JPH08218093A - High bulk density granular detergent composition - Google Patents

Abstract

(57) [Summary] [Structure] (a) Anionic surfactant 10 to 40 wt%,
(b) 5 to 20% by weight of a polyoxyethylene alkyl ether type nonionic surfactant containing 60% by weight or more of a polyoxyethylene alkyl ether type nonionic surfactant having an alkyl group having 12 carbon atoms, (c) Detergent builder 10
-60% by weight, and the weight ratio of component (a) and component (b)
(a) / (b) is 8/1 to 3/2, and the weight ratio of [(a) + (b)] / (c) is 1/2 to 2/1. High bulk density of 600 g / liter or more. Bulk density granular detergent composition. [Effect] Excellent cleaning power and excellent solubility in cold water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-density granular detergent composition, and more particularly to a high-density granular detergent composition having excellent dispersibility even in cold water.

[0002]

2. Description of the Related Art In recent years, powder detergents of high density have been widely used from the viewpoint of resource saving, transportation, convenience of carrying and placing. For example, JP-A-48-61511 discloses a granulated detergent composition containing 30% or more of a surfactant, having a bulk density of 0.5 g / cm ³ or more and a particle size of 0.5 to 5 mm. It is disclosed. Further, JP-A-48-61511 discloses a detergent having a bulk density of 0.55 g / cm ³ or more, which is obtained by dry blending 30% to 70% of a surfactant and various detergent builders in a specific amount. Further, JP-A-58-132093 discloses a granular detergent composition having an improved solubility, which contains an anionic surfactant and an anionic polymer which are intimately mixed. This publication was prepared by adding a water-soluble neutral or alkaline salt and a mixture thereof by preparing a mixture of a specific water-soluble anionic polymer and a non-soap anionic surfactant in advance. High density (eg 0.67 g / g) obtained by blending spray-dried granular mixture with other detergent ingredients
It is an invention relating to a granular detergent of cm ³ ).

However, such a high-density powder detergent generally does not have a satisfactory dispersibility / solubility, and even in the example described in JP-A-58-132093, it is generally used in winter. Under such conditions that cold water is used and the detergent particle population is allowed to stand for a certain time or longer without being subjected to a relatively large mechanical force, its dispersive solubility is still insufficient, which is a fundamental solution to the problem. It hasn't arrived.

For example, when using a fully automatic washing machine in a general household, first put a detergent (the amount used in one wash is about 25 g / 30 liters or less) into the washing machine, and then press the start button. Water injection starts. During the water injection, the washing machine's agitation is stopped, so that the detergent particles exist in a localized, undispersed state, are slowly permeated by water and, at the same time, have a very high concentration on the particle surface. A paste-like phase in which the detergent component and water are mixed is formed, and coalescence of particles occurs. As a result, the entire localized detergent particles are covered with a hydrated, highly viscous, paste-like phase, which cannot be dispersed by the mechanical force of only the washing cycle started after water injection, and the undissolved residue is left unsolved during normal washing time. May occur. The formation of a paste-like phase is more remarkable as the temperature of tap water is lower, and is particularly likely to occur when the surfactant component of the composition is mainly an anionic surfactant. On the other hand, in a conventional low-density detergent such as a simple spray drying agent, the detergent particles are porous and contain a large amount of air, so that they easily float in water and disperse due to buoyancy. However, since the density of the population itself is low and a relatively large amount of air is included, it is easily redispersed and dissolved by mechanical force, and such a problem is hard to occur.

[0005]

In view of the above problems, the present applicant has previously focused on crystalline inorganic salts present in detergent particles as a cause of decreased solubility, and as a means of improving the solubility, soda ash. It has been proposed to limit the addition amount of crystalline inorganic salts such as the above in the detergent dough to dry-orient the inorganic salts (JP-A-62-167399). However, in this method, it is necessary to control the particle size and bulk density of the detergent dough and the crystalline particles in order to prevent the particles from being classified, and in addition, since a step of dry blending the crystalline particles with the detergent particles is required, It is disadvantageous in terms of manufacturing equipment as compared with the conventional method.

On the other hand, JP-A-5-271700 and JP-A-6-2000 propose the addition of potassium carbonate to the detergent slurry in order to suppress the dry mixing amount of the crystalline inorganic salt. However, since potassium carbonate is expensive, it cannot be said to be practically preferable.

[0007]

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have considered a compact size of about 25 g / 30 liters or less and a bulk density of 0.6 g / cm ³ or more. As a result of reviewing the low temperature dispersion solubility of concentrated powder detergent, when anionic surfactant was used as the main base, a specific amount of polyoxyethylene glycol ether type nonionic surfactant with a specific alkyl distribution was blended. It was found that by doing so, the solubility in cold water is improved.

That is, the present invention provides the following components (a), (b) and (c)
And the weight ratio of component (a) to component (b) (a) / (b)
Is 9/1 to 3/2, and the weight ratio of [(a) + (b)] / (c) is 1
The present invention provides a high bulk density granular detergent composition having a bulk density of 600 g / liter or more, which is / 2 to 2/1. (a) 10-40% by weight of anionic surfactant (b) Polyoxyethylene alkyl containing 60% by weight or more of polyoxyethylene alkyl ether type nonionic surfactant in which the alkyl group has 12 carbon atoms Ether type nonionic surfactant 4 to 20% by weight (c) Detergent builder 10 to 60% by weight.

Examples of the anionic surfactant as the component (a) include the following. (1) Linear or branched (preferably linear) alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16 (2) Linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20 And ethylene oxide or ethylene oxide / propylene oxide = 0.1
/9.9 to 9.9 / 0.1 or ethylene oxide / butylene oxide 0.1 / 9.9 to 9.9 / 0.1 added in an average of 1 to 8 moles in one molecule, preferably an alkyl or alkenyl ether sulfate, preferably a primary carbon number of 12 to 18 Ethylene oxide on average in linear or branched alkyl groups of
To 3 added alkyl ether sulfate (3) Alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20 (4) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule (5) Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule (6) Saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule (7) Average of 10 to 20 Having an alkyl or alkenyl group,
Ethylene oxide or propylene oxide /
Ethylene oxide / Propylene oxide = 0.1 / 9.9
~ 9.9 / 0.1, or ethylene oxide / butylene oxide = 0.1 / 9.9 to 9.9 / 0.1 added in an average of 0.5 to 8 mol per molecule on average in an alkyl or alkenyl ether carboxylate (8) α represented by the following formula -Sulfo fatty acid salts or esters

[0010]

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(In the formula, Y is an alkyl group having 1 to 3 carbon atoms (preferably a methyl group) or a counter ion. Z is a counter ion. R is an alkyl group or an alkenyl group having 10 to 20 carbon atoms. () (9) Other examples include saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. .

Among the above, particularly preferable anionic activators are (1), (2), (3) and (6).

The anionic surfactant as the component (a) is incorporated in the detergent composition in an amount of 15 to 40% by weight, preferably 20 to 35% by weight. If the content of the component (a) is less than 15% by weight, sufficient detergency cannot be obtained, and if it exceeds 40% by weight, the low-temperature solubility, which is the main effect, decreases.

The polyoxyethylene alkyl ether type nonionic surfactant as the component (b) has been suggested for use in detergents, but the present invention is characterized by the carbon number distribution of its alkyl chain. Yes, the carbon number of the alkyl group is 12
It is necessary to contain the above compound in an amount of 60% by weight or more, preferably 70% by weight, more preferably 95% by weight or more in the total polyoxyethylene alkyl ether type nonionic surfactant. Generally, the amount of alcohol obtained when using natural fats and oils is about 48% by weight when it is derived from coconut oil containing a relatively large amount of alcohol having 12 carbon atoms, and about 50% by weight when it is derived from palm kernel oil. . In the component (b), when the polyoxyethylene alkyl ether type nonionic surfactant having an alkyl group having 12 carbon atoms is less than 60% by weight, this effect cannot be obtained.

The alcohol used as a raw material of the specific polyoxyethylene alkyl ether type nonionic surfactant which is the component (b) of the present invention is, for example, an alkyl alcohol obtained by distilling the aliphatic alcohol derived from natural fats and oils under reduced pressure. It is possible to easily obtain a group having a carbon number distribution of a given ratio. The component (b) of the present invention can be obtained by adding ethylene oxide to a mixture of such alcohols having different carbon numbers of alkyl groups, or a single alcohol added with ethylene oxide is specified in the present invention. It can also be obtained by mixing so as to have a ratio. In either case, the average number of added moles of ethylene oxide is 5 to 12 moles, preferably 6 to 11 moles. If the average added mole number of ethylene oxide is too low, the solubility tends to decrease.

The specific polyoxyethylene alkyl ether type nonionic surfactant as the component (b) is compounded in an amount of 4 to 20% by weight in the detergent composition. If it is less than 4% by weight, the solubility will be reduced, and if it exceeds 20% by weight, the detergent itself will easily cake.

In addition to the above polyoxyethylene glycol ether type nonionic surfactant, other nonionic surfactants may be used in combination to the extent that this effect is not impaired.
Examples thereof include polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoside, fatty acid glycerin monoester, alkylamine oxide and the like. The following nonionic surfactants are particularly preferable. (1) An alkyl phenyl ether having an alkyl group having an average carbon number of 9 to 12, to which 1 to 25 mol of ethylene oxide is added. (2) An alkyl glycoside represented by the following general formula. R (OC ₂ H ₄ ) _{xG y} (wherein R is an alkyl group having 9 to 14 carbon atoms, X is a number from 0 to 2, G is a glucose, fructose, maltose or sucrose residue, and y is 1 to 4). The number is preferably 1, 2 to 3.) As the detergent builder as the component (c), those known as builders for ordinary detergents can be used. Things can be used.

(I) Inorganic Builder 1) Sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, JIS 1
No.1 Alkaline salts represented by alkali metal silicates such as sodium silicate. 2) Neutral salt such as sodium sulfate. 3) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate (alkali metal salts such as sodium and potassium). 4) Further, the following crystalline aluminosilicates or crystalline layered silicates different from the above-mentioned alkali metal silicates can also be mentioned. Specifically, a crystalline aluminosilicate represented by the following formula can be given. x '(M ₂ O) ・ Al ₂ O ₃・ y' (SiO ₂ ) ・ w '(H ₂ O) (In the formula, M is an alkali metal atom such as sodium or potassium, x', y ', w' Represents the number of moles of each component, and generally,
0.7 ≦ x ′ ≦ 1.5, 0.8 ≦ y ′ ≦ 6, and w ′ are arbitrary constants. Among these, those represented by the following general formula are particularly preferable. Na ₂ O ・ Al ₂ O ₃・ ySiO ₂・ wH ₂ O (where y is a number from 1.8 to 3.0 and w is a number from 1 to 6) Further, the following formula M ₂ Si _x O _{(2x + 1)}・ Y (H ₂ O) (In the formula, M represents an alkali metal, and x and y are 1.5 ≦ x
≤4, y ≤25, preferably y ≤20, more preferably y =
0. Also included are crystalline layered silicates represented by (4). The production method of this compound is described in JP-A-60-227895, and it is generally obtained by firing amorphous glassy sodium silicate at 200 to 1000 ° C. to make it crystalline. For details of the synthetic method, see, for example, Phys.Chem.Gla.
sses.7,127-138 (1966), Z.Kristallogr., 129, 396-404
(1969) etc. This crystalline layered silicate is commercially available from Hoechst under the trade name "Na-SKS-6" (σ-
As Na ₂ Si ₂ O ₅ ), fine powder, powder, and granules are available, and in the present invention, particles having a particle size of 10 to 500 μm can be used, but preferably 10 to 300 μm. .

5) Further, an oil-absorbing amorphous aluminosilicate represented by the following general formula (1) is exemplified as an oil-absorbing carrier having high oil absorption and high cation exchange ability. Oil-absorptive carriers are the preferred builders in the case of powdered detergents using liquid nonionic surfactants. a (M ₂ O) ・ Al ₂ O ₃・ b (SiO ₂ ) ・ c (H ₂ O) (1) (In the formula, M represents an alkali metal atom, and a, b, and c represent the number of moles of each component. , 0.7 ≤ a ≤ 2.0, 0.8 ≤ b <4, and c are arbitrary positive numbers. ] Particularly, the following general formula (2) Na ₂ O ・ Al ₂ O ₃・ m (SiO ₂ ) ・ c (H ₂ O) (2) [where m is 1.8 to 3.2 and c is a number of 1 to 6] Represents ]
What is represented by is preferable. The method for producing the amorphous aluminosilicate having high oil absorption and high ion exchange capacity usable in the present invention is, for example, SiO ₂ and M ₂ O (M means an alkali metal) having a molar ratio of SiO ₂ / M ₂ O = 1.0 to 4.0 and H ₂ O
And M ₂ O have a molar ratio of H ₂ O / M ₂ O = 12 to 200 to an aqueous solution of alkali metal silicate, the molar ratio of M ₂ O and Al ₂ O ₃ is M ₂ O / Al ₂ O.
₃ = 1.0 to 2.0, and the molar ratio of H ₂ O and M ₂ O is H ₂ O / M ₂ O.
= 6.0-500 low alkali aluminate alkali metal salt aqueous solution is added under strong stirring at a temperature of 15-60 ° C, preferably 30-50 ° C. Further, an aqueous solution of alkali metal silicate may be added to the aqueous solution of alkali metal aluminate. Then, the white precipitate slurry formed is 70 to 100 ° C.,
It can be advantageously obtained by heat treatment at a temperature of 90 to 100 ° C. for 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. By this method, ion exchange capacity 100 CaCO ₃ mg / g or more, oil absorption capacity 200 ml
/ 100 g or more of an amorphous aluminosilicate oil-absorbing carrier can be easily obtained (JP-A-62-191417, JP-A-SHO).
62-191419).

Among these inorganic builders, sodium tripolyphosphate, sodium carbonate, crystalline aluminosilicate and crystalline layered silicate are more preferable. Particularly, as crystalline aluminosilicate (zeolite), the average particle size of primary particles represented by A-type and X-type zeolite is 0.1 to 10
μm synthetic zeolites are preferably used. Zeolite is mixed as zeolite agglomerated dry particles obtained by drying powder and / or zeolite slurry. Zeolites may usually be incorporated in an amount of 5 to 60% by weight based on the total composition.

(II) Organic Builder The following substances are exemplified as the organic builder. 1) ethane-1,1-diphosphonic acid, ethane-1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane- 1,2-dicarboxy-1,2-diphosphonic acid, salts of phosphonic acids such as methanehydroxyphosphonic acid 2) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, Salts of phosphonocarboxylic acids such as α-methylphosphonosuccinic acid 3) Salts of amino acids such as aspartic acid and glutamic acid 4) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate and diethylenediaminepentaacetate 5) Polyacrylic acid, polyglyoxylate salt described in JP-A-54-52196, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, Limethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, anhydrous Maleic acid-ethylene copolymer, maleic anhydride-ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic acid ester copolymer, anhydrous Maleic acid-butadiene copolymer, maleic anhydride-isoprene copolymer, poly-β-ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid, ethylene copolymer, itaconic acid-aconic acid copolymer Combined, itaconic acid-maleic acid copolymer, itaconic acid-acetic acid Le acid copolymer, malonic acid - methylene copolymer, itaconic acid - fumaric acid copolymer,
Acrylic acid-maleic acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, Polyester polyaldehyde carboxylic acid having quaternary ammonium group, cis-isomer of epoxysuccinic acid, poly [N, N-bis (carboxymethyl) acrylamide], poly (oxycarboxylic acid), denbunsuccinic acid, maleic acid or terephthalic acid ester , Polyelectrolytes such as starch phosphate, dicarboxy starch, dicarboxymethyl starch, carboxymethyl cellulose, succinate 6) Polyethylene glycol, polyvinyl alcohol,
Polyvinylpyrrolidone, carboxymethylcellulose,
Non-dissociated polymers such as cold water soluble urethanized polyvinyl alcohol 7) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3, 4-tetracarboxylic acid, tetrahydrofuran-2,2,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, saccharose, lactose, carboxymethylated products such as raffinose, pentaerythritol carboxymethylated product, gluconic acid carboxy Methylated products, condensation products of polyhydric alcohols or sugars with maleic anhydride or succinic anhydride, condensation products of oxycarboxylic acids with maleic anhydride or succinic anhydride, benzene polycarboxylic acids represented by mellitic acid, ethane- 1,1,2,2-tetracarboxylic acid, ethene-1,
1,2,2-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, propane-1,2,3-tricarboxylic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid,
Decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid,
Organic acid salts such as gluconic acid, CMOS and Builder M.

Among these organic builders, citrate, polyacrylate, polyglyoxylate, acrylic acid-maleic acid copolymer and polyethylene glycol are more preferable.

The detergent builder has the role of improving the detergency of the detergent itself by exhibiting at least the sequestering ability, the alkaline ability and the fine particle dispersing ability. Although the classification of builders exhibiting the above properties is not clear, there are substances having any of the properties of, but crystalline aluminosilicate (A, X or P type zeolite) is mainly used as a component for expressing , Crystalline layered silicates, polycarboxylic acid salts (sodium citrate, etc.) or unsaturated aliphatic carboxylic acid polymers (average molecular weight 50
00 to 200,000 acrylic acid-maleic acid copolymer, etc.),
Alkali metal carbonates (soda ash, sodium bicarbonate, etc.) or alkali metal silicates (JIS No. 1 sodium silicate, etc.) as a component that mainly develops an unsaturated aliphatic carboxylic acid Polymer (sodium acrylate with average molecular weight of 10,000 or less) or cellulose derivative (carboxymethyl cellulose, etc.)
Substances such as are shown as representatives, and in the present invention, it is preferable to blend at least one selected from these components. The detergent builder as the component (c) is incorporated in the detergent composition in an amount of 10 to 60% by weight.

In the detergent composition of the present invention,
The weight ratio of the component (a) and the component (b) is (a) / (b) = 9/1 to
3/2, and the weight ratio of the total amount of the components (a) and (b) to the component (c) is [(a) + (b)] / (c) = 1/2 to 2/1. It is necessary to improve the solubility of detergent particles. Particularly preferably (a) / (b) = 3/1 to 8/1, and [(a) + (b)] / (c) = 1/2 to 4/5.

The high bulk density granular detergent composition of the present invention may contain the following components.

(1) Other surfactants Betaine type amphoteric surfactants, sulfonic acid type amphoteric surfactants, phosphate ester type surfactants, or cationic surfactants (including amines), etc. (2) Bleaching agents, such as sodium percarbonate, sodium perborate (preferably monohydrate), sodium sulfate hydrogen peroxide adduct and the like can be mentioned, and sodium percarbonate is particularly preferable. (3) Bleach activator Tetraacetylethylenediamine, acetoxybenzenesulfonate, JP-A-59-22999, JP-A-63-25
8447, or the organic peracid precursor described in JP-A-6-316700, or a metal catalyst in which a transition metal is stabilized with a sequestering agent, etc. (4) Enzyme (Original enzyme action during washing step According to the reactivity of the enzyme, hydrolases, hydrolases, oxidoreductases, desmolases, transferases and isomerases can be mentioned, but any of them can be applied to the present invention. Particularly preferred are hydrolases, such as proteases, esterases,
Includes lipases, carbohydrases, nucleases, cellulases and amylases. Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin,
BPN, papain, promerin, carboxypeptidase A and B, aminopeptidase, and aspergillopeptidase A and B. As commercial products, sabinase, alcalase (Novo Industry Co., Ltd.), API 21 (Showa Denko)
Proc. K-14 or K- described in JP-A-5-43892.
There are 16. Specific examples of esterases include gastric lipases, pancreatic lipases, plant lipases, phospholipases, cholinesterases and phosphotases. For example, as the lipase, a commercially available lipase such as lipolase (Novo Industry) can be used. Specific examples of carbohydrases include cellulase, maltase, saccharase, amylase, pectinase, lysozyme, α-glycosidase and β-glycosidase. Also, as cellulase,
For example, a commercially available cellzyme (Novo Industry Co., Ltd.) or the cellulase described in claim 4 of JP-A No. 63-264699 can be used, and as the amylase, for example, commercially available Termamyl (Novo Industry Co., Ltd.) and the like can be used.

(5) enzyme stabilizer reducing agent (sodium sulfite, sodium bisulfite),
Calcium salt, magnesium salt, polyol, boron compound, etc. (6) Bluing agent Various bluing agents can be added as required. For example, the structures of the following formulas (i) and (ii) are recommended.

[0028]

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(Wherein D ₁ represents a blue to purple monoazo, disazo or anthraquinone dye residue, and X ₁ and
Y ₁ is a hydroxyl group; an amino group, a hydroxyl group, a sulfonic acid group, an aliphatic amino group which may be substituted with a carboxylic acid group or an alkoxy group; a halogen atom, a hydroxyl group, a sulfonic acid group,
It represents an aromatic amino group or a cycloaliphatic amino group which may be substituted with a carboxylic acid group, a lower alkyl group or a lower alkoxy group, and R 2 represents a hydrogen atom or a lower alkyl group. However, when R represents a hydrogen atom, X ₁ and Y ₁ simultaneously represent a hydroxyl group or an alkanolamino group, and _one of X ₁ and Y ₁ is a hydroxyl group, and the other is an alkanolamino group. Excluding cases. n represents an integer of 2 or more. )

[0030]

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(Wherein D ₂ represents a blue to purple azo or anthraquinone dye residue, R represents a hydrogen atom or a lower alkyl group, and X ₂ and Y ₂ are the same or different alkanolamino groups or hydroxyl groups. (7) Anti-Caking Agent Examples of anti-caking agents include paratoluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like. It should be noted that porous silica such as fine powder silica can be used as a carrier for the nonionic surfactant. Clay (smectite-like clay) is also effective as a softening agent.

(8) Antioxidant As the antioxidant, tertiary butyl hydroxytoluene,
4,4'-butylidene bis- (6-tert-butyl-3-methylphenol), 2,2'-butylidene bis- (6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, mono Examples thereof include styrenated phenol, distyrenated phenol, and 1,1′-bis- (4-hydroxyphenyl) cyclohexane.

(9) Fluorescent dye As a fluorescent dye, 4,4'-bis- (2-sulfostyryl)
-Biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis (triazol-2-yl) stilbene derivative The bis (triazinylamino) stilbenedisulfonic acid derivative may be contained in the composition in an amount of 0 to 1% by weight. (10) Photo-activated bleaching agent One or two kinds of sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine are used in the composition in an amount of 0 to 0.2.
It may be contained in a weight percentage. (11) Fragrance As the fragrance, fragrances conventionally used in detergents, for example, fragrances described in JP-A-63-101496 can be used. (12) Defoaming agent Examples of the defoaming agent include silicone / silica-based defoaming agents, and defoaming agent granules produced by the method described in JP-A-3-186307 may be used.

The cleaning composition of the present invention comprises (a), (b) and
Although the particles of the component (c) are intimately mixed, it is preferable to use a slurry obtained by drying and pulverizing a slurry containing all of the component (a) and at least the components (b) and (c). A conventional manufacturing method can be used to increase the bulk density, for example, JP-A-61-69897, JP-A-61-69899, JP-A-61-69900, and JP-A-60-. 72999, JP-A-2-222498, and JP-A-2-22499. The method using the spray drying method is
When a large amount of the component (b) is blended, it may be difficult to pulverize it. In that case, the spray-dried particles obtained may be added when the bulk density is increased. In addition, enzyme, bleach,
It is preferable that the bleaching activator is separately granulated and then dry-mixed. Of course, it is preferable to use a conventionally known stabilization technique for the other particles.

The bulk detergent composition of the present invention has a bulk density of 600 g.
/ Liter or more, preferably 650 to 850 g / liter,
More preferably, it is 700 to 820 g / liter.

[0036]

EFFECTS OF THE INVENTION The high-density granular detergent composition of the present invention has excellent solubility in water and excellent detergency despite its high density.

[0037]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

Example 1 Powder detergents having the formulations shown in Tables 1 and 2 were prepared, and the powder solubility was compared and examined. The results are also shown in Tables 1 and 2. Hereinafter, a detergent manufacturing method and a method for measuring powder bulk density and powder solubility will be described.

(1) Detergent manufacturing method Tables 1 and 2 show the final detergent composition. Of the detergent components shown in Tables 1 and 2, 15 of crystalline aluminosilicate (zeolite)
A slurry containing 50% by weight of water is prepared with the composition excluding the components that should be dry-mixed after the mixing of the weight% and the enzyme, and the resulting powder is spray-dried to obtain a powder obtained with a high-speed mixer (stirring rolling). Granulating machine, manufactured by Fukae Kogyo Co., Ltd.) and added with 10% by weight of the crystalline aluminosilicate previously removed for granulation, and further with 3% by weight of the crystalline aluminosilicate for granulation. The obtained particles are dry mixed with 2% by weight of the remaining crystalline aluminosilicate and a small amount of additives such as enzymes to obtain a high density granular detergent having a bulk density of 0.70 to 0.80 g / cm ^3. It was

(2) Powder bulk density Measured by the method of JIS K 3362 (3) Measurement of powder solubility Household washing machine made by Matsushita Electric Co., Ltd. "Gentle Aizuma No. NA-F42
40g of detergent is put together on one end of the bottom of the washing tub using "Y1", and clothes (60 parts by weight of cotton underwear and polyester /
Add 2 kg of cotton-blended shirt (40 parts by weight) and tap water (5
C.) at a flow rate of 8 liters per minute so that the detergent does not come into direct contact with water, and is slowly poured over 5 minutes to 40 liters. After that, stirring is started, the mixture is stirred for 1 minute, then drained, dehydrated for 3 minutes, and the detergent remaining in the clothes and the washing tub is visually determined. The criteria are shown below. ○: No detergent residue. Δ: A large number of small granular residual detergents or slightly lumpy residual detergents were present. ×: A lot of residual detergent in a lump form remains.

In the present measuring method, the detergent particle population is exposed to water for a period of 5 minutes during water injection in a state where it is hardly subjected to physical mechanical force, and after being permeated with water, it is subjected to mechanical force by stirring. become.

[0042]

[Table 1]

[0043]

[Table 2]

LAS-Na: sodium linear alkylbenzene sulfonate AS-Na: sodium alkyl sulfate ester AE: polyoxyethylene alkyl ether α-SFE: sodium α-sulfofatty acid methyl ester AA / MA copolymer: maleic acid-acrylic acid copolyester Combined Na salt (monomer ratio 4/6, average molecular weight 70000) Polyethylene glycol: average molecular weight 10000 Sodium polyacrylate: average molecular weight 10000 Small amount additive: defoaming agent (defoaming agent described in Examples of JP-A-3-186307) Granules), fluorescent dye (stilbene type / biphenyl type = 1/1 weight ratio), fragrance Enzyme: protease / cellulase = 2/1 weight ratio In addition, the water content in the table is the crystal of zeolite from the absolute water content. It is the value after subtracting water.

Claims (2)

[Claims] 1. The following components (a), (b) and (c) are contained, and the weight ratio (a) / (b) of the components (a) and (b) is 9/1 to 3: 1.
/ 2, [(a) + (b)] / (c) weight ratio is 1/2 to 2/1
A high bulk density granular detergent composition having a bulk density of 600 g / liter or more. (a) 10-40% by weight of anionic surfactant (b) Polyoxyethylene alkyl containing 60% by weight or more of polyoxyethylene alkyl ether type nonionic surfactant in which the alkyl group has 12 carbon atoms Ether type nonionic surfactant 4-20% by weight (c) Detergent builder 10-60% by weight 2. The high bulk density granular detergent composition according to claim 1, wherein the polyoxyethylene alkyl ether type nonionic surfactant as the component (b) has an average added mole number of ethylene oxide of 5 to 12.