JPH0633437B2 - High bulk density granular detergent composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high bulk density granular detergent composition having good solubility.

2. Description of the Related Art Conventional detergents are made into bead-shaped hollow particles having an average particle size of about 200 to 800 μm by spray drying for the purpose of improving solubility. As a result, the bulk density is as low as 0.3 g / cc,
There is a drawback that not only the transportation cost is high, but also a considerable space is required for storage and display. In addition to this, there are problems such as a problem in the place of storage in general households and difficulty in weighing.

Further, in this spray drying method, detergent components such as a surfactant and a builder are mixed with added water to form a slurry having a water content of 35 to 50 wt%, and then the slurry is heated and spray dried to form granules. Therefore, it is necessary to remove 30 to 40% of water by drying, and there is a problem that a large amount of energy is consumed.

Therefore, the development of a high bulk density detergent that solves the above drawbacks of the present spray-dried detergent and can be washed with a small amount of detergent has been struggling.

As a method for producing a granular detergent that does not depend on the spray drying method, Japanese Patent Publication No. 46-7586, Japanese Patent Publication No. 49-74703, and Japanese Patent Publication No. 55-
In JP 49535, etc., a substance having crystal water in advance as a raw material or a substance which is easily melted by heating is used, and thermal operation is performed to release crystal water or cause melting of a melted product, which is used as a binder. There is a method of coagulating and granulating several to several tens.

However, these methods are not practical methods because they have problems such as a wide particle size distribution of the obtained granular detergent and poor solubility in water.

Further, JP-A-53-43710 discloses a method for producing a high bulk density detergent in which porous beads mainly composed of an inorganic builder are sprayed with a nonionic surfactant. However, since this detergent is mainly composed of a nonionic surfactant, it has a low foaming property and is not suitable as a detergent which requires high foaming properties like Japan. Further, in this manufacturing method, the spray drying method is used to manufacture the inorganic porous beads, which is a complicated and energy-consuming manufacturing method.

The present inventors produced a high bulk density detergent by first kneading the detergent composition intimately, mixing and kneading the kneaded product, and then coating with a water-insoluble fine powder having an average primary particle size of 10 μm or less. A method was proposed (Japanese Patent Laid-Open No. 60-96698). However,
Although the detergent obtained by this method has an excellent powder substance, its solubility in water is not always sufficient, and further improvement has been struggled.

OBJECT OF THE INVENTION It is an object of the present invention to obtain a high bulk density detergent having dramatically improved solubility in cold water.

Composition of the Invention The high bulk density granular detergent composition of the present invention has a bulk density of 0.5 to 1.2 g / cc, and is a composition obtained by coating a crushed product of a detergent composition mixture with a water-soluble fine powder having an average particle size of 10 μm or less. And the weight ratio of the following components (a) and (b) is (a) / (b) = 2
(A) Anion containing at least 10% by weight or more of a potassium salt of a linear alkylbenzene sulfonic acid having an alkyl group having 8 to 16 carbon atoms in the detergent composition. Surfactant: 20-50% by weight.

(b) Nonionic surfactant obtained by adding 8 to 30 mol of ethylene oxide to a primary or secondary alcohol having 8 to 18 carbon atoms, or ethylene oxide to a primary or secondary alcohol having 8 to 18 carbon atoms on average. ˜20 mol and nonionic surfactant added with propylene oxide on average 3 to 15 mol: 1 to 5% by weight.

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

The anionic surfactant as the component (a) is contained in the detergent composition in an amount of 20 to 5
0% by weight, preferably 25-40% by weight. If the blending amount is less than 20% by weight, the detergency is low and there is a practical problem, and if it exceeds 50% by weight, the production becomes difficult.

The anionic surfactant as the component (a) has an average carbon number of 8
It is necessary to use at least potassium salt of linear alkylbenzene sulfonic acid having 16 to 16 alkyl groups (LAS-K), and LAS-K is added so as to be contained in the detergent composition in an amount of 10% by weight or more. When the amount of LAS-K is less than 10% by weight, the solubility is poor and it is not preferable. The amount of the anionic surfactant can be entirely occupied by LAS-K, or the anionic surfactant can be used in combination with other surfactants to form an anionic surfactant mixture. Specific examples of these anionic surfactants include linear alkylbenzene sulfonates having an alkyl group having an average carbon number of 8 to 16, olefin sulfonates having an average carbon number of 10 to 20 and alkyl sulfates having an average carbon number of 10 to 20. , An alkyl ether sulfate obtained by adding an average of 0.5 to 8 mol of ethylene oxide to an alcohol having an average of 10 to 20 carbon atoms, and the like. As the salt in these anionic surfactants, sodium, potassium, ethanolamine, ammonium salt and the like can be used, and the potassium salt is preferable from the viewpoint of solubility.

The α-olefin sulfonate has a function of improving the storage stability of the high bulk density granular detergent composition and preventing blocking during storage. In order to fully exert this effect, it is preferable to mix the detergent composition so that the α-olefin sulfonate is contained in an amount of at least 5% by weight.

As the nonionic surfactant as the component (b), the following (b-1) or (b-2) is used.

(b-1): An average of 8 to 30 moles of ethylene oxide (EO) was added to a primary or secondary alcohol having an average of 8 to 18 carbon atoms.
EO nonionic surfactant.

(b-2): EO-PO type nonionic surfactant obtained by adding 8 to 20 EO on average and 3 to 15 mol on average propylene oxide (PO) to primary or secondary alcohol having 8 to 18 carbon atoms.

The EO-type nonionic surfactant is poor in the effect of improving the solubility when the number of moles of EO added is less than 8, and on the other hand, when it exceeds 30 moles, kneading becomes difficult, which is not preferable in production. The same applies to the EO-PO type nonionic surfactant, and if the number of added moles of EO and PO is small, the effect of improving solubility is poor, while if it is too large, manufacturing problems occur. The preferred EO-added mole number of the EO nonionic surfactant is 10 to 20.
In the O type, those having additional mole numbers of EO = 8 to 15 and PO = 5 to 15 are preferable.

Among the nonionic surfactants as the component (b), those in which the alcohol has a branched chain, particularly EO nonionic surfactants of secondary alcohols are preferable.

The nonionic surfactant as the component (b) is blended so as to be contained in an amount of 1 to 5% by weight based on the detergent composition. If the content is less than 1% by weight, the effect of improving the solubility cannot be sufficiently obtained, while if it exceeds 5% by weight, foaming is reduced, which is not preferable.

Furthermore, the nonionic surfactant of the component (b) is (a) / (b) = 20/1 to 3/1, preferably 10/1 to 4 / based on the anionic surfactant of the component (a). It is necessary to mix them in a ratio of 1. If this value is less than 20/1, the solubility improving effect is poor, while if it exceeds 3/1, the foaming power is reduced, which is preferable.
Manufacturing is also difficult.

Although the reason why the nonionic surfactant of the present invention improves the solubility is not clear, it forms a hydrate, particularly a liquid crystal, when the anionic surfactant comes into contact with water during dissolution to form an extremely viscous substance. And inhibits the solubility, but it is considered that the formation of the hydrate is blocked by the nonionic surfactant.

In the high bulk density detergent composition of the present invention, various optional components can be added, if necessary, in addition to the above-mentioned anion activator and nonionic activator. For example, as a so-called chelate builder that captures hardness components in the washing liquid, zeolite, sodium citrate, sodium nitrilotriacetic acid (N
TA), ethylenediaminetetraacid (EDTA), polyacrylic acid, polyacetal carboxylate, etc .; sodium silicate, sodium carbonate, potassium carbonate as an alkali builder,
Sodium metasilicate, sodium borate, etc .; In addition, oxygen such as protease, amylase, lipase, cellulase, bleaching agents such as sodium percarbonate and sodium perborate, reducing agents such as sulfites, fluorescent agents, fragrances, etc. are required. Can be used depending on.

The high bulk density detergent composition of the present invention is disclosed in, for example, JP-A-60-9669.
As described in Japanese Patent Publication No. 8, the detergent components are kneaded, mixed, crushed, and then coated with a water-insoluble fine powder having an average primary particle size of 10 μm or less. The detergent composition obtained has a bulk density of 0.5 to 1.2 g / cc.

Upon kneading and mixing, it is preferable to use, as the linear alkylbenzene sulfonate, one obtained by neutralizing alkylbenzene sulfonic acid with concentrated sodium hydroxide or potassium hydroxide aqueous solution. In particular, by using potassium hydroxide as the neutralizing agent, the solubility of the obtained high-bulk density granular detergent in cold water can be further improved. The concentrated aqueous solution of potassium hydroxide is preferably such a concentration that does not bring in a detrimental amount of water when it is kneaded and mixed with other detergent components to be crushed, and the concentration is 40% by weight or more, preferably Is 45% by weight or more. Also, in this neutralization step, along with the alkylbenzene sulfonic acid,
Other sulphates or sulphonates such as alkyl sulphates can also be used.

Further, zeolite is added to the granular detergent composition in an amount of 5 to 35% by weight.
It is preferably compounded so as to be contained, and more preferably 10 to 30% by weight. Zeolite is also used as a water-insoluble fine powder in the subsequent step, but 70% or more of the amount contained in the final composition, preferably 80% or more is added in the kneading step in the kneading step. Is preferred. When the blending amount of zeolite in the kneading process is small,
The kneaded product obtained becomes soft, and the kneaded product must be cooled prior to crushing, or a large amount of powder such as zeolite must be added as a crushing aid during crushing. is there. Addition of a large amount of disintegration aid causes a problem of dust generation.

From the viewpoint of facilitating the handling of the kneaded product and improving the properties as a crushing raw material in the subsequent step, the kneaded product should have a water content of 5 to 15% by weight. It is preferable to adjust the water content and mix the components.
If the water content is too small, it is easily pulverized and dust is generated at the time of crushing. On the other hand, if the water content is too large, the adherence to the inside of the crusher becomes remarkable and the crusher melts to make continuous operation difficult. Here, the water content is an amount that also includes crystal water such as zeolite.

The detergent raw material compact that has been uniformly kneaded with a kneader or the like is then crushed by a crusher and granulated. At the time of crushing, the temperature of the crushed material rises due to frictional heat, so it is preferable to introduce cold air, for example, cool air of 20 ° C. or less, into the crusher for treatment, and it is desirable to introduce 10 or more cold air per kg of crushed material. .

For crushing, use a crusher equipped with a classifying function such as screen classifier, wind classifier or the like, or classify the crushed product with a sieve and recycle the undesired particle size product to obtain a narrow range. It is desirable to granulate to a particle size distribution, for example, an average particle size of 300 to 2000 μm. As the crusher, a crusher having a multistage rotary crushing blade and discharging the crushed material through a 360 ° release screen is used. This type of crusher can set an arbitrary upper limit particle size by adjusting the opening of the screen, and prevents over-crushing by shortening the residence time of the crushed material in the crushing chamber, It is possible to obtain a sharp particle size distribution in which the amount is extremely small.

The granulated product obtained by the crushing is then coated with a water-insoluble fine powder for surface modification. In addition, the water-insoluble fine powder referred to in the present invention includes a poorly water-soluble fine powder.

As the water-insoluble fine powder, those having an average primary particle size of 10 μm or less, preferably 4 μm or less are used. If the particle size is too large, the coating will not be uniform and, as a result, the fluidity and storage stability will not be improved.

As the coating device, any of a rolling type, a fluidized bed type, a mixing type and the like is used, and the water-insoluble fine powder adheres to the surface of the granulated product. The amount of the water-insoluble fine powder added during coating is preferably 0.5 to 5% by weight based on the granulated product. Specific examples of the water-insoluble fine powder include calcium stearate, magnesium stearate, aluminosilicates such as type A zeolite, calcium carbonate, magnesium carbonate, magnesium silicate, silicon dioxide (white carbon), titanium dioxide and the like. By coating in this manner, adhesion between detergent particles is suppressed and blocking due to storage is prevented. Further, the coating of the fine particles improves the surface properties and improves the fluidity, and the surplus water remains in the particles to improve the solubility.

Furthermore, the granular detergent obtained as described above may be used as a product as it is by adding a trace amount of components such as fragrances, or as a cyclone-like product by entraining it in marmelizer (Fuji Paudal (substitute)) or air flow. It is also possible to adjust the water content by introducing it into the above apparatus to bring it into contact with the wall surface, to uniformize the particle shape into a substantially spherical shape, or by drying with a slight amount of warm air.

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a detergent composition having a good solubility in cold water, a large bulk density, and a large content of an active agent.

Example 1 Using a non-pulsating pump, the mixture was introduced into a static mixer (SWJ25-12, manufactured by Toray) at the following ratio and neutralized to produce high-concentration linear alkylbenzenesulfonate potassium.

C _{10 ~ 14} linear alkyl benzene sulfonic acid having an alkyl group of (active ingredient 96%) 17.9kg / Hr potassium hydroxide (48% solids aqueous solution) 7.1 kg / Hr resulting neutralized product is the active ingredient 82% And, the medium reaction rate was 99% or more. At this time, in order to prevent deterioration of the color tone of the neutralized product due to the heat of the neutralization reaction, jacket cooling water at 10 ° C. was flowed at 5 / min. Neutralized product discharge temperature is 50 ℃, low concentration neutralization (active ingredient
A color tone similar to that of a 35% aqueous solution) was obtained.

Next, a predetermined amount of detergent components shown in Table 1 below such as a nonionic surfactant were mixed with a ribbon mixer and charged into a powder quantitative feeder.

Then, this powder mixture and the above-mentioned potassium linear alkylbenzene sulfonate were kneaded (Kurimoto Tekko KRC Kneader #
2 type), and a uniform kneaded product was obtained from the outlet.

The obtained uniform kneaded product was in the form of a sheet having a thickness of 3 mm and a width of 50 mm, and the temperature was 50 to 55 ° C.

To make this easier to crush, a pelleter (Fuji Paudal
5 mmφ x 5 mm, thrown into pelleter double EXDF-60)
Cylindrical pellets. The pellet temperature was the same as that of the kneaded product, and the product was discharged at 50-55 ℃. The pellets were quantitatively fed to a crusher (Okada Seiko Speed Mill ND-30).
At this time, cold air at 15 ° C. was introduced together with this crushed material at a ratio of 15 / kg of crushed material. The crusher rotates a crushing blade with a diameter of 15 cm at 3000 rpm with 4 stages of cross, the screen is 2 mmφ, the opening rate is 20%.
The punching metal of was used.

Next, 97 parts by weight of the obtained crushed product and 3 parts by weight of A-type zeolite having an average primary particle size of 3 μm are added to a rolling drum (D = 30 cmφ, L
= 60 cm), quantitative coating, coating at 30 rpm, distillation time 5 minutes, high bulk density 00.8-0.
A granular detergent composition having 9 (g / cc) was obtained.

The solubility and foaming of the obtained detergent composition were evaluated as follows and shown in Table 1.

Solubility Put water 1 at 25 ℃ in a beaker and insert a cell for measuring conductivity into it. Then, 1 g of each detergent composition particle having the composition shown in Table 1 was added to water, and a constant speed stirrer was used.
The mixture was stirred at a speed of 250 rpm, and the time taken for 90% of the added detergent particles to dissolve was measured and designated as T ₉₀ (seconds). Here, HORIBA CONDUCTIVE METER DS-8F type was used as the conductivity meter.

Foaming test A 10 wt% benzene solution of organic dirt containing the following dirt components was uniformly applied to a skin shirt so that the amount of fiber was 0.1 wt%, air-dried, and evaluated under the following conditions.

Soil composition Soil composition (wt%) Oleic acid 40.6 Triolein 22.4 Cholesterol oleate 17.5 Liquid paraffin 3.6 Squalene 3.6 Cholesterol 2.3 Gelatin 10.0 Evaluation method Using a washing machine and 3 ° DH water, bath volume 30, bath ratio 1: 3
Under the washing conditions of 0, detergent concentration 0.083% and temperature 25 ° C, after washing the skin shirt with the organic dirt for 10 minutes, the bubbles are leveled over the entire liquid surface and the bubble height is measured at any three locations. Then, the foaming power was evaluated by the average foam height.

Here, foaming of 15 mm or more was judged to be good.

Further, the abbreviations and details of the detergent components in Table-1 are as follows.

LAS-K: linear alkylbenzene sulfonate potassium having 10 to 14 carbon alkyls AOS-Na: sodium α-olefin sulfonate having 14 to 18 carbon atoms Zeolite: synthetic A-type zeolite (Mizusawa Chemical “Silton B”) polyacetal Carboxylate: Sodium polyacrylate: Powdered silica: Na ₂ O: SiO ₂ = 1: 2.2, water content 22% (Nippon Kagaku) Sodium carbonate: reagent product Potassium carbonate: reagent product

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Claims (1)

[Claims] 1. A crushed product of a detergent component mixture has an average particle size of 10 μm.
A composition coated with the following water-insoluble fine powder, wherein the following components (a) and (b) are used in a weight ratio of (a) / (b) = 2
Bulk density of 0.5 to 1.2 characterized by including in the range of 0/1 to 3/1
High bulk density granular detergent composition of g / cc. (a) Anionic surfactant containing at least 10% by weight or more of a potassium salt of a linear alkylbenzene sulfonic acid having an alkyl group having 8 to 16 carbon atoms in the detergent composition: 20 to 50% by weight (b) 8 to 8 carbon atoms Nonionic surfactant obtained by adding 8 to 30 mol of ethylene oxide to 18 primary or secondary alcohols on average, or 8 to 20 mol of ethylene oxide on average and propylene oxide to primary or secondary alcohol having 8 to 18 carbon atoms. Nonionic surfactant added 3 to 15 mol on average: 1 to 5% by weight