０００～１００，０００、より好ましくは３，０００～５０，０００、更に好ましくは５，０００～２０，０００、より更に好ましくは５，０００～１０，０００である、前記＜１＞～＜８＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜１０＞さらに、消泡剤（Ｇ）として、炭素数８以上の１級アルコールを含有する、前記＜１＞～＜９＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜１１＞消泡剤（Ｇ）の配合量が、０．１重量％以上が好ましく、０．３重量％以上がより好ましく、１重量％以下が好ましく、０．７重量％以下がより好ましい、前記＜１０＞に記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜１２＞さらに、前記＜１＞～＜１１＞のいずれかに記載の製造方法で得られた鋼板用アルカリ洗浄剤組成物を１０℃以上５０℃以下で７日以上保存する工程（３）、及び
　水と、前記保存した鋼板用アルカリ洗浄剤組成物とを混合し、水希釈の第２の鋼板用アルカリ洗浄剤組成物を得る工程（４）
　を有する、第２の鋼板用アルカリ洗浄剤組成物の製造方法。
＜１３＞前記工程（２）において、前記攪拌翼を周速０．４５ｍ／ｓ以上で回転させて各成分を混合する、前記＜１＞～＜１２＞いずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜１４＞前記工程（２）において、前記攪拌翼を周速０．４５ｍ／ｓ以上、０．４８ｍ／ｓ以上が好ましく、０．５２ｍ／ｓ以上がより好ましく、０．７５ｍ／ｓ以上が更に好ましく、１．２０ｍ／ｓ以下が好ましく、１．１０ｍ／ｓ以下がより好ましく、０．９０ｍ／ｓ以下が更に好ましく、回転させて各成分を混合する時間が３０分間以上、６０分間以上が好ましく、１００分間以上がより好ましく、３００分間以下、２００分間以下が好ましく、１５０分間以下がより好ましい、前記＜１＞～＜１３＞いずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。
＜１５＞アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含有する鋼板用アルカリ洗浄剤組成物であって、前記各成分の割合が、
アルカリ剤（Ａ）３４重量％以上であり、３５重量％以上が好ましく、３７重量％以上がより好ましく、４５重量％以下であり、４２重量％以下が好ましく、４０重量％以下がより好ましく、
キレート剤（Ｂ）０．５重量％以上であり、１重量％以上が好ましく、３重量％以上がより好ましく、５重量％以上が更に好ましく、６重量％以上がより更に好ましく、１２重量％以下であり、１０重量％以下が好ましく、８重量％以下が好ましく、
非イオン性界面活性剤（Ｃ）０．１重量％以上であり、０．５重量％以上がより好ましく、０．８重量％以上が更に好ましく、８重量％以下であり、５重量％以下がより好ましく、３重量％以下が更に好ましく、
スラリー化剤（Ｄ）０．４重量％以上であり、１重量％以上が好ましく、１．２重量％以上がより好ましく、４．５重量％以下であり、３重量％以下が好ましく、２重量％以下がより好ましく、
分散剤（Ｅ）０．０５重量％以上であり、０．１重量％以上が好ましく、０．３重量％以上がより好ましく、０．４重量％以上が更に好ましく、２．０重量％以下であり、１．８重量％以下が好ましく１．５重量％以下が更に好ましく、１．０重量％以下がより更に好ましく、
　前記分散剤（Ｅ）が、下記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、
Figure JPOXMLDOC01-appb-C000033
 〔前記一般式（１）中、Ｒ１は炭素数１以上であり、４以下であり、３以下が好ましい炭化水素基、Ｒ２は水素原子又は炭素数１以上であり、３以下であり、２以下が好ましい炭化水素基、Ｒ３は水素原子又はメチル基、水素原子が好ましい。〕
Figure JPOXMLDOC01-appb-C000034
 〔前記一般式（２）中、Ｒ４は炭素数１以上であり、２以上が好ましく、３以上がより好ましく、６以下であり、５以下が好ましく、４以下がより好ましい炭化水素基、Ａ１Ｏは炭素数２又は３のアルキレンオキシ基、ｍはＡ１Ｏの平均付加モル数で０以上であり、１以上が好ましく、３以下であり、２以下が好ましく、（Ａ１Ｏ）ｍの総炭素数は０以上であり、２以上が好ましく、６以下であり、４以下が好ましい。〕
Figure JPOXMLDOC01-appb-C000035
 〔前記一般式（３）中、Ｒ５は水素原子又は炭素数１又は２の炭化水素基である。〕
Figure JPOXMLDOC01-appb-C000036
 〔前記一般式（４）中、Ｒ６は水素原子又はメチル基である。〕
Figure JPOXMLDOC01-appb-C000037
 〔前記一般式（５）中、Ｒ７は－（Ａ２Ｏ）ｎ３－Ｈ、又は下記一般式（６）で表される化合物であり、
Figure JPOXMLDOC01-appb-C000038
 Ａ２Ｏは炭素数２又は３、好ましくは２のアルキレンオキシ基、ｎ１、ｎ２、ｎ３及びｎ４は、それぞれＡ２Ｏの付加モル数を示す整数であり、ｎ１、ｎ２、ｎ３及びｎ４の合計の平均値は０．５以上、好ましくは１．０以上、より好ましくは１．５以上、８以下、好ましくは５．０以下、より好ましくは３．５以下、更に好ましくは２．５以下である。〕
　前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物。
＜１６＞前記非イオン性界面活性剤（Ｃ）が、下記一般式（７）及び（８）で表される化合物からなる群より選ばれる１種以上である、前記＜１５＞に記載の鋼板用アルカリ洗浄剤組成物。
Figure JPOXMLDOC01-appb-C000039
 〔前記一般式（７）中、Ｒ８は炭素数８以上が好ましく、１８以下が好ましく、１４以下がより好ましく、１２以下が更に好ましい炭化水素基、Ａ３Ｏは炭素数２以上４以下のアルキレンオキシ基が好ましく、ｏはＡ３Ｏの平均付加モル数で２以上が好ましく、４以上がより好ましく、２０以下が好ましく、１６以下がより好ましい。〕
Figure JPOXMLDOC01-appb-C000040
 〔前記一般式（８）中、Ｒ９は炭素数８以上が好ましく、１２以上がより好ましく、１６以上が更に好ましく、１８以下が好ましい炭化水素基、Ａ４Ｏは炭素数２以上４以下のアルキレンオキシ基が好ましく、エチレンオキシ基がより好ましく、ｐ及びｑはそれぞれＡ４Ｏの平均付加モル数を表し、ｐ＋ｑが２以上が好ましく、５以上がより好ましく、８以上が更に好ましく、２０以下が好ましく、１２以下がより好ましい。〕
＜１７＞前記スラリー化剤（Ｄ）が水溶性高分子カルボン酸である、前記＜１５＞又は＜１６＞に記載の鋼板用アルカリ洗浄剤組成物。
＜１８＞前記スラリー化剤（Ｄ）と前記非イオン界面活性剤（Ｃ）の重量比、スラリー化剤（Ｄ）／非イオン界面活性剤（Ｃ）が、０．１以上が好ましく、１以上がより好ましく、５０以下が好ましく、１５以下がより好ましく、５以下が更に好ましく、２以下がより更に好ましい、前記＜１４＞～＜１７＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物。
＜１９＞前記水（Ｆ）の割合が、４５重量％以上が好ましく、５０重量％以上がより好ましく、７０重量％以下が好ましく、６５重量％以下がより好ましく、６０重量％以下が更に好ましく、５５重量％以下がより更に好ましい、前記＜１５＞～＜１８＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物。
＜２０＞前記分散剤（Ｅ）が、
（１’）メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、セナンダリーブタノール、ターシャリーブタノール、ｎ－ペンタノール及びｎ－ヘキサノール、メチルグリコール、メチルトリグリコール、イソプロピルグリコール、イソプロピルジグリコール、ブチルグリコール、ブチルジグリコール、ブチルトリグリコール、イソブチルグリコール、イソブチルジグリコール、イソブチルトリグリコール、ヘキシルグリコール、メチルプロピレングリコール、メチルプロピレンジグリコール、アリルグリコール、
（２’）エチレングリコール、プロピレングリコール、ブチレングリコール、
（３’）Ｎ－メチルエタノールアミン、Ｎ－エチルエタノールアミン、Ｎ－ｎ－ブチルエタノールアミン、Ｎ－イソブチルエタノールアミン、Ｎ－タシャリーブチルエタノールアミン、Ｎ－メチルイソプロパノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、Ｎ，Ｎ－メチルエチルエタノールアミン、Ｎ，Ｎ－ジメチルイソプロパノールアミン、
（４’）Ｎ－（β－アミノエーテル）エタノールアミン及びＮ－（β－アミノエーテル）イソプロパノールアミン、
（５’）グリセリン及びジグリセリンから選ばれる１種以上の化合物、にエチレンオキサイド及び／又はプロピレンオキサイドを付加した化合物
からなる群より選ばれる１種以上である、前記＜１５＞～＜１９＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物。
＜２１＞分散剤（Ｅ）と非イオン界面活性剤（Ｃ）の重量比〔分散剤（Ｅ）／非イオン界面活性剤（Ｃ）〕が、０．１以上が好ましく、０．４以上がより好ましく、４．０以下が好ましく、２．０以下がより好ましく、１．５以下が更に好ましい、前記＜１５＞～＜２０＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物。
＜２２＞スラリー化剤（Ｄ）の重量平均分子量（ＭＷ）が、好ましくは１，０００～１００，０００、より好ましくは３，０００～５０，０００、更に好ましくは５，０００～２０，０００、より更に好ましくは５，０００～１０，０００である、前記＜１５＞～＜２１＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物。
＜２３＞さらに、消泡剤（Ｇ）として、炭素数８以上の１級アルコールを含有する、前記＜１５＞～＜２２＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物。
＜２４＞消泡剤（Ｇ）の含有量が、０．１重量％以上が好ましく、０．３重量％以上がより好ましく、１重量％以下が好ましく、０．７重量％以下がより好ましい、前記＜２３＞に記載の鋼板用アルカリ洗浄剤組成物。
＜２５＞前記＜１５＞～＜２４＞のいずれかに記載の鋼板用アルカリ洗浄剤組成物の鋼板の洗浄剤としての使用。 The present invention further discloses the following production method, composition, or application regarding the above-described embodiment.
<1> Components containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E), and water (F) are mixed with a stirring blade. A step (1) of introducing the mixture into a stirring tank having a step, and a step (2) of mixing the components by rotating the stirring blade
A method for producing an alkaline detergent composition for steel sheet, comprising:
In the step (1), the ratio of the components to be introduced into the stirring tank is
Alkaline agent (A) is 34% by weight or more, preferably 35% by weight or more, more preferably 37% by weight or more, 45% by weight or less, preferably 42% by weight or less, more preferably 40% by weight or less,
Chelating agent (B) 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, still more preferably 6% by weight or more, and 12% by weight or less. 10 wt% or less is preferable, 8 wt% or less is preferable,
Nonionic surfactant (C) is 0.1 wt% or more, preferably 0.5 wt% or more, more preferably 0.8 wt% or more, 8 wt% or less, and preferably 5 wt% or less. 3% by weight or less is more preferable,
Slurry agent (D) is 0.4 wt% or more, preferably 1 wt% or more, more preferably 1.2 wt% or more, 4.5 wt% or less, preferably 3 wt% or less, 2 wt% % Or less is more preferable,
The dispersant (E) is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.4% by weight or more, and 2.0% by weight or less. There is preferably 1.8% by weight or less, more preferably 1.5% by weight or less, still more preferably 1.0% by weight or less,
The dispersant (E) is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (5),
Figure JPOXMLDOC01-appb-C000025
 [In the general formula (1), R 1 is a hydrocarbon group having 1 or more carbon atoms and 4 or less, preferably 3 or less, and R 2 is a hydrogen atom or 1 or more carbon atoms and 3 or less, A hydrocarbon group of 2 or less is preferred, and R 3 is preferably a hydrogen atom, a methyl group or a hydrogen atom. ]
Figure JPOXMLDOC01-appb-C000026
 [In the general formula (2), R 4 has 1 or more carbon atoms, preferably 2 or more, more preferably 3 or more, 6 or less, preferably 5 or less, more preferably 4 or less, A 1 O is an alkyleneoxy group having 2 or 3 carbon atoms, m is an average added mole number of A 1 O of 0 or more, preferably 1 or more, 3 or less, and preferably 2 or less, (A 1 O) m The total number of carbon atoms is 0 or more, preferably 2 or more, 6 or less, and 4 or less. ]
Figure JPOXMLDOC01-appb-C000027
 [In the general formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. ]
Figure JPOXMLDOC01-appb-C000028
 [In the general formula (4), R 6 is a hydrogen atom or a methyl group. ]
Figure JPOXMLDOC01-appb-C000029
 [In the general formula (5), R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
Figure JPOXMLDOC01-appb-C000030
 A 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, preferably 2; n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the total of n1, n2, n3 and n4 The average value is 0.5 or more, preferably 1.0 or more, more preferably 1.5 or more and 8 or less, preferably 5.0 or less, more preferably 3.5 or less, still more preferably 2.5 or less. is there. ]
The steel sheet alkaline detergent composition is a dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 μm are dispersed in a phase containing water (F). A method for producing the composition.
<2> In the step (2), the stirring blade is preferably at least 3.5 kw / kg, more preferably at least 6.0 kw / kg, preferably at most 20 kw / kg, more preferably at most 18 kw / kg, even more preferably Is a method for producing an alkaline detergent composition for steel sheet according to the above <1>, wherein each component is mixed by rotating at an electric energy of 17 kw / kg or less.
<3> The <1> or <2>, wherein the nonionic surfactant (C) is at least one selected from the group consisting of compounds represented by the following general formulas (7) and (8). The manufacturing method of the alkali-cleaner composition for steel plates as described in any one of.
Figure JPOXMLDOC01-appb-C000031
 [In the general formula (7), R 8 preferably has 8 or more carbon atoms, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less, and A 3 O has 2 to 4 carbon atoms. An alkyleneoxy group is preferable, and o is an average added mole number of A 3 O, preferably 2 or more, more preferably 4 or more, preferably 20 or less, and more preferably 16 or less. ]
Figure JPOXMLDOC01-appb-C000032
 [In the general formula (8), R 9 preferably has 8 or more carbon atoms, more preferably 12 or more, still more preferably 16 or more, and more preferably 18 or less, and A 4 O has 2 to 4 carbon atoms. An alkyleneoxy group is preferable, an ethyleneoxy group is more preferable, p and q each represent an average added mole number of A 4 O, p + q is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and 20 or less Is preferable, and 12 or less is more preferable. ]
<4> The method for producing an alkaline detergent composition for a steel sheet according to any one of <1> to <3>, wherein the slurry agent (D) is a water-soluble polymer carboxylic acid.
<5> The weight ratio of the slurry agent (D) and the nonionic surfactant (C), and the slurry agent (D) / nonionic surfactant (C) is preferably 0.1 or more, and preferably 1 or more. Is more preferably 50 or less, more preferably 15 or less, still more preferably 5 or less, and even more preferably 2 or less of the alkaline detergent composition for steel sheet according to any one of the above <1> to <4> Production method.
<6> The proportion of water (F) is preferably 45% by weight or more, more preferably 50% by weight or more, preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 60% by weight or less, 55 The method for producing an alkaline detergent composition for a steel sheet according to any one of <1> to <5>, wherein the weight percent or less is even more preferable.
<7> The dispersant (E) is
(1 ') Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, senandary butanol, tertiary butanol, n-pentanol and n-hexanol, methyl glycol, methyl triglycol, isopropyl glycol, isopropyldi Glycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, isobutyl triglycol, hexyl glycol, methyl propylene glycol, methyl propylene diglycol, allyl glycol,
(2 ′) ethylene glycol, propylene glycol, butylene glycol,
(3 ′) N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N-isobutylethanolamine, N-tert-butylethanolamine, N-methylisopropanolamine, N, N-dimethylethanol Amine, N, N-diethylethanolamine, N, N-methylethylethanolamine, N, N-dimethylisopropanolamine,
(4 ′) N- (β-aminoether) ethanolamine and N- (β-aminoether) isopropanolamine,
(5 ′) one or more selected from the group consisting of compounds obtained by adding ethylene oxide and / or propylene oxide to one or more compounds selected from glycerol and diglycerol; The manufacturing method of the alkali cleaning composition for steel plates in any one.
<8> The weight ratio of the dispersant (E) to the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is preferably 0.1 or more, and 0.4 or more. More preferably, 4.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less, the method for producing an alkaline detergent composition for steel sheet according to any one of the above <1> to <7> .
<9> The weight average molecular weight (MW) of the slurry agent (D) is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 20,000, The method for producing an alkaline detergent composition for steel sheets according to any one of <1> to <8>, further preferably from 5,000 to 10,000.
<10> The method for producing an alkaline detergent composition for steel sheets according to any one of <1> to <9>, further comprising a primary alcohol having 8 or more carbon atoms as the antifoaming agent (G).
<11> The content of the antifoaming agent (G) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, preferably 1% by weight or less, more preferably 0.7% by weight or less. The manufacturing method of the alkaline detergent composition for steel plates as described in said <10>.
<12> Further, a step (3) of storing the alkaline detergent composition for a steel sheet obtained by the production method according to any one of <1> to <11> at 10 ° C. or more and 50 ° C. or less for 7 days or more, And the step of mixing the water and the stored alkaline detergent composition for steel plate to obtain a diluted second alkaline detergent composition for steel plate (4)
The manufacturing method of the 2nd alkali-cleaner composition for steel plates which has these.
<13> The alkaline detergent for steel sheet according to any one of <1> to <12>, wherein in the step (2), the components are mixed by rotating the stirring blade at a peripheral speed of 0.45 m / s or more. A method for producing the composition.
<14> In the step (2), the stirring blade has a peripheral speed of 0.45 m / s or more, preferably 0.48 m / s or more, more preferably 0.52 m / s or more, and further 0.75 m / s or more. Preferably, 1.20 m / s or less is preferable, 1.10 m / s or less is more preferable, 0.90 m / s or less is more preferable, and the time for rotating and mixing each component is preferably 30 minutes or more and 60 minutes or more The method for producing an alkaline detergent composition for steel sheets according to any one of <1> to <13>, wherein 100 minutes or more is more preferable, 300 minutes or less, 200 minutes or less is preferable, and 150 minutes or less is more preferable.
<15> An alkaline detergent for steel sheet containing an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F) A composition, wherein the proportion of each component is
Alkaline agent (A) is 34% by weight or more, preferably 35% by weight or more, more preferably 37% by weight or more, 45% by weight or less, preferably 42% by weight or less, more preferably 40% by weight or less,
Chelating agent (B) 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, still more preferably 5% by weight or more, still more preferably 6% by weight or more, and 12% by weight or less. 10 wt% or less is preferable, 8 wt% or less is preferable,
The nonionic surfactant (C) is 0.1% by weight or more, more preferably 0.5% by weight or more, still more preferably 0.8% by weight or more, 8% by weight or less, and 5% by weight or less. More preferably, 3% by weight or less is more preferable,
Slurry agent (D) is 0.4 wt% or more, preferably 1 wt% or more, more preferably 1.2 wt% or more, 4.5 wt% or less, preferably 3 wt% or less, 2 wt% % Or less is more preferable,
The dispersant (E) is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, still more preferably 0.4% by weight or more, and 2.0% by weight or less. There is preferably 1.8% by weight or less, more preferably 1.5% by weight or less, still more preferably 1.0% by weight or less,
The dispersant (E) is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (5),
Figure JPOXMLDOC01-appb-C000033
 [In the general formula (1), R 1 is a hydrocarbon group having 1 or more carbon atoms and 4 or less, preferably 3 or less, and R 2 is a hydrogen atom or 1 or more carbon atoms and 3 or less, A hydrocarbon group of 2 or less is preferred, and R 3 is preferably a hydrogen atom, a methyl group or a hydrogen atom. ]
Figure JPOXMLDOC01-appb-C000034
 [In the general formula (2), R 4 has 1 or more carbon atoms, preferably 2 or more, more preferably 3 or more, 6 or less, preferably 5 or less, more preferably 4 or less, A 1 O is an alkyleneoxy group having 2 or 3 carbon atoms, m is an average added mole number of A 1 O of 0 or more, preferably 1 or more, 3 or less, and preferably 2 or less, (A 1 O) m The total number of carbon atoms is 0 or more, preferably 2 or more, 6 or less, and 4 or less. ]
Figure JPOXMLDOC01-appb-C000035
 [In the general formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. ]
Figure JPOXMLDOC01-appb-C000036
 [In the general formula (4), R 6 is a hydrogen atom or a methyl group. ]
Figure JPOXMLDOC01-appb-C000037
 [In the general formula (5), R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
Figure JPOXMLDOC01-appb-C000038
 A 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, preferably 2; n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the total of n1, n2, n3 and n4 The average value is 0.5 or more, preferably 1.0 or more, more preferably 1.5 or more and 8 or less, preferably 5.0 or less, more preferably 3.5 or less, still more preferably 2.5 or less. is there. ]
The steel sheet alkaline detergent composition is a dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 μm are dispersed in a phase containing water (F). Composition.
<16> The steel sheet according to <15>, wherein the nonionic surfactant (C) is at least one selected from the group consisting of compounds represented by the following general formulas (7) and (8). Alkaline detergent composition.
Figure JPOXMLDOC01-appb-C000039
 [In the general formula (7), R 8 preferably has 8 or more carbon atoms, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less, and A 3 O has 2 to 4 carbon atoms. An alkyleneoxy group is preferable, and o is an average added mole number of A 3 O, preferably 2 or more, more preferably 4 or more, preferably 20 or less, and more preferably 16 or less. ]
Figure JPOXMLDOC01-appb-C000040
 [In the general formula (8), R 9 preferably has 8 or more carbon atoms, more preferably 12 or more, still more preferably 16 or more, and more preferably 18 or less, and A 4 O has 2 to 4 carbon atoms. An alkyleneoxy group is preferable, an ethyleneoxy group is more preferable, p and q each represent an average added mole number of A 4 O, p + q is preferably 2 or more, more preferably 5 or more, still more preferably 8 or more, and 20 or less Is preferable, and 12 or less is more preferable. ]
<17> The alkaline detergent composition for steel sheet according to <15> or <16>, wherein the slurry agent (D) is a water-soluble polymer carboxylic acid.
<18> The weight ratio of the slurry agent (D) and the nonionic surfactant (C), and the slurry agent (D) / nonionic surfactant (C) is preferably 0.1 or more, and preferably 1 or more. Is more preferably 50 or less, more preferably 15 or less, still more preferably 5 or less, and even more preferably 2 or less, and the alkaline detergent composition for steel sheet according to any one of the above items <14> to <17>.
<19> The proportion of water (F) is preferably 45% by weight or more, more preferably 50% by weight or more, preferably 70% by weight or less, more preferably 65% by weight or less, still more preferably 60% by weight or less, The alkaline detergent composition for steel sheets according to any one of <15> to <18>, wherein 55% by weight or less is even more preferable.
<20> The dispersant (E) is
(1 ') Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, senandary butanol, tertiary butanol, n-pentanol and n-hexanol, methyl glycol, methyl triglycol, isopropyl glycol, isopropyldi Glycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, isobutyl triglycol, hexyl glycol, methyl propylene glycol, methyl propylene diglycol, allyl glycol,
(2 ′) ethylene glycol, propylene glycol, butylene glycol,
(3 ′) N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N-isobutylethanolamine, N-tert-butylethanolamine, N-methylisopropanolamine, N, N-dimethylethanol Amine, N, N-diethylethanolamine, N, N-methylethylethanolamine, N, N-dimethylisopropanolamine,
(4 ′) N- (β-aminoether) ethanolamine and N- (β-aminoether) isopropanolamine,
(5 ′) one or more selected from the group consisting of compounds obtained by adding ethylene oxide and / or propylene oxide to one or more compounds selected from glycerin and diglycerin; The alkaline detergent composition for steel sheets according to any one of the above.
<21> The weight ratio of the dispersant (E) and the nonionic surfactant (C) [dispersant (E) / nonionic surfactant (C)] is preferably 0.1 or more, and 0.4 or more. More preferably, 4.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less, the alkaline detergent composition for steel sheet according to any one of <15> to <20>.
<22> The weight average molecular weight (MW) of the slurry agent (D) is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 20,000, The alkaline cleaner composition for steel sheets according to any one of the above <15> to <21>, further preferably 5,000 to 10,000.
<23> The alkaline detergent composition for steel sheets according to any one of <15> to <22>, further comprising a primary alcohol having 8 or more carbon atoms as the antifoaming agent (G).
<24> The content of the antifoaming agent (G) is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, preferably 1% by weight or less, more preferably 0.7% by weight or less, The alkaline detergent composition for steel sheets according to <23>.
<25> Use of the alkaline detergent composition for steel sheets according to any one of <15> to <24> as a steel sheet detergent.
　以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例によりなんら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
＜鋼板用アルカリ洗浄剤組成物の調製＞
＜実施例１＞
　工程（１）：キレート剤としてグルコン酸ナトリウム６０．０ｇ（１０．０重量％）と水８８．６ｇ（１４．８重量％）とを、容量５００ｍｌのガラスビーカ（内径８０．５ｍｍ）に入れ、キレート剤水溶液を調製した。次いで、非イオン性界面活性剤としてポリオキシエチレン（１０モル付加）ポリオキシプロピレン（２モル付加）アルキルセカンダリーエーテル（ラウリル、ミリスチルの混合物）３．０ｇ（０．５重量％）、消泡剤としてイソトリデシルアルコール３．０ｇ（０．５重量％）、分散剤としてエチルエタノールアミン２．４ｇ（０．４重量％）、スラリー化剤としてポリアクリル酸ナトリウム（固形分４２％）１８．０ｇ（固形分として１．２６重量％）を攪拌混合し、更に、アルカリ剤として４８％水酸化ナトリウムを４２５．０ｇ（ＮａＯＨとして３４．０重量％）加え混合物を得た。
　工程（２）：当該混合物を攪拌翼（４枚ピッチドパドル、直径：８０ｍｍ、翼高さがビーカの２００ｍｌの位置）を有する攪拌装置にて５３０ｒｐｍで４０分間攪拌し鋼板用アルカリ洗浄剤組成物を得た。なお周速は０．７１ｍ／ｓである。 <Preparation of alkaline detergent composition for steel plate>
<Example 1>
Step (1): As a chelating agent, 60.0 g (10.0 wt%) of sodium gluconate and 88.6 g (14.8 wt%) of water are put into a glass beaker (inner diameter 80.5 mm) having a capacity of 500 ml, An aqueous chelating agent solution was prepared. Next, polyoxyethylene (10 mole addition) polyoxypropylene (2 mole addition) alkyl secondary ether (mixture of lauryl and myristyl) 3.0 g (0.5 wt%) as a nonionic surfactant, as an antifoaming agent Isotridecyl alcohol 3.0 g (0.5 wt%), ethyl ethanolamine 2.4 g (0.4 wt%) as a dispersing agent, sodium polyacrylate (solid content 42%) 18.0 g as a slurry agent The solid content was 1.26% by weight), and the mixture was further mixed with 425.0 g of 48% sodium hydroxide (34.0% by weight as NaOH) as an alkaline agent to obtain a mixture.
Step (2): The mixture is stirred for 40 minutes at 530 rpm with a stirrer having a stirring blade (four pitched paddles, diameter: 80 mm, blade height is 200 ml of beaker) to obtain an alkaline cleaning composition for steel sheet. It was. The peripheral speed is 0.71 m / s.
＜実施例２～５５、実施例２－１～２－１２、比較例１～３２、比較例２－１～２－５＞
　表１～７に示した成分及びその量を用いた以外は、実施例１と同様の方法で調製した。表１～７に記載の配合量の単位は重量％である。 <Examples 2 to 55, Examples 2-1 to 2-12, Comparative Examples 1 to 32, Comparative Examples 2-1 to 2-5>
Prepared in the same manner as in Example 1 except that the components and amounts shown in Tables 1 to 7 were used. The unit of the amount described in Tables 1 to 7 is% by weight.
＜原料について＞
　表１～７、及び表８（後述）に記載の各成分は以下を用いた。
Ａ）アルカリ剤
・水酸化ナトリウム
Ｂ）キレート剤
・グルコン酸ナトリウム
Ｃ）非イオン界面活性剤
・ポリオキシエチレン（８モル付加）ポリオキシプロピレン（４モル付加）デシルエーテル（下記非イオン界面活性剤の製造例１で製造したもの）
・ポリオキシエチレン（１０モル付加）ポリオキシプロピレン（２モル付加）ラウリルミリスチルセカンダリーエーテル（下記非イオン界面活性剤の製造例１と同様の方法で製造したもの）
・ポリオキシエチレン（４モル付加）２－エチルヘキシルエーテル：ニューコール１００４　日本乳化剤（株）製
・ポリオキシエチレン（１２モル付加）ポリオキシプロピレン（３モル付加）ラウリルミリスチルセカンダリーエーテル：ソフタノール１２０３０　（株）日本触媒製
・ポリオキシエチレン（１３モル付加）ステアリルエーテル：エマルゲン３２０Ｐ　花王（株）製
・ポリオキシエチレン（９モル付加）ステアリルアミン：ブラウノンＬ２１０　青木油脂工業（株）製
Ｄ）スラリー化剤
・ポリアクリル酸ナトリウム：重量平均分子量６０００
Ｅ）分散剤
・エチルエタノールアミン：日本乳化剤（株）製
・グリセリンＡ（下記分散剤の製造例１で製造したもの）
・グリセリンＢ（下記分散剤の製造例２で製造したもの）
・グリセリンＣ（下記分散剤の製造例３で製造したもの）
・グリセリンＤ（下記分散剤の製造例４で製造したもの）
・グリセリンＥ（下記分散剤の製造例５で製造したもの）
・グリセリンＦ（下記分散剤の製造例６で製造したもの）
・グリセリンＧ（下記分散剤の製造例７で製造したもの）
・グリセリンＨ（下記分散剤の製造例８で製造したもの）
・グリセリンＩ（下記分散剤の製造例９で製造したもの）
・グリセリンＪ：グリセリン　花王（株）製
・グリセリンＫ（下記分散剤の製造例１０で製造したもの）
・グリセリンＬ（下記分散剤の製造例１１で製造したもの）
・グリセリンＭ（下記分散剤の製造例１２で製造したもの）
・グリセリンＮ（下記分散剤の製造例１３で製造したもの）
・ジグリセリンＡ（下記分散剤の製造例１４で製造したもの）
・ジグリセリンＢ（下記分散剤の製造例１５で製造したもの）
・ジグリセリンＣ（下記分散剤の製造例１６で製造したもの）
Ｇ）消泡剤
・イソトリデシルアルコール：トリデカノール、協和発酵ケミカル（株）製
・イソステアリルアルコール：ファインオキソコール１８０、日産化学工業（株）製 <About raw materials>
The following components were used in Table 1 to 7 and Table 8 (described later).
A) Alkali agent, sodium hydroxide B) chelating agent, sodium gluconate C) nonionic surfactant, polyoxyethylene (8 mol addition) polyoxypropylene (4 mol addition) decyl ether (of the following nonionic surfactant) (Manufactured in Production Example 1)
Polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether (produced by the same method as in Production Example 1 of the following nonionic surfactant)
・ Polyoxyethylene (4 mol addition) 2-ethylhexyl ether: New Coal 1004 manufactured by Nippon Emulsifier Co., Ltd. ・ Polyoxyethylene (12 mol addition) polyoxypropylene (3 mol addition) lauryl myristyl secondary ether: Softanol 12030 Nippon Shokubai, polyoxyethylene (13 mol addition) stearyl ether: Emulgen 320P, Kao Co., Ltd., polyoxyethylene (9 mol addition) stearylamine: Braunon L210, Aoki Yushi Kogyo Co., Ltd. D) Slurry agent, poly Sodium acrylate: weight average molecular weight 6000
E) Dispersant / Ethylethanolamine: manufactured by Nippon Emulsifier Co., Ltd./glycerin A (produced in Production Example 1 of Dispersant below)
・ Glycerin B (produced in Production Example 2 of dispersant below)
・ Glycerin C (manufactured in Dispersant Production Example 3 below)
・ Glycerin D (produced in Production Example 4 of the following dispersant)
・ Glycerin E (produced in Production Example 5 of dispersant below)
・ Glycerin F (produced in Production Example 6 of dispersant below)
・ Glycerin G (produced in Production Example 7 of dispersant below)
・ Glycerin H (produced in Production Example 8 of dispersant below)
・ Glycerin I (produced in Production Example 9 of dispersant below)
・ Glycerin J: Glycerin Kao Co., Ltd. ・ Glycerin K (produced in Production Example 10 of Dispersant below)
・ Glycerin L (produced in Production Example 11 of dispersant below)
・ Glycerin M (manufactured in Dispersant Production Example 12 below)
・ Glycerin N (produced in Production Example 13 of dispersant below)
Diglycerin A (produced in Production Example 14 of the following dispersant)
Diglycerin B (produced in Production Example 15 of the following dispersant)
Diglycerin C (manufactured in Dispersant Production Example 16 below)
G) Antifoaming agent • Isotridecyl alcohol: Tridecanol, manufactured by Kyowa Hakko Chemical Co., Ltd. • Isostearyl alcohol: Fine Oxocol 180, manufactured by Nissan Chemical Industries, Ltd.
＜非イオン界面活性剤の製造例１＞
　オートクレーブにｎ－デカノール１５８．２ｇ（１モル）及びＫＯＨ（触媒）０．３０ｇ（０．４重量％）を仕込み、オートクレーブ内の空気を窒素で置換した後、ｎ－デカノールを攪拌しながらオートクレーブ内の温度を１３０℃に昇温した。エチレンオキサイド３５２ｇ（８モル）を３．５ｋｇ／ｃｍ２の圧力（ゲージ圧）でオートクレーブ中に導入し、前記圧力が低下して一定になるまでｎ－デカノールとエチレンオキサイドとを反応させた後、オートクレーブ内の温度を１２０℃まで下げた。次いで、プロピレンオキサイド２３２ｇ（４モル）を３．５ｋｇ／ｃｍ２の圧力（ゲージ圧）でオートクレーブ中に導入した。前記圧力が低下して一定になるまでプロピレンオキサイドを反応させた後、オートクレーブ内の温度を室温まで低下させて、ポリオキシエチレン（８モル付加）ポリオキシプロピレン（４モル付加）デシルエーテルを約７４０ｇ得た。 <Production Example 1 of Nonionic Surfactant>
An autoclave was charged with 158.2 g (1 mol) of n-decanol and 0.30 g (0.4 wt%) of KOH (catalyst), and the air in the autoclave was replaced with nitrogen, and then the n-decanol was stirred and stirred in the autoclave. The temperature of was raised to 130 ° C. After 352 g (8 mol) of ethylene oxide was introduced into the autoclave at a pressure (gauge pressure) of 3.5 kg / cm 2 , n-decanol and ethylene oxide were reacted until the pressure decreased and became constant, The temperature in the autoclave was lowered to 120 ° C. Next, 232 g (4 mol) of propylene oxide was introduced into the autoclave at a pressure (gauge pressure) of 3.5 kg / cm 2 . After reacting propylene oxide until the pressure decreases and becomes constant, the temperature in the autoclave is lowered to room temperature, and about 740 g of polyoxyethylene (8 mol addition) polyoxypropylene (4 mol addition) decyl ether is obtained. Obtained.
＜分散剤の製造例１＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、プロピレンオキサイドを５８．１ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が１モルのグリセリンのＰＯ付加物（グリセリンＡ）を得た。 <Production Example 1 of Dispersant>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 58.1 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, and then extracted, and an average addition mole number of PO adduct of glycerin with 1 mol (glycerin A) Got.
＜分散剤の製造例２＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、プロピレンオキサイドを１１６．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が２モルのグリセリンのＰＯ付加物（グリセリンＢ）を得た。 <Production Example 2 of Dispersant>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 116.2 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 2 mol glycerin PO adduct (glycerin B) Got.
＜分散剤の製造例３＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、プロピレンオキサイドを１７４．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が３モルのグリセリンのＰＯ付加物（グリセリンＣ）を得た。 <Production Example 3 of Dispersant>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 174.2 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 3 mol glycerin PO adduct (glycerin C). Got.
＜分散剤の製造例４＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、プロピレンオキサイドを４０６．６ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が７モルのグリセリンのＰＯ付加物（グリセリンＤ）を得た。 <Production Example 4 of Dispersant>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 406.6 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 7 mol glycerin PO adduct (glycerin D) Got.
＜分散剤の製造例５＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを４４．１ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が１モルのグリセリンのＥＯ付加物（グリセリンＥ）を得た。 <Dispersant Production Example 5>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 44.1 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of glycerol EO adduct (glycerin E) was 1 mol. Got.
＜分散剤の製造例６＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを８８．１ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が２モルのグリセリンのＥＯ付加物（グリセリンＦ）を得た。 <Dispersant Production Example 6>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 88.1 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an EO adduct of glycerin having an average addition mole number of 2 mol (glycerin F). Got.
＜分散剤の製造例７＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを１３２．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が３モルのグリセリンのＥＯ付加物（グリセリンＧ）を得た。 <Dispersant Production Example 7>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 132.2 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an EO adduct of glycerin having an average addition mole number of 3 mol (glycerin G). Got.
＜分散剤の製造例８＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを１７６．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が４モルのグリセリンのＥＯ付加物（グリセリンＨ）を得た。 <Dispersant Production Example 8>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 176.2 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an EO adduct of glycerin having an average addition mole number of 4 mol (glycerin H). Got.
＜分散剤の製造例９＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを１３２．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、次いでプロピレンオキサイドを５８．１ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数がＥＯ３モルとＰＯ１モルのグリセリンのＥＯＰＯ付加物（グリセリンＩ）を得た。 <Dispersant Production Example 9>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 132.2 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, 58.1 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an EOPO adduct of glycerin having an average addition mole number of EO 3 mol and PO 1 mol ( Glycerol I) was obtained.
＜分散剤の製造例１０＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、プロピレンオキサイドを６９７．０ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が１２モルのグリセリンのＰＯ付加物（グリセリンＫ）を得た。 <Dispersant Production Example 10>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 697.0 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an average addition mole number of 12 mol glycerin PO adduct (glycerin K) Got.
＜分散剤の製造例１１＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、プロピレンオキサイドを１３９４ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が２４モルのグリセリンのＰＯ付加物（グリセリンＬ）を得た。 <Dispersant Production Example 11>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 1394 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, and then extracted, and the glycerin PO adduct (glycerin L) having an average addition mole number of 24 mol. Got.
＜分散剤の製造例１２＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを３９６．５ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が９モルのグリセリンのＥＯ付加物（グリセリンＭ）を得た。 <Dispersant Production Example 12>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 396.5 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an EO adduct of glycerin having an average addition mole number of 9 mol (glycerin M). Got.
＜分散剤の製造例１３＞
　オートクレーブに、グリセリン９２．１ｇとＫＯＨ１．４ｇ（１．５重量％）を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを８８．１ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、次いでプロピレンオキサイドを５８１．０ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数がＥＯ２モルとＰＯ１０モルのグリセリンのＥＯＰＯ付加物（グリセリンＮ）を得た。 <Dispersant Production Example 13>
The autoclave was charged with 92.1 g of glycerin and 1.4 g (1.5 wt%) of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 88.1 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, 581.0 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, 3.0 g of acetic acid was added to the autoclave and kept at 80 ° C. for 30 minutes, followed by extraction, and an EOPO adduct of glycerin with an average addition mole number of EO 2 mol and PO 10 mol ( Glycerin N) was obtained.
＜分散剤の製造例１４＞
　オートクレーブに、ジグリセリン１６６．２ｇとＫＯＨ２．０ｇを仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを１７６．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が４モルのジグリセリンのＥＯ付加物（ジグリセリンＡ）を得た。 <Production Example 14 of Dispersant>
The autoclave was charged with 166.2 g of diglycerin and 2.0 g of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and then 176.2 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and an EO adduct (diglycerin) having an average addition mole number of 4 mol. A) was obtained.
＜分散剤の製造例１５＞
　オートクレーブに、ジグリセリン１６６．２ｇとＫＯＨ２．０ｇを仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、プロピレンオキサイドを１１６．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数が２モルのジグリセリンのＰＯ付加物（ジグリセリンＢ）を得た。 <Dispersant Production Example 15>
The autoclave was charged with 166.2 g of diglycerin and 2.0 g of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 116.2 g of propylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, then extracted, and a PO adduct of diglycerin having an average addition mole number of 2 mol (diglycerin). B) was obtained.
＜分散剤の製造例１６＞
　オートクレーブに、ジグリセリン１６６．２ｇとＫＯＨ２．０ｇを仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、オートクレーブ内の空気を窒素で置換し、オートクレーブ内の温度を１３０℃まで昇温した後、エチレンオキサイドを８８．１ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応エチレンオキサイドを除去した。未反応のエチレンオキサイドを除去した後、次いでプロピレンオキサイドを１１６．２ｇ仕込んだ。１３０℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで３０分間オートクレーブ内の未反応プロピレンオキサイドを除去した。未反応のプロピレンオキサイドを除去した後、酢酸３．０ｇをオートクレーブ内に加え、８０℃で３０分間保持した後、抜き出しを行い、平均付加モル数がＥＯ２モルとＰＯ２モルのジグリセリンのＥＯＰＯ付加物（ジグリセリンＣ）を得た。 <Dispersant Production Example 16>
The autoclave was charged with 166.2 g of diglycerin and 2.0 g of KOH, and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, the air in the autoclave was replaced with nitrogen, the temperature in the autoclave was raised to 130 ° C., and 88.1 g of ethylene oxide was charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted ethylene oxide, 116.2 g of propylene oxide was then charged. After addition reaction and aging at 130 ° C., the mixture was cooled to 80 ° C., and unreacted propylene oxide in the autoclave was removed at 4.0 kPa for 30 minutes. After removing unreacted propylene oxide, acetic acid (3.0 g) was added to the autoclave, kept at 80 ° C. for 30 minutes, and then extracted, and EOPO adduct of diglycerin having an average addition mole number of EO2 mol and PO2 mol. (Diglycerin C) was obtained.
＜評価方法＞
＜重量平均分子量＞
　ゲルパーミエーションクロマトグラフィーにより、標準ポリエチレン換算にて重量平均分子量を測定した。
［測定条件］
　東ソー株式会社製ゲル濾過クロマトグラフＳＣ－８０２０シリーズ・ビルドアップシステム
　カラム：Ｇ２０００ＨＸＬ＋Ｇ４０００ＨＸＬ
　検出器：ＵＶ２２０ｎｍ
　キャリヤ：テトラヒドロフラン１ｍＬ／分
　カラム温度：３８℃
＜油滴の粒子径＞
　前記各鋼板用アルカリ洗浄剤組成物をスライドグラス上に約０．０３ｍｌ（パスツールピペットで１滴）落とし、光学顕微鏡（ＮＩＫＯＮ社製）を用い、拡大率２００倍で写真を撮影した。写真中の油滴の中で、粒子径が最大の油滴の直径を物差しで測定し最大粒子径とした。最大粒子径は５０μｍ未満であると保存安定性に優れるものである。表１～７において分離や析出が観察され粒子径を測定しなかった場合は「－」と記した。 <Evaluation method>
<Weight average molecular weight>
The weight average molecular weight was measured in terms of standard polyethylene by gel permeation chromatography.
[Measurement condition]
Gel filtration chromatograph SC-8020 series build-up system manufactured by Tosoh Corporation Column: G2000HXL + G4000HXL
Detector: UV220nm
Carrier: Tetrahydrofuran 1mL / min Column temperature: 38 ° C
<Particle size of oil droplet>
About 0.03 ml (one drop with a Pasteur pipette) of the alkaline detergent composition for each steel plate was dropped on a slide glass, and a photograph was taken at 200 times magnification using an optical microscope (manufactured by NIKON). Among the oil droplets in the photograph, the diameter of the oil droplet with the largest particle size was measured with a ruler to obtain the maximum particle size. When the maximum particle size is less than 50 μm, the storage stability is excellent. In Tables 1 to 7, when separation or precipitation was observed and the particle size was not measured, “-” was indicated.
＜状態＞
　前記各鋼板用アルカリ洗浄剤組成物を容量５００ｍｌの透明なポリプロピレンビンに入れ、室温（２０℃～２５℃）で２４時間保存し、各鋼板用アルカリ洗浄剤組成物の外観を目視で観察した。そして、上層分離、増粘、固化等の有無を評価した。異常が見られなかった場合は「ＯＫ」とし、異常が見られた場合は、その状態（分離、気泡、析出、等）を表１～７に記した。
＜電力量＞
　撹拌機のモーターのコンセントを検電器につなぎ測定した。検電器で表示される、実効電圧（Ｖ）×実効電流（Ａ）×力率（Ｐ．Ｆ．）で電力量（ｋｗ／ｋｇ）を計算した。 <State>
The alkaline detergent composition for each steel plate was placed in a transparent polypropylene bottle having a capacity of 500 ml and stored at room temperature (20 ° C. to 25 ° C.) for 24 hours, and the appearance of the alkaline detergent composition for each steel plate was visually observed. And the presence or absence of upper layer separation, thickening, solidification, etc. was evaluated. When no abnormality was found, “OK” was set. When an abnormality was found, the state (separation, bubbles, precipitation, etc.) is shown in Tables 1 to 7.
<Electricity>
The outlet of the motor of the stirrer was connected to a voltage detector and measured. The electric energy (kw / kg) was calculated by the effective voltage (V) × the effective current (A) × the power factor (PF) displayed by the voltage detector.
　前記評価結果を表１～７に示す。表中の数値は、洗浄剤中の各成分の含有量（重量％）、Ｄ／Ｃ重量比はスラリー化剤（Ｄ）／非イオン界面活性剤（Ｃ）の含有量の重量比、Ｅ／Ｃ重量比は分散剤（Ｅ）と非イオン界面活性剤（Ｃ）の含有量の重量比を示す。 The evaluation results are shown in Tables 1-7. The numerical values in the table are the content (% by weight) of each component in the cleaning agent, the D / C weight ratio is the weight ratio of the slurrying agent (D) / nonionic surfactant (C) content, E / C weight ratio shows weight ratio of content of a dispersing agent (E) and nonionic surfactant (C).
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
＜実施例５６～５９、比較例３３～３５＞
　混合物の調製は、表８に示した成分及びその量を用いた以外は、実施例１と同様に行った。表７に記載の配合量の単位は重量％である。この混合物を、攪拌翼（４枚ピッチドパドル、直径：８０ｍｍ、翼高さがビーカの２００ｍｌの位置）を有する攪拌装置で、表７に記載の攪拌条件で攪拌し鋼板用アルカリ洗浄剤組成物を得た。 <Examples 56 to 59, Comparative Examples 33 to 35>
The mixture was prepared in the same manner as in Example 1 except that the components and amounts shown in Table 8 were used. The unit of the blending amount shown in Table 7 is% by weight. This mixture was stirred with a stirring device having a stirring blade (four pitched paddles, diameter: 80 mm, blade height 200 ml position of beaker) under the stirring conditions shown in Table 7 to obtain an alkaline detergent composition for steel sheet. It was.
＜実施例６０＞
　工程（１）：キレート剤としてグルコン酸ナトリウム５０．４ｇ（６．３重量％）と水７８．７ｇ（９．８重量％）とを、容量１０００ｍｌのガラス製トールビーカ（内径９２．６ｍｍ）に入れ、キレート剤水溶液を調製した。次いで、非イオン性界面活性剤としてポリオキシエチレン（１０モル付加）ポリオキシプロピレン（２モル付加）ラウリルミリスチルセカンダリーエーテル８．０ｇ（１．０重量％）、消泡剤としてイソトリデシルアルコール４．０ｇ（０．５重量％）、分散剤としてエチルエタノールアミン３．２ｇ（０．４重量％）、スラリー化剤としてポリアクリル酸ナトリウム（固形分４２％）２４．０ｇ（固形分として１．２６重量％）を攪拌混合し、更に、アルカリ剤として４８％水酸化ナトリウムを６３１．７ｇ（ＮａＯＨとして３７．９重量％）加え混合物を得た。
　工程（２）：この混合物を攪拌翼（４枚ピッチドパドル、直径：８０ｍｍ、翼高さがビーカの３００ｍｌの位置）を有する攪拌装置にて６３０ｒｐｍで１２０分間攪拌し鋼板用アルカリ洗浄剤組成物を得た。なお周速は０．８４ｍ／ｓである。 <Example 60>
Step (1): As a chelating agent, 50.4 g (6.3% by weight) of sodium gluconate and 78.7 g (9.8% by weight) of water are put into a glass tall beaker (inner diameter 92.6 mm) having a capacity of 1000 ml. A chelating agent aqueous solution was prepared. Subsequently, 8.0 g (1.0% by weight) of polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether as a nonionic surfactant, and isotridecyl alcohol as an antifoaming agent 4. 0 g (0.5 wt%), 3.2 g (0.4 wt%) of ethyl ethanolamine as a dispersant, 24.0 g of sodium polyacrylate (solid content 42%) as a slurrying agent (1.26 as solid content) % By weight) and 631.7 g (37.9% by weight as NaOH) of 48% sodium hydroxide as an alkaline agent were added to obtain a mixture.
Step (2): This mixture was stirred at 630 rpm for 120 minutes with a stirrer having a stirring blade (4 pitched paddles, diameter: 80 mm, blade height 300 ml of beaker) to obtain an alkaline cleaning composition for steel sheet. It was. The peripheral speed is 0.84 m / s.
＜比較例３６＞
　表８に示した成分及びその量を用いた以外は、実施例６０と同様の方法で調製した。 <Comparative Example 36>
The components were prepared in the same manner as in Example 60 except that the components and amounts shown in Table 8 were used.
＜実施例６１＞
　工程（１）：キレート剤としてグルコン酸ナトリウム１２６．０ｇ（６．３重量％）と水１９６．８ｇ（９．８重量％）とを、容量２０００ｍｌのガラス製ビーカ（内径１３０ｍｍ）に入れ、キレート剤水溶液を調製した。次いで、非イオン性界面活性剤としてポリオキシエチレン（１０モル付加）ポリオキシプロピレン（２モル付加）ラウリルミリスチルセカンダリーエーテル２０．０ｇ（１．０重量％）、消泡剤としてイソトリデシルアルコール１０．０ｇ（０．５重量％）、分散剤としてエチルエタノールアミン８．０ｇ（０．４重量％）、スラリー化剤としてポリアクリル酸ナトリウム（固形分４２％）６０．０ｇ（固形分として１．２６重量％）を攪拌混合し、更に、アルカリ剤として４８％水酸化ナトリウムを１５７９．２ｇ（ＮａＯＨとして３７．９重量％）加え混合物を得た。
　工程（２）：この混合物を攪拌翼（４枚ピッチドパドル、直径：８０ｍｍ、翼高さがビーカの７５０ｍｌの位置）を有する攪拌装置にて７７０ｒｐｍで１２０分間攪拌し鋼板用アルカリ洗浄剤組成物を得た。なお周速は１．０３ｍ／ｓである。 <Example 61>
Step (1): As a chelating agent, 126.0 g (6.3 wt%) of sodium gluconate and 196.8 g (9.8 wt%) of water are put in a glass beaker (inner diameter 130 mm) having a capacity of 2000 ml and chelated. An aqueous agent solution was prepared. Subsequently, 20.0 g (1.0% by weight) of polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether as a nonionic surfactant, and isotridecyl alcohol 10. 0 g (0.5 wt%), ethyl ethanolamine 8.0 g (0.4 wt%) as a dispersant, sodium polyacrylate (solid content 42%) 60.0 g (solid content 1.26 as slurry agent) The mixture was further mixed with 1579.2 g of 48% sodium hydroxide (37.9% by weight as NaOH) as an alkali agent.
Step (2): This mixture was stirred at 770 rpm for 120 minutes with a stirrer having a stirring blade (4 pitched paddles, diameter: 80 mm, blade height 750 ml position of beaker) to obtain an alkaline cleaning composition for steel sheet. It was. The peripheral speed is 1.03 m / s.
＜比較例３７＞
　表８に示した成分及びその量を用いた以外は、実施例６１と同様の方法で調製した。 <Comparative Example 37>
The components were prepared in the same manner as in Example 61 except that the components and amounts shown in Table 8 were used.
＜参考例１＞
　キレート剤としてグルコン酸ナトリウム１２６．０ｇ（６．３重量％）と水１９６．８ｇ（９．８重量％）とを、容量２０００ｍｌのガラス製ビーカに入れ、キレート剤水溶液を調製した。次いで、スラリー化剤としてポリアクリル酸ナトリウム（固形分４２％）６０．０ｇ（固形分として１．２６重量％）を攪拌混合し、更に、アルカリ剤として４８％水酸化ナトリウムを１５７９．２ｇ（ＮａＯＨとして３７．９重量％）加え、非イオン性界面活性剤としてポリオキシエチレン（１０モル付加）ポリオキシプロピレン（２モル付加）ラウリルミリスチルセカンダリーエーテル２０．０ｇ（１．０重量％）、消泡剤としてイソトリデシルアルコール１０．０ｇ（０．５重量％）、分散剤としてエチルエタノールアミン８．０ｇ（０．４重量％）を加え、高剪断力（ホモミキサー：１００００ｒｐｍ）により均一攪拌し鋼板用アルカリ洗浄剤組成物を得た。 <Reference Example 1>
As a chelating agent, 126.0 g (6.3% by weight) of sodium gluconate and 196.8 g (9.8% by weight) of water were placed in a glass beaker having a capacity of 2000 ml to prepare an aqueous chelating agent solution. Next, 60.0 g of sodium polyacrylate (solid content 42%) as a slurrying agent was stirred and mixed, and 1579.2 g (NaOH) of 48% sodium hydroxide as an alkaline agent was further mixed. As a nonionic surfactant, polyoxyethylene (10 mol addition) polyoxypropylene (2 mol addition) lauryl myristyl secondary ether 20.0 g (1.0 wt%), antifoaming agent As a steel plate, 10.0 g (0.5% by weight) of isotridecyl alcohol and 8.0 g (0.4% by weight) of ethylethanolamine as a dispersing agent are added and stirred uniformly with high shear force (homomixer: 10,000 rpm). An alkaline detergent composition was obtained.
＜参考例２＞
　表８に示した成分及びその量を用いた以外は、参考例１と同様の方法で調製した。 <Reference Example 2>
It was prepared in the same manner as in Reference Example 1 except that the components and amounts shown in Table 8 were used.
＜評価方法＞
＜油滴の粒子径＞
　実施例１の油滴の粒子径の測定と同様の方法で最大粒子径を測定した。最大粒子径が５０μｍ未満であると保存安定性に優れるものである。 <Evaluation method>
<Particle size of oil droplet>
The maximum particle size was measured by the same method as the measurement of the particle size of the oil droplet of Example 1. When the maximum particle size is less than 50 μm, the storage stability is excellent.
＜比重＞
　前記鋼板用アルカリ洗浄剤組成物をＪＩＳ　Ｒ　３５０３で規定されているゲーリュサック型比重瓶に入れ、３０℃にてＪＩＳ　Ｋ　００６１の方法で比重を測定した。鋼板用アルカリ洗浄剤組成物は、調製時に気泡を巻き込むと保存安定性が低下する傾向がある。気泡を巻き込むと鋼板用アルカリ洗浄剤組成物の比重は低下するので、比重は低下しないことが望ましい。 <Specific gravity>
The steel sheet alkaline detergent composition was placed in a gallusac type specific gravity bottle defined in JIS R 3503, and the specific gravity was measured at 30 ° C. by the method of JIS K 0061. When the alkaline detergent composition for a steel sheet involves air bubbles during preparation, the storage stability tends to decrease. When bubbles are involved, the specific gravity of the alkaline detergent composition for steel sheet decreases, so it is desirable that the specific gravity does not decrease.
　前記評価結果を表８に示す。表中の数値は、洗浄剤中の各成分の含有量（重量％）、Ｄ／Ｃ重量比はスラリー化剤（Ｄ）／非イオン界面活性剤（Ｃ）の含有量の重量比、Ｅ／Ｃ重量比は分散剤（Ｅ）と非イオン界面活性剤（Ｃ）の含有量の重量比を示す。 The evaluation results are shown in Table 8. The numerical values in the table are the content (% by weight) of each component in the cleaning agent, the D / C weight ratio is the weight ratio of the slurrying agent (D) / nonionic surfactant (C) content, E / C weight ratio shows weight ratio of content of a dispersing agent (E) and nonionic surfactant (C).
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
　比較例に係る鋼板用アルカリ洗浄剤組成物では攪拌時の周速を１．０３ｍ／ｓにて製造すれば目標の粒子径を得られるが、気泡の巻き込みが多く比重が低下し、安定性が得られない。 In the alkaline detergent composition for steel sheet according to the comparative example, the target particle size can be obtained if the peripheral speed during stirring is produced at 1.03 m / s. However, the entrainment of air bubbles is large, the specific gravity is decreased, and the stability is improved. I can't get it.
　一方、実施例に係る鋼板用アルカリ洗浄剤組成物は、攪拌時の周速を増加しても気泡の巻き込みを抑制し、安定した鋼板用アルカリ洗浄剤組成物を製造することができる。なお、実施例６１及び比較例３７は、実施例６０及び比較例３６よりも周速が大きいにもかかわらず、電力量は小さくなった。これは攪拌により渦（ボルテックス）ができ、攪拌翼が液面上に露出したためである。 On the other hand, the alkaline detergent composition for steel sheet according to the example can suppress the entrainment of bubbles even when the peripheral speed during stirring is increased, and can produce a stable alkaline detergent composition for steel sheet. In Example 61 and Comparative Example 37, although the peripheral speed was higher than that in Example 60 and Comparative Example 36, the amount of power was small. This is because a vortex is formed by stirring and the stirring blade is exposed on the liquid surface.
＜第２の鋼板用アルカリ洗浄剤組成物の調製＞
　工程３：実施例５９の鋼板用アルカリ洗浄剤組成物と参考例２の鋼板用アルカリ洗浄剤組成物を３０℃で３０日間保存した。
　工程４：そして、保存後の実施例５９の鋼板用アルカリ洗浄剤組成物と参考例２の鋼板用アルカリ洗浄剤組成物を、攪拌し更にそれぞれ水で２５倍に希釈して第２の鋼板用アルカリ洗浄剤組成物を調製した。 <Preparation of second alkaline detergent composition for steel plate>
Step 3: The alkaline detergent composition for steel plate of Example 59 and the alkaline detergent composition for steel plate of Reference Example 2 were stored at 30 ° C. for 30 days.
Step 4: After the storage, the alkaline detergent composition for steel plate of Example 59 and the alkaline detergent composition for steel plate of Reference Example 2 were stirred and further diluted 25 times with water, respectively, for the second steel plate. An alkaline detergent composition was prepared.
＜鋼板洗浄試験＞
　（１）アルカリ洗浄剤
　前記実施例５９の鋼板用アルカリ洗浄剤組成物から調製した第２の鋼板用アルカリ洗浄剤組成物、及び前記参考例２の鋼板用アルカリ洗浄剤組成物から調製した第２の鋼板用アルカリ洗浄剤組成物をそれぞれアルカリ洗浄剤として用いた。 <Steel plate cleaning test>
(1) Alkali cleaning agent The 2nd alkaline detergent composition for steel plates prepared from the alkaline cleaning composition for steel plates of Example 59 and the alkaline cleaning composition for steel plates of Reference Example 2 was prepared. Each of the alkaline detergent compositions for steel sheets was used as an alkaline detergent.
　（２）被洗浄鋼板
　被洗浄鋼板は全て以下の手順で調製した。即ち、パーム油を含有する合成エステル系圧延油で冷間圧延された厚さ０．４ｍｍの鋼板を、２５ｍｍ×５０ｍｍの大きさに切断したものを被洗浄鋼板とした。被洗浄鋼板の付着油分量は、１６０ｍｇ／ｍ２であった。 (2) Steel plate to be cleaned All steel plates to be cleaned were prepared by the following procedure. That is, a steel sheet having a thickness of 0.4 mm that was cold-rolled with a synthetic ester-based rolling oil containing palm oil and cut into a size of 25 mm × 50 mm was used as a steel sheet to be cleaned. The amount of oil adhered to the steel plate to be cleaned was 160 mg / m 2 .
　（３）洗浄試験手順
　洗浄試験は全て以下の手順で行った。即ち、各例の第２のアルカリ洗浄剤組成物（汚れなし洗浄液）中に、それぞれ設置した縦１００ｍｍ×横５０ｍｍの大きさの電極板一対（電極間距離は２０ｍｍ）から等距離かつ中心に被洗浄鋼板を１秒間浸漬し、その後続けて電流密度５Ａ／ｄｍ２で鋼板電位を負から正にそれぞれ０．５秒間ずつ一度切り替えて電解洗浄し、水でスプレーリンス（６０℃の水をスプレー圧：０．２ＭＰａで１秒間スプレー）し、更に６０℃の水中に１秒間浸漬することによってリンスした後、温風乾燥した。なお、試験洗浄剤の温度は、７０℃とした。 (3) Cleaning test procedure All cleaning tests were performed according to the following procedure. That is, in the second alkaline detergent composition (cleaning solution without stains) of each example, the electrode plate pair having a size of 100 mm in length and 50 mm in width (distance between electrodes is 20 mm) is equidistant and covered at the center. The washed steel plate is immersed for 1 second, and then the steel plate potential is switched from negative to positive once for 0.5 seconds each at a current density of 5 A / dm 2 , and then electrolytically cleaned. Spray rinse with water (60 ° C water spray pressure) : Sprayed at 0.2 MPa for 1 second), and further rinsed by immersing in 60 ° C. water for 1 second, followed by drying with warm air. The temperature of the test cleaning agent was 70 ° C.
　（４）残存付着油分量測定方法
　洗浄試験後の鋼板表面に残存する付着油分量（残存付着油分量）を、鋼板付着油量測定装置ＥＭＩＡ－１１１（堀場製作所社製）を用いて測定した。測定値は５回測定の平均値である。残存付着油分量が少ないほど、鋼板の洗浄性に優れることを表す。 (4) Method for measuring the amount of remaining adhered oil The amount of adhered oil remaining on the surface of the steel sheet after the cleaning test (the amount of remaining adhered oil) was measured using a steel sheet adhered oil amount measuring device EMIA-111 (manufactured by Horiba, Ltd.). The measured value is an average value of five measurements. It represents that the smaller the amount of residual adhered oil, the better the cleaning performance of the steel sheet.
　その結果、前記実施例５９の鋼板用アルカリ洗浄剤組成物から調製した第２の鋼板用アルカリ洗浄剤組成物で洗浄した場合の残存付着油分量は１５．７ｍｇ／ｍ２、前記参考例２の鋼板用アルカリ洗浄剤組成物から調製した第２の鋼板用アルカリ洗浄剤組成物で洗浄した場合の残存付着油分量は１４．１ｍｇ／ｍ２で同等であり、鋼板に対してどちらも優れた洗浄性を有した。 As a result, the amount of residual adhered oil when washed with the second alkaline detergent composition for steel sheet prepared from the alkaline detergent composition for steel sheet of Example 59 was 15.7 mg / m 2 . The amount of residual adhered oil when washed with the second alkaline detergent composition for steel sheet prepared from the alkaline detergent composition for steel sheet is equivalent to 14.1 mg / m 2 , both of which are excellent cleaning for steel sheet Had sex.

Claims (15)

  1. 　アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含む成分を、攪拌翼を有する攪拌槽に導入する工程（１）、及び
    　前記攪拌翼を回転させて各成分を混合する工程（２）
    を有する鋼板用アルカリ洗浄剤組成物の製造方法であって、
    　前記工程（１）において前記攪拌槽に導入する前記成分の割合が、アルカリ剤（Ａ）３４重量％以上４５重量％以下、キレート剤（Ｂ）０．５重量％以上１２重量％以下、非イオン性界面活性剤（Ｃ）０．１重量％以上８重量％以下、スラリー化剤（Ｄ）０．４重量％以上４．５重量％以下、分散剤（Ｅ）０．０５重量％以上２．０重量％以下であり、
    　前記分散剤（Ｅ）が、下記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、
    Figure JPOXMLDOC01-appb-C000001
     〔前記一般式（１）中、Ｒ１は炭素数１以上４以下の炭化水素基、Ｒ２は水素原子又は炭素数１以上３以下の炭化水素基、Ｒ３は水素原子又はメチル基である。〕
    Figure JPOXMLDOC01-appb-C000002
     〔前記一般式（２）中、Ｒ４は炭素数１以上６以下の炭化水素基、Ａ１Ｏは炭素数２又は３のアルキレンオキシ基、ｍはＡ１Ｏの平均付加モル数で０以上３以下、（Ａ１Ｏ）ｍの総炭素数は０以上６以下である。〕
    Figure JPOXMLDOC01-appb-C000003
     〔前記一般式（３）中、Ｒ５は水素原子又は炭素数１又は２の炭化水素基である。〕
    Figure JPOXMLDOC01-appb-C000004
     〔前記一般式（４）中、Ｒ６は水素原子又はメチル基である。〕
    Figure JPOXMLDOC01-appb-C000005
     〔前記一般式（５）中、Ｒ７は－（Ａ２Ｏ）ｎ３－Ｈ、又は下記一般式（６）で表される化合物であり、
    Figure JPOXMLDOC01-appb-C000006
     Ａ２Ｏは炭素数２又は３のアルキレンオキシ基、ｎ１、ｎ２、ｎ３及びｎ４は、それぞれＡ２Ｏの付加モル数を示す整数であり、ｎ１、ｎ２、ｎ３及びｎ４の合計の平均値は０．５以上８以下である。〕
    　前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物の製造方法。     A stirrer having a stirring blade for components including an alkali agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersant (E) and water (F) Step (1) to be introduced into the step, and step (2) of mixing the components by rotating the stirring blade
    A method for producing an alkaline detergent composition for steel sheet, comprising:
    In the step (1), the proportion of the component introduced into the stirring vessel is 34% by weight to 45% by weight of the alkali agent (A), 0.5% by weight to 12% by weight of the chelating agent (B), nonionic Surfactant (C) 0.1 wt% or more and 8 wt% or less, slurrying agent (D) 0.4 wt% or more and 4.5 wt% or less, dispersant (E) 0.05 wt% or more 2. 0% by weight or less,
    The dispersant (E) is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (5),
    Figure JPOXMLDOC01-appb-C000001
     [In the general formula (1), R 1 is a hydrocarbon group having 1 to 4 carbon atoms, R 2 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group. . ]
    Figure JPOXMLDOC01-appb-C000002
     [In the general formula (2), R 4 is a hydrocarbon group having 1 to 6 carbon atoms, A 1 O is an alkyleneoxy group having 2 or 3 carbon atoms, and m is an average added mole number of A 1 O of 0 or more. 3 or less, and the total number of carbon atoms of (A 1 O) m is 0 or more and 6 or less. ]
    Figure JPOXMLDOC01-appb-C000003
     [In the general formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. ]
    Figure JPOXMLDOC01-appb-C000004
     [In the general formula (4), R 6 is a hydrogen atom or a methyl group. ]
    Figure JPOXMLDOC01-appb-C000005
     [In the general formula (5), R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
    Figure JPOXMLDOC01-appb-C000006
     A 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the average value of the total of n1, n2, n3 and n4 is 0.5 or more and 8 or less. ]
    The steel sheet alkaline detergent composition is a dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 μm are dispersed in a phase containing water (F). A method for producing the composition.
  2. 　前記工程（２）において、前記攪拌翼を３．５ｋｗ／ｋｇ以上の電力量で回転させて各成分を混合する、請求項１に記載の鋼板用アルカリ洗浄剤組成物の製造方法。 The method for producing an alkaline detergent composition for a steel sheet according to claim 1, wherein in the step (2), the components are mixed by rotating the stirring blade with an electric energy of 3.5 kw / kg or more.
  3. 　前記非イオン性界面活性剤（Ｃ）が、下記一般式（７）及び（８）で表される化合物からなる群より選ばれる１種以上の化合物である、請求項１又は２に記載の鋼板用アルカリ洗浄剤組成物の製造方法。
    Figure JPOXMLDOC01-appb-C000007
     〔前記一般式（７）中、Ｒ８は炭素数８以上１８以下の炭化水素基、Ａ３Ｏは炭素数２以上４以下のアルキレンオキシ基、ｏはＡ３Ｏの平均付加モル数で２以上２０以下である。〕
    Figure JPOXMLDOC01-appb-C000008
     〔前記一般式（８）中、Ｒ９は炭素数８以上１８以下の炭化水素基、Ａ４Ｏは炭素数２以上４以下のアルキレンオキシ基、ｐ及びｑはそれぞれＡ４Ｏの平均付加モル数を表し、ｐ＋ｑが２以上２０以下である。〕     The steel sheet according to claim 1 or 2, wherein the nonionic surfactant (C) is one or more compounds selected from the group consisting of compounds represented by the following general formulas (7) and (8). For producing an alkaline detergent composition for use.
    Figure JPOXMLDOC01-appb-C000007
     [In the general formula (7), R 8 is a hydrocarbon group having 8 to 18 carbon atoms, A 3 O is an alkyleneoxy group having 2 to 4 carbon atoms, and o is 2 in terms of the average added mole number of A 3 O. It is 20 or less. ]
    Figure JPOXMLDOC01-appb-C000008
     [In the general formula (8), R 9 is a hydrocarbon group having 8 to 18 carbon atoms, A 4 O is an alkyleneoxy group having 2 to 4 carbon atoms, p and q are average addition moles of A 4 O, respectively. Represents a number, and p + q is 2 or more and 20 or less. ]
  4. 　前記スラリー化剤（Ｄ）が水溶性高分子カルボン酸である、請求項１～３のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。 The method for producing an alkaline detergent composition for steel sheets according to any one of claims 1 to 3, wherein the slurrying agent (D) is a water-soluble polymer carboxylic acid.
  5. 　前記分散剤（Ｅ）と前記非イオン界面活性剤（Ｃ）の重量比、分散剤（Ｅ）／非イオン界面活性剤（Ｃ）が０．１以上４．０以下である、請求項１～４のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。 The weight ratio of the dispersant (E) to the nonionic surfactant (C), wherein the dispersant (E) / nonionic surfactant (C) is 0.1 or more and 4.0 or less. 4. A method for producing an alkaline detergent composition for steel sheet according to any one of 4 above.
  6. 　前記水（Ｆ）の割合が４５重量％以上７０重量％以下である、請求項１～５のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。 The method for producing an alkaline detergent composition for steel sheets according to any one of claims 1 to 5, wherein the proportion of water (F) is 45 wt% or more and 70 wt% or less.
  7. 　前記工程（２）において、前記攪拌翼を周速０．４５ｍ／ｓ以上で回転させて各成分を混合する、請求項１～６のいずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。 The method for producing an alkaline detergent composition for steel sheets according to any one of claims 1 to 6, wherein in the step (2), the components are mixed by rotating the stirring blade at a peripheral speed of 0.45 m / s or more. .
  8. 　前記工程（２）において、前記攪拌翼で混合する時間が３０分間以上３００分間以下である、請求項１～７いずれかに記載の鋼板用アルカリ洗浄剤組成物の製造方法。 The method for producing an alkaline detergent composition for a steel sheet according to any one of claims 1 to 7, wherein in the step (2), the time for mixing with the stirring blade is from 30 minutes to 300 minutes.
  9. 　さらに、請求項１～８のいずれかに記載の製造方法で得られた鋼板用アルカリ洗浄剤組成物を１０℃以上５０℃以下で保存する工程（３）、及び水と、前記保存した鋼板用アルカリ洗浄剤組成物とを混合し、水希釈の第２の鋼板用アルカリ洗浄剤組成物を得る工程（４）
    　を有する、第２の鋼板用アルカリ洗浄剤組成物の製造方法。     Furthermore, the step (3) of storing the alkaline detergent composition for steel sheet obtained by the production method according to any one of claims 1 to 8 at 10 ° C or higher and 50 ° C or lower, water, and the stored steel sheet Step (4) of mixing with an alkaline detergent composition to obtain a second diluted aqueous alkaline detergent composition for steel sheet
    The manufacturing method of the 2nd alkali-cleaner composition for steel plates which has these.
  10. 　アルカリ剤（Ａ）、キレート剤（Ｂ）、非イオン性界面活性剤（Ｃ）、スラリー化剤（Ｄ）、分散剤（Ｅ）及び水（Ｆ）を含有する鋼板用アルカリ洗浄剤組成物であって、前記各成分の割合が、アルカリ剤（Ａ）３４重量％以上４５重量％以下、キレート剤（Ｂ）０．５重量％以上１２重量％以下、非イオン性界面活性剤（Ｃ）０．１重量％以上８重量％以下、スラリー化剤（Ｄ）０．４重量％以上４．５重量％以下、分散剤（Ｅ）０．０５重量％以上２．０重量％以下であり、
    　前記分散剤（Ｅ）が、下記一般式（１）～（５）で表される化合物からなる群より選ばれる１種以上であり、
    Figure JPOXMLDOC01-appb-C000009
     〔前記一般式（１）中、Ｒ１は炭素数１以上４以下の炭化水素基、Ｒ２は水素原子又は炭素数１以上３以下の炭化水素基、Ｒ３は水素原子又はメチル基である。〕
    Figure JPOXMLDOC01-appb-C000010
     〔前記一般式（２）中、Ｒ４は炭素数１以上６以下の炭化水素基、Ａ１Ｏは炭素数２又は３のアルキレンオキシ基、ｍはＡ１Ｏの平均付加モル数で０以上３以下、（Ａ１Ｏ）ｍの総炭素数は０以上６以下である。〕
    Figure JPOXMLDOC01-appb-C000011
     〔前記一般式（３）中、Ｒ５は水素原子又は炭素数１又は２の炭化水素基である。〕
    Figure JPOXMLDOC01-appb-C000012
     〔前記一般式（４）中、Ｒ６は水素原子又はメチル基である。〕
    Figure JPOXMLDOC01-appb-C000013
     〔前記一般式（５）中、Ｒ７は－（Ａ２Ｏ）ｎ３－Ｈ、又は下記一般式（６）で表される化合物であり、
    Figure JPOXMLDOC01-appb-C000014
     Ａ２Ｏは炭素数２又は３のアルキレンオキシ基、ｎ１、ｎ２、ｎ３及びｎ４は、それぞれＡ２Ｏの付加モル数を示す整数であり、ｎ１、ｎ２、ｎ３及びｎ４の合計の平均値は０．５以上８以下である。〕
    　前記鋼板用アルカリ洗浄剤組成物が、水（Ｆ）を含む相に粒子径が５０μｍ未満の前記非イオン性界面活性剤（Ｃ）の油滴が分散した分散体である、鋼板用アルカリ洗浄剤組成物。     An alkaline detergent composition for steel sheet containing an alkaline agent (A), a chelating agent (B), a nonionic surfactant (C), a slurrying agent (D), a dispersing agent (E) and water (F). The proportion of each of the components is from 34% by weight to 45% by weight of the alkali agent (A), 0.5% by weight to 12% by weight of the chelating agent (B), nonionic surfactant (C) 0 1 wt% or more and 8 wt% or less, slurrying agent (D) 0.4 wt% or more and 4.5 wt% or less, dispersant (E) 0.05 wt% or more and 2.0 wt% or less,
    The dispersant (E) is one or more selected from the group consisting of compounds represented by the following general formulas (1) to (5),
    Figure JPOXMLDOC01-appb-C000009
     [In the general formula (1), R 1 is a hydrocarbon group having 1 to 4 carbon atoms, R 2 is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 is a hydrogen atom or a methyl group. . ]
    Figure JPOXMLDOC01-appb-C000010
     [In the general formula (2), R 4 is a hydrocarbon group having 1 to 6 carbon atoms, A 1 O is an alkyleneoxy group having 2 or 3 carbon atoms, and m is an average added mole number of A 1 O of 0 or more. 3 or less, and the total number of carbon atoms of (A 1 O) m is 0 or more and 6 or less. ]
    Figure JPOXMLDOC01-appb-C000011
     [In the general formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. ]
    Figure JPOXMLDOC01-appb-C000012
     [In the general formula (4), R 6 is a hydrogen atom or a methyl group. ]
    Figure JPOXMLDOC01-appb-C000013
     [In the general formula (5), R 7 is — (A 2 O) n3 —H or a compound represented by the following general formula (6);
    Figure JPOXMLDOC01-appb-C000014
     A 2 O is an alkyleneoxy group having 2 or 3 carbon atoms, n1, n2, n3 and n4 are each an integer indicating the number of moles of A 2 O added, and the average value of the total of n1, n2, n3 and n4 is 0.5 or more and 8 or less. ]
    The steel sheet alkaline detergent composition is a dispersion in which oil droplets of the nonionic surfactant (C) having a particle diameter of less than 50 μm are dispersed in a phase containing water (F). Composition.
  11. 　前記非イオン性界面活性剤（Ｃ）が、下記一般式（７）及び（８）で表される化合物からなる群より選ばれる１種以上の化合物である、請求項１０に記載の鋼板用アルカリ洗浄剤組成物。
    Figure JPOXMLDOC01-appb-C000015
     〔前記一般式（７）中、Ｒ８は炭素数８以上１８以下の炭化水素基、Ａ３Ｏは炭素数２以上４以下のアルキレンオキシ基、ｏはＡ３Ｏの平均付加モル数で２以上２０以下である。〕
    Figure JPOXMLDOC01-appb-C000016
     〔前記一般式（８）中、Ｒ９は炭素数８以上１８以下の炭化水素基、Ａ４Ｏは炭素数２以上４以下のアルキレンオキシ基、ｐ及びｑはそれぞれＡ４Ｏの平均付加モル数を表し、ｐ＋ｑが２以上２０以下である。〕     The steel sheet alkali according to claim 10, wherein the nonionic surfactant (C) is one or more compounds selected from the group consisting of compounds represented by the following general formulas (7) and (8). Cleaning composition.
    Figure JPOXMLDOC01-appb-C000015
     [In the general formula (7), R 8 is a hydrocarbon group having 8 to 18 carbon atoms, A 3 O is an alkyleneoxy group having 2 to 4 carbon atoms, and o is 2 in terms of the average added mole number of A 3 O. It is 20 or less. ]
    Figure JPOXMLDOC01-appb-C000016
     [In the general formula (8), R 9 is a hydrocarbon group having 8 to 18 carbon atoms, A 4 O is an alkyleneoxy group having 2 to 4 carbon atoms, p and q are average addition moles of A 4 O, respectively. Represents a number, and p + q is 2 or more and 20 or less. ]
  12. 　前記スラリー化剤（Ｄ）が水溶性高分子カルボン酸である、請求項１０又は１１に記載の鋼板用アルカリ洗浄剤組成物。 The alkaline cleaning composition for steel sheet according to claim 10 or 11, wherein the slurrying agent (D) is a water-soluble polymer carboxylic acid.
  13. 　前記分散剤（Ｅ）と前記非イオン界面活性剤（Ｃ）の重量比、分散剤（Ｅ）／非イオン界面活性剤（Ｃ）が０．１以上４．０以下である、請求項１０～１２のいずれかに記載の鋼板用アルカリ洗浄剤組成物。 The weight ratio of the dispersant (E) to the nonionic surfactant (C), and the dispersant (E) / nonionic surfactant (C) is 0.1 or more and 4.0 or less. 12. The alkaline detergent composition for steel sheet according to any one of 12 above.
  14. 　前記水（Ｆ）の割合が４５重量％以上７０重量％以下である、請求項１０～１３のいずれかに記載の鋼板用アルカリ洗浄剤組成物。 The alkaline detergent composition for steel sheet according to any one of claims 10 to 13, wherein a ratio of the water (F) is 45 wt% or more and 70 wt% or less.
  15. 　請求項１０～１４のいずれかに記載の鋼板用アルカリ洗浄剤組成物の鋼板の洗浄剤としての使用。 Use of the alkaline cleaning composition for steel sheet according to any one of claims 10 to 14 as a steel sheet cleaning agent.
PCT/JP2013/067637 2012-06-29 2013-06-27 Method for producing alkali detergent composition for steel plate WO2014003112A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104498227A (en) * 2014-11-27 2015-04-08 镇江润德节能科技有限公司 Preparation method of environmentally-friendly nontoxic industrial detergent
CN105696005A (en) * 2016-02-24 2016-06-22 苏州龙腾万里化工科技有限公司 High-performance alkaline degreaser

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6576653B2 (en) 2015-03-05 2019-09-18 日華化学株式会社 Cleaning composition for hard surface
CN104694946A (en) * 2015-03-13 2015-06-10 武汉钢铁(集团)公司 Phosphorus-free degreaser
CN105755497A (en) * 2016-02-22 2016-07-13 苏州龙腾万里化工科技有限公司 Lead screw cleaning agent
JP6850603B2 (en) * 2016-12-26 2021-03-31 花王株式会社 Cleaning agent composition for steel sheet
CN107043941A (en) * 2017-01-20 2017-08-15 昌邑市龙港无机硅有限公司 A kind of metal cleaner
JP6959087B2 (en) * 2017-09-20 2021-11-02 花王株式会社 Rinse composition for steel sheet
KR102042508B1 (en) * 2018-07-25 2019-11-08 (주)피스코 Composition for cleaning heat sinks of heat exchanger and method for manufacturing the same
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CN112410135A (en) * 2020-12-10 2021-02-26 深圳市恒纬祥科技有限公司 Industrial cleaning agent universal for spraying and soaking

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04359096A (en) * 1991-06-03 1992-12-11 Lion Corp Liquid alkaline detergent composition
JPH11181587A (en) * 1996-11-12 1999-07-06 Nippon Parkerizing Co Ltd Alkaline liquid detergent for metal and its production and use
JP2001262384A (en) * 2000-03-21 2001-09-26 Lion Corp Aqueous liquid metal detergent
JP2004002778A (en) * 2002-03-29 2004-01-08 Sanyo Chem Ind Ltd Alkali cleaner
JP2007099935A (en) * 2005-10-05 2007-04-19 Kao Corp Cleanser composition for plated steel sheet
JP2007177265A (en) * 2005-12-27 2007-07-12 Kao Corp Cleaning agent composition for single tank type steel strip cleaning
JP2009299099A (en) * 2008-06-10 2009-12-24 Kao Corp Detergent composition for cold rolled steel sheet

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3875170B2 (en) * 2002-09-27 2007-01-31 花王株式会社 Alkaline detergent composition for steel sheet
JP4896405B2 (en) * 2004-02-24 2012-03-14 花王株式会社 Method for producing emulsion
US20050205835A1 (en) * 2004-03-19 2005-09-22 Tamboli Dnyanesh C Alkaline post-chemical mechanical planarization cleaning compositions
CN100497571C (en) * 2007-03-12 2009-06-10 常州君合达克罗涂覆工程技术有限公司 Solar energy silicon crystal chip cleaning agent
CN102978022B (en) * 2012-12-12 2014-05-21 辽宁科技大学 Phosphorus-free foam-free low-temperature steel plate surface cleaning agent and preparation method thereof
CN103131546A (en) * 2013-02-26 2013-06-05 金红叶纸业集团有限公司 Cleaning composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04359096A (en) * 1991-06-03 1992-12-11 Lion Corp Liquid alkaline detergent composition
JPH11181587A (en) * 1996-11-12 1999-07-06 Nippon Parkerizing Co Ltd Alkaline liquid detergent for metal and its production and use
JP2001262384A (en) * 2000-03-21 2001-09-26 Lion Corp Aqueous liquid metal detergent
JP2004002778A (en) * 2002-03-29 2004-01-08 Sanyo Chem Ind Ltd Alkali cleaner
JP2007099935A (en) * 2005-10-05 2007-04-19 Kao Corp Cleanser composition for plated steel sheet
JP2007177265A (en) * 2005-12-27 2007-07-12 Kao Corp Cleaning agent composition for single tank type steel strip cleaning
JP2009299099A (en) * 2008-06-10 2009-12-24 Kao Corp Detergent composition for cold rolled steel sheet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104498227A (en) * 2014-11-27 2015-04-08 镇江润德节能科技有限公司 Preparation method of environmentally-friendly nontoxic industrial detergent
CN105696005A (en) * 2016-02-24 2016-06-22 苏州龙腾万里化工科技有限公司 High-performance alkaline degreaser

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