KR100267274B1 - Detergent composition and its manufacturing method - Google Patents

Abstract

PURPOSE: A highly condensed non-ionic granular detergent composition is provided to achieve excellent caking resistance, powder characteristics, washability and solubility without causing tears of the non-ionic surfactant at a room temperature. CONSTITUTION: The composition for a highly condensed non-ionic granular detergent having the density of 0.75g per square centimeters is composed of non-ionic surfactant of 1.-40 wt.%, anion surfactant of 5-20 wt.%, sodium carbonate of 5-35 wt.%, and X-type zeolite of 10-40 wt.%, consisting of silicon and aluminum at a ratio of 1:2 or below, has calcium ion exchange capacity of higher than 130mg CaO per gram and oil-retaining capacity of higher than 70g per 100g. The non-ionic surfactant is liquid or paste below 40 deg.C, and it has HLB value of 5-15, being selected from a group of polyoxyethylene alkylether, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester and fatty acid alkanolamide.

Description

Highly concentrated nonionic granular detergent composition and its preparation method

The present invention relates to a detergent composition comprising a nonionic surfactant as a main cleaning base and containing an anionic surfactant. Even when stored for a long time, the liquid nonionic surfactant is not leaked at room temperature, and the flowability and resistance of the powder are improved. The present invention relates to a highly concentrated nonionic granular detergent composition excellent in anti-caking properties and a method for producing the same.

Nonionic surfactants are important as cleaning surfactants because they have not only good water resistance but also good cleaning and dispersing properties, and very good biodegradability. However, nonionic surfactants usually used in detergents are usually liquid at room temperature. Therefore, when a large amount of the nonionic surfactant is applied to the powder detergent, the nonionic surfactant flows out over the seal and adheres to the inner wall of the product packaging material, resulting in extremely low fluidity of the product itself and caking to the final product. There was a disadvantage that the detergent is solidified.

Many studies have been attempted in the art to compensate for the drawbacks of detergents based on such nonionic surfactants.

Representative examples include a method of using a specific additive to prevent leakage of the nonionic surfactant, and a method of supporting the nonionic surfactant on a new oil absorption carrier having high oil absorption capacity.

Methods of using such specific additives are disclosed in Japanese Patent Laid-Open Nos. 7-268399, 7-268395, and 7-268400. This technique mainly utilizes the gelling properties of nonionic surfactants. The gelling agent is incorporated to induce gelation of nonionic surfactants to prevent leakage and improve powder flowability. However, this method requires a separate process and facility according to the addition of the gelling agent, and there are various limitations in the selection of the gelling agent.

In addition, as a method of supporting a nonionic surfactant on an oil absorption carrier having a high oil absorption capacity, a method of supporting a nonionic surfactant in amorphous aluminosilicate is disclosed in Japanese Patent Laid-Open No. 4-363400. . This technique is required to supplement the cation exchange capacity because the nonionic surfactant is supported on the amorphous aluminosilicate having a low cation exchange capacity. In addition, when a large amount of amorphous aluminosilicate-based builders are used, there is a high possibility that a white aluminosilicate precipitate remains on the bottom of the washing machine outlet and the washed cloth.

On the other hand, as a manufacturing method of the granular detergent composition containing a nonionic surfactant, the manufacturing method which mixes a nonionic surfactant with a detergent slurry, and spray-drys and obtains a granular detergent composition is proposed. However, this method has a problem in that the actual content of the nonionic surfactant is limited because the nonionic surfactant can be decomposed by the hot air during the drying process. In order to solve this problem, Japanese Patent Laid-Open No. 62-263299 proposes a manufacturing method of uniformly mixing a nonionic surfactant and a builder to form a solid detergent, and then crushing it to obtain a granular detergent composition. In this method, it is difficult to obtain a nonionic granular detergent composition excellent in fluidity, and a large amount of fine powder is produced, which is not preferable.

In addition, Japanese Patent Application Laid-Open No. 5-209200 discloses a step of mixing detergent raw materials such as builders, spray dried particles, porous oil absorption carriers, nonionic surfactants, and the like to form a detergent raw material adhesion layer between the wall surface and the stirring blade. A method of obtaining nonionic detergent particles comprising granulation using a specific granulator and coating with fine powder is described.

This method reduces the size of the cavity in which the nonionic surfactant is absorbed in the process of consolidation with a specific granulator. Also, since a large amount of the nonionic surfactant is added only once, the time for absorbing or supporting the oil is reduced. There is a problem that non-ionic surfactants and the like are locally localized because the oil absorption or the support of the relatively long conventional builder or the porous oil absorption carrier is not uniform. In addition, mutual adhesion is triggered by highly viscous detergent raw materials such as anionic surfactants in spray dried particles, resulting in detergent particles of unnecessary size, and coarse particles remain intact even when coated with fine powder and large amounts of fine powder are generated. Because of this, it is difficult to obtain a detergent granule having excellent fluidity.

As a conventional method for solving the conventional problems as described above, Patent Application Publication No. 96-15153 (Application Date: 1994.06.27) by the present applicant proposes a granular high-density nonionic detergent composition and a method of manufacturing the same The detergent composition is a crystalline aluminosilicate, which has a high calcium ion exchange capacity but a very low magnesium ion exchange ability (type A zeolite (Na ₂ O · A1 ₂ O ₃ · 2SiO ₂ · 4.5H ₂ O) or the above-mentioned low). conventional detergent for X-type zeolite to compensate for magnesium ion exchange capacity and uses a synthetic zeolite as _{(Na 2 O · A1 2 O} 3 · 2.4~3.0SiO 2 · 4.5H 2 O). However, the conventional X-type zeolite described above has excellent ion exchange ability as the Si / Al ratio approaches 1). In addition, in order to increase the content of the liquid nonionic surfactant at room temperature in order to improve the cleaning function and the concentration characteristics of the detergent composition, it is necessary to use a carrier having a high oil absorption ability, such as amorphous aluminosilicate or amorphous silica. Such porous oil-absorbing carriers have an extremely low ion exchange capacity, and when contained in a large amount, the cleaning ability of the detergent composition may be lowered, and the solubility may be reduced, the hygroscopicity may be increased, and the problem of remaining in the laundry as white powder after washing may be caused.

Therefore, the present invention is to solve the above-mentioned conventional problems, the first object of the present invention is a non-ionic surfactant that is liquid at room temperature as the main cleaning base, it is possible to high concentration and accordingly excellent cleaning power, It is to provide a highly concentrated non-ionic granular detergent composition having no leaking phenomenon of the ionic surfactant and also having excellent caking resistance and storage property and excellent solubility.

The second object of the present invention is to improve the process efficiency by continuously preparing a highly concentrated nonionic granular detergent composition according to the first object of the present invention as described above, and to support a large amount of nonionic surfactants. Yet it is to provide a method for producing the composition described above without the problem of coarsening of detergent particles.

According to a preferred aspect of the present invention for achieving the first object of the present invention, 10 to 30 parts by weight of a nonionic surfactant as a main cleaning base; 10-40 parts by weight of crystalline aluminosilicate (type X zeolite: MAX (Maximum aluminum X) type zeolite) having a silicon-to-aluminum ratio of 1.2 or less, calcium ion exchange capacity of 130 mg CaO / g or more and oil absorption ability of 70 g / 100 g or more ; 5-20 parts by weight of anionic surfactant; And it is provided a highly concentrated nonionic granular detergent composition composed of 5 to 35 parts by weight sodium carbonate.

In addition, according to a preferred aspect of the present invention for achieving the second object of the present invention, a conventional detergent slurry composed of a mixture of anionic surfactant as a main cleaning base and a cleaning aid in a first high speed mixing / granulator. After mixing the inorganic builders in a ratio of 90:10 to 10:90 to the dry powder spray-dried, and then granulating while impregnating 1 to 20 parts by weight of the nonionic surfactant to 80 to 99 parts by weight of the mixture described above Basic powder preparation step as granulation step; And mixing and grinding 20-50 parts by weight of the above-mentioned base powder and 30-60 parts by weight of the inorganic builder in the second high-speed mixing / granulator, and then impregnating 1-20 parts by weight of the nonionic surfactant. It consists of two granulation stages: The inorganic builder described above has a silicon-to-aluminum ratio of 1.2 or less, calcium ion exchange capacity of 130 mg CaO / g or more, oil absorption capacity of 70 g / 100 g or more, type X zeolite, type 4A zeolite, type P zeolite Inorganic, used in at least a second granulation step of the above-mentioned inorganic builders used in the first and second granulation steps, consisting of at least one selected from the group consisting of sodium carbonate, and amorphous aluminosilicates The builder must include the above-described X-type zeolite, and includes 10 to 40 parts by weight of the X-type zeolite and 10 to 30 parts by weight of the nonionic surfactant in the whole composition. Provided is a method of preparing a highly concentrated nonionic granular detergent composition.

Hereinafter, the present invention will be described in more detail.

The nonionic surfactant as the main cleaning base in the detergent composition according to the present invention is liquid or paste at 40 ° C. or lower and has an HLB value of 5 to 15. For example, polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester And sucrose fatty acid ester, polyoxyethylene fatty acid ester, fatty acid alkanolamide, and the like. Of these, ethylene oxide is a linear or branched linear or branched alcohol having 6 to 22 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 12 to 14 carbon atoms, and an average added mole number of ethylene oxide is 3 Most preferable is polyoxyethylene alkyl ether which is -20, Preferably it is 5-15. The content of the nonionic surfactant is 10 to 30 parts by weight, preferably 12 to 25 parts by weight based on the total composition.

Anionic surfactants used in the detergent compositions of the present invention include straight chain alkylbenzenesulfonates (R- (C ₆ H ₆ ) -SO ₃ M: such as R = C _10-18 , M = Na or K); Alkyl or alkenyl sulfates (R-OSO ₃ M: for example R = C _10-18 , M = Na or K); a- _{olefinsulfonates} (a mixture of R— _{CH═CHCH 2} —SO ₃ M and R—CH (OH) —CH ₂ CH ₂ —SO ₃ M: eg _{R═C 10-18} , M = Na or K) ; a-sulfofatty acid ester salts (R-CH (SO ₃ M) -COOCH ₃ , such as R = C _10-18 , M = Na or K); Fatty acid salts (R—CH ₂ —COOM, such as _{R═C 10-18} , M = Na or K); Alkyl or _{alkenylethercarboxylates} (RO (CH ₂ CH ₂ O) ₂ CH ₂ COOM, such as _{R═C 10-18} , M = Na or K); _{Alkanesulfonates} (R—CH ₂ SO ₃ M or R ′ R ″ CH—SO ₃ M, such as _{R═C 10-18} , R ′ + R ″ _{═C 10-18} , M = Na or K); Sulfohobic acid alkyl ester salts (R′-OOCCH ₂ CH (COOR ″) SO ₃ M, such as R ′ + R ″ = C _10-18 , M = Na or K); _{Acylaminoalkanesulfonates} ( _R'CO -NH-R "-SO ₃ M, such as R '+ R" = C _10-18 , M = Na or K), all of which are widely used in conventional detergent compositions These are well known in the art and are obvious to those skilled in the art. The content of the anionic surfactant is 5 to 20 parts by weight, preferably 8 to 15 parts by weight based on the total composition.

As sodium carbonate used for the detergent composition of this invention, heavy sodium carbonate (medium ash) of 1 g / cm <3> or more of apparent density, and hard sodium carbonate (lightening) of 0.8 g / cm <3> or less of apparent density can be used individually or in combination. The content of sodium carbonate is 5 to 35 parts by weight based on the total composition.

X-type zeolite used in the detergent composition of the present invention has a ratio of silicon to aluminum in the composition represented by the general formula Na ₂ O · A 1 ₂ O ₃ · 1.8 to 3.0 SiO ₂ .1.0 to 6.0H ₂ O of 1.2 or less and calcium ion exchange capacity. X-type zeolites with an anhydride content of 130 mg CaO / g or more and an oil absorption capacity of 70 g / 100 g or more on an anhydride basis (unless stated below) are used as a measuring method according to KS M 6558. It contains ˜40 parts by weight. Particularly preferred as such an X-type zeolite is represented by the general formula _{Na 2 O · A1 2 O 3} · 1.8~2.4SiO 2 · an X-type zeolite having a composition shown in 5.0~6.0H ₂ O, 'X-type zeolite used herein The term 'should not be understood to refer to conventional X-type zeolites unless otherwise indicated, but to mean special X-type zeolites as defined above.

For synthesis examples of the X-type zeolites used in the detergent composition of the present invention, see US Pat. No. 4,606,899 for a method for producing a maximum aluminum X-type zeolite having a ratio of silicon to aluminum from meta kaolin of 1.2 or less. Commercial X-type zeolites having a silicon-to-aluminum ratio of 1.2 or less can be obtained in fine powder or powder form (Wesalis: trade name Wssalith XD; manufactured by Degussa AG), and the present invention has a particle size of 1 to 10 µm. It is preferable to use.

On the other hand, in the powder detergent composition of the present invention, in addition to the above components, a cleaning auxiliary additive which is usually combined with a cleaning agent may be blended. For example, 4A or P-type zeolite, nitrile triacetate, ethylenediaminetetraacetate, acryl and / or Water softeners such as maleic acid (co) polymers; Alkaline inorganic salts such as sesquicarbonate and silicate; Neutral inorganic salts such as sulfates; Antifouling agents such as carboxyketylcellulose, carboxymethyl starch, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and the like; Fluorescent dyes; Antioxidants and the like.

Examples of the auxiliary additives washed zeolites, as described above, in the general formula _{Na 2 O · A1 2 O 3} · rSiO 2 · wH 2 O ( wherein, r = 1.8~3.0; w = 1.0~6.0 ) is represented by an average And 4A type and P type zeolites having a particle diameter of 0.1 to 10 µm. The powder, granules or zeolite slurry may be dried to be suitably blended as zeolite dry particles. P-type zeolites have a ratio of silicon to aluminum in the composition of 1.08 to 1.678, among them, calcium ion exchange capacity of 130 mg CaO / 100 g or more, and preferably silicon to aluminum ratio of 1.2 or less. As said P-type zeolite, Wesalith NaP (trade name: Wessalith NaP) of Degussa AG Co., Ltd. is mentioned, 5-30 weight part is suitable when used for this invention.

In addition to the auxiliary additives described above, the detergent composition according to the present invention may be blended with a heat sensitive component that is susceptible to deterioration by heat, and the mixing time is preferably after the second granulation. Examples of the heat sensitive component that can be added include enzymes such as proteases, lipases, cellulases, amylases, bleaches such as sodium percarbonate, sodium perborate monohydrate or bleach, bleach activators, and flavors.

On the other hand, in the manufacturing method of the present invention, the first step is to prepare a basic powder as a first granulation step, for example, the collision mechanism is arranged radially on the horizontal central axis inside the cylindrical drum, 80-99 A mixture of spray-dried detergent particles containing at least one organic and inorganic detergent component and an inorganic builder in a ratio of 90:10 to 10:90 in an axially rotating high speed mixing / granulator. Granulated while impregnated with 1 to 20 parts by weight of the nonionic surfactant described above in parts by weight to prepare a basic powder.

That is, spray drying particles are obtained by spray drying a detergent slurry having a water content of 30 to 60% by dissolving a conventional organic and inorganic detergent component including at least one conventional anionic surfactant in water. The above-mentioned detergent slurry is a conventional thing using an anionic surfactant as a main washing | cleaning agent, and is clear for those skilled in the art. Thereafter, the spray dried detergent particles and the inorganic builder are mixed in a weight ratio of 90:10 to 10:90. 80 to 99 parts by weight of the base powder and 1 to 20 parts by weight of nonionic surfactant based on the base powder are continuously supplied to the high speed mixing / granulator to impregnate the base powder.

Examples of the inorganic builder used in the first granulation step include X-type zeolites having a silicon-to-aluminum ratio of 1.2 or less, calcium ion exchange capacity of 130 mg CaO / g or more, and oil absorption capacity of 70 g / 100 g or more; 4A zeolite; P-type zeolites; Sodium carbonate; Or at least two or more selected from the group consisting of amorphous aluminosilicates are used, preferably at least one other such compound, including sodium carbonate, is selected.

The spray-drying detergent particles described above preferably have a water content of 8 parts by weight or less, but more preferably 5 parts by weight or less in terms of greater absorption of the nonionic surfactant. In order to facilitate the production of particles in the first granulation step, liquid sodium silicate No. 1, No. 2 or No. 3 in the liquid phase may be combined after spray drying. This is to use the difference in viscosity according to the difference in temperature and moisture content, such as sodium silicate, the amount is preferably 4 parts by weight or less based on the base powder. If the amount exceeds 4 parts by weight, the impregnating degree of the nonionic surfactant may be inferior, and a drier such as a fluidized bed drier is required after the basic powder is manufactured. Therefore, it is preferable to add sodium silicate when preparing the detergent slurry.

In addition, when the weight ratio of the spray-drying detergent particles supplied to the first granulation step and the inorganic builder is 90:10 to 10:90, the amount of the nonionic surfactant may be reduced when the inorganic builder is less than 10 parts by weight. On the other hand, if the inorganic builder exceeds 90 parts by weight, it is because it is difficult to include the anionic surfactant and the like of the desired content based on the total composition.

The addition of the nonionic surfactant in the basic powder preparation step is 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on the base powder. If it is less than 1 part by weight, there is a risk of deterioration of cleaning ability or concentration of the final product, and may be accompanied by problems such as generation of fine dust in the process, and if it is more than 20 parts by weight, poor fluidity of powder. It is also undesirable because it can lead to

Preferred examples of the high speed mixing / granulating machine that can be used in the first granulation step as the basic powder preparation step include the Ketmix reactor (trade name: Kettemix reator; manufactured by Ballestra Co.), and the horizontal center of the cylindrical drum. A powerful collision mechanism arranged radially on the shaft is built in, and it can be granulated while impregnating detergent liquid raw materials such as nonionic surfactants while rotating at high speed in the axial direction.

In the second granulation step in the production method of the present invention, the highly concentrated nonionics are supplied by supplying the basic powder obtained in the first granulation step together with the inorganic builders in the high loss mixing / granulator, and mixing and impregnating the nonionic surfactant. Prepare granular powder detergent. In this case, the nonionic surfactant is preferably fed in a spray manner so as to prevent excessive particle formation. In addition, some of the zeolites as inorganic builders are preferably added as surface coatings at the end of impregnation of the nonionic surfactant, and some amorphous aluminosilicates may be added. In such a case, the obtained highly concentrated nonionic granular powder detergent has better fluidity and caking resistance.

Amorphous aluminosilicate has a porosity of 10 to 600 cm3 / 100 g (measured by mercury porosimetry), specific surface area of 10 to 700 m2 / g (measured by BET method), oil absorption 100 ml / 100 g (measured according to KS M 6558) It is suitable to have. When mix | blending amorphous aluminosilicate, it is preferable to make the compounding quantity into 3 weight part or less on the basis of a precursor. If it exceeds 3 parts by weight, it is not preferable because problems such as white precipitates may remain on the bottom of the washing machine outlet and the washed cloth.

The average particle diameter of the granular detergent obtained in the second granulation step is preferably controlled within the range of 200-1000 μm, because when the particle size is less than 200 μm, there may be a problem of dust generation and fluidity deterioration. On the other hand, if the thickness exceeds 1000 μm, the solubility may be inferior, resulting in a problem of remaining attached to the object to be cleaned.

As an example of the high speed mixing / granulator which can be preferably used in the second granulation step, a high speed mixer (trade name: High Speed Mixer; manufactured by Fukae Powtec Co.), a Rödige mixer (trade name: Lodige Mixer; Gebrude Lodige Maxhinenbau- GamgH Co., Ltd., Henschel Mixer (trade name: Henschel Mixer; manufactured by Mitsui Miike Machinary Co.), Vertical Granulator (trade name: Vertical Granulator; manufactured by Powrex), Flowshare Mixer (trade name: Plough Share Mixer; Pacific Machinary Co. ) Or a V-type mixer (trade name: V-type Mixer; manufactured by Fuji Paudal Co.).

In addition, the preparation method according to the present invention may also include a step of adding a heat sensitive component as a third step of adding a heat sensitive component after the above-described second granulation step. The addition of the heat sensitive component after the second granulation step is because the temperature conditions during the manufacturing process of the base powder or the granular powder may lead to the deterioration of the efficacy or the denaturation of the heat sensitive component. As an example of the heat sensitive component which can be added, enzymes, such as a protease, a lipase, a cellulase, an amylase, a bleaching agent, a bleach activator, a fragrance, etc., such as sodium percarbonate, sodium perborate 1 or tetrahydrate, etc. are mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples, which are not intended to limit the scope of the present invention but are merely illustrative, and various changes and modifications can be made by those skilled in the art within the scope of the present invention. It should also be understood that this is also included within the scope of the present invention.

[Production example]

Preparation of the Basic Powder

Anionic surfactants of linear alkylbenzenesulfonate and sodium fatty acid; Cleaning aid additives of type 4A zeolite, sodium carbonate, sodium silicate and sodium polyacrylate; And a spray slurry of the detergent slurry containing the other trace components to prepare a spray dried powder. The prepared spray-dried powder was continuously added to the above-mentioned ketmix reactor with any one of type 4A, X, or P type zeolite as an inorganic builder and sodium carbonate, and then polyoxyethylene alkyl ether as a nonionic surfactant was added. Injection was carried out to prepare basic powders A, B and C. The composition of the prepared base powder is shown in Table 1 below.

TABLE 1

EXAMPLES 1-5

A liquid nonionic surfactant was added to the basic powders A, B, or C in the above-described preparation, and an inorganic builder of 4A, X or P-type zeolite, amorphous aluminosilicate and / or sodium carbonate was put in a high speed mixer and mixed at high speed. The impregnated granulation was started by slowly spray mixing the above-mentioned polyoxyethylene alkyl ether. At the end of the impregnation, 4A, X, or P-type zeolites, and / or silica derivatives (amorphous aluminosilicates) were added as a surface coating agent in order to enhance the flowability and the caking resistance of the powder, and mixed at low speed for 1 minute. Subsequently, the granular detergent composition according to the present invention was prepared by blending the fragrance and enzyme which are heat sensitive components, and Examples 1 to 5 were used, and the composition thereof is shown in Table 2 below.

[Comparative Examples 1 to 4]

The granular detergent composition was prepared in substantially the same manner as in Examples 1 to 5, except that zeolite X as defined above was not used as the inorganic builder in any of the first and second granulation steps. It was prepared and Comparative Examples 1 to 4, the composition ratio is shown in Table 2 below.

TABLE 2

As shown in Table 2, the detergent compositions of Examples 1 to 5 according to the present invention showed better results in leakage, flowability, and caking resistance than the detergent compositions of the comparative example, and the cleaning power was also found to be excellent.

In addition, according to the continuous preparation method of the above-described detergent composition according to the present invention, which uses a nonionic surfactant as a main cleaning base and uses a special X-type zeolite as defined above, It contains a large amount and can be highly concentrated, and manufacturing efficiency is high.

[Physical Evaluation Test]

The physical properties and cleaning power of the nonionic powder detergent compositions prepared in Examples and Comparative Examples were evaluated by the following method.

1. Apparent Density (g / cm 3): The apparent density measurement was in accordance with KS M 2709 3.3.

2. Leakage: Using a filter paper (640 g / cm 3), a box of 10 cm in length, 7 cm in width and 4 cm in height was made and 100 g of the prepared sample was put therein, and a load of 300 g was applied thereto. After standing for 7 days in a thermo-hygrostat of% RH, it was determined as follows.

A: There is no leakage inside the box.

B: The inside of the box is slightly damp

C: The whole inside of the box is damp

D: moist to the outside of the box

E: More than 1/3 of the outside of the box is damp.

3. Fluidity (cm3 / sec): Measure the passage time per unit time by measuring the time the powder passes between the mark (40cm) between the top and bottom of the inner diameter of 3.5cm and the length of 60cm glass tube. The flowability of the powder was evaluated. Larger values indicate better fluidity.

4. Caking property (%): 1 kg of the sample was placed in a container made of paper work, and left for 1 week under the condition of 30 ° C. and 70% RH to obtain a portion that failed to pass 4 meshes. The lower the value, the better the caking resistance.

5. Cleaning power (%): After stirring 0.5g / 1 detergent for 1 minute at 25 ° C using a Terg-O-Tometer, artificial contaminant WFK-20D (Pigment / Sebum), AS- 3 pieces of 10 (pigment / oil / milk) and 3 pieces of AS-12 (pigment / oil / milk) are added, washed at 100ppm (as CaCO ₃ ) for 10 minutes, using Minolta color meter CR-200. After measuring the whiteness, the cleaning power was calculated according to the following equation, and the weight of each contaminant was calculated as 15% for AS-10, 50% for AS-12, and 35% for WFK-20D.

6. Cation exchange capacity:

1) Calcium ion exchange capacity: A 300 mg CaO / L aqueous solution was prepared as CaCl ₂ , 1 L of the aqueous solution was adjusted to pH 10 with NaOH, and 1 g of the sample was accurately weighed and dispersed. The mixture was stirred vigorously at 25 ° C. for 15 minutes, filtered through a 0.2 μm filter paper, and then the residual hardness (Rh) of the filtrate was determined using a calcium electrode and determined by the 300-Rh difference.

2) Magnesium ion exchange capacity: A 300 mg MgO / L aqueous solution was prepared with MgCl ₂ , 1 L of the aqueous solution was adjusted to pH 10 using NaOH, and then 1 g of the sample was accurately weighed and dispersed. The mixture was stirred vigorously at 25 ° C. for 15 minutes, filtered through a 0.2 μm filter paper, and then added to the filtrate with an Eriochrone Black T indicator, titrated as 0.01 M EDTA, to determine the residual hardness (Rh), which was determined as a 300-Rh difference. .

7. Absorption capacity: According to KS M 6558.

Examples of X-type zeolites having a silicon-to-aluminum ratio of 1.2 or less, commercial 4A zeolites, and P-type zeolites having a silicon-to-aluminum ratio of 1.2 or less are shown in Table 3 as follows.

TABLE 3

In addition, the oil absorption capacity and cation exchange capacity of the zeolite was measured by the method described above, and the results are shown in Table 4.

TABLE 4

No content.

Claims (9)

A highly concentrated nonionic granular detergent composition containing the following ingredients and having an apparent density of at least 0.75 g / cm 3: (a) 10 to 30 parts by weight of nonionic surfactant as main cleaning base (b) 5-20 parts by weight of anionic surfactant (c) 5-35 parts by weight of sodium carbonate, and (d) 10-40 weight part of X-type zeolite whose ratio of silicon-to-aluminum is 1.2 or less, calcium ion exchange capacity is 130 mg CaO / g or more and oil absorption ability is 70 g / 100 g or more on an anhydride basis. The nonionic surfactant according to claim 1, wherein the nonionic surfactant is liquid or paste at 40 ° C. or lower, has an HLB value of 5 to 15, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, and polyoxyethylene. A highly concentrated nonionic granular detergent composition which is a compound selected from the group consisting of sorbitan fatty acid esters, polyoxyethylene fatty acid esters and fatty acid alkanolamides. 3. The polyoxyethylene according to claim 1 or 2, wherein said nonionic surfactant has an average added mole number of ethylene oxide of a linear or branched primary or secondary alcohol having 6 to 22 carbon atoms of an alkyl group. Highly concentrated nonionic granular detergent composition which is an alkyl ether. 4. The highly concentrated nonionic granular detergent according to claim 3, wherein the polyoxyethylene alkyl ether has an average molar number of 5 to 15 ethylene oxide of a linear or branched primary or secondary alcohol having 10 to 20 carbon atoms in its alkyl group. Composition. The highly concentrated nonionic granular detergent composition according to claim 1, further comprising 5 to 30 parts by weight of a P-type zeolite having a ratio of silicon to aluminum of 1.2 or less and a calcium ion exchange capacity of 130 mg CaO / g or more. The method of claim 1, wherein the thermally sensitive component as an auxiliary additive comprises at least one enzyme selected from the group consisting of proteases, lipases, amylases and cerulases; At least one bleach selected from the group consisting of sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate; Bleach activators; And at least two selected from the group consisting of fragrances. Method for producing a highly concentrated nonionic granular detergent composition comprising the following steps: Inorganic builders were mixed in a dry powder obtained by spray drying a conventional detergent slurry composed of a mixture of anionic surfactant as a main cleaning base and a cleaning aid in a first high-speed mixing / granulator in a ratio of 90:10 to 10:90. A basic powder preparation step as a first granulation step, followed by granulation while impregnating 80 to 99 parts by weight of the mixture with 1 to 20 parts by weight of a nonionic surfactant; And A second granulation with 20 to 50 parts by weight of the above-mentioned base powder and 30 to 60 parts by weight of the inorganic builder in a second high speed mixing / granulator, followed by granulation with impregnation of 1 to 20 parts by weight of the nonionic surfactant. The granulation step consists of: The above-mentioned inorganic builders have X-type zeolites, 4A-type zeolites, P-type zeolites, sodium carbonates, and amorphous aluminos having a ratio of silicon to aluminum of 1.2 or less, calcium ion exchange capacity of 130 mg CaO / g or more, and oil absorption capacity of 70 g / 100 g or more. At least one selected from the group consisting of silicates, the inorganic builder used in at least the second granulation step of the above-mentioned inorganic builders used in the first and second granulation step, the X-type zeolite Is included, 10-40 weight part of said X-type zeolites and 10-30 weight part of said nonionic surfactants are contained in the whole composition. 10. The method of claim 8, further comprising the step of adding a heat sensitive component, followed by the second granulation step, to add a heat sensitive component. The method according to claim 8, wherein in the second granulation step, the nonionic surfactant is introduced in a spraying manner, and after the spray introduction of the nonionic surfactant, at the end of the second granulation step. A method for producing a highly concentrated nonionic granular detergent composition, wherein at least one inorganic builder selected from the group consisting of X zeolite, P zeolite, and amorphous aluminosilicate is added as a surface coating agent.