JPS6166798A - Production of high density granular detergent having improved solubility - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a granular detergent, and more particularly, a free-flowing detergent containing a 7-ionic surfactant at a high density and concentration. [Prior art and problems] Conventionally, powdered detergents have been produced either by spray drying or by dry compounding.

Further, as cleaning active substances, mainly C, anionic and nonionic surfactants are usually used.

Some small and medium-sized detergent and cleaning agent manufacturers use the dry compounding method, which does not require large capital investment compared to the spray drying method. Mainly used.

Due to the washing habits in Japan, foaming during washing is considered a problem, and it is necessary to incorporate an anionic surfactant.
In the dry blending method, it is difficult to blend only a few percent or less of anionic surfactant in view of the viscosity and caking properties of detergent products. For this reason, major detergent manufacturers prepare an aqueous slurry containing an anionic surfactant and an inorganic builder, and spray-dry this to obtain a detergent product.

However, in recent years, with the emphasis on saving resources and energy, the bulk of detergents has become a problem in terms of transportation and for housewives to carry them.

From the perspective of energy saving, several methods have been proposed for producing detergents containing anionic surfactants that do not require gjtmt drying. A method for producing a powdered heavy duty detergent that is neutralized with soda carbonate is disclosed. However, this method requires heating, the resulting detergent often has insufficient solubility, and is soap-based, resulting in poor cleaning power. US Pat. No. 5,454,974 discloses a method of neutralizing an alkylbenzenesulfonic acid with sodium bicarbonate, sodium tripolyline, and the like. However, due to the use of sodium bicarbonate and the relatively large amount of water contained in this method, the resulting detergent was limited to rod-shaped detergents.

Further, US Pat. No. 3,597,361 discloses a method in which a concentrated solution of alkylbenzene sulfonic acid and sodium hydroxide is sprayed into a drum containing powder containing sodium tripolyphosphate as a builder and rotating nine times. However, this method has a major drawback in that zeolite cannot be used as a builder. The present invention was completed as a result of intensive research in order to obtain an energy-saving ultra-concentrated powder detergent with high free-flowing properties that contains a high concentration of anionic surfactant t-.

That is, 1. the present invention includes a step of neutralizing unneutralized sulfonated products and/or sulfated products (hereinafter referred to as unneutralized products), and a process in which all or part of the unneutralized products are neutralized by the neutralization step. To provide a method for producing a high-density granular detergent with improved solubility, characterized by comprising a step of cooling and aging the detergent, and a step of pulverizing or crushing and granulating it together with other detergent formulations. I can buy things.

The unintermediate phase sulfonated product or V&oxide used in the present invention is 1, for example, a straight or branched chain alkylbenzene sulfonic acid having an average carbon number of 10 to 16 alkyl groups;
Alkyl sulfate having an alkyl group with an average RIA number of 10-18, or an alkenyl group t-V and an average of 0.5 to 8 moles of ethylene oxide or ethylene oxide and butyrene oxide or butylene oxide in one molecule. Examples include alkenyl ether sulfate esters with mixed alkylene oxides added.

In carrying out the present invention, a combination system with toalkyl sulfate of linear or branched rubenzenesulfonate in alcohol satisfies production costs and cleaning performance, and has excellent crushing and granulation properties in the subsequent process. This is preferable because it allows you to obtain products. Further, in practice, a combination such as a combination of sodium alkyl sulfate and neutralized rubenzenesulfonic acid in alcohol, in which one is not neutralized, may also be used.

Things that neutralize the unneutralized substance used in the present invention include:
Alkaline substances such as sodium carbonate, sodium hydrogen carbonate, and sodium silicate can be used, but sodium carbonate is preferred from the viewpoint of reactivity, production cost, availability of raw materials, etc. These alkaline substances are preferably used in an amount of 2 to 10% per mole of unneutralized material. Sodium carbonate may be either dense ash (apparent specific gravity 1.0) or light ash (apparent specific gravity 0.6), but the reaction mainly occurs through the surface of IJium. From what happens,
Light ash with a larger specific surface area has better reactivity.

Moreover, it is also possible to use a pulverized product of sodium carbonate, and the reactivity becomes even better. Moreover, anhydrous or monohydrate can be used as sodium carbonate.

Although the reaction is possible even if the amount of sodium carbonate is less than 2 moles per mole of unneutralized material, the reaction takes a long time. The t-reaction is possible when the amount of sodium carbonate exceeds 10 mol, but from the economical and the purpose of increasing the concentration of the activator,
It is preferably 0 mol or less. Water can be introduced from the water of other components added during neutralization, the water in the sodium carbonate, and the water in the unneutralized product, or it is possible to add water alone.

Other components added during neutralization include a high molecular weight M containing aqueous sodium hydroxide solution, sodium silicate and its water.
During neutralization, substances that can effectively act as detergent ingredients such as machine 1 combinations and their aqueous solutions, polyalkylene glycols and their bath solutions, fragrances and their aqueous solutions, fluorescent dyes and their aqueous solutions, pigments and their aqueous solutions, etc. Although it is possible to use a small amount of zeolite builder, it is not preferable to add a large amount because the skeletal structure of the zeolite is damaged by the acid and the ion exchange ability of the zeolite itself is reduced.

Some of these components that can be introduced have the effect of promoting the neutralization reaction. For example, a small amount of hydroxide)
Addition of the IJium aqueous solution and the sodium silicate aqueous solution accelerates the neutralization reaction and, as an alkali component, contributes to the reaction with unneutralized substances. As sodium silicate,
Various sodium salts of silicic acid can be used, such as sodium metasilicate and its hydrates in various proportions, sodium orthosilicate, and even water glass.

A polymer with a molecular weight of 50G to 100 and an aqueous solution thereof containing a carboxylic acid, a carboxyl group, and (or) a hydroxyl group are effective as detergent ingredients, and those with a molecular weight of 50G to 100 and GooO are usually used.These components can be neutralized. By introducing it at the time of mixing, it is possible to obtain an appropriate hardness as a detergent, and it may have an effective effect on crushing and granulation in the subsequent process.

Compounds suitable as high molecular weight organic complexes containing carboxyl and/or hydroxy groups include acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid,
Examples include polymers and copolymers of mesaconic acid, aconitic acid and the like, and polyvinyl alcohol. Examples of polyols include polyethylene glycol and polypropylene glycol.

In the present invention, the neutralization reaction is possible even in the case of less than 1 mole of water per mole of unneutralized material, but the reaction rate is slow and a long residence time is required to complete the reaction. This is not desirable as it requires time. -1 per mole of unneutralized product
Although it is possible to introduce more than 0 mole of water, it is not preferable because the resulting neutralized product becomes so sticky that it becomes impossible to crush it in a grinder in the subsequent step. The amount of water is preferably in the range of 1 to 10 moles per mole of unneutralized material,
More preferably, the amount is in the range of 1 to 5 mol per mol of the unneutralized product.

The device used for the neutralization reaction in the present invention is one that can apply strong shearing force, such as a kneader, and includes a Honda Continuous Kneader (1 Honda Iron Works Co., Ltd.),
Multi-purpose continuous mixer (BAKER
Examples include PKRKINS INO), KRG kneader (Kurimoto Iron Works (redacted)), and Nesco kneader (Fuji Sangyo Co., Ltd.).

All of the above-mentioned crosstalk machines have a mechanism that increases the chance of contact between unneutralized substances and sodium carbonate, and are characterized by a continuous self-cleaning mechanism. Usually about 1 minute is sufficient.

The unneutralized material is introduced into the neutralization device by means of a metering pump.I-chain or branched alkylbenzene sulfonic acids can usually be introduced from a storage tank, or in the case of alkyl sulfates or alkenyl ether sulfates,
To prevent decomposition during storage, it is sulfated and sent to a neutralization device immediately. In some cases, it is possible to temporarily store the argyl sulfate or alkenyl ether sulfate, but it is desirable to keep the residence time within several hours and at a temperature as low as possible above the melting point of the unneutralized product.

Neutralization reactions are initiated within devices with these self-cleaning mechanisms, or anti-nuisances are removed from the device through the exhaust layer, cooling and
It is aged and transferred to the grinding process. The middle phase is completed in the neutralization device or during cooling and aging, but it is sufficient that it is completed before being transferred to the pulverization process.

Usually, the reaction within the neutralization device is preferably about 40 to 80%, and the remaining neutralization is completed by cooling and aging, but the reaction may be 100% completed within the neutralization device. During the cooling/ripening process, hypocarbon dioxide gas generated during neutralization and/or generated during neutralization escapes from the neutralized product! A cavity is formed. Cavities caused by the generation of carbon dioxide gas have the effect of significantly increasing the solubility of the final detergent product, and also have an effect on the subsequent crushability. In addition, cooling and aging have the effect of increasing the crystallization of neutralized products and soda carbonate, etc., making them brittle against shearing forces, which has a significant effect on subsequent crushability. The required cooling/ripening time varies depending on the amount of unneutralized material and the degree of crystallization, or the residence time at 40° C. or lower is at least 1 minute, preferably 5 minutes, and more preferably 10 minutes or more. ~60 minutes is appropriate.

The anionic surfactant produced by the above neutralization and ripening has an implication in the granular detergent of more than 20 nursery rhymes.

Cooling and maturation can be carried out by cooling in a fluidized bed, cooling in a belt type cooler, cooling in a pneumatic transporter air slider, stirring cooling, etc., but all or part of the unneutralized substances are neutralized and the next one is heated to a diameter of 2. ~2Qlii By molding into pellets of length 2 to 20 degrees, it is possible to select a more efficient cooling machine and cooling operation, and also transport the neutralized product to the cooling machine, transport to the crusher, etc. This has a noticeable effect on handling.

Pellets with a diameter of less than 2 feet or a length of less than 2,181 mm are difficult to mold uniformly and have poor retention as pellets, so pellets with a diameter of more than 20 m or a length of more than 20 u are not acceptable. It is unsuitable because it is difficult to transport to the cooler and the crusher, and it is difficult to supply a constant quantity to the crusher. Therefore, when molding all of the unneutralized product or -m neutralized, the pellet size is preferably 2 to 201 m in diameter and 2 to 20 cm in length, preferably 5 Siom in diameter. .

The length is 5 to 15 pieces. A conventional extruder, extrusion granulator, etc. can be used to mold all or part of the unneutralized product into pellets.

Normally, the temperature of the neutralized product discharged from the neutralizer is between 40°C and 100°C, and is brought down to below 40°C by cooling. cooling e
During aging, the neutralization reaction is completed at least before the pulverization step.

The cooled and aged neutralized product is added to other detergent formulations and pulverized, and it is desirable to add powdered zeolite at this time because it increases the pulverizability and improves the powder properties of the final detergent.

Through this operation, a granular detergent with excellent fluidity can be obtained.

The trc of the powdered zeolite is determined by the amount blended into the final product, and is usually 10 to 40% by weight. Other detergent formulations spread during grinding include calcium carbonate,
Sodium carbonate, sodium bicarbonate, sulfates such as sodium sulfate, magnesium sulfate, sodium tripolyphosphate, sodium birophosphate, sodium orne phosphate, sodium metasilicate, sodium orne silicate, etc. etc. can be mentioned.

The final detergent product is obtained by mixing the crushed detergent powder with other detergent formulations. Such other detergent formulations include non-ionic surfactants, foam stabilizers, fabric softeners, bleaches, bleaches, fluorescent dyes, pigments and fragrances.

The mixture is, for example, Shugi Mix.
er), Lodige Mix
er), Pattern Kelly Blender (P-K Ble
It can be carried out using a pan granulator, a fluidized bed, etc.

Introduction of liquid components such as nonionic surfactants, perfumes, etc. can be carried out by crushing and spraying onto the 7C powder particles in these devices.

In the case of introduction of a small amount of liquid component, the powder is transferred to the spray position tI! of the conveyor belt. This may be done when passing through c. Furthermore, in order to impart fluidity and smoothness to the granulated detergent thus obtained, it is also possible to add a small amount of an additive for improving fluidity, such as powdered zeolite. The appearance of a detergent depends on the raw materials used, the final composition, the cooling aging method, and the 8% content of the final detergent product.
0.5 Sl, 01/as', usually 0
．． The apparent ratio of powdered detergent obtained by spray drying is usually 0.25 to 0.
．． It is concentrated in 4mm7On' and concentrated 2 to 5 times by volume. Furthermore, the resulting high-density granular detergent has the advantage that it can also have a high active agent content compared to conventional spray-dried powder detergents.

In the case of powdered detergent made by the usual spray drying method, the amount of detergent used during washing is approximately 140 ba per 30 liters of water, but in the case of the method of the present invention, the amount of detergent used is about 20 cc - = 50 cc of detergent, which is about the same amount. The cleaning performance is satisfied.

Thus, the resulting detergent is attractive to consumers because it not only reduces manufacturing costs but also packaging and transportation costs, and has fluidity comparable to or better than that of powdered detergents produced by conventional spray-drying methods. . In addition, regarding solubility, it has a dissolution rate equivalent to that of powdered detergent manufactured by spray drying, and its properties regarding caking are also better than conventional products. Even when used, it has extremely precise properties.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A quantitative amount of raw materials having the following composition was supplied to an FM-NEB-120 type Nesco kneader (manufactured by Fudosan Kuri Co., Ltd.).The alkylbenzenesulfonic acid was sulfated by a conventional method and then stored at about 30°C. The purity was 96%, the free sulfuric acid was 1.2~, the water was 0.4%, and the oil was 2.4%.The alkyl sulfate was prepared using a known method to obtain a sulfuric acid fossil, which was immediately used in this example. used.

The average residence time in the Nigu was about 1 minute, and the composition temperature at the outlet was about 70°C. This will melt in 30 minutes immediately, and will hold for about 10 minutes once the temperature drops below 40°C. Neutralization has been completely completed. Cooling Layer The following composition was obtained.

20 g parts of powdered zeolite (Toyo Ippen Co., Ltd.! Jj!, Toyo Builder powder product) per 80 parts by weight of this composition.
- Added, mixed and ground to less than 1000 microns using a hammer mill. Grinding was easy and the resulting powder detergent was highly fluid and had low caking properties. The appearance of the obtained powdered detergent is 1O07i7a::Dometsutomo. The obtained powder detergent was evaluated for cleaning power, foaming power, solubility, caking property, etc.

The evaluation results are shown in Table 1, and the cleaning performance is the same as that of a commercially available detergent (surfactant 25% by weight) based on the amount of active agent used.
Other powder physical properties are also the same.

Example 2 A composition produced in the same manner as in Example 1 and having an outlet temperature of about 70°C was mixed into an EXD60 type Berenter double (Fuji Pakudal).
After molding into pellets with a diameter of 5 mm and a length of about 10 mm using a cutting device and cutting equipment,
Cooled to 0°C. The cooling time was 15 minutes, and once the temperature dropped to 40°C or lower, it was maintained for about 10 minutes. Neutralization had been completely completed. Cooling Layer The following composition was obtained.

This composition 80] [2 parts to QQgiit part of powdered zeolite (manufactured by Toyo Soda Co., Ltd., Toyovir Goo powder product)
The mixture was mixed using a T-210 mill, and then ground to less than 1000 microns using a hammer mill. Grinding was easy, and the powder detergent obtained was highly fluid and had low caking properties. The obtained powder detergent had an apparent specific gravity of 0.7 El/(A).The obtained powder detergent was evaluated for detergency, foaming power, solubility, caking property, etc.

The evaluation results are shown in 'te1, but commercially available detergents (surfactant 2)
5% by weight) and the amount of active agent used, the cleaning performance is the same, and the other powder physical properties are also the same.

The evaluation method for detergents in Table 1 is as follows.

I) Detergent power: Measured according to JIS method using Schiffe's paired comparison method using a commercially available detergent as a standard.

The danger rate is 5%, and it is inferior to the top ten. Foaming power: 50 Jt of tap water at 20°C was poured into a commercially available electric washing machine, and 209 t of the detergent of the present invention (compared commercially available detergent was 40.9 t) was added. and dissolve. 1 kg of cotton underwear and artificial oily dirt (cottonseed oil) were added, and the foaming state was determined after 10 minutes of strong inversion.

Soluble ion exchange water 1! Keep it at 10℃ and stir it gently with a magnetic stirrer, then add the detergent 1. s 3mm t
l15TlrI. After 5 minutes, the detergent solution was passed through a 200-mesh sieve, and the amount remaining on the sieve was weighed. The product of this invention is 220II (91) x 3
0.5 m(H) x 6.5 m(n) cD 2.
6kgf, control product is 25.5 x S 7.5 x 1
2.6 kg was sealed in a box of 0. After cooling for S weeks at 50°C and 80% RH, the powder was poured onto a 4 mm2 x 4 M sieve.
Measure Child B (9) and calculate the passage rate (Cal) using the formula below.

B Table 1 [Effects] As is clear from the results (Table 1), the solubility is improved and the anti-caking property is also good.

Claims (1)

[Claims] 1. A step of neutralizing unneutralized sulfonated products and/or sulfated products (hereinafter referred to as unneutralized products), and neutralizing all or part of the unneutralized products through the neutralization step. 1. A method for producing a high-density granular detergent with improved solubility, which comprises the steps of cooling and aging the blended detergent, and pulverizing or crushing and granulating it together with other detergent formulations. 2. In the neutralization step, the amount of unneutralized material is 2 to 2 to 1 mole of unneutralized material.
2. A process according to claim 1, wherein the process is wholly or partially neutralized by mixing in a high shear device with 10 moles of sodium carbonate and 1 to 10 moles of water. 3. A method according to claim 1, in which detergent formulations and cleaning aids such as sodium silicate, high molecular weight organic polymers containing carboxyl groups and/or hydroxyl groups are added in the neutralization step. 4. The unneutralized product has a linear or branched alkylbenzenesulfonic acid having an alkyl group having an average of 10 to 16 carbon atoms, an alkyl sulfate ester or an alkenyl group having an alkyl group having an average of 10 to 18 carbon atoms, 1 Average of 0.5 in molecule
The method according to claim 1, wherein the alkenyl ether sulfate is an alkenyl ether sulfate to which ~8 mol of ethylene oxide or a mixed alkylene oxide of ethylene oxide and propylene oxide or butylene oxide is added. 5. Cooling all or part of the unneutralized product,
The method according to claim 1, wherein the aging is carried out at a temperature of 40° C. or less for at least 1 minute. 6. All or part of the unneutralized material is neutralized and the diameter is 2~
The method according to claim 1, wherein the pellets are molded into pellets of 20 mm and 2 to 20 mm in length, and then cooled and aged. 7. The method according to claim 1, wherein the content of the anionic surfactant produced by neutralization and aging in the granular detergent is 20% by weight or more. 8. The bulk density of granular detergent is 0.5 to 1.0 g/cm^3
The method according to claim 1.