JPH09279194A - Production of high-bulk density granular detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject detergent with no insoluble residue when used, by incorporating a green detergent prepared by evaporating a specific anionic surfactant-contg. slurry to dryness with a polyoxyalkylene alkyl ether fatty acid ester and crystalline silicate powder during crushing and granulation of the green detergent. SOLUTION: This high-bulk density granular detergent suppressed in the development of insoluble residues when used, is obtained by incorporating a green detergent prepared by evaporating a slurry containing a nono-saponaceous anionic surfactant (e.g. alkylbenzenesulfonic acid salt) to dryness with a polyoxyalkylene alkyl ether fatty acid ester of the formula (R1 CO is a 6-22C saturated or unsaturated fatty acid residue; R2 is a 2-4C alkylene; R3 is a 1-4C alkyl; (n) is the average added number of moles of OR2 , being 5-30) and crystalline silicate powder during crushing and granulation of the green detergent. This detergent has a bulk density of >=0.65g/cm<3> .

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a high bulk density granular detergent composition.

[0002]

2. Description of the Related Art Conventionally, powder detergents are mainly low-density products obtained by a spray-drying method, but in recent years, more compact high-density detergents have been developed due to convenience of transportation, carrying and place of detergents. It is on the market. Such a high-density detergent
Generally, it is obtained by drying an aqueous slurry containing a surfactant and a detergent builder to obtain a detergent composition and densifying it. Various methods are known for this densification method. For example, JP-A-51-67302 discloses a method for densifying spray-dried particles with a specific granulating device called Marumerizer (trade name). Have been described.

In recent years, so-called vertical mixers such as high speed mixers (stirring tumbling granulators) and Henschel mixers (high speed stirring granulators) for spray-dried particles, and Loedige mixers, etc. Methods for achieving high density by stirring granulation with a so-called horizontal mixer are known, and examples thereof include stirring and granulating spray-dried particles as disclosed in JP-A-61-69897. High bulk density granular detergent, and Japanese Patent Laid-Open No. 62-16990.
As disclosed in No. 0 and JP-A-62-366897, there is a method in which spray-dried particles are compacted and then pulverized and granulated to obtain a high bulk density granular detergent.

On the other hand, recently, as a high-performance cleaning component usable for a high-bulk density granular detergent, it has recently been disclosed in JP-A-60-227895.
It has been proposed to use crystalline silicates such as those described in JP-A-5-184946. The crystalline silicate is C
2) Effective in cleaning of a-ion trapping ability and alkaline buffering ability
Since it has both effects, it is an effective ingredient in formulating the composition of a detergent that exerts a cleaning effect in a smaller amount, and is considered to be effective in making the detergent compact.

[0005]

The usual method of incorporating crystalline silicates into granular detergents is by addition in powder form. When the crystalline silicate dissolves in water, it becomes the same as a general amorphous silicate, and the Ca ion capturing ability is reduced or eliminated, resulting in a reduction in cleaning performance. for that reason,
The addition of crystalline silicates to detergent slurries is disadvantageous.
Further, the crystalline silicate also becomes amorphous when it comes into contact with water, and the Ca ion trapping ability also decreases or disappears, resulting in a decrease in cleaning performance.

Further, since the crystalline silicate is blended into the detergent in the form of powder, it becomes hardly soluble or insoluble together with the ingredient which is also blended in the detergent when it is made amorphous, such as zeolite, so that it becomes clothes after washing. There is a risk that it will remain in the tub of a washing machine, and it is necessary to devise ways to keep water out as much as possible by refraining from the use of ingredients that easily bring in water and by drying more than necessary.

As a technique for blending a crystalline silicate into a high bulk density granular detergent, for example, Japanese Patent Application Laid-Open No. 2-178398.
No. 7, JP-A-7-53992, JP-A-7-109490.
However, there is no disclosure related to the stable incorporation of crystalline silicate into high-density granular detergents and the prevention of the formation of residual products, which is a problem when using the granular detergents. Is also insufficient.

On the other hand, since the high-bulk-density granular detergent sinks when it is poured into water, it may cause solubility in cold water, especially when it is used in the winter, and generation of a residual residue due to the fact that the particles are dense inside. Although it is necessary to deal with this problem, when crystalline silicate is used, the degree of freedom of the compounding and manufacturing method is limited to prevent the generation of the residual product, and these points have not been sufficiently solved.

[0009]

Means for Solving the Problems As a result of earnest research by the present inventors, when a detergent bulk obtained by drying a detergent slurry is crushed and granulated to produce a high bulk density granular detergent, the detergent is used. By adding a specific polyoxyalkylene alkyl ether fatty acid ester and a crystalline silicate powder at the time of crushing and / or granulating the dough, the crystalline silicate can be stably blended with the high-bulk density granular detergent, and further obtained The present inventors have found that the solubility of the obtained granular detergent in water is improved, the generation of the leftover residue can be suppressed, and the leftover residue hardly adheres to and remains on the clothes, thus completing the present invention.

That is, according to the present invention, a detergent dough obtained by drying a detergent slurry containing a non-soap anionic surfactant is crushed and granulated to obtain a bulk density of 0.6.
In the method for producing a high bulk density granular detergent of 5 g / cm ³ or more, when the detergent cloth is crushed and / or granulated, a polyoxyalkylene alkyl ether fatty acid ester represented by the following general formula (1) is added to the detergent cloth. The present invention provides a method for producing a high bulk density granular detergent, which is characterized by adding a crystalline silicate powder.

[0011]

Embedded image

[Wherein R ₁ CO: a saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms R ₂ : an alkylene group having 2 to 4 carbon atoms R ₃ : an alkyl group having 1 to 4 carbon atoms n: OR ₂ The average number of added moles of 5 to 30 is shown].

In the production method of the present invention, a detergent dough obtained from a detergent slurry containing an anionic surfactant is crushed with a high bulk density granular detergent containing a crystalline silicate and having a bulk density of 0.65 g / cm ³ or more. In granulating and producing, during the crushing and / or granulating of the dry detergent dough, that is, before the granulated product particles are completed, the crystalline silicate powder and the polyoxyalkylene alkyl ether fatty acid ester are added to form granules. This method is characterized in that a detergent is produced, and in this method, the contact between the water content in the outside air and the crystalline silicate, which is involved in the amorphization of the crystalline silicate, is reduced as much as possible, and the method is represented by the general formula (1). Granulation can be favorably promoted by adding a specific nonionic surfactant. For this reason, suppression of amorphization of the crystalline silicate is achieved, and stable blending of the crystalline silicate is possible. Therefore, it is possible to obtain a high bulk density detergent that is used in a smaller amount than ever before. In addition, the incorporation of the fatty acid ester type nonionic surfactant improves the solubility in cold water, suppresses the generation of the residue, and makes it difficult for the residue to remain on the clothes.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, first, an aqueous slurry containing a non-soap anionic surfactant, a detergent builder, and optionally other optional ingredients is prepared, and a known method is used. For example, it is dried by drum drying, airflow drying, vacuum thin film drying, or preferably, a dry detergent dough is prepared as spray-dried particles by a countercurrent spray-drying device or the like. In the case of spray-dried particles, the average particle size is 300 to 1000
About μm is preferable.

As the non-soap anionic surfactant to be added to the slurry, alkylbenzene sulfonate, alkyl sulfate, α-olefin sulfonate, α-sulfo fatty acid ester salt, alkyl or alkenyl which are usually used in detergents are used. Examples include ether sulfates, α-sulfo fatty acid salts, alkane sulfonates, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. It As the anionic surfactant, alkylbenzene sulfonate and alkyl sulfate are particularly preferable. Further, the non-soap anionic surfactant is contained in the final high bulk density granular detergent in an amount of 10 to 10.
It is blended so as to be 40% by weight, preferably 15 to 35% by weight. The saturated or unsaturated fatty acid salt may be added to the slurry in an amount of 0 to 10% by weight.

In the present invention, it is preferable that the volatile content in the obtained dry detergent fabric is 1.5 to 6% by weight. The volatile matter content in the dry detergent dough may be adjusted by any method such as adjusting the water content in the slurry, blending components, adjusting the drying conditions, and further drying (secondary drying) the dry detergent dough. In the present invention, the “volatile matter” means a weight loss when dried at 105 ° C. for 2 hours, and it is considered that most of it is water. This further suppresses the amorphization of the crystalline silicate.

Next, the obtained dry detergent dough is crushed and granulated to produce a high bulk density granular detergent having a bulk density of 0.65 g / cm ³ or more. In the present invention, the dry detergent dough is crushed and / or When granulating, polyoxyalkylene alkyl ether fatty acid ester and crystalline silicate are added. The method of making the dry detergent fabric of the present invention is preferably a method by spray drying. As a preferred production method, the spray-dried particles are mixed with crystalline silicate and other detergent raw materials in a vertical or horizontal stirring granulator (Japanese Patent Laid-Open No. 61-69897, Japanese Patent Laid-Open No. 61-6).
9900 gazette) and agitating and granulating the polyoxyalkylene alkyl ether fatty acid ester using the binder as a binder, and spray-dried particles and crystalline silicate or polyoxyalkylene alkyl ether fatty acid ester and other detergent raw materials as a kneader. Or kneading with a ribbon mixer or the like, and then using a extrusion molding machine to perform columnar consolidation or sheet-form consolidation between two rolls, and then compacting these compacts with a hammer mill, cutter mill or speed mill. A method of granulating with a crushing (crushing) granulator such as

The polyoxyalkylene alkyl ether fatty acid ester used at the time of crushing and / or granulating the dry detergent dough has an average of 5 saturated or unsaturated fatty acids having 6 to 22 carbon atoms and oxyalkylene groups having 2 to 4 carbon atoms. An ester with a polyoxyalkylene lower alkyl (methyl, ethyl, propyl or butyl) ether to which 30 to 30 moles are added is preferable, and a fatty acid having 10 to 16 carbon atoms and an average carbon number of 12 to 14 and ethylene oxide are 4 to 4 on average.
An ester with 12 mol, preferably 4 to 10 mol of polyoxyethylene methyl ether added is desirable. The polyoxyalkylene alkyl ether fatty acid ester added at the time of crushing and / or granulating the dry detergent dough is preferably added so as to be 0.5 to 8% by weight in the final composition. When the polyoxyalkylene alkyl ether fatty acid ester is added in this range, good granulation can be performed, the solubility in cold water is improved, the generation of undissolved substances is suppressed, and the cleaning performance is improved. Further, the fluidity and solidification preventing property of the resulting granular detergent are also good. Incidentally, although the present invention crushes the dry detergent dough and then granulates the same, the destruction and the granulation are performed using separate devices. Alternatively, a device such as a high speed mixer that allows granulation to proceed while being crushed may be used.

Further, the polyoxyalkylene alkyl ether fatty acid ester may contain other compatible components (polyethylene glycol, polypropylene glycol, fatty acid (preferably having a carbon number of 8 to 22), etc.). The amount is preferably an amount that can maintain compatibility. Dispersing the compatible components evenly in the granulated particles improves the detergency, physical properties of powder, and storage stability.

In the present invention, a crystalline silicate is added together with the above polyoxyalkylene alkyl ether fatty acid ester when the dry detergent dough is crushed and / or granulated. By adding crystalline silicate at the time of granulation, the crystalline silicate is surrounded by a crushed product of dry detergent dough, which suppresses the amorphization of crystalline silicate due to moisture from the outside. Crushing and / or granulation The amount of crystalline silicate powder to be added at the time is, in terms of the cleaning performance and the effect of suppressing the generation of residual products during washing,
The amount in the final composition is preferably 1 to 10% by weight. The average particle size of the crystalline silicate powder is preferably 1 to 40 μm. If the particle size is too small, it becomes more amorphous due to contact with water, and the cleaning performance and quality are likely to deteriorate, while if it is too large, it remains as a residue on clothes and the washing machine. The crystalline silicate having such an average particle size and particle size distribution can be prepared by pulverizing with a pulverizer such as a vibration mill, a hammer mill, a ball mill and a roller mill. The average particle size and particle size distribution of the crystalline silicate were measured by using a laser diffraction type particle size distribution measuring device. That is, laser diffraction type particle size distribution measuring apparatus LA
-Approximately 2 in the measuring cell of 910 type (manufactured by Horiba, Ltd.)
Inject 00 ml of ethanol and sample about 0.5-5 mg
Was suspended. Subsequently, the mixture was stirred for 1 minute while being irradiated with ultrasonic waves, and after sufficiently dispersing the sample, a He-Ne laser (632.8 nm) was incident, and the particle size distribution was measured from the diffraction / scattering pattern. Analysis is Fraunhofe
Using the r diffraction theory and the Mie scattering theory together, the particle size distribution of suspended particles in the liquid was measured in the range of 0.04 to 262 μm. The average particle size was the median size of the particle size distribution.

Most of the crystalline silicate powder exists in a state of being dispersed inside the final detergent particles and is not substantially exposed on the surface of the final detergent particles. It is preferable in order to prevent deterioration of cleaning performance due to crystallization and further deterioration of alkaline buffering capacity due to carbon dioxide gas,
Further, in order to suppress insolubilization and insolubilization involving surrounding components that occur after amorphization, it is preferable that they are dispersed inside.

The crystalline silicate used in the present invention will be specifically described below. The crystalline silicate used in the present invention has a pH of 11 or more in a 0.1 wt% dispersion liquid and exhibits excellent alkaline ability. Further, after adding 0.1 g of the crystalline silicate to 1 liter of ion-exchanged water and stirring for 3 minutes to sufficiently dissolve or disperse the silicate, the pH of the solution is 11 or more. It has an alkaline buffering capacity such that the amount until the pH reaches 10 is at least 3 ml by adding 0.1 N hydrochloric acid.

The crystalline silicate used in the present invention is preferably an alkali metal silicate, particularly SiO ₂ / M ₂
Those having O (wherein M represents an alkali metal) of 1.0 to 2.6 are used. On the other hand, the crystalline silicate used in JP-A-60-227895 has a SiO ₂ / Na ₂ O ratio (S
/ N ratio) is 1.9 to 4.0, but in the present invention S / N
Care should be taken because silicates with a ratio of over 2.6 have poor detergency, and with a ratio of less than 1.0, the physical properties of the powder may deteriorate.

As the crystalline silicate used in the present invention,
Preferably, those having the following composition are exemplified. _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (2) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa, or a combination of two or more selected from Group VIII elements, y / x = 1.0 to 2.6, z
/X=0.01 to 1.0, n / m = 0.5 to 2.0, and w = 0 to 20. _{) M 2 O · x'SiO 2 ·} y'H 2 O (3) ( wherein, M represents an alkali metal, x '= 1.5~2.6, y'
= 0 to 20. ) First, the crystalline silicate having the above composition will be described.
In the general formula (2), M is selected from the group Ia elements of the periodic table, and examples of the group Ia elements include Na and K.
These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to form the M ₂ O component. Me is selected from the IIa, IIb, IIIa, IVa, or VIII group elements of the periodic table, and examples thereof include Mg, Ca, Zn, Y, Ti, Zr, and Fe. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. Further, it may be mixed alone, or two or more kinds, for example MgO, may constitute the Me _m O _n component by mixing and CaO. Further, the crystalline silicate in the present invention may be a hydrate, and the hydration amount in this case is in the range of w = 0 to 20.

In the general formula, y / x is 1.0 to 2.6, preferably 1.5 to 2.2. If y / x is less than 1.0, the powder properties of the detergent composition such as caking property are adversely affected. If y / x exceeds 2.6, the detergency is reduced. z / x is 0.01 to 1.0, preferably 0.02 to 0.9
It is. If z / x is less than 0.01, the water resistance is insufficient, and if it exceeds 1.0, the ion exchange capacity is low and the ion exchanger is insufficient. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. When xM ₂ O is, for example, x ′ Na ₂ O · x ″ K ₂ O as described above, x is x ′ +
the x ". This relationship is the same in the z in the case of ZME _m O _n component composed of two or more. Further, n / m = 0.5 to 2.0 is coordinated to the element Indicates the number of oxygen ions, which is substantially 0.5, 1.0, 1.5, 2.0
Is selected from the values of

The crystalline silicate having the composition of the present invention has M ₂ O, SiO ₂ , and
It has become than the three components of Me _m O _n. Therefore, in order to produce the crystalline silicate in the present invention, each component is required as a raw material thereof, but in the present invention, a known compound is appropriately used without particular limitation. For example, M ₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. Specifically, for example, M ₂ O
Raw materials for the components include NaOH, KOH, Na ₂ CO ₃ ,
_{K 2 CO 3, Na 2 SO} 4 and the like, as a material of Me _m O _{n component, CaCO 3, MgCO 3, Ca} (OH) 2, Mg (O
H) ₂ , MgO, ZrO ₂ , dolomite and the like.
As the SiO ₂ component, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.

The method of preparing the crystalline silicate having the composition of the present invention is as follows. The above raw material components are mixed in a predetermined quantitative ratio so that x, y and z values of the desired crystalline silicate are obtained. Usually, a method of crystallization by firing at 300 to 1500 ° C, preferably 500 to 1000 ° C, more preferably 600 to 900 ° C is exemplified. In this case, if the heating temperature is less than 300 ° C., crystallization is insufficient and water resistance is poor, and if it exceeds 1500 ° C., coarse particles are formed and the ion exchange ability is lowered. Normal heating time
0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

The crystalline silicate of the composition of the present invention has an ion exchange capacity of at least 100 CaCO ₃ mg.
/ G or more, preferably 200 to 600 CaCO ₃ mg / g.

The amount of Si eluted into water is usually 110 mg / g or less in terms of SiO ₂ , and it is substantially insoluble in water.
In the present invention, “substantially insoluble in water” means that the amount of Si eluted when 2 g of a sample is added to 100 g of ion-exchanged water and stirred at 25 ° C. for 30 minutes is usually 110 in terms of SiO _2.
less than mg / g, but in the present invention,
The amount of 0 mg / g or less is more preferable for satisfying this effect.

Next, the crystalline silicate having the above composition will be described. This crystalline silicate is represented by the general formula (3) M ₂ O · x′SiO ₂ · y′H ₂ O (3) (wherein M represents an alkali metal, x ′ = 1.5 to 2.6, y ′).
= 0 to 20. ), X'and y'in the general formula (3) are preferably 1.7 ≤ x '≤ 2.2 and y' = 0, and the cation exchange capacity is 100 to 400 CaCO ₃ mg. /
The substance of g can be used and is one of the substances having an ion-trapping ability in the present invention.

Such a crystalline silicate is disclosed in JP-A-60-227895.
The production method is described in Japanese Patent Laid-Open Publication No. 1988-96, and it is generally obtained by firing amorphous glassy sodium silicate at 200 to 1000 ° C. to make it crystalline. For details of the synthesis method, see
Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristal
logr., 129 , 396-404 (1969) and the like. The crystalline silicate is available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ) in powder or granular form. In the present invention, the crystalline silicates having the above compositions and can be used alone or in combination of two or more kinds.

In the production method of the present invention, in order to obtain a high bulk density granular detergent having even better fluidity, inorganic powder fine particles having an average particle diameter of 0.1 to 10 μm, preferably water-insoluble inorganic powder. The surface of the detergent particles can be coated with the inorganic powder fine particles by adding the body fine particles immediately before the completion of the stirring granulation or by allowing the compact compacts to be present during the pulverization and granulation. From the viewpoint of coating effect, it is preferable to add the inorganic powder fine particles in an amount of 1 to 10% by weight in the final composition. The surface coating with the inorganic powder fine particles not only improves the physical properties of the powder but also prevents the deterioration of the crystalline silicate. In addition, it is possible to use the inorganic powder fine particles for purposes other than the surface coating of the detergent particles, for example, for improving fluidity and adhesiveness during granulation for the purpose of controlling granulation property. The amount of the inorganic powder fine particles used for such a purpose is not included in the amount of the inorganic powder fine particles used for the purpose of surface coating. When the inorganic powder fine particles are added, the total amount of the inorganic powder fine particles may be added all at once, or may be gradually added in plural times. It is also possible to mix and use a plurality of types of inorganic powder fine particles or to add them separately. In addition, the detergent particles after granulation and the inorganic powder fine particles having an average particle diameter of 0.1 to 10 μm are put into a mixing device such as a rotary kiln or a V blender which is hard to apply a direct mechanical force, and mixed. Also, the surface of the detergent particles can be coated with the inorganic powder fine particles. In this case, a suitable amount of the inorganic powder fine particles is 0.5 to 8% by weight in the final composition. Examples of the inorganic powder fine particles include aluminosilicate, silicon dioxide, amorphous silica derivative, sodium carbonate (dense ash) and the like.

Further, in the production method of the present invention, the total amount of nonionic surfactants in the final detergent particles can be increased by adding a nonionic surfactant also in the dry detergent dough, and further washing can be performed. The performance can be improved.
The inclusion of the nonionic activator in the dry detergent dough is achieved by blending the nonionic activator in the detergent slurry to be dried and drying, preferably spray drying. The nonionic surfactant to be present in the dry detergent cloth is preferably a higher alcohol having an alkyl chain length of 12 to 15 and an average carbon number of 12 to 13 to which ethylene oxide is added in an average of 7 to 12 mol. Further, the nonionic surfactant to be present in the dry detergent dough is blended in the dry detergent dough in an amount of 0.5 to 8% by weight. In addition, the aluminosilicate may be added to the slurry, and specifically, it is preferable to add the amount used for coating from the amount added during crushing and / or granulation of the dry detergent dough. As the aluminosilicate, a commonly known one can be used, and in addition to the crystalline A, X or P type zeolite, an amorphous one can also be used. The aluminosilicate has an average particle size of 0.1 to 10 μm, preferably 0.1 to 5 μm, and the final high bulk density detergent particles, including the amount used as a coating agent, are 8 to 50% by weight in terms of water content, Preferably 10
40% by weight is blended.

Further, in the present invention, the amorphous silicate can be blended with the detergent slurry so as to be present in the dry detergent cloth. The presence of the amorphous silicate in the dry detergent dough makes the dry particles have an appropriate strength to improve the handling property, and even after being granulated into the high bulk density detergent particles, the solidifying property and the fluidity are maintained. improves. The preferable amount of the amorphous silicate compounded is 3 to 12% by weight based on the final detergent composition from the viewpoints of the effect of improving the physical properties of the powder and the suppression of the generation of undissolved residue during washing. Examples of the amorphous silicate include amorphous sodium silicate, which is preferably SiO ₂ / Na ₂ O = 1.5 to 2.6, and JIS No. 1 silicate and JIS No. 2 silicate correspond thereto.

Further, in the production method of the present invention, at least one of polyacrylic acid salt having an average molecular weight of 10,000, preferably 15,000 or more, a copolymer of maleic acid and acrylic acid or olefin, and polyacetal carboxylate is used in the detergent composition. Can be blended. These can be incorporated into a spray dried slurry. These polymers or copolymers have a composition of 0.5 to
10% by weight, preferably 2-8% by weight. By blending these polymers or copolymers,
Adhesion of water-insoluble matter derived from crystalline aluminosilicate to clothes in high-hardness laundry is further suppressed.

In the production method of the present invention, other general detergent builders can be added. As the builder, carbonate such as soda ash, sulfate, sulfite, silicate, tripolyphosphate, pyrophosphate, inorganic builder such as orthophosphate, citrate, oxydisuccinate, organic such as nitrilotriacetic acid Builders. Further, an organic chelating agent such as EDTA can be added. In addition, an enzyme can be blended, and specific examples thereof include protease, cellulase, amylase, lipase and the like, and generally commercially available granules can be used. Further, polyethylene glycol having an average molecular weight of 5000 to 15000 may be added to improve the physical properties of the powder, and polyvinylpyrrolidone may be added to prevent color transfer. Other trace ingredients include usual fragrances, foam suppressors such as silica and silicone, biphenyl type optical brighteners or stilbene type optical brighteners or fluorescent whitening agents using them in combination, anti-caking agents, rinse aids. Agents can be added. In order to maintain dispersion solubility in cold water, the amount of sodium carbonate contained in the final granular detergent is preferably 20% by weight or less, and the amount of sodium sulfate is preferably 10% by weight or less.

A bleaching composition can be added to the production method of the present invention. The bleaching composition is composed of sodium percarbonate, sodium perborate, preferably sodium percarbonate and various bleach activators, etc., which are separately granulated and dry blended with the present high bulk density granular detergent.
Further, the above-mentioned enzyme and foam suppressor are separately granulated and dry-blended.

[0038]

According to the present invention, it is possible to obtain a high bulk density granular detergent which has a high detergency and a good fluidity and does not cause the problem of the residue left on the clothes or the washing machine.

[0039]

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

Example 1 (1) Preparation of spray-dried particles The components shown in Table 1 were mixed with water to prepare a detergent slurry having a solid content of 50% by weight (temperature: 65 ° C.). This detergent slurry was spray-dried with a countercurrent spray dryer to obtain spray-dried particles. The volatile content (105 ° C., weight loss for 2 hours) of the obtained spray-dried particles was 4%.

[0041]

[Table 1]

(Note) The symbols in Table 1 have the following meanings. _{· LAS-Na (C 10 ~C} 13); linear alkyl (C ₁₀ ~C ₁₃₎ sodium benzenesulfonate _{· AS-Na (C 12 ~C} 16); alkyl (C ₁₂ ~C ₁₆₎ Sodium Nonionic sulfate Surfactant A; polyoxyethylene alkyl ether [carbon of the alkyl group 12 to 14 (average 12.
8) Average of 8 moles of ethylene oxide added to primary saturated alcohol] AA / MA copolymer; acrylic acid / maleic acid copolymer sodium salt (monomer ratio 3: 7, Mw≈5000)
0, neutralization degree ≈80 mol%)-Tinopearl CBS-X; fluorescent dye, distyrylbiphenyl derivative (manufactured by Ciba-Geigy) -Whitetex SA; fluorescent dye, bis- (triazinylamino) -stilbene-disulfonic acid derivative ( (2) Preparation of high bulk density detergent composition 78 parts by weight of the spray-dried particles obtained above and crystalline aluminosilicate powder (4A type zeolite powder, average particle size 2.
7 μm; Tosoh Co., Ltd.) 3 parts by weight in advance, and then crushed crystalline silicate powder [SKS-6 (powder); Hoechst Tokuyama Co., Ltd., average particle size = 27
μm (Laser diffraction particle size distribution analyzer, LA-910
Type, measured by Horiba, Ltd.)] 5 parts by weight were put into a high-speed mixer (manufactured by Fukae Industry Co., Ltd.),
The spray-dried particles were crushed and granulated with stirring. At this time, 4 parts by weight of a nonionic surfactant (ester of saturated fatty acid having 12 carbon atoms and polyoxyethylene methyl ether to which ethylene oxide added 6 mol on average) was sprayed and added. 30 seconds before the end of granulation, 5 parts by weight of the same powdery zeolite as that mixed with the spray-dried particles was added to perform surface coating. Next, this granulated product was sieved with a sieve having an opening of 1.3 mm, and coarse particles on the sieve were crushed with a Fitz mill (manufactured by Hosokawa Micron Co., Ltd.) and then mixed with a sieve pass-through. 4 parts by weight of powdered zeolite and enzyme (API
-21H; Showa Denko KK) (1 part by weight) was mixed with a V blender to carry out a treatment which also served as a complement to the particle surface coating, to obtain a final granular detergent.

Example 2 As the nonionic surfactant to be added at the time of crushing and granulating the spray-dried particles in Example 1, saturated fatty acid having 12 carbon atoms of 60% by weight and 14 carbon atoms of 40% by weight and ethylene oxide are 15 on average. Amorphous aluminosilicate powder (0..M) was used as an inorganic powder fine particle added 30 minutes before the end of granulation, using an ester with polyoxyethylene methyl ether added in moles.
8Na ₂ O · Al ₂ O ₃ · 6.5SiO ₂ , average particle size 2.
A granular detergent was obtained in the same manner as in Example 1 except that 1 μm) was used.

Comparative Example 1 Uncrushed SKS-6 as crystalline silicate powder in Example 1
A granular detergent was prepared in the same procedure as in Example 1 except that (powder) was used.

Comparative Example 2 A granular detergent was prepared in the same manner as in Example 1 except that the nonionic surfactant was not added during granulation. However, granulation did not proceed well, and the resulting granular detergent had a low bulk density,
The average particle size was also small.

Comparative Example 3 Granulation was performed by replacing the crystalline silicate powder added at the time of crushing and granulation in Example 1 with the powdered zeolite added by the V blender, and the crystalline silicate powder was washed with the enzyme in a V blender for detergent. Mixed with particles. A powder detergent was prepared in the same manner as in Example 1 except for the above.

[Evaluation of Granular Detergent] For Examples 1 and 2 and Comparative Examples 1, 2 and 3, the bulk density and average particle size of the obtained granular detergent, and the carton in which the granular detergent is used as a commercial detergent After storing it for 1 month under the condition of 30 ° C and 80% RH (assuming storage in a warehouse in summer),
The detergency and the residual residue of the residue were evaluated by the following methods. Table 2 shows the results.

(1) Evaluation of Detergency 5 pieces of 10 × 10 cm artificially contaminated cloth coated with dirt having the following composition were put into 1 liter of an aqueous detergent solution for evaluation, and a targometer was used to measure 100 r. p. m. And washed under the following conditions. * Artificial dirt composition Cotton seed oil 60% by weight Cholesterol 10% by weight Oleic acid 10% by weight Palmitic acid 10% by weight Liquid and solid paraffin 10% by weight * Washing conditions: Washing time: 10 minutes Washing concentration: 0.067% by weight Water temperature: 20 ° C Water hardness ； 4 ° DH rinse ； 5 minutes with tap water Detergency was measured with a colorimeter to measure the reflectance of the original cloth before contamination (carbon black was regularly mixed as an indicator) and the contaminated cloth before and after washing, Cleaning rate D (%)
I asked. D (%) = [(L ₂ −L ₁ ) / (L ₀ −L ₁ )] × 100 L ₀ ; reflectance of original cloth L ₁ ; reflectance of soiled cloth before washing L ₂ ; of soiled cloth after washing Reflectivity (2) Evaluation of residual residue of Matsumura Denki Sangyo Co., Ltd. Full-automatic washing machine 5.0 kg "Gentle Aizuma NA-F50Al" was used, and 5 pieces of cotton broad cloth (# 40) black cloth (One is 30 cm x 40 cm)
600g of cotton and cotton clothes are put in, 40 liters of water at 5 ° C and 26.7g of detergent are used for washing (normal) → rinsing (usually 2 times) → dehydration (usually 1 time) for a total of 30 minutes. After drying, the dehydrated black cloth is air-dried and the residual amount of the residue remaining on the surface is evaluated according to the following criteria. 4; White deposits are on the entire surface of the test cloth 3; White deposits are on 3/4 of the test cloth 2; White deposits are on 1/2 of the test cloth 1; White deposits are on the test cloth 1 / 4 is 0.5; white deposits are on 1/8 of the test cloth 0; no white deposits are at all 5 test cloths are evaluated for each front and back, and the average value of all the scores is used as the evaluation score. (0 is the best). If it is 0.2 or more, it is judged that there is a practical problem.

[0049]

[Table 2]

As can be seen from Table 2, if the particle size of the crystalline silicate powder to be used is too large, the detergency is lowered and a residual material is generated, which is a practical problem. In addition, if the nonionic surfactant is not added during crushing / granulation, the detergency is low, and the granulation does not proceed well, and the crystalline silicate is not well incorporated into the detergent particles. Is bad. Also, if the crystalline silicate is not added at the time of granulation and only the detergent granules and the powder are mixed together, the crystalline silicate will deteriorate due to moisture or carbon dioxide in the outside air. The detergency deteriorates and the residual residue remains poor.

Example 3 (1) Preparation of spray-dried particles The components shown in Table 3 were mixed with water to prepare a detergent slurry having a solid content of 50% by weight (temperature: 65 ° C.). This detergent slurry was spray-dried with a countercurrent spray dryer to obtain spray-dried particles. The volatile content (105 ° C., weight loss for 2 hours) of the obtained spray-dried particles was 2.8%.

[0052]

[Table 3]

(Note) The symbols in Table 3 have the following meanings. _{· LAS-K (C 10 ~C} 13); linear alkyl (C ₁₀ ~C ₁₃₎ potassium benzenesulfonate _{· AOS-K (C 14 ~C} 18); α- olefin (C ₁₄ ~C ₁₈₎ sulfonic acid Potassium-α-SFE-Na (C _{14 to} C ₁₆ ); α-sulfo fatty acid (C ₁₄
~ C ₁₆ ) Methyl ester sodium nonionic surfactant B; polyoxyethylene polyoxypropylene alkyl ether [alkyl group carbon 12
~ 14 (average 12.8) primary saturated alcohol with 10 moles of ethylene oxide on average and 5 on average of propylene oxide.
Molybdenum added] -Tinopearl CBS-X; fluorescent dye, distyrylbiphenyl derivative (manufactured by Ciba-Geigy) -Whitetex SA; fluorescent dye, bis- (triazinylamino) -stilbene-disulfonic acid derivative (Sumitomo Chemical Co., Ltd. )).

(2) Preparation of High Bulk Density Detergent Composition 68 parts by weight of the spray-dried particles obtained above and crystalline silicate powder [SKS-6 (powder); crushed by Hoechst Tokuyama Corp.], Average particle size = 27 μm (same as in Example 1) 8 parts by weight was added to anhydrous potassium carbonate powder (Asahi Denka Co., Ltd.).
(Manufactured by K.K.) together with 10 parts by weight into a ribbon mixer, and sprayed with 4 parts by weight of a nonionic surfactant (saturated fatty acid having 12 carbon atoms and an ester of polyoxyethylene methyl ether having 7 mol of ethylene oxide added on average). Then, the mixture was added. The mixture was extruded into a cylindrical column having a diameter of 10 mm by a pre-extrusion type twin-screw extrusion granulator (Pelletter Double; manufactured by Fuji Paudal Co., Ltd.) to be consolidated. The molded product was pulverized and granulated with 5 parts by weight of crystalline aluminosilicate powder (the same as in Example 1) using a flash mill (manufactured by Fuji Paudal Co., Ltd.) to perform surface coating. This granulated product was sieved with a sieve having a mesh of 1.3 mm, and coarse particles on the sieve were pulverized again by the flash mill and then mixed with the sieved material. For this sieving finished product, 4 parts by weight of powdered zeolite and enzyme (sabinase 12.0T; manufactured by Novo Co.
Wt% and lipolase 100T; 10 wt% of Novo Co. mixed with enzyme granules) 1 part by weight was mixed with a V blender to perform a treatment also as a complement of particle surface coating to obtain a final granular detergent. .

Example 4 A granular detergent was prepared in the same manner as in Example 3 except that the crystalline silicate had an average particle size of 8 μm.

Comparative Example 4 A granular detergent was prepared in the same manner as in Example 3 except that the nonionic surfactant was not added during granulation.

Comparative Example 5 Granulation was carried out by exchanging the crystalline silicate powder added at the time of crushing and granulation in Example 3 with the powdered zeolite added by the V blender, and the crystalline silicate powder was washed with the enzyme by a V blender in a detergent. Mixed with particles. A powder detergent was prepared in the same manner as in Example 3 except for the above.

[Evaluation of Granular Detergent] In Examples 3 and 4 and Comparative Examples 4 and 5, the bulk density and the average particle diameter of the obtained granular detergent, the detergency and the residual residue of the residue are shown in Examples 1 to 1. It evaluated similarly to 2 and Comparative Examples 1-4. The results are shown in Table 4.

[0059]

[Table 4]

Example 5 Inorganic powder fine particles which were added at the time of pulverizing and granulating a detergent molded article in Example 3 to coat the surface of the detergent particles were replaced with sodium carbonate (dense ash) instead of crystalline aluminosilicate powder. Was pulverized with a dry attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.) (average particle size 7.5 μm). A powder detergent was obtained in the same manner as in Example 3 except for the above. The obtained powder detergent was evaluated in the same manner as in Examples 1-2 and Comparative Examples 1-4. The bulk density was 0.78 g / cm ³ , the average particle size was 510 μm, the cleaning rate was 68%, and the residual residue The material residual property was 0.00.

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Claims (11)

[Claims] 1. A high bulk density granular detergent having a bulk density of 0.65 g / cm ³ or more by crushing and granulating a detergent dough obtained by drying a detergent slurry containing a non-soap anionic surfactant. In the method for producing, the crushing and / or granulating of the detergent dough, the polyoxyalkylene alkyl ether fatty acid ester represented by the following general formula (1) and crystalline silicate powder are added to the detergent dough. A method for producing a high bulk density granular detergent characterized by the following. Embedded image [Wherein R ₁ CO: a saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms R ₂ : an alkylene group having 2 to 4 carbon atoms R ₃ : an alkyl group having 1 to 4 carbon atoms n: average addition of OR ₂ Indicates the number of moles and is a number from 5 to 30] 2. The method for producing a high bulk density granular detergent according to claim 1, wherein the volatile content in the detergent fabric is 1.5 to 6% by weight. 3. The method for producing a high bulk density granular detergent according to claim 1, wherein the content of the non-soap anionic surfactant is 10 to 40% by weight in the final granular detergent. 4. The polyoxyalkylene alkyl ether fatty acid ester is an ester of a fatty acid having substantially 12 to 16 carbon atoms and polyoxyethylene methyl ether to which 4 to 12 moles of ethylene oxide are added on average. Item 4. A method for producing the high bulk density granular detergent according to any one of Items 1 to 3. 5. The amount of the polyoxyalkylene alkyl ether fatty acid ester added is 0.5 in the final granular detergent.
It is -8 wt%, The manufacturing method of the high bulk density granular detergent of any one of Claims 1-4. 6. The method for producing a high bulk density granular detergent according to claim 1, wherein the crystalline silicate powder is added in an amount of 1 to 10% by weight in the final granular detergent. 7. The average particle size of the crystalline silicate powder is 1
It is -40 micrometers, The manufacturing method of the high bulk density granular detergent in any one of Claims 1-6. 8. The crystalline silicate is SiO ₂ / M ₂ O =
It is 1.0-2.6 (M is a group Ia element of a periodic table), The manufacturing method of the high bulk density granular detergent in any one of Claims 1-7. 9. The crystalline silicate has the following general formula (2):
The method for producing a high bulk density granular detergent according to claim 8, which is a compound represented by _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (2) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa, or a combination of two or more elements selected from Group VIII elements, y / x = 1.0 to
2.6, z / x = 0.01 to 1.0, n / m = 0.5 to
2.0 and w = 0 to 20. ) 10. The method for producing a high bulk density granular detergent according to claim 8, wherein the crystalline silicate is a compound represented by the following general formula (3). M ₂ O · x′SiO ₂ · y′H ₂ O (3) (In the formula, M represents an Ia group element of the periodic table, and x ′ = 1.
It is 5-2.6 and y '= 0-20. ) 11. A step of coating the surface of detergent particles with inorganic powder fine particles by adding inorganic powder fine particles having an average particle diameter of 0.1 to 10 μm during or after granulation. 10. The method for producing a high bulk density granular detergent according to any one of 10 to 10.