EP0889116B1 - High-density granular detergent composition - Google Patents
High-density granular detergent composition Download PDFInfo
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- EP0889116B1 EP0889116B1 EP97907351A EP97907351A EP0889116B1 EP 0889116 B1 EP0889116 B1 EP 0889116B1 EP 97907351 A EP97907351 A EP 97907351A EP 97907351 A EP97907351 A EP 97907351A EP 0889116 B1 EP0889116 B1 EP 0889116B1
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- alkali metal
- detergent composition
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
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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
- 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
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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
- C11D3/08—Silicates
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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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
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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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Definitions
- the present invention relates to a phosphorus-free, high-density granular detergent composition. More specifically, the present invention relates to a high-density granular detergent composition exhibiting excellent detergency even when a small amount of dosage is used.
- chelating agents various kinds of chelating agents, ion exchange materials, alkalizing agents, and dispersants have been known to be used for builders which are blended in detergents.
- the phosphoric acid-based chelating agents comprising tripolyphosphates as a main component thereof have good water solubility and detergency, so that they have been formulated as main detergent builder ingredients.
- Japanese Patent Laid-Open Nos. 62-167396, 62-167399, and 62-253699 disclose a remarkable decrease in the amount of crystalline inorganic salts such as sodium sulfate used as powdering aids conventionally contained in detergents.
- Japanese Patent Laid-Open Nos. 61-69897, 61-69899, 61-69900, and 5-209200 disclose that an increase in the bulk density of the detergents.
- detergents having a bulk density of from 0.60 to 1.00 g/ml, whose standard amount of dosage is from 25 to 30 g/30 L, can be produced, thereby resulting in making the detergents compact to a level of a standard volumetric amount of from 25 to 50 ml/30 L.
- sebum dirt stains ascribed to human bodies, the most typical dirt stains adhered to clothes (most likely to be observed on collars and sleeves), are taken as examples.
- the sebum dirt stains contains oily components, such as free fatty acids and glycerides, with a high content of 70% or more (Ichiro KASHIWA et al., "Yukagaku,” 19 , 1095 (1969)), of which the disclosure is incorporated herein by reference.
- the oily components lock carbon and dirt in dust and peeled keratin, so that the resulting substance is observed as dirt stains.
- conventionally detergents are designed based on a washing mechanism mainly by making these oily components soluble with micelle of surfactants, thereby detaching carbon, dirt, and keratin from clothes.
- This technical idea has been widely established among those of ordinary skill in the art, and even when the conventional detergents are shifted to compact detergents, substantially no changes took place in the surfactant concentration in the washing liquid. This fact is described in "Dictionary for Detergents and Washing," Haruhiko OKUYAMA et al., p. 428, 1990, First Edition, Asakura Publishing Company Limited, of which the disclosure is incorporated herein by reference, which shows that there are substantially no changes in concentrations in the washing liquid for components other than sodium sulfate.
- the surfactant concentration in the washing liquid has to be made high in order to achieve high washing power, so that a large amount of surfactants has to be blended in the detergent composition. Therefore, a drastic reduction in the standard amount of dosage of the detergents was actually difficult.
- the presently known production method substantially enables to increase the bulk density to a level of about at most 1.00 g/ml. Therefore, a further reduction in the standard volumetric amount was deemed to be technically extremely difficult problem.
- crystalline alkali metal silicates having particular structure disclosed in Japanese Patent Laid-Open Nos. 5-184946 and 60-227895, of which the disclosure is incorporated herein by reference, shows not only good ion exchange capacity but also actions of alkalizing agents (alkalizing ability). Therefore, possibility of more compact detergents has been studied because both of the functions which conventionally have been satisfied by two different components, including metal ion capturing agents, such as zeolites, and alkalizing agents, such as sodium carbonate, can be satisfied with the above crystalline alkali metal silicates alone.
- metal ion capturing agents such as zeolites
- alkalizing agents such as sodium carbonate
- Japanese Patent Laid-Open No. 6-116588 of which the disclosure is incorporated herein by reference, is concerned with a detergent composition containing a crystalline alkali metal silicate.
- the detergent composition has a washing power substantially the same as conventional detergent compositions.
- the composition has a high surfactant concentration. Therefore, the ion exchange capacity are ascribed solely to the crystalline alkali metal silicates contained therein, so that the ion exchange capacity is insufficient for that needed for detergent compositions.
- the functions of the crystalline alkali metal silicates as alkalizing agents are prioritized over their functions as metal ion capturing agents, and the function as the metal ion capturing agent is not sufficiently exhibited, so that the washing power of the detergent composition is not always satisfactory. Therefore, if the amount of dosage of the detergent composition were reduced, a good washing power is not able to be maintained.
- Japanese Patent Unexamined Publication No. 6-502199 discloses a detergent comprising a layered crystalline silicate, a zeolite, and a polycarboxylate in particular proportions, to thereby provide a detergent which is free from providing film layer formation on fibers and has excellent washing power and bleaching agent stability.
- metal ion capturing agents such as zeolites
- conventional detergent granules include alkalizing agents and metal ion capturing agents.
- the detergent granules are generally produced by the following method.
- a slurry comprising aqueous dispersion of surfactants, mainly comprising anionic surfactants and nonionic surfactant; alkalizing agents, such as sodium carbonate and sodium silicates; calcium ion capturing agents (metal ion capturing agents), such as zeolites and sodium tripolyphosphate; fillers, such as sodium sulfate; and other components which are stable against heat is prepared. Thereafter, the resulting slurry is dried to be formed into granules. Subsequently, materials including perfumes which are unstable against heat, and in certain cases, bleaching agents and bleaching activators are post-blended, to give desired detergent granules.
- surfactants mainly comprising anionic surfactants and nonionic surfactant
- alkalizing agents such as sodium carbonate and sodium silicates
- calcium ion capturing agents such as zeolites and sodium tripolyphosphate
- fillers such as sodium sulfate
- other components which are stable against heat is
- phosphorus-based metal ion capturing agents typically exemplified by tripolyphosphates have been formulated in dry granules, the tripolyphosphates being generally employed as calcium ion capturing agents before the use of zeolites. This is because the phosphorus-based metal ion capturing agents have a function of alkalizing agents besides the calcium ion capturing capacity and also have most suitable properties for improving powder properties, such as flowability, of the dried granules.
- the alkalizing agents such as alkali metal carbonates and alkali metal silicates, also have characteristics of improving flowability by mechanically strengthening the granules themselves, the alkalizing agents act to form surfactants with plasticity and form zeolite fine particles into granules, so that the alkalizing agents are generally included in the same granules as the surfactants and the zeolites.
- the dissolution of these components may simultaneously show alkalizing ability and metal ion capturing capacity in the washing liquid.
- the alkalizing ability is exhibited earlier than the metal ion capturing capacity because a rate of reaction of the metal ion capturing agents with calcium ions and magnesium ions in water is delayed more than a rate of reaction of an alkalizing agent and water.
- liquid detergents wherein the metal ion capturing agents and the alkalizing agents are mixed in the same liquid, the alkalizing ability and the metal ion capturing capacity may be simultaneously shown, or the alkalizing ability is shown earlier than the metal ion capturing capacity.
- most man-derived sebum dirt stains contain fatty acids.
- calcium and magnesium ions together with fatty acids form a scum, thereby lowering dissolution and inhibiting the dispersion of the dirt stains in water.
- the present inventors have found that the scum-formation rate becomes faster as the alkalization degree (pH) becomes higher, and that washing performance cannot be optimally exhibited in conventional washing methods.
- the alkalizing agents are blended simply for the following purposes: Since the zeolites are water-insoluble, the zeolites are added for preventing the zeolites to remain on fibers caused by the action of the silicates to suppress the dispersion of the zeolite in cases where the zeolites are blended with silicates in the form of fine particles. Also, the zeolites are added to improve caking resistance and solubility of the detergents. Moreover, in the conventional detergents mentioned above, since the alkalizing agents directly contact the washing liquid, the initiation of the alkalizing effect is faster than the case where the metal ion capturing agent and the surfactants are formulated in the same granules.
- US-A-4 632 768 refers to clay fabric softener agglomerates to overcome the problem of cloging dispensers in automatic washing machines.
- the softener clays are formed into agglomerates and coated with a dispensing aid, wherein water-soluble quaternary ammonium compounds are preferred.
- a smectite clay agglomerate is coated with a saturated aqueous solution of tallow alkyl trimethyl ammonium chloride, and the coated agglomerate is mixed with a base granulate comprising an alkyl benzene sulfonate and EDTA.
- An object of the present invention is to provide a most effective high-detergent granular detergent composition for exhibiting excellent detergency even when the amount of dosage is small in the formulation composition comprising crystalline alkali metal silicates.
- the present inventors have found that since the granular detergent composition comprises particular blending ratios, wherein the granules containing the crystalline alkali metal silicates and granules containing the metal ion capturing agents are blended as separate granules, an optimum detergency can be obtained even when the amount of dosage is small.
- the present invention has been completed based on these findings.
- the present invention is concerned with the following.
- A is an intersection of the extension of the linear portion of Line Q with the abscissa (horizontal axis); P shows the data of the blank solution (buffer solution without using the chelating agent); and Q shows the data for the chelating agent-containing buffer solution.
- the high-density granular detergent composition of the present invention comprises the following components:
- the high-density granular detergent composition of the present invention preferably has a bulk density exceeding 0.5 g/cc, more preferably from 0.7 to 1.1 g/cc.
- the surfactants usable in the present invention are not particularly limited, and any ones generally used for detergents are used, in which the amount of a nonionic surfactant is preferably from 50 to 100% by weight, more preferably from 65 to 100% by weight, of the entire surfactant.
- they may be one or more surfactants selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, each being exemplified below.
- the surfactants can be chosen such that the surfactants of the same kind are chosen, as in the case where a plurality of the nonionic surfactants are chosen.
- the surfactants of the different kinds can be chosen, as in the case where the anionic surfactant and the nonionic surfactant are respectively chosen.
- soap surfactants do not contribute to detergency, their formulated amounts are not counted as the amounts of the surfactant components in the present invention.
- nonionic surfactants examples include:
- Polyoxyethylene alkyl ethers polyoxyethylene alkylphenyl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alkyl esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene castor oils, polyoxyethylene alkylamines, glycerol fatty acid esters, higher fatty acid alkanolamides, alkylglycosides, alkylglucosamides, and alkylamine oxides.
- polyoxyethylene alkyl ethers which are ethylene oxide adducts of primary or secondary alcohols, whose alkyl moieties are linear or branched, each having 10 to 18 carbon atoms, and the average molar number of ethylene oxide is from 5 to 15. It is more desired that polyoxyethylene alkyl ethers which are ethylene oxide adducts of primary or secondary alcohols, whose alkyl moieties are linear or branched, each having 12 to 14 carbon atoms, and the average molar number of ethylene oxide is from 6 to 10.
- anionic surfactants examples include alkylbenzenesulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, ⁇ -olefinsulfonates, ⁇ -sulfofatty acid salts, ⁇ -sulfofatty acid ester salts, alkyl or alkenyl ether carboxylates, amino acid-type surfactants, and N-acyl amino acid-type surfactants, with a preference given to alkylbenzenesulfonates, alkyl or alkenyl ether sulfates, and alkyl or alkenyl sulfates.
- Examples of the cationic surfactants include quaternary ammonium salts, such as alkyl trimethylamine salts.
- Examples of the amphoteric surfactants include carboxy-type and sulfobetaine-type amphoteric surfactants.
- the surfactant content is preferably from 1 to 45% by weight in the entire detergent composition, and the surfactant content is particularly in the following ranges, depending on the types of water for washing used.
- the content is preferably not lower than the lower limit of the above range, from the aspect of obtaining sufficient detergency, and the content is preferably not higher than the upper limit of the above range, from the aspect of maintaining good proportions of the alkalizing agents and the metal ion capturing agents, thereby making it possible to achieve good detergency.
- the crystalline alkali metal silicates are suitably used.
- Crystalline and amorphous alkali metal silicates have been known as the alkali metal silicates, but the crystalline silicates are highly preferred owing to its good ion capturing ability as well as its good alkalizing ability, so that the standard amount of dosage of the detergent composition can be even further reduced. Therefore, crystalline alkali metal silicates are preferred.
- the crystalline alkali metal silicates usable in the present invention include alkali metal silicates preferably having SiO 2 /M 2 O molar ratios of from 0.5 to 2.6, wherein M stands for an alkali metal atom. Also, the preferred ranges of the SiO 2 /M 2 O molar ratios are 1.5 to 2.2.
- the above molar ratio is preferably 0.5 or more from the aspect of obtaining good ion exchange capacity and hygroscopic property, and the molar ratio is preferably 2.6 or less from the aspect of obtaining good alkalizing ability.
- the crystalline alkali metal silicates used in patent publications discussed in BACKGROUND ART section of the present invention have SiO 2 /Na 2 O molar ratios (S/N ratio) of from 1.9 to 4.0.
- S/N ratio SiO 2 /Na 2 O molar ratios
- crystalline alkali metal silicates usable in the present invention
- M stands for an element in Group Ia of the Periodic Table
- Me stands for one or more members selected from the group consisting of elements in Groups IIa, IIb, IIIa, IVa, and VIII of the Periodic Table
- y/x is from 0.5 to 2.6
- z/x is from 0.01 to 1.0
- n/m is from 0.5 to 2.0
- w is from 0 to 20.
- M 2 O•x'SiO 2 •y'H 2 O wherein M stands for an alkali metal atom; x' is from 1.5 to 2.6; and y' is from 0 to 20.
- M stands for an element selected from elements in Group Ia of the Periodic Table, wherein the Group Ia elements may be exemplified by Na, K, etc.
- the Group Ia elements may be used alone, or in combination of two or more kinds. For instance, such compounds as Na 2 O and K 2 O may be mixed to constitute an M 2 O component.
- Me stands for one or more members selected from the group consisting of elements in Group IIa, IIb, IIIa, IVa, and VIII of the Periodic Table, and examples thereof include Mg, Ca, Zn, Y, Ti, Zr, and Fe, which are not particularly limited to the above examples.
- Mg and Ca from the viewpoint of resource stock and safety.
- these elements may be used alone, or in combination of two or more kinds.
- such compounds as MgO and CaO may be mixed to constitute an Me m O n component.
- the crystalline alkali metal silicates in the present invention may be in the form of hydrates, wherein the amount of hydration (w) is usually in the range of from 0 to 20 moles of H 2 O.
- y/x is from 0.5 to 2.6, more preferably from 1.5 to 2.2.
- y/x is preferably 0.5 or more.
- powder properties of the detergent composition such as caking properties, solubility, etc. are drastically lowered.
- y/x is preferably 2.6 or less.
- z/x it is preferably from 0.01 to 1.0, more preferably from 0.02 to 0.9, still more preferably from 0.02 to 0.5. From the aspect of the anti-solubility in water, z/x is preferably 0.01 or more, and from the aspect of sufficiently functioning as ion exchange materials, z/x is preferably 1.0 or less.
- y/x and z/x there are no limitations, as long as y/x and z/x have the above relationships.
- xM 2 O for example, is x'Na 2 O•x"K 2 O as described above, x equals to x' + x".
- zMe m O n comprises two or more components.
- "n/m is from 0.5 to 2.0" indicates the number of oxygen ions coordinated to the above elements, which actually takes values selected from 0.5, 1.0, 1.5, and 2.0.
- the crystalline alkali metal silicate having the composition (1) consists of three components, M 2 O, SiO 2 , and Me m O n . Materials which can be converted to each of these components, therefore, are indispensable for starting materials for producing the crystalline alkali metal silicates in the present invention.
- known compounds can be suitably used for starting materials for the crystalline alkali metal silicates without limitations.
- the M 2 O component and the Me m O n component include simple or complex oxides, hydroxides and salts of respective elements; and minerals containing respective elements.
- examples of the starting materials for the M 2 O component include NaOH, KOH, Na 2 CO 3 , K 2 CO 3 , and Na 2 SO 4 .
- Examples of the starting materials for the Me m O n component include CaCO 3 , MgCO 3 , Ca(OH) 2 , Mg(OH) 2 , MgO, ZrO 2 , and dolomite.
- Examples of the starting materials for the SiO 2 component include silica sand, kaolin, talc, fused silica, and sodium silicate.
- the method of producing the crystalline alkali metal silicate having the composition (1) may be exemplified by blending these starting material components to provide a desired composition in x, y, and z for the crystalline alkali metal silicate, and baking the resulting mixture at a temperature in the range of preferably from 300° to 1500°C, more preferably from 500° to 1000°C, still more preferably from 600° to 900°C, to form crystals.
- the heating temperature is preferably 300°C or more in order to sufficiently complete the crystallization. When the crystallization is insufficient, it may result in poor anti-solubility in water of the resulting crystalline alkali metal silicate.
- the heating temperature is preferably 1500°C or less, so that the formation of coarse grains are likely to be prevented. When the coarse grains are formed, it may result in a decrease in the ion exchange capacity of the resulting crystalline alkali metal silicate.
- the heating time is preferably 0.1 to 24 hours. Such baking can be preferably carried out in a heating furnace such as an electric furnace or a gas furnace.
- the crystalline alkali metal silicate in the present invention has an excellent alkalizing ability, to a level that its maximum pH value exceeds 11 at 25°C in a 0.1% by weight dispersion. Also, it has an excellent alkaline buffering ability to a level that it takes 10 ml or more of a 0.1 N HCl aqueous solution to lower its pH to 10 at 25°C in 100 ml of a 0.1% by weight dispersion. In addition, the crystalline alkali metal silicate particularly has an excellent alkaline buffering effects, showing remarkably superior alkaline buffering effects to those of sodium carbonate and potassium carbonate.
- the crystalline alkali metal silicate in the present invention preferably has an ion exchange capacity of 100 CaCO 3 mg/g or more, more preferably from 200 to 600 CaCO 3 mg/g. Therefore, the crystalline alkali metal silicate is one of the materials having ion capturing ability in the present invention.
- the amount of Si dissolved in water is preferably 110 mg/g or less, when calculated as SiO 2 , indicating that the crystalline alkali metal silicate is substantially insoluble in water.
- substantially insoluble in water refers to those having an amount of Si dissolved, when calculated as SiO 2 , of preferably less than 110 mg/g, measurement being taken when adding a 2 g sample 100 g of ion-exchanged water and stirring the mixture at 25°C for 30 minutes.
- the crystalline alkali metal silicate having an amount of Si dissolved in water of 100 mg/g or less are more preferred.
- the crystalline alkali metal silicate in the present invention has not only good alkalizing ability and alkaline buffering effects but also good ion exchange capacity, good detergency can be obtained by adding suitable amounts of the crystalline alkali metal silicate.
- the crystalline alkali metal silicate has an average particle size of preferably from 0.1 to 50 ⁇ m, more preferably from 1 to 35 ⁇ m, still more preferably from 5 to 25 ⁇ m.
- the average particle size of the crystalline alkali metal silicate is preferably 50 ⁇ m or less.
- the average particle is preferably 0.1 ⁇ m or more.
- the crystalline alkali metal silicate having the average particle size and the particle size distribution described above is prepared by pulverizing using pulverizing devices, such as vibration mills, hammer mills, ball-mills, and roller mills.
- pulverizing devices such as vibration mills, hammer mills, ball-mills, and roller mills.
- the crystalline alkali metal silicate can be easily obtained by pulverizing the material with a vibrating mill "HB-O" (manufactured by Chuo Kakohki Co., Ltd.).
- the content of the crystalline alkali metal silicate having the general formula (1) is preferably from 4 to 75% by weight in the entire composition, with a particular preference given to the following compositions depending upon the water hardness of the water for washing used.
- the content of the crystalline alkali metal silicate is preferably within the above range from the aspect of satisfying good detergency.
- These crystalline alkali metal silicates are represented by the general formula (2): M 2 O•x'SiO 2 •y'H 2 O, wherein M stands for an alkali metal atom; x' is from 1.5 to 2.6; and y' is from 0 to 20.
- M stands for an alkali metal atom
- x' is from 1.5 to 2.6
- y' is from 0 to 20.
- the above crystalline alkali metal silicates are one of the materials having ion capturing ability in the present invention.
- the crystalline alkali metal silicate in the present invention has not only good alkalizing ability and alkaline buffering capacity but also good ion exchange capacity, good detergency can be obtained by adding suitable amounts of the crystalline alkali metal silicate.
- the content of the crystalline alkali metal silicate having the general formula (2) is preferably 4 to 75% by weight in the entire composition, with a particular preference given to the following compositions depending upon the water hardness of the water for washing used.
- the content of the crystalline alkali metal silicate is preferably within the above range from the aspect of satisfying good detergency.
- a method for producing the above crystalline alkali metal silicates is disclosed in Japanese Patent Laid-Open No. 60-227895, of which the disclosure is incorporated herein by reference.
- the crystalline alkali metal silicates may be generally produced by baking glassy amorphous sodium silicate at a temperature of from 200° to 1000°C. Details of the production method is disclosed in "Phys. Chem. Glasses, 7 , pp.127-138 (1966), Z. Kristallogr., 129 , pp.396-404(1969)," of which the disclosure is incorporated herein by reference.
- the crystalline alkali metal silicates are commercially available in powdery or granular forms under a trade name "Na-SKS-6" ( ⁇ -Na 2 Si 2 O 5 ) (manufactured by Hoechst).
- Japanese Patent Laid-Open No. 7-187655 discloses a crystalline alkali metal silicate containing not only sodium but also a particular amount of potassium.
- the crystalline alkali metal silicates having the composition (2) have an average particle size of preferably from 0.1 to 50 ⁇ m, more preferably from 1 to 35 ⁇ m, still more preferably from 5 to 25 ⁇ m.
- the crystalline alkali metal silicates having the compositions (1) and (2) may be used alone or in combination. It is preferred that the crystalline alkali metal silicates occupy 50 to 100% by weight, more preferably from 70 to 100% by weight, of the total content of the alkalizing agents.
- the metal ion capturing agents of Component C in the present invention are preferably those having a calcium ion capturing capacity of 200 CaCO 3 mg/g or more, and any one of those conventionally formulated in detergent compositions other than Component B may be used.
- an aluminosilicate having an ion exchange capacity of 200 CaCO 3 mg/g or more and having the following formula (3): x"(M 2 O)•Al 2 O 3 •y"(SiO 2 )•w"(H 2 O), wherein M stands for an alkali metal atom, such as sodium or potassium atom; x", y", and w" each stands for a molar number of each component; and generally, x" is from 0.7 to 1.5; y" is from 0.8 to 6.0; and w" is from 0 to 20.
- aluminosilicates mentioned above may be crystalline or amorphous, and among the crystalline aluminosilicates, a particular preference is given to those having the following general formula: Na 2 O•Al 2 O 3 •ySiO 2 •wH 2 O, wherein y is a number of from 1.8 to 3.0; and w is a number of from 1 to 6.
- zeolites As for the crystalline aluminosilicates (zeolites), synthetic zeolites having an average, primary particle size of from 0.1 to 10 ⁇ m, which are typically exemplified by A-type zeolite, X-type zeolite, and P-type zeolite, are suitably used.
- the zeolites may be used in the forms of powder, a zeolite slurry, or dried particles comprising zeolite agglomerates obtained by drying the slurry.
- the zeolites of the above forms may also be used in combination.
- the amorphous aluminosilicates represented by the same general formula as the above crystalline aluminosilicate are also obtainable by conventional methods.
- the intended product may be advantageously obtained by heat-treating a white slurry of precipitates thus formed preferably at 70° to 100°C, more preferably 90° to 100°C, for preferably 10 minutes or more and 10 hours or less, more preferably 5 hours or less, followed by filtration, washing and drying.
- the addition method may comprise adding the aqueous solution of an alkali metal silicate to the aqueous solution of a low-alkali alkali metal aluminate.
- the oil-absorbing amorphous aluminosilicate carrier having an ion exchange capacity of preferably 100 CaCO 3 mg/g or more and an oil-absorbing capacity of preferably 80 ml/100 g or more can be easily obtained (see Japanese Patent Laid-Open Nos. 62-191417 and 62-191419, of which the disclosure is incorporated herein by reference).
- the metal ion capturing agents containing a carboxylate polymer in an amount of 10% by weight or more.
- the above carboxylate polymer include polymers or copolymers, each having repeating units represented by the general formula (4): wherein X 1 stands for a methyl group, a hydrogen atom, or a COOX 3 group; X 2 stands for a methyl group, a hydrogen atom, or a hydroxyl group; X 3 stands for a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or 2-hydroxyethylammonium ion.
- examples of the alkali metal ions include Na, K, and Li ions
- examples of the alkaline earth metal ions include Ca and Mg ions.
- polymers or copolymers usable in the present invention include those obtainable by polymerization reactions of acrylic acid, (anhydrous) maleic acid, methacrylic acid, ⁇ -hydroxyacrylic acid, crotonic acid, isocrotonic acid, and salts thereof; copolymerization reactions of each of the monomers; or copolymerization reactions of the above monomers with other copolymerizable monomers.
- examples of the other polymerizable monomers used in copolymerization reaction include aconitic acid, itaconic acid, citraconic acid, fumaric acid, vinyl phosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, propylene, isobutylene, pentene, butadiene, isoprene, vinyl acetate (vinyl alcohols in cases where hydrolysis takes place after copolymerization), and acrylic ester, without particularly being limited thereto.
- polyacetal carboxylic acid polymers such as polyglyoxylic acids disclosed in Japanese Patent Laid-Open No. 54-52196, of which the disclosure is incorporated herein by reference, are also usable for the polymers in the present invention.
- the above polymers and copolymers preferably have a weight-average molecular weight of from 800 to 1,000,000, more preferably from 5,000 to 200,000.
- the above polymers or copolymers may be formulated in an amount of preferably from 1 to 50% by weight, more preferably 2 to 30% by weight, still more preferably from 5 to 15% by weight, in the entire composition.
- examples of the other metal ion capturing agents of Component C include aminotri(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), and salts thereof; salts of phosphonocarboxylic acids, such as salts of 2-phosphonobutane-1,2-dicarboxylic acid; amino acid salts, such as aspartates and glutamates; polycarboxylates, such as citrates and tartrates; and aminopolyacetates, such as nitrilotriacetates and ethylenediaminetetraacetates.
- the surfactants, the crystalline alkali metal silicate, and the metal ion capturing agents are needed to be formulated in particular compositional weight ratios.
- the crystalline alkali metal silicates are explained in detail above.
- the crystalline layered silicates disclosed in Japanese Patent Laid-Open No. 60-227895 shows good alkalizing ability as well as good ion exchange capacity.
- the present inventors have found that it would be difficult to achieve the objects of the present inventions by a mere substitution with the crystalline alkali metal silicate.
- the simple substitution with the crystalline alkali metal silicate would cause to drastically impair the compositional balance as a whole detergent, so that sufficiently good detergency cannot be obtained.
- the metal ion capturing agents other than the crystalline alkali metal silicate are essential ingredients, and the effects of the present invention cannot be obtained unless the other metal ion capturing agents are formulated in a particular compositional weight ratio to the crystalline alkali metal silicate in the granular detergent composition.
- the present inventors have found that the surfactant concentration in the washing liquid can be notably lowered when the crystalline alkali metal silicate and the other metal ion capturing agents are formulated in a particular compositional weight ratio in the detergent composition.
- the standard amount of dosage of the detergent composition can be further lowered.
- the granular detergent composition comprises granules (I) containing the crystalline alkali metal silicate of Component B and the granules (II) containing the metal ion capturing agents of Component C, the granules (I) and the granules (II) being present in substantially separate granules, the detergent composition exhibits the highest washing capability.
- the amount of the alkalizing agents other than Component B included in the high-density granular detergent composition of the present invention is preferably 20% by weight or less, more preferably 10% or less, of the entire granular detergent composition. It is preferred that the crystalline alkali metal silicate of Component B is substantially present in the granules (I), and that the granules (I) are granulated products of the crystalline alkali metal silicate.
- the granulation is preferably carried out in a non-aqueous system, wherein organic substances and/or inorganic substance are preferably used as granulating agents (binders). Specifically ingredients including Component B in the granules (I) are coated by binders comprising the organic substances.
- the organic substances usable for binders include nonionic surfactants in a solid state at room temperature, polyethylene glycols, and gel-formable anionic surfactants.
- the binders made of the organic substances comprise nonionic surfactants, the nonionic surfactants being contained in an amount of preferably 50% by weight or more of the entire binders comprising organic substances.
- the amount of the nonionic surfactants is preferably 50% by weight or more from the aspect of having good detergency, thereby making it possible to wash items with a small standard amount of dosage without impairing its detergency.
- the nonionic surfactants which may be usable for binders are not particularly limited, and any of conventionally known ones may be used. Examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene fatty acid esters, alkyl polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene castor oils, polyoxyethylene alkylamines, glycerol fatty acid esters, higher fatty acid alkanolamides, alkylglycosides, alkylglucosamides, and alkylamine oxides.
- nonionic surfactants a preference is given to at least one member selected from polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers, from the aspect of detergency.
- the gel-formable anionic surfactants are not particularly limited, and any of conventionally known ones may be used. Examples thereof include alkali metal salts of saturated or unsaturated fatty acids, of which the alkyl moiety preferably has from 10 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms; alkyl sulfates, of which the alkyl moiety preferably has from 10 to 22 carbon atoms, more preferably from 12 to 14 carbon atoms; salts of ⁇ -sulfonated fatty acids, of which the alkyl moiety preferably has from 10 to 22 carbon atoms, more preferably from 14 to 16 carbon atoms; and polyoxyethylene alkyl ether sulfates, of which the alkyl moiety has preferably from 10 to 22, and the average molar number of ethylene oxide moiety is from 0.2 to 2.0, and more preferably, polyoxyethylene alkyl ether sulfates, of which the alkyl moiety has preferably from 12 to 14, and the average m
- each of the above compounds listed above it has preferably 10 or more carbon atoms from the viewpoints of detergency and odor, and it has preferably 22 or less carbon atoms from the viewpoints of detergency and solubility.
- the gel-formable anionic surfactants may be added in the form of acids, and then neutralized with the crystalline alkali metal silicate in a solid state.
- the polyethylene glycols used herein include those having a weight-average molecular weight of preferably 3000 or more, more preferably from 3000 to 20000, still more preferably from 5000 to 13000.
- binders usable in the present invention include at least one of saturated fatty acids and unsaturated fatty acids, of which the alkyl moiety has 12 to 20 carbon atoms. Besides them, polyvinyl alcohols, hydroxypropylmethyl cellulose, hydroxypropyl starches, and carboxymethyl cellulose having a low polymerization degree may be also included as binder ingredients. Also, metal soaps having a high water repellency, calcium carbonate, and silica powder may be also used therefor. Incidentally, in the case where a surfactant is used for a binder, it is considered as a part of a whole part of Component A.
- particularly preferred examples include polyoxyethylene alkyl ethers and mixtures of the polyoxyethylene alkyl ethers and gel-formable anionic surfactants.
- composition comprising zeolite and a crystalline alkali metal silicate in separate granules is disclosed, but the granules comprise a zeolite-containing granule containing large amounts of sodium carbonate as an alkalizing agent, never suggesting the detergent composition of the present invention.
- the binder is preferably added at a level needed for surface-coating such ingredients as the crystalline alkali metal silicate.
- the exhibition of the alkalizing ability in the washing liquid would be delayed, so that the scum formation rate in the sebum dirt stains which has been conventionally speeded up by the alkalis is slowed down, and that the metal ion capturing agents in the granules (II) can effectively function.
- the fatty acids in the sebum dirt stains act as soaps so as to aid the micelle formation of the dirt stains, thereby improving detergency.
- the binder is added in the granules (I) in an amount of preferably from 10 to 80% by weight, more preferably from 30 to 70% by weight, depending upon the kinds of binders used.
- the method for preparing the granules (I) there may be included a method for granulating an alkalizing agent by using a sufficient amount of an organic substance exemplified above as a binder.
- a method for coating an alkalizing agent with a coating agent in a fluidized bed the coating agent being exemplified by polyvinyl alcohols, hydroxypropylmethyl cellulose, hydroxpropyl starches, and carboxymethyl cellulose having a low polymerization degree.
- metal soaps having high water repellency, and hardly soluble calcium carbonate and silica powder may be also added.
- ingredients which may be formulated in the granules (I) include optional ingredients which can be generally formulated in the detergent compositions exemplified below.
- the aluminosilicates may be optionally formulated.
- the amorphous aluminosilicates having good oil-absorbing capacity may be formulated to thereby reduce the bleed-out of the nonionic surfactants and improve anti-caking property.
- the surfaces of the granules may be coated to thereby have good flowability of the powder.
- the aluminosilicates also have an ion exchange capacity, it is preferred that a major portion of the aluminosilicates is not being present in the granules (I) except for those used for improving the powder properties.
- the granules (I) preferably have an average particle size of from 300 to 1000 ⁇ m, with a preference to given those having a narrow particle size distribution with an even size as much as possible.
- the granules (I) may be easily prepared by spraying binders to the powder starting materials in a mixer in which agitation, tumbling and mixing are usually carried out.
- the granules (II) may comprise one or more metal ion capturing agents of Component C, such as aluminosilicates and polycarboxylates, without a binder, or the granules (II) may be granules prepared by using a binder.
- Component C such as aluminosilicates and polycarboxylates
- the granules (II) may be prepared by the following method:
- the metal ion capturing agents such as aluminosilicates, polycarboxylates, and carboxylic polymers, anionic surfactants used as base surfactants, nonionic surfactants, such as salts of fatty acids and polyoxyethylene alkyl ethers, and inorganic substances, such as sodium sulfate, are added to prepare a slurry, the anionic surfactants being one or more members selected from alkylbenzenesulfonates, ⁇ -olefinsulfonates, alkyl sulfates, polyoxyalkylene alkyl ether sulfates, and methyl ester of ⁇ -sulfofatty acids.
- the resulting slurry is spray-dried and formed into powder to be used as the granules (II). More preferably, in order to increase the bulk density of the resulting granules (II), the spray-dried granules are further subjected to disintegration and granulation as disclosed in Japanese Patent Laid-Open Nos. 61-69897, 61-69898, and 61-69900, of which the disclosure is incorporated herein by reference. By utilizing the methods for increasing density, the granules (II) having excellent solubility can be obtained, thereby making it possible to allow the ion exchanging to take place prior to the action of the alkalizing agent.
- the alkalizing agents are not included in the granules (II), for the purposes of easily carrying out the spray-drying process and of increasing mechanical strength of the granules, amorphous sodium silicates as defined in JIS may be formulated.
- substantially all of the alkalizing agents are preferably contained in the granules (I) mentioned above.
- the crystalline alkali metal silicate contained in the granules (I) occupies preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, of the alkalizing agents in the entire high-density granular detergent composition.
- the granules (I) may, for instance, comprise the following constituents: Crystalline alkali metal silicates of Component B, binders, aluminosilicates, the aluminosilicates being added in an amount sufficient for improving powder properties, and optionally other alkalizing agents and detergent additives, such as perfumes and fluorescent dyes.
- the granules (II) may, for instance, comprise anionic surfactants; aluminosilicates, such as zeolites; polycarboxylates and carboxylic polymers; inorganic salts, such as sodium sulfate; and optionally amorphous sodium silicates added as backbone substances and detergent additives, such as perfumes and fluorescent dyes.
- the most effective construction in the present invention is such that substantially all of the metal ion capturing agents other than Component B (namely Component C) are contained in the granules (II). Further, it is most effective when the granules (I) have such a construction that the alkalizing agents included therein are coated with a relatively large amount of the binders.
- sodium carbonate may be used as an alkalizing agent, it is preferred that the sodium carbonate is contained in the granules (I) as described above. However, in a case where a large amount of sodium carbonate is formulated in the granules, it is likely to have water of crystallization by its hygroscopicity, which externally precipitates, thereby causing to lower the bulk density. Therefore, it is preferred that the content of sodium carbonate is 10% by weight or less, preferably 5% by weight or less, of the entire detergent composition.
- the following ingredients may be also contained in the granular detergent composition of the present invention.
- enzymes such as proteases, lipases, cellulases, and amylases
- caking preventives such as lower alkylbenzenesulfonates whose alkyl moieties have about 1 to 4 carbon atoms, sulfosuccinates, talc, and calcium silicates
- antioxidants such as tert-butylhydroxytoluene and distyrenated cresol
- bleaching agents such as sodium percarbonate
- bleaching activators such as tetraacetyl ethylenediamine
- fluorescent dyes such as blueing agents
- perfumes may be included in the detergent composition.
- optional ingredients enzymes, bleaching agents, and bleaching activators may be formed into separate third granules and blended in the detergent composition of the present invention.
- the optional ingredients are not particularly limited, and they may be blended so as to give desired compositions suitable for their purposes.
- examples of the alkalizing agents included in the high-density detergent composition of the present invention other than Component B include sodium carbonate, sodium hydrogen carbonate, and a small amount of a sodium silicate such as JIS No. 1 or No. 2 so as not to lower the dissolution.
- the tap water has water hardness greatly differing in various countries and geographical circumstances throughout the world. For instance, while the tap water has a water hardness of usually around 4°DH in Japan, the tap water having a water hardness of 6°DH or more in the U.S., and that exceeding 10°DH in European countries is used for the water for washing. Therefore, since the required absolute amount of the metal ion capturing agents varies, the standard detergent concentration would be optimally adjusted accordingly.
- the detergent concentrations are as follows:
- the DH water hardness is measured by an ion coupling plasma method (ICP method).
- the ion capturing ability is measured by the following different methods in accordance with a case where the materials used having a metal ion capturing capacity are ion exchange materials and a case where the materials are chelating agents.
- the ion capturing capacity of the metal ion capturing agents are expressed by CEC (calcium ion exchange capacity) in Tables as in the same manner as in alkali metal silicates.
- the DH water hardness is measured by ion-coupling plasma method (ICP method).
- the amount 0.1 g of an ion exchange material is accurately weighed and added to 100 ml of a calcium chloride aqueous solution (500 ppm concentration, when calculated as CaCO 3 ), followed by stirring at 25°C for 60 minutes. Thereafter, the mixture is filtered using a membrane filter (made of nitrocellulose; manufactured by Advantech) with 0.2 ⁇ m pore size. The amount 10 ml of the filtrate is assayed for Ca content by an EDTA titration, and the calcium ion exchange capacity (cationic exchange capacity) of the ion exchange material is calculated from the titer.
- the calcium ion capturing capacity of the chelating agent is measured by the following method using a calcium ion electrode.
- the solution used herein is prepared with the following buffer solution:
- a standard calcium ion solution is prepared and voltage readings are taken to prepare a calibration curve showing the relationships between the logarithm of the calcium ion concentration and the voltage, as shown in Figure 1.
- a chelating agent About 0.1 g of a chelating agent is weighed, and a 100 ml volumetric flask is charged with the chelating agent. The volumetric flask is filled up to a volume of 100 ml with the above buffer solution.
- a CaCl 2 aqueous solution (pH 10.0) having a calcium ion concentration of 20,000 ppm calculated as CaCO 3 is added dropwise from a burette. The dropwise addition is made in an amount of 0.1 to 0.2 ml for each voltage reading.
- the buffer solution without containing the chelating agent is also subjected to the same dropwise treatment of the CaCl 2 aqueous solution.
- a calcium ion concentration is calculated from the calibration curve given in Figure 1 by taking a voltage reading.
- the relationship between the amount of the CaCl 2 aqueous solution added dropwise and the calcium ion concentration is shown in a graph ( Figure 2).
- Figure 2 Line P shows the data of the blank solution (buffer solution without using the chelating agent), and Line Q shows the data for the chelating agent-containing buffer solution.
- the point where the extension of the linear portion of Line Q intersects with the abscissa (horizontal axis) is called "A.”
- the calcium ion capturing capacity of the chelating agent is obtained from the calcium ion concentration at "A" of the blank solution.
- the average particle size and the particle size distribution are measured by using a laser scattering particle size distribution analyzer. Specifically, about 200 ml of ethanol is poured into a measurement cell of a laser scattering particle size distribution analyzer ("LA-700," manufactured by HORIBA Ltd.), and about 0.5 to 5 mg of the crystalline alkali metal silicate is suspended in ethanol. Next, while subjecting the obtained ethanol suspension to ultrasonic wave irradiation, the mixture is agitated for one minute, to thereby sufficiently disperse the crystalline alkali metal silicate. Thereafter, the resulting mixture is subjected to an He-Ne laser beam (632.8 nm) irradiation to measure diffraction/scattering patterns.
- LA-700 laser scattering particle size distribution analyzer
- the particle size distribution is obtained from the diffraction/scattering patterns.
- the analysis is made based on the combined theories of Fraunhofer diffraction theory and Mie scattering theory.
- the particle size distribution of the suspended particles in the liquid is measured within the size range of from 0.04 to 262 ⁇ m.
- the average particle size is a median diameter of the particle size distribution.
- Sodium carbonate was dissolved in ion-exchanged water, to prepare an aqueous solution with 6% by weight concentration.
- 132 g of the above aqueous solution and 38.28 g of a sodium aluminate aqueous solution (conc. 50% by weight) were placed in a 1000-ml reaction vessel equipped with baffles.
- 201.4 g of a solution of No. 3 liquid glass diluted with twice the amount of water were added dropwise to the above mixed solution by under vigorous agitation at a temperature of 40°C over a period of 20 minutes.
- the reaction speed was optimized by adjusting the pH of the reaction system to 10.5 by blowing a CO 2 gas thereinto.
- the reaction system was heated up to a temperature of 50°C and stirred at 50°C for 30 minutes. Subsequently, an excess alkali was neutralized by blowing a CO 2 gas thereinto, and the pH of the reaction system was adjusted to 9.0.
- the obtained neutralized slurry was filtered under a reduced pressure using a filter paper (No. 5C, manufactured by Toyo Roshi Kaisha, Ltd.). The filtered cake was rinsed with water in an amount of 1000-folds that of the cake, and the rinsed cake was filtered and dried under the conditions of 105°C, 300 Torr, and 10 hours. Further, the dried cake was disintegrated, to give an amorphous aluminosilicate powder.
- the sodium aluminate aqueous solution was prepared by the steps of adding and mixing 243 g of Al(OH) 3 and 298.7 g of a 48% by weight NaOH aqueous solution in a 1000 ml four-necked flask, heating the mixture to a temperature of 110°C with stirring, and dissolving the components in 30 minutes to prepare a composition.
- the calcium ion capturing capacity was 176 CaCO 3 mg/g, and the oil-absorbing capacity was 285 ml/100 g.
- the content of the microporous capacity having a microporous diameter of less than 0.1 ⁇ m was 9.4% by volume in the entire micropores, and the content of the microporous capacity having a microporous diameter of not less than 0.1 ⁇ m and not more than 2.0 ⁇ m was 76.3% by volume in the entire micropores.
- the water content was 11.2% by weight.
- Crystalline Alkali Metal Silicate (simply abbreviated as "Crystalline Silicate” in the tables)
- a prepared in Preparation Example 1 (average particle size: 8 ⁇ m) were supplied in a Lödige Mixer (Matsuzaka Giken Co., Ltd., equipped with a jacket), and the components were agitated while keeping the jacket temperature at 70°C.
- the above components were further subjected to granulation by blending in advance at 70°C to prepare a mixture comprising 10.0 parts by weight of a polyoxyethylene alkyl ether ("NONIDET R-7,” manufactured by Mitsubishi Chemical Corporation, an alkylene oxide adduct, of which the alkyl moiety has 12 to 15 carbon atoms, and the ethylene oxide moiety has a molar number of 7.2) and 5.0 parts by weight of palmitic acid (“LUNAC P-95,” manufactured by Kao Corporation), and spraying the resulting mixture to the above components while agitating.
- a polyoxyethylene alkyl ether (“NONIDET R-7,” manufactured by Mitsubishi Chemical Corporation, an alkylene oxide adduct, of which the alkyl moiety has 12 to 15 carbon atoms, and the ethylene oxide moiety has a molar number of 7.2) and 5.0 parts by weight of palmitic acid (“LUNAC P-95,” manufactured by Kao Corporation
- a part or a whole part of the fatty acid was neutralized to form salts of the fatty acid on the surface of Crystalline Alkali Metal Silicate A having a high alkalizing ability, and thereby the surfaces of Crystalline Alkali Metal Silicate A were coated with gelated products comprising the polyoxyethylene alkyl ether and the salts of the fatty acid. Further, the resulting granules were surface-coated for improving the powder properties by adding 3.0 parts by weight of a zeolite (4A-type; average particle size: 3 ⁇ m, manufactured by Tosoh Corporation).
- crystalline alkali metal silicate granules (hereinafter simply referred to as "crystalline silicate granules") (I) thus obtained had a bulk density of 0.89 g/cm 3 and an average particle size of 452 ⁇ m.
- a zeolite (4A-type; average particle size: 3 ⁇ m, manufactured by Tosoh Corporation), 5.0 parts by weight of an acrylic acid-maleic acid copolymer ("SOKALAN CP-5,” manufactured by BASF; weight-average molecular weight: 70,000), 6.0 parts by weight of sodium sulfate, 1.0 part by weight of sodium sulfite, and 0.4 parts by weight of Fluorescent Dye B (“CINOPEARL CBS-X,” manufactured by Ciba Geigy AG) were added to prepare an aqueous slurry of 50% by weight solid content.
- SOKALAN CP-5 acrylic acid-maleic acid copolymer
- BASF weight-average molecular weight: 70,000
- 6.0 parts by weight of sodium sulfate 1.0 part by weight of sodium sulfite
- Fluorescent Dye B (“CINOPEARL CBS-X,” manufactured by Ciba Geigy AG) were added to prepare an aqueous slurry of 50% by weight solid content.
- the resulting slurry was spray-dried using a countercurrent flow spray drier, to give spray-dried granules L having a water content of about 5% by weight of the dead weight. Thereafter, 30.5 parts by weight of the spray-dried granules L prepared above and 4.6 parts by weight of amorphous aluminosilicate prepared in Preparation Example 2 were supplied in a Lödige Mixer (Matsuzaka Giken Co., Ltd., equipped with a jacket) and stirred while keeping the jacket temperature at 70°C.
- a Lödige Mixer Matsuzaka Giken Co., Ltd., equipped with a jacket
- the above components were further subjected to granulation by blending in advance at 70°C to prepare a mixture comprising 8.0 parts by weight of a polyoxyethylene alkyl ether ("NONIDET R-7,” manufactured by Mitsubishi Chemical Corporation, an alkylene oxide adduct, of which the alkyl moiety has 12 to 15 carbon atoms, and the ethylene oxide moiety has a molar number of 7.2) and 1.0 part by weight of a polyethylene glycol (“KPEG,” manufactured by Kao Corporation; weight-average molecular weight: 8000), and spraying the resulting mixture to the above components while agitating.
- a polyoxyethylene alkyl ether (“NONIDET R-7,” manufactured by Mitsubishi Chemical Corporation, an alkylene oxide adduct, of which the alkyl moiety has 12 to 15 carbon atoms, and the ethylene oxide moiety has a molar number of 7.2) and 1.0 part by weight of a polyethylene glycol (“KPEG,” manufactured by Kao Corporation; weight-average mole
- the granules were surface-coated for improving the powder properties by adding 3.0 parts by weight of the zeolite (4A-type).
- the metal ion capturing agent granules (I) thus obtained had a bulk density of 0.79 g/cm 3 and an average particle size of 405 ⁇ m.
- the above components were further subjected to granulation by blending in advance at 70°C to prepare a mixture comprising 18.0 parts by weight of the polyoxyethylene alkyl ether ("NONIDET R-7"), 5.0 parts by weight of palmitic acid (“LUNAC P-95”), and 1.0 part by weight of the polyethylene glycol (“KPEG”), and spraying the resulting mixture to the above components while agitating. Further, the resulting granules were surface-coated for improving the powder properties by adding 6.0 parts by weight of the zeolite (4A-type).
- NONIDET R-7 polyoxyethylene alkyl ether
- LNAC P-95 palmitic acid
- KPEG polyethylene glycol
- a mixture comprising 11.0 parts by weight of a polyoxyethylene alkyl ether (tradename: "EMULGEN 108,” manufactured by Kao Corporation, of which an ethylene oxide moiety has an average molar number of 6.0 and an alkyl moiety has 12 carbon atoms), 2.5 parts by weight of semi-cured beef tallow-derived fatty acid (“LUNAC TH,” manufactured by Kao Corporation), and 2.5 parts by weight of a polyethylene glycol (manufactured by Kao Corporation; weight-average molecular weight: 10000), and spraying the resulting mixture to the above contents in the mixer while agitating.
- a polyoxyethylene alkyl ether tradename: "EMULGEN 108,” manufactured by Kao Corporation, of which an ethylene oxide moiety has an average molar number of 6.0 and an alkyl moiety has 12 carbon atoms
- LNAC TH semi-cured beef tallow-derived fatty acid
- a polyethylene glycol manufactured by Kao Corporation; weight-average molecular weight: 10
- a part or a whole part of the fatty acid was neutralized to form salts of the fatty acid on the surface of Crystalline Alkali Metal Silicate A having a high alkalizing ability, and thereby the surfaces of Crystalline Alkali Metal Silicate A were coated with gelated products comprising the polyoxyethylene alkyl ether, the salts of the fatty acid, and the polyethylene glycol. Further, the resulting granules were surface-coated for improving the powder properties by adding 3.0 parts by weight of a zeolite (4A-type, manufactured by Tosoh Corporation; average particle size: 3 ⁇ m). The crystalline silicate granules (II) thus obtained had a bulk density of 0.87 g/cm 3 and an average particle size of 468 ⁇ m.
- the granules were surface-coated for improving the powder properties by adding 3.0 parts by weight of the zeolite (4A-type).
- the metal ion capturing agent granules (II) thus obtained had a bulk density of 0.75 g/cm 3 and an average particle size of 426 ⁇ m.
- the above components were further subjected to granulation by blending in advance at 80°C to prepare a mixture comprising 11.0 parts by weight of the polyoxyethylene alkyl ether ("EMULGEN 108"), 2.5 parts by weight of semi-cured beef tallow-derived fatty acid (“LUNAC TH”), and 2.5 parts by weight of the polyethylene glycol (weight-average molecular weight: 10000), and spraying the resulting mixture to the above components while agitating. Further, the resulting granules were surface-coated for improving the powder properties by adding 6.0 parts by weight of the zeolite (4A-type).
- EMULGEN 108 polyoxyethylene alkyl ether
- LNAC TH semi-cured beef tallow-derived fatty acid
- 10000 polyethylene glycol
- Crystalline Alkali Metal Silicate B ( ⁇ -Na 2 O•2SiO 2 , prepared by pulverizing SKS-6TM powder product using a hammer mill to an average particle size of 23 ⁇ m; SKS-6: average particle size: 23 ⁇ m, 248 CaCO 3 mg/g), 6.0 parts by weight of amorphous aluminosilicate prepared in Preparation Example 2, and 0.2 parts by weight of Fluorescent Dye S were supplied in a Lödige Mixer (Matsuzaka Giken Co., Ltd., equipped with a jacket), and the above components were agitated while keeping the jacket temperature at 70°C.
- a Lödige Mixer Matsuzaka Giken Co., Ltd., equipped with a jacket
- the surfaces of Crystalline Alkali Metal Silicate B were coated with the gelated products comprising the polyoxyethylene alkyl ether and the polyethylene glycol. Further, the resulting granules were surface-coated for improving the powder properties by adding 3.0 parts by weight of the zeolite (4A-type).
- the crystalline silicate granules (III) thus obtained had a bulk density of 0.85 g/cm 3 and an average particle size of 465 ⁇ m.
- the resulting slurry was spray-dried using a countercurrent flow spray drier to give spray-dried granules N having a water content of about 6% by weight of the dead weight. Thereafter, 46.1 parts by weight of the spray-dried granules N were supplied in a High-Speed Mixer (manufactured by Fukae Powtec Corp.), and the contents were agitated and granulated, while 1.2 parts by weight of polyoxyethylene alkyl ether ("SOFTANOL 70") which was previously heated at 70°C as mentioned above was being added thereto. Further, the resulting granules were surface-coated for improving the powder properties by adding 3.0 parts by weight of the zeolite (4A-type).
- the metal ion capturing agent granules (III) thus obtained had a bulk density of 0.74 g/cm 3 and an average particle size of 407 ⁇ m.
- the components were further subjected to granulation by blending in advance at 70°C to prepare a mixture comprising 11.2 parts by weight of the polyoxyethylene alkyl ether ("SOFTANOL 70") and 4.0 parts by weight of the polyethylene glycol (weight-average molecular weight: 10000), and spraying the resulting mixture to the above components in the mixer while agitating. Further, the resulting granules were surface-coated for improving the powder properties by adding 6.0 parts by weight of the zeolite (4A-type).
- SOFTANOL 70 polyoxyethylene alkyl ether
- An artificial staining liquid having the following compositions is adhered to a cloth (#2003 calico, manufactured by Tanigashira Shoten) to prepare an artificially stained cloth.
- Artificial staining liquid is printed on a cloth by an engravure staining machine equipped with an engravure roll coater.
- the process for adhering the artificial staining liquid to a cloth to prepare an artificially stained cloth is carried out under the conditions of a cell capacity of a gravure roll of 58 cm 3 /cm 2 , a coating speed of 1.0 m/min, a drying temperature of 100°C, and a drying time of one minute.
- the unit "°DH" refers to a water hardness which is calculated by replacing Mg ions with equimolar amounts of Ca ions.
- compositions and detergency rates of the detergent compositions are listed in Tables 1 to 3.
- the calcium ion capturing capacity of the metal ion capturing agents other than Component B are as follows:
- a detergent formulated with 36.0 parts by weight of the crystalline alkali metal silicate granules (I) and 62.5 parts by weight of the metal ion capturing agent granules (II) prepared in Example 1, and balance being the same as the after-blended product of Example 1 is prepared, and a detergency test is carried out under the following conditions.
- the detergency test is carried out by changing the water used to 8°DH, the washing temperature to 30°C, and the used concentration to 1.2 g/L. Other conditions are the same as Test Example. As a result, when compared to a detergent composition comprising the crystalline alkaline metal silicate component and the metal ion capturing agent component in the same granule, excellent detergency can be obtained.
- the detergency test is carried out by changing the water used to 15°DH, the washing temperature to 40°C, and the used concentration to 2.5 g/L. Other conditions are the same as Test Example. As a result, when compared to a detergent composition comprising the crystalline alkaline metal silicate component and the metal ion capturing agent component in the same granule, excellent detergency can be obtained.
- a high-density granular detergent composition of the present invention comprises the granules containing the crystalline alkali metal silicate and the granules containing the metal ion capturing agent, wherein each of the granules is contained in the detergent composition as separate granules, an excellent detergency can be exhibited with a smaller standard amount of dosage.
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP90131/96 | 1996-03-19 | ||
JP9013196 | 1996-03-19 | ||
JP9013196 | 1996-03-19 | ||
PCT/JP1997/000859 WO1997034978A1 (fr) | 1996-03-19 | 1997-03-17 | Composition detergente granulaire a haute densite |
Publications (3)
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EP0889116A1 EP0889116A1 (en) | 1999-01-07 |
EP0889116A4 EP0889116A4 (en) | 2002-04-03 |
EP0889116B1 true EP0889116B1 (en) | 2004-05-26 |
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EP97907351A Expired - Lifetime EP0889116B1 (en) | 1996-03-19 | 1997-03-17 | High-density granular detergent composition |
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EP (1) | EP0889116B1 (id) |
JP (1) | JP3187437B2 (id) |
DE (1) | DE69729287T2 (id) |
ID (1) | ID16280A (id) |
TW (1) | TW403781B (id) |
WO (1) | WO1997034978A1 (id) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1222605C (zh) * | 1998-06-04 | 2005-10-12 | 花王株式会社 | 表面活性剂组合物 |
JP2003503549A (ja) * | 1999-06-21 | 2003-01-28 | ザ、プロクター、エンド、ギャンブル、カンパニー | 洗剤粒子およびその製造方法 |
US6579844B1 (en) | 2000-06-20 | 2003-06-17 | The Procter & Gamble Co. | Detergent particles and methods for making them |
JP4573960B2 (ja) * | 2000-07-10 | 2010-11-04 | 花王株式会社 | 洗剤組成物 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8414877D0 (en) * | 1984-06-11 | 1984-07-18 | Procter & Gamble | Fabric softener agglomerates |
JP2672814B2 (ja) * | 1987-07-13 | 1997-11-05 | 花王株式会社 | 高密度粒状洗剤組成物 |
JP2662221B2 (ja) * | 1987-07-15 | 1997-10-08 | 花王株式会社 | 高密度粒状濃縮洗剤組成物 |
JPH02178399A (ja) * | 1988-12-29 | 1990-07-11 | Lion Corp | 粒状洗剤組成物 |
JPH02178398A (ja) * | 1988-12-29 | 1990-07-11 | Lion Corp | 高嵩密度洗剤組成物 |
JPH0436398A (ja) * | 1990-06-01 | 1992-02-06 | Lion Corp | 高嵩密度粒状洗剤組成物 |
GB9018157D0 (en) * | 1990-08-17 | 1990-10-03 | Procter & Gamble | Detergent compositions |
GB9216409D0 (en) * | 1992-08-01 | 1992-09-16 | Procter & Gamble | Detergent compositions |
-
1997
- 1997-03-17 JP JP53335397A patent/JP3187437B2/ja not_active Expired - Fee Related
- 1997-03-17 TW TW86103302A patent/TW403781B/zh not_active IP Right Cessation
- 1997-03-17 EP EP97907351A patent/EP0889116B1/en not_active Expired - Lifetime
- 1997-03-17 WO PCT/JP1997/000859 patent/WO1997034978A1/ja active IP Right Grant
- 1997-03-17 DE DE69729287T patent/DE69729287T2/de not_active Expired - Lifetime
- 1997-03-18 ID IDP970877A patent/ID16280A/id unknown
Also Published As
Publication number | Publication date |
---|---|
TW403781B (en) | 2000-09-01 |
ID16280A (id) | 1997-09-18 |
JP3187437B2 (ja) | 2001-07-11 |
EP0889116A4 (en) | 2002-04-03 |
WO1997034978A1 (fr) | 1997-09-25 |
DE69729287D1 (de) | 2004-07-01 |
EP0889116A1 (en) | 1999-01-07 |
DE69729287T2 (de) | 2005-06-02 |
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