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WO2000077160A1 - Detergent particulaire - Google Patents

Detergent particulaire Download PDF

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Publication number
WO2000077160A1
WO2000077160A1 PCT/JP2000/003872 JP0003872W WO0077160A1 WO 2000077160 A1 WO2000077160 A1 WO 2000077160A1 JP 0003872 W JP0003872 W JP 0003872W WO 0077160 A1 WO0077160 A1 WO 0077160A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent
detergent particles
weight
water
particles
Prior art date
Application number
PCT/JP2000/003872
Other languages
English (en)
Japanese (ja)
Inventor
Hiroyuki Saijo
Hitoshi Takaya
Hideichi Nitta
Shu Yamaguchi
Hiroyuki Yamashita
Original Assignee
Kao Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corporation filed Critical Kao Corporation
Priority to EP00937229A priority Critical patent/EP1186651A4/fr
Publication of WO2000077160A1 publication Critical patent/WO2000077160A1/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
    • C11D3/046—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a detergent particle group and a detergent composition containing the detergent particle group.
  • Heavy-duty detergents are used for washing in a washing machine, but may be used for hand-washing when there is a lot of soil on the fiber.
  • hand-washing it has been empirically known that if a heavy detergent solution is applied to soil, the use of heavy-duty detergent directly on the part to be washed wet with water will result in good washing efficiency. ing. In this case, sufficient foaming is required to improve slippage between the fibers in order to rub the portions to be washed together or the portion to be washed and another fiber portion by hand.
  • a powdered heavy detergent containing a phosphate builder containing a large amount of an anionic surfactant has an advantage that it shows sufficient foaming during hand washing and has a good slip between objects to be washed.
  • a powdered heavy detergent containing a phosphate builder containing a large amount of an anionic surfactant has an advantage that it shows sufficient foaming during hand washing and has a good slip between objects to be washed.
  • the fluidity of the powder is high.
  • washing machines are being designed in consideration of consumer demand, water saving and energy saving.
  • Japanese-made washing machines have been increasing in capacity and conserving water since the mid-1990s, and have been set to a short-time washing mode, or a weak agitation mode that appeals to reduce clothing damage.
  • These are all the work load of the washing machine (mechanical power X time)
  • European and American washing machines it is important to lower the washing temperature from the viewpoint of energy saving during washing, and a detergent with good solubility is required.
  • an acid precursor of an anionic activator is dry-neutralized with a granular solid alkali agent and then granulated by adding a liquid binder.
  • These compositions had high foaming properties due to the high mixing ratio of anionic surfactant / nonionic surfactant, but had insufficient solubility. If the obtained detergent particles are simply atomized to improve solubility, the powder fluidity is low, making it difficult for the detergent powder to act on clothing during hand washing and low water temperature in the washing machine. There was a problem that detergent particles aggregated during washing in the washing machine.
  • a substrate bead containing a phosphate builder is sprayed with about 12 to 30% by weight of a nonionic activator.
  • a detergent containing phosphate builder which has a characteristic high fluidity.However, the solubility is insufficient, and the foaming properties are insufficient due to the high content of nonionic activator.
  • Japanese Examined Patent Publication No. 6-49789 states that, as a surfactant composition suitable for a washing method, it is desirable for a product for hand washing to contain a relatively large amount of an anionic surfactant. Have been. In order to make washing by hand washing more efficient, high fluidity and a high dissolution rate resulted in fast foaming and easy washing, and no detergent containing phosphate builder was obtained. Disclosure of the invention
  • An object of the present invention is to improve the particle solubility and fluidity of a phosphate-containing high-density powder detergent containing a highly foaming anionic surfactant in order to improve the ease of washing during hand washing.
  • An object of the present invention is to provide an enhanced detergent particle group and a detergent composition containing the detergent particle group.
  • Another object of the present invention is to provide a phosphate-containing and high-density detergent particle having excellent detergency because of its excellent particle solubility and dispersibility even when the work load of the washing machine and the washing temperature are low. And a detergent composition comprising the detergent particles.
  • a group of detergent particles containing a phosphate builder having an average particle size of 150 to 500 fim ⁇ , a bulk density of 500 gZL or more, and a flow time of 10 seconds or less.
  • the detergent particle group contains detergent particles capable of releasing bubbles having a particle size of 1 Z10 or more from the inside of the particles during the process of dissolving in water, and the detergent particle group contains 5 particles of water.
  • Dissolution rate (%) ⁇ 1-(T / S) ⁇ 100 (1)
  • a detergent particle group containing phosphate builder having an average particle size of 150 to 5
  • a group of detergent particles comprising a base granule containing a water-soluble salt and a surfactant carried thereon, wherein the base granule has an uneven distribution in which a larger amount of a water-soluble polymer is present near the surface than inside the base granule in its structure.
  • a detergent composition comprising 50% by weight or more of the detergent particles according to [1] or [2].
  • FIG. 1 is a graph comparing the results of FT-IRZ PAS measurement of the base granule group 1 as it is or the base granule group 1 uniformly ground.
  • the solid line is the data of the base granules as they are, and the dashed line is the data of the base granules in a uniformly ground state.
  • BEST MODE FOR CARRYING OUT THE INVENTION The detergent particles in the present invention are particles containing a surfactant, a builder and the like, and the detergent particle group means an aggregate thereof.
  • the detergent composition contains the detergent particles, and further contains detergent components (eg, builder granules, fluorescent dyes, enzymes, fragrances, defoamers, bleaching agents, bleaching agents) which are separately added in addition to the detergent particles. Agent etc.).
  • detergent components eg, builder granules, fluorescent dyes, enzymes, fragrances, defoamers, bleaching agents, bleaching agents
  • the detergent particles of the present invention contain detergent particles capable of releasing bubbles having a particle diameter of lZi0 or more from the inside of the particles during the process of dissolving in water (hereinafter referred to as bubble releasing detergent particles). Do it.
  • bubble releasing detergent particles capable of releasing bubbles having a particle diameter of lZi0 or more from the inside of the particles during the process of dissolving in water.
  • Such a dissolution behavior is such that when the bubble-emitting detergent particles are dissolved in water, the particle size of the particles is 10 to 10 or more, preferably 15 or more, more preferably 1/4 or more, and further preferably The phenomenon of releasing bubbles with a diameter of 1 Z 3 or more (hereinafter referred to as bubbles of a predetermined size) can be confirmed with a digital microscope and an optical microscope.
  • the size of most generated bubbles is less than 1 Z 10 of the detergent particle size, and it does not cause self-disintegration of the particles themselves. I can not get the nature.
  • bubbles of a predetermined size are preferably generated within 120 seconds, more preferably within 60 seconds, and more preferably within 45 seconds. Within a second is more preferred.
  • the bubble releasing detergent particles only need to have pores (single or plural) capable of releasing bubbles of a predetermined size, and are not particularly limited to the shape and structure of the particles.
  • the bubble release detergent particles are preferably contained in a detergent particle group in an amount of 40% by weight or more, more preferably 60% by weight or more, still more preferably 80% by weight or more.
  • the bubble diameter is measured as follows.
  • the equivalent circle diameter (m) of each particle is measured from an image obtained using a digital microscope.
  • the digital microscope for example, “VH-6300J” manufactured by KE YEN CE can be used.
  • the pore diameter can be measured as follows.
  • the cut surface is observed with a scanning electron microscope (SEM), and the equivalent circle diameter (particle diameter) of the cut surface of the cut particles (particle diameter) (7 / m) and, if pores are confirmed inside the particles, are equivalent to the pore circles Measure the diameter (pore diameter) (5 m). If multiple pores are observed, Let the equivalent circle diameter of the largest pore be (5) and find the ratio of the pore diameter to the particle diameter (5a).
  • the bubble releasing detergent particles are mononuclear from the viewpoint of dramatically increasing the dissolution rate.
  • the bubble releasing detergent particles are constituted by base granules described later in the second section
  • the base granules have a particle diameter of 10 to 4/5, preferably 15 to 45 in the inside thereof.
  • a structure having pores is preferred. The pore diameter can be measured by the method described above.
  • the detergent particle group of the present invention high-speed dissolution from the particle surface is recognized separately from or together with the dissolution mechanism by the release of bubbles as described above. It is characterized by a detergent particle group comprising a base particle group containing a phosphate builder, a water-soluble polymer and a water-soluble salt excluding the phosphate builder, and a surfactant carried thereon,
  • the water-soluble polymer is present nearer to the surface than in the inner part, and has the uneven distribution property (hereinafter referred to as the uneven distribution property of the base granules).
  • the base granules in which a large amount of the water-soluble polymer is unevenly distributed near the surface exhibit a dissolving behavior in which the water-soluble components near the surface dissolve faster in water, and the disintegration of the detergent particles from the particle surface is promoted. It can express fast solubility.
  • the most preferred embodiment for exhibiting high-speed solubility is the above-mentioned uneven distribution and also bubble-release detergent particles. In this case, not only mononuclear detergent particles but also polynuclear detergent particles may be used.
  • the base granules constituting the detergent particles of the present invention mainly consist of phosphate builders (A), water-soluble polymers (B), and water-soluble salts (C) excluding phosphate builders. It is composed of particles that are used to carry a surfactant, and the aggregate is called a base particle group.
  • tripolyphosphate, orthophosphate and pyrophosphate are preferred, but the content of tripolyphosphate in the total phosphate builder is at least 60% by weight, more preferably It is preferably at least 70% by weight, more preferably at least 80% by weight. At this time, the content of orthophosphate is preferably 1 to 10% by weight, and the content of pyrophosphate is preferably 2 to 10% by weight. Yes (weight ratio calculated as anhydride). As the counter ion, alkali metals are preferable, and sodium, Z or potassium is particularly preferable. The amount of the phosphate builder is preferably 3 to 60% by weight in the detergent composition.
  • the component (B) examples include a carboxylic acid polymer, carboxymethyl cellulose, soluble starch, and saccharides.
  • a carboxylic acid polymer is preferable.
  • salts of acrylic acid-maleic acid copolymers and polyacrylates are excellent.
  • the molecular weight is preferably from 1,000 to 80,000.
  • polymers such as polyglyoxylate, cellulose derivatives such as carboxymethylcellulose, and aminocarboxylic acid-based polymers such as polyaspartate can also be used.
  • the component (C) is a water-soluble salt excluding the component (A), and includes, for example, inorganic salts such as carbonates, hydrogen carbonates, sulfates, sulfites, hydrogen sulfates, and halides, and citrates. ⁇ Low molecular weight water-soluble organic acid salts such as fumarate salts can be mentioned. Of these, carbonates, sulfates and sulfites are preferred. Particularly preferred are sodium carbonate, potassium carbonate and sodium sulfate.
  • the inorganic salt is preferred since it generates heat of hydration and heat of dissolution by reaction with water after preparation of the base granules, thereby thermally expanding bubbles in the detergent particles and promoting self-disintegration of the particles.
  • sodium carbonate is an alkaline agent that shows a suitable pH buffer region in the washing liquid.
  • alkaline agents include amorphous and crystalline silicates.
  • Amorphous silicate water glass
  • sodium silicate is contained, so that a spray-dried carrier composed of sodium sulfate, sodium carbonate, a nonionic surfactant, and sodium polyacrylate is used as a carrier. It is described that the strength is increased.
  • an amorphous silicate is used to increase the particle strength of the base granules.
  • the content of the amorphous silicate is preferably less than 8% by weight, more preferably less than 5% by weight, more preferably less than 3% by weight, and most preferably substantially no content of the base granules. It is.
  • salts having a high degree of dissociation such as sulfates and sulfites, increase the ionic strength of the washing liquid and suitably act on sebum dirt washing and the like.
  • Sulfite also reduces hypochlorite ion contained in tap water and has the effect of preventing oxidative deterioration of detergent components such as enzymes and fragrances.
  • a base having a large pKCa2 + and a large Z or cation exchange capacity is preferable in view of the ability to sequester a metal ion.
  • anions different from carbonates such as sulfates and sulfites and cations different from sodium such as potassium and ammonium are mixed in the base granules, the effect of masking resistance is obtained. .
  • component (A) is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, and most preferably 15 to 60% by weight.
  • the component (B) is preferably 2 to 30% by weight, more preferably 3 to 20% by weight, and 5 to 20% by weight. Most preferred.
  • the content is preferably 5% by weight or more, more preferably 7% by weight.
  • Component (C) is preferably from 5 to 78% by weight, more preferably from 10 to 70% by weight, further preferably from 10 to 67% by weight, particularly preferably from 20 to 60% by weight, and preferably from 20 to 60% by weight. 55% by weight is most preferred.
  • the amount of the amorphous silicate in the base granules is preferably less than 3% by weight, more preferably 1% by weight, from the viewpoint of solubility. Less, most preferably substantially free of.
  • the amount of the water-soluble polymer is preferably 2% by weight or more, preferably 4% by weight or more, more preferably 6% by weight or more, and 30% by weight or less, preferably 25% by weight or less. More preferably, it is not more than 20% by weight.
  • the base granule is suitable for taking a structure in which the vicinity of the surface is coated with a water-soluble polymer, the coating layer on the surface of the particle is sufficiently formed, and the particle strength may be sufficient. It is also preferable in terms of solubility of the detergent composition.
  • an auxiliary component such as a fluorescent dye, a pigment, or a dye may be included in the base granule group.
  • a water-insoluble inorganic substance such as zeolite in order to enhance the uneven distribution of the base granules.
  • a surfactant particularly an anionic surfactant
  • the content of anionic surfactant in the base granules is preferably less than 10% by weight, more preferably less than 7% by weight, and even more preferably less than 5% by weight. It is preferable that the anionic surfactant is contained in a mixed solution of surfactants described below and is supported on the base granules.
  • water-insoluble inorganic substance those having an average primary particle size of 0.1 to 20111 are preferable, for example, crystalline or amorphous aluminosilicate, silicon dioxide, hydrated silicate compound, There are clay compounds such as perlite and bentonite.
  • the surfactant is not essentially an essential component of the base granules, but may be added to the slurry prepared in step (a). It may be added to improve the drying efficiency in step (b).
  • the addition amount is preferably 10% by weight or less in the slurry, more preferably 0.1 to 10% by weight, and most preferably 0.1 to 5% by weight. These amounts are based on the solid content of the slurry.
  • Factors that improve the loading capacity of the base granules include the use of both carbonates and sulfates as water-soluble salts excluding phosphate builders. It is preferable to use 10% by weight or more of sodium carbonate or Z and potassium carbonate as carbonates and 3% by weight or more of sodium sulfate as sulfates in the base granules. In particular, when the content of the phosphate builder is lower than 20% by weight, it is more preferable to use such that the ratio of sodium sulfate / carbonate is 21 to 1Z4. .
  • Another factor that improves the ability to carry the base granules is to use a base having a large carrying capacity (oil absorption capacity) for water-insoluble inorganic substances. For example, A-type zeolite is preferable in terms of metal ion sealing ability and economy. Here, type A zeolite, J I S K
  • the value of the oil absorption capacity according to the 5101 method is 4 OmL / 100 g or more (for example, trade name: Toyovirda-1; manufactured by Tosoh-1 Co., Ltd.).
  • P type for example, Douci 1 A24 and ZSE 064, etc .; manufactured by Crossfield; oil absorption capacity 60 to 15 OmL / 100 g
  • X type for example, trade name: We ssa 1 it hXD; manufactured by Degussa; oil absorption capacity: 80 to 10 OmLZl 100 g
  • hybrid zeolite described in W098 / 42622 pamphlet for example, trade name: Toyovirda-1; manufactured by Tosoh-1 Co., Ltd.
  • P type for example, Douci 1 A24 and ZSE 064, etc .; manufactured by Crossfield; oil absorption capacity 60 to 15 OmL / 100 g
  • X type for example, trade name: We ssa 1 it hXD; manufactured by Deguss
  • amorphous silica and amorphous aluminosilicate which have a low metal ion sequestering ability but a high oil absorbing ability, can also be used as the water-insoluble inorganic substance.
  • Non-patented aluminosilicates (oil absorption capacity 285 mLZl 0 g) described in column 2 line 18 to column 3 line 47 of JP-A No. 8-119622 can be exemplified.
  • Tokuseal NR (Tokuyama Soda Co., Ltd.: oil-absorbing ability 2 1 0 ⁇ 27 OmL Zl OO g)
  • FLORITE (same: oil-absorbing ability 4 0 0 ⁇ 600mL / / 1 0 0 g)
  • Oil-absorbing carriers such as I XOLEX 25 (manufactured by Han France Chemical Co., Ltd .: oil absorption capacity 2 SOZT OmLZl OO g) and Silopure (manufactured by Fuji Divison Co., Ltd .: oil absorption capacity 240-280 mLZl 100 g) can be used. .
  • the oil absorbing carrier is disclosed in
  • FT-IR Fourier transform infrared spectroscopy
  • PAS photoacoustic spectroscopy
  • FT—I RZPAS is the material of the substance in the depth direction from the surface of the sample as described in APPL IED S PECTROSCOPY vol. 4 7 1 3 1 1—1 3 16 (1993). The distribution state can be confirmed, and the measurement method is exemplified below.
  • the structure of the base granule can be specified by filling the cell with the base granules in two different states, performing FT-IR PAS measurement, and comparing the results.
  • FT-IR / PAS measurement was performed on the base granules while maintaining the target structure, and the comparative sample was FT-IR / PAS of the base granules, which were sufficiently ground in an agate mortar or the like to make them uniform.
  • Perform the measurement is performed, for example, using an FTS-600A / 896 type infrared spectrophotometer manufactured by Bio-Rad Laboratories, and using a 300 type photoacoustic detector manufactured by MTEC as a PAS cell.
  • 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 base granule to about 10 m. PAS of the base granule In the spectrum, for example, the characteristic peaks of sodium tripolyphosphate and sodium polyacrylate each have a peak near 900 cm 1 (an antisymmetric stretching vibration of P ⁇ P, and a broad peak extending from 850 to 950 cm 1). ) And 1 576 cm— 1 (reverse symmetrical stretching vibration of CO 2 —) Read the area intensity of the peaks.
  • the relative area intensity of the characteristic peak of the water-soluble polymer to the characteristic peak of the phosphate builder and the characteristic peak of the water-soluble polymer to the characteristic peak of the phosphate builder determined in each case .
  • Can be by comparing the relative area intensity identify structural features of base granules also if it contains Zeoraito based granules, Zeorai Bok characteristic peak (1 00 9 cm- 1; S i — 0— Structural characteristics of the base granules used to compare the relative area intensity of the characteristic peaks of the water-soluble polymer with respect to the inverse symmetric stretching vibration of Si) can be estimated.
  • the relative area intensity to the characteristic peak of phosphate builder such as triribophosphate when measured while maintaining the uneven distribution structure of the components is the phosphorus when crushed and measured as a uniform state.
  • the ratio of the relative area intensity to the characteristic peak of the salt builder is calculated, the ratio of water-soluble polymer Above, preferably 1.3 or more, more preferably 1.5 or more. It can be said that it has an eccentric structure when it has these relative area strengths.
  • water-soluble salts such as carbonates other than phosphate builder are unevenly distributed so that the relative area intensity with respect to the characteristic peak of phosphate builder is 1.1 or more, preferably 1.3 or more. Is also a preferred embodiment of the present invention.
  • FT-IR / PAS was measured with the base granules as they were or evenly ground, and the results normalized by the peak intensity of sodium tripolyphosphate are shown in Fig. 1. From Fig. 1, the relative area strength of sodium polypolyacrylate to sodium tripolyphosphate when the base granules are measured as they are is higher than the relative area strength when the measurements are made in a uniform state after grinding. I understand. In the first view carbonate Natoriumu: - also seen as a high summer and has this relative area intensity for Toriboririn acid Natoriu ⁇ of (characteristic peaks 1434 cm- 1 C 0 3 2 Shin contraction motion). In addition, as the base granules illustrated in FIG. 1, the base granule group 1 of the product of the present invention shown in Examples described later was used.
  • EDS energy dispersive X-ray spectroscopy
  • EPMA electron probe micro-folding
  • Elements measured for C, Na, P, S and, when zeolite, etc. are used on the cut surface of the base granule particles obtained by embedding the base granule particles in a resin and cutting out with a microtome, etc.
  • the distribution of elements is such that there are many elements such as Na, S, and C outside the particle cross section, P, Al, and Si in the center, many water-soluble polymers near the surface, and phosphoric acid in the center It is possible to confirm the structure of salt builder and also base granules containing a large amount of water-insoluble inorganic substances. 4.
  • the detergent particles of the present invention preferably contain mononuclear detergent particles from the viewpoint of the fluidity and high-speed solubility of the detergent particles.
  • mononuclear detergent particles refers to detergent particles in which a surfactant is supported on base granules, and one detergent particle having one base granule as a core.
  • the degree of particle growth defined by the following formula can be used, and is preferably 1.5 or less, more preferably 1.3 or less, and particularly preferably 1.2 or less.
  • Particle growth degree (average particle size of final detergent particle group) Z (average particle size of base particle group)
  • the final detergent particle group is a group of detergent particles after a surfactant is loaded on the base particle group, Or any of the detergent particles obtained by subjecting the particles to a surface modification treatment.
  • examples of the surfactant supported on the base granule include one or more of an anionic surfactant and a nonionic surfactant, and if necessary, an amphoteric surfactant and a cationic surfactant.
  • anionic surfactant examples include a sulfate, an alkylbenzene sulfonate, a paraffin sulfonate, a paraffin sulfonate, a monosulfide sulfonate, a monosulfo fatty acid salt of an alcohol or an alkoxylated product thereof, and an ester salt or a fatty acid salt thereof.
  • a linear alkylbenzene sulfonate having an alkyl chain having 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms is preferable, and as a counter ion, alkali metals and diamines are preferable. Potassium, monoethanolamine and diethanolamine are preferred.
  • nonionic surfactants include polyoxyalkylene alkyl ether, alkyl polyglycoside, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbin fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene.
  • Block polymer Lioxyalkylene alkylolamide and the like.
  • the amount of the surfactant is preferably 5 to 80 parts by weight, more preferably 5 to 60 parts by weight, and more preferably 10 to 60 parts by weight, based on 100 parts by weight of the base granules. Preferred is 20 to 60 parts by weight, especially preferred.
  • the loading amount of the anionic surfactant is preferably 1 to 60 parts by weight, more preferably 1 to 50 parts by weight, and particularly preferably 3 to 40 parts by weight.
  • the loading amount of the nonionic surfactant is preferably 1 to 45 parts by weight, more preferably 1 to 35 parts by weight, and preferably 4 to 25 parts by weight.
  • the anionic surfactant and the nonionic surfactant are preferably used as a mixture in view of foaming properties at the time of hand washing, detergency, and physical properties of the surfactant mixture to be carried.
  • the mixing ratio (weight ratio) of the anionic surfactant Z and the nonionic surfactant is 4Z1 to 1Z3, preferably 3Z1 to 1Z2, and more preferably 2Z1 to 1Z1.5.
  • an amphoteric surfactant or a cationic surfactant can be used in combination.
  • the amount of the surfactant carried here does not include the amount of the surfactant when the surfactant is added during the slurry preparation in the step (a) of Section 5.1 described later. Oh.
  • Preferred physical properties of the base granules used in the present invention are as follows. 4.1 Physical Properties of Base Granules
  • the bulk density is measured by a method specified by JISK3362. Within this range, the detergent particles have a good bulk solubility with a bulk density of 500 gZL or more. Is obtained.
  • the average particle size is determined using a sieve specified in JIS Z8801.
  • the aperture is 2 0 0 0 jum, 1 4 0 0 / m, 1 0 0 0 m, 7 1 0 m, 5 0 0 jam, 3 5 5 ⁇ m, 2 5 0 jum, 1 8 0 ⁇ m, Using a 9-stage sieve and a pan of 125 1m, attached to a low tapping machine (manufactured by HE IK ⁇ SE I SAKUSHO, tapping: 156 times, rolling: 290 times / minute), 10 After sieving the 0 g sample for 10 minutes with shaking, the pan, 125 m, 180 m, 250 m, 350 m, 500 m, 710 m , 100 000 m, 140 000 m, and 200 000 m in order, the weight frequency is accumulated on the pan and each sieve.
  • the sieve used should be adjusted appropriately so that the particle size distribution of the measured powder can be accurately estimated.
  • Particle strength in the range of 50 to 200 kg kgcm2, and the preferred particle strength in the step of formulating with a surfactant mixed solution containing an anionic surfactant is 10 0 0 to 150 kg / cm 2 , particularly preferably 150 to 10000 k g / cm 2 .
  • the weight ratio of anionic surfactant Z nonionic surfactant in the surfactant mixture is 4Z1-1Z3, the particle strength is 150-1000kg / cm. 2 is preferred.
  • the base granules exhibit good disintegration properties, and detergent particles having good fast dissolving properties are obtained.
  • the method for measuring the particle strength is as follows.
  • Supporting capacity 2 OmLZl 00 g or more, preferably 4 OmL / 100 g or more. Within this range, agglomeration between base granules is suppressed in the step of formulating with a surfactant mixture containing an anionic surfactant, and is suitable for maintaining mononuclear properties of particles in the detergent particles group. It is.
  • the method for measuring the carrying capacity is as follows.
  • linseed oil is added at about 1 OmL / min at 25 ° C while stirring at 350 rpm.
  • the amount of linseed oil charged when the stirring power is the highest is used as the loading capacity.
  • Moisture 20% or less by weight, preferably 10% by weight or less, particularly preferably 5% by weight or less. Within this range, a group of base granules with good physical properties can be obtained.
  • Can be The method for measuring moisture is as follows.
  • the mononuclearity of the detergent particles can be confirmed by at least one of the following methods (a), (b) and (c).
  • the detergent particles containing the mononuclear detergent particles of the present invention have a high solubility.
  • the fast solubility of the mononuclear detergent particles can be evaluated by the dissolution rate for 60 seconds.
  • the fast solubility of the detergent particles in terms of the dissolution rate for 60 seconds refers to the elimination of detergent particles during hand washing.
  • the solubility of the detergent particle group calculated by the following method is 90% or more, preferably 94% or more, and more preferably 97% or more.
  • the operation time from the start of filtration to collection of the sieve shall be 10 ⁇ 2 seconds.
  • the collected residue of detergent particles was dried in an electric dryer heated at 105 ° C for 1 hour, and then kept in a silica gel-containing dessicator at 25 ° C for 30 minutes for cooling. I do. After cooling, the total weight of the dried residue of the detergent, the sieve, and the collection container is measured, and the dissolution rate (%) of the detergent particles is calculated by the above equation (1).
  • the detergent particle group of the present invention shows a high solubility.
  • the detergent particles and / or agglomerates of the detergent particles dissolve very quickly, which is advantageous in that hand-washing can be easily performed.
  • the excellent solubility of the present invention not only has the effect of improving the washing power by dissolving the washing components more quickly in the washing and irrigation bath, but also has a hand washing course adopted in a fully automatic washing machine, a weak stirring. It has a great merit in terms of quality that does not leave undissolved detergent even with low mechanical power such as course and speed washing and short washing.
  • Suitable physical properties of the detergent particle group preferably containing mononuclear detergent particles obtained in the present invention are as follows. The methods for measuring the bulk density and the average particle size are the same as those for the base granules.
  • the detergent composition of the present invention also shows remarkably excellent hand-washing solubility as compared with conventional detergent compositions.
  • the hand-washing solubility is a measure of the solubility when the detergent composition is previously dissolved in a container such as a basin before hand washing of contaminated clothing, and is indicated by a dissolution time.
  • Hand washing is a common washing habit for pre-washing contaminated clothing, etc., not only for users who mainly use hand washing but also for those who mainly use a washing machine. Is important as a measure of greater convenience.
  • a specific measuring method is a polypropylene basin with a maximum opening diameter of 31 cm, a bottom part of 24 cm, and a height of 13 cm (for example, a KW-30 type washing tub manufactured by YAZAKI, content volume 8.2 L) ), Add 5.0 L of tap water at 25 ° C. Then, spray 15 g of the detergent composition to be tested uniformly and quickly (within 3 seconds as a guide) over the entire surface of the water so that it does not solidify in one place. From that point, the panelist spreads five fingers with one hand (dominant arm), and at the fingertips (ventral side of the finger), while sensing detergent particles present at the bottom of the basin (lightly stroke the bottom of the basin with the fingertips). ) Start stirring.
  • the stirring is performed in such a way that the clockwise rotation and the counterclockwise rotation are alternately repeated in 5 rotation cycles, and stirring is performed so that the sample solution does not spill from the basin wall. In this case, it should be about 1.0 second at rest). In this way, stirring is continued until detergent particles are no longer detected, and the time is measured.
  • the panelist repeats the test until the standard deviation of three consecutive measurement times of the test sample is within ⁇ 5%, and the three average times are the hand-washing dissolution time of the panelist.
  • Panelists are more than 10 people, middle rank excluding the top 20% and bottom 20% panelists 60% of the average time of dissolution of hand washing by panelists is taken as the time of hand washing dissolution of the tested detergent composition.
  • the solubility in hand washing of the detergent composition of the present invention is preferably 80 seconds or less, more preferably 60 seconds or less, and still more preferably 40 seconds or less.
  • Average particle size 150 to 500 m, preferably 180 to 400 m, more preferably 200 to 350 m, and 220 to 300 / m m is particularly preferred o
  • the flow time is 10 seconds or less, preferably 8 seconds or less, and more preferably 7 seconds or less.
  • the flow time is defined as the time required for 10 OmL of powder to flow out of the hopper for bulk density measurement specified by JIS K3362.
  • the weight frequency of the classified particles having a particle size of less than 125 m is preferably 0.2 or less, more preferably 0.12 or less, and further preferably 0.07 or less.
  • the sieve passing rate is preferably 90% or more, more preferably 95% or more.
  • the test method is as follows. Make a box without a top with a length of 10.2 cm x width 6.2 cm x height 4 cm with filter paper (AD 0.2, manufactured by ADVANTEC) and stapling the four corners with a stapler. Place 50 g of the sample in this box, and put the total weight of the acrylic resin plate and the lead plate (or iron plate) of 15 g + 250 g on top of it. Temperature 3 Leave in a thermo-hygrostat at 0 ° C and judge the caking state after 7 days or 1 month. The determination is made by obtaining the pass rate as follows.
  • the sample is placed on a sieve (4760 urn specified in JIS Z8801), weighed, and the weight of the powder that has passed is measured to determine the pass rate (%) based on the weight of the entire sample.
  • Rank 5 Bleed width of oil-based marker is 2 cm or more.
  • Rank 4 The bleeding width of the oil-based marker is 1 cm or more.
  • Oily marker bleed width is 0.5 cm or more.
  • the detergent particles of the present invention can be produced by a process including the following steps (a) to (c).
  • a surface modification step (d) after the step (c). Preferred embodiments of each of the steps (a) to (c) and the surface modification step (d) will be described below.
  • the slurry used in the present invention may be any non-curable slurry that can be sent by a pump. Also, the method and order of adding the components can be appropriately changed depending on the situation.
  • the phosphate builder (A) in the slurry is 3 to 45% by weight, and the water-soluble polymer and the water-soluble salt excluding phosphate (B and C) in the slurry are 1 to 15% by weight and 3 to 15% by weight, respectively. ⁇ 40% by weight is preferred.
  • the temperature of the slurry is usually preferably 30 to 80 ° C. When the temperature of the slurry is in this range, it is preferable in terms of solubility of the water-soluble polymer (B) and pumping of the solution.
  • a slurry for example, all or almost all of water is first added to the mixing tank, and preferably, the other components are added sequentially or simultaneously after the water temperature has almost reached the operating temperature.
  • the usual order of addition is to add a liquid component such as a surfactant and a polyacrylate first, and then add a water-soluble powder material such as soda ash.
  • auxiliary components such as fluorescent dyes are added.
  • a phosphate builder such as tripolyphosphate is added.
  • the water-insoluble component may be added in two or more portions for the purpose of improving the mixing efficiency.
  • powder materials are pre-mixed After that, these may be added to the aqueous medium.
  • water may be added to adjust the viscosity / slurry / water content.
  • water may be added to adjust the viscosity / slurry / water content.
  • the base granules have pores capable of releasing the desired air bubbles characterized by the present invention, and in order to take an uneven distribution structure of the components.
  • Spray drying in which the particle shape is substantially spherical, is particularly preferred.
  • the spray-drying tower may be either a counter-current tower or a co-current tower, but is more preferably a counter-current tower from the viewpoint of improving the particle strength of the base granules.
  • the apparatus for atomizing the slurry may be any of a pressure spray nozzle, a two-fluid spray nozzle, and a rotating disk type, but the average particle size of the base granules is 150 to 500 zm, preferably 18 A pressure spray nozzle is particularly preferred because it is 0 to 300 m.
  • the temperature of the hot gas supplied to the drying tower is usually preferably from 150 to 300 ° C, more preferably from 170 to 250 ° C.
  • the temperature of the gas discharged from the drying tower is usually preferably 70 to 125 ° C, more preferably 80 to 115 ° C.
  • the method of supporting the surfactant on the base granules can be carried out, for example, using a batch type or continuous mixer.
  • the method of charging the base granules and the surfactant into the mixer can be, for example, the following various methods.
  • the methods (1) to (3) are performed while the mixer is operating.
  • the base granules are charged into a mixer, and then a surfactant is added.
  • a surfactant is added.
  • the base granules and the surfactant are charged in small amounts in a mixer.
  • the remaining base granules and the surfactant are added in small amounts. Put in.
  • the surfactant is preferably added in a liquid state, and more preferably, the surfactant in a liquid state is sprayed and supplied.
  • surfactants those which exist in a solid or base state even when the temperature is raised within a practical temperature range, are prepared by preliminarily adding them to a low-viscosity nonionic surfactant, or an aqueous solution or water thereof.
  • a mixed solution or aqueous solution of the surfactant can be prepared by dispersing or dissolving, and can be added to the base particles in the form of the mixed solution or aqueous solution. According to this method, a solid or paste-like surfactant can be easily added to the base granules, which is advantageous for the production of detergent particles containing mononuclear detergent particles.
  • the mixing ratio of the low-viscosity surfactant or water and the solid or paste-like surfactant is preferably within a viscosity range in which the obtained mixed liquid or aqueous solution can be sprayed.
  • anionic surfactants excluding acid precursors
  • they are often in a solid state or in a paste state with a very high degree of fineness. Therefore, they are mixed with a non-ionic surfactant in a liquid state to form a base particle group. It is preferable to adjust the viscosity so that it can be supported on the surface. From this point, it is preferable that the weight ratio of the anionic surfactant and the nonionic surfactant is 4: 1 to 1Z3.
  • the weight ratio of anionic surfactant / nonionic surfactant is from 3 / l to 1Z2, more preferably from 2Z1 to 1Z1.5.
  • a surfactant mixture that can be easily sprayed can be obtained by adjusting the ratio of the two to a range of 1: 1.4 or less.
  • the content of the anionic surfactant is high, it is preferable to add a component other than the surfactant as a viscosity reducing agent.
  • viscosity reducing agent examples include polyethylene glycol having a molecular weight of 300 to 100,000, polypropylene glycol, a co-adduct of polyethylene glycol and polypropylene glycol, and polyhydric alcohols such as ethylene glycol and glycerin.
  • Method for producing the above mixed solution include a method of adding a low-viscosity surfactant or a solid or base surfactant to water and mixing the mixture, or a method of preparing a surfactant in a low-viscosity surfactant or in water.
  • a surfactant mixture may be prepared by neutralizing the acid precursor with an alkaline agent (eg, an aqueous caustic soda solution or an aqueous caustic aqueous solution).
  • an acid precursor of the anionic surfactant before, simultaneously with, during or after the addition of the surfactant.
  • an anionic surfactant acid precursor By adding an anionic surfactant acid precursor, the surfactant is highly compounded, the oil absorption of the base particles is controlled, the non-ionic surfactant of the detergent particles is prevented from bleeding, and the physical properties such as fluidity ⁇ Quality can be improved.
  • Examples of the acid precursor of the anionic surfactant that can be used in the present invention include: alkyl benzene sulfonic acid, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, hyole sulfonic acid, hysulfonated fatty acid, Examples include alkyl or alkenyl ether carboxylic acids, fatty acids and the like. In particular, it is preferable to add the fatty acid after the addition of the surfactant from the viewpoint of improving the fluidity of the detergent particles.
  • the amount of the acid precursor to be used is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the base granules. Within this range, the mononuclear properties of the particles in the detergent particle group tend to be maintained, thus exhibiting good high-speed solubility.
  • the liquid precursor at room temperature is supplied by spraying, and the solid precursor at room temperature may be added as a powder. It may be supplied by spraying. However, when the powder is added, it is preferable to raise the temperature of the detergent particles in the mixer to a temperature at which the powder melts.
  • Apparatuses preferably used in the step (c) include, for example, a Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.), a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), a vertical granule, and a one-night one (PAREK Co., Ltd.) Made), Redige Mixer (Matsusaka Giken) Inc.), Proshare Mixer (manufactured by Taiheiyo Kikai Co., Ltd.), Now Yuichi Mixer (manufactured by Hosokawa Micron Corp.), etc.
  • a preferred mixer is a device that hardly exerts a strong shearing force on the base granules (hardly disintegrates the base granules) from the viewpoint of producing a detergent particle group containing a large amount of mononuclear detergent particles.
  • a device having high mixing efficiency is preferable.
  • a surfactant may be carried by the base granules using a continuous apparatus of the above mixer.
  • continuous mixers other than those described above include, for example, a flexomics type (manufactured by Bauretsu Co., Ltd.) and a Yuichi Burizer-1 (manufactured by Hosokawa Micron Corporation).
  • the Froude number of the main shaft is preferably from 0.5 to 8, and more preferably from 0.5 to 4, from the viewpoint of suppressing the disintegration of the base granules and the mixing efficiency. Further, when the mixing machine has a crushing blade, the Froude number of the crushing blade is preferably 200 or less, and it is more preferable that the mixing blade is not practically rotated.
  • a nonionic surfactant having a melting point of 45 to 100 ° C and a molecular weight of 10,000 to 30,000 as a melting point raising agent for the surfactant is used.
  • Organic compound hereinafter referred to as “melting point enhancer”
  • melting point enhancer By adding the melting point increasing agent, it is possible to suppress the caking property and the stain removal property of the surfactant in the detergent particles.
  • the melting point enhancer include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic nonionic surfactant.
  • the amount of the melting point enhancer to be used is preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the base granules. This range is included in the detergent particle group. This is preferred from the viewpoints of maintaining the mononuclear property of the detergent particles, rapid dissolution, and suppression of spotting and caking properties.
  • As a method of adding the melting point increasing agent mixing with a surfactant in an arbitrary manner in advance or adding the melting point increasing agent after the addition of the surfactant can be used to remove the detergent particles. It is advantageous for suppressing the nature.
  • the temperature in the mixer be increased to the melting point of the surfactant or higher to perform mixing.
  • the temperature for raising the temperature may be higher than the pour point of the surfactant added to promote the loading of the surfactant, but in a practical range, the temperature may exceed the pour point and exceed the pour point by 5%.
  • the temperature is preferably up to 0 ° C higher, more preferably 10 to 30 ° C higher than the pour point.
  • the melting point of the surfactant is measured by the method of JIS K 269.
  • the acid precursor of the anionic surfactant is added in this step, it is more preferable that the temperature is raised to a temperature at which the acid precursor of the anionic surfactant can react, and mixing is performed.
  • the batch mixing time for obtaining a suitable detergent particle group and the average residence time in continuous mixing are preferably from 1 to 20 minutes, more preferably from 2 to 10 minutes.
  • a step of drying during and / or after mixing excess water may be included.
  • the powdered surfactant and Z or powder builder before, simultaneously with, during or after the addition of the surfactant. By adding the powder builder, the particle size of the detergent particles can be controlled, and the cleaning power can be improved.
  • the powder builder refers to a powder detergency enhancer other than the surfactant, and specifically, a base having sequestering ability such as zeolite, citrate and tripolyphosphate, and the like. Bases that show strength of sodium carbonate, potassium carbonate, etc., sequestering ability of crystalline silicates, etc. Agent Point to.
  • the fine powder used in this step is used after adjusting the particle size by pulverization or the like as required.
  • the crystalline silicate described in the lower right column, line 18 to page 4, upper right column, line 3 can be used as the powder builder.
  • an alkali metal silicate having a Si 0 2 ZM 20 (where M represents an alkali metal) of 0.5 to 3.2, preferably 1.5 to 2.6 is suitably used.
  • the amount of the powder builder to be used is preferably 0.5 to 12 parts by weight, more preferably 1 to 6 parts by weight, based on 100 parts by weight of the base granules.
  • the detergent particles contained in the detergent particle group can maintain the mononuclear property, obtain good high-speed solubility, and can suitably control the particle size.
  • the surface modification step of adding a surface coating agent such as (1) a fine powder and (2) a liquid material may be performed one step or two steps.
  • the surface modification step is preferred from the viewpoint of improving the fluidity and non-caking properties of the detergent particles.
  • the apparatus used in the surface modification step is not particularly limited, and the mixer exemplified in the above step (c) is preferable.
  • the surface coating agent will be described below.
  • the average particle size of the secondary particles is preferably 10 ⁇ m or less, more preferably 0.1 to 10 / m. Within this range, the coverage of the particle surface of the detergent particles is improved, which is preferable from the viewpoint of improving the fluidity and the anti-caking properties of the detergent particles.
  • the average particle size is determined by a method using light scattering, for example, a particle analyzer (Horiba (Manufactured by Seisakusho Co., Ltd.) or by microscopic observation. Further, it is preferable from the viewpoint of cleaning that the fine powder has high ion exchange ability and high power. As the fine powder, a crystalline or amorphous aluminosilicate is desirable.
  • fine powders such as sodium triphosphate polyphosphate, sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, and silicate compounds such as crystalline silicate compounds are also preferable.
  • the fine powder used in the surface modification step is used by adjusting the particle size by pulverization or the like as desired. If tripolyphosphate or sodium sulfate is used as a fine powder in the surface modification step and no water-insoluble builder is used for the base granules, the detergent particles dissolve transparently to translucently during washing. In this case, it is preferable that the state of stain removal is easy to understand in hand washing.
  • Detergent particle group Metallic stones having primary particles of 0.1 to 10 zm, powdered surfactants (eg, alkyl sulfates, etc.) and water-soluble organic salts can also be used.
  • powdered surfactants eg, alkyl sulfates, etc.
  • water-soluble organic salts can also be used.
  • a crystalline silicate compound it is preferable to use the crystalline silicate compound as a mixture with a fine powder other than the crystalline silicate compound in order to prevent the crystalline silicate from being deteriorated due to aggregation or the like due to moisture absorption or carbon dioxide gas.
  • the amount of the fine powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 2 to 20 parts by weight based on 100 parts by weight of the detergent particles. Within this range, the flowability is improved and the consumer feels good.
  • liquid material examples include an aqueous solution and a melt of a water-soluble polymer or a fatty acid.
  • water-soluble polymer examples include carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, a copolymer of acrylic acid and maleic acid, or a salt thereof. And the like.
  • the amount of the water-soluble polymer used is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 2 to 6 parts by weight with respect to 100 parts by weight of the detergent particles. . Within this range, it is possible to maintain the mononuclear properties of the detergent particles contained in the detergent particle group and obtain a powder exhibiting good fluidity and anti-caking properties while obtaining good high-speed dissolution.
  • the fatty acid examples include a fatty acid having 10 to 22 carbon atoms.
  • the amount of the fatty acid to be used is preferably 0.5 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight, per 100 parts by weight of the detergent particles.
  • the mixture is heated to a temperature at which fluidity is exhibited and then supplied by spraying.
  • the contents of the phosphate builder, the anionic surfactant, and the nonionic surfactant in the detergent particles are as follows.
  • the content of the phosphate builder is preferably 5 to 50% by weight, more preferably 7 to 40% by weight, and still more preferably 9 to 35% by weight. Further, the content of the anionic surfactant is preferably 5 to 40% by weight, more preferably 6 to 35% by weight, and further preferably 7 to 35% by weight. The content of the nonionic surfactant is preferably 1 to 30% by weight, more preferably 1 to 25% by weight, and still more preferably 1 to 20% by weight.
  • the above components are the sum of the amounts used in at least one of the steps (a) to (d).
  • the detergent particles of the present invention can contain polynuclear detergent particles.
  • the polynuclear detergent particles may be those obtained by aggregating the base granules constituting the aforementioned mononuclear detergent particles, or those formed by aggregating water-soluble salts, such as sodium carbonate, as nuclei. It is preferable that air bubbles of a predetermined size can be generated.
  • the uneven distribution of the base granules also contributes, and the high-speed dissolution is further improved.
  • the base granules in the above-described mononuclear detergent particles can be used, and the surfactants that can be supported on the base granules can also use the surfactants in the above-described mononuclear detergent particles. Further, by increasing the amount of the surfactant, polynuclear detergent particles can be easily formed. Note that a foaming agent such as baking soda or percarbonate may be used to promote the dissolution between base granules.
  • the polynuclear detergent particles of the present invention exhibit the same high dissolution rate as the detergent particles containing mononuclear detergent particles, and have higher solubility than conventional detergents.
  • the high-speed solubility of the detergent particles is confirmed by the method described in Section 4.2.2.
  • the values of the detergent particle group containing mononuclear detergent particles in Sections 4.2.3 to 4.2.7 are used. It is preferable to show the same physical properties as in the case.
  • the detergent composition of the present invention comprises (a): a detergent particle group containing mononuclear detergent particles and Z or polynuclear detergent particles, and (b): a detergent component added separately from the component (a). It contains.
  • the detergent composition contains 50% by weight or more, preferably 60% by weight or more, more preferably 80% by weight or more of the detergent particles in the detergent composition.
  • the detergent composition during the process of dissolving the detergent composition in water, bubbles having a diameter of preferably 1/10 or more of the particles constituting the detergent composition are released from the inside of the particles and dissolved.
  • the particles constituting the detergent composition preferably account for at least 40% by weight, more preferably at least 60% by weight, of all the particles constituting the detergent composition. More preferably, it accounts for at least 80% by weight.
  • the fast dissolving property is determined by the method described in the above-mentioned Section 4.2.2 (in this case, “detergent particle group” is replaced with “detergent composition”). ).
  • Base granule group 1 was prepared by the following procedure.
  • This slurry was sprayed at a spray pressure of 25 kg / cm 2 from a pressure spray nozzle installed near the top of the spray drying tower to obtain a base granule group 1.
  • the hot gas supplied to the spray-drying tower was supplied at a temperature of 225 ° C from the bottom of the tower and discharged at a temperature of 105 ° C from the top of the tower.
  • base granules 2 to 4 were prepared. Table 1 shows the composition and physical properties of each base granule group. When the base granule group 4 was observed by SEM, pores having a pore diameter of 110 to 45 or more of the particle diameter were observed in the particles of 80% or more.
  • a detergent particle group of the present invention was obtained by adding a surfactant to the base particle group 1 at a ratio shown in Table 2 and supporting the surfactant.
  • Neo Belex F 65 ( ⁇ alkyl (10 to 13 lines) benzene sulfone thorium) (manufactured by Corporation)
  • Neoperex FS linear alkyl (10 to 13 weaves) benzenesulfonic acid (manufactured by K.K.)
  • the stirring conditions were changed to the main shaft: 150 rpm and the chopper: 500 rpm, and 12 parts by weight of the crystalline aluminosilicate and the crystalline silicate were 6 parts by weight on the particle surface of the detergent particles. The part was surface-coated. Table 2 shows the physical properties of the obtained detergent particles.
  • polyethylene glycol further improved the caking resistance of the detergent particles and further suppressed the non-ionic surfactant from bleeding.
  • Example 3 The addition of polyethylene glycol further improved the caking resistance of the detergent particles and further suppressed the non-ionic surfactant from bleeding.
  • a detergent particle group of the present invention was obtained by adding a surfactant and the like to the base granule group 3 in the ratio shown in Table 2 in the same manner as in Example 1.
  • the surface of the particles of the detergent particles was coated with 16% by weight of ground tripolyphosphate sodium.
  • Table 2 shows the physical properties of the obtained detergent particles.
  • Base granule group 3 was sieved as the base granule group, and the base granule group classified between 125 m and 180 sieves was used. Further, as a method of adding the anionic surfactant, an acid precursor of the anionic surfactant is used. After the nonionic surfactant is added to the mixer without mixing with the acid precursor, the anionic surfactant is added.
  • the detergent particles of the present invention were obtained by adding a surfactant acid precursor (dodecyl benzene sulfonic acid) to a mixer.
  • a detergent particle group of the present invention was obtained by adding a surfactant and the like to the base particle group 4 at the ratio shown in Table 2.
  • Detergent particles were obtained in the same manner as in Example 1, except that 13 parts of sodium tripolyphosphate ground and crystalline sodium aluminogate were used on the surface of the detergent particles.
  • a detergent particle group of the present invention was obtained by adding a surfactant and the like to the base granule group 3 in the ratio shown in Table 2 in the same manner as in Example 1.
  • the surface of the particles of the detergent particles was coated with 25.6 parts by weight of ground tripolyphosphate sodium. Table 2 shows the physical properties of the obtained detergent particles.
  • 60% of the particles had pores having a pore diameter of 110 to 45 of the particle diameter.
  • the detergent granules of the present invention were obtained by adding the enzyme granules to the detergent particles of Example 4 at the ratios shown in Table 3.
  • Table 3 shows the physical properties of the obtained detergent composition.
  • the enzyme of the enzyme granulated product in Table 3 was Savinase 18T type W manufactured by Novo.
  • Table 4 shows the results of the particle solubility and hand wash solubility of eight representative detergent compositions marketed or previously marketed in Asia, Europe, and the United States. The results in Table 4 show that these commercially available detergents have a low level of particle solubility, and are also poor in hand wash solubility. In addition, among the commercially available detergents A to H, A, which has the highest particle solubility and hand washing solubility, had extremely poor fluidity. Table 4
  • the detergent composition of the present invention has excellent detergency even when the work load of the washing machine is low, and has excellent fluidity, particle solubility and dispersibility so that it can be easily washed by hand washing.
  • the present invention described above there are clearly a large number of those in the range of identity. Such variations are not considered to depart from the spirit and scope of the invention, and all such changes that are obvious to those skilled in the art are included within the scope of the following claims.

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Abstract

L'invention porte sur un détergent particulaire comportant de 5 à 50 % en poids de phosphate, de 5 à 40 % en poids d'un tensio-actif anionique, de 1 à 30 % en poids de tensio-actif non anionique, et dont le diamètre moyen des particules est compris entre 150 et 500 νm, le poids volumique, de 500g/l ou plus, et le temps d'écoulement, de 10 s ou moins. Les particules du détergent peuvent dégager de leurs parties internes lors de leur dissolution dans l'eau des bulles d'un diamètre au moins égal à un dixième de leur diamètre, et leur solubilité, calculée selon l'équation (1), est de 90 % ou plus. Les qualités renforcées de solubilité et de flottabilité dudit détergent en améliorent l'aptitude au lavage à la main. L'équation (1) a la forme suivante: solubilité (%) = [1-(T/S)] x 100, S étant la quantité de particules ajoutées par adjonction de détergent (g), et T, la quantité de résidus restant sur le tamis après brassage (g).
PCT/JP2000/003872 1999-06-16 2000-06-15 Detergent particulaire WO2000077160A1 (fr)

Priority Applications (1)

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EP00937229A EP1186651A4 (fr) 1999-06-16 2000-06-15 Detergent particulaire

Applications Claiming Priority (2)

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JP16935099 1999-06-16
JP11/169350 1999-06-16

Publications (1)

Publication Number Publication Date
WO2000077160A1 true WO2000077160A1 (fr) 2000-12-21

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EP (1) EP1186651A4 (fr)
CN (1) CN1179032C (fr)
WO (1) WO2000077160A1 (fr)

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JP2006056985A (ja) * 2004-08-19 2006-03-02 Kao Corp 洗剤組成物
WO2012033006A1 (fr) * 2010-09-06 2012-03-15 花王株式会社 Procédé pour la production d'un groupe de particules de détergent
JP2013155211A (ja) * 2012-01-26 2013-08-15 Asahi Kasei Chemicals Corp 粒状洗浄剤、及びその製造方法、並びに成形機の洗浄方法
JP2015143323A (ja) * 2013-12-26 2015-08-06 花王株式会社 洗剤粒子群の製造方法

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EP1698687A1 (fr) * 2005-02-07 2006-09-06 The Procter & Gamble Company Compositions détergentes
US20170260482A1 (en) * 2016-03-08 2017-09-14 The Procter & Gamble Company Particles including enzyme

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006056985A (ja) * 2004-08-19 2006-03-02 Kao Corp 洗剤組成物
WO2012033006A1 (fr) * 2010-09-06 2012-03-15 花王株式会社 Procédé pour la production d'un groupe de particules de détergent
JP2012056984A (ja) * 2010-09-06 2012-03-22 Kao Corp 洗剤粒子群の製造方法
CN103108947A (zh) * 2010-09-06 2013-05-15 花王株式会社 洗涤剂颗粒群的制造方法
CN103108947B (zh) * 2010-09-06 2015-12-02 花王株式会社 洗涤剂颗粒群的制造方法
JP2013155211A (ja) * 2012-01-26 2013-08-15 Asahi Kasei Chemicals Corp 粒状洗浄剤、及びその製造方法、並びに成形機の洗浄方法
JP2015143323A (ja) * 2013-12-26 2015-08-06 花王株式会社 洗剤粒子群の製造方法

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EP1186651A1 (fr) 2002-03-13
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CN1369002A (zh) 2002-09-11

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