JP3367801B2 - Method for producing high bulk density granular detergent and high bulk density granular detergent particles - Google Patents

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 obtaining spray-dried particles from an aqueous slurry containing a surfactant and a detergent builder and densifying them. 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.

Nowadays, further reduction of the usage amount of such a compacted high bulk density granular detergent is attempted, and the conventional usage amount of the detergent was about 25 g per 30 liters of washing water. Recently, a more compact type of 20 g for 30 liters has been introduced. As described above, in order to obtain a high-density detergent that exhibits a cleaning effect with a smaller amount, a technique for stably blending components having higher performance than ever before is required.

A crystalline silicate is mentioned as a high-performance cleaning component usable for a high bulk density granular detergent. The crystalline silicate has two effective effects for washing, namely, Ca ion trapping ability and alkaline buffering ability, so it is an effective ingredient in formulating the composition of a detergent that exerts a washing effect with a smaller amount. It is considered to be effective for compactification.

[0006]

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 during spray drying is inconvenient. 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 in the detergent in a powder form, when it is made amorphous, it becomes hardly soluble or insoluble together with a component that is also blended in the detergent, such as zeolite, so that it becomes clothes after washing. Or remains in the washing machine tub (so-called water-insoluble matter is generated). Techniques for blending a crystalline silicate into a high bulk density granular detergent are disclosed in, for example, JP-A-2-178398, JP-A-7-53992, JP-A-7-109490 and the like. Stable blending of the above with a high-density granular detergent to prevent the formation of a residual residue which is a problem when using the granular detergent is insufficiently studied.

On the other hand, since the high-bulk-density granular detergent sinks when it is poured into water, the solubility in cold water and the generation of undissolved residues due to the particles being dense inside, especially when used in winter. It is necessary to deal with it, but this point has not been fully resolved yet.

[0009]

Means for Solving the Problems As a result of earnest studies by the present inventors, the volatile content of the spray-dried particles was 1. when the spray-dried particles were crushed and granulated to produce a high-bulk density granular detergent. By adding 5 to 5% and polyoxyalkylene alkyl ether and crystalline silicate powder at the time of crushing and / or granulating, the crystalline silicate can be stably blended with the high bulk density granular detergent, and The present invention has been completed by finding that it is possible to suppress the generation of leftovers when a granular detergent is used.

That is, the present invention is a method for producing a high bulk density granular detergent having a bulk density of 0.65 g / cm ³ or more by crushing and granulating spray-dried particles containing a non-soapy anionic surfactant. In the above, the volatile content in the spray-dried particles is 1.5 to 5%, and at the time of crushing and / or granulation of the spray-dried particles, the spray-dried particles have polyoxyalkylene alkyl ether and crystalline silicate powder. The present invention provides a method for producing a high-bulk-density granular detergent characterized by adding and.

In the production method of the present invention, a high bulk density granular detergent containing a crystalline silicate and a bulk density of 0.65 g / cm ³ or more is crushed into granules by crushing spray-dried particles containing an anionic surfactant. During production, the volatile content is 1.5-5%
And to make a granular detergent by using the spray-dried particles made lower and adding the crystalline silicate powder and the polyoxyalkylene alkyl ether at the time of crushing and / or granulation, that is, before the granule particles are completed. In this method, the water content in the system involved in the amorphization of the crystalline silicate is reduced as much as possible, and the addition of a nonionic surfactant makes it difficult for granulation to proceed due to the reduction of volatile components. It is possible to make up for the part that has become defective and to proceed with granulation. 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.

[0012]

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, spray-dried particles are prepared by a countercurrent spray-drying device or the like. The average particle size of the spray-dried particles is preferably about 300 to 1000 μm.

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 is usually used in detergents is used. Ether sulfate, α-sulfo fatty acid salt, alkane sulfonate, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N-
Examples thereof include acylamino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof. As the anionic surfactant, in particular, alkylbenzene sulfonate,
Alkyl sulfates are preferred. Also, the non-soap anionic surfactant is added in an amount of 10% in the final high bulk density granular detergent.
-40% by weight, preferably 15-35% 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, the volatile content in the obtained spray-dried particles needs to be 1.5 to 5% by weight. The volatile matter in the spray-dried particles may be adjusted by any method such as adjusting the water content in the slurry, the blending components, adjusting the spray-drying conditions, and drying the spray-dried particles (secondary drying). 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.

Next, the obtained spray-dried particles are 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 spray-dried particles are crushed and / or When granulating, polyoxyalkylene alkyl ether and crystalline silicate are added. As a method thereof, spray-dried particles are mixed with a crystalline silicate or other detergent raw material in a vertical or horizontal stirring granulator (exemplified in JP-A-61-69897 and JP-A-61-69900). A method of stirring and granulating by using a polyoxyalkylene alkyl ether as a binder after kneading or mixing spray-dried particles with crystalline silicate or polyoxyalkylene alkyl ether and other detergent raw materials in a kneader or ribbon mixer. Extruder can be used to perform columnar consolidation molding or 2
Examples include a method in which the sheet is compacted into a sheet shape between rolls of a book, and the compacted body is granulated with a crushing (crushing) granulator such as a hammer mill, a cutter mill or a speed mill.

The polyoxyalkylene alkyl ether used at the time of crushing and / or granulating the spray-dried particles is preferably an alcohol having an alkyl chain length of 12 to 22 to which 4 to 15 mol of ethylene oxide and / or propylene oxide is added. , Especially alkyl chain length 12-15,
A polyoxyethylene alkyl ether obtained by adding 4 to 12 mol, and preferably 4 to 10 mol of ethylene oxide on average to a higher alcohol having an average carbon number of 12 to 13 is desirable. The polyoxyalkylene alkyl ether added at the time of crushing and / or granulation is 0.5 to 8 in the final composition.
It is preferable to add it so as to be in a weight%. When the polyoxyalkylene alkyl ether is added within this range, good granulation can be performed and the cleaning performance is improved. In addition, the polyoxyalkylene alkyl ether added at the time of crushing and / or granulation, which has good fluidity and solidification preventing property of the resulting granular detergent, may contain water. The amount is preferably 20% by weight or less, more preferably 5 to 15% by weight. Moisture in the polyoxyalkylene alkyl ether added during crushing and / or granulation combines with the unhydrated hydratable salts in the detergent to improve the disperse solubility of the granular detergent in cold water. By mixing with the polyoxyalkylene alkyl ether, water does not act directly on the crystalline silicate, and during the granulation, it binds to the hydratable salt throughout the granules. It has different properties from that of water. Although the present invention granulates after crushing the spray-dried particles, separate devices may be used for crushing and granulating so that granulation proceeds while being crushed like a high speed mixer. Any device may be used.

Further, polyoxyalkylene alkyl ether is another compatible component (polyethylene glycol, polypropylene glycol, fatty acid (having 8 to 2 carbon atoms).
2) are preferable) and the like). 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 when crushing and / or granulating the spray-dried particles. Crushing and / or granulation by adding crystalline silicate at the time of granulation to surround the crystalline silicate with spray-dried particle crushed material and suppressing the amorphization of crystalline silicate due to moisture from the outside The amount of the crystalline silicate powder added at this time is 1 to 1 as the amount in the final composition from the viewpoint of the cleaning performance and the effect of suppressing the generation of the residue on washing.
0% by weight is preferred. 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, about 200 ml of ethanol was injected into the measuring cell of a laser diffraction type particle size distribution analyzer LA-910 type (manufactured by Horiba, Ltd.) to suspend about 0.5 to 5 mg of a sample. Then, while irradiating with ultrasonic waves, the mixture was stirred for 1 minute to sufficiently disperse the sample, and then a He-Ne laser (632.8 nm) was incident, and the particle size distribution was measured from the diffraction / scattering pattern.
In the analysis, the Fraunhofer diffraction theory and the Mie scattering theory are used together, and the particle size distribution of suspended particles in the liquid is 0.04 to
It was measured in the range of 262 μm. The average particle size is 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, it is preferable that the crystalline silicate used in the present invention is dispersed inside in order to suppress insolubilization and insolubilization involving surrounding components that occur after amorphization, and the crystalline silicate used in the present invention will be specifically described below. The crystalline silicate used in the present invention is
It exhibits a pH of 11 or more in a 0.1% by weight dispersion 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
O (where M represents an alkali metal) of 1.5 to 2.6 is 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
It should be noted that silicates with a ratio of over 2.6 will have poor detergency, and if it is less than 1.5, the physical properties of powder may be degraded.

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 (1) ( 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 the group VIII elements, y / x = 1.5 to 2.6,
z / x = 0.01 to 1.0, n / m = 0.5 to 2.0, w = 0 to 20
Is. _{) M 2 O · x'SiO 2 ·} y'H 2 O (2) ( 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 (1), 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 as 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 Mg and Ca are preferable from the viewpoint of resources and safety. Also,
These may be used alone or in combination of two or more,
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 1.5 to 2.6, preferably 1.5 to 2.2. If y / x is less than 1.5, 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
It is ~ 0.9. 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, z are y /
It is not particularly limited as long as it has a relationship as shown by 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 ′.
+ X becomes ". 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 ~2.0 is coordinated to the element Indicates the number of oxygen ions, which is substantially 0.5, 1.0, 1.5
, Value of 2.0.

The crystalline silicate of 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 for 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 of the desired crystalline silicate can be 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.

Further, 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.
Although it means less than mg / g, in the present invention, 10
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 (2) M ₂ O · x′SiO ₂ · y′H ₂ O (2) (wherein M represents an alkali metal, and x ′ = 1.5 to 2.6, y ′.
= 0 to 20. ), X'and y'in the general formula (2) 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. Further, 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 the fluidity of spray-dried particles and for improving the tackiness for the purpose of controlling the 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. Mixing multiple types of inorganic powder particles,
It is also possible 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. Such inorganic powder fine particles include aluminosilicate, silicon dioxide,
Examples thereof include amorphous silica derivatives and sodium carbonate (dense ash).

Further, in the production method of the present invention, by adding the nonionic surfactant also in the spray-dried particles, the total amount of the nonionic surfactants in the final detergent particles can be increased and further washing can be performed. The performance can be improved.
The inclusion of the nonionic activator in the spray-dried particles can be achieved by blending the nonionic activator in the detergent slurry to be spray-dried and spray-drying. The nonionic surfactant present in the spray-dried particles has an alkyl chain length of 12 to
15, higher alcohols having an average carbon number of 12 to 13 to which ethylene oxide is added in an average of 7 to 12 mol are preferable. Further, the nonionic surfactant to be present in the spray-dried particles is blended in the final composition so as to be 0.5 to 5% by weight. Moreover, you may mix | blend an aluminosilicate in a slurry. 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, It is preferably mixed in an amount of 10 to 40% by weight.

It is not preferred to incorporate the crystalline silicate into the detergent slurry in an attempt to previously incorporate the crystalline silicate into the spray dried particles. This is because the detergent slurry contains a large amount of water (usually 30 to 50%) and is 60 ° C.
More often than not. Therefore, if a crystalline silicate is added to such a detergent slurry, it will be immediately dissolved to form an amorphous silicate. Conversely, the amorphous silicate can be incorporated into the detergent slurry and present in the spray dried particles.
The presence of amorphous silicates in the spray-dried particles improves the handling properties of the spray-dried particles with appropriate strength, and solidifies and flows even after granulation into high-bulk density detergent particles. Is improved. 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 salt 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 agent 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 and the like, and is dry blended with the present high bulk density granular detergent.

[0035]

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.

[0036]

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%.

[0038]

[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; polyoxyethylene alkyl ether [carbon of the alkyl group 12 to 14 (average 12.8)
Average of 8 ethylene oxide in primary saturated alcohol
Mole-added] 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 that time, a nonionic surfactant (polyoxyethylene alkyl ether obtained by adding 6 mol of ethylene oxide to a primary saturated alcohol having 12 carbon atoms in the alkyl group, water content 10% by weight) 4
The treatment was carried out while spraying and adding parts by weight. 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)
1 part by weight (manufactured by K.K. Co., Ltd.) was mixed with a V blender to perform a treatment which also served as a complement to the surface coating of the particles, to obtain a final granular detergent.

Example 2 As a nonionic surfactant added at the time of crushing and granulating the spray-dried particles in Example 1, an alkyl group having a carbon number of 12 and a primary saturated alcohol having a carbon number of 60% by weight and 40% by weight was used. Amorphous aluminosilicate powder (0.8Na ₂ O.Al ₂ O ₃ .6 was used as inorganic powder fine particles added 30 seconds before the end of granulation, using polyoxyethylene alkyl ether to which ethylene oxide was added on average 15 mol. A granular detergent was obtained in the same manner as in Example 1 except that 0.5 SiO ₂ and an average particle diameter of 2.1 μm) were used.

Comparative Example 1 A granular detergent was prepared in the same manner as in Example 1 except that the volatile content of the spray-dried particles was 8%.

Comparative Example 2 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 3 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 4 Granulation was carried out 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. The results are shown in Table 2.

(1) Evaluation of Detergency 5 pieces of 10 × 10 cm artificially contaminated cloth coated with dirt having the following composition were put in 1 liter of an aqueous detergent solution for evaluation, and a targotometer 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 in tap water Detergency is measured with a colorimeter to measure the reflectance of the original cloth before contamination (carbon black is commonly 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 L _{1 of} original cloth; reflectance L _{2 of} soiled cloth before washing; Reflectance (2) Evaluation of residual residue residue Matsushita Electric Industrial Co., Ltd. full-automatic washing machine 5.0kg "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 1/8 of the test cloth 0; 5 test cloths with no white deposits are evaluated for the front and back sides, 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.

[0047]

[Table 2]

As can be seen from Table 2, if the water content of the spray-dried particles is too high, or if the particle size of the crystalline silicate powder used is too large, the detergency is reduced and a residue remains, which is practically used. I have a 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%.

[0050]

[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 surfactants; polyoxyethylene / polyoxypropylene alkyl ethers [carbon of alkyl group 12-
14 (average 12.8) primary saturated alcohol with an average of 10 moles of ethylene oxide and 5 moles of propylene oxide added] -Tinopearl CBS-X; fluorescent dye, distyryl biphenyl derivative (manufactured by Ciba Geigy) -Whitex 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 spray-dried particles obtained above Crystalline silicate powder [SKS-6 (powder); crushed from Hoechst Tokuyama Co., Ltd., 8 parts by weight of average particle diameter = 27 μm (same as in Example 1)] were added to anhydrous potassium carbonate powder (Asahi Denka Co., Ltd.).
10 parts by weight of the nonionic surfactant (alkyl group having 1 to 12 carbon atoms)
4 parts by weight of polyoxyethylene alkyl ether in which 7 mol of ethylene oxide was added to the graded saturated alcohol on average was sprayed and mixed. 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.) for consolidation. 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. 4 parts by weight of powdered zeolite and enzyme (sabinase 12.0T; Novo;
90% by weight of the product and Lipolase 100T; 10% by weight of the product of Novo are mixed with the enzyme granules) 1 part by weight is mixed with a V blender to perform a treatment which also serves as a complement to the particle surface coating, and the final granules are obtained. I got a detergent.

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

Comparative Example 5 A granular detergent was prepared in the same procedure as in Example 3 except that the volatile content of the spray-dried particles was changed to 6%.

Comparative Example 6 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 7 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 in a V blender for 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] With respect to Examples 3 and 4 and Comparative Examples 5, 6 and 7, the bulk density and the average particle size of the obtained granular detergent, the detergency and the residual residue are
It evaluated similarly to Examples 1-2 and Comparative Examples 1-4. The results are shown in Table 4.

[0057]

[Table 4]

Example 5 In place of the crystalline aluminosilicate powder as the inorganic powder fine particles added in the pulverization and granulation of the detergent molded product in Example 3 to coat the surface of the detergent particles, sodium carbonate (dense grain ash) is used. 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C11D 3:08) (72) Inventor Shuji Takana 1334 Minao Minato, Wakayama City, Wakayama Prefecture (56) References 2-178398 (JP, A) JP-A-4-36398 (JP, A) JP-A-9-87690 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1/00 -17/08

Claims (10)

(57) [Claims] 1. A method for producing a high bulk density granular detergent having a bulk density of 0.65 g / cm ³ or more by crushing and granulating spray-dried particles containing a non-soap anionic surfactant, Volatile content in spray-dried particles is 1.5
˜5%, and at the time of crushing and / or granulating the spray-dried particles, add polyoxyalkylene alkyl ether and crystalline silicate powder having an average particle size of 1-40 μm to the spray-dried particles. A method for producing a high bulk density granular detergent comprising: 2. 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. 3. The polyoxyalkylene alkyl ether, wherein the higher alcohol whose alkyl chain has 12 to 15 carbon atoms and whose average value is between 12 and 13 has 4 to 12 ethylene oxide on average. The method for producing a high bulk density granular detergent according to claim 1 or 2, wherein the detergent is added in a mole. 4. The method for producing a high bulk density granular detergent according to claim 1, wherein the amount of the polyoxyalkylene alkyl ether added is 0.5 to 8% by weight in the final granular detergent. 5. The method for producing a high bulk density granular detergent according to claim 1, wherein the amount of the crystalline silicate powder added is 1 to 10% by weight in the final granular detergent. 6. The crystalline silicate is SiO ₂ / M ₂ O =
1.5 to 2.6 (M periodic Ia group element Table) high bulk density method for producing a granular detergent as claimed in any one of claims 1 to 5 is. 7. The crystalline silicate has the following general formula (1):
The method for producing a high bulk density granular detergent according to claim 6 , which is a compound represented by: _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (1) ( 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 the group VIII elements, y / x = 1.5 to
2.6, z / x = 0.01 to 1.0, n / m = 0.5 to
2.0 and w = 0 to 20. ) 8. The method for producing a high bulk density granular detergent according to claim 6 , wherein the crystalline silicate is a compound represented by the following general formula (2). M ₂ O · x′SiO ₂ · y′H ₂ O (2) (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. ) 9. By adding inorganic powder fine particles having an average particle diameter of 0.1 to 10 μm during or after granulation,
The method for producing a high bulk density granular detergent according to any one of claims 1 to 9 , comprising a step of coating the surface of the detergent particles with inorganic powder fine particles. 10. The manufacturing method according to claim 1.
Manufactured by the method , the average particle size inside the final detergent particles
Most of the crystalline silicate powder having a particle size of 1 to 40 μm is present in a dispersed state and is not substantially exposed on the surface of the final detergent particles.