WO1997033967A1

WO1997033967A1 - High-density granular detergent composition

Info

Publication number: WO1997033967A1
Application number: PCT/JP1997/000664
Authority: WO
Inventors: Shuji Tagata; Hirokazu Uenaka; Makoto Kubo; Takaya Sakai; Masaaki Yamamura; Noboru Moriyama
Original assignee: Kao Corporation
Priority date: 1996-03-13
Filing date: 1997-03-05
Publication date: 1997-09-18
Also published as: ID16227A; JP3513313B2; JPH09241677A

Abstract

A high-density granular detergent composition having a bulk density of 0.6 to 1.2 g/ml which comprises (a) an anionic surfactant and (b) an amidoamine oxide surfactant represented by general formula (I) at a specific ratio, wherein R1 is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, R2 and R3 each is H, an alkyl group or an alkenyl group having 1 to 3 carbon atoms, R4 is H, an alkyl group or an alkenyl group having 1 to 5 carbon atoms, and n is from 1 to 5. A granular detergent composition has excellent biodegradation properties and safety as well as a high detergency.

Description

DESCRIPTION

HIGH-DENSITY GRANULAR DETERGENT COMPOSITION Background of the Invention Field of the Invention

The present invention relates to a high-density granular detergent composition. More specifically, the invention relates to a high-density granular detergent composition which is improved in detergency by blendi a suitable amount of an amide oxide type surfactant having excellent biodegradation properties and safety with an anionic surfactant.

A detergent for clothes fundamentally comprises a surfactant for solubilizing soils and dissolving or dispersing them from the fibers into a washing solution, an alkali agent for promoting the degradation and the solubilization (emulsification) of the soils, a polymeric compound for dispersing the soils, a sequestering agent for removing, from the washing solution, calcium, magnesium and the like which deteriorate the ability of the surfactant, and the like. Among these components, a substance, which does not show a washing performance by itself but which can improve a washing power when combined with the surfactant, is usually called a builder for washing, or simply a builder. The builder is the extremely important substance to more effectively exert the performance of the surfactant.

The surfactant has a main function of removing the soils from the fibers, as described above. The surfactant which is used in the detergent can be roughly classified into the surfactant mainly comprising an anionic component and the surfactant mainly comprising a nonionic component. Examples of the surfactant mainly comprising the anionic component include alkylbenzene sulfonates having 10 to 16 carbon atoms, sulfate esters of higher alcohols having 10 to 18 carbon atoms, a -olefin sulfonates, a - sulfonic higher fatty acid ester salts and alkane sulfonates (SASs). Examples of the surfactant mainly comprising the nonionic component include polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether. JP-A-7-53992 discloses a composition comprising an anionic surfactant, a nonionic sufractant, a zeolite and a silicate, and JP-A-62-62-20596 discloses a composition comprising an amidoamine oxide and N-acylamino acid series surfactants.

The investigation of making the detergent high density, compact and small is being advanced in accordance with a commercial demand from the viewpoint of resources saving, energy saving and the reduction of a transportation cost. However, the above-mentioned surfactants and the like are still used, and so the surfactant having a higher washing ability suitable for the high density detergent is desired.

In recent year, detergent compositions comprising an aluminosilicate and a crystalline silicate as a builder are proposed (JP-A-7-53992). It is disclosed that these compositions may contain, as a surfactant, an anion activator, a nonion activator, a cation activator, an amphoteric activator and a mixture thereof, and, as examples thereof, a blend composition comprising an anion activator such as alkylbenzenesulfonates as a base and a small amount of a noinon activator is cited. An anion activator-base detergent exhibits high detergency to mud soil. However, this detergent is not sufficient for sebaceous soil or in biodegration.

Summary of the Invention

The present inventors have intensively investigated, and as a result, it has been found that washing properties can be remarkably improved and detergents exhibiting excellent biodegration can be obtained by using a specific amidoamine oxide and a surfactant mainly comprising an anionic surfactant in a specific ratio. The invention provides a high density, granular detergent composition comprising:

(a) 10 to 50 percent by weight of an anionic surfactant,

(b) 1.0 to 20 percent by weight of an amidoamine oxide surfactant having the formula (I):

R2

I RιCON(CH₂)n— N→O (I)

I I

wherein Rj is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, R2 and R3 each is H, an alkyl group or an alkenyl group having 1 to 3 carbon atoms, R4 is H, an alkyl group or an alkenyl group having 1 to 5 carbon atoms, and n is from 1 to 5.

(c) 1 to 60 percent by weight of an aluminosilicate,

(d) 5 to 30 percent by weight of a crystalline silicate, having a weight ratio of (b) (a) ranging from 1/100 to 100/100, having an apparant density of 0.6~ 1.2g/^/m^.

It is preferable that (d) is a crystalline silicate having the formula (II) a d/or (III): x(M₂0) ^• y(Si0₂) ^• z(Me_mO_n) w(H₂0) (II) wherein M is an element in the la group of the periodic table, Me is one or a combination of two or more selected from the group consisting of elements in the Ila group, the lib group, Ilia group, IVa group and the VIII group of the periodic table, y/x is from 0.5 to 2.6, z/x is from 0.01 to 1.0, is from 0 to 20, and n/m is from 0.5 to 2.0;

M₂0 ^• x'(Si0₂) ^• y'(H₂0) (III) wherein M is an alkali metal, x' is from 1.5 to 2.6, and y' is from 0 to 20.

Detailed description of the Invention

Next, the high-density granular detergent composition of the present invention will be described. (a) Anionic surfactant

Examples of the anionic surfactant which can be used in the present invention include higher fatty acid salts having 8 to 18 carbon atoms, sulfuric acid ester salts of linear and branched primary or secondary alcohols having 8 to 18 carbon atoms, sulfuric acid ester salts of ethoxylate compounds of Hnear and branched primary or secondary alcohols having 8 to 20 carbon atoms, alkylbenzenesulfonates in which an alkyl group has 8 to 16 carbon atoms, alkane sulfonates (SASs), a -olefin sulfonates, a -sulfonic fatty acid salts and a -sulfonic fatty acid alkyl ester salts, and they can be used singly or in a combination of two or more thereof. As salts of these anionic surfactants, the salt of Na, K, NH4 are suitable. The component (a) is blended in an amount of 15 to 50% by weight, preferably 20 to 40% by weight based on the weight of the composition.

Preferably, (a) anionic surfactant is at least one selected from the group consisting of higher fatty acid salts having 10 to 18 carbon atoms, sulfuric acid ester salts of straight or branched chain primary or secondary alcohols having 10 to 18 carbon atoms, sulfuric acid ester salts of ethoxylate compounds of alcohols having 8 to 20 carbon atoms, alkylbenzenesulfonic acid salts in which an alkyl group has 8 to 16 carbon atoms, alkane sulfonates, a -olefin sulfonates, a -sulfonic fatty acid salts and a -sulfonic fatty acid alkyl ester salts.

In addition, the present composition may contain 1 to 15% by weight of nonionic surfactant. Preferred nonionic surfactant is one selected from the group consisting of polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylenesorbitan fatty acid esters, polyoxyalkylene giycol ethers, polyoxyethylene polyoxypropylene block polymers and alkanoyl N-methylglucamine.

Moreover, the composition may contain a polycarboxylate having an average molecular weight of 1000 to 100000.

The composition may comprises 2 to 10 percent by weight of (b), having a weight ratio of (b)/(a) ranging from 3/100 to 50/100. (b) Arnidoamine oxide surfactant

The amidoamine oxide surfactant which can be used in the present invention is represented by the above-mentioned general formula (1). In the case that R and R3 are methyl groups, the highest effect can be attained. Furthermore, in the case that R^ has 12 to 14 carbon atoms, the highest effect can be attained.

In the present invention, the amidoamine oxide surfactant of the component (b) is blended in an amount of 1 to 20% by weight, preferably 2 to 10% by weight in the composition. If the component (b) is out of above- mentioned range, a detergency deteriorates.

Furthermore, in the present invention, the weight ratio of the component (b)/the component (a) is in the range of 1/100 to 100/100, preferably 3/100 to 50/100. If the weight ratio of the component (b)/the component (a) is out of this range, the detergency deteriorates. The amidoamine oxide type surfactant of the component (b) has been known as a shampoo or a liquid detergent for a long time, and many patent applications regarding them have been submitted.

When an aluminosilicate, a crystalline silicate, an organic builder having good biodegradation properties, a polycarboxylate or the like which will be described hereinafter is blended with the surfactants of the above- mentioned components (a) and (b), the high-density granular detergent composition having the improved detergency can be obtained. <Aluminosilicate>

As the aluminosilicate, there can be used both of amorphous and crystalline aluminosilicates. It is preferable that the amorphous aluminosilicate contains 30% by weight or more, preferably 40% by weight or more of silicon in terms of Si0₂.

Moreover, when a 5% aluminosilicate dispersion having pH 9 or more is used, the solubility deterioration of the detergent after a high-humidity storage can be inhibited.

Example of the amorphous aluminosilicate which can be used in the invention include aluminosilicates represented by the following general formula (i), and they have a high oil absorbing ability and a high cation- exchange ability. a(M₂0) - A?₂0₃ - b(Si0₂) - c(H₂0) (i) wherein M is an alkali metal atom, and a, b and c denote mol numbers of the components, respectively, and in general, a is 0.7 ≤ a≤ 2.0, b is 0.8 ≤b<4, and c is an optional positive number. Aluminosilicates represented by the general formula (ii) are particularly preferable:

Na₂OA ₂θ3 - b(Si0₂) ' c(H₂0) (ii) wherein b is a value of 1.8 to 3.2, and c is a number of 1 to 6. Preferred amorphous aluminosilicates have the ion-exchange capacity of 100 CaCθ3 mg/g or more and the oil absorbing capacity of 200 m^/100 g or more.

By selecting the amorphous aluminosilicate whose 5% dispersion has a pH of 9.0 or more, a high-density detergent composition whose solubility does not deteriorate during storage under high humidity conditions can be obtained. A pH of a 5% dispersion of the amorphous aluminosilicate is measured on the basis of JIS K 6220. That is to say, about 5 g of a sample is placed in a hard Erlenmeyer flask, and 100 nu? of carbonic acid-free water is then poured into the flask. Afterward, the flask is plugged and then shaken for 5 minutes. For the thus shaken and mixed solution which is an analyte, its pH is measured by a glass electrode method (JIS Z 8802-7.2.3).

Moreover, when the alkalinity of the detergent is very high or the storage conditions are very severe, it is preferable to select the amorphous aluminosilicate which can meet severer conditions that the amount of the amorphous aluminosilicate dissolved in a 2% aqueous NaOH solution is 0.5 g or less.

That is to say, the amorphous aluminosilicate to be selected meets the following requirements. 10 g of the amorphous aluminosilicate is dispersed in 100 m£ of 2% aqueous NaOH solution, and the dispersion is then stirred at a constant temperature of 25°C for 16 hours. Afterward, for Si0 in the resulting filtrate, colorimetry [with regard to the colorimetry, see "Yu- kagaku (Oil Chemistry)", Volume 25, p. 156, (1976)] is carried out. In this case, the amount of the dissolved amorphous aluminosilicate should be 0.5 g or less.

Furthermore, the crystalline aluminosilicate is usually called a zeolite, which is represented by the following formula a'(M2θ) - A ₂θ3 -b'(Si0₂) - w(H₂0) (iϋ) wherein M is an alkali metal atom, and a', b' and w denote molar ratios of the components, respectively, and in general, a' is 0.7 ≤ a' ≤ 1.5, b' is 0.8 ≤b'<6, and w is an optional positive number, and above all, the aluminosilicates represented by the general formula (iv) are particularly preferable:

Na₂0 -A 2θ3 - n(Si0₂) - w(H₂0) (iv) wherein b is a value of 1.8 to 3.0, and w is a number of 1 to 6. Examples of the preferably usable crystalline aluminosilicate (the zeolite) include synthetic zeolites having an average primary particle diameter of 0.1 to 10 U m typified by A type, X type and P type zeolites. The zeolite may be blended in the form of cohered zeolite dry particles obtained by drying a zeolite powder and/or a zeolite slurry.

In the present invention, the aluminosilicate is blended in an amount of 1 to 60% by weight, preferably 8 to 30% by weight in the composition. If the content of the aluminosilicate is out of the above-mentioned range, the detergency deteriorates. <Crystalline aluminosilicate >

The suitable crystalline silicate which can be used in the invention has the following composition.

© x(M₂0) - y(Si0₂) - z(Me_mO_n) - w(H₂0) (H) wherein M is an element in the la group of the periodic table, Me is one or a combination of two or more selected from the group consisting of elements in the Ha group, the lib group, the Ilia group, the IVa group and the VIII group of the periodic table, y/x is from 0.5 to 2.6, z/x is from 0.01 to 1.0, w is from 0 to 20, and n/m is from 0.5 to 2.0. © M₂0 ^• x'(Si0₂) ^• y'(H₂0) (in) wherein M is an alkali metal, x' is from 1.5 to 2.6, and y' is from 0 to 20. First, the crystalline silicate represented by the general formula (II) in the above-mentioned paragraph φ will be described.

In the general formula (II), M is selected from the elements in the group la of the periodic table, and examples of the elements in the group la include Na and K. They may be used singly, or for example, Na₂0 and K₂0 may be mixed to constitute an M₂0 component.

Me is selected from the elements in the Ila group, the lib group, Ilia group, IVa group and the VIII group of the periodic table, and for example, examples of Me include Mg, Ca, Zn, Y, Ti, Zr and Fe. They are not particularly limited, but Mg and Ca are preferable from the viewpoint of resources and safety. Moreover, they may be used singly or in a mixture of two or more thereof, and for example, MgO, CaO and the like may be mixed to constitute an Me_mO_n component.

Furthermore, in the general formula (II), y/x is in the range of 0.5 to 2.6, preferably 1.5 to 2.2. If y/x is less than 0.5, water dissolution resistance is insufficient, and the composition is considerably inferior in caking, solubility and powdery property. If y/x is more than 2.6, the composition is unsuitable as an aJialine agent for low alkali ability and also it is unsuitable for ion exchanger for low ion-exchange ability. In the general formula (II), z/x is in the range of 0.01 to 1.0, preferably 0.02 to 0.9. If z/x is less than 0.01, water dissolution resistance is insufficient. If z/x is more than 1.0, the composition is unsuitable for ion exchanger for low ion exchange capacity. Aforementioned x, y and z are not specifically limited so long as the y/x ratio and the z/x ratio satisfy above-mentioned relations. As mentioned above, when x(M₂0) is x'(Na 0) *x"(K₂0), x is x'+x". Such a relation is also applicable to z when a z(Me_mO_n) component is constituted of 2 or more components. In addition, n/m represents an oxygen ion number which coordinates the element, and substantially, n/m is selected from values of 0.5, 1.0, 1,5 and 2.0.

The crystalline silicate represented by the general formula (II) comprises three components of M₂0, Si0₂ and Me_mO_n. Therefore, in order to prepare the crystalline silicate represented by the general formula (II), the respective components are necessary as their raw materials, but in the present invention, known compounds can be suitably used without any particular restriction. For example, as the M₂0 component and the MβmOn component, there can be used oxides, hydroxides and salts containing the elements singly or compositely elements as well as element- containing minerals. Examples of the raw material for the M₂0 component include NaOH, KOH, Na₂Cθ3, K₂CU3 and Na₂Sθ4, and examples of the raw material for the Me_mO_n component include CaCθ3, MgCθ3, Ca(OH) , Mg(OH)₂, MgO, Zr0₂ and dolomite. Usable examples of the Si0₂ include siliceous ore, kaolin, talc, molten silica and sodium silicate.

The preparation method for the crystalline silicate represented by the general formula (II) is as follows. The above-mentioned components are mixed so that a x, y and z ratio is adjusted to that of a desired crystalline sihcate, and the mixed material is fired to crystallize the silicate usually at 300 to 1500°C, preferably 500 to 1000°C, more preferably 600 to 900°C. In this case, if a heating temperature is less than 300°C, the silicate suffers from insufficient crystallization and the silicate is inferior in water dissolution resistance. If the heating temperature is more than 1500°C, the granules of the silicate are coarse, and accordingly the ion-exchange capacity of the product deteriorates. The heating time is usually in the range of 0.1 to 24 hours. Such a firing can usually be conducted in a heating furnace such as an electric furnace and a gas furnace.

The crystalline silicate represented by the general formula (II) obtained in this way exhibits a pH of 11 or more in a 0.1 wt% aqueous dispersion and shows the excellent alkali ability. In addition, this crystalline silicate is also excellent in alkali buffer effect and the alkali buffer effect of the crystalline silicate is superior to that of sodium carbonate or potassium carbonate. The crystalline silicate represented by general formula (II) has an ion- exchange capacity of 100 CaC03 mg/g or more, preferably 200 to 600 CaC03 mg/g, and the crystalline silicate is one of the substances which have an ion capturing ability in the present invention.

The crystalline silicate represented by general formula (II) has the alkalinity, the alkali buffer effect, and additionally the ion-exchange capacity as described above, and therefore, by suitably adjusting its blend amount, the above-mentioned washing conditions can be preferably regulated.

An average particle diameter of the crystalline silicate represented by the general formula (II) is preferably in the range from 0.1 to 100 μ m, more preferred on is in the range from 1 to 60 μ m. If the average particle diameter is more than 100 μ m, a development speed of the ion exchange tends to low, which leads to the deterioration of detergency. In addition, if the average particle diameter is less than 0.1 μ m, hygroscopicity and C0₂ absorbability tend to increase owing to an increased specific surface area, so that the deterioration of a product quality is liable to be noticeable. Incidentally, the average particle diameter referred to herein is a median diameter of particle size distribution.

The crystalline silicate having such an average particle diameter and particle size distribution can be prepared by grinding with a mill such as a vibration mill, a hammer mill, a bowl mill, a roller mill or the like. For example, the crystalline silicate can be easily obtained by using an HB-0 type vibration mill (trademark, made by Chuo Kakoki Co., Ltd.).

Next, the crystalline silicate represented by the general formula (III) in the above-mentioned paragraph (D will be described.

This crystalline silicate is represented by the general formula (III) M₂0 - x'(Si0₂) - y'(H₂0) (HI) wherein M is an alkali metal, and x' is from 1.5 to 2.6, and y' is from 0 to 20, but the crystalline silicate in which x' and y' in the general formula (III) are

1.7 ≤.x' ≤2.2 and y'=0 is preferable, and the crystalline silicate having a cation exchange capacity of 100 to 400 CaCθ3 mg/g can be used. This kind of crystalline silicate is one of the substances having an ion capturing ability in the present invention. The crystalline silicate represented by the general formula (III) has the alkalinity, the alkali buffer effect and moreover the ion exchange ability as described above, and therefore the above-mentioned washing conditions can be suitably regulated by suitably adjusting the amount of the crystalline silicate. A preparation method of the crystalline silicate represented by the general formula (III) is described in JP-A-60-227895. With regard to the crystalline silicate represented by the general formula (III), its powder and granules are commercially available from Hoechst Corp. under a trade name of "Na-SKS-6" ( <5 -Na₂Si₂0₅). With regard to the crystalline silicate represented by the general formula (III) in the present invention, its average particle diameter is preferably in the range of 0.1 to 100 μ m, more preferably 1 to 60 μ m, as in the case of the crystalline silicate represented by the general formula (II). In the present invention, the crystalline silicate represented by the general formula (II) and the crystalline silicate represented by the general formula (III) can be used singly or in a combination of two or more thereof. In the present invention, an amount of the crystalline silicate is in the range of 0 to 40% by weight, preferably 5 to 35% by weight in the composition. If the amount of the crystalline sihcate to be blended is small, the detergency deteriorates, and if it is more than 40% by weight, hygroscopicity increases and powdery property such as caking deteriorates. <Alkali agent>

Examples of the alkali agent include sodium carbonate, potassium carbonate, sodium silicate, sodium bicarbonate, potassium bicarbonate, sodium sulfite, potassium sulfite, sodium sesquicarbonate, sodium orthophosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate in addition to the above-mentioned crystalline silicate. Of the alkali agents contained in the composition, the amount of the crystalline silicate is in the range of 0 to 100% by weight, preferably 20 to 100%) by weight, more preferably 60 to 90% by weight. <Nonionic surfactant>

The nonionic surfactant is one or a blend of two or more selected from the group consisting of polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylenesorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyethylene polyoxypropylene block polymers and alkanoyl N-methylglucamine. Above all, polyoxyethylene alkyl ethers having an HLB value being in the range of 10.5 to 15.0 are particularly preferable. The nonionic surfactant is preferably blended in the composition in an amount of 1 to 15% by weight. <Polycarboxylate>

Among polycarboxylates having a molecular weight of several million to 100,000, the salts of the acrylic acid-maleic acid copolymer and the salts of the polyacrylic acid (of Na, K or NH4, respectively) are particularly excellent.

Its molecular weight is preferably in the range of 1000 to 80000. In addition, the following components can be blended in addition to the above-mentioned materials.

For example, bleachi g agents, bleaching activators, enzymes, enzyme stabilizers, various bluing agents, caking resistants, antioxidants, fluorescent dyes, perfumes, etc. The high-density detergent composition of the present invention is a powdery or granular composition, but no particular restriction is put on its preparation method and a conventional known method can be used. As a technique of giving a high-bulk-density state, for example, there are a method which comprises spraying a nonionic surfactant on the spray-dried particles, and another method which comprises directly occluding a nonionic surfactant in a powdery component containing an oil absorbing carrier. Furthermore, in the case that a crystalline silicate is blended, this crystalline silicate is preferably added at the time of providing the high- bulk-density or by dry blending. Moreover, when an alkali metal carbonate is blended, it may be added to a slurry, during the granulation or by dry blending.

In this connection, the amidoamine oxide which is the component (B) may be added before or after the spray drying step.

The average particle diameter of the high-density detergent composition of the present invention is preferably in the range of 200 to

1000 μ m, more preferably 200 to 600 μ m. Furthermore, the bulk-density of the detergent composition of the present invention is in the range of 0.5 to 1.2 g/m*, preferably 0.6 to 1.2 gfml> ^more preferably ₀.6 to 1.0 g/mi.

The detergent composition of the present invention, when used, can be regulated so as to have a concentration suitable for each washing in compliance with a washing method such as washing by a washing machine or immersion washing, the amount of clothes to be washed, the degree of soil, the usage of the machine and the like. For example, in the case of the washing by the washing machine, the detergent composition can be used at a detergent concentration of 0.03 to 0.3% by weight.

According to the present invention, there can be obtained a high- density detergent composition having a high detergency, excellent biodegration and safety b y blending the amidoamine oxide surfactant to the anionic activator in the specific ratio. Examples

Next, the present invention will be described in detail, but the scope of the present invention should not be limited to these examples. Example 1

(1) A product 1 of the present invention in Table 1 was prepared by the following procedure.

A slurry having a water content of 50% by weight was prepared from 0.5 kg of a zeolite, 2.62 kg of AS, 0.5 kg of AM, 1.25 kg of soda ash, 0.1 kg of PEG and 0.05 kg of a fluorescent dye (4,4'-bis-(2-sulfostyryl)-biphenyl salt), and then spray-dried to obtain a powder. Next, the thus obtained powder was thrown into a high-speed mixer (a stirring rolling granulator, made by Fukae Kogyo Co., Ltd.), and 0.5 kg of the zeolite, 0.88 kg of an antidoamine oxide (AO-1) and 2.0 kg of a silicate (II) were then added. Furthermore, 0.5 kg of the zeolite was added, followed by granulation. Afterward, the obtained granules were dry-mixed with 0.5 kg of the remaining zeolite and 0.1 kg of an enzyme to obtain a high-density granular detergent composition (average particle diameter = 420 μ g, bulk density = 800 g/liter). The other high-bulk-density granular detergent compositions, i.e., the products of the present invention and products for comparison described in Tables 1 to 3 were also prepared at blend ratios in accordance with the above-mentioned scheme.

In the case that the blend of the zeolite was small as in products 18 and 19 of the present invention, the zeolite was not added before the spray drying, and it was divided and used in the subsequent steps.

(2) Invention product 27 was prepared by the following procedure.

A slurry having a water content of 50% by weight was prepared from 1.0 kg of a zeolite, 2.62 kg of AS, 0.5 kg of AM, 1.25 kg of soda ash, 0.1 kg of PEG, 0.05 kg of a fluorescent dye (4,4'-bis-(2-sulfostyryl)-biphenyl salt) and 0.88 kg (in terms of AO-1) of an aqueous solution of an amidoamine oxide (AO- 1), and then spray-dried to obtain a powder. Next, the thus obtained powder was thrown into a high-speed mixer (a stirring rollin granulator, made by Fukae Kogyo Co., Ltd.), and 0.5 kg of the zeolite and 2.0 kg of a sihcate (II) were then added. Furthermore, 0.25 kg of the zeolite was added, followed by granulation. Afterward, the obtained granules were dry-mixed with 0.25 kg of the remaining zeolite and 0.1 kg of an enzyme to obtain a high-density granular detergent composition (average particle diameter = 490 μ g, bulk density = 760 g/liter (0.76 glml). The other high-density granular detergent compositions, i.e., Invention products 28 to 30 and Comparative products 7 to 9 in Table 4 were also prepared at blend ratios in accordance with the above-mentioned scheme.

However, ASDA which was blended in Invention product 29 was added to the slurry before the spray drying. Furthermore, with regard to Comparative product 10, 1.0 kg of a porous silica compound was added to the high-speed mixer in the same manner as in the case of a silicate, Glauber's salt or the like, and a predetermined amount of AE- 1 which was heated up to 70°C was further added, followed by granulation. Next, 0.5 kg of the porous silica compound was added, and the mixture was then granulated. Afterward, 0.5 kg of the remaining porous silica compound was further added, followed by granulation, thereby obtaining a high-density granular detergent composition. In addition, in Comparative product 10, the blend of the zeolite was small, and so the zeolite was not added before the spray drying, and it was divided and used in the subsequent steps. (3) For the thus obtained high-density granular detergent compositions, detergency power tests were carried out in the following manner. The results are shown in Tables 1 to 4. <Detergency test>

(Preparation of an artificially soiled cloth) An artificial soiling solution having the following composition was stuck to a cloth to prepare an artificially soiled cloth. The sticking of the artificial soiling solution to the cloth was carried out by the use of a gravure roll coater. The step in which the artificial soiling solution was stuck to the cloth to prepare the artificially soiled cloth was carried out under conditions that the cell volume of the gravure roll was 58 cm^/m^, a coating velocity was 1.0 m/min, a drying temperature was 100°C, and a drying time was 1 min. As the cloth, a cotton cloth 2003 (made by Yatou Shoten Co., Ltd.) was used.

[Composition of the artificial soiling solution] Laurie acid 0.44 wt%

Myristic acid 3.09 wt%

Pentadecanoic acid 2.31 wt%

Palmitic acid 6.18 wt%

Heptadecanoic acid 0.44 wt% Stearic acid 1.57 wt% Oleic acid 7.75 wt%

Trioleic acid 13.06 wt% n-Hexadecyl palmitate 2.18 wt%

Squalene 6.53 wt% Albumen lecithin liquid crystal 1.94 wt%

Kanuma red clay 8.11 wt%

Carbon black 0.01 wt%

Tap water Balance

(Washing conditions and evaluation method) Five of the artificially soiled clothes having a size of 10 cm x 10 cm prepared above were placed in 1 hter of an aqueous detergent solution for evaluation, and they were then washed at 100 rpm by a tergotometer. Washing conditions are as follows.

Washing conditions: Washing time 10 min

Detergent concentration 0.067%

Hardness of water 4° DH

Water temperature 20°C

Rinsing with tap water for 5 min The detergency was determined as follows. Reflectances at 550 nm of the original unsoiled clothes as well as the soiled clothes before and after the washing were measured by a self colorimeter (made by Shimadzu Seisakusho Ltd.), and a detergency (%) was calculated in accordance with the following equation. An average value of the measured values of the five clothes was regarded as the detergency. (Reflectance after washing) - (Reflectance before washing)

Detergency (%) = x 100

(Reflectance of original cloth) - (Reflectance before washing)

Table 3

Invention Product Comparative Product

_C _Cttennom_pom_en S_oponam pie No. 22 23 24 25 26 1 2 3 4 5 6 ₍₎ 19.7 16.2 13.5 26.2 35.0 0 34.8 9.0 30.0 0 _(b)a AS 26.2

LAS 0 0 0 0 0 0 0 0 0 0 30.0

FA 0 0 0 0 0 0 35.0 0 0 0 0

AO- 1 8.8 6.5 5.6 4.5 8.8 0 0 0.2 3.3 0 0

4-3

AO-2 0 0 0 0 0 0 0 0 0 0 0

CO

4-3 t d

CD d o a Zeolite 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 ε o Silicate (II) 0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 O CO

4-3 d Silicate (III) 0 0 0 0 0 0 0 0 0 0 0 d CD

CD d Sodium Carbonate 12.5 12.5 12.δ1 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 o 3 ft Sodium Silicate No. 0 0 0 0 0 0 0 0 0 0 0 o ε 2 ϋ Organic Builder 0 0 0 0 0 0 0 0 0 0 0

CD

X AE-1 0 0 0 0 0 0 0 0 0 5.0 5.0 o 4-3

Dispersant AM AM AM AM 0 AM AM AM AM AM AM 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0

Common Component 27.5 16.3 20.7 24.5 12.5 7.5 7.5 7.5 30.1 7.5 7.5

Total (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Results Detergency (%) 67.1 70.2 68.1 65.4 70.2 60.8 61.1 63.3 63.2 62.1 62.5

AS: Na salt of alkyl (C 14) sulf ate ester LAS: Na salt of linear alkyl (C12) benzenesulfonic acid FA: Na salt of palmitic acid AO-1: Lauroylamidopropylάimethylamine oxide AO-2: Myristyloylamidopropyldimethylamine oxide

Zeolite (crystalline aluminosilicate: Composition M2O ^• A^O_β •

2Siθ2 ' 2H2O, average particle diameter 2 μ , ion exchange capacity

290 CaC0₃ mg/g, M is Na, K) Silicate (II): Composition M₂0 ^• 1.8Si0₂ ^• 0.02MO (wherein M: Na, K, K/Na=0.03, M'=Ca, Mg, Mg/Ca=0.01), ion exchange capacity 290 CaCU3 mg/g, average particle diameter 30 μm (a crystalline silicate represented by the general formula (II))

Silicate (III): Composition M2O ^• 2Siθ2, ion exchange capacity 224 CaCU3 mg/g, average particle diameter 30 μ m (a crystalline silicate represented by the general formula (III)) AE-1: Nonionic activator, polyoxyethylene dodecyl ether (HLB=13.1) AM: Na salt of acrylic acid/maleic acid (molar ratio 7/3) copolymer, average molecular weight 70,000 PA: Na salt of polyacrylic acid, average molecular weight 8000 HIDS: Hyc oxviminodisuccinic acid derivative ASDA: Aspartic acid diacetic acid derivative

PEG: Polyethylene giycol having an average molecular weight of 7000 Common components: 1% of PEG, 1% of enzyme [a mixture of API-21H (made by Showa Denko K.K.), Lipolase 100T (made by Novo Nordisk Co., Ltd.), Cellzaim O.lT (made by Novo Nordisk Co., Ltd.), Termamil 60T (made by Nobonoldisc Co., Ltd.) in a ratio of 2: 1: 1:1], 0.5% of a fluorescent dye and Glauber's salt, and preparation was made so that the total amount might be 100% with Glauber's salt.

Claims

1. A high density, granular detergent composition comprising: (a) 10 to 50 percent by weight of an anionic surfactant, (b) 1.0 to 20 percent by weight of an amidoamine oxide surfactant having the formula (I):

R2

RιCON(CH₂)n— N-→O (I)

I I

R4 R3

wherein Rj is an alkyl group or an alkenyl group having 10 to 20 carbon atoms, R2 and R3 each is H, an alkyl group or an alkenyl group having

1 to 3 carbon atoms, R4 is H, an alkyl group or an alkenyl group having 1 to 5 carbon atoms, and n is from 1 to 5.

(c) 1 to 60 percent by weight of an aluniinosilicate, (d) 5 to 30 percent by weight of a crystalline silicate, having a weight ratio of (b)/ (a) ranging from l/lOO to 100/100, having an apparant density of 0.6~ 1.2g/ m '.

2. The composition as claimed in Claim 1, wherein the crystalline silicate (d) is represented by the formula (II) and/or (III): x(M₂0) ^• y(Si0₂) ^• z(Me_mO_n) w(H₂0) (IT) wherein M is an element in the la group of the periodic table, Me is one or a combination of two or more selected from the group consisting of elements in the Ila group, the lib group, Ilia group, PVa group and the Vffl group of the periodic table, y/x is from 0.5 to 2.6, z/x is from 0.01 to 1.0, w is from 0 to 20, and n/m is from 0.5 to 2.0; M₂0 ^• χ'(Si0₂) ^• y'(H₂0) (111) wherein M is an alkali metal, x' is from 1.5 to 2.6, and y' is from 0 to 20.

3- The composition as claimed in Claim 1, wherein the anionic surfactant (a) is at least one selected from the group consisting of higher fatty acid salts having 10 to 18 carbon atoms, sulfuric acid ester salts of straight or branched chain primary or secondary alcohols having 10 to 18 carbon atoms, sulfuric acid ester salts of ethoxylate compounds of alcohols having 8 to 20 carbon atoms, alkylbenzenesulfonic acid salts in which an alkyl group has 8 to 16 carbon atoms, alkane sulfonates, -olefin sulfonates, a -sulfonic fatty acid salts and a -sulfonic fatty acid alkyl ester salts.

4. The composition as claimed in Claim 1, which contains 1 to 15% by weight of the nonionic surfactant.

5. The composition as claimed in Claim 4, wherein the nonionic surfactant is one or more selected from the group consisting of polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylenesorbitan fatty acid esters, polyoxyalkylene giycol ethers, polyoxyethylene polyoxypropylene block polymers and alkanoyl N- methylglucamine.

6. The composition as claimed in Claim 1, which contains a polycarboxylate having an average molecular weight of 1000 to 100000.

7. The composition as claimed in Claim 1, comprising 2 to 10 percent by weight of (b), having a weight ratio of (b)/(a) ranging from 3/100 to 50/ 100.