JPH11302698A - Production of high-bulk-density granular detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a high-bulk-density granular detergent into which a nonionic surfactant can be compounded stably in a large amt. SOLUTION: In a process for producing a high-bulk-density granular detergent having a bulk density of 0.65 g/cm<3> or higher by crushing and granulating spray- dried particles contg. a nonsoapy anionic surfactant, the volatile content of the spray-dried particles is set at 1.5-5 wt.%; and a nonionic surfactant, a fatty acid, and a crystalline silicate powder are added to the spray-dried particles when the particles are crushed and/or granulated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a high bulk density granular detergent composition.

[0002]

2. Description of the Related Art Conventionally, low-density detergents obtained by a spray-drying method have been mainly used as powder detergents. In recent years, however, high-density detergents having been miniaturized for convenience in transporting, carrying and placing detergents have been developed. Has been launched. Such high-density detergents
Generally, it is obtained by obtaining spray-dried particles from an aqueous slurry containing a surfactant and a detergent builder and densifying the particles. Various methods are known for this densification method. For example, Japanese Patent Application Laid-Open No. Sho 51-67302 discloses a method for densifying spray-dried particles using a specific granulation apparatus called a marmellaizer (trade name). Are listed.

In recent years, so-called vertical mixers such as high-speed mixers (stirring-rolling granulators) and Henschel mixers (high-speed stirring granulators), and so-called vertical mixers such as Loedige mixers have been used. A method of achieving high density by stirring and granulating with a so-called horizontal mixer is known. Examples thereof include stirring and granulating spray-dried particles as disclosed in JP-A-61-69897. A high bulk density granular detergent;
No. 0 and JP-A-62-266897, a method of forming a spray-dried particle into a compact and then pulverizing and granulating it to obtain a high bulk density granular detergent.

[0004] Today, further reductions in the amount of use of such compact, high-bulk density granular detergents have been attempted. In the past, the amount of detergent used 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 exhibiting a cleaning effect with a smaller amount, a technique for stably blending a higher-performance component than before is required.

[0005]

Generally, the higher the concentration of the activator in the detergent, the better the cleaning performance. However, increasing the amount of anionic surfactant in the detergent causes problems such as a decrease in bulk density of the product and solidification during long-term storage. In the case of a detergent containing anionic surfactant as a main base, anionic surfactant As the content of the agent increases, the amount of the nonionic surfactant that can be blended decreases, and if the nonionic surfactant is blended beyond the amount that can be blended, a problem such as seepage from the product surface occurs. The exudation of nonionic surfactant can be suppressed by blending an oil-absorbing carrier, etc.
In that case, a substance that does not contribute much to the cleaning performance will be compounded, causing problems such as a decrease in bulk density and an increase in the amount used.

[0006]

SUMMARY OF THE INVENTION The present invention provides a high bulk density granule 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. In the method for producing a detergent, a volatile content in the spray-dried particles is 1.5 to 5% by weight, and a nonionic surfactant is added to the spray-dried particles during crushing and / or granulation of the spray-dried particles; It is intended to provide a method for producing a high bulk density granular detergent, characterized by adding a fatty acid and a crystalline silicate powder.

That is, in the production method of the present invention, the nonionic surfactant (1) is used at the time of crushing and / or granulation, that is, before the granulated particles are completed, using the spray-dried particles,
By adding a fatty acid (2) and a crystalline silicate powder (3) to produce a granular detergent, it is possible to reduce as much as possible the water in the system involved in the amorphization of the crystalline silicate, By adding a surfactant and a fatty acid, a portion where granulation is difficult to progress due to a reduction in volatile components can be supplemented and granulation can proceed. For this reason, the suppression of amorphization of the crystalline silicate is achieved, and the stable blending of the crystalline silicate becomes possible, and the blendable amount of the nonionic surfactant can be increased. Therefore, a high bulk density detergent with a smaller amount of use than before can be obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The production method of the present invention comprises first preparing an aqueous slurry containing a non-soap anionic surfactant, a detergent builder, and further, if necessary, any optional components. 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.

The non-soap anionic surfactants to be added to the slurry include alkylbenzene sulfonates, alkyl sulfates, α-olefin sulfonates, α-sulfofatty acid ester salts, alkyl and alkenyl salts commonly used in detergents. Ether sulfate, α-sulfo fatty acid salt, alkane sulfonate, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N-
An acyl amino acid type surfactant, an alkyl or alkenyl phosphate or a salt thereof is exemplified. As anionic surfactants, in particular, alkyl benzene sulfonate,
Alkyl sulfates are preferred. In addition, the non-soap anionic surfactant is used in an amount of 10 in the final high bulk density granular detergent.
To 40% by weight, preferably 15 to 35% by weight. In addition, a saturated or unsaturated fatty acid salt may be blended in the slurry in an amount of 0.5 to 10% by weight.

[0010] In the present invention, it is necessary that the obtained spray-dried particles have a volatile content of 1.5 to 5% by weight.
5% by weight is preferred. The volatile components in the spray-dried particles may be adjusted by any method such as adjusting the water content and the components in the slurry, adjusting the spray-drying conditions, and drying (secondary drying) the spray-dried particles. In the present invention, the “volatile content” means weight loss when dried at 105 ° C. for 2 hours, and is considered to be mostly water.

Next, the obtained spray-dried particles are crushed and granulated to produce a 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 crushed. During granulation, a nonionic surfactant, a fatty acid and a crystalline silicate powder are added. As the method, spray-dried particles are mixed with a crystalline silicate and other detergent raw materials in a vertical or horizontal stirring granulator (exemplified in JP-A-61-69897 and JP-A-61-69900). A method in which fatty acids are individually added when stirring and granulating using a nonionic surfactant as a binder, or a method in which a liquid prepared by mixing and preparing a nonionic surfactant and a fatty acid in advance is added and agitated and granulated. Is mentioned. Also, the spray-dried particles and the crystalline silicate, nonionic surfactant, fatty acid and other detergent raw materials are kneaded or mixed by a kneader or a ribbon mixer, and then compacted into a cylindrical shape by an extruder or two rolls. And compacting them into a sheet, and granulating these compacts with a pulverizing (crushing) granulator such as a hammer mill, a cutter mill or a speed mill.

The nonionic surfactant used for crushing and / or granulating the spray-dried particles is preferably a polyoxyalkylene alkyl ether. Among them, an alcohol having an alkyl chain length of 12 to 22 is mixed with ethylene oxide and / or propylene oxide. Polyoxyethylene obtained by adding ethylene oxide to a higher alcohol having an alkyl chain length of 12 to 15 and an average carbon number of 12 to 13 on average of 4 to 12 moles, preferably 4 to 10 moles, is preferred. Alkyl ethers are preferred.

In the present invention, a fatty acid is added at the time of crushing and / or granulating the spray-dried particles. This has the effect of reacting with a part of the crystalline silicate to support the nonionic surfactant in the gel structure, thereby suppressing the exudation of the nonionic surfactant. Such fatty acids are saturated or unsaturated fatty acids having 8 to 22 carbon atoms, preferably saturated or unsaturated fatty acids having 12 to 18 carbon atoms, and specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid And a mixture of one or more selected from the group consisting of saturated fatty acids such as oleic acid and unsaturated fatty acids such as oleic acid. The weight ratio of polyoxyalkylene alkyl ether to fatty acid is from 1: 1 to 20: 1, preferably 1.
The ratio is 5: 1 to 10: 1, particularly preferably 2: 1 to 7: 1. The nonionic surfactant added at the time of crushing and / or granulation is preferably added so as to be 0.5 to 10% by weight in the final composition. When the addition of the nonionic surfactant and the fatty acid is performed within this range, good granulation can be performed, and the cleaning performance is improved. In addition, the resulting granular detergent has good fluidity and anti-solidification properties.

It is preferable to use polyethylene glycol in combination with the nonionic surfactant and the fatty acid which are added at the time of crushing and / or granulating the spray-dried particles. It is useful for preventing the crystalline silicate from becoming amorphous, and the particle size distribution of the granulated material is more uniform, so that high quality of the product can be expected. Polyethylene glycol has an average molecular weight of 1,000
~ 20,000 are preferred. Further, it is preferable that the polyethylene glycol is blended so as to be 0.5 to 3% by weight in the final composition.

In the present invention, when crushing and / or granulating the spray-dried particles, a crystalline silicate powder is added together with the above-mentioned nonionic surfactant and fatty acid. By adding the crystalline silicate during granulation, the crystalline silicate is surrounded by the crushed spray-dried particles, thereby suppressing the crystalline silicate from becoming amorphous due to moisture from the outside. It is preferable to add the crystalline silicate powder so as to be 1 to 10% by weight in the final composition.

The average particle size of the crystalline silicate powder is 1
４０40 μm is preferred. If the particle size is too small, it becomes more amorphous due to contact with moisture, and the cleaning performance and quality tend to deteriorate. If the particle size is too large, it tends to remain as dissolved residue in clothes and washing machines. The crystalline silicate having such an average particle size and particle size distribution can be prepared by crushing using a crusher such as a vibration mill, a hammer mill, a ball mill, and a roller mill. The average particle size and the particle size distribution of the crystalline silicate were measured using a laser diffraction type particle size distribution analyzer. That is, about 200 ml of ethanol was injected into a measuring cell of a laser diffraction type particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.), and about 0.5 to 5 mg of a sample was suspended. Subsequently, the mixture was stirred for 1 minute while irradiating ultrasonic waves to sufficiently disperse the sample.
-Ne laser (632.8 nm) was incident, and the particle size distribution was measured from the diffraction / scattering pattern. The analysis is Fr
The particle size distribution of suspended particles in the liquid is 0.04 to 262 μm by using both the aunhofer diffraction theory and the Mie scattering theory.
It measured in the range of. The average particle size was the median size of the particle size distribution.

Most of the crystalline silicate powder is present in a state of being dispersed inside the final detergent particles, and is substantially not exposed on the surface of the final detergent particles. It is preferable to prevent a decrease in washing performance due to crystallization and a decrease in alkali buffering ability due to carbon dioxide gas,
In order to suppress insolubilization and insolubilization involving surrounding components that occur after amorphization, it is preferable that the components are dispersed inside. Hereinafter, the crystalline silicate used in the present invention will be specifically described. Crystalline silicate used in the present invention,
It shows a pH of 11 or more in a 0.1% by weight dispersion and shows excellent alkalinity. After adding 0.1 g of crystalline silicate to 1 liter of ion-exchanged water and stirring for 3 minutes, the pH of the solution after sufficiently dissolving or dispersing the silicate is 11 or more. The alkaline buffer capacity is such that at least 3 ml or more until 0.1 pH of hydrochloric acid is added thereto until the pH reaches 10 is at least 3 ml.

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
Care should be taken when the silicate ratio exceeds 2.6, the detergency decreases, and when it is less than 1.5, the powder properties may decrease.

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, one or a combination of two or more elements selected from group IIIa, group IVa or group VIII, y / x = 1.5 to 2.6,
z / x = 0.01-1.0, n / m = 0.5-2.0, w = 0-20
It 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 Group Ia elements of the periodic table, and examples of 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 Group IIa, IIb, IIIa, IVa or Group VIII elements of the periodic table, and includes, for example, Mg, Ca, Zn, Y, Ti, Zr, Fe and the like. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. Also,
These may be used alone or as a mixture of two or more,
For example MgO, may constitute the Me _m O _n component by mixing and CaO. The crystalline silicate of 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. When y / x is less than 1.5, the powder properties of the detergent composition such as caking properties are adversely affected. When y / x exceeds 2.6, the detergency decreases. z / x is 0.01 to 1.0, preferably 0.02
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 lowered and the ion exchanger is insufficient. x, y, z are the above y /
The relationship is not particularly limited as long as the relationship is represented by x and z / x. When xM ₂ O is, for example, x ′ Na ₂ O · x ″ K ₂ O, 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, and is substantially 0.5, 1.0, 1.5
, 2.0.

The crystalline silicate having the composition according to the present invention may be composed of M ₂ O, SiO ₂ ,
It has become than the three components of Me _m O _n. Therefore, in order to produce the crystalline silicate of the present invention, each component is required as a raw material. In the present invention, a known compound is appropriately used without any 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
The raw materials of 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.

In the method for preparing a crystalline silicate having the composition according to the present invention, the above-mentioned raw material components are mixed in a predetermined quantitative ratio so that the desired values of x, y and z of the crystalline silicate are obtained. Usually, a method of firing and crystallizing at a temperature in the range of 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 lower than 300 ° C., crystallization is insufficient and the water resistance is poor, and if it exceeds 1500 ° C., coarse particles are formed and the ion exchange ability is reduced. Heating time is usually
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 according to the invention has an ion exchange capacity of at least 100 CaCO ₃ mg
/ G, preferably 200-600 CaCO ₃ mg / g.

The amount of Si eluted in water is usually 110 mg / g or less in terms of SiO ₂ , and is substantially insoluble in water.
In the present invention, the term “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,
Those having 0 mg / g or less are more preferable for satisfying the present 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, x ′ = 1.5 to 2.6, y ′)
= 0 to 20. Wherein 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. /
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 the official gazette, which is generally obtained by firing amorphous glassy sodium silicate at 200 to 1000 ° C. to make it crystalline. For details of the synthesis method, for example,
Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristal
logr., 129 , 396-404 (1969). The crystalline silicate is available in powder or granule form, for example, under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ) from Hoechst. In the present invention, the crystalline silicates having the above compositions can be used alone or in combination of two or more.

In the production method of the present invention, in order to obtain a high bulk density granular detergent having 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 particles by putting the body particles just before the end of the stirring granulation or by allowing the particles to be present when the compacted product is pulverized and granulated. It is preferable to add the inorganic powder particles in an amount of 1 to 10% by weight in the final composition from the viewpoint of the coating effect. The surface coating with the inorganic powder particles prevents the deterioration of the crystalline silicate in addition to the improvement of the powder properties. In addition, the inorganic fine particles can be used 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 adhesiveness for the purpose of controlling granulation. The amount of the inorganic powder particles used for such a purpose is not included in the amount of the inorganic powder particles used for the surface coating.
When adding inorganic powder fine particles, the entire amount may be added at once, or may be added gradually over a plurality of times. Mixing and using multiple types of inorganic powder fine particles,
It is also possible to add them separately. Also, 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 to the detergent particles and mixed. Also, the surface of the detergent particles can be coated with inorganic fine particles. In this case, the preferred amount of the inorganic fine particles is 0.5 to 8% by weight in the final composition. Such inorganic powder fine particles include aluminosilicate, silicon dioxide,
Examples include amorphous silica derivatives, sodium carbonate (dense ash) and the like.

Further, in the production method of the present invention, by including a nonionic surfactant also in the spray-dried particles, the total amount of nonionic surfactant in the final detergent particles can be increased, and further washing can be achieved. Performance can be improved.
The incorporation of the nonionic activator into the spray-dried particles is achieved by blending the nonionic activator into a detergent slurry to be subjected to spray drying and spray-drying. The nonionic surfactant present in the spray-dried particles has an alkyl chain length of 12 to
15, those obtained by adding on average 7 to 12 mol of ethylene oxide to a higher alcohol having an average carbon number of 12 to 13; The nonionic surfactant to be present in the spray-dried particles is blended in the final composition in an amount of 0.5 to 5% by weight. Further, an aluminosilicate may be blended in the slurry. As the aluminosilicate, generally known ones can be used, and in addition to crystalline A, X or P type zeolites, amorphous ones can also be used. The average particle size of the aluminosilicate is 0.1 to 10 μm, preferably 0.1 to 5 μm, and 8 to 50% by weight in terms of anhydrous in the final high bulk density detergent particles including the amount used as the coating agent. Preferably, the content is 10 to 40% by weight.

It is not preferable to incorporate a crystalline silicate into a detergent slurry in an attempt to incorporate a crystalline silicate into the spray-dried particles in advance. Because the detergent slurry contains a large amount of water (usually 30 to 50%),
Often this is the case. Therefore, when a crystalline silicate is blended in such a detergent slurry, it is immediately dissolved and becomes an amorphous silicate. Conversely, the amorphous silicate can be incorporated into the detergent slurry and be present in the spray-dried particles.
When the amorphous silicate is present in the spray-dried particles, the spray-dried particles have an appropriate strength to improve the handleability, and even after being granulated into high-bulk-density detergent particles, the solidification property and the fluidity are improved. Is improved. The preferred amount of the amorphous silicate is preferably 3 to 12% by weight with respect to the final detergent composition from the viewpoint of improving the physical properties of the powder and suppressing the generation of dissolved residues 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 a polyacrylate, a copolymer of maleic acid and acrylic acid or olefin, and a polyacetal carboxylate having an average molecular weight of 10,000 and preferably 15,000 or more in the detergent composition. Can be blended. These can be incorporated into the spray-dried slurry. These polymers or copolymers may be present in the composition in an amount of from 0.5 to
10% by weight, preferably 2 to 8% by weight is blended. By blending these polymers or copolymers,
Adhesion of a water-insoluble matter derived from a crystalline aluminosilicate to clothing in high-hardness washing is further suppressed.

In the production method of the present invention, other general detergent builders can be blended. Examples of the builder include inorganic builders such as carbonates such as soda ash, sulfates, sulfites, silicates, tripolyphosphates, pyrophosphates, and orthophosphates; and organics such as citrates, oxydisuccinates, and nitrilotriacetates. 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, and lipase, and generally commercially available granules can be used. Further, polyethylene glycol having an average molecular weight of 5,000 to 15,000 may be blended into the spray-dried particles in order to further improve the physical properties of the powder, or polyvinylpyrrolidone may be added to prevent color transfer. Other minor components include ordinary fragrances, foam inhibitors such as silica and silicone, biphenyl-type optical brighteners or stilbene-type optical brighteners, or optical brighteners 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.

In the production method of the present invention, a bleaching composition can be added. The bleach composition comprises sodium percarbonate, sodium perborate, preferably sodium percarbonate and various bleach activators, and is dry blended with the present high bulk density granular detergent.

[0033]

According to the present invention, there can be obtained a high bulk density granular detergent having high detergency, good fluidity, and almost no exudation of nonionic surfactant.

[0034]

【Example】

Example 1 (1) Preparation of spray-dried particles The following components were mixed with water to prepare a detergent slurry having a solid content of 50% by weight (temperature: 65 ° C). The detergent slurry was spray-dried with a countercurrent spray-drying device to obtain spray-dried particles. The volatile content of the obtained spray-dried particles (105 ° C., weight loss for 2 hours) was 4%. _{LAS-Na (C 10 ~C 13} ) 23 parts by weight of _{AS-Na (C 12 ~C 16} ) 5 parts by weight nonionic surfactant, 3 parts by weight Soap (C ₁₄ ~C ₂₀₎ 1 part by weight of zeolite 4A 6.3 Parts by weight No. 1 sodium silicate 11 parts by weight sodium carbonate 13 parts by weight sodium sulfate 1 part by weight sodium sulfite 0.5 part by weight AA / MA copolymer 4 parts by weight Tinopearl CBS-X 0.1 part by weight Whitex SA 0.1 part by weight (Note) The above symbols 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 sulfate Nonionic surfactant; polyoxyethylene alkyl (C ₁₂ ) ether (average number of moles of ethylene oxide added: 8) AA / MA copolymer; acrylic acid / maleic acid copolymer sodium salt (monomer ratio 3: 7, Mw) $ 5000
0, degree of neutralization ≒ 80 mol%) Tinopearl CBS-X; fluorescent dye, distyrylbiphenyl derivative (manufactured by Ciba Geigy) Whitex SA; fluorescent dye, bis- (triazinylamino) -stilbene-dylsulfonic acid derivative ( (Sumitomo Chemical Co., Ltd.).

(2) Preparation of granular detergent A nonionic surfactant (alkyl group having 12 carbon atoms)
6 averages of ethylene oxide in primary saturated alcohol
Mole-added polyoxyethylene alkyl ether) 4
A heated mixture of 2 parts by weight and 2 parts by weight of fatty acid (palmitic acid) is prepared and heated to 70 ° C. 74 parts by weight of the spray-dried particles obtained above and crystalline silicate powder (SKS-6;
10 parts by weight of Hoechst Tokuyama Co., Ltd.) were put into a vertical granulator (manufactured by Powrex Co., Ltd., capacity: 50 liters) equipped with a jacket at 70 ° C. together with 10 parts by weight, and the spray-dried particles were crushed and agitated and granulated. . At that time, the treatment was performed while spraying and adding 6 parts by weight of the mixed liquid of the nonionic activator and the fatty acid. End of granulation 3
0 parts before, 6 parts by weight of the same powder zeolite as that mixed with the spray-dried particles was added to perform surface coating. Next, this granulated material was sieved with a sieve having a mesh opening of 1.4 mm, and coarse particles on the sieve were pulverized with a Fitzmill (manufactured by Hosokawa Micron Corp.) and then mixed with the material passed through the sieve. 3 parts by weight of zeolite powder and 1 part by weight of an enzyme (API-21H; manufactured by Showa Denko KK) were added to the finished product.
The mixture was mixed with a blender to perform a treatment which also complemented the particle surface coating, to obtain a final granular detergent.

Example 2 A nonionic surfactant (an alkyl group having 12 carbon atoms)
6 averages of ethylene oxide in primary saturated alcohol
Mole-added polyoxyethylene alkyl ether) 5
A heated mixture of 1 part by weight of a fatty acid (palmitic acid) and 2 parts by weight of a fatty acid (palmitic acid) and 1 part by weight of a polyethylene glycol (average molecular weight: 6000) is prepared and heated to 70 ° C. 72 parts by weight of the spray-dried particles obtained in Example 1 and crystalline silicate powder (SK
S-6: pulverized Hoechst Tokuyama Co., Ltd.) 1
The spray-dried particles were stirred and granulated by adding the mixture together with 0 parts by weight to a Loedige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 liters) equipped with a jacket at 70 ° C. At that time, 8 parts by weight of a mixed solution of the nonionic surfactant, fatty acid and polyethylene glycol was sprayed. Thirty seconds before the end of granulation, 6 parts by weight of the same powder zeolite as that mixed with the spray-dried particles was added to perform surface coating. Thereafter, a granular detergent was obtained in the same manner as in Example 1.

COMPARATIVE EXAMPLE 1 In Example 1, a mixture of 4 parts by weight of a nonionic surfactant and 2 parts by weight of a fatty acid was used when the spray-dried particles were crushed and stirred and granulated.
Instead of spraying parts by weight, a nonionic surfactant (polyoxyethylene alkyl ether obtained by adding 6 moles of ethylene oxide on average to a primary saturated alcohol having 12 alkyl groups) was sprayed and added, followed by treatment. went. Otherwise, the procedure of Example 1 was repeated to prepare a powder detergent.

COMPARATIVE EXAMPLE 2 In Example 1, a mixture of 4 parts by weight of a nonionic surfactant and 2 parts by weight of a fatty acid was used when crushing and granulating the spray-dried particles by stirring.
Instead of spraying parts by weight, 4 parts by weight of nonionic surfactant (polyoxyethylene alkyl ether obtained by adding an average of 6 moles of ethylene oxide to a primary saturated alcohol having 12 carbon atoms in the alkyl group) is sprayed and added while treating. went. Otherwise, the procedure of Example 1 was repeated to prepare a powder detergent.

[Evaluation of Granular Detergent] The granular detergents obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated for bulk density and average particle diameter, fluidity, detergency, and seepage. Table 1 shows the results.

(1) Evaluation of Detergency An artificially stained cloth having the following composition was adhered to a cloth to prepare an artificially stained cloth. The artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater.
The step of making the artificially contaminated cloth by attaching the artificially contaminated liquid to the cloth includes a gravure roll cell capacity of 58 cm ³ / m ² , an application speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 hour.
Went in minutes. The cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten).

(Composition of artificial contaminated liquid) Lauric acid 0.44% by weight Myristic acid 3.09% by weight 2.31% by weight pentadecanoic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57 Weight% oleic acid 7.75 weight% triolein 13.06 weight% n-hexadecyl palmitate 2.18 weight% squalene 6.53 weight% egg white lecithin liquid crystal 1.94 weight% Kanuma red soil 8.11 weight% carbon black 0.01% by weight tap water balance.

(Cleaning Conditions and Evaluation Method) One liter of the aqueous detergent solution for evaluation was added to the 10 cm × 10 cm prepared above.
5 pieces of artificially stained cloth of
Washed at rpm. The washing conditions are as follows. Washing time: 10 minutes Washing concentration: 0.05% by weight Water temperature; 20 ° C. Water hardness; 4 ° DH rinsing; 5 minutes with tap water The cleaning power is 550 n of the original cloth before and after the cleaning.
The reflectance at m was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), the cleaning rate (%) was determined by the following equation, and the measured average value of the five sheets was shown as the cleaning power.

[0043]

(Equation 1)

(2) Evaluation of Bulk Density / Average Particle Size / Fluidity The bulk density was measured by the method specified in JIS K3362. The average particle size was measured from the weight fraction based on the size of the sieve after vibrating for 5 minutes using a standard sieve of JIS Z8801. The fluidity of the powder is measured according to JIS K3
From the hopper for bulk density measurement specified in 362, 10
The evaluation was based on the time required for 0 ml of the powder to flow out.

(3) Evaluation of bleeding 10.2 cm long × 6. Wide using filter paper (Toyo Filter Paper No. 2).
Make a 2cm x 4cm height box without a top, and staple the four corners. A 50 g sample is put in this box, and a total of 15 g of an acrylic resin plate and a lead plate (or iron plate) is placed thereon.
Put +250 g. This is left in a thermo-hygrostat at a temperature of 30 ° C. and a humidity of 80%, and a judgment is made after 7 days. For the judgment, the state of seepage of the nonionic activator at the bottom of the filter paper (the surface not in contact with the powder) was visually evaluated. The evaluation criterion was determined based on the wet area of the bottom, and was ranked from 1 to 5 ranks. The status of each rank is as follows. Rank 1: not wet. Rank 2: about 1/4 surface is wet. Rank 3: about 1/2 surface is wet. Rank 4: 3/4 surface is wet. Rank 5: The entire surface is wet.

[0046]

[Table 1]

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Claims (4)

[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
To 5% by weight, and adding a nonionic surfactant, a fatty acid, and a crystalline silicate powder to the spray-dried particles during crushing and / or granulation of the spray-dried particles. Method for producing high density granular detergent. 2. The method according to claim 1, wherein polyethylene glycol is further added to the spray-dried particles. 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 method according to claim 1, wherein the weight ratio of the nonionic surfactant to the fatty acid is 1: 1 to 20: 1.