WO2000077159A1 - Particules d'addition a un detergent - Google Patents

Particules d'addition a un detergent Download PDF

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Publication number
WO2000077159A1
WO2000077159A1 PCT/JP2000/003857 JP0003857W WO0077159A1 WO 2000077159 A1 WO2000077159 A1 WO 2000077159A1 JP 0003857 W JP0003857 W JP 0003857W WO 0077159 A1 WO0077159 A1 WO 0077159A1
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WO
WIPO (PCT)
Prior art keywords
detergent
particles
water
particle
weight
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Ceased
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PCT/JP2000/003857
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English (en)
Japanese (ja)
Inventor
Shuji Takana
Shu Yamaguchi
Hiroyuki Saijo
Hiroyuki Yamashita
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Kao Corp
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Kao Corp
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Application filed by Kao Corp filed Critical Kao Corp
Priority to JP2001503996A priority Critical patent/JP3249815B2/ja
Priority to EP00939055.0A priority patent/EP1193310B2/fr
Priority to DE60040462T priority patent/DE60040462D1/de
Publication of WO2000077159A1 publication Critical patent/WO2000077159A1/fr
Anticipated expiration legal-status Critical
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D3/37—Polymers

Definitions

  • the present invention relates to a detergent additive particle group, a composite detergent particle group, and a granular detergent composition.
  • granular detergent compositions have become the mainstream of laundry detergents.
  • the granular detergent composition is manufactured by using various techniques such as mixing, granulation, compression, and pulverization, and has great advantages in simplicity in use and reduction in transportation cost.
  • granular detergent compositions tend to be less soluble than low-bulk-density detergents, and in particular, drum-type washing in which the granular detergent compositions placed in a cluster are distributed (flowed) into the washing tub by pouring water.
  • dispensers detergent input trays
  • fully automatic washing machines there is a problem that troubles often remain due to aggregates (pastes) of the granular detergent composition.
  • Japanese Unexamined Patent Publication (Kokai) No. 7-509927 discloses a base powder having less than 10% by weight of particles of less than 150 m and less than 10% by weight of particles of more than 1700 / m.
  • a detergent composition in which fine or coarse powder of sodium carbonate or sodium citrate is added as a filler. This improves the bulk density and improves the dispensability from the dispenser by reducing the amount of surfactant-containing fines and post-adding fine or coarse, rapidly dissolving ungelled particles. is there.
  • 11-35998 describes that the weight frequency of a 50% diameter and a particle diameter of less than 125 m and the weight frequency of a particle
  • a granular high-density detergent wherein the composition of the weight frequency of the particle size is limited to a specific range is disclosed. This seeks to improve both the dispersibility and the particle solubility of the granular detergent composition by controlling the particle size distribution and is suitable for use in dispensers. Is shown. These technologies improve the dispensability from the dispenser and reduce the frequency or amount of troubles in which the paste-like high-density detergent composition remains in the dispenser, but reduce the water pressure during water injection and the water temperature. There is still a concern that the amount of the detergent composition may remain in the dispenser depending on the method of water injection, the type of dispenser, and the like. Therefore, it is desired to further improve the distribution of the granular detergent composition in the dispenser. Disclosure of the invention
  • the present invention relates to a granular detergent composition excellent in distributability when poured into a dispenser of a drum-type washing machine, a fully automatic washing machine, and the like; a composite detergent particle contained in the granular detergent composition; It is an object of the present invention to provide a detergent additive particle group contained in the particle group.
  • the present invention is a.
  • [1] Contains two or more water-soluble substances of 30 to 100% by weight, and may further contain less than 10% by weight of a surfactant and 70% by weight or less of Z or a water-insoluble substance.
  • a group of particles for adding detergent having an average particle size of 150 to 600 / m, a bulk density of 300 to 100 gZL, and water particles at 5 ° C. When the particles are charged and stirred for 60 seconds under the stirring conditions shown below and passed through a standard JISZ8801 standard sieve (mesh size: 74 m), the dissolution of the particles calculated by formula (1)
  • a detergent-added particle group (a) having a ratio of 90% or more;
  • Average particle size 150-600 tm, bulk density 500-1000 gZL, detergent particles containing surfactant 50-500% by weight (b) Composite detergent particles that are dry-mixed,
  • Dissolution rate (%) ⁇ 1-(TZS) ⁇ X 100 (1)
  • a granular detergent composition comprising 50 to 100% by weight of the composite detergent particles according to [1],
  • a detergent-adding particle group that contains 30 to 100% by weight of two or more water-soluble substances and may further contain less than 10% by weight of a surfactant and 70% by weight or less of Z or a water-insoluble substance.
  • the average particle size is 150 to 600 m
  • the bulk density is 300 to 100 Og / L
  • the particle group is put in water at 5 ° C, and under stirring conditions shown below.
  • JISZ8801 standard sieve mesh size 74 ⁇ m) after stirring for 60 seconds, and the detergent for dissolving ratio of the particle group calculated by the formula (1) is 90% or more.
  • the particle group (a). BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a schematic diagram of the detergent-adding particles as viewed from the surface centered on the depression hole.
  • S1 indicates the projected area of the particle measured around the opening of the depression.
  • S2 indicates the projected area of the hole measured as the opening.
  • FIG. 2 is a schematic side view of a cross section of the depressed particles cut perpendicular to a plane centered on the depressed hole as indicated by a broken line in FIG.
  • X indicates the tangent to the opening surface of the depression.
  • Y indicates the tangent to the bottom of the hole parallel to tangent X.
  • d indicates the distance between tangent X and tangent Y.
  • the present invention prepares a detergent-adding particle group (a) having a specific composition, a specific powder physical property and a specific high dissolution rate that does not contain a surfactant or has a low surfactant content, It has been found that the dispersibility of the composite detergent particles (a) + (b) obtained by mixing with the detergent particles (b) containing a large amount of the detergent significantly improves in the dispenser.
  • the residual trouble in the dispenser of the granular detergent composition can be greatly improved by being present in the granular detergent composition in a specific amount or more.
  • Detergent-adding particles are particles that may contain less than 10% by weight of a surfactant and a builder, and the detergent-adding particles are an aggregate thereof.
  • the detergent particles are particles containing 10 to 50% by weight of a surfactant, and the detergent particle group is an aggregate thereof.
  • the composite detergent particles are an aggregate obtained by dry-mixing the detergent-adding particles and the detergent particles.
  • the granular detergent composition means a finished granular detergent comprising a composite detergent particle group obtained by dry-mixing a detergent additive particle group and a detergent particle group, and a detergent component added separately as required (for example, Builder granules, fluorescent dyes, enzymes, fragrances, antifoaming agents, bleaching agents, bleaching activators, etc.), and those containing particles other than the above-mentioned detergent-adding particles and detergent particles.
  • the detergent-adding particles of the present invention which exhibit excellent dispenser dispersibility in the granular detergent composition by being blended as a component of the granular detergent composition, contain no surfactant or have a surfactant content of 1%. It is extremely low at less than 0% by weight and has the following characteristics. 2-1. High-speed solubility of detergent-added particles
  • the present invention provides a method for enhancing the distribution of a particulate detergent composition by discontinuing a continuous, high-concentration surfactant paste layer formed by the particulate detergent composition when poured into a dispenser.
  • a detergent additive particle group having a specific composition and specific powder physical properties is mixed with the granular detergent composition, and further, the detergent additive particle group has a high-speed solubility described later. It is.
  • a high-concentration paste layer of a surfactant formed during water injection is rapidly discontinued and the detergent is formed.
  • the granular detergent composition can be quickly and efficiently distributed from the dispenser by the action of the additive particles dissolving in the water injection at a high speed.
  • particles with a low dissolution rate are mixed with detergent particles, the paste formed when water is injected with the dispenser becomes harder and harder, and a phenomenon is seen that the dispersibility from the dispenser is reduced. It is very important that the particles for the application have high-speed solubility.
  • the high-speed solubility of the detergent additive particle group can be confirmed as showing a remarkably high dissolution rate when dispersed into individual constituent particles in water.
  • the high-speed solubility of the particles for detergent addition according to the present invention is determined by the following formula (1) when agitated for 60 seconds and passed through a standard JISZ8801 standard sieve (opening 74 urn) according to the method described below. It indicates that the dissolution rate calculated by is 90% or more.
  • the dissolution rate is preferably 92% or more, more preferably 94% or more, more preferably 96% or more, and more preferably 97% or more. 8% is more preferable, and 99% or more is most preferable.
  • the particle group dispersion liquid in the beaker was filtered through a standard sieve (diameter 100 mm) having a mesh size of 74 m and having a mesh size of JISZ8801, and the water-containing particles remaining on the sieve were filtered. Collect the group together with the sieve in an open container of known weight.
  • the operation time from the start of filtration to the collection of the sieve is 10 soil 2 seconds.
  • One of the means to express high-speed solubility when the detergent-adding particles are dispersed in water is to add detergents in consideration of the relationship between the particle diameters of the detergent-adding particles and the dissolution rate. Adjusting the particle size distribution of the particles is an effective means. In other words, the dissolution rate per unit time is measured for detergent-added particles that have been classified into a plurality of stages according to the size of the particle diameter, and when the dependence of the particle diameter on the dissolution rate is high, sieving is performed. High-speed solubility can be exhibited by a method of reconstituting the classified particle group for detergent addition into a particle size distribution having a high solubility. 2- 1 -2. High-speed solubility due to voids in particles
  • the dissolution rate of the (detergent-adding particles) can also be achieved by significantly increasing the dissolution rate of the (detergent-adding particles).
  • High-speed solubility can be exhibited by forming the detergent-adding particles from particles having fine spaces inside the particles.
  • the detergent-adding particles having a fine space inside the particles not only gradually dissolve from the surface but also after the surface is dissolved, water infiltrates into the fine spaces inside the particles, and dissolves from the inside by the penetrated water and disintegration of the particles.
  • the dissolution rate per unit time is increased.
  • the fine space inside the particles can be measured as a pore volume of 0.01 to 4 xzm by a mercury intrusion method, and the pore volume is preferably at least 0.3 ZmLZg.
  • the pore volume is more preferably 0.25 mLZg or more, and still more preferably 0.2 mLZg or more. It is at least 3 mLZg, most preferably at least 0.35 mLZg.
  • the pore volume is preferably equal to or less than 1.2 mL / g, more preferably equal to or less than 1.0 mLZg, and still more preferably equal to or less than 0.8 mLZg.
  • Pore volume is the value of the pore volume from 0.01 to 4 m, measured with a mercury porosimeter on a sample of the shrunken sample detergent.
  • detergent-added particles having a structure capable of releasing bubbles having a particle diameter of 1 Z 10 or more during the process of dissolving in water
  • detergent-added particles Fast dissolving property can be exhibited by the composition of (bubble releasing detergent addition particles).
  • the detergent-added particles not only dissolve from the surface but also inside the particles. Water infiltrates into the inside of the particles due to the release of bubbles from the surface, and dissolution from inside due to the infiltrated water and disintegration of the particles increase the dissolution rate per unit time.
  • Such dissolution behavior is such that, when the particles for adding the bubble releasing detergent are dissolved in water, the particle size of the particles is 1 Z 10 or more, preferably 1 Z 5 or more, more preferably 1 Z 4 or more, and The phenomenon of releasing bubbles having a diameter of preferably 1 Z 3 or more, preferably 1 Z 2 or more (hereinafter referred to as bubbles of a predetermined size) can be confirmed by a digital microscope, an optical microscope, or the like. .
  • bubbles of a predetermined size are preferably generated within 120 seconds, more preferably within 60 seconds, and more preferably within 40 seconds. Within 5 seconds is more preferable, within 30 seconds is more preferable, within 20 seconds is more preferable, and within 10 seconds is most preferable.
  • the bubble-adding detergent-adding particles only need to have pores (single or plural) capable of releasing bubbles of a predetermined size.
  • the particles are not limited to the form and structure of the particles.
  • detergent-adding particles that release a single bubble may be used, or detergent-adding particles that release a plurality of bubbles obtained by aggregating the detergent-adding particles may be used.
  • the bubble-adding detergent-adding particles are preferably contained in the detergent-adding particles at 50% by weight or more, more preferably 60% by weight or more, more preferably 70% by weight or more, and 80% by weight. The above is more preferable, and 90% by weight or more is most preferable.
  • the granular detergent composition is added when the water is injected into the dispenser. Distribubility is also improved by the release of air bubbles from the object and the associated effect of water intrusion.
  • the bubble diameter is measured as follows.
  • Preferred particles for adding a bubble releasing detergent include particles having a particle diameter of 10 to 4/5, preferably 1 to 5 to 4/5, more preferably 1 to 4 to 5, more preferably 1 to 4 to 5 in the inside of the particles. It is preferable that pores having a diameter of 1 Z 3 to 4/5, particularly preferably 1 Z 2 to 4 Z 5 are present.
  • the pore diameter can be measured as follows.
  • a shape having a hollow portion inside the particle and having an opening at the surface of the particle and communicating with the hollow portion inside (the surface of the particle is depressed) may be mentioned.
  • Detergent-adding particles (recessed particles) having the recessed holes rapidly release pores from the inside of the particles, so that water enters the inside of the particles quickly, and dissolution from the inside and disintegration of the particles due to the penetrated water are prevented. It has the advantage of being expedited.
  • the preferred size of the depressed hole in the depressed particles included in the detergent-added particles of the present invention will be described.
  • the equivalent circle diameter of the particles Particles are photographed using a microscope centering on the mouth, and the projection area (S 1) of the particles measured from the photographed particle image is used to obtain the equation (2).
  • Particle equivalent circle diameter 2 X (S ⁇ / ⁇ ) 1/2 (2)
  • the circle equivalent diameter of a hole (recessed hole) is measured by the same method as the above-mentioned projected area of the particle as an opening.
  • KEYENCE An SEM such as a digital microscope VH-6300 manufactured by Hitachi, Ltd. or a S-4000 type manufactured by Hitachi field emission scanning electron microscope can be used.
  • WinRo0f made by Mitani or the like can be used.
  • the preferred diameter of the hole present in the depressed particles included in the detergent-added particles of the present invention is as follows: [(Equivalent circle diameter of the hole) / (Equivalent circle diameter of particle)] X100 is 2% These are the holes.
  • the ratio is more preferably 2 to 70%, further preferably 4 to 60%. , 6 to 50% is more preferable, 8 to 40% is further preferable, and 10 to 30% is most preferable.
  • the depth of the hole present in the particles contained in the detergent-added particles of the present invention is determined by the tangent X to the opening surface of the depression and the tangent Y to the bottom of the hole parallel to the tangent X.
  • the ratio of (the distance d) / (the circle equivalent diameter of the particle)] X100 is the ratio of the distance d to the circle equivalent diameter of the particle.
  • the particle is cut with a scalpel or the like on a plane perpendicular to the opening of the depression, and the cross section is photographed with an SEM or the like.
  • the ratio of the depth of the holes present in the depressed particles included in the detergent-added particles of the present invention is preferably 10% or more. Further, from the viewpoint of further increasing the amount of water entering the inside of the particles and ensuring the strength of the particles, the ratio is more preferably 10 to 90%, and still more preferably 15 to 80%. 20-70% is particularly preferred.
  • the depressed particles are preferably contained in the detergent additive particles at 50% by weight or more, more preferably 60% by weight or more, more preferably 70% by weight or more, and more preferably 80% by weight or more. Most preferred is 90% by weight or more.
  • the characteristic feature is that the particles constituting the particle group obtained by the drying process used as the detergent-adding particle group or as a main component of the detergent-adding particle group are unevenly distributed in the structure between the inside and the vicinity of the surface in the structure. Is to have.
  • the particles obtained by the drying step are composed of a water-soluble substance and a water-insoluble substance
  • the water-soluble substance has an uneven distribution in which the water-soluble substance is present more in the vicinity of the surface than in the inside thereof, so that the surface of the particle is in the water.
  • the water-soluble substance is a substance having a solubility in water of 25 or more of 0.5 gZ100.
  • water-soluble salts are those having a molecular weight of less than 1,000
  • water-soluble polymers are organic polymers having a molecular weight of 1,000 or more.
  • a water-insoluble substance is one having a solubility in water at 25 ° C. of less than 0.5 g / 100 g.
  • the particles obtained by the drying process are composed only of a water-soluble substance, high-speed solubility can be exhibited by the uneven distribution of the composition between the inside and the vicinity of the surface.
  • the water-soluble polymer near the surface dissolves faster in water due to the uneven distribution of the water-soluble polymer near the surface rather than inside. Then, the particles exhibit a dissolution behavior in which the strength of the particles is reduced and the disintegration is promoted, whereby high-speed solubility can be exhibited.
  • the most preferable embodiment for achieving high-speed solubility is the uneven distribution structure of the composition, a fine space inside the particle, and further, a hollow portion, and the surface of the particle is opened to form an inner space. It is a particle group for detergent addition having a shape communicating with the hollow part of the part.
  • the uneven distribution is confirmed as follows.
  • FT-IR Fourier transform infrared spectroscopy
  • PAS photoacoustic spectroscopy
  • a measurement method for specifying the structure of the detergent-added particles of the present invention will be exemplified below. Filling a cell with two different types of detergent-adding particles in two different states, performing FT-IR / PAS measurement, and comparing the results to identify the structure of the detergent-adding particles. In other words, one is to perform FT-I RZPAS measurement while maintaining the desired structure of the detergent-adding particles, and to compare the comparative sample with the detergent-adding particles that were sufficiently pulverized in an agate mortar or the like to make them uniform.
  • FT—I Perform RZPAS measurement is to perform FT-I RZPAS measurement while maintaining the desired structure of the detergent-adding particles, and to compare the comparative sample with the detergent-adding particles that were sufficiently pulverized in an agate mortar or the like to make them uniform.
  • FT—IR / PAS is measured using, for example, an “FTS-60A / 896-type infrared spectrophotometer” manufactured by Bio-Rad Labor atories, and a 300-inch photoacoustic detector manufactured by MTEC as a PAS cell. Done using The measurement conditions are as follows: resolution 8 cm “ 1 , scan speed 0.63 cmZs, totaling 128 times. These measurement conditions include information from the surface of the particles for detergent addition up to about 10 m from the particle surface.
  • the relative area intensity with respect to the characteristic peak of a reference substance (select a substance inside rather than near the surface), which was measured while maintaining the uneven distribution structure of the components, was uniform by grinding.
  • the ratio of the relative area intensity to the characteristic peak of the above-mentioned reference material when measured in an appropriate state is determined, it is found that at least one kind of material other than the above-mentioned reference material has a superior fast dissolution of 1.1 or more. From the viewpoint of exhibiting the property, it is preferably 1.2 or more, more preferably 1.3 or more, still more preferably 1.4 or more, and particularly preferably 1.5 or more. It can be said that it has an unevenly distributed structure when it has these relative area intensities.
  • EDS energy dispersive X-ray spectroscopy
  • EPMA electron probe microanalysis
  • the detergent-addition particles are embedded in a resin, and the cut surface of the detergent-addition particles cut out by a microtome is used.
  • the distribution of elements measured for Na, Al, Si, S, etc. is as follows: (:, Na, S, many elements, A1, Si, many at center And more water-soluble salts near the surface It can be confirmed that the structure contains a large amount of water-insoluble substances in the center.
  • the detergent-added particles of the present invention comprise two or more water-soluble substances 3! ) To 100% by weight, and may further contain less than 10% by weight of a surfactant and 70% by weight or less of a Z or water-insoluble substance.
  • the water-soluble substance in the present invention is a substance that dissolves in 0.1 g or more with respect to 100 g of pure water at 20 ° C, and the water-insoluble substance is pure water at 100 ° C at 20 ° C. Shows that the amount dissolved per g is less than 0.1 g.
  • crystalline silicates are handled as water-insoluble substances, and surfactants are handled without being included in water-soluble substances and water-insoluble substances.
  • a characteristic feature of the composition of the particles for detergent addition according to the present invention is that no surfactant is contained or the content of the surfactant is extremely small, and the content of the surfactant is less than 10% by weight. .
  • the preferable content of the surfactant is 0 to 8% by weight, more preferably less than 6% by weight, more preferably less than 4% by weight, More preferably, it is less than 2% by weight, more preferably less than 1% by weight, and most preferably it is substantially free of surfactant.
  • the water-soluble substance according to the present invention exerts the effect of causing the detergent additive particles to exhibit high-speed solubility and discontinuing the surfactant paste layer formed by the granular detergent composition when poured into the dispenser.
  • the blending amount must be 30 to 100% by weight.
  • it is preferably at least 40% by weight, more preferably at least 50% by weight. , More preferably 60% by weight or more , More preferably 70% by weight or more, more preferably 80% by weight or more, more preferably 90% by weight or more, and most preferably substantially consist only of a water-soluble substance.
  • the substance was moistened by the phenomenon that the paste of the granular detergent composition formed when water was injected in the dispenser was hardened by the water-insoluble substance, that is, the rheological property exhibited when the water-insoluble substance was mixed with water.
  • the content of the water-insoluble substance needs to be 70% by weight or less in order to improve the distribution property from the dispenser by reducing the phenomenon that the flowability of the granular detergent composition decreases.
  • the content of the water-insoluble substance is preferably 60% by weight or less, more preferably 5% by weight or less.
  • wt% or less 0 wt% or less, more preferably 40 wt% or less, more preferably 30 wt% or less, more preferably 20 wt% or less, more preferably 10 wt% or less, most preferably substantially water-insoluble Substance-free.
  • Examples of the water-soluble substance in the present invention include alkali having a carbonate group, a hydrogen carbonate group, a sulfate group, a sulfite group, a hydrogen sulfate group, a hydrochloric acid group, a bromate group, an iodate group, a silicate group or a phosphate group.
  • Examples include water-soluble inorganic salts such as metal salts, ammonium salts, and amine salts, and low-molecular-weight water-soluble organic acid salts such as citrate and fumarate (however, surfactants are included. Make it not exist) .
  • a carbonate group, a sulfate group and a sulfite group are preferred.
  • the water-soluble inorganic salt reacts with water to generate heat of hydration and heat of dissolution, thereby disintegrating the detergent-adding particles in water and expanding bubbles when the detergent-adding particles are bubble-emitting particles. It is preferable because it promotes self-disintegration.
  • the water-soluble substance is a single water-soluble substance that forms hydrated crystals at low temperatures (eg, sodium carbonate, sodium sulfate, etc.) alone, if the temperature of the water to be injected is high, the mixture of the detergent-added particles is mixed.
  • the partitioning effect of the granular detergent composition is sufficiently improved by the discontinuous effect of the high-concentration surfactant paste layer, the water-soluble substance is hydrated when colder water is injected.
  • the phenomenon that the water-containing granular detergent composition hardens due to precipitation as crystals occurs, and the effect of improving the dispenser distribution property by mixing the detergent-adding particles tends to decrease.
  • a water-soluble substance that forms hydrated crystals in low-temperature water is a preferable content form of a water-soluble substance from the viewpoint of exhibiting an excellent effect of improving the distribution property of the detergent-adding particles even when low-temperature water is injected. If the substance and water-soluble substances whose solubility decreases as the water temperature decreases and crystals precipitate, etc., hydration with a single water-soluble substance by coexisting two or more water-soluble substances It is preferable to suppress and delay the growth of crystals and the like. More specifically, it is preferable that one or more water-soluble substances are contained in a molar ratio of 9/1 or less with respect to one water-soluble substance contained in the detergent-added particles. Preferably, it is contained in a molar ratio of 8Z2 or less, more preferably 7Z3 or less, particularly preferably 64 or less, most preferably about 5Z5.
  • sodium carbonate is also preferable as an alkaline agent showing a suitable pH buffer region in the washing liquid.
  • alkaline agents include amorphous silicates.
  • salts with a high degree of dissociation such as sodium sulfate, sulfuric acid lime, and sodium sulfite, increase the ionic strength of the washing liquid, and suitably act on sebum dirt washing properties.
  • Sulfurous acid groups also reduce the amount of hypochlorous acid contained in tap water and have the effect of preventing oxidative deterioration of detergent components such as enzymes and fragrances.
  • sodium tripolyphosphate which is excellent in sequestering ability and alkaline ability is preferably used.
  • a base having a large pKC a 2 + and a large Z or cation exchange capacity is preferable in view of the ability to sequester a metal ion.
  • methyl iminodiacetate, iminodisuccinate, ethylenediamine disuccinate, taurine Acetate, hydroxyethyl iminodiacetate, S-alanine diacetate, hydroxyiminodisuccinate, methylglycine diacetate, glutamine diacetate, asparagine diacetate, serine diacetate and the like can be mentioned.
  • the water-soluble polymer has the effect of increasing the particle strength of the detergent-adding particles when the detergent-adding particles of the present invention are obtained by a production method including a drying process, and when the drying process is a spray drying process.
  • the particles have a bubble release structure, an uneven distribution structure of the composition, a fine space inside the particles, and a hollow portion, and have a function of imparting a shape that is open to the surface of the particles and communicates with the inside hollow portion. Is preferred.
  • the detergent-addition particles preferably contain 1 to 40% by weight, more preferably Is preferably 2 to 30% by weight, more preferably 3 to 20% by weight, more preferably 4 to 15% by weight, particularly preferably 5 to 10% by weight.
  • the water-soluble polymer include carboxylic acid-based polymers, carboxymethylcellulose, soluble starch, and saccharides. Among them, sulfonic acid-based polymers are preferred from the viewpoint of improving the washing performance of the granular detergent composition. Particularly Akuriru acid - salt of maleic acid copolymers and polyacrylates (N a, K, ⁇ ⁇ 4 , etc.) are particularly excellent.
  • the molecular weight of the water-soluble polymer is from 1,000 to 100,000, more preferably from 2,000 to 80,000, and particularly preferably from 5,000 to 50,000.
  • polymers such as polyglyoxylate, cellulose derivatives such as carboxymethyl cellulose and aminocarboxylic acids such as polyaspartate also have sequestering ability, dispersing ability and the like. Has the ability to prevent re-contamination.
  • PVP polyvinylpyrrolidone
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PVA is preferred as a color transfer inhibitor and has a molecular weight of about 100,000 to 20,000. £ 0 and? ? ⁇
  • the aggregate of the bright granular detergent composition is preferable because it has an effect of further reducing the viscosity of the paste produced by containing water.
  • the surfactant in the present invention at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used.
  • the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, Hichiseki refine sulfonate, polysulfo fatty acid salt or its ester, alkyl or alkenyl ether carbonate, and amino acid type interface.
  • Surfactants and N-amino acid type surfactants are examples of the anionic surfactant.
  • straight-chain alkylbenzene sulfonates having 10 to 14 carbon atoms and alkyl or alkyl ether sulfates having 10 to 18 carbon atoms are mentioned, and the counter ions thereof are sodium, potassium, monoethanolamine, diethanolamine. Min is preferred.
  • a fatty acid salt having 12 to 18 carbon atoms can be used in combination to obtain an antifoaming effect.
  • nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polypropylene propylene alkyl ether, and the trademark “polyoxyethylene polyoxy represented by pull-out nick j”.
  • those having high hydrophilicity and / or mixed with water a polyoxyalkylene alkyl ether having low ability to form a liquid crystal or not producing a liquid crystal is preferable, and a polyoxyalkylene alkyl ether is particularly preferable.
  • EO oxide
  • PO propylene oxide
  • R represents an alkyl group or an alkenyl group
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group
  • X, ⁇ , and ⁇ ⁇ ⁇ ⁇ each represent an average number of moles added.
  • cationic surfactant examples include a quaternary ammonium salt such as an alkyltrimethylammonium salt.
  • amphoteric surfactant examples include a carbobetaine type and a sulfobetaine type.
  • the water-insoluble inorganic substance which is a water-insoluble substance, is preferably a fine particle having an average primary particle size of less than 0.1 to 20 / m, for example, crystalline or amorphous alumino.
  • Silicates, silicon dioxide, hydrated silicate compounds, clay compounds such as perlite and bentonite can be used, and crystalline or amorphous aluminosilicates, silicon dioxide and hydrated silicate compounds are preferred.
  • crystalline aluminosilicate is preferable as the sequestering agent.
  • the (average) particle size of the primary particles of the crystalline aluminosilicate may be 0.1 to less than 20 / m, but in consideration of the cation exchange rate and persistence in laundry clothes, the primary particles Is preferably smaller.
  • the particle size can be confirmed with a scanning electron microscope. Also,
  • Aggregates of primary particles can also be used.
  • zeolite A can be used in terms of sequestering ability and cost.
  • a liquid component for example, a liquid surfactant on the detergent-added particles
  • A-type zeolite has an oil absorption value of 40 to 5 OmLZl 00 g according to the JIS K 5101 method (for example, trade name: Toyo Builder; manufactured by Tosoh Corporation).
  • P type for example, product name Douci 1 A24 or ZSE 064, etc .; manufactured by Crosfild Co., Ltd .; oil absorption capacity 60 to 150 mLZl 00 g
  • X type for example, product name Douci 1 A24 or ZSE 064, etc .
  • Hybrid zeolite described in WO 98 42622 is also mentioned as a suitable crystalline aluminosilicate.
  • Amorphous silica or amorphous aluminosilicate which has a low sequestering ability but a high oil absorbing ability, can also be used as a water-insoluble substance.
  • Amorphous aluminosilicates JP-A-9-132794, column 17, line 46 to column 18, line 38, JP-A-7-10526 column 3, line 3 to line 5
  • Amorphous aluminosilicate (oil absorption capacity 285 mL / 100) described in line 47 can be mentioned.
  • the water-insoluble substance in the present invention preferably contains a crystalline silicate.
  • the crystalline silicate described in (1) is an example of a base having both alkali ability and sequestering ability.
  • the alkali metal silicate S i 0 2 / U 20 (where M represents an alkali metal) is preferably from 0.5 to 3.2, more preferably from 1.5 to 2.6. It is preferably used.
  • a preferred compounding method is a method of pulverizing to a size of 1 to less than 20 m, preferably 1 to less than 10 m, and then using it as a surface modifier.
  • the average particle size of the detergent-added particles of the present invention is measured from the weight fraction based on the size of the sieve after vibrating for 5 minutes using a JISZ8801 standard sieve.
  • the average particle size is set to 15 or more in order to suppress dusting when handling a granular detergent composition obtained by mixing the particle groups, and to ensure high-speed solubility of the detergent-adding particle groups. From the viewpoint of satisfying the above requirements and suppressing the classification of the detergent-added particles in the granular detergent composition, it is preferably 170 to 500 m, more preferably Is 180-450 ⁇ m, preferably 190-400 / 111, 200-350 zm is most preferred.
  • the average particle size is preferably close to the average particle size of the detergent particle group (b) described below from the viewpoint of efficiently discontinuing the surfactant layer paste formed by the particle group.
  • the difference between the preferred detergent additive particle group and the detergent particle group (b) is preferably within 350 m, more preferably within 30 O xm, more preferably within 250 m, more preferably within 200 m, more preferably It is preferably within 150 m, more preferably within 100 m, and most preferably within 50 m.
  • the bulk density of the detergent-added particles of the present invention is measured by JIS K3362.
  • the bulk density imparts more excellent high-speed solubility, improves the dispersibility of the granular detergent composition obtained by mixing the detergent-adding particles in a dispenser, and has a preferable bulk density of the granular detergent composition.
  • the detergent additive particle group of the present invention is manufactured by a process including the following processes (X) and (Y).
  • the solution is a water-soluble substance or an aqueous solution of a water-soluble substance and a surfactant
  • the suspension is a substance containing an undissolved substance of a water-soluble substance and Z or a water-insoluble substance. Includes slurry and paste forms.
  • the detergent additive particle group of the present invention is produced by including the above-described steps, a step of adjusting the particle size distribution described later can be added as necessary.
  • the particle size distribution adjusting step includes, for example, a crushing and pulverizing step for obtaining a desired particle size, a classifying step by a sieve, a crushing and pulverizing step of coarse particles generated at that time, wind power and several steps of sieve.
  • a step of re-adjusting the particle size distribution using the method can be added.
  • the addition of the particle size distribution adjusting step is such that the particles obtained in the above-mentioned step (Y) emit bubbles, uneven distribution of the composition, have a fine space inside the particles, and further have a hollow portion, and the surface of the particles is open. Then, it is particularly preferred from the viewpoint of imparting high-speed solubility to the particle group, in which the particles have a high-speed solubility due to a particle structure having a shape communicating with the internal hollow portion.
  • a step of post-adding a surfactant and a precursor thereof in an amount limited to the composition range of the detergent-adding particles of the present invention and adding a water-soluble substance in the form of a paste, a slurry or a solution.
  • the total amount of the substance added in the post-addition step is determined in the drying step (Y) in order to sufficiently exhibit the dispersibility improving effect in the dispenser of the particles obtained in the drying step (Y).
  • the weight ratio is preferably 1 Z4 or less, more preferably 1 Z9 or less, more preferably 1 19 or less, more preferably 1 Z49 or less, more preferably 1 Z4 or less with respect to the obtained particle group. Z99 or less, most preferably no additional addition.
  • Process (X) Slurry, etc. should be non-curable as long as they can be sent by pump.
  • each component such as a water-soluble substance in the slurry is as described above.
  • any drying method for example, freeze drying, reduced pressure drying, etc. can be used.
  • the particle structure after drying is 0.2 V / g or more inside the particles.
  • Instantaneous drying of slurry, etc. is required in order to have a structure with pores, a structure with depressions, and a structure with uneven distribution of Z or components that can release bubbles with a diameter of 110 or more with respect to the diameter.
  • a preferred and particularly preferred drying method is a spray drying method.
  • a detergent particle group used in an ordinary granular detergent composition can be used, and the detergent particle group can be produced by any method as long as the detergent particle group has the following composition and powder properties. May be.
  • the detergent particles (b) containing 1 (3% by weight or more) of the surfactant supplement the cleaning performance of the detergent-added particles (a) with the insufficient surfactant.
  • the particles for detergent addition (a) are dry-mixed to form a composite detergent particle group, whereby the effect of improving the dispensing property in the dispenser is more remarkably exhibited.
  • the surfactant having a liquid crystal forming ability is a surfactant in which a lamella type or hexagonal type liquid crystal is observed in a water content range of 0 to 99% and a temperature range of 5 to 70 ° C. 3-1.
  • the surfactant content of the detergent particle group (b) is 10 to 5 in the detergent particle group (b) in order to impart detergency to the composite detergent particle group and to give the detergent particle group desired physical properties.
  • 0% by weight preferably 15 to 49% by weight, more preferably 20 to 48% by weight, more preferably 25 to 47% by weight, particularly preferably 30 to 46% by weight.
  • the detergent particle group contains a yin surfactant and a Z or non-ionic surfactant, and may contain a positive surfactant and an amphoteric surfactant as necessary.
  • the detergent particles may contain a water-soluble substance as a component other than the above-mentioned surfactant.
  • the preferred content of the water-soluble substance is 20 to 90% by weight, and the water-soluble substance used for the detergent particles is the same as the water-soluble substance used for the detergent-added particles described above. Are exemplified.
  • a water-insoluble substance can be contained.
  • the preferred content of the water-insoluble substance is 0 to 70% by weight.
  • Examples of the water-insoluble substance used in the detergent particles include the same as those exemplified in the above-mentioned detergent-addition particles.
  • the average particle size of the detergent particles measured using a JISZ8801 standard sieve is at least 150 m in order to suppress dusting when handling a granular detergent composition comprising the detergent particles. In order to ensure the solubility in the washing tub after the detergent particles have been dispensed from the dispenser, it is 600 m or less, more preferably 170 to 500 m, and more preferably 180 to 450 0 111, more preferably 190 to 40 0 m, most preferably 200-350 m.
  • the bulk density of the detergent particles as measured by JISK 3362 is 500 to 100 gZL, which improves the transport efficiency of the granular detergent composition containing the detergent particles and simplifies the user's use. In consideration of the above, it is preferably 550 to 1000 gZL, more preferably 600 to 1000 gZL, and still more preferably 650 to 1000 gZL, and more preferably 700 to 100 gZL.
  • a method for producing the detergent particles a method of obtaining spray-dried particles from a surfactant or a builder and increasing the density of the particles can be used.
  • a method of increasing the bulk density by stirring and granulating the spray-dried particles with a vertical or horizontal mixer can be mentioned. Examples thereof include a method of stirring and granulating spray-dried particles described in Japanese Patent Application Laid-Open No. 61-96997, and a method of molding dry particles described in Japanese Patent Application Laid-Open No. 62-169900.
  • a temperature at which a mixture of an acid precursor of a nonionic surfactant and an anionic surfactant capable of lamella orientation can be neutralized with a neutralizing agent described in Japanese Patent Application Laid-Open No. H10-176620.
  • a method of granulating while rolling with a stirring granulator can be used o
  • the method may include a step of separating particles to be formed (coarse particles) with a sieve or the like, and the coarse particles may be crushed to be reduced in particle size and used as a detergent particle group.
  • the coarse particle crusher include an impact crusher such as a hammer crusher, an impact crusher such as an atomizer and a pin mill, and a shear crusher such as a flash mill. These may be a single-stage operation or a multi-stage operation of the same or different types of pulverizers. In this case, it is preferable to add fine powder as an in-machine adhesion inhibitor or a pulverized surface modifying agent.
  • the fine powder is preferably an inorganic powder such as aluminosilicate, silicon dioxide, bentonite, talc, clay amorphous silica derivative, and particularly preferably a crystalline or amorphous aluminosilicate. Fine powders of water-soluble substances such as sodium carbonate, sodium sulfate and sodium tripolyphosphate are also used.
  • a surface modification step may be provided for the purpose of fixing and smoothing the surface modifier in order to improve the fluidity of the crushed particles.
  • the composition is fed batchwise or continuously into a rotary cylinder machine or a stirrer to perform rolling or stirring.
  • the composite detergent particles of the present invention are obtained by dry-mixing the above-described detergent-adding particles (a) and the detergent particles (b), and by dry-mixing the detergent-adding particles (a). It has excellent dispersibility from a dispenser and excellent washing performance by dry-mixing the detergent particles (b). That is, a continuous, high-concentration surfactant paste layer formed by the detergent particles (b) when water is injected into the dispenser forms a detergent layer having a specific composition, specific powder properties and high-speed solubility. Discontinuity can be rapidly achieved by the addition particles (a). Furthermore, due to the action of the detergent addition particles (a) dissolving at a high speed in the water injection together with the interruption, the composite detergent particles can be distributed quickly and efficiently in the dispenser.
  • the detergent additive particles (a) and the detergent particles (b) are preferred.
  • the weight ratio of (a) / (b) is preferably from 1/99 to 70/30, more preferably from 298 to 60/40, and still more preferably from 397 to 70/70.
  • the degree of dry mixing of the detergent-adding particles (a) and the detergent particles (b) although the dispersibility improving effect in the dispenser is exhibited even if the degree of mixing is low, the dispersing effect is improved. And the surfactant-containing paste layer formed when water is injected can be more efficiently discontinued by the detergent-adding particles (a). Therefore, from this viewpoint, it is preferable that the degree of dry mixing is high.
  • the difference in the surfactant content of about 20 g of a sample collected at two locations at random was determined by dry mixing.
  • the difference in the surfactant content is preferably within 7%, more preferably within 5%, even more preferably within 3%, and within 1%. Is most preferred.
  • a batch type or continuous type blending method such as a V-type mixer can be used.
  • the granular detergent composition of the present invention contains the above composite detergent particles in an amount of 50 to 100% by weight, and has excellent dispensability from a dispenser. Further, from the viewpoint of further reflecting the excellent dispenser dispensing property of the composite detergent particles in the detergent composition, the content of the composite detergent particles is preferably 60% by weight or more, more preferably 70% by weight or more. Most preferably, it is at least 80% by weight, more preferably at least 80% by weight, more preferably at least 85% by weight, more preferably at least 90% by weight, at least 95% by weight.
  • the preferable content of the detergent-added particles (a) in the granular detergent composition is preferably 1 to 70% by weight, more preferably 2 to 6% by weight, from the viewpoint of achieving both the dispersibility from the dispenser and the cleaning performance. 0% by weight, more preferably 3 to 55% by weight, more preferably 5 to 50% by weight, more preferably 10 to 45% by weight, more preferably 15 to 40% by weight, and 20 to 50% by weight. 35% by weight is most preferred.
  • the granular detergent composition of the present invention in which the dispersibility from a dispenser is improved by containing the detergent additive particles (a), includes bleaching agents such as percarbonate and effervescent percarbonate, and granules.
  • bleaching agents such as percarbonate and effervescent percarbonate, and granules.
  • Example 1 Example 1
  • the detergent additive particle group 1 of the present invention was prepared by the method described below. Water 4 1 5 kg was added to the mixing tank lm 3 having a stirring blade, to adjust the water temperature to 5 0 ° C, of 1 3 5 kg, sodium carbonate 1 1 5 kg, 4 0% by weight sodium sulfate polyacrylic 100 kg of an aqueous solution of sodium acid was added. After stirring for a further 15 minutes at 50 ° C while stirring, add 18.5 kg of zeolite and further stir for 30 minutes while controlling the temperature at 50 ° C to obtain a homogeneous slurry. Was.
  • This slurry was supplied to a spray drying tower by a pump, and sprayed at a spray pressure of 25 kg / cm 2 from a pressure spray nozzle installed near the top of the tower.
  • the high-temperature gas supplied to the spray drying tower was supplied at a temperature of 220 ° C from the lower part of the tower, and was discharged at 103 ° C from the top of the tower.
  • the particles for coarse detergent addition obtained from the bottom of the tower are reduced to a water content of 5% by weight. It was dried in a fluidized bed with hot air at 100 ° C.
  • the obtained coarse particles of the particle group were removed by a sieve of 1.410; tm to obtain Particle Group 1 for detergent addition.
  • Table 1 shows the composition and physical properties of the obtained Particle Group 1.
  • the pore volume of 0.01 to 4 of the detergent addition particle group 1 measured with a mercury porosimeter was 0.40 mL / g.
  • bubbles having a particle diameter of 1Z10 or more were released from 92% of the particles.
  • the average value of the bubble diameter and particle diameter released from the 92% particles was 5.8 / 10.
  • an analysis of the depressed hole was performed for the detergent-added particle group 1. As a result, it contained 82% of depressed particles having one or more holes having a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the circle equivalent diameter of the particles.
  • the average of [the circular equivalent diameter of the hole] equivalent to the dented hole X100 determined for the 82% of the depressed particles was 22%.
  • the average depth of the depressions was 50% of the equivalent circle diameter of the particles.
  • particles 1 for detergent addition were analyzed by FT-IRZPAS and EDS, the ratio of zeolite was high inside the particles, and water-soluble polymers and inorganic It was confirmed that the particles had a structure with a high salt ratio and uneven distribution.
  • the detergent additive particle group 2 of the present invention was prepared by the method described below.
  • Water 3 9 0 kg was added to mixing tank lm 3 having a stirring blade, to adjust the water temperature to 5 0 ° C, it was added 5 0 wt% of alkyl benzene sulfonic acid Natoriumu aqueous 5 0 kg. After stirring for 15 minutes, 125 kg of sodium sulfate and 100 kg of an aqueous solution of sodium polyacrylate of 110 k.40% by weight were added. Further in After stirring while a temperature adjusted to 5 0 e C 1 5 minutes, the addition of Zeoraito 1 75 kg, to obtain a homogeneous slurry was stirred while a further temperature adjusted to 3 0 min 5 0 ° C .
  • This slurry was supplied to a spray drying tower by a pump, and spraying was performed at a spray pressure of 25 kg / cm 2 from a pressure spray nozzle installed near the top of the tower.
  • the high-temperature gas supplied to the spray drying tower was supplied at a temperature of 218 ° C from the bottom of the tower, and was discharged at a temperature of 101 ° C from the top of the tower.
  • the particles for crude detergent addition obtained from below the column were dried in a fluidized bed with hot air at 100 ° C. until the water content became 5% by weight.
  • the coarse particles of the particle group were removed by a sieve of 1.410 m to obtain a particle group 2 for detergent addition.
  • Table 1 shows the composition and physical properties of the obtained Particle Group 2.
  • the pore volume of 0.01 to 4 m measured with a mercury porosimeter was 0.44 mLZg.
  • bubbles having a particle diameter of 10 or more were released from 88% of the particles.
  • the average value of the bubble diameter Z particle diameter released from the above 88 particles was 6.0 / ⁇ 0.
  • the average of [the equivalent circle diameter of the hole Z, the equivalent circle diameter of the particle] X100 of the recessed hole determined for the 11% of the recessed particles was 14%.
  • the average depth of the depression was 61% of the equivalent circle diameter of the particle.
  • Particle group 3 for detergent addition of the present invention was prepared by the method described below.
  • This slurry is supplied to the spray drying tower by a pump, and the pressure spray nozzle installed near the top of the tower is used. Spraying was performed from the spill at a spray pressure of 25 kg / cm 2 .
  • the high-temperature gas supplied to the spray-drying tower was supplied at a temperature of 228 ° C from the lower part of the tower and discharged at 100 ° C from the top of the tower.
  • the coarse detergent additive particles obtained from below the tower were dried with hot air at 100 ° C. in a fluidized bed until the water content became 5% by weight.
  • the obtained coarse particles of the particle group were removed by a sieve of 1.410 zm to obtain a particle group 3 for detergent addition.
  • Table 1 shows the composition and physical properties of the obtained Particle Group 3.
  • the pore volume of 0.01 to 4 / zm measured by a mercury porosimeter was 0.50 mLZg.
  • bubbles having a particle diameter of 1Z10 or more were released from 90% of the particles.
  • the average value of the bubble diameter and the particle diameter released from the above 90% of the particles was 6.3 / ⁇ 0.
  • the results of the analysis of the depressed holes for the detergent addition particle group 3 were performed. It contained 27% of depressed particles having one or more holes having a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the circle equivalent diameter of the particles.
  • the average of [equivalent circle diameter of the hole] equivalent to the dented holes X100 determined for the 27% of the depressed particles was 18%.
  • the average of the depth of the depression was 68% with respect to the equivalent circle diameter of the particle.
  • the detergent addition particle group 3 was analyzed by FT-IRZ PAS and EDS, the ratio of the polymer inside the particles was low, and the ratio of the polymer was high near the particle surface. Was confirmed.
  • the detergent additive particle group 4 of the present invention was prepared by the method described below.
  • the pore volume of 0.01 to 4 / m measured with a mercury porosimeter was 0.38 mLZg.
  • the results of the analysis of the sinking hole for the detergent addition particle group 4 were performed. It contained 80% of depressed particles having one or more holes having a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the equivalent circle diameter of the particles.
  • the average of [the equivalent circle diameter of the hole Z, the equivalent circle diameter of the particle] X100 of the depression hole obtained for the 80% of the depression particles was 21.
  • the average depth of the depression was 49% with respect to the equivalent circle diameter of the particles.
  • the detergent additive particle group 5 of the present invention was prepared by the method described below.
  • the pore volume of 0.01 to 4 zm measured by a mercury porosimeter was 0.21 mLZg. Also, the results of observing the dissolution behavior with a digital microscope It was confirmed that bubbles having a particle diameter of 1 Z 10 or more were released from 9% of the particles. (The average value of the bubble diameter Z particle diameter released from the above 9% of the particles was 1.7 / 10.)
  • the results of the analysis of the sinking hole for the detergent addition particle group 5 were performed. Depressed particles having one or more holes having a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the equivalent circle diameter of the particles were not observed. Further, when particle group 5 for detergent addition was analyzed by FT-IRZPAS and EDS, no clear uneven distribution was observed. Comparative particle group 1 as a comparative example of the present invention was prepared by the method described below.
  • This slurry was supplied to a spray drying tower by a pump, and spraying was performed at a spray pressure of 25 kgZcm 2 from a pressure spray nozzle installed near the top of the tower.
  • the hot gas supplied to the spray-drying tower was supplied at a temperature of 222 from the bottom of the tower, and was discharged at 105 ° C from the top of the tower.
  • the particles obtained from below the column were dried in a fluidized bed with hot air at 100 ° C. until the water content became 5% by weight.
  • the coarse particles of the obtained particle group were removed by a sieve of 1.410 m to obtain Comparative Particle Group 1.
  • Table 1 shows the composition and physical properties of Comparative Particle Group 1.
  • the pore volume of 0.01 to 4 tzm measured by a mercury porosimeter was 0.43 mLZg.
  • bubbles having a particle diameter of 1Z10 or more were released from 85% of the particles.
  • the average value of the bubble diameter Z particle diameter released from the above 85% particles was 6.2 / ⁇ 0.
  • the particles It contained 8% of depressed particles having one or more holes having a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the circle equivalent diameter.
  • Comparative particle group 2 as a comparative example of the present invention was prepared by the method described below.
  • the batch kneader equipped with a jacket was heated to 50 ° C., 20.5 kg of water was added, and 9 kg of a 50% by weight aqueous solution of sodium alkylbenzenesulfonate was added. After stirring for 15 minutes, 6.9 kg of sodium sulfate, 6 kg of sodium carbonate, and 5.25 kg of a 40% by weight aqueous solution of sodium polyacrylate were added. After stirring for 15 minutes while adjusting the temperature to 50 ° C, 9 kg of zeolite was added, and after stirring for 30 minutes while adjusting the temperature to 50 ° C, the temperature of the jacket was lowered.
  • Comparative Particle Group 2 The temperature was raised to 80 and the pressure in the mixing tank of the batch kneader was reduced to dryness until the water content became 5% by weight. The coarse particles of the obtained particle group were removed by a sieve of 1000 zm to obtain Comparative Particle Group 2. Table 1 shows the composition and physical properties of Comparative Particle Group 2.
  • the pore volume of 0.0 l to 4 m measured by mercury porosimetry was 0.19 mLZg. Further, as a result of observing the dissolution behavior with a digital microscope, it was confirmed that bubbles having a particle diameter of 1Z10 or more were released from 8% of the particles. (Note that the average value of the bubble diameter and the particle diameter released from the above 8% particles is 1.6 / 1 It was 0. In addition, as a result of analyzing the collapsed hole for the comparative particle group 2, it was found that at least one hole with a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the circle equivalent diameter of the particle was found. No sinking particles were found.
  • Neo Belex F65 manufactured by Hanashi
  • Emulgen 108KM, average addition mole number of ethylene oxide 8.5 (manufactured by Kao Corporation)
  • Detergent particle group 1 was prepared by the method described below.
  • the raw materials of the detergent particle group 1 shown in Table 2 components excluding 50% by weight of the polyoxyethylene alkyl ether compounding amount, the total amount of the crystalline silicate compounding and 50% by weight of the zeolite compounding amount
  • the slurry having a water content of 48% was spray-dried to obtain a spray-dried dough having a bulk density of 310 g ZL.
  • the spray-dried dough is put into a high-speed mixer (agitated tumbling granulator, equipped with a jacket, manufactured by Fukae Kogyo Co., Ltd.), and 20% by weight of zeolite compounding amount and crystalline silicate are mixed.
  • Detergent particle group 2 was prepared by the method described below.
  • the spray-dried dough is put into a high-speed mixer (agitated tumbling granulator, equipped with a jacket, manufactured by Fukae Kogyo Co., Ltd.), and the weight of 20 weight of zeolite and the weight of crystalline silicate The total amount was added, and the remaining 50% by weight of the polyoxyethylene alkyl ether, which had been heated to 70 ° C, was spray-added to perform the granulation operation.
  • a granulated product was obtained by surface treatment with the addition of 20% by weight. Further, detergent particles are used for the granules. The same treatment as in group 1 was performed to obtain detergent particle group 2.
  • Detergent particle group 3 was prepared by the method described below.
  • Moisture content of 50% by weight including sodium polyacrylate, PEG, sodium sulfate, sodium sulfite, stone, 50% by weight of fluorescent dye and 50% by weight of zeolite, and 50% by weight of sodium carbonate The slurry was spray-dried to obtain a spray-dried dough having a bulk density of 460 g ZL. The remaining 50% by weight of the total amount of the obtained spray-dried dough, the amorphous aluminosilicate and the crystalline silicate and the sodium carbonate was added to a Loedige mixer, and stirring was started. Hot water at 40 ° C was flowed through the jacket. The total blended amount of polyoxyethylene alkyl ether heated to 70 ° C was added by spraying to perform granulation.
  • a granulated product was obtained by adding 30% by weight of zeolite and subjecting to surface treatment.
  • the obtained granules are sieved with a sieve having a mesh size of 1.410 cm, and 20% by weight of the zeolite compounding amount is added to coarse particles having a particle size of 140 mm or more, and a balverizer is added. (Pulverizer manufactured by Hosokawa Micron Co., Ltd.), and then mixed with the material passed through a sieve to obtain detergent particle group 3.
  • the detergent additive particle groups 1 to 5 and the comparative particle group 1 to 5 of the present invention and the detergent particle groups 1 to 3 were each assigned a weight ratio of 5Z95, 10 / 90.30Z70 as V
  • the composite detergent particles of the present invention and the composite detergent particles as a comparative example were obtained by dry-mixing for 5 minutes with a mold mixer.
  • 1 part by weight of the enzyme granulated product (cellulase (Kao Corporation, "KAC500”) is added to the detergent particles 1 to 3 and the composite detergent particles 99 to 9 parts by weight.
  • 0.3 parts by weight of protease Novo Nordisk, "Sapinase 12.0T-WJ"
  • 0.3 parts by weight of lipase (Noponordisk, 100% by weight of Ribolase 100 TJ) was added and dry-mixed with a V-type mixer for 5 minutes to obtain a granular detergent composition of the present invention and a granular detergent composition as a comparative example.
  • the dispersibility of the granular detergent composition obtained above in a dispenser of a drum type washing machine was evaluated by the following method.
  • Detergent particle group o / ioo (weight ratio)
  • Detergent particles 5Z95 (weight ratio)
  • Detergent particles 30 70 (weight S ratio)
  • the detergent-adding particles of the present invention have an effect of increasing the distribution of a granular detergent composition obtained by mixing the detergent particles with running water, and the granular detergent composition is applied to a washing machine such as a drum-type washing machine.
  • a washing machine such as a drum-type washing machine.
  • the particulate detergent composition is well distributed in the irrigation tub and the troubles remaining as agglomerates in the dispenser are improved.

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Abstract

L'invention porte sur des particules (a) destinées à être ajoutées à un détergent qui comprennent entre 30 et 100 % en poids d'au moins deux sortes de substances solubles dans l'eau et qui ont un diamètre moyen compris entre 150 et 600 νm, un poids volumique apparent compris entre 300 et 1000 g/L et une solubilité calculée selon l'équation (1) égale ou supérieure à 90 %. L'invention porte également sur un détergent composite particulaire obtenu par mélange sec des particules (a) et des particules détergentes (b) dont le diamètre moyen est compris entre 150 et 600 νm, le poids volumique apparent entre 300 et 1000 g/L et une teneur en tensioactif comprise entre 10 et 50 % en poids. L'invention porte d'autre part sur une composition détergente particulaire comprenant entre 50 et 100 % du détergent composite particulaire. Les particules d'addition au détergent ont une excellente capacité à se dissoudre rapidement. Le détergent et la composition détergente présentent donc une excellente distribution lorsque l'eau est introduite dans le distributeur d'une machine à laver à tambour, d'une machine à laver entièrement automatique, etc. Equation (1): solubilité (%) = [1 (T/S)] x 100; S: quantité de particules ajoutées pour addition (g) au détergent; T: quantité sèche de résidu sur le tamis après mélange (g).
PCT/JP2000/003857 1999-06-16 2000-06-14 Particules d'addition a un detergent Ceased WO2000077159A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2001503996A JP3249815B2 (ja) 1999-06-16 2000-06-14 洗剤添加用粒子群
EP00939055.0A EP1193310B2 (fr) 1999-06-16 2000-06-14 Particules d'addition a un detergent
DE60040462T DE60040462D1 (de) 1999-06-16 2000-06-14 Teilchenförmiges waschmitteladditiv

Applications Claiming Priority (2)

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JP11/170127 1999-06-16
JP17012799 1999-06-16

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WO2000077159A1 true WO2000077159A1 (fr) 2000-12-21

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EP (1) EP1193310B2 (fr)
JP (1) JP3249815B2 (fr)
DE (1) DE60040462D1 (fr)
WO (1) WO2000077159A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2003183699A (ja) * 2001-12-21 2003-07-03 Kao Corp 粉末洗剤組成物
JP2006056985A (ja) * 2004-08-19 2006-03-02 Kao Corp 洗剤組成物
CN100545254C (zh) * 2003-02-06 2009-09-30 狮王株式会社 粒状洗涤剂组合物及其生产方法
JP2022026081A (ja) * 2020-07-30 2022-02-10 ライオン株式会社 衣料用粒状洗剤組成物及び衣料用粒状洗剤組成物の製造方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3352977B2 (ja) 1999-06-15 2002-12-03 花王株式会社 固形状洗剤
WO2007020949A1 (fr) * 2005-08-15 2007-02-22 Kao Corporation Procédé de lavage et composition de détergent en poudre
WO2025108695A1 (fr) 2023-11-22 2025-05-30 Unilever Ip Holdings B.V. Composition de lessive

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JPS5548300A (en) * 1978-09-14 1980-04-05 Mizusawa Industrial Chem Granular detergent builder composition
GB2097419A (en) * 1981-02-26 1982-11-03 Colgate Palmolive Co Base beads for manufacture of detergent compositions
EP0168102A2 (fr) * 1984-07-06 1986-01-15 Unilever N.V. Procédé de préparation d'une composition détergente en poudre à densité en vrac élevée
EP0342043A2 (fr) * 1988-05-13 1989-11-15 The Procter & Gamble Company Compositions détergentes granulaires
EP0466485A2 (fr) * 1990-07-13 1992-01-15 Unilever Plc Compositions détergentes
WO1992006167A1 (fr) * 1990-10-08 1992-04-16 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage contenant du percarbonate
WO1994016052A1 (fr) * 1993-01-08 1994-07-21 Unilever Plc Composition detergente et son procede de production
WO1999029830A1 (fr) * 1997-12-10 1999-06-17 Kao Corporation Particules detergentes
WO2000023560A1 (fr) * 1998-10-16 2000-04-27 Kao Corporation Procede de fabrication de particules de detergent

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JPS5548300A (en) * 1978-09-14 1980-04-05 Mizusawa Industrial Chem Granular detergent builder composition
GB2097419A (en) * 1981-02-26 1982-11-03 Colgate Palmolive Co Base beads for manufacture of detergent compositions
EP0168102A2 (fr) * 1984-07-06 1986-01-15 Unilever N.V. Procédé de préparation d'une composition détergente en poudre à densité en vrac élevée
EP0342043A2 (fr) * 1988-05-13 1989-11-15 The Procter & Gamble Company Compositions détergentes granulaires
EP0466485A2 (fr) * 1990-07-13 1992-01-15 Unilever Plc Compositions détergentes
WO1992006167A1 (fr) * 1990-10-08 1992-04-16 Henkel Kommanditgesellschaft Auf Aktien Produit de lavage contenant du percarbonate
WO1994016052A1 (fr) * 1993-01-08 1994-07-21 Unilever Plc Composition detergente et son procede de production
WO1999029830A1 (fr) * 1997-12-10 1999-06-17 Kao Corporation Particules detergentes
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003183699A (ja) * 2001-12-21 2003-07-03 Kao Corp 粉末洗剤組成物
CN100545254C (zh) * 2003-02-06 2009-09-30 狮王株式会社 粒状洗涤剂组合物及其生产方法
JP2006056985A (ja) * 2004-08-19 2006-03-02 Kao Corp 洗剤組成物
JP2022026081A (ja) * 2020-07-30 2022-02-10 ライオン株式会社 衣料用粒状洗剤組成物及び衣料用粒状洗剤組成物の製造方法

Also Published As

Publication number Publication date
JP3249815B2 (ja) 2002-01-21
EP1193310B1 (fr) 2008-10-08
EP1193310A1 (fr) 2002-04-03
EP1193310B2 (fr) 2016-06-29
EP1193310A4 (fr) 2004-07-28
DE60040462D1 (de) 2008-11-20

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