WO2012067227A1 - Procédé de fabrication de granules de détergeant - Google Patents

Procédé de fabrication de granules de détergeant Download PDF

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Publication number
WO2012067227A1
WO2012067227A1 PCT/JP2011/076653 JP2011076653W WO2012067227A1 WO 2012067227 A1 WO2012067227 A1 WO 2012067227A1 JP 2011076653 W JP2011076653 W JP 2011076653W WO 2012067227 A1 WO2012067227 A1 WO 2012067227A1
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WIPO (PCT)
Prior art keywords
particles
water
detergent
anionic surfactant
mass
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PCT/JP2011/076653
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English (en)
Japanese (ja)
Inventor
将寛 山口
中山　高志
浩章 割田
今泉　義信
Original Assignee
花王株式会社
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Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201180055720.2A priority Critical patent/CN103228776B/zh
Publication of WO2012067227A1 publication Critical patent/WO2012067227A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • the present invention relates to a method for producing detergent particles, and more particularly to a method for producing detergent particles including particles prepared using a spray dryer and particles prepared using a container rotating mixer.
  • high bulk density detergents greater than 600 g / L
  • medium bulk density detergents 400 to 600 g / L
  • low bulk density detergents 250 g / L to 400 g. / L
  • liquid detergents for example, high bulk density detergents are often used in Japan, but there are also many demands for medium and low bulk density detergents in Asia, Oceania and Europe.
  • the production method includes a method in which an anionic surfactant and other builder are blended in a slurry and produced by spray drying.
  • a method has been proposed in which an anionic surfactant and other builder are blended in a slurry and spray-dried, followed by a high bulk density treatment.
  • medium bulk density detergent an anionic surfactant and other builder are mixed in a slurry and spray dried to prepare low bulk density spray dried particles, and then the spray dried particles and previously obtained high bulk density particles For example, and a method of mixing to increase the bulk density (see Patent Document 1).
  • the present invention provides a method for producing a medium and low bulk density detergent particle group having good fluidity and suppressed classification, and capable of reducing the ratio of spray-dried particles to be used. About. Furthermore, the present invention relates to providing detergent particles with high yield and low coarse rate.
  • a medium and low bulk density detergent particle group having good fluidity and reduced classification with a reduced spray-dried particle ratio to be used is obtained with a high yield and a low coarse particle ratio. I can do it.
  • Step (A) A step of preparing particles (A) containing 5 to 40% by mass of an anionic surfactant in the particles by spray drying a slurry containing an anionic surfactant;
  • Step (B) A step of preparing particles (B) by granulating a powder raw material for detergent using a container rotary mixer,
  • the detergent powder raw material is a water-soluble solid alkaline inorganic substance and / or a water-soluble inorganic salt, The amount of the water-soluble solid alkali inorganic substance and the water-soluble inorganic salt in the particles (B) is 30 to 88% by mass, and the container rotating mixer is a drum mixer or a pan mixer, A step of adding an anionic surfactant and / or a precursor thereof into the container rotary mixer using a multi-fluid nozzle to prepare particles (B); and step (C): particles (A) and particles.
  • a step of mixing (B) A detergent particle group is obtained using a method for producing a detergent particle
  • the granulation method using such a mixer is a non-consolidated granulation method.
  • an anionic surfactant and / or an acid precursor thereof in this specification, “an anionic surfactant and / or an acid precursor thereof” is indicated as “component C”). Since the granulation does not proceed unless the adhesiveness when in contact with the powder is strong, it is necessary to develop the adhesiveness when in contact with the powder.
  • a multi-fluid nozzle such as a two-fluid nozzle is used to spray the component C that develops tackiness when it comes into contact with the powder and is supplied into the rotating container of the container, unexpectedly, the coarse particles It was found that uniform granulation was possible while suppressing formation. This is because component C is made into fine droplets in advance using a multi-fluid nozzle, so that high dispersion of component C can be achieved even in a container-rotating mixer, and a large liquid mass forming coarse particles is generated. It is thought that it does not. Therefore, it is also one of the features of the present invention that the component C that develops adhesiveness when it comes into contact with the powder is added into the container rotary mixer using a multi-fluid nozzle.
  • a combination of a container rotating type mixer and a multi-fluid nozzle can be used to contain an anionic surfactant in a high ratio, which cannot be expected from the case where each is used alone.
  • Bulk density particles can be obtained, and further, by mixing the particles and spray-dried particles, an effect of obtaining a medium / low bulk density detergent having good fluidity at a low spray-dry particle ratio can be obtained.
  • the detergent particles are particles containing a surfactant and a builder, and the detergent particle group means an aggregate thereof.
  • the detergent composition contains detergent particles and is optionally added separately from the detergent particles (for example, builder granules, fluorescent dyes, enzymes, fragrances, antifoams, bleaches, bleach activators) Etc.).
  • Step (A) is a step of spray-drying a slurry containing an anionic surfactant to prepare particles (A) (spray-dried particles) containing 5 to 40% by mass of an anionic surfactant in the particles. is there.
  • the bulk density of the particles (A) is preferably 200 to 600 g / L, more preferably 200 to 550 g / L, and more preferably 200 to 550 g / L, from the viewpoint of reducing the ratio of spray-dried particles to obtain a medium and low bulk density detergent particle group. 500 g / L is more preferable.
  • the average particle size of all the particles (A) is preferably 150 to 500 ⁇ m, more preferably 200 to 400 ⁇ m, and still more preferably 200 to 350 ⁇ m from the viewpoint of solubility.
  • the fluidity of the particles (A) is preferably 4 to 12 seconds, more preferably 4 to 10 seconds, and further preferably 4 to 8 seconds, from the viewpoint of ease of charging into the mixer.
  • the angle of repose of the particles (A) is preferably 20 to 55 °, more preferably 25 to 50 °, and further preferably 30 to 50 °, from the viewpoint of ease of charging into the mixer and difficulty in bridging the particles. preferable. Below, each component used for this invention is demonstrated.
  • Anionic surfactant What is generally used can be used as an anionic surfactant. Examples thereof include linear alkylbenzene sulfonate, ⁇ -olefin sulfonate, alkyl sulfate, polyoxyethylene alkyl sulfate, and fatty acid ester sulfonate. Such an anionic surfactant may be used alone or in combination of two or more components.
  • the counter ion is preferably an alkali metal, particularly sodium. Of these, linear alkylbenzene sodium sulfonate and sodium alkyl sulfate are preferred from the viewpoints of economy, thermal stability and foaming.
  • the acid precursor is added to the slurry, and the acid precursor is neutralized in the slurry with a sodium hydroxide aqueous solution or the like added to the slurry separately.
  • a method of adding a previously neutralized anionic surfactant to the slurry may be used.
  • the amount of the anionic surfactant added to the slurry is preferably 5% by mass or more, more preferably 10% by mass or more, and further 15% by mass or more in the obtained spray-dried particles. preferable.
  • the amount added is preferably 40% by mass or less, and more preferably 35% by mass or less.
  • an anionic surfactant As an essential component for the spray-dried particles in the present invention, only an anionic surfactant is used, but from the viewpoint of cleaning performance, particle size distribution, and particle strength, it is usually used in detergent compositions as needed.
  • Other ingredients can be included in the spray-dried particles. Examples of other components include water-soluble solid alkali inorganic substances, chelating agents, water-soluble inorganic salts, water-soluble polymers, water-insoluble excipients, nonionic surfactants, and other auxiliary components. It is preferable to blend a water-soluble solid alkali inorganic substance, a chelating agent, a water-soluble inorganic salt and / or a water-soluble polymer.
  • Such other components are added to the spray-dried particles by being added to the slurry in the same manner as the anionic surfactant.
  • the amount of other components added to the slurry is not particularly limited, and is the remaining amount of the anionic surfactant and water in the resulting spray-dried particles.
  • the amount of other components added to the slurry is preferably 45 to 94% by mass in the resulting spray-dried particles. Specific examples of other components will be described below.
  • Water-soluble solid alkali inorganic substance is an alkali inorganic substance that is solid at room temperature (20 ° C.), and the water-soluble solid alkali inorganic substance is not particularly limited. Examples thereof include sodium, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium silicate and the like. Among them, sodium carbonate and sodium silicate are preferable as an alkaline agent that exhibits a suitable pH buffer region in the washing liquid.
  • Chelating agents can be incorporated into spray-dried particles in order to suppress the cleaning action inhibition by metal ions. Examples include water-soluble chelating agents and water-insoluble chelating agents. It is also possible to mix.
  • the water-soluble chelating agent is not particularly limited, but for example, tripolyphosphate, orthophosphate, pyrophosphate, etc. can be used. Further, as the counter ion, an alkali metal salt is preferable, and sodium and / or potassium is particularly preferable.
  • the water-insoluble chelating agent may be added for the purpose of improving the sequestering ability and the strength of the spray-dried particles.
  • examples thereof include crystalline or non-crystalline alkali metal aluminosilicates (zeolites), and metal ions.
  • zeolites crystalline or non-crystalline alkali metal aluminosilicates
  • metal ions metal ions.
  • A-type zeolite is preferable in terms of sealing ability and economy.
  • the average particle size of the particles is preferably from 0.1 to 20 ⁇ m, more preferably from 0.5 to 10 ⁇ m.
  • Water-soluble inorganic salt The water-soluble inorganic salt is preferably added to the spray-dried particles in order to increase the ionic strength of the washing liquid and improve the effect of cleaning sebum dirt.
  • the water-soluble inorganic salt for example, sodium sulfate, sodium chloride, sodium sulfite and potassium sulfate having a high degree of ionic dissociation are preferable. From the viewpoint of improving the dissolution rate of the detergent particles, the combined use of magnesium sulfate is also effective.
  • Water-soluble polymer It is also preferable to blend a water-soluble polymer having effects such as metal ion scavenging ability and mud dirt dispersibility.
  • a water-soluble polymer having effects such as metal ion scavenging ability and mud dirt dispersibility.
  • polyethylene glycol, carboxylic acid polymer, carboxymethyl cellulose, soluble starch, saccharide and the like can be mentioned.
  • polyethylene glycol having a weight average molecular weight of 5,000 to 20,000 and a carboxylic acid polymer having a weight average molecular weight of several thousand to 100,000 are preferable from the viewpoint of sequestering ability, dispersibility of solid dirt, particle dirt, etc.
  • Particularly preferred are salts of acrylic acid-maleic acid copolymers and polyacrylates.
  • Water-insoluble excipient is not particularly limited as long as it is a substance that has good dispersibility in water and does not adversely affect detergency.
  • clay compounds such as silicon dioxide, hydrated silicate compound, barlite, bentonite and the like can be mentioned.
  • the primary particles preferably have an average particle size of 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • the moisture in the spray-dried particles is preferably 15% by mass or less in the spray-dried particles from the viewpoint of the particle strength of the spray-dried particles, and preferably 0.5% by mass or more from the viewpoint of energy efficiency.
  • Fluorescent dyes, pigments, dyes and the like may be blended in the spray-dried particles.
  • Spray-dried particles used in the present invention can be obtained by spray-drying the slurry obtained by adding and mixing the above components.
  • spray-dried particles can be obtained by the production method described in, for example, the well-known collection of conventional techniques (powder detergent for clothing) issued by the Japan Patent Office.
  • Step (B) is a step of preparing particles (B) that are granulated products using a container rotating mixer and a multi-fluid nozzle. That is, the particle (B) is prepared by adding the component C using a multi-fluid nozzle into the container rotary mixer into which the powder raw material for detergent is charged.
  • the bulk density of the particles (B) is preferably 400 to 650 g / L, more preferably 420 to 620 g / L, still more preferably 440 to 600 g / L.
  • the bulk density of the particles (B) is preferably 650 g / L or less, more preferably 620 g / L or less, and even more preferably 600 g / L or less from the viewpoint of reducing the ratio of spray-dried particles and from the viewpoint of suppressing classification during transportation. From the viewpoint of transportation cost, 400 g / L or more is preferable, 420 g / L or more is more preferable, and 440 g / L or more is more preferable.
  • the average particle size of the particles (B) is preferably from 150 to 700 ⁇ m, more preferably from 180 to 650 ⁇ m, and even more preferably from 200 to 600 ⁇ m, from the viewpoints of solubility and powdering.
  • the fluidity of the particles (B) is preferably 4 to 12 seconds, more preferably 4 to 10 seconds, and still more preferably 4 to 8 seconds, from the viewpoint of ease of charging into the mixer.
  • the angle of repose of the particles (B) is preferably 20 to 60 °, more preferably 25 to 55 °, and more preferably 30 to 50 ° from the viewpoint of ease of charging into the mixer and difficulty in bridging of the particles. Is more preferable, and 35 to 45 ° is more preferable.
  • the granulation yield of the particles (B) is preferably 85 to 100%, more preferably 90 to 100%, still more preferably 95 to 100%.
  • the coarse particle ratio of the particles (B) is preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and particularly preferably 10% or less from the viewpoints of appearance and solubility.
  • the anionic surfactant acid precursor used in step (B) is an anionic surfactant precursor that shows an acid form and is liquid at room temperature. Good, salt is formed by neutralization reaction. Accordingly, the acid precursor is not particularly limited as long as it is a precursor of a known anionic surfactant and has the above-mentioned properties, but linear alkylbenzene sulfonic acid, ⁇ -olefin sulfonic acid, alkyl sulfuric acid, polysulfate, Examples thereof include oxyethylene alkyl sulfuric acid and fatty acid ester sulfonic acid. Such an acid precursor may use only one component, and may use it in combination of 2 or more components. Of these, linear alkylbenzenesulfonic acid and alkylsulfuric acid are preferred from the viewpoints of economy, storage stability and foaming.
  • a predetermined amount of an inorganic acid such as sulfuric acid may be mixed in advance with the acid precursor.
  • Anionic surfactants as component C are: This was obtained by neutralizing the acid precursor of the anionic surfactant. Such an anionic surfactant may be used alone or in combination of two or more components. Of these, alkyl sulfates and polyoxyethylene alkyl sulfates are preferred from the viewpoints of economy and foaming. 1. An aqueous alkali solution is used as a neutralizer for the acid precursor of the anionic surfactant.
  • aqueous alkali solution Although it does not specifically limit as a kind of aqueous alkali solution, for example, strong alkali aqueous solutions, such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, are mentioned, Sodium hydroxide aqueous solution is preferable from an economical viewpoint.
  • the anionic surfactant used in the step (B) contains an anionic surfactant and water, and has a viscosity at 60 ° C. of 100 Pa ⁇ s or less.
  • the viscosity of an anionic surfactant varies greatly depending on its water content. Therefore, it is preferable to adjust the concentration of the aqueous alkali solution used for neutralizing the acid precursor to prepare an anionic surfactant having a desired water content, that is, having a desired viscosity.
  • the anionic surfactant contains 25 to 70 parts by weight of water (the water content of the surfactant composition is about 20 to 40%) with respect to 100 parts by weight of the anionic surfactant.
  • the viscosity of the paste-like anionic surfactant has a temperature range of preferably 10 Pa ⁇ s or less, more preferably 5 Pa ⁇ s or less, from the viewpoint of handleability in production. Such a use temperature range is preferably up to 70 ° C., more preferably up to 60 ° C., from the viewpoint of the stability of the anionic surfactant.
  • the viscosity is determined by measuring at a shear rate of 50 [1 / s] with a coaxial double cylindrical rotational viscometer (manufactured by HAAKE, sensor: SV-DIN).
  • the acid precursors of the anionic surfactant those which are very unstable and easily decomposed are preferably prepared so that the decomposition can be suppressed.
  • the preparation method is not particularly limited, and a known method can be used. For example, using a loop reactor, the heat of neutralization is removed by a heat exchanger or the like, and the production may be performed while paying attention to the temperature control of the acid precursor and the anionic surfactant.
  • the obtained anionic surfactant preferably has an excessive alkalinity from the viewpoint of suppressing decomposition.
  • unreacted alcohol and unreacted polyoxyethylene alkyl ether at the time of producing the acid precursor, sodium sulfate as a by-product during the neutralization reaction, and neutralization reaction can be added to the anionic surfactant
  • a pH buffering agent, a decoloring agent, etc. may be contained.
  • the amount of the anionic surfactant is preferably 10 to 45% by mass and more preferably 13 to 35% by mass in the particles (B) from the viewpoint of detergency and granulation. Since the anionic surfactant acid precursor is neutralized in the detergent particle group, the anionic interface in the detergent particle group can be obtained even when the anionic surfactant acid precursor is added. Calculated as the amount of activator.
  • the anionic surfactant and / or its acid precursor has the ability to form a granulated product by combining powder raw materials for detergent, and as described in the above paragraph, component C It is one of the important points that the adhesiveness develops when it comes into contact with the powder raw material for detergent. The presumed mechanism about adhesive expression is demonstrated below.
  • an anionic surfactant acid precursor when added to a water-soluble solid alkaline inorganic material that is a powder raw material for detergents, the neutralization reaction proceeds on the surface of the particles, and the anionic surfactant has an adhesive property. A neutralized product of the acid precursor of the ionic surfactant is formed.
  • an anionic surfactant when the anionic surfactant is added to the detergent powder raw material, the water in the anionic surfactant is hydrated with the detergent powder raw material. Or when the temperature of the powder raw material for detergent is lower than the temperature of the anionic surfactant, the temperature of the anionic surfactant is lowered to near or below its melting point. When the anionic surfactant is solidified, adhesiveness is developed.
  • the component C is a detergent.
  • the viscosity when contacted with the powder raw material is preferably 2 Pa ⁇ s or more, and more preferably 3 Pa ⁇ s or more.
  • the viscosity was measured when component C was in contact with the powder raw material for detergent at a shear rate of 50 [1 / s] using a coaxial double cylindrical rotational viscometer (manufactured by HAAKE, sensor: SV-DIN). The temperature and moisture value may be adjusted and measured so as to be the same.
  • the powder raw material for the detergent is a water-soluble solid alkali inorganic material and / or a water-soluble inorganic salt.
  • Water-soluble solid alkaline inorganic substance in the present invention, when an anionic surfactant acid precursor is used as a component added by a multi-fluid nozzle, a water-soluble solid alkaline inorganic substance is used to dry neutralize the acid precursor. Is an essential component.
  • the water-soluble solid alkali-inorganic substance is an alkali inorganic substance that is solid at room temperature (20 ° C.), and the water-soluble solid alkali-inorganic substance is not particularly limited.
  • sodium carbonate, sodium bicarbonate, carbonate Examples thereof include potassium and sodium silicate.
  • sodium carbonate is preferable as an alkaline agent that exhibits a suitable pH buffer region in the washing liquid.
  • These water-soluble solid alkali inorganic materials may be used alone or in combination of two or more.
  • both light soda ash (light ash) and heavy soda ash (dense ash) can be used, but light ash is used from the viewpoint of reactivity with the acid precursor. preferable.
  • the water-soluble solid alkaline inorganic substance can function as a detergent builder and an alkaline agent in the final composition. Therefore, the addition amount of the water-soluble solid alkaline inorganic substance is the amount necessary for neutralizing the acid precursor of the anionic surfactant blended as component C (neutralization equivalent) to exert the above function. Preferably an amount is added. That is, the addition amount of the water-soluble solid alkali inorganic substance is preferably the neutralization equivalent or an amount substantially larger than the neutralization equivalent, for example, preferably 1 to 35 times the neutralization equivalent, more preferably 2 -30 times, more preferably 3-25 times.
  • an inorganic acid may be used in combination with an acid precursor. In that case, the neutralization equivalent is added with an amount necessary for neutralization of the inorganic acid.
  • the amount specified here does not include water-soluble solid alkaline inorganic materials derived from spray-dried particles.
  • the average particle diameter of the water-soluble solid alkali inorganic substance is not particularly limited, but when the surfactant is highly blended, it may be pulverized to 1 to 50 ⁇ m from the viewpoint of improving the yield.
  • the average particle size of the water-soluble solid alkali inorganic substance is calculated on a volume basis, and is measured using, for example, a laser diffraction particle size distribution analyzer: LA-920 (manufactured by Horiba, Ltd.). Value.
  • Water-soluble inorganic salt The water-soluble inorganic salt is preferably used as a powder raw material for detergents in order to increase the ionic strength of the washing liquid and improve the effects of sebum stain cleaning.
  • As the water-soluble inorganic salt for example, sodium sulfate, sodium chloride, sodium sulfite and potassium sulfate having a high degree of ionic dissociation are preferable. From the viewpoint of improving the dissolution rate, the combined use of magnesium sulfate is also effective.
  • the average particle size of the water-soluble inorganic salt is not particularly limited, but when an anionic surfactant is highly blended, it may be pulverized to 1 to 50 ⁇ m from the viewpoint of improving the yield of the detergent particles. .
  • the average particle diameter of the water-soluble inorganic salt is calculated on a volume basis. For example, it is a value measured using a laser diffraction particle size distribution analyzer: LA-920 (manufactured by Horiba, Ltd.). is there.
  • the exemplified raw materials may be used alone, or two or more kinds may be mixed and used.
  • the amount of the water-soluble solid alkali inorganic substance and the water-soluble inorganic salt in the particles (B) is 30% by mass to 88% by mass from the viewpoint of detergency and powdering of the particles (B). 85% by mass is preferable, and 40% by mass to 80% by mass is more preferable.
  • the amount of the other powder component in the particles (B) is preferably 0.2 to 30% by mass, and more preferably 0.3 to 25% by mass.
  • the amount specified here does not include powder components derived from spray-dried particles.
  • Such materials include surface modifiers (aluminosilicate, sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate, primary particles having an average particle size of 0. .1 to 10 ⁇ m metal soap, powdered surfactant (eg, alkyl sulfate), water-soluble organic salt, etc., chelating agent (tripolyphosphate, orthophosphate, pyrophosphate, etc.) crystalline or non-crystalline Alkali metal aluminosilicate), water-soluble polymer powder (carboxylic acid polymer, carboxymethylcellulose, soluble starch, sugar, polyethylene glycol), water-insoluble excipient (silicon dioxide, hydrated silicate compound, bar)
  • surface modifiers aluminosilicate, sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate, primary particles having an average
  • the above-mentioned substances may be added together with the powder raw material for detergent before adding component C, or may be added after adding component C.
  • a surface modifier such as an alkali metal aluminosilicate
  • the operation of adding other powder components may be performed in a container rotary mixer, or after discharging the particles (B) obtained in the step (B) from the container rotary mixer, another mixer / manufacturer is prepared. You may carry out using a granulator.
  • liquid components In the present invention, other liquid components may be added to produce the detergent particle group. Other liquid components to be added can be appropriately selected according to the composition of the detergent particle group to be obtained.
  • the addition timing of the liquid component is not particularly limited.
  • the liquid component may be mixed with the component C in advance, or may be performed before, during or after the addition of the component C. When performing, it is preferable before the addition of the surface modifier.
  • the liquid component When the liquid component is added after component C is added, the liquid component may be added using a container rotary mixer, or the detergent particles obtained by the production method of the present invention are removed from the container rotary mixer. After discharging, the obtained detergent particles may be charged into another mixer / granulator and the liquid component added thereto.
  • a surfactant for example, a nonionic surfactant, a fatty acid, a water-soluble polymer (carboxylic acid polymer, carboxymethyl cellulose, soluble starch, saccharides, polyethylene glycol, etc.) and the like are used in ordinary detergent compositions. Any liquid component may be mentioned. As the liquid component, only one component may be used, or two or more components may be used in combination.
  • the liquid component may be added as a liquid at a temperature equal to or higher than its melting point, or may be added in the form of an aqueous solution or dispersion.
  • the amount of the net liquid component excluding the medium is preferably 15% by mass or less, and more preferably 10% by mass or less of the detergent particle group as the final product, from the viewpoint of suppressing aggregation of the detergent particle group.
  • the nonionic surfactant used as the liquid component is not particularly limited, but from the viewpoint of detergency, for example, a polyoxyalkylene alkyl obtained by adding 6 to 22 moles of alkylene oxide to an alcohol having 10 to 14 carbon atoms. Ether is preferred.
  • spraying can be performed with any nozzle, not depending on the multi-fluid nozzle described in the present invention.
  • a drum mixer or a pan mixer is used as the container rotating mixer.
  • the drum-type mixer is not particularly limited as long as the drum-shaped cylinder rotates and performs processing.
  • the conical drum-type granulator is used. (Mixer), multi-stage conical drum granulator (mixer), etc. can also be used. These apparatuses can be used in both batch and continuous processes.
  • baffle plates baffles ( ) May be attached. This makes it possible to cause the particle group to perform an upward movement, and improves the powder mixing property and the solid-liquid mixing property.
  • the operating condition of the container rotation type mixer is not particularly limited as long as the components in the mixer can be stirred.
  • the operating condition is that the fluid number defined by the following formula is 0.005 to 1.0.
  • An operating condition of 0.01 to 0.6 is more preferable.
  • Fr V 2 / (R ⁇ g)
  • V Circumferential speed [m / s]
  • R Radius from the center of rotation to the circumference of the rotating object [m]
  • g Gravity acceleration [m / s 2 ]
  • Multi-fluid nozzle In the present invention, it is one feature that the component C is supplied using a multi-fluid nozzle. By using such a nozzle, the droplets can be made fine and dispersed.
  • a multi-fluid nozzle is a nozzle that mixes and atomizes a liquid and atomizing gas (air, nitrogen, etc.) through an independent channel to the vicinity of the nozzle tip.
  • a four-fluid nozzle or the like can be used.
  • the type of the mixing part of the component C and the atomizing gas may be either an internal mixing type for mixing inside the nozzle tip or an external mixing type for mixing outside the nozzle tip.
  • an internal mixed type two-fluid nozzle such as manufactured by Spraying Systems Japan Co., Ltd., manufactured by Kyoritsu Alloy Manufacturing Co., Ltd., or manufactured by Ikeuchi Co., Ltd., manufactured by Spraying Systems Japan Co., Ltd.
  • an external mixing type two-fluid nozzle manufactured by Kyoritsu Alloy Mfg. Co., Ltd. and Atmax Co., Ltd. an external mixing type four-fluid nozzle manufactured by Fujisaki Electric Co., Ltd., and the like.
  • the droplet diameter of the component C droplet can be adjusted by changing the balance between the flow rate and the atomization gas flow rate. That is, as the flow rate of the atomizing gas is increased with respect to the component C having a certain flow rate, the droplet diameter becomes smaller. Furthermore, the droplet diameter becomes smaller as the flow rate of the component C is decreased with respect to the atomizing gas having a certain flow rate.
  • the flow rate of the atomizing gas can be easily adjusted by adjusting the atomizing gas spray pressure.
  • the atomizing gas atomizing pressure [gauge pressure] is 0.1 MPa or more.
  • 1.0 MPa or less is preferable from the viewpoint of equipment load.
  • the average particle diameter of the component C droplet diameter is 1 to 300 ⁇ m. From the viewpoint, it is preferably 1 to 200 ⁇ m, more preferably 1 to 150 ⁇ m.
  • an anionic surfactant that is a high-viscosity paste can be uniformly dispersed, and the yield can be improved and a detergent particle group having a sharp particle size distribution can be obtained.
  • the average particle diameter of the droplet diameter of the component C is calculated on a volume basis, and is a value measured using a laser diffraction type particle size distribution measuring apparatus: Spray Tech (manufactured by Malvern).
  • component C Since component C is added through the multi-fluid nozzle, it is supplied to the multi-fluid nozzle as a fluid.
  • the anionic surfactant and / or the acid precursor thereof may be supplied as they are if they are liquid or paste at room temperature, may be diluted with water or the like to be liquid or paste, and heated to be liquid or paste It is good. Therefore, the temperature range at the time of supplying the component C to the nozzle (that is, at the time of addition into the mixer) is preferably 10 to 80 ° C., more preferably 20 to 70 ° C. from the viewpoint of stability and handling properties.
  • Step (C) is a step of mixing particles (A) and particles (B).
  • the blending amount of the particles (A) is preferably 20 to 70% by mass, more preferably 20 to 60% by mass, based on the total mass of the particles (A) and the particles (B).
  • components such as a surface modifier, an enzyme, a fragrance, a bleaching agent, and a pigment may be added and mixed.
  • the surface modifier include those described in the item [Other powder components].
  • the addition amount of these components is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total mass of the particles (A) and the particles (B) from the viewpoint of exerting a desired effect by addition, 0.2 to 20 parts by mass is more preferable, 0.3 to 10 parts by mass is further preferable, and 0.5 to 5 parts by mass is even more preferable.
  • Mixing in the step (C) may be performed using a known mixer.
  • a suitable mixer in this case, a mixer which is difficult to be compacted against detergent particles is preferable, and examples thereof include a rotary kiln, a ribbon mixer, a drum mixer, a planetary mixer, and the like.
  • the value obtained by dividing the bulk density of the particles (B) by the bulk density of the particles (A) is preferably 0.5 to 3.5 or less, more preferably 0.7 to 3.0, and 0 A range of .8 to 2.5 is more preferable.
  • a detergent particle group of the present invention by mixing (A) particles and (B) particles, fluidity that can be produced at a low spray-dried particle ratio is good and classification is suppressed.
  • a medium and low bulk density detergent particle group can be obtained with a high yield and a low coarse particle ratio.
  • the bulk density of the detergent particle group is preferably a medium to low bulk density of 250 to 600 g / L, more preferably 300 to 550 g / L, and still more preferably 300 to 500 g / L.
  • the average particle size of the detergent particles is preferably 200 to 800 ⁇ m, and more preferably 200 to 600 ⁇ m. From the viewpoint of appearance and solubility, the average particle size is preferably 800 ⁇ m or less.
  • the fluidity of the detergent particles is preferably 4 to 12 seconds, more preferably 4 to 10 seconds, and still more preferably 4 to 8 seconds.
  • the angle of repose is preferably 20 ° to 45 ° from the viewpoint of easy filling of the product.
  • the granulation yield of the detergent particle group is preferably 90 to 100%, more preferably 95 to 100%.
  • the coarse particle ratio of the detergent particle group is preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and particularly preferably 10% or less from the viewpoint of appearance and solubility.
  • Average Particle Size For the average particle size, the median diameter is calculated from the mass fraction depending on the size of the mesh after vibrating for 5 minutes using a standard sieve of JIS Z 8801 (aperture 2000 to 45 ⁇ m). More specifically, using a 12-stage sieve having a mesh opening of 45 ⁇ m, 63 ⁇ m, 90 ⁇ m, 125 ⁇ m, 180 ⁇ m, 250 ⁇ m, 355 ⁇ m, 500 ⁇ m, 710 ⁇ m, 1000 ⁇ m, 1410 ⁇ m, and 2000 ⁇ m, a small sieve with a mesh on the tray Stack in order, add 100 g of particles from the top of the top 2000 ⁇ m sieve, cover and attach to a low-tap sieve shaker (manufactured by HEIKO, tapping 156 times / minute, rolling: 290 times / minute) After vibrating for 5 minutes, the mass of the particles remaining on each sieve and the saucer is measured, and the mass ratio (%) of the particles on each sieve is
  • the flow time is defined as the time required for 100 mL of powder to flow out from the bulk density measurement hopper defined by JIS K 3362.
  • liquidity is measured with the remaining particle
  • Angle of repose A cylinder having an inner diameter of 77 mm and a height of 55 mm is placed on a fluidity measurement table (80 mm diameter circular platform) placed on a flat place, and a sample is poured from the upper surface of the cylinder at a height of 1 to 2 cm above. Fill from the upper surface of the cylinder to a position of about 0 to 1 cm in a pile. The cylinder is then gently moved upwards and removed, and the filled sample is naturally discharged by gravity. Thereafter, an angle (inclination angle) formed between the surface of the sample remaining on the approximate measurement table and the horizontal plane is read using a protractor, and the angle is defined as an angle of repose.
  • Granulation yield The granulation yield in this invention shows the ratio (mass) of the particle
  • the mass of the particles of 2000 ⁇ m or less is the above-mentioned 2. The measurement was performed using the same apparatus as used for the average particle diameter. The granulation yield of the particles (B) is also determined by the same method.
  • the coarse grain ratio in the present invention indicates the ratio (mass) of particles of 1000 ⁇ m or more in the manufactured detergent particle group.
  • the mass of the particles of 1000 ⁇ m or more is the above 2.
  • the measurement was performed using the same apparatus as used for the average particle diameter.
  • the coarse particle ratio of the particles (B) is also obtained by the same method.
  • the present invention further discloses the following manufacturing method regarding the above-described embodiment.
  • the container rotating mixer is a drum type mixer or a pan type mixer
  • the blending amount of the particles (A) is 20 to 70% by mass of the total mass of the particles (A) and the particles (B), preferably 60% by mass or less, more preferably 20 to 60% by mass, [1] The production method according to [1].
  • the anionic surfactant and / or precursor thereof used in the step (B) are linear alkylbenzene sulfonic acid, alkyl sulfuric acid, polyoxyethylene alkyl sulfuric acid, ⁇ -olefin sulfonic acid, fatty acid ester sulfonic acid and the like.
  • the amount of the anionic surfactant used in the step (B) is 10 to 45% by mass in the particles (B), preferably 13% by mass or more, preferably 35% by mass or less, and 13 to 35% by mass. % Is more preferable, The production method according to any one of [1] to [4].
  • the amount of the water-soluble solid alkali inorganic substance added in the step (B) is 1 to 35 times the neutralization equivalent of the acid precursor of the anionic surfactant used in the step (B), and more than 2 times Any of the above-mentioned [1] to [5], preferably 3 times or more, more preferably 30 times or less, more preferably 25 times or less, further preferably 2 to 30 times, further preferably 3 to 25 times. 2.
  • the bulk density of the particles (B) is 400 to 650 g / L, preferably 420 g / L or more, more preferably 440 g / L or more, preferably 620 g / L or less, more preferably 600 g / L or less, 420
  • the production method according to any one of [1] to [6], further preferably ⁇ 620 g / L, more preferably 440 ⁇ 600 g / L.
  • Any one of [1] to [7], wherein the water-soluble solid alkali inorganic material is at least one selected from the group consisting of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, and sodium silicate. Manufacturing method.
  • the bulk density of the particles (A) is 200 to 600 g / L, preferably 550 g / L or less, more preferably 500 g / L or less, further preferably 200 to 550 g / L, further 200 to 500 g / L.
  • the bulk density of the detergent particles is 250 to 600 g / L, preferably 300 g / L or more, preferably 550 g / L or less, more preferably 500 g / L or less, further preferably 300 to 550 g / L,
  • a 122L drum mixer ( ⁇ 50 cm ⁇ L62 cm) having a baffle plate was used as a container rotating mixer.
  • a two-fluid nozzle (manufactured by Atmax Co., Ltd .: model number BN160) was used.
  • the value described as the spray pressure of the two-fluid nozzle is the gauge pressure.
  • the slurry was sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the spray drying tower to obtain spray-dried particles.
  • the hot gas supplied to the spray-drying tower was supplied at a temperature of 220 ° C. from the bottom of the tower and discharged at 110 ° C. from the top of the tower.
  • the obtained spray-dried particles were designated as spray-dried particles (A-1), and their compositions and physical properties are shown in Table 1.
  • (A-2) Spray-dried particles (A-2) were obtained in the same manner as (A-1) except that the amount of water and the like added to the mixing tank was changed and silicate was not added. Table 1 shows the composition and physical properties of (A-2).
  • (A-4) Sprayed in the same manner as (A-1) except that the amount of water added to the mixing tank was changed, and paste-like (60 ° C.) sodium alkyl sulfate was added as an anionic surfactant. Dry particles (A-4) were obtained. The addition of sodium alkyl sulfate was performed after the addition of sodium polyacrylate. The composition and physical properties of (A-4) are shown in Table 1.
  • (B-2) and (B-3) Particles were obtained by the same method as (B-1) except that the amount of raw material added to the drum mixer and the amount of anionic surfactant sprayed were changed.
  • Table 2 shows the composition and physical properties of the obtained particles (B-2) and (B-3).
  • (B-6) Particles were obtained in the same manner as in (B-1) except that the amount of raw material added to the drum mixer and the amount of anionic surfactant sprayed were changed and sodium sulfate was added. Table 2 shows the composition and physical properties of the obtained particles (B-6).
  • the detergent particles obtained in Examples 1 to 14 have a spray-dried particle ratio in the range of 20 to 70%, good fluidity and a bulk density of 350 to 600 g / L. It turned out to be a group.
  • Particles (B-1) to (B-6) have a bulk density of 470 to 600 g / L, which is a medium bulk density particle, and since (A) the difference in bulk density from the particles is small, Even if A) particles and (B) particles are mixed, classification during transportation or the like is suppressed. Furthermore, the granulation yield of the obtained detergent particle group was as high as 90% or more, and the coarse particle ratio was as low as 20% or less.
  • Comparative Examples 1 to 3 the fluidity is very poor and the angle of repose is large, so that it is difficult to inject the detergent particles as a product into the container, and the handling property of the consumer during use is poor. Met. Furthermore, it was found that each of Comparative Examples 1 to 3 had a bulk density of 77 g / L or more higher than that of the detergent particle group of Example when the same spray-dried particle ratio as in Example was used (Example 12). To 14, Comparative Examples 1 to 3). Therefore, in order to obtain a detergent particle group having the same bulk density as that of the detergent particle group produced according to the present invention, it is necessary to increase the spray-dried particle ratio, which increases the environmental load. Moreover, regarding the granulation yield and the coarse particle ratio of the detergent particles, the performance was lower than that obtained by the production method of the present invention.
  • Comparative Example 5 Although the fluidity and angle of repose are good, the difference in the bulk density between the particles (B) and the particles (A) is large because one fluid nozzle was used for the production of the particles (B-9). It is expected that classification will occur. Moreover, regarding the granulation yield and the coarse particle ratio of the detergent particles, the performance was lower than that obtained by the production method of the present invention.
  • a medium and low bulk density detergent particle group having good fluidity with a good yield and a low coarse particle ratio while reducing the spray-dried particle ratio.
  • Such a detergent particle group can be preferably used as a detergent composition for various uses such as clothing, or as one component of such a detergent composition.

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Abstract

L'invention concerne un procédé de fabrication de granules de détergeant qui comporte les étapes suivantes. Étape (A) : une étape de préparation de granules (A) comportant 5 à 40% en masse d'un agent tensio-actif anionique par granule, au moyen d'un séchage par pulvérisation d'une bouillie comprenant un agent tensio-actif anionique. Étape (B) : une étape de préparation de granules (B) par granulation d'un matériau de base en poudre pour détergeant, à l'aide d'un mélangeur de type à récipient rotatif; au cours de cette étape (B) l'agent tensio-actif anionique, ou son précurseur est ajouté à l'intérieur dudit mélangeur de type à récipient rotatif via une buse à fluide multiple; le matériau de base en poudre pour détergeant consiste en une substance inorganique alcaline solide hydrosoluble et/ou un sel inorganique hydrosoluble; la masse de la substance inorganique alcaline solide hydrosoluble et du sel inorganique hydrosoluble représente 30 à 88% en masse des granules (B); et le mélangeur de type à récipient rotatif est un mélangeur de type à tambour ou un mélangeur de type à pétrin. Étape (C) : une étape de mélange des granules (A) et (B). Ainsi, selon le procédé de fabrication de granules de détergeant de l'invention, il est possible d'obtenir selon un bon rendement des granules de détergeant de densité apparente moyenne ou faible, et dans lesquelles le pourcentage de granules séchées par pulvérisation mises en œuvre, est réduit.
PCT/JP2011/076653 2010-11-19 2011-11-18 Procédé de fabrication de granules de détergeant WO2012067227A1 (fr)

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WO2018003905A1 (fr) * 2016-06-30 2018-01-04 ライオン株式会社 Composition détergente en poudre et son procédé de production
CN106544181A (zh) * 2016-10-27 2017-03-29 陆腾蛟 一种洗洁产品及生产设备及工艺
CN106361588A (zh) * 2016-10-27 2017-02-01 陆腾蛟 一种洁齿产品及生产设备及工艺
JP7368399B2 (ja) * 2021-01-07 2023-10-24 花王株式会社 粒状洗剤組成物

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JP2003105397A (ja) * 2001-09-28 2003-04-09 Lion Corp 高嵩密度粒状洗剤組成物の製造方法
JP2004176055A (ja) * 2002-11-15 2004-06-24 Lion Corp 粒状洗剤の製造方法
JP2005344109A (ja) * 2004-05-06 2005-12-15 Lion Corp 粒状洗剤の製造方法
JP2008063419A (ja) * 2006-09-06 2008-03-21 Lion Corp 衣料用中嵩密度粉末洗剤とその製造方法
WO2009142135A1 (fr) * 2008-05-19 2009-11-26 花王株式会社 Amas de granulés portant un agent tensioactif

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TW397862B (en) * 1996-09-06 2000-07-11 Kao Corp Detergent granules and method for producing the same, and high-bulk density detergent composition
CN1175099C (zh) * 1998-10-16 2004-11-10 花王株式会社 洗涤剂颗粒的制备方法
AU744708B2 (en) * 1999-06-14 2002-02-28 Kao Corporation Granules for carrying surfactant and method for producing the same

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JP2003105397A (ja) * 2001-09-28 2003-04-09 Lion Corp 高嵩密度粒状洗剤組成物の製造方法
JP2004176055A (ja) * 2002-11-15 2004-06-24 Lion Corp 粒状洗剤の製造方法
JP2005344109A (ja) * 2004-05-06 2005-12-15 Lion Corp 粒状洗剤の製造方法
JP2008063419A (ja) * 2006-09-06 2008-03-21 Lion Corp 衣料用中嵩密度粉末洗剤とその製造方法
WO2009142135A1 (fr) * 2008-05-19 2009-11-26 花王株式会社 Amas de granulés portant un agent tensioactif

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