AU649504B2 - Nonionic powder detergent composition - Google Patents

Description

64

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION NAME OF APPLICANT(S): Kao Corporation ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street, Melbourne, 3000.

INVENTION TITLE: d ~t~donionic detergent comporition x 9@9* 0~ 9000 00S0 o S S 0S S The following statement is a full description of of performing it known to me/us:this invention, including the best method

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[Field of the Invention] The present invention relates to a powdered detergent composition comprising a nonionic surfactant as a main base material.

Particularly, the present invention relates to a powdered detergent composition which is free from the exudation of a nonionic surfactant liquid at ordinary temperatures to be excellent in fluidity and caking resistance, and which has a solubility which is not S S.

deteriorated during storage.

[Description of the Related Art] A nonionic surfactant is characterized by excellent stability in hard water, high detergency and soil-dispersing power and e'ctremely excellent biodegradability and is therefore noted as an important surfactant for detergents.

However, most of conventional nonionic surfactants for detergents are liquid at ordinary i temperatures. Therefore, when such a liquid nonionic surfactant is contained in a powdered detergent as *such in a large amount, the nonionic surfactant gradually exudes with the lapse of time to cause problems that the surfactant soaks into the inside wall of a paper case and that the fluidity of the lapowdered detergent is impaired to result in caking finally with a lowering in the commercial value of the detergent.

Japanese Patent Laid-Open No. 119813/1975 discloses a fluid detergent comprising 30 to 100% of a premix comprising zeolite or a mixture thereof with an inorganic peroxide which generates hydrogen peroxide in water, and a nonionic surfactant dispersed thereon (which may further contain at most 4% of a highly S. dispersible silicic acid) and 0 to 70% of a spraydried detergent. Further, Japanese Patent Laid-Open No. 89300/1986 discloses that a nonionic surfactantcontaining granular detergent prepared by spraying a o nonionic surfactant on a mixture comprising a watersoluble powdery or granular material and powdered silica, adding powdered zeolite to the obtained mixture, granulating the mixture thus prepared and compounding the obtained granule with an anionic surfactant-base granular detergent is excellent in fluidity to be free from caking. Both of the techniques relate to nonionic surfactant-containing o additives which are each post-added to a spray-dried

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detergent comprising an anionic surfactant as a main base detergent. Thus, there have not been made many studies on such a nonionic surfactant-base detergent 2 as disclosed in the present invention.

Japanese Patent Laid-Open No. 41708/1976 discloses a free-flow detergent composition comprising a porous aggregate of a synthetic amorphous silica derivative and a nonionic surfactant.

It is known that a siliceous substance can be used for improving the fluidity of a nonionic surfactant-containing detergent as shown by the above-described examples.

However, the effect which is exhibited by the G above-described techniques is unsufficient.

e 0o f.t• [Summary of the Invention] t. Under these circumstances, the inventors of the •ft present invention have made intensive studies on nonionic surfactant-base detergents and have found that a nonionic surfactant-base powdered detergent eas*: containing a crystalline aluminosilicate, an oil- 4 absorptive amorphous carrier and sodium carbonate at a specific ratio is remarkably reduced in the exudation of the liquid nonionic surfactant and is improved in fluidity and caking resistance.

The inventors have also found that a nonionic surfactant-base powdered detergent containing an oil-absorptive carrier having specified properties is remarkably reduced in the exudation of the liquid 3 -4nonionic surfactant and is improved in fluidity and caking resistance even by storage under high-humidity conditions.

The present invention has been accomplished on the basis of these findings.

Namely, the present invention provides a nonionic powder detergent composition comprising: 12 to 35 wt.% of a nonionic surfactant having a melting point of 40*C or below; 10 to 60 wt.% of a crystalline aluminosilicate; and 5 to 20 wt.% of an oil-absorbing carrier selected from amorphous silica and an amorphous aluminosilicate containing at least 30 wt.% of silicon in terms of SiO 2 and having an oil-absorbing capacity of at least 80 ml/100 g, said carrier giving a dispersion with a pH value of at least 9 or being soluble in a 2% aqueous NaOH solution in an amount of 0.5 g or less.

The powdered nonionic detergent composition may further comprise 5 to 35% by weight of sodium carbonate and/or (e) polyethylene glycol having a molecular weight of 4000 to 25 20000.

940318.p:operdab,9009pe,4 The invention moreover provides a process for producing a nonionic powder detergent composition according to claim 1, which comprises the steps of mixing a crystalline aluminosilicate with an oil-absorbing carrier while adding to or spraying onto the mixture a nonionic surfactant having a melting point of 40 0 C or below gradually to obtain a homogeneous mixture of and and then adding to the mixture further crystalline aluminosilicate to obtain a powder detergent composition.

As for optional ingredients, sodium carbonate may be added in the first step, and a perfume and an enzyme may be added in the second step.

The invention moreover provides nonionic powder detergent product comprising the nonionic powder detergent composition of the present invention, packed in a container made of converted paper laminated with a polymer selected from polyethylene or polypropylene.

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o 940318,p:\operdab,90092.spe,5 -6- The invention also includes following embodiments to Embodiment (A) A nonionic powder detergent composition comprising the following components and ia nonionic surfactant having a melting point of 40°C or below; 12 to 35% by weight, a crystalline aluminosilicate; to 20% by weight, an oil-absorptive amorphous silica; to 20% by weight, and sodium carbonate to 35% by weight.

Embodiment (B) A nonionic powder detergent composition comprising the following components and a nonionic surfactant having a melting point of 40°C or below; 12 to 35% by weight, 25 a crystalline aluminosilicate; 10 to 60% by weight, 9

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940318,p:operdab,9O92.spe,6 -7an oil-absorptive amorphous aluminosilicate and/or an oil-absorptive amorphous calcium silicate; 5 to 20% by weight, and sodium carbonate to 35% by weight.

Embodiment (C) A nonionic powder detergent composition comprising the following components and a nonionic surfactant having a melting point of 40 0 C or below; 12 to 35% by weight, a crystalline aluminosilicate; to 20% by weight, and an oil-absorptive carrier containing at least 30% by weight of silicon in terms of SiO 2 has an oilabsorbing capacity of at least 80 ml/100 g and gives a dispersion with a pH value of at least 9 (c-3) or is soluble in a 2% aqueous NaOH solution in an amount of 0.5 g or less 25 5 to 20% by weight.

Embodiment (D) A nonionic powder detergent composition comprising the following components and o* o o 940318,p:~op&dab,90092.pe,7 -8a nonionic surfactant having a melting point of 40°C or below; 12 to 35% by weight, a crystalline aluminosilicate; to 60% by weight, and an oil-absorptive carrier contains 30 to 40% by weight of silicon in terms of Si02, has an oil-absorbing capacity of at least 80 ml/100 g, and is soluble in a 2% aqueous NaOH solution in an amount of 0.5 g or less; to 20% by weight.

Embodiment (E) A nonionic powder detergent composition comprising the following components and a nonionic surfactant having a melting point of 40"C or below; 12 to 35% by weight, a crystalline aluminosilicate; to 60% by weight, "and an oil-absorptive carrier contains 30 to 40% by weight S 25 of silicon in terms of Si02, has an oil-absorbing capacity of at least 80 ml/100 g, and gives a dispersion 0 with a pH value of at least 9; 5 to 20% by weight.

e S S 94o318,p:oper\dab,90092.sp,8 Embodiment (F) A nonionic powder detergent composition comprising the components and a nonionic surfactant having a melting point of 400C or below; 12 to 35t by weight, a crystalline aluminosilicat'e-; 10 to 60t by weight, and an oil-absorptive carrier containing at least 30% by weight of silicon in terms Of S102, has an oil-absorbing capacity of 80 -to 150 ml/100 g, and gives a dispersion with a pH value of at least 9; to 20t by weight.

Embodiment (G) A nonionic powder detergent composition comprising the following components and a nonionic surf~ctant having a melting point of 400C or below; ol 12 to 35% by weight, a crystalline aluminosilicate; eeeo..: 25 10 to 60% by weight, an oil-absorptive amorphous aluminosilicate has an oil- :..absorbing capacity of at least 80 ml/100 g, and is ""soluble in a 2% aqueous NaOH solution in an amount of 0.05 to 0.5 g; 30 5 to 20% by weight.

o~e JA e:oprda,002M Embodiment (H) A nonionic powder detergent composition comprising the following components and a nonionic surfactant having a melting point of 40*C or below; 12 to 35% by weight, a crystalline aluminosilicate; 10 to 60% by weight, an oil-absorptive amorphous aluminosilicate has an oilabsorbing capacity of 80 to 200 ml/100 g, and is soluble in a 2% aqueous NaOH solution in an amount of 0.5 g or less; 5 to 20% by weight.

[Detailed Description of the Invention] The nonionic surfactant, which is used as a component (a) in the present invention, is favorably one having a melting point of 40 0 C 'or below and an HLB value of 9.0 to 16.0, preferably 9.0 to 14.0, from the viewpoint of the removal of dirt as well as foaming and rinsing properties. The term "HL.

value" used in this specification is defined as follows: Namely, it is one calculated according to the equation give in J.T. Davies and E.K. Rideal, Interfacial Phenomena, Academic Press, New York, 1963, pp. 371 to 383: 940318,poper\dab,9009 o.

O p r HLB =7 (group value of hydrophilic group) (group value of hydrophobic group) The group values of atomic groups used in the above calculation are as follows: AJtoml c group Group valuie o Hydrophilic ester 6.8 group (sorbitan. ring) ester (free) -2.4 -COOH 2.1 OH (free) 1.3 ,Dee a &0 o a0 -0-1 OH (sorbitan ring) o Lipophilic group

-CH-

-OH

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=CH-

0.475 0 0 0*'4 00 4 0 0 8 00 00 a 09, 0 *000 0~ 0 0 0 o Derivative group (OH 2

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(CH

2 -CH-0) 0.33 0 Particular examples of the component (a) include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylenesorbitan fatty acid ester, polyoxyethylenesorbitol fatty acid ester, 11 polyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylenealkylteine, glycerol fatty acid ester, higher fatty acid alkanolamide, alkyl glycoside and alkylamine oxide.

Among them, preferred main nonionic surfactants are polyoxyethylene alkyl ethers of straight-chain or branched, primary or secondary alcohols having an C o alkyl chain of 10 to 20, preferably 12 to l1 and o particularly preferably 12 to 14 carbon atoms having seo* to 15 mol, preferably 6 to 12 mol, still preferably 6 to 10 mol, on average of ethylene oxide added thereto.

e The polyoxyethylene alkyl ethers usua2'v contain a large amount of alkyl ethers having a low molar number of ethylene oxide added thereto. Those

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comprising 35% by weight or less, or preferably 25% by weight or less, of 0 to 3 mol of ethylene oxide added are desirably used.

The component is contained in an amount of 12 to 35% by weight, preferably 15 to 30% by weight, based on the whole composition.

The crystalline aluminosilicates (zeolites) used as the component in the present invention are those represented by the following formula 12 x(M 2 0) -A1 2 0 3 y(Si0 2 )-w(H 2 0) (3) wherein M represents an alkali metal atom and x, y. and 3 each represent a molar number of the respective components which are generally as follows: 0.7 x 1.5, 0.8 y 6 and w is an arbitrary positive number.

Among them, those of the following general formula Na 2 0- A1 2 0 3 n(SiO 2 w(H 2 0) (4) soSS a S. wherein n represents a number of 1.8 to 3.0 and A 0eS* represents a number of 1 to 6, are preferred. The crystalline aluminosilicates (zeolites) preferably used are synthetic zeolites having an average primary particle diameter of 0.1 to

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10 g typified by zeolite A and zeolite X. Zeolite is

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e* SS a incorporated in the form of a powder and/or a dry particle of zeolite aggregate obtained by drying a zeolite slurry.

The component is incorporated into the composition in an amount of 10 to 60% by weight, preferably 20 to 60% by weight and particularly preferably 30 to 50% by weight based on the whole composition.

13 The oil-absorptive carriers used as the component in the present invention include an amorphous silica, an amorphous aluminosilicate or silicoaluminate, a (amorphous and crystalline) calcium silicate and a clayey substance. The oil-absorptive carriers, each having a mean particle diameter of about 200 im or below, are commercially available, among which those each having a pore volume of 200 to 600 cm 3 /100 g are preferably used in the present 0* invention as the component Examples of the oil-absorptive amorphous silicas 0 S *moo include oil-absorptive carriers available on the 0* 0G. market under the trade names of Tokusil (Tokuyama Soda Co., Ltd.) and White carbon (Kofran Chemical), etc., definitely Tokusil AL-1 (mfd. by Tokuyama Soda Co., Ltd.), Nipsil NA (mfd. by Nippon Silica Ind.), Carplex #100 (mfd. by Shionogi Pharmacy) and Sipernat (Degussa Examples of the oil-absorptive amorphous aluminosilicate include an oil-absorptive carrier available on the market under a trade name of to Tixolex 25 (Kofran Chemical). Examples of the oil-absorptive amorphous aluminosilicates and the oil-absorptive calcium silicates include those commercially available under the trade names of Florite (Tokuyama Soda Co., Ltd.). Examples of the 14 clayey substances include sodium mordenite HSZ-640 NAA (mfd. by Tosoh Corp.).

The oil-absorptive carriers illustrated above have scarcely any cation exchange capacity. Cationexchanging oil-absorptive carriers are advantageous, since they act also as a builder for detergent.

Examples of the oil-absorptive carriers having a high oil-absorbency and a high cation exchange capacity include oil-absorptive amorphous aluminosilicates of the following general formula e a(M 2 Al 2 03 b(Si 2 c(H 2 0) (1) wherein M represents an alkali metal atom and a, bh, and a. each represent the molar number of the respective components which are usually as follows: 0.7 g a 2.0, 0.8 g b 4 and c is an arbitrary positive number.

Particularly preferred are those of the following general formula *o Na 2 0- A1 2 0 3 m(SiO 2 c (H 2 0) (2) wherein m represents a number of 1.8 to 3.2 and c.

represents a number of 1 to 6.

The amorphous aluminosilicates having a high oil absorbency and a high ion-exchange capacity usable in 15 the present invention are prepared advantageously by the following steps: adding an aqueous solution of a low-alkali alkali metal aluminate having a M 2 0/A1 2 0 3 (M being an alkali metal) molar ratio of 1.0 to 2.0 and a H 2 0/M 2 0 molar ratio of 6.0 to 500 to an aqueous solution of an alkali metal silicate having a SiO2/M 2 0 molar ratio of "to 4.0 and a H 2 0/M 2 0 molar ratio of 12 to 200 under vigorous stirring at 15 to 60°C, preferably 30 to (Alternatively, the aqueous solution of an alkali *00* metal silicate may be added to the aqueous solution of 0000 "ooo an alkali metal aluminate.); 0o00 heat-treating a white slurry of precipitates thus 00 00 0 formed at 70 to 100 0 C, preferably 90 to 100 0 C, for min to 10 h, preferably not longer than 5 h, followed by filtration, washing and drying.

Thus the oil-absorptive amorphous aluminosilicate carrier having an ion-exchange capacity of at least 0w 0 100 CaCO 3 mg/g and an oil-absorptive capacity of at least 200 ml/100 g can be easily obtained (refer to Japanese Patent Laid-Open Nos. 191417/19,d;' i c« 191419/1987).

By selecting an oil-absorptive carrier havln, tbe following properties, the deterioration of the solubility of a zeolite-containing nonionic powdery 18 I detergent composition during storage under highhumidity conditions is prevented.

That is, the oil-absorptive carriers used as the component in the present invention include ones containing at least 30% by weight, preferably at least by weight and still preferably at least 70% by weight (in terms of SiO 2 versus the weight of said carrier in an anhydrous state, of silicon, having an oil-absorptive capacity of at least 80 ml/100 g, preferably at least 150 ml/100 g and still preferably s at least 200 ml/100 g, and giving a dispersion with a pH of at least 9.

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The pH of the dispersion of the oil-absorptive carrier is determined according to JIS K 6220. In particular, about 5 g of the sample is weighed into a hard Erlemneyer flask and 100 ml of water free from carbon dioxide is added thereto. The flask is stoppered and shaken for 5 min. The liquid thus obtained is used as a test solution to determine the

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pH by a glass electrode method (JIS Z 8802-7.2.3).

When the detergent has a quite high alkalinity or the storage conditions are quite severe, it is preferable to select an oil-absorptive carrier satisfying a severer condition such that the soluble amount in a 2% aqueous NaOH solution is 0.5 g or less.

17 More specifically, it is preferable to select such an oil-absorptive carrier that when 10 g thereof is dispersed in 100 ml of a 2% aqueous NaOH solution, the dispersion is stirred for 16 h while the temperature is kept at 25"C, and Si02 in the filtrate is subjected to colorimetric determination [as for the colorimetric determination, refer to Yukagaku, Vol.

p. 158 (1976)], the solubility thereof is 0.5 g or less. The oil-absorptive carriers satisfying this condition include sodium mordenite HSZ-640 NAA mfd. by Tosoh Corp. and some of the amorphous aluminosilicates b of the above general formula o On the other hand, the oil-absorptive carriers include also one wherein the pH of a 5% dispersion thereof is below 9.0 but the solubility thereof in a 2% aqueous NaOH solution is 0.5 g or below. Such an oil-absorptive carrier is also within the scope of the 0* present invention. For example, Perlite 4159 which is S" a clayey substance mfd. by Dicalite Orient Co., Ltd.

has such properties and is usable as the oil-absorptive carrier in the present invention.

The component which is at least one compound selected from the group consisting of an oil-absorptive amorphous silica, an oil-absorptive amorphous aluminosilicate, an oil-absorptive calcium 18 silicate and a clayey substance, is used in an amount of 5 to 20% by weight, preferably 5 to 10% by weight based onthe whole composition.

The composition of the present invention preferably contains sodium carbonate as an alkali.

Sodium carbonate includes heavy sodium carbonate (heavy ash) and light sodium carbonate (light ash).

It has an average particle diameter of 10 to 2000 gm, preferably 100 to 1000 gm. Sodium carbonate is incorporated in an amount of 5 to 35% by weight, preferably 5 to 25% by weight, based on the whole composition.

.8 The powder properties of the composition of the present invention during storage over a long period of time are further improved by incorporating 1 to 5% by g weight, preferably 1 to 3% by weight, of polyethylene 0 glycol having a molecular weight of 4000 to 20000 thereinto. 1 *The powder, detergent composition of the present invention may contain, in addition to the abovedescribed components, an alkali such as sodium silicate, an inorganic electrolyte such as sodium sulfate, an organic chelating agent such as an aminopolyacetate or polyacrylate, an antiredeposition agent such as carboxymethylcellulose, an enzyme such 19 as protease, lipase, cellulase or amylase, an antioxidant, a fluorescent dye, a blueing agent, a flavor, etc., which are usually incorporated into detergents. The amount of sodium silicate incorporated is preferably not more than still preferably not more than 1% by weight, since it might interact with zeolite to increase the amount of water-insoluble matter to thereby pose a problem of adhesion to the cloth. When the composition is a bleach-detergent composition, a bleaching agent such O't as sodium percarbonate or sodium perborate mono- or tetrahydrate, a stabilizer for a peroxide, such as a "oo* magnesium silicate, and a bleaching activator can be incorporated into the composition. When the composition is a softening detergent, a small amount of a cationic surfactant may be incorporated thereinto 0 and when a power for deterging a muddy dirt is to be increased, a small amount of an anionic surfactant may 0S be incorporated thereinto.

The-pw4aee4 nonionic\detergent composition of the present invention can be easily produced by mixing a crystalline aluminosilicate, an oil-absorptive carrier and, if necessary, a powdery component such as sodium carbonate together while (a) a liquid nonionic surfactant is gradually added 20 -21thereto or sprayed thereon to obtain a homogeneous mixture and then mixing it with minor components such as perfume cr enzyme, a crystalline aluminosilicate powder as the surface-modifying agent, a bleaching agent used when the composition is a bleach-detergent, etc. When the particle diameter of the powder detergent is increased (200 to 1000 pm, preferably 300 to 700 pm), the properties of the powder during the storage for a long period of time are further improved.

An agitation tumbling granulator which can conduct mixing, granulation and screening simultaneously, for example, Ledegue mixer can be used as a mixer to produce above-described powder detergent.

The nonionic powJer detergent composition of the present invention thus produced has a bulk density of about, 0.6 to 1.2 g/ml, preferably 0.7 to 0.9 g/ml.

The nonionic powder detergent composition of the present inention is desirably packed in a converted paper container, of which inner walls are laminated with a polymer, to obtain a nonionic powder detergent product. The polymers used for the laminat.ion are preferably ones having a solubility o. 25 parameter value of 7.5 to 11.5 [cal/cm 3 more preferably to 10.0 [cal/cm3]4 and still preferably a* *a.

a a •a a a 940318p;Xoperdab,9009spe,21 to 9.0 [cal/cm 3 1 2 The solubility parameter value of the polymer herein indicates a value defined in R.

F, Fedors, "Polymer Engineering and Science", 1A, 147 (1,974).

The polymers used for the lamination are ones havring a solubility parameter value lower than the HLB value of the nonionic surfactant of the powdered detergent to be packed. Particularly preferred polymers satisfying these conditions are polyethylene and polypropylene. When the solubility parameter value of the polymer is equal to or higher than the HLB value of the nonionic surfactant or when it 0 exceeds 11.5, the powder detergent inclines to firmly adhere to the wall of the container.

The lamination can be conducted by any conventional process. It is preferred, however, to 0 apply the polymer to the surface of a paper having a basis weight of 400 to 700 g/m 2 to form a polymer film *0 having a thickness of 5 to 40 2, preferably 10 to r°0 i. The shape of the container is preferably one having only little bonded parts.

S" [Examples] The present invention will now be described in more detail by referring to the following Examples, though the present invention is not limited to them.

22 Example 1 Powder detergent compositions each having a formulation which will be described in Table 1 were examined for exudation resistance, fluidity and caking resistance. The results were given in Table 1.

The compositions were each prepared as follows: That is, raw materials for a powder detergent were fed into a continuous kneader (mfd. by Irie Shokai, Bench Kneader PNV-1). A liquid nonionic surfactant and polyethylene glycol were successively added into the kneader gradually, while maintaining the contents at 40"C. Thus, a dense homogeneous mixture was obtained.

e S (Evaluation methods) 1. exudation test An open box having a length of 10.2 cm, a width a of 6.2 cm and a height of 4 cm was made of a coated board (640 g/m 2 and fastened in the corners with a 0" stapler. 100 g of a sample was put in this box and an acrylic resin plate (35 g) and a lead plate (250 g) ,0 (total weight: 265 g) were placed thereon. The Ce 0 S* *resulting box was allowed to .tand in a thermohygrostatic chamber at 30*C and 80% RH for 7 days. Thereafter, the extent of exudation was evaluated based on the soak into the coated board 23 according to the following criteria: A no exudate was observed on the inner wall of the box, B the inner wall of the box was slightly wet, C the whole inner wall of the box was wet, D a part of the outer wall of the box was also wet, and E at least 1/3 of the outer wall of the box a. "a was wet.

2. fluidity test The fluidity of a sample was determined according 90** o 0 to "Flow Rate" of "Flow Rate of Metal Powders" described in ASTM: B213-48 by using a stand and a funnel specified in JIS k 3362 "Testing Methods for Synthetic Detergent".

3. caking test An open box having a length of 10.2 cm, a width of 6.2 cm and a height of 4 cm was made of a filter paper (Toyo filter paper No. 2) and fastened in the corners with a stapler.

*4 50 g of a sample was put in the above box and an acrylic resin plate (15 g) and a lead plate or an iron plate (250 g) (total weight: 265 g) were placed thereon.

24 The resulting box was allowed to stand in a thermohygrostatic chamber at 30 0 C and 80% for 7 days to evaluate the caking resistance.

judgement: The caking resistance was judged by determining the degree of passing according to the following method: degree of passing The sample after the above test was gently poured on a metal net or sieve (mesh 5 mm x 5 mm) to determine the weight of the powder passing through the net or sieve, from which the degree of passing was calculated according to the following equation: *69* degree of passing weight(g) of passing powder x 100 weight(g) of the whole sample

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0- *5 C C

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0 Be **W e 0 *o *e 6 o Table 1 Formulation by wt.) Invention Product Comparative Product 1 2 3 4 5 6 7 8 9 Component polyoxyethylene dodecyl ether* 1 25 28 15 15 [EO F(average number of the ethylene oxide molecule added) m.p. 15 0 C, HLB 10.14] synthetic primary alcohol 25 35 ethoxylate* (C 12 1 4 EO m.p. 22 0 C, HLB 11.28) secondary alcohol ethoxylate* 1

(C

12 1 4 EO p=7, m.p. -3 0

C,

HLB 10.28) coconut oil diethanolamide 2 Component zeolite 4A 45 50 50 35 50 10 18 6L (mean particle diameter: 3pm) Component Tokusil NR*2 10 5 10 3 Nipsil E 20PA4 3 TXISOSIL 38" 4 FLORITE RN* 5 FLORITE R* 7 Component sodium carbonate 20 18 10 23 22 35 33 19 (mean particle diameter: 290pm) sodium silicate No. 2 4 13 (mean particle diameter: 160pm) sodium sulfate 8 polyethylene glycol (MW 13000) _2 1 2 3 2 2 3 2 Results exudation resistance A B A B A B A B A B A B A B B A B of fludity (sec) 8.0 8.1 8.2 8.3 8.0 8.1 8.0 8.0 8.8 evalua- caking resistance 100 100 100 100 100 100 100 58 67 tion (degree of passing Note) *1 The contents of alkyl ethers of adducts of 3 or fewer ethylene oxide molecules are 21.6, 14.3 and 0% by weight respectively in the order of line.

*2 mean particle diameter 150 Vm, pore volume 3.09 cm 3 /g *3 mean particle diameter 2.0 Vm, pore volu-ue 2.26 cm 3 /g *4 mean particle diameter 20 Vm, Spore volume 2.88 em 3 /g *5 mean particle diameter 27 pm, pore volume 4.50 cm 3 /g moo* *6 mean particle diameter 25 pm, 6pore volume 4.90 cm 3 /g 27 Example 2 polyoxyethylene dodecyl ether 20% by wt.

coconut oil diethanolamide 3 tallow soap 2 zeolite A (mean particle 40 diameter: 5 pm) Tokusil NR (Trade Name) 8 sodium carbonate (mean 10 particle diameter: 290 pm) sodium silicate No. 2 5 Glauber's salt 4.7 polyethylene glycol (MW 6000) 2 carboxymethylcellulose 2 polysodium acrylate (MW 8000) 2 enzyme 0.5 perfume 0.3 fluorescent dye 0.5 S S Among above-described components, powdery raw materials [tallow soap and zeolite A (of an amount *69 corresponding to 35% by Tokusil NR, sodium e* S* carbonate, sodium silicate No. 2, carboxymethylcellulose and polysodium acrylate] were fed into an agitation tumbling granulator (Ledegue mixer).

Polyoxyethylene dodecyl ether (the average number of 28 the ethylene oxide molecules added: 8, the content of alkyl ethers of adducts of 3 or fewer ethylene oxide molecules: 21.6% by wt., 15°C, HLB: 10.14) and coconut oil diethanolamide were gradually fed thereinto, followed by the addition of molten polyethylene glycol. Thus, a powder detergent base having a mean particle diameter of 412 pm was obtained. An enzyme, a perfume and a small amount (corresponding to 5% by wt.) of zeolite A were added to the base, followed by mixing. Thus, a final detergent product (Invention Product 10) having the above formulation and a bulk density of 0.7 g/ml was obtained.

The product was examined in a similar manner to that of Example 1. The exudation resistance was A to B, the fluidity was 8.1 seconds and the caking resistance was 100%.

Example 3 3 by weight of tallow soap, zeolite 4A in an S" amount of (a number specified in Table 3 minus 5) by weight, an oil-absorptive carrier having properties as specified in Table 2 (wherein the pH of 5% dispersion was determined according to JIS K 6220) in an amount as specified in Table 3, the balance of sodium carbonate, 3% by weight of sodium polyacrylate and 29 by weight of a fluorescent dye were placed in a batch kneader (Bench Kneader PNV-1 of Irie Shokai). A liquid nonionic surfactant was gradually introduced thereinto and then 2% by weight of molten polyethylene glycol having an average molecular weight of 12000 was added thereto to obtain a powder, detergent base having an average particle diameter of 385 rim.

Further 0.5% by weight of an enzyme, 0.3% by weight of a perfume and 5% by weight of zeolite 4A were added thereto and mixed together to obtain a final detergent 8.

product having a composition as specified in Table 3.

Exudation resistance, fluidity and caking resistance were examined in a similar manner to that of Example 1. Solubility change of the detergent upon storage was tested by the following methods.

The results were given in Table 3.

(Evaluation method) 4a a Test of solubility change upon storage: *E The powder detergent was placed in a Petri dish a a and left to stand at 30 0 C and 70% RH for 3 days. After then, 0.83 g of the detergent was taken as the sample, which was added to 1 a of city water at 10 0 C and the solution was stirred with a magnetic stirrer for min and filtered through a 200-mesh metal gauze.

After drying, the filtration residue rate was 30 determined.

Table 2 .4

B,

*4 40*0 4 4 0 a~ 4 4 4 ~e SO a, OS 0 0e 0 *0 I 00 a Big 0

B

04£.

Og 0.

4 4 pH of 5% Amount of Si0 2 Kind dispersion absorbed content oil (mi/lO0g) TOKUSIL AL-10 9.2 255 94 (Tokuyama Soda Co., Ltd.) NISLNAO 10.2 245 93 (Nippon Silica Ind.) TIXOLEX 250 9.8 235 72 (Kofran Chemical) CARPLEX 01000~ 10.4 230 93 (Shionogi Pharmacy) SIPERNAT D 100 10.3 240 98 (Degussa AG) TOKUSIL NRO 5.8 280 94 (Tokuyama Soda Co., Ltd.) FLORITE RNO 8.1 380 61 (Tokuyama Soda Co., Ltd.) TIXOSIL 38's 6.5 280 (Kof ran Chemical) 31 000 S 0* 00 a.

''OS

0

O

*0 S a 0 o *e *r S 5O 0 .J 05 3 4 1953008 *0( OOGS~ SO *5 00 5 0 00, ~O e 0. 0 8 O .5 f* Table 3 Invention Product Comparative Composition Product 11 12 13 14 15 16 17 18 19 20 21 polyoxyethylene dodecyl ether 24 24 24 24 24 24 24 24 15 (EOp=8, m.p. 15*C, HLB 10.14) primary synthetic alcohol ethoxylate (Czi.

14 EO=10, m.p. 22"C, HLB 11.28) Component (a) Component Zeolite 4A (average particle 30 30 30 30 30 30 30 30 45 55 diameter: 3 An) TOKUSIL AL-10 10 5 3 Component NIPSIL NAO 10.5 TIXOLEX 25* 10.5 CARPLEX #100 11i SIPERNAT D10* 10.5 TOKUSIL NR* FLORITE RN* TIXOSIL 380 10.5 exudation resistance A-B A-B A-B A-B A-B A-B A-B A-B A-B A-B B Evaluation results fluidity (sec) 8.0 8.1 8.0 8.0 8.0 8.1 8.1 8.1 8.2 8.1 caking resistance 100 100 100 100 100 100 100 100 100 100 [degree of passing solubility change upon storage 0.6 0.7 0.7 0.6 0.5 3.8 4.5 4.7 0.8 0.9 1.2 [filtration residue (M)1 EOF In the table represents average molar number of ethylene oxide added.

A Example 4 3 by weight of tallow soap, zeolite A in an amount of (a number specified in Table 5 nimus 5) by weight, an oil-absorptive carrier having properties as specified in Table 4 (wherein the oil-absorptive capacity was determined according to JIS K 6220) in an amount as specified in Table 5, the balance of sodium carbonate, 3% by weight of sodium polyacrylate and by weight of a fluorescent dye were placed in a batch kneader (Bench Kneader PNV-1 of Irie Shokai). A liquid nonionic surfactant in an amount as specified ein Table 5 was gradually introduced thereinto and then

*S

2% by weight of molten polyethylene glycol having an average molecular weight of 6000 was added thereto.

Further 0.5% by weight of an enzyme, 0.3% by weight of a perfume, 5% by weight of zeolite A and 2% by weight of water were added thereto and mixed together to obtain a final detergent product, having 11 composition as specified in Table Exudation resistance, fluidity, caking resistance and change in solubility with time of the detergent 0 ,.00 product were examined in a similar manner to that of 0 0* Example 3.

The results were given in Table The results were given in Table 33 i.

0* 0 Ce 0e0 BC S 0 C. 0* 0 SC 0o S 0 00 S. L *550 Table 4 Oil- Amount Si0z absorptive pH of 5% dissolved Kind content capacity dispersion in 2% (ml/100 g) NaOH aq.

soln.(g) PERLITE® 72.7 165 7.8 0.01

(DICALITE,

PERLITE 4159, DICALITE ORIENT, Co., Ltd.) Na-Mordenite® 87.5 110 10.7 0.12 (HSZ-640NAA, Tosoh Corp.) TOKUSIL NR® 94 280 5.8 2.35 (Tokuyama Soda Co., Ltd.) FLORITE RN® 61 380 8.1 2.18 (Tokuyama Soda Co., Ltd.) The quantity of the oil-absorptive carrier dissolved in a 2% aqueous NaOH solution was determined by dispersing 10 g of the oil-absorptive carrier in 100 ml of a 2% aqueous NaOH solution, stirring the dispersion for 16 h while the temperature was maintained at 25°C and dertermining SiO 2 in the filtrate by colorimetric determination [as for the colorimetric determination, refer to Yukagaku, Vol.

25, p. 156 (1976)]. Namely, the quantity of the oil-absorptive carrier dissolved in the aqueous NaOH solution calculated from the SiO 2 content of the oilabsorptive carrier previously determined by elementary analysis was calculated.

34 0 00 0.0

C

00 0 0 0 0 0 *0 0 0 Table Invention Product Comparative Composition _Product 22 23 24 25 26 27 28 Component (a) polyoxyethylene synthetic alcohol

(C

12 to C 14 ether 15"C, EOp=7, HLB 9.8) polyoxyethylene dodecyl ether 15*C, EO=8, HLB 10.14) 24 Component Zeolite A 27 27 27 27 45 45 PERLITE* 20 15 3 Component (c) Na-Mordenite 16 22 TOKUSIL NR* FLORITE RNO 7 exudation resistance A-B A-B A-B A-B A-B A-B B Evaluation results fluidity (sec) 8.0 8.1 8.2 8.1 8.2 8.1 9.1 caking resistance 100 100 100 100 100 100 72 [degree of passing 0.3 solubility change upon storage 0.2 0.1 3.4 3.5 0.2 0.2 [filtration residue EOp in the table represents average molar number of ethylene oxide added.

Example Synthesis of amorphous sluminosilicate: 700 g of an aqueous sodium silicate solution (Na 2 0: 2.71% by weight, SiO 2 8.29% by weight and Si02/Na2O molar ratio: 3.15) was heated to 60 0 C and 1010 g of an aqueous sodium aluminate solution (Na 9

O:

1.63% by weight, Al 2 0 3 2.26% by weight and Na 2 0/Al 2 0 3 molar ratio: 1.18) was added to the solution under stirring at 1500 rpm. After the completion of the addition, the solution was heat-treated at that temperature for 15 min and the resulting wet cake was dried at 110 0 C and pulverized to obtain 100 g of fine powder of the aluminosilicate which was found to be amorphous by X-ray crystallography. The composition 9 of the resulting amorphous aluminosilicate was: Na 2 0:Si0 2 :Al 2 0 3 29.4:44.5:26.1. The resulting amorphous aluminosilicate had an ion-exchange capacity of 121 CaCO 3 mg/g, an oil-absorptive capacity of 225 ml/100 g, and a solubility in a 2% aqueous NaOH solution of 0.01 g, and the pH of a 5% dispersion thereof was 11.2.

Preparation of detergent: A detergent was prepared by using the amorphous aluminosilicate as will be described below.

3 by weight of tallow soap, zrolite A in an 36 amount of a number specified in Table 6 nimus 5) by weight, an oil-absorptive carrier (amorphous aluminosilicate) in an amount as specified in Table 6, the balance of sodium carbonate, 1% by weight of No. 2 sodium silicate, 2% by weight of sodium polyacrylate and 0.5% by weight of a fluorescent dye were placed in a batch kneader (Bench Kneader PNV-1 of Irie Shokai).

A liquid nonionic surfactant in an amount as specified in Table 6 was slowly introduced thereinto and then 2% by weight of molten polyethylene glycol was added thereto. Further 0.5% by weight of an enzyme. 0.5% by weight of a perfume, 5% by weight of zeolite A and 2% by weight of water were added thereto and mixed together to obtain a final detergent product having a composition as specified in Table 6.

of 0 Exudation resistance, fluidity, caking resistance and change in solubility with time of the detergent product were examined in a similar manner to that of Example 3.

The results were given in Table 6.

S

S

eeeo@ 37 0 0 a 0 a 0 000 a a a. U a *a *a* a a a 0 0 0 a a 0 0 0 *0 0 0 a 0 00 0 a a a a 0 0 0 a0 U 0 Table 6 Invention Product' Comparative f Invention Invention Product Product 29 30 31 32 33 34 polyoxyethylene synthetic alcohol (CI 2 to C 14 ether 25 20 15 15 20 Composition 15-C, E0TF-7. HLB 9.8) (w.)zeolite A 20 25 s0 55 30 amorphous aluminosilicate 20 10 6 3 amorphous silica (Tokusil NR mfd. by Tokuyana Soda and 8 having oil-absorptive capacity of 280 m1/100 g and solubility in 2% aqueous NaOH solution of 2.35 g) amorphous silica (Florite RN ufd. by Tokuyama Soda and having oil-absorptive capacity of 280 m1/100 g and In 2% aqueous NaOH solution of 2.18 g) exudation resistance A-B A-B A-B B A-Bj B Evaluation results fluidity (see) 8.2 8.0 8.3 9.2 8.2 8.2 caking resistance [degree of passing 100 100 100 63 100 100 solubility change upon storage 0.3 0.2 0.3 0.2 5.0 3.6 [filtration residue II_1 Note) EOP in the Table represents the average solar number of ethylene oxide added.

Example 6 Synthesis of amorphous aluminosilicate: 100 parts by weight of No. 3 water glass (prepared-by adding 150 parts by weight of deionized water to 100 parts by weight of commercially available No. 3 water glass) was added dropwise to 800 parts by weight of an aqueous sodium aluminate solution (prepared by adding 2000 parts by weight of deionized water to 100 parts by weight of an aqueous sodiam aluminate solution having Na20:Al 2 0 3

:H

2 0 weight ratio of 20.3:28.2:51.5) over 20 min. After then, the reaction 0* o. was conducted for 10 min, and the reaction mixture was heated at 100*C and aged for 10 min. The resulting cake was taken by filtration and it was washed until the pH of the filtrate reached 12.0, dried at 100°C for 11 h and finely pulverized with a pulverizer to obtain an amorphous aluminosilicate. The composition of the resulting amorphous aluminosilicate was: Na 2 0:SiO2:Al 2 0 3 19.59:47.39:33.03. The resulting amorphous aluminosilicate had an ion-exchange capacity 00 of 115 CaCO 3 mg/g and an oil-absorptive capacity of 250 ml/100 g, and the pH of a 5% dispersion thereof was 11.2 (solubility in a 2% NaOH solution was 0.02 g).

A detergent having the following composition was prepared by using the amorphous aluminosilicate 39 S SO s 0 O o0 e 6 0 AS 0 0

S

5 0 n' S synthesized as described above.

Detergent composition: polyoxyethylene dodecyl ether (average molar number of ethylene oxide added: 8, melting point: HLB: 10.14) coconut oil fatty acid diethanolamide Stallow soap zeolite A (average particle diameter: 4 Am) amorphous aluminosilicate synthesized as above sodium carbonate (average particle diameter: 290 Am) No. 2 sodium silicate Glauber's salt polyethylene glycol (MW: 6000) carboxymethylcellulose sodium polyacrylate (MW: 8000) enzyme perfume fluorescent dye 20% by wt.

3 2 8 4.7 2 2 2 0.3 The above-described powder starting materials [tallow soap, zeolite A (in an amount corresponding to 40 by weight), amorphous aluminosilicate, sodium carbonate (average particle diameter: 290 pm), No. 2 sodium silicate, Glauber's salt, carboxymethylcellulose, sodium polyacrylate and fluororescent dye] were placed in a batch kneader (Bench Kneader PNV-1 mfd. by Irie Shokai). Polyoxyethylene dodecyl ether and coconut oil fatty acid diethanolamide were gradually introduced thereinto and then molten polyethylene glycol was added thereto to obtain a powder detergent base having an average particle diameter of 402 pm. The enzyme, perfume and a small

S

amount (corresponding to 15% by weight) of zeolite A were added thereto and mixed together to obtain a final detergent product (Invention Product 35) having a composition described above and a bulk density of 0.75 g/mi.

The detergent was evaluated in the same manner as that of Example 3 to find that the exudation S@00 resistance was A-B, the fluidity was 8.0 sec, the caking resistance was 100% and the change in solubility with time was 0.2%.

Example 7 3% by weight of tallow soap, zeolite 4A in an amount of (a number specified in Table 7 nimus 5) by weight, an oil-absorptive carrier in an amount as 41 specified in Table 7, the balance of sodium carbonate, 3% by weight of sodium polyacrylate and 0.5% by weight of a fluorescent dye were placed In a batch kneader (Bench Kneader PNV-1 of Irie Shokai). A liquid nonionic surfactant in an amount as specified in Table 7 was gradually introduced thereinto and then 2% by weight of molten polyethylene glycol was added thereto to obtain a powder detergent base having an average particle diameter of 385 pm. 0.5% by weight of an onzyme, 0.3% by weight of a perfume and 5% by weight of zeolite 4A were added thereto and mixed together to obtain a powder nonionic detergent having a bulk density of 0.7 g/ml.

1500 g of the powder nonionic detergent see* prepared as described above was placed in a paper container (14.8 cm width x 8.7 cm length x 16 cm height) of which inner walls were laminated with a polymer specified in Table 7 to form a film having a *.00 thickness of about 25 im. An acrylic resin plate g) and a lead plate (250 g) (total weight: 265 g) were S placed thereon and they were left to stand in a thermohygrostatic chamber at 30 0 C and 80% RH for e days.

After the test, the detergent was carefully removed from the container and the extent of adhesion 42 of the powder, nonionic detergent to the inner wall of the container was classified into the following groups. The results were given in Table 7.

o: no adhesion of the powder, detergent was obrerved at all, A: slight adhesion of the powder detergent was observed, and x: the adhesion of the powder detergent to the whole surface was observed.

Table 7 0. s .0CC OaO a.

90 a *090o a 0 ar 0 Composition Invention Product 36 37 Component polyoxyethylene dodecyl ether 20 (average molar number of ethylene oxide added: 8, 15°C, HLB: 10.14) Component Zeolite 4A (average particle 30 diameter: 3 pm) Component TOKUSIL AL-1® 10 10.5 (Tokuyama Soda Co., Ltd.) (oil-absorptive capacity: 255 ml/100 g, SiO content: 94%) Container laminating polymer PE* PP' (lamination of paper having basis weight of 640 g/m 2 solubility parameter 8.56 8.02 determined by Fedors method (cal/cm 3 Results adhesion to the wall surface o o *PE: polyethylene PP: polypropylene 43 43a Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer group of integers but not the exclusion of any other integer or group of integers.

o 00 4 940318,p:'topeAdab,90092-Ve,43

Claims (9)

1. A nonionic powder detergent composition comprising: 12 to 35 wt.% of a nonionic surfactant having a melting point of 40 0 C or below; 10 to 60 wt.% of a crystalline aluminosilicate; and 5 to 20 wt.% of an oil-absorbing carrier selected from amorphous silica and an amorphous aluminosilicate containing at least 30 wt.% of silicon in terms of Si0 2 and having an oil-absorbing capacity of at least 80 ml/100 g, said carrier giving a dispersion with a pH value of at least 9 or being soluble in a 2% aqueous NaOH solution in an amount of 0.5 g or less.

2. The nonionic powder detergent composition according to Claim 1, which further comprises 5 to 35% by weight of sodium carbonate.

3. The nonionic powder detergent composition according to Claim 1, wherein the nonionic surfactant is selected from the group of polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyethylene glycol fatty acid esters, S 25 polyoxyethylene/polyoxypropylene alkyl ethers, polyoxyethylene castor oil, polyoxyethylene-hardened castor oil, polyoxyethylene alkylamines, glycerol fatty acid esters, higher fatty acid alkanolamides, alkyl glucosides and alkyl amine oxides. 0 sate so

4. The nonionic powder detergent composition according to 4 Claim 1, wherein the amorphous aluminosilicate is one represented by the following general formula *0 00 35 a(M 2 0).71 2 0 3 .b(SiO 2 ).c(H 2 0) (1) a 0 940318p:\operdab,90092spe,44 wherein M represents an alkali metal atom and a, b and c each represent the molar number of the respective components which are as follows: 0.7 s a s 2,0, 0.8 s b 4 and c is a positive number.

The nonionic powder detergent composition according to Claim 1, wherein the nonionic surfactant is a polyoxyethylene alkyl ether having 10 to 20 carbon atoms and an average molar number of added ethylene oxide of 5 to

6. The nonionic powder detergent composition according to Claim 1, which further comprises 1 to 5% by weight of a polyethylene glycol having a molecular weight of 4000 to

20000.

7. The nonionic powder detergent composition according to Claim 1, which has a sodium silicate content of 5% by weight or below.

8. The nonionic powder detergent composition according to Claim 1, which is substantially free from any phosphate builder. 0S

9. The nonionic powder detergent composition according to Claim 1, which has a bulk density of 0.6 to 1.2 g/cm 3 and an average particles diameter of 200 to 1000 p. A process for producing a nonionic powder detergent 30 composition according to claim 1, which comprises the steps of mixing a crystalline aluminosilicate with an oil- absorbing carrier while adding to or spraying onto the mixture a nonionic surfactant having a melting point of o• or below gradually to obtain a homogeneous mixture of 35 and and then adding to the mixture further crystalline aluminosilicate to obtain a powder detergent composition. 940318,p operdab,99Zspe,45 -46- 11. A nonionic powder detergent product comprising a nonionic powder detergent composition according to Claim 1, packed into a container made of converted paper laminated with a polymer selected from polyethylene or polypropylene. 12. The composition as claimed in Claim 1, which comprises 12 to 35 wt.% of 20 to 60 wt.% of and 5 to 20 wt.% of an oil-absorbing carrier containing at least 40 wt.% of silicon in terms of SiO 2 and having an oil-absorbing capacity of at least 150 ml/100 g, said carrier giving a dispersion with a pH value of at least 9. 13. The composition as claimed in Claim 1, which comprises 12 to 35 wt.% of 20 to 60 wt.% of and 5 to 30 wt.% of an oil-absorbing carrier containing at least 40 wt.% of silicon in terms of SiO 2 and having an oil-absorbing capacity of at least 80 ml/100 g, said carrier being soluble in a 2% NaOH solution in an amount of 0.5 g or less. 14. The composition as claimed in Claim 1, which comprises 12 to 35 wt.% of 20 to 60 wt.% of and 5 to 30 wt.% I of a non-crystalline aluminosilicate having an oil- absorbing capacity of at least 200 ml/100 g, said carrier 25 being soluble in a 2% aqueous NaOH solution in an amount of 0.05 g or less. 00 A powdered nonionic detergent composition and a process for the production the production thereof, substantially as 30 hereinbefore described with reference to the Examples. 00* g e o0 DATED this 18th day of March, 1994 35 Kao Corporation By Its Patent Attorneys DAVIES COLLISON CAVE 940318,poper\b,90092.spe,46 4 [Abstract] A powdered nonionic detergent composition which is free from the exudation of a nonionic surfactant liquid, which cause in a powdered nonionic detergent composition comprising a liquid nonionic surfactant, and therefore excellent in fluidity and caking resistance was provided. .A powdered nonionic detergent composition which is free from the exudation of a nonionic surfactant U liquid, and therefore excellent in fluidity and caking -resistance, and also a solubility thereof is not Sdeteriorated was provided. The construction of the present invention is, a powdered nonionic detergent composition comprising (a) a nonionic surfactant having a melting point of or below and an HLB value of 9.0 to 16.0, a i OV eal" crystalline aluminosilicate, at least one oil-absorptive carrier selected from the group consisting of an oil-absorptive amorphous silica, an .o oil-absorptive amorphous aluminosilicate, an oil-absorptive calcium silicate and a clayey substance at a specific ratio.