EP1184451A1 - Waschmittelzusammensetzung - Google Patents

Waschmittelzusammensetzung Download PDF

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Publication number
EP1184451A1
EP1184451A1 EP00937205A EP00937205A EP1184451A1 EP 1184451 A1 EP1184451 A1 EP 1184451A1 EP 00937205 A EP00937205 A EP 00937205A EP 00937205 A EP00937205 A EP 00937205A EP 1184451 A1 EP1184451 A1 EP 1184451A1
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Prior art keywords
granules
detergent
weight
less
classified
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English (en)
French (fr)
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EP1184451A4 (de
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Hiroyuki Kao Corporation SAIJO
Hideichi Kao Corporation NITTA
Shu Kao Corporation YAMAGUCHI
Hiroyuki Kao Corporation YAMASHITA
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Kao Corp
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Kao Corp
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    • 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
    • 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

Definitions

  • the present invention relates to a detergent composition and a process for preparing the same.
  • a powdery heavy duty detergent has been used for washing using a washing machine, and when there is a great load of stains on fibers, it may be subjected to hand-washing.
  • hand-washing it has been known from experience that the washing efficiency is excellent when the hand-washing is started by directly dispersing the powdery heavy duty detergent to a part of the washing items wetted with water, in order to act a concentrated detergent solution on stains.
  • the parts of the washing items themselves or the part of the washing items with other fabric parts are rubbed together with hands, sufficient foaming is necessitated in order to have excellent sliding between the fibers.
  • a powdery heavy duty detergent having a high content in the water-soluble components is preferable.
  • the washing liquid in the washtub is transparent, it is preferable also for visually confirming whether or not the stains are sufficiently washed off as a consequence of washing.
  • a powdery heavy duty detergent having a high content in the water-soluble components namely a powdery heavy duty detergent containing a large amount of a phosphate builder, is preferable. Further, in order to disperse a desired amount of the powder heavy duty detergent to a part of the washing items, it is necessary that the flowability of the powder is high.
  • the powdery heavy duty detergent has been highly densified.
  • the detergent granules do not readily dissolve during washing, and that the foaming rate which gives sliding between cloths is lowered.
  • the washing machine has been developed to have a design for meeting consumers' demands and in considerations of water conservation and energy conservation.
  • the washing machines since the mid 1990's, the washing machines have the tendency of large volume capacity and water conservation, and short-period washing mode or gentle stirring mode for meeting the demands of reduction in clothes damaging has been set.
  • the amount of work (i.e. mechanical power x time) of the washing machine tends to be lowered.
  • the dissolubility of the detergent granules is drastically lowered, so that the detergency becomes poor, and that the insoluble remnants remain on clothes.
  • the European-made washing machines and the U.S.-made washing machines it is considered to be important to lower the washing temperature, from the viewpoint of energy conservation during washing. Therefore, there has been a demand for a detergent having excellent dissolubility.
  • the detergent comprising a phosphate builder, and having a high powder flowability, fast foaming, easy washing, and quick disappearance of aggregates of the detergent granules.
  • An object of the present invention is to provide a detergent composition comprising a phosphate builder, which is excellent in the detergency even when the amount of work of the washing machine is low, and excellent in the dissolubility of the granules and the dispersibility so as to easily carry out hand-washing.
  • the present invention relates to a detergent composition
  • a detergent composition comprising 5 to 60% by weight of a phosphate builder and 10 to 60% by weight of a surfactant, wherein the detergent composition has a bulk density of from 600 to 1200 g/L, and a flow time of 10 sec or less, and has a total summation of a product of a mass base frequency Wi of each group of classified granules obtained by classifying detergent granules by using a classifier and a dissolving rate Vi of each group of classified granules, which satisfies the following formula (1): ⁇ (Wi•Vi) ⁇ 90(%) and wherein a mass base frequency of the classified granules having a size of less than 125 ⁇ m is 0.10 or less, wherein the classifier comprises sieves each having a sieve-opening 2000 ⁇ m, 1410 ⁇ m, 1000 ⁇ m, 710 ⁇ m, 500 ⁇ m, 355 ⁇ m, 250 ⁇ m
  • Figure 1 (1) and (2) each shows a scheme of classification operation in the process of the present invention.
  • the phosphate builder in the present invention has a content of from 5 to 60% by weight, preferably from 10 to 50% by weight, more preferably from 15 to 45% by weight, of the detergent composition, from the viewpoint of the sliding of the clothes to be washed during hand-washing.
  • the phosphate builders are preferably one or more kinds selected from tripolyphosphates, orthophosphates, pyrophosphates, and the like. It is favorable that the content of the tripolyphosphate is from 80 to 97% by weight, that the content of the orthophosphate is from 1 to 10% by weight, or that the content of the pyrophosphate is from 2 to 10% by weight, of the entire phosphate builder (the content is calculated as an anhydride).
  • the counter ions the alkali metal ions are preferable, especially, sodium ions and potassium ions are preferable.
  • the sodium ions and potassium ions are contained in an amount of preferably 70% by weight or more, more preferably 85% by weight or more, in the entire counter ions.
  • the surfactant in the present invention has a content of from 10 to 60% by weight, preferably from 20 to 50% by weight, more preferably from 27 to 45% by weight, of the detergent composition, from the viewpoints of obtaining the detergency and the desired powder properties, and the like.
  • the surfactant comprises an anionic surfactant and/or a nonionic surfactant, and may comprise a cationic surfactant and an amphoteric surfactant as occasion demands.
  • the anionic surfactants include alkylbenzenesulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, ⁇ -olefinsulfonates, ⁇ -sulfofatty acid salts or esters thereof, alkyl or alkenyl ether carboxylates, fatty acid salts, and the like.
  • the anionic surfactant has a content of preferably from 1 to 50% by weight, more preferably from 5 to 30% by weight, of the detergent composition, from the viewpoint of the detergency.
  • the alkali metal ions are preferable, from the viewpoint of improvement in the detergency.
  • potassium ions are preferable, from the viewpoint of the improvement in the dissolution speed.
  • the potassium ions have a content of preferably 5% by weight or more, more preferably 20% by weight or more, particularly preferably 40% by weight or more, of the entire counter ions.
  • the nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene fatty acid esters, polyoxyethylene-polyoxypropylene alkyl ethers, polyoxyalkylene alkylamines, glycerol fatty acid esters, higher fatty acid alkanolamides, alkylglycosides, alkylglucosamides, alkylamine oxides, and the like.
  • polyoxyalkylene alkyl ethers are preferable, which are ethylene oxide adducts, or a mixture adduct of ethylene oxide and propylene oxide, each of which alcohol moiety has 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, the average moles of each alkylene oxide being 5 to 30, preferably 6 to 15.
  • the polyoxyethylene-polyoxypropylene-polyoxyethylene alkyl ether is preferable, from the viewpoints of the detergency and the dissolubility.
  • the compound can be obtained by reacting an ethylene oxide adduct of which alcohol moiety has 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms with propylene oxide and subsequently with ethylene oxide.
  • the polyoxyethylene alkyl ethers mentioned above those having a narrow distribution of an alkylene oxide chain are preferable.
  • the nonionic surfactant has a content of preferably from 1 to 50% by weight, more preferably from 5 to 30% by weight, of the detergent composition, from the viewpoint of the detergency.
  • the cationic surfactants include alkyl trimethylammonium salts, and the amphoteric surfactants include carbobetaine-type and sulfobetaine-type surfactants.
  • the cationic surfactant and amphoteric surfactant each has a content of preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, of the detergent composition.
  • the detergent composition of the present invention there can be formulated water-soluble inorganic salts such as carbonates, hydrogencarbonates, silicates, sulfates, sulfites, and phosphates.
  • the counter ions the alkali metal ions such as sodium ions and potassium ions are particularly preferable.
  • the above salts, in particular, the carbonates are contained, calculated as an anhydride, in an amount of preferably 40% by weight or less, more preferably from 5 to 30% by weight, still more preferably from 5 to 25% by weight, of the detergent composition, from the viewpoint of the low-temperature dispersibility after allowing the detergent composition to stand in cold water for a long period of time.
  • crystalline silicates can be formulated.
  • the SiO 2 /M 2 O molar ratio (wherein M is an alkali metal atom) is preferably 0.5 or more, from the viewpoints of the metal ion capturing ability and the anti-hygroscopic property, and the molar ratio is preferably 2.6 or less, particularly preferably from 1.5 to 2.2, from the viewpoint of the alkalizing ability.
  • a preferable crystalline silicate has an average particle size of from about 1 to about 40 ⁇ m, from the viewpoints of the fast dissolubility and the powder properties, and its content is preferably from 0.5 to 40% by weight, more preferably from 1 to 25% by weight, of the detergent composition, from the viewpoints of the powder properties and the detergency after storage. Especially, its combined use with sodium carbonate is preferable.
  • a cationic exchange-type polymer having carboxyl group and/or sulfonic group in the detergent composition of the present invention, from the viewpoints of the metal ion capturing ability, the dispersibility of the solid particle stains, and the like.
  • salts of acrylic acid-maleic acid copolymers and polyacrylates each having a molecular weight of 1000 to 100000; or salts of polyacetal carboxylic acids such as polyglyoxylic acid having a molecular weight of 800 to 1000000, preferably from 5000 to 200000 described in Japanese Patent Laid-Open No. Sho 54-52196.
  • the cationic exchange-type polymer is contained in an amount of preferably from 0.5 to 12% by weight, more preferably from 1 to 7% by weight, particularly preferably from 2 to 5% by weight, of the detergent composition, from the viewpoint of the detergency.
  • a crystalline aluminosilicate such as A-type, X-type, or P-type zeolite can be formulated.
  • the average primary particle size is preferably from 0.1 to 10 ⁇ m.
  • the crystalline aluminosilicate preferably has a content of preferably from 3 to 15% by weight of the detergent composition.
  • Suitable crystalline aluminosilicates are A-type zeolite (for example, trade name: "TOYOBUILDER,” manufactured by Tosoh Corporation), which is also preferable from the viewpoints of the metal ion capturing ability and economic advantages.
  • the value of the oil-absorbing ability of A-type zeolite measured by a method according to JIS K 5101 is preferably 40 mL/100 g or more.
  • the suitable crystalline aluminosilicates also include P-type zeolite (for example, trade names: "Doucil A24" and “ZSEO64", both manufactured by Crosfield B.V.; oil-absorbing ability: 60 to 150 mL/100 g); X-type zeolite (for example, trade name: "Wessalith XD” manufactured by Degussa-AG; oil-absorbing ability: 80 to 100 mL/100 g); and hybrid zeolite described in WO 9842622.
  • amorphous aluminosilicates of which oil-absorbing ability measured by a method according to JIS K 5101 is 80 mL/100 g or more.
  • the amorphous aluminosilicates from the viewpoint of maintaining high dissolubility even after being stored for a long period of time (without undergoing property changes), it is desirable that the aluminosilicate has an SiO 2 /Al 2 O 3 (molar ratio) of 4.0 or less, preferably 3.3 or less.
  • the amorphous aluminosilicates include those having properties described on Japanese Patent Laid-Open No.
  • those with 0 to 0.7 mL/g of pores having a pore size, as determined by a mercury porosimeter (manufactured by SHIMADZU CORPORATION, "SHIMADZU Poresizer 9320”), of 0.015 to 0.5 ⁇ m, and with 0.30 mL/g or more of pores having a pore size of 0.5 to 2 ⁇ m, are preferable.
  • the amorphous aluminosilicate has a content of preferably from 0.1 to 20% by weight of the detergent composition.
  • the total formulation amount of the crystalline aluminosilicate and the amorphous aluminosilicate, each of which is a water-insoluble inorganic salt in the present invention, and the crystalline silicates which have a delayed dissolution speed in water is preferably less than 25% by weight, more preferably less than 20% by weight, still more preferably less than 15% by weight, of the detergent composition, from the viewpoint of the easy hand-washing. Also, it is desirable that the total formulation amount, on a weight-ratio basis, is less than 200% by weight, preferably less than 100% by weight, based on the phosphate builder.
  • the detergent composition of the present invention can be appropriately formulated with organic acid salts such as citrates and ethylenediaminetetraacetate; dispersing agents or dye-transfer inhibitors such as carboxymethyl cellulose, polyethylene glycols, polyvinyl pyrrolidones and polyvinyl alcohols; bleaching agents such as percarbonates; bleaching activators such as compounds listed in Japanese Patent Laid-Open No. Hei 6-316700 and tetraacetylethylenediamine; enzymes such as protease, cellulase, amylase, and lipase; biphenyl-type or stilbene-type fluorescent dyes; defoaming agents; antioxidants; blueing agents; perfumes, and the like.
  • organic acid salts such as citrates and ethylenediaminetetraacetate
  • dispersing agents or dye-transfer inhibitors such as carboxymethyl cellulose, polyethylene glycols, polyvinyl pyrrolidones and polyvinyl alcohols
  • the bulk density of the detergent composition determined in accordance with JIS K 3362 is from 600 to 1200 g/L. From the viewpoints of improvement in the transportation efficiency and the convenience of the users, the bulk density is 600 g/L or more, preferably 650 g/L or more, more preferably 700 g/L or more. From the viewpoint of securing the air gaps between the granules and improving the dispersibility owing to the suppression of the increase in a number of contact points between the granules, the bulk density is 1200 g/L or less, preferably 1000 g/L or less, more preferably 850 g/L or less.
  • the detergent composition of the present invention is excellent in the dissolubility per one granule of the detergent granules and the aggregation-preventing property of the detergent granules.
  • the aggregation of the detergent granules refers to a phenomenon where after initiation of dissolving a part of a surfactant capable of forming liquid crystals and an inorganic salt forming hydrated crystals of carbonates, sulfates and the like, the remainder part forms highly viscous liquid crystals of the detergent granules or recrystallizes into a hydrate more quickly than being dissolved under the conditions of a low mechanical power, cold water, and the like.
  • the particle size distribution of the detergent composition of the present invention is such that the mass base frequency of the classified granules having a size of less than 125 ⁇ m is 0.10 or less.
  • the content of the fine powder in the detergent composition is low.
  • the mass base frequency of the classified granules having a particle size of less than 125 ⁇ m is 0.10 or less, preferably 0.08 or less, more preferably 0.06 or less, particularly preferably 0.04 or less.
  • the mass base frequency of the classified granules having a particle size of 125 ⁇ m or more and less than 180 ⁇ m is preferably 0.20 or less, more preferably 0.10 or less, particularly preferably 0.05 or less.
  • each mass base frequency satisfies the relationship such that the mass base frequency is [classified granules having a particle size of less than 125 ⁇ m] ⁇ [classified granules having a particle size of 125 ⁇ m or more and less than 180 ⁇ m].
  • the content of the coarse granules in the detergent composition is low.
  • the mass base frequency of the classified granules having a particle size of 1000 ⁇ m or more is preferably 0.03 or less, more preferably 0.01 or less, particularly preferably substantially none.
  • the mass base frequency of the classified granules having a particle size of 710 ⁇ m or more and less than 1000 ⁇ m is preferably 0.10 or less, more preferably 0.05 or less, particularly preferably 0.03 or less.
  • the mass base frequency of the classified granules having a particle size of 500 ⁇ m or more and less than 710 ⁇ m is preferably 0.10 or less, more preferably 0.05 or less, still more preferably 0.03 or less.
  • each mass base frequency satisfies the relationship such that the mass base frequency is [classified granules having a particle size of 1000 ⁇ m or more] ⁇ [classified granules having a particle size of 710 ⁇ m or more and less than 1000 ⁇ m] ⁇ [classified granules having a particle size of 500 ⁇ m or more and less than 710 ⁇ m].
  • the detergent composition of the present invention has an average particle size of preferably from 150 to 500 ⁇ m, more preferably from 200 to 400 ⁇ m, particularly preferably from 250 to 350 ⁇ m.
  • the average particle size (Dp) is a 50% mass base diameter, and can be determined by using the classifier mentioned above. Specifically, after-classification operation, the mass base frequency is accumulated sequentially from finer powders to coarser granules.
  • the average particle size can be calculated according to the equation (3).
  • the insoluble remnants of each group of the classified granules remaining on the sieve are subjected to drying operation together with the sieve for 1 hour in an electric dryer at 105°C, and allowed to cool for 30 minutes in a desiccator (25°C) containing an activated silica gel therein. Thereafter, the weight is determined. By subtracting the weight of the sieve from this determined weight, the dry weight of the insoluble remnants of each group of the classified granules can be calculated.
  • the concrete determination conditions are as described for the conditions for dissolubility determination described above. Under the conditions, it has been found that the powdery detergent composition having a dissolution rate of 90% or more is extremely easier to dissolve and disappear and has a fast foaming speed even in hand-washing at ambient temperature or a lower temperature.
  • the dissolubility of the detergent composition of the present invention is expressed by a total summation of a product of a mass base frequency Wi of each group of the classified granules and a dissolution rate Vi of each group of the classified particles [namely ⁇ (Wi•Vi)].
  • the dissolubility of the detergent composition of the present invention is 90% or more, preferably 94% or more, more preferably 97% or more.
  • the dissolution rate Vi of the classified particles is calculated by the following equation (2), wherein "i" means each group of the classified particles.
  • Vi [1 - Ti/Si] x 100 (%) wherein Si is a weight (g) of each group of the classified particles supplied; and Ti is a dry weight (g) of insoluble remnants of each group of the classified particles remaining on the sieve after filtration.
  • the detergent composition of the present invention in hand-washing, a desired amount is easily dispersed to washing items, the dissolution of the granules is fast, and the foaming speed is excellent. Therefore, hand-washing can be extremely efficiently carried out because the detergent composition comprises a phosphate builder as a main builder. Also, since the detergent composition has extremely high dissolubility even under cold water conditions, the probability of generating insoluble remnants even washing under the conditions of super-low mechanical power is extremely low, aside from having such effects that the detergency is increased by eluting the deterging components more quickly in the washtub.
  • the detergent composition of the present invention also exhibits remarkably excellent hand-washing dissolubility as compared to those of conventional detergent compositions.
  • the hand-washing dissolubility refers to a measure of the dissolubility when a detergent composition is previously dissolved in a vessel such as a washbowl in a case where stained garments are hand-washed, and expressed by dissolution period of time.
  • Hand-washing is customarily widely employed for washing not only as a matter of course for users whose main washing method is hand-washing but also as pre-washing of stained garments for users whose main washing method is machine washing. Therefore, the hand-washing dissolubility is important as a measure for reflecting a more excellent easy-to-use property.
  • a concrete method for measurement is as follows.
  • a washbowl for example, Model "KW-30" washtub manufactured by YAZAKI, inner volume: 8.2 L
  • a washbowl made of polypropylene having a largest opening diameter of 31 cm, a bottom diameter of 24 cm and a height of 13 cm
  • 15 g of a detergent composition to be tested is added and dispersed on entire water surface uniformly and quickly (within 3 seconds or so as a standard) so as not to aggregate in one site.
  • a skilled panelist initiates stirring with one hand (the dominant hand), with widely stretched five fingers sensing the detergent granules existing at the bottom of the washbowl with finger tips (inner side of the fingers), in such a manner of gently touching the bottom of washbowl with finger tips.
  • stirring is carried out by repeating each clockwise rotations and counterclockwise rotations alternating with a period of 5 rotations.
  • the stirring is carried out so as not to spill the sample solution from the side wall of the washbowl (the stirring is carried out in about 1.0 second per one rotation, and when reversely rotated, a stand-still is held for about 1.0 second as a standard.).
  • the stirring is continued until the detergent granules are no longer sensed, and the period of time is measured.
  • a panelist repeats a test for a test sample until the deviation of the determined period of time for three runs is within ⁇ 5%, and the average period of time of the three runs is referred to as the period of time for the hand-washing dissolubility of the panelist.
  • the evaluation is carried out by panelists of 10 or more, and an average value of the period of time for the hand-washing dissolubility for the middle 60% of the panelists, excluding the top 20% and the bottom 20% of the panelists, is referred to as the period of time of the hand-washing dissolubility of the tested detergent composition.
  • the hand washing dissolubility of the detergent composition of the present invention is preferably 80 seconds or less, more preferably 60 seconds or less, still more preferably 50 seconds or less, particularly preferably 40 seconds or less.
  • the flowability as flow time (a time period required for cascading 100 mL of powder from a hopper used in a measurement of bulk density according to JIS K 3362) is 10 seconds or shorter, preferably 8 seconds or shorter, more preferably 6.5 seconds or shorter.
  • the detergent composition of the present invention can be prepared by subjecting unclassified detergent granules, comprising 5 to 60% by weight of a phosphate builder and 10 to 60% by weight of a surfactant, to classification operation and particle size adjustment operation (the detergent granules being hereinafter also referred to as "base detergent granules"; here, classified granules obtained by subjecting base detergent granules to a plural times of classification operation and operation for particle size adjustment may be also included in the base detergent granules).
  • a process for preparing base detergent granules there can be employed a process comprising preparing spray-dried particles comprising a surfactant and a builder, and increasing bulk density of the granules.
  • a process includes, for instance, a process comprising stirring and granulating spray-dried particles in a vertical or horizontal mixer, thereby increasing the bulk density.
  • a process disclosed in Japanese Patent Laid-Open No. Hei 2-49100 comprising stirring and granulating spray-dried particles; a process disclosed in Japanese Patent Laid-Open No.
  • Sho 62-169900 comprising forming dried particles, and thereafter disintegrating and granulating the dried particles; a process disclosed in Japanese Patent Laid-Open No. Sho 62-236897, comprising disintegrating a solid detergent obtained by kneading and mixing detergent raw materials; a process disclosed in Japanese Patent Laid-Open No. Hei 3-33199, comprising neutralizing in a dry state an acid precursor of an anionic surfactant with a granular, solid alkalizing agent in a high-speed mixer, and thereafter adding a liquid binder to form granules, and the like.
  • a process for preparing base detergent granules there can be employed a process disclosed in Japanese Patent Laid-Open No. Hei 10-176200, comprising granulating a mixture comprising a nonionic surfactant, an acid precursor of an anionic surfactant capable of having a lamellar orientation, and an alkalizing agent, while tumbling with a granulator at a temperature not less than the temperature capable of neutralizing the mixture, and the like.
  • the base detergent granules are subjected to classification and particle size adjustment, whereby the detergent composition of the present invention can be obtained.
  • the classification method therefor includes a method employing a circular or sectoral vibration sieve; an ultrasonic vibration sieve comprising the vibration sieve and an ultrasonic oscillator attached thereto; an air classifier or centrifugal classifier, and the like.
  • the detergent composition can be obtained by subjecting base detergent granules to at least one step of classification operation; thereafter determining a mass base frequency for each group of sieve-on classified granules and sieve-pass classified granules against an amount of the base detergent granules supplied; and blending each group of classified granules such that the formula (1) as defined above is satisfied, and that a mass base frequency of the classified granules having a size of less than 125 ⁇ m is 0.10 or less.
  • the classification operation may be single-step operation as shown in Figure 1 (1), or two or more steps of operations as shown in Figure 1 (2) as occasion demands.
  • a desired detergent composition can be obtained, for instance, by separating coarse granules in the first-step classification operation, from the viewpoint of the fast dissolubility per one granule; separating fine powder, for instance, classified granules having a size of less than 125 ⁇ m, in the second-step classification operation, from the viewpoint of the low-temperature dispersibility; and subjecting part or entire fine powder to granulation operation to be supplied again as the base detergent granules.
  • the blending method there can be employed a blending method in a batch process with a V-type mixer, or the like, or in continuous process.
  • the detergent composition can be obtained in a high yield by granulating and/or disintegrating the base detergent granules which are excess base detergent granules not subjected to particle size adjustment; and thereafter reusing as the base detergent granules.
  • those granules, like fine powder having a size of less than 125 ⁇ m having excellent dissolubility per one granule but having a concern for decreasing the dispersibility of the detergent composition by an increase in the number of contact points between the granules can be reused as base detergent granules after subjecting to a treatment for increasing particle size such as granulation operation.
  • the detergent composition of the present invention it is especially important for the detergent composition of the present invention to reduce the mass base frequency of the classified granules having a size of less than 125 ⁇ m, and by carrying out the above operations, the process becomes economically advantageous.
  • excess coarse granules which are poor in the dissolubility per one granule can be reused as base detergent granules after subjecting the coarse granules to a treatment for decreasing particle size such as disintegration operation.
  • the classified granules not used in Steps 1 and 2 mentioned above are preferably reused as base detergent granules in reference to the dissolution rate Vi, in a case where, for instance, fine powder having Vi of 90% or more is subjected to granulation operation, or coarse granules having Vi of less than 90% are subjected to disintegration operation, whereby the granules are preferably reused as base detergent granules.
  • the fine powder granulation operation and the coarse granules disintegration operation are exemplified below.
  • Excess fine powder may be collected by adding them in the form of fine powder without treatment during the preparation process of Step 1 for the base detergent granules.
  • the excess fine powder may be collected by a process comprising consolidating and granulating in a vertical or horizontal agitation granulator; an extruding granulation process employing an extrusion granulator; a compression-granulation method such as briquetting, and the like.
  • a binder can be added during granulation.
  • Excess coarse granules can be reused as base detergent granules by, for instance, disintegrating the coarse granules, thereby decreasing their particle size.
  • the disintegrator for coarse granules includes impact crushers such as hammer crusher; impact pulverizers such as atomizers and pin mills; shearing rough pulverizers such as flash mills. These disintegrators may comprise single-step operation, or multi-step operations with the same or different disintegrators.
  • the fine powder is preferably inorganic powders such as tripolyphosphates, aluminosilicates, silicon dioxide, bentonite, talc and clay amorphous silica derivatives, and especially, crystalline or amorphous aluminosilicates are preferable.
  • fine powders of inorganic salts such as sodium carbonate and sodium sulfate can be used.
  • a surface-modifying step can be provided in the process.
  • the process comprising supplying a composition in a batch process or continuous process into a rotary cylindrical mixer or an agitator, thereby subjecting the composition to tumbling or stirring treatment.
  • the detergent composition can be economically advantageously obtained in a high yield from the excess classified detergent granules in Step 2.
  • a washing net (model number: AXW22A-5RU0, sieve-opening: 300 x 640 ⁇ m) was attached to a side wall portion of a washtub of a washing machine "AISAIGO NA-F70VP1" manufactured by Matsushita Electric Industrial Co., Ltd.
  • 3 kg of clothes cotton underwear: 50% by weight, dress shirt made of mixed fabric of polyester/cotton: 50% by weight
  • 44.0 g of each detergent composition of Examples was added with uniform dispersion.
  • each detergent composition of Examples was placed in an aggregated state near the outer periphery of one of the dents of a sector, a six-divided section of a pulsator of washing machine "AISAIGO NA-F42Y1" manufactured by Matsushita Electric Industrial Co., Ltd.
  • the amount 1.5 kg of the clothes was placed in the washtub, without disintegrating the aggregation.
  • Twenty-two liters of tap water at 5°C was poured thereto at a flow rate of 10 L/min in such a way that the water did not directly hit the detergent composition. After the termination of water-pouring, the aqueous mixture was allowed to stand.
  • the stir was started with gentle water flow (handwashing-mode). After stirring for 3 minutes, water was discharged, and the states of detergent compositions remained on the clothes and the washtub were visually determined by the following evaluation criteria.
  • the stir strength of this evaluation was very weak as compared to that of the standard mode, so that the evaluation criteria I and II indicated that the detergent compositions had excellent dispersibility.
  • the term "aggregates” described below refers to a mass of aggregated detergent granules having a diameter of 3 mm or more.
  • the hand-washing dissolubility was determined by the measurement method described in the above "[6] Hand-Washing Dissolubility of Detergent Composition.”
  • the washbowl the Model KW-30 washtub manufactured by YAZAKI was used, and the hand-washing dissolubility was measured by 10 panelists.
  • the resulting slurry was dried by using a countercurrent flow type spray-dryer to give granules having a bulk density of about 300 g/L.
  • the content of volatile matter was 2.1% by weight (amount lost at 105°C for 2 hours).
  • 87 parts of the granules and 0.5 parts of zeolite 4A were introduced into a High-Speed Mixer (manufactured by Fukae Powtec Corp., volume capacity: 25 L), and mixed.
  • crystalline silicate powders (pulverized product of SKS-6, average particle size: 27 ⁇ m) were introduced into the mixer, and the mixture was further pulverized and granulated with stirring, while spraying 4 parts of the above nonionic surfactant thereto.
  • 3.5 parts of the above powdery zeolite was added for surface-coating immediately before the termination of the process, to give base detergent granules. The entire charged amount was 5 kg.
  • the resulting mixture was pelletized by using a twin-screw extruder ("PELLETER DOUBLE,” manufactured by Fuji Paudal Co., Ltd.) arranged at the discharge outlet of the kneader, to give cylindrical pellets having a diameter of about 3 mm.
  • Base detergent granules (1) were prepared in an amount of 35 kg for each unit from 32% by weight of a linear alkylbenzenesulfonic acid (LAS; molecular weight: 322); 20% by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 ⁇ m), 12% by weight of zeolite; 29.9% by weight of sodium carbonate; 1.6% by weight of sodium sulfate; 0.5% by weight of an acrylic acid-maleic acid copolymer ("Sokalan CP5"); fluorescent dyes (0.2% by weight of "Tinopal CBS-X” and 0.1% by weight of "WHITEX SA”), 0.5% by weight of an enzyme (manufactured by NOVO Nordisk, "Savinase 18T Type W”), 0.2% by weight of a perfume, and 3.0% by weight of water, using a high-speed mixer Lödige Mixer "FKM-130D” (manufactured by Matsubo Co., Ltd.). This mixer was equipped with agitator
  • the solid ingredients comprising 7.0 parts of sodium tripolyphosphate, 12.61 parts of sodium carbonate ("LIGHT ASH," manufactured by Central Glass Co., Ltd.; average particle size: 56.1 ⁇ m), and 0.11 parts of a fluorescent dye were blended for one minute under the conditions of a rotational speed of agitator blades of 130 rpm (peripheral speed: 3.4 m/s) and a rotational speed of a shearing device of 2850 rpm (peripheral speed: 27 m/s) by the Lödige Mixer.
  • Classification operations were carried out with each group of the base detergent granules of Preparation Examples 1 to 3 using the classifier described above. Specifically, 100 g/batch of a sample was first supplied on a 2000- ⁇ m sieve arranged at top of the classifier. Thereafter, the classifier was capped, and attached to a rotating and tapping shaker machine (manufactured by HEIKO SEISAKUSHO, tapping: 156 times/min, rolling: 290 times/min), and vibrated for 10 minutes.
  • HEIKO SEISAKUSHO rotating and tapping shaker machine
  • the samples remaining on each of the sieves and a receiving tray were individually collected to obtain necessary amounts of samples of each group of the classified granules having sizes of 1410 ⁇ m or more to less than 2000 ⁇ m, 1000 ⁇ m or more to less than 1410 ⁇ m, 710 ⁇ m or more to less than 1000 ⁇ m, 500 ⁇ m or more to less than 710 ⁇ m, 355 ⁇ m or more to less than 500 ⁇ m, 250 ⁇ m or more to less than 355 ⁇ m, 180 ⁇ m or more to less than 250 ⁇ m, 125 ⁇ m or more to less than 180 ⁇ m, and ones on the tray to 125 ⁇ m (less than 125 ⁇ m).
  • High-bulk density detergent compositions of Cases 1 to 9 were obtained using the classified granules of the base detergent granules obtained in Preparation Examples 1 to 3 and Enzyme Granules A by carrying out particle size adjustment in accordance with the following process.
  • the average particle size, the bulk density, the flowability and ⁇ (Wi ⁇ Vi) of each of the resulting detergent compositions are shown in Table 2.
  • Each group of the classified granules was weighed so that each sample weighed 200 g in accordance with a mass base frequency distribution of the particle size shown in Table 2, and each sample was mixed for 2 minutes by a rocking mixer (manufactured by Aichi Electronics Co., Ltd.) to prepare various detergent compositions of which particle size was adjusted.
  • Each of the detergent compositions of Cases 10 to 14 was obtained using the classified granules of the base detergent granules (1) obtained in Preparation Example 3 by carrying out particle size adjustment in accordance with the following process.
  • the average particle size, the bulk density, the flowability and ⁇ (Wi•Vi) of each of the resulting detergent compositions are shown in Table 3.
  • the amount 55.1 parts of the detergent composition of Case 10 was introduced as base detergent granules into a gyratory screen having a screen having a 125 ⁇ m-sieve opening to remove fine particles having a size of less than 125 ⁇ m, thereby giving 51.1 parts of the detergent composition of Case 11.
  • the first-step pulverized granules were fed into the second step of the Fitz Mill to give second-step pulverized granules.
  • the opening of the screen of the Fitz Mill for the firststep had a diameter of 2 mm and that for the second-step had a diameter of 1 mm.
  • the average particle size of the second-step pulverized granules was 376 ⁇ m.
  • the second-step pulverized granules were introduced into the above gyratory screen having a screen having a 500 ⁇ m-sieve opening, and classified into sieve-on granules B and sieve-pass granules B.
  • the amount 25.0 parts of sieve-pass granules B and 55.5 parts of the sieve-pass granules A were blended to give 80.5 parts of the detergent composition of Case 12.
  • the amount 80.5 parts of the detergent composition of Case 12 was introduced into the above gyratory screen having a screen having a 125 ⁇ m-sieve opening to remove fine particles having a size of less than 125 ⁇ m, thereby giving 76.2 parts of the detergent composition of Case 13.
  • the amount 80.5 parts of the detergent composition of Example 12 was introduced into a gyratory screen having a screen having a 180 ⁇ m-sieve opening, and classified into sieve-on granules C and sieve-pass granules C.
  • the weights of the sieve-on granules C and the sieve-pass granules C were 65.1 parts and 15.4 parts, respectively.
  • the sieve-pass granules C were granulated according to the following operations.
  • the amount 15.4 parts of the sieve-pass granules C were introduced into the above High-Speed Mixer, and 0.77 parts of the above nonionic surfactant was sprayed thereto over a period of 1.3 minutes. Thereafter, the mixture was granulated with stirring for 10 minutes. Subsequently, the resulting granules were subjected to a surface-coating treatment for 1 minute by adding 0.92 parts of zeolite (average particle size: about 3 ⁇ m), to give base detergent granules (2) (average particle size: 662 ⁇ m).
  • the base detergent granules were classified into sieve-on granules A' and sieve-pass granules A' using a gyratory screen having a 500 ⁇ m-sieve opening.
  • the sieve-on granules A' were subjected to two-step pulverizing, using a Fitz Mill to classify the resulting pulverized granules into sieve-on granules B' and sieve-pass granules B' using a gyratory screen having a 500 ⁇ m-sieve opening. Thereafter, the sieve-pass granules B', the sieve-pass granules A' and the sieve-pass granules C were blended to give 80.0 parts of the detergent composition of Case 14.
  • the detergent composition of the present invention rapidly dissolves after supplying to water, even with cold water, is excellent in dissolubility when subjected to hand-washing, and the dispersibility owing to aggregation of the granules, and is excellent in detergency and dissolubility even under washing conditions of low-mechanical power as employed in recent washing machines.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP00937205A 1999-06-14 2000-06-12 Waschmittelzusammensetzung Withdrawn EP1184451A4 (de)

Applications Claiming Priority (3)

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JP16626299 1999-06-14
JP16626299 1999-06-14
PCT/JP2000/003792 WO2000077157A1 (fr) 1999-06-14 2000-06-12 Composition de detergent

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EP1184451A4 EP1184451A4 (de) 2004-08-04

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JP2006056985A (ja) * 2004-08-19 2006-03-02 Kao Corp 洗剤組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080222A1 (de) * 1981-11-16 1983-06-01 The Procter & Gamble Company Verfahren zur Herstellung granulierter Detergenszusammensetzungen, die in inniger Mischung ein anionisches Tensid und ein anionisches Polymer enthalten
EP0229671A2 (de) * 1986-01-17 1987-07-22 Kao Corporation Granuliertes Reinigungsmittel von hoher Dichte
WO1999029829A1 (en) * 1997-12-10 1999-06-17 Kao Corporation Detergent particles and method for producing the same

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JP2951743B2 (ja) * 1991-05-09 1999-09-20 花王株式会社 高嵩密度粒状洗剤の製造方法
JP2954425B2 (ja) * 1992-06-22 1999-09-27 花王株式会社 高密度粒状洗剤組成物の製造方法
JPH06279797A (ja) * 1993-03-26 1994-10-04 Lion Corp 粒状洗剤組成物
JP4497488B2 (ja) * 1996-08-26 2010-07-07 花王株式会社 高嵩密度洗剤組成物の製造方法
JP3616234B2 (ja) * 1997-07-17 2005-02-02 花王株式会社 高密度粒状洗剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080222A1 (de) * 1981-11-16 1983-06-01 The Procter & Gamble Company Verfahren zur Herstellung granulierter Detergenszusammensetzungen, die in inniger Mischung ein anionisches Tensid und ein anionisches Polymer enthalten
EP0229671A2 (de) * 1986-01-17 1987-07-22 Kao Corporation Granuliertes Reinigungsmittel von hoher Dichte
WO1999029829A1 (en) * 1997-12-10 1999-06-17 Kao Corporation Detergent particles and method for producing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 05, 31 May 1999 (1999-05-31) & JP 11 035998 A (KAO CORP), 9 February 1999 (1999-02-09) -& DATABASE WPI Section Ch, Week 199916 Derwent Publications Ltd., London, GB; Class D25, AN 1999-186636 XP002282484 -& JP 11 035998 A (KAO CORP) 9 February 1999 (1999-02-09) *
See also references of WO0077157A1 *

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