KR920000114B1 - Detergent compositions and process for preparing them - Google Patents

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Description

[Name of invention]

Detergent composition and its manufacturing method

Detailed description of the invention

The present invention relates to a high bulk density granular detergent composition or component and a method for producing the same by a dry neutralization process.

In the recent detergent industry, there has been considerable interest in the production of detergent powders having a relatively high bulk density, for example 650 g / l or more. It is proposed that such powders containing anionic surfactants, such as alkylbenzenesulfonates, may be prepared by a process comprising a process of self neutralizing the acid precursors of the anionic surfactant and alkalis such as sodium hydroxide or sodium carbonate. have.

For example, Japanese Patent No. 60 072999A (Ko) and British Patent No. 2 166 452B (Kao) disclose the following method. That is, detergent sulfonic acid, sodium carbonate and water are mixed in an apparatus providing strong shear force, the solid mass thus produced is pulverized by cooling to 40 ° C. or lower, and then the final powder is granulated. This process is typical of those published in the art, where the product of the neutralization reaction is a kneaded mass, which requires a device such as a mixer, which requires considerable high energy, to obtain granular detergent products of acceptable levels. The grinding and granulating steps must be carried out separately using other equipment.

Also of great interest in recent years is the use of high speed mixers / granulators to produce high bulk density detergent powders. For example, European Patent No. 158 419B (Hashimura) discloses a high content of nonionics made of sodium carbonate by mixing and granulating nonionic surfactants and soda ash in reactors with horizontal and vertical blades rotating at different speeds. A method for producing a detergent powder containing a surfactant has been published.

British Patent 1404 317 (Bell) discloses a method for producing detergent powders of low or medium bulk density by a dry neutralization process. In other words, the product is prepared in the form of powder without fluid by mixing detergent sulfonic acid with an excess of soda ash in the presence of a sufficient amount of water to initiate the neutralization reaction, but the amount of the resulting product does not become damp. This process is carried out in equipment such as ribbon mixers, planetary rotary mixers, air-moving mixers, etc., where the reactants are “scrambled and loosened” so that the carbon dioxide produced during the neutralization reaction is entrained in the product particles. This process produces light, porous particles such as those produced by spray drying.

British Patent No. 1 369 269 (Colgate) discloses a method for preparing anionic detergents by thoroughly mixing detergent sulfonic acid and sodium carbonate powder in a mixer with a cutting device, such as a Lbdige moisturizing mixer.

In order to obtain a granular product that is not a dough-like mass, detergent sulfonic acid must be injected via gaseous vapor for proper fluidization and mixing of the reactants. This requires a fairly complex deformation of the mixer. Since water is not added to proceed with the neutralization reaction, the reaction proceeds slowly, and a relatively coarse product is produced, which requires an additional size reduction step. In general, the temperature during the neutralization reaction is raised to about 80 ℃.

U.S. Patent No. 4 690 785 (Witco) discloses a method for preparing an alkylbenzenesulfonate powder by neutralizing an alkylbenzenesulfonic acid with a base in solid or solution form. At the start of this process, a significant amount of water is present, and the heat generated by the exothermic reaction is used to remove the water produced in the water and the reaction itself. The reaction temperature is usually about 100 ° C.

The present inventors have found that the non-flowable detergent powder and the detergent powder component with high bulk density and small particle size can be prepared by drying neutralization at relatively low temperature using a single device, a mixer / granulator with simultaneous stirring and cutting action. I found out.

Accordingly, the present invention provides a method for preparing a granular detergent composition or component having a bulk density of 650 g / L or more, the process comprising the step of neutralizing the liquid acid precursor of the anionic surfactant and the solid water-soluble alkaline inorganic material, (i) Mixing and fluidizing a water-soluble alkaline inorganic material in the form of a particulate solid in a high speed mixer / granulator having both stirring and cutting operations together with one or more other particulate solid materials, optionally ii) gradually adding the acid precursor into the high speed mixer / granulator while maintaining the temperature below 55 ° C., so that the acid precursor is neutralized by the water-soluble alkaline inorganic material and the mixture is kept in the form of particles, (iii) the mixture Is granulated in a high speed mixer / granulator in the presence of a liquid binder. It provides a method for producing a granular detergent composition or component having a bulk density of 650g / L or more.

The present invention also provides granular detergent compositions or components prepared by such a manufacturing process.

It is an object of the present invention to prepare a high bulk density detergent powder by a process comprising dry neutralization of an acid precursor and an alkaline solid of an anionic surfactant. This process is carried out in a high speed mixer / granulator and consists of the process steps (i), (ii) and (iii) described above.

A very important feature of the process of the present invention is that the reaction mixture is present in the form of particles or granules. The product after the granulation step does not require an additional site size reduction process since there is no tendency for caking, bowling, and kneading. Usually the process of the present invention produces granular products containing at least 50% by weight, preferably at least 70% by weight, of particles of 1700 microns or less. This can only be achieved if the liquid component, especially the acid anionic surfactant precursor, does not have the opportunity to act as a binder or flocculant.

First, in step (i), an excess of particulate solids must be present relative to the liquid to be added before the liquid substance can be added. The total amount of solids present in step (i) is preferably at least 60% by weight, preferably at least 67% by weight of the total composition present in step (ii). It is therefore advantageous to add the solid component as high as possible at this stage. (ii) The ratio of liquid to solid at the completion of the neutralization step preferably does not exceed 0.6, preferably 0.55, in particular ideally 0.50.

Of course, the solid material should contain at least the amount of particulate water-soluble alkaline inorganic material (neutralizing agent) necessary for neutralization. The terms "particulate solid water-soluble alkaline inorganic material" and "neutralizing agent" as well as combinations of two or more of these materials may be included. Used. If the neutralizing agent is a substance which by itself can serve a useful purpose in the final composition, an amount greater than the above-mentioned amount may be used.

According to a preferred embodiment of the invention, the neutralizing agent consists of sodium carbonate alone or in admixture with one or more other particulate water-soluble alkaline inorganic substances, for example sodium bicarbonate and / or sodium silicate. Sodium carbonate is, of course, also useful as a determinant and alkaline giver of the final composition. Therefore, this embodiment of the present invention is advantageously used to prepare a detergent powder in which sodium carbonate is the only builder or main builder, and in which there is more than the amount of sodium carbonate necessary for neutralization.

However, the sodium carbonate embodiment of the present invention is also suitably used for the preparation of detergent compositions in which a significant amount of other builders are present. It is preferred to be present in this other builder i (i) step high speed mixer / granulator. Examples of such builders include crystalline and amorphous alkali metal aluminosilicates, alkali metal phosphates and mixtures thereof. Nevertheless, it may be present in excess of the amount necessary for neutralization to impart alkalinity to the sodium carbonate product. Sodium carbonate is preferably present in an excess of about 10-15% by weight. The solid material present in step (i) may also contain any other desired solid components. Examples thereof include fluorescent agents; Polycarboxylate polymers; Anti-deposition agents such as sodium carboxymethylcellulose; Fatty acids which neutralize themselves to form soaps; Fillers such as sodium sulfate, diatomaceous earth, calcite, kaolin or bentonite, and the like.

If desired, solid particulate surfactants such as alkylbenzene sulfonates and / or alkyl sulphates in powder form may be included as part of the solid charge in step (i). Thus, for example, the detergent powder prepared by the process of the present invention may contain some of the alkylbenzene sulfonate prepared in (i) as a powder and some in (ii).

Alternatively or additionally, the spray dried detergent base powder may be contained as part of the solid charge of step (i).

According to one preferred embodiment of the present invention, the solid material present in step (i) contains a microparticulate flow aid. This flow aid is preferably present in an amount of more than 2-8% by weight of the final composition, preferably 5-7% by weight. Suitable flow aids include crystalline or alkali metal aluminosilicates, heat treated pearlite, calcite, diatomaceous earth, and mixtures thereof.

Preferred flow aids are diatomaceous earth, particularly heat treated perlite indicamol (Dicamol: 424). This material has a silica content of 80-87% by weight and a water absorption of 250-300% by weight. Such materials, when present in the solid mixture before and during the addition of the acid anionic surfactant precursor, are advantageous in preventing excessive agglomeration and maintaining the reaction mixture in particulate form.

An important feature of the fixation of the present invention is that the solid material is mixed and fluidized very efficiently before the addition of the liquid component. Here, "fluidization" means that the mass of particles is covered in air for some time with a strong mechanically induced state of stirring and does not necessarily mean the injection of gas. This state can be achieved by the selection of a device, ie a high speed mixer / granulator with simultaneous stirring and cutting action. The high speed mixer / granulator is preferably equipped with a rotatable stirrer and cutter that can be operated independently of each other at a rate that can be changed separately. Such mixers have the ability to simultaneously perform cutting action and high energy stirring input, but can also be used to provide other gentle stirring regimes with or without cutter operation.

A high speed mixer / granulator of a preferred form for use in the process of the invention preferably has a bowl shape and in principle has a vertical stirring shaft.

A particularly preferred high speed mixer / granulator is the Fukae (trade name) FS-G series manufactured by Fukae Powtech Koygo Co. of Japan. The device is a bowl-type bowl-filled container with a stirrer with a vertical axis at the base and a cutter on the side wall.

The stirrer and cutter can be operated independently of each other at a speed that can be varied separately. The vessel may be equipped with a cooling jacket or, if necessary, a freezer. A similar Indian-made quick mixer / granulator is the Sapphire® RMG series, available in several sizes, such as a Puka mixer. The appliance is a bowl-type container inflated by air operation to seal against a fixed lid. The three-blade stirrer and the four-blade cutter share a single vertical axis fixed to the lid. The stirrer and cutter operate independently of each other. The stirrer is operated at a speed of 75 rpm or 150 rpm and the cutter at a speed of 1440 rpm or 2880 rpm. The vessel may be equipped with a coolant jacket.

The Sapphire RMG-100 Mixer, suitable for handling 60 kg batches of detergent powder, is a bowl with a diameter of about 1 meter and a depth of 0.3 meters. The working capacity is 200 meters. The blade of the stirrer is 1 meter in diameter, and the blade of the cutter is 0.1 meter in diameter.

hne 제품인 디오스나(Dicsna : 상표) ν 시리즈 ; 및 영국의 TK Tielder Ltd. 제품인 파마 매트릭스(Pharma Matrix : 상표)등이 있다. 기타 본 발명의 공정에 사용하기 적합한 혼합기로는 일본의 Fuji Sangyo Co. 제품인 후지(Fuji : 상표)Vg-C 시리즈 ; 및 이탈리아의 Zanchotta ＆amp; Co srl 제품인 로토(Roto : 상표)등이 있다.Other mixers suitable for use in the process of the present invention include the German Diorks & S

Diosna (trademark) ν series of hne products; And TK Tielder Ltd. of the United Kingdom. Products such as Pharma Matrix (trademark). Other mixers suitable for use in the process of the present invention include Fuji Sangyo Co., Ltd. of Japan. The product Fuji (trademark) Vg-C series; And Zanchotta & Co srl product Roto (trademark).

dige : 상표) FM 시리즈 배치 혼합기이다. 이 기기는 교반기가 수평축을 가진다는 점에서 상술한 혼합기와 다르다. 그러나 이 기기는(i)단계에서의 혼합 및 유동화가 효율적이지 못한 결점을 가지므로, 상술한 영국 특허 제1 369 269호(Colgate)에 기술한 바와같이 기체 주입에 의해 보완시킬 필요가 있다.Another mixer suitable for use in the process of the invention is the Morton Machine Co., Scotland. Ltd. Product Lloydage (L

dige: brand) is an FM series batch mixer. This device differs from the mixer described above in that the stirrer has a horizontal axis. However, the device has the drawback of inefficient mixing and fluidization in step (i) and therefore needs to be supplemented by gas injection as described in British Patent No. 1 369 269 (Colgate) above.

The next step (ii) of the present invention is the addition of an acid surfactant precursor. How this step is performed is a factor in determining the success of the process. Of particular importance is that the amount of liquid present during the neutralization step should not be so high that it can actually lead to coagulation.

However, the efficiently fluidized solid must be wetted with an amount of water suitable to initiate and promote the neutralization reaction before contacting the acid precursor. Therefore, the amount of free water present in step (ii) is very important. "Free water" as used herein means water that is not strongly bound as a hydrated or crystalline water of an inorganic substance. If the free water is present in insufficient amounts, the reaction will not proceed quickly and unreacted detergent acid precursors will collect in the mixer and act as a binder resulting in coagulation, bowling and even dough formation. Therefore, enough water should be present to wet all solids. However, this water itself should not be an amount sufficient to act as a binder.

The solid material itself may contain sufficient free water to satisfy these conditions. For example, a spray-drying detergent base powder mixed with a relatively large amount of water can provide the total or substantial amount of free water required. If there is originally an insufficient amount of free water in the solid charge, a carefully controlled amount of water should be added prior to or concurrently with (or separately from) the addition of the acid precursor. In order to thoroughly wet the solid material before adding the precursor, all water can be added before the addition of the precursor. Alternatively, the acid precursor and water can be added to the mixer at the same time.

If desired, a small amount of water sufficient to initiate the neutralization reaction, but not enough to cause coagulation, may be premixed with the acid precursor before adding it to the high speed mixer / granulator. If a colored product is desired, the dye may be simply premixed with the acid precursor and water before the dye is added into the high speed mixer / granulator. The amount of water added depends on the kind of solids present. An amount in the range of 0.5-2.0%, preferably 0.5-1.5% by weight of the total amount of solids present in steps (i) and (ii) has good results in the preferred embodiment of the present invention wherein the neutralizing agent is sodium carbonate. .

Another important condition for step (ii) is that acid precursors must be added gradually so that they do not tend to be consumed immediately and collect in unreacted form in the mixer. Of course, the preferred time to add the acid precursor depends on the amount to be added, but is generally at least 1 minute, more preferably 2-12 minutes, particularly preferably 3-10 minutes.

Other liquid detergent components may be added during step (ii). Examples of such components include nonionic surfactants, low melting point fatty acids that neutralize themselves to form soap. (ii) The neutralization step usually takes 2-12 minutes, and as described above, prior to the gradual addition of acid precursors (optionally with other liquid components), water (optionally with other liquid components) A separate step may be preceded by adding to the mixer.

As described above, the temperature of the powder mass present in the high speed mixer / granulator is maintained at 55 ° C. or lower, preferably 50 ° C. or lower, more preferably 47 ° C. or lower, ideally 40 ° C. or lower during step (ii). Should be. This allows the use of a water jacket. For example, a jacket supplied with water at 25 ° C is usually suitable for maintaining a temperature below 47 ° C. In some cases, however, a freezer may be required to inject cooling liquid or gas (eg liquid nitrogen) into the powder mass. Leaving the temperature elevated causes coagulation and lump formation.

A very important feature of the process of the invention is the granulation in a high speed mixer / granulator. This granulation is generally carried out in the form of a separate granulation step (iii) after the addition and neutralization of the acid precursor is complete. However, when the addition of the liquid substance is made for a relatively long time, the granulation is performed before the addition is completed, so that no separate granulation step (iii) is necessary. In this case, steps (ii) and (iii) of the process are considered to be combined into one continuous step (ii) / (iii).

Granulation or densification processes can produce products of very high bulk density. Granulation of the process of the present invention requires the presence of a liquid binder, but the amount is considerably less than the amount used to granulate the powder in a conventional apparatus such as a pan granulator. For example, 3-8%, especially about 5% by weight, relative to 10-15% by weight of the total composition. The binder is added before granulation and after the neutralizer is completed. The binder generally consists of water and / or liquid detergent components (eg aqueous polycarboxylate polymer solutions or nonionic surfactants) or mixtures thereof.

When calculating the amount of binder required, it is important to consider the free water already present in the composition and the free water that can be released at process temperatures, usually about 30-50 ° C. For example, hydrated zeolites (containing 27 moles of water per mole or about 20% by weight of bound water) are thought to release about 20% by weight (4% by weight of total weight) of water at this temperature. Sodium tripolyphosphate hexahydrate, on the other hand, emits little or no.

The total amount of free water allowed in the whole process is limited and usually should not exceed 8% by weight, preferably 4% by weight of the total composition. (ii) Considering the need for water in the neutralization step, it is not necessary to add a liquid binder if sufficient free moisture for granulation can be obtained from the powder mass itself.

The product of the granulation step (iii) is a particulate solid having a high bulk density, ie at least 650 g / l, preferably at least 750 g / l, more preferably at least 800 g / l. As mentioned above, the particle size distribution is generally at least 50 wt%, preferably at least 70 wt%, more preferably at least 85 wt%, of less than 1700 microns, and the amount of microparticles is small. In general, no additional treatment is required to remove oversize or fine particles.

If desired, additional ingredients may be mixed into the granulated product of step (iii). Trace solids such as, for example, fluorescent agents and sodium carboxymethylcellulose are added at this stage rather than contained in the initial solid mixture.

In general, products have good flow properties, low compression rates and little caking tendency, but these properties can be further improved by mixing microparticulate flow aids or builder salts after granulation is complete and bulk density can be increased. . Preferred as builder salts which can be added later is sodium tripolyphosphate. The addition of such optional ingredients is particularly important for powders in which the main or only builder is sodium carbonate.

The flow aids described above are also suitable for addition to later stages. The amount added depends on the flow aid selected, but about 0.2-12.0% by weight of the total product is suitable.

Suitable flow aids consist of crystalline and amorphous alkali metal aluminosilicates having an average particle size of about 0.1-20 microns, preferably about 1-10 microns. The crystalline material (zeolite) is preferably added in an amount of 3.0-12.0%, more preferably 4.0-10.0% by weight of the total product. As the amorphous material is more effective in terms of weight, it is preferably added in an amount of 0.2-5.0% by weight, more preferably 0.5-3.0% by weight of the total product. Suitable amorphous materials are commercially available from Crosfield Chemicale Ltd. under the trade name Alusil from Cheshire, Warrington, England. If desired, crystalline aluminosilicates and amorphous aluminosilicates can be used simultaneously or sequentially as flow aids.

Other flow aids described above, ie heat treated pearlite, calcite, diatomaceous earth and the like, are also suitably added in an amount of 0.2-5.0% by weight, preferably 0.5-3.0% by weight of the total product.

Other flow aids suitable for use in the process of the present invention include precipitated silica, such as Neosyl (trademark) and precipitated calcium silicate, such as Macrocal (trademark), both of which are Crosfield. Chemicals Ltd. Can be purchased from

Process for mixing microparticulate amorphous sodium aluminosilicate to densify granular detergent compositions containing surfactants and builders, and for manufacturing and / or densifying in a high speed mixer / granulator, filed April 27, 1989 One of our co-pending European patent application No. 89 304205.1.

As mentioned above, the process of the present invention contains a surfactant and a builder and produces a granular high bulk density solid having a bulk density of at least 650 g / l, preferably at least 700 g / l. In addition, the solid has a particularly low porosity and is characterized by being less than 0.25 or more preferably 0.20 or less, which is also distinguished from the high density powder produced by spray drying.

This final granule can be used as a complete detergent composition by itself. Alternatively, they may be mixed with other ingredients or mixtures prepared separately to form a substantial portion or portion of the final product.

In general, additional ingredients such as enzymes, bleaches, and pharmaceuticals, which are not suitable for the granulation process and the preceding steps, are mixed into the granules to form the final product.

Generally, the densified granules make up 40-100% by weight of the final product. According to one embodiment of the present invention, the densified granules produced by the present invention are "additives" consisting of a relatively high content of detergent active material in the inorganic carrier. The granules are mixed with other ingredients in small amounts to form the final product.

The process can be advantageously used to prepare detergent compositions containing 5-45% by weight, in particular 5-35% by weight, of anionic surfactants. At this time, all or part of the anionic surfactant is induced by the self-neutralization of step (ii).

The process of the present invention is particularly useful for the preparation of detergent powders or components containing relatively high contents, such as 15-30% by weight, more preferably 20-30% by weight, of anionic surfactants. However, it is equally useful for the production of powders containing a low content of anionic surfactants.

Anionic surfactants, at least partly prepared by self-neutralization, are for example selected from linear alkylbenzenesulfonates, alpha-olefin sulfonates, internal olefin sulfonates, fatty acid ester sulfonates and combinations thereof. The process of the present invention is particularly useful for preparing compositions containing alkylbenzenesulfonic acid salts by self-neutralization of the corresponding alkylbenzenesulfonic acids.

Other anionic surfactants that may be present in the compositions prepared by the process of the present invention include first and second alkylsulfonates, alkyl ethersulfonates, and dialkylsulfosuccinates. Of course, anionic surfactants are well known and those skilled in the art will be able to further add to the examples described above with reference to the standard text.

In particular, when it is desired to contain a high content of anionic surfactants, additional anionic surfactants are added after granulation in salt form (generally in aqueous paste or aqueous solution) rather than in the form of acid precursors. In a preferred embodiment of the present invention the anionic surfactant added later is an alpha-olefin sulfonate.

Solid particulate anionic surfactants that may be added at an early stage of the process have already been mentioned. Therefore, the process of the present invention is a flexible method that may mix high content of anionic surfactants in high bulk density powders.

As described above, nonionic surfactants may also be contained. Nonionic surfactants are also well known to those skilled in the art, including first and second alcohol ethoxylates and the like.

Other types of non-soap surfactants, such as cationic, zwitterionic, amphoteric or semipolar surfactants, may also be included as needed. Many suitable detergent active compounds are commercially available and described in detail in the literature (eg, “Suface-Active Agents and Detergants”, Volumes I and II).

If desired, soap may also be included for foam control, additional cleansing power and builder ability.

Generally, the detergent composition prepared by the process of the present invention contains 10-35% by weight of anionic surfactant, 0-10% by weight of nonionic surfactant, and 0-5% by weight of fatty acid soap.

Representative Products of the Invention

The following compositions are general and non-limiting examples of compositions that can be readily prepared by the process of the present invention.

(1) The composition consisting of the following components.

(a) 5-45% by weight of anionic surfactant, (b) 20-70% by weight of inorganic builder salt selected from crystalline or amorphous alkali metal aluminosilicate, sodium tripolyphosphate, sodium carbonate, sodium silicate or combinations thereof, (c 0-20% by weight of fillers and / or flow aids selected from diatomaceous earth, silica, calcite, sodium sulfate, bentonite, kaolin or combinations thereof and optionally other cleaning ingredients, in particular (1a) sodium tripolyphosphate, neutralizing as main builder (A) 15-30% by weight of anionic surfactant, (b1) 10-60% by weight of sodium tripolyphosphate, (b2) 5-60% by weight of sodium carbonate, (c) diatomaceous earth, silica, calcite, containing sodium carbonate as alkali A composition consisting of 0-20% by weight of a filler and / or a flow aid selected from sodium sulfate, bentonite, kaolin or combinations thereof and optionally other detergent ingredients. (1b) 15-30 weight of anionic surfactants, (b) 20-70 weight percent of sodium carbonate, (c) diatomaceous earth, silica, calcite, sodium sulfate, bentonite, kaolin or combinations thereof, containing sodium carbonate as the main builder A composition consisting of 0-20% by weight of a filler and / or flow aid selected from among others and optionally other detergent ingredients.

(2) 5-35% by weight of a soap-free detergent active material comprising, as a detergent builder, crystalline or amorphous alkali metal aluminosilicates, especially crystalline zeolites and zeolites 4A, at least in part consisting of anionic surfactants, (b A composition consisting of 15-45% by weight of crystalline or amorphous alkali metal aluminosilicate (based on anhydride) and other optional detergent components, including excess neutralizing agent for anionic surfactants, wherein (b) vs. (a) It is preferable that a weight ratio is 0.9: 1 or more).

A particularly preferred class of detergent compositions prepared by the process of the invention are described in our co-pending European patent application No. 89304242.4, filed April 27, 1989, with the claims. The composition comprises (a) 17-35% by weight of a soap-free detergent active substance, at least in part composed of anionic surfactants, (b) 28-45% by weight of crystalline or amorphous alkali metal aluminosilicates, and optionally other detergent components. Wherein the weight ratio of (b) to (a) is 0.9: 1-2.6: 1, preferably 1.2: 1-1.1.8: 1.

(3) a composition described in our co-pending European patent application No. 89304210.1, filed April 27, 1989, comprising: (a) 12-70% by weight of a soap-free detergent active material, (b) sodium tripolyphosphate And / or at least 15% by weight of a water-soluble crystalline inorganic salt comprising sodium carbonate and optionally other detergent components, wherein the weight ratio of (b) to (a) is 0.4: 1-9: 1, more preferably 0.4: 1-5: 1 composition.

Such compositions preferably contain a total of 15-70% by weight of a water-soluble crystalline inorganic salt selected from, for example, sodium sulfate, ortho- or sodium pyrophosphate, or meta- or sodium orthosilicate. Particularly preferred compositions contain 15-50% by weight, more preferably 20-40% by weight sodium tripolyphosphate.

As mentioned above, all such preferred detergent compositions prepared by the process of the present invention are conventional ingredients such as bleaches, enzymes, suitable foaming or antifoaming agents, anti-deposition and anti-enveloping agents, fragrances, dyes, fluorescents and the like. In conventional amounts. Such ingredients may be incorporated into the product at a suitable stage, and the skilled detergent formulator will determine without difficulty whether any ingredient is suitable for mixing in a high speed mixer / granulator.

The process of the present invention has advantages over conventional spray drying processes that do not involve high temperatures.

That is, less restrictions are placed on how to incorporate heat sensitive components such as surface agents and enzymes into the product.

The invention is further illustrated by the following non-limiting examples. Where parts and percentages are by weight unless otherwise indicated.

Example 1

A high bulk density detergent powder 750 kg batch having the following composition was prepared using a high speed mixer / granulator Pukae (trademark) FS-1200.

The ratio of zeolite (anhydride) to total soapless surfactant in this composition was 1.29: 1. The process was carried out as follows.

(i) The solid components specified below were dry mixed for one minute at a stirrer speed of 100 rpm and a cutter speed of 2000 rpm in a Fuca mixer.

* This amount of sodium carbonate is 4.9 times more than the amount required for the neutralization of alkylbenzenesulfonic acid (see paragraph (ii))

(ii) After adding water (0.375 parts = 0.61% by weight of total solids), the mixer was operated for 1 minute and 30 seconds at the same stirrer speed and cutter speed. Linear alkylbenzenesulfonic acid (23.5 parts) was added over 5 minutes while the mixer was running at a stirrer speed of 80 rpm and a cutter speed of 2000 rpm. The temperature was kept below 50 ° C. by a cooling jacket filled with water. At this stage the reaction mixture remained in particle form.

(ii) The ratio of liquid to solids at the completion of step was 0.39.

(iii) After the neutralization reaction was completed, additional water (1.4 parts) and nonionic surfactant (2.0 parts) as a binder were added to the mixer, and then granulated by operating at an agitator speed of 100 rpm and a cutter speed of 2000 rpm for 3 minutes. . The temperature was kept below 50 ° C. by means of a cooling jacket filled with water. The product of this step was a granular solid.

(iii) The ratio of liquid to solids at the completion of the step was 0.44.

(iv) The zeolite (additional 11 parts) was added as a flow aid while the mixer was run without the cutter and the stirrer speed was running at 90 rpm for 2 minutes.

The resulting powder was not flowable and had a bulk density of 850 g / l and contained 73 weight percent of particles below 1700 microns. The particle porosity was 0.15.

Coloring speckle (0.8 parts) and enzyme granules (0.6 parts) of the same powder are mixed with the powder using a rolling drum and then sprayed with fragrance (0.25 parts) to form a fully formulated high bulk density detergent with excellent powder properties. A powder was obtained.

Example 2

The method of Example 1 was repeated except that a nonionic surfactant was added as a mixture with acid, instead of adding in step (iii). As a result, a similar powder was obtained.

Example 3

The method of Example 1 was repeated but only 5 parts of zeolite was added to the mixer after addition of the binder in step (iii) before granulation was made and only the remaining 6 parts of zeolite was added as flow aid in step (iv). As a result, a similar powder was obtained.

Example 4

le 제품)로서 (i)단계에 가하였다. 그 결과 유사한 분말을 얻었다.Example 2 was repeated, except that half of the anionic surfactants were in powder form (Marlon ™ A390, H

le product) was added in step (i). As a result, a similar powder was obtained.

Example 5

This example illustrates the process of granulating the mixture in a high speed mixer / granulator by adding a spray-dried base powder after self-neutralization.

A batch of 750 Kg of high bulk density detergent powder having the following composition was prepared using a high speed mixer / granulator Fukae® Fs-1200.

The ratio of zeolite (anhydride) to total soapless surfactant in this composition was 1.29: 1. The process was carried out as follows.

(i) The solid components specified below were dry mixed for one minute at a stirrer speed of 100 rpm and a cutter speed of 2000 rpm in a Fuca mixer.

* This amount is 5.98 times more than the amount needed for neutralization

(ii) After adding water (3Kg = 1.22% by weight of total solids), the mixer was operated for 1 minute at 60 rpm stirrer speed and 2000 rpm cutter speed. The following mixed liquid was then added over three minutes while the mixer was running at the same stirrer speed and cutter speed.

The solid material was therefore 70.4% by weight of the liquid / solid mixture during the neutralization step. The ratio of liquid to solids at the completion of the neutralization step was 0.42. The temperature was kept below 50 ° C. by a cooling jacket filled with water. At this stage the reaction mixture remained in particle form.

(iii) After the neutralization reaction was completed, a spray dried basic powder (336 Kg) having the following composition was added to the mixer.

The total mixture was granulated for 4 minutes at a stirrer speed of 80 rpm and a cutter speed of 2000 rpm. The spray dried base powder contained sufficient free water, and besides adding water in step (ii), it was not necessary to add water as a binder.

(iv) The zeolite (additional 60 Kg) was added as a flow aid while the mixer was run without the cutter and the stirrer speed was running at 80 rpm for 1 minute.

The resulting powder was not flowable and had a bulk density of 981 g / l and contained 80% by weight of particles up to 1700 microns.

EXAMPLES 6 AND 7

This example is intended to illustrate the advantages of (ii) cooling with liquid nitrogen during the neutralization step.

Two batches of 750 Kg of high bulk density detergent powders (Examples 6 and 7) having the composition specified in Example 5 were prepared using a high speed mixer / granulator Pukaer FS-1200. The process was carried out as follows.

(i) The solid components specified below were dry mixed for 1 minute at a stirrer speed of 100 rpm and a cutter speed of 2000 rpm in a pocae mixer.

(ii) After adding water (6Kg = 1.24% by weight of total solids), the mixer was operated for 1 minute at 75 rpm stirrer speed and 2000 rpm cutter speed. The following mixed liquid was then added over 5 minutes while operating the mixer at the same stirrer speed and cutter speed.

After the addition of liquid material was complete the speed of the mixer was increased to 100 rpm / 2000 rpm for 2 minutes. In Example 6 the temperature was maintained below 35 ° C. by spraying liquid nitrogen on the powder during the neutralization step. In Example 7, liquid nitrogen cooling was omitted and the temperature became 52 degreeC. In both examples the reaction mixture remained in particulate form during the neutralization step.

(iii) After the neutralization reaction was completed, additional water (6Kg) as a binder was added to a mixer operated at a stirrer / cutter speed of 80 rpm / 2000 rpm and then operated at the same stirrer speed and cutter speed for 3 minutes to achieve granulation.

(iv) The zeolite (additional 57 Kg) was added as a flow aid while the mixer was run without the cutter and the stirrer speed was running at 80 rpm for 1 minute.

The resulting powder of Example 6 was not flowable and had a bulk density of 821 g / l and contained 81 wt% of particles of 1700 microns or less. The powder of Example 7 was a powder with nearly the same bulk density but contained only 69% by weight of particles of 1700 microns or less.

Example 8

A high bulk density detergent powder 20Kg batch having the following composition was prepared using a high speed mixer / granulator Fuca FS-30.

The ratio of zeolite (anhydride) to total soapless surfactant in this composition was 1.44: 1. The process was carried out as follows.

(i) The solid components specified below were dry-mixed for one minute at a stirrer speed of 300 rpm and a cutter speed of 3000 rpm in a Fuca mixer.

* This sodium carbonate amount is about 5 times more than the amount required for the neutralization of alkylbenzenesulfonic acid and fatty acids. This amount corresponds to 15.0% by weight of the final composition to provide alkalinity.

(ii) After addition of water (0.375 parts = 0.61% by weight of total solids), the mixer was operated at agitator speed of 100 rpm and cutter speed of 3000 rpm for 1 minute 30 seconds. The following mixed liquid was then added over 5 minutes while operating the mixer at the same stirrer speed and cutter speed.

The temperature was kept below 50 ° C. by a cooling jacket filled with water. At this stage the reaction mixture remained in particle form.

(iii) After the neutralization reaction was completed, the following binder mixture was added.

The mixture was operated at stirrer speed of 300 rpm and cutter speed of 3000 rpm to allow granulation. The temperature was kept below 50 ° C. by a cooling jacket filled with water. The product at this stage was a granular solid.

(iv) 7.5 parts of zeolite and 1 part of amorphous sodium aluminosilicate (1 part of Alusyl (R), manufactured by Crosrield Chemicals Ltd.) as flow aids, while the mixer was operated without the cutter and the stirrer speed was operated at 90 rpm for 2 minutes. It was.

The resulting powder was not flowable and had a bulk density of 830 g / l and contained 85% by weight of particles of 1700 microns or less.

Fully formulated high bulk density detergent with good powder properties by mixing colored speckles (0.8 parts) and enzyme granules (0.61 parts) of the same powder with the powder using a rolling drum and then spraying fragrances (0.25 parts). A powder was obtained.

Example 9

A high bulk density detergent powder 20Kg batch made of sodium tripolyphosphate and sodium carbonate, having the following composition, was prepared using a high speed mixer / granulator Pukaer FS-30.

The ratio of crystalline water soluble inorganic salt to total soapless surfactant in this composition was 1.9: 1.

Sodium carbonate is present in this composition as an important part of the builder system.

The sodium carbonate added in step (i) (described below) is about 8 times greater than the amount required for the neutralization of alkylbenzenesulfonic acid (see step (ii)). The process was carried out as follows.

(i) The solid components specified below were dry mixed for 1 minute at a stirrer speed of 300 rpm and a cutter speed of 3000 rpm in a Fuca mixer.

(ii) After adding water (2 parts), the mixer was operated for 1 minute at agitator speed of 100 rpm and cutter speed of 3000 rpm. Then linear alkylbenzenesulfonic acid (29.96 parts) was added over 1 minute while running the mixer at the same stirrer speed and cutter speed. The temperature was kept below 50 ° C. by a cooling jacket filled with water. At this stage the reaction mixture remained in particle form.

(iii) After the neutralization reaction is completed, additional water (4.0) as a binder is added to the mixer while the mixer is operated at agitator speed of 100 rpm and cutter speed of 3000 rpm for 1 minute. The mixer was then operated at stirrer speed 300 rpm and cutter speed 3000 rpm for 4 minutes to achieve granulation. The temperature was kept below 50 ° C. by a cooling jacket filled with water. The product of this step was a granular solid.

(iv) Alusil (2 parts) was added as a flow aid, while the mixer was running without cutter and agitator speed at 90 rpm for 1 minute.

The resulting powder was not flowable and had a bulk density of 875 g / L and contained 75 wt% of particles of 1700 microns or less. The powder characteristics were excellent. In other words, the dynamic flow rate was 133 ml / s and the compressibility was 2% v / v.

Example 10

A high bulk density detergent powder 750 Kg batch made of sodium tripolyphosphate and sodium carbonate, having the following composition, was prepared using a high speed mixer / granulator Fuca FS-1200.

The ratio of crystalline water soluble inorganic salt to total soapless surfactant in this composition was 2.5: 1. The process was carried out as follows.

(i) The solid components specified below were dry mixed for one minute at a stirrer speed of 100 rpm and a cutter speed of 1200 rpm in a Fuca mixer.

(ii) / (iii) Water and alkylbenzenesulfonic acid were added over 10 minutes while the mixer was operated at a stirrer speed of 35 rpm and a cutter speed of 1200 rpm. The temperature was maintained at about 45 ° C. by a cooling jacket filled with water. Since the acid was added slowly, granulation occurred as soon as the addition of the acid was completed. Thus no separate granulation step was required.

(iv) Alusil was added while the mixer was operated at a stirrer speed of 80 rpm and a cutter speed of 1200 rpm for 1.5 minutes.

The resulting detergent powder was not flowable and had an extremely high bulk density of 1050 g / l and contained about 70% by weight of particles up to 1700 microns. The dynamic flow rate was 71 ml / s and the extrusion rate was 4.7% v / v.

Example 11

60Kg batch of high bulk density detergent powder having the following composition was prepared using a high-speed mixer / granulator Sapphire (R) RMG-100.

1 added before neutralization step (described later)

2 added after neutralization step (described below)

3 Water added is about 1-1.5% by weight. The remainder is produced by neutralization from raw materials

The process was carried out as follows.

(i) The solid components specified below were dry mixed for 1 minute in a sapphire mixer at a stirrer speed of 75 rpm and a cutter speed of 2880 rpm.

This amount of sodium carbonate is 4.47 times greater than the amount required for the neutralization of alkylbenzenesulfonic acid (see step (ii)).

(ii) 0.1 parts of phthalocyanine blue dye and 1.0 parts of water were mixed in a silver hand mixer to prepare a mixture in the liquid, followed by alkylbenzenesulfonic acid having 93% purity of this dye dispersion and 29.19 parts in a silver hand mixer. Was mixed.

While the sapphire mixer was operated at a stirrer speed of 75 rpm and a cutter speed of 2880 rpm, the admixture to the liquid was added to the sapphire mixer for 5 minutes at a 0.47 ratio of liquid to solid material. The temperature was kept below 50 ° C. by a cooling jacket filled with water at 25 ° C. and circulated. At this stage the reaction mixture remained in the form of particles.

(iii) After neutralization was completed, the stirrer speed was maintained at 75 rpm and the cutter speed was reduced to 1440 rpm, followed by addition of the trace solid material (sodium carboxymethyl cellulose, mold) with an additional flow aid (dicamole 424) for 1 minute. It was. The mixture was granulated for 1 minute at a stirrer speed of 75 rpm and a cutter speed of 2880 rpm. Then, the foreign material was kept at 75 rpm for 1 minute without the cutter running.

The resultant powder was not flowable, homogeneous blue, and had a bulk density of 800 g / l. And 90% of the particles below 1700 microns and the average particle size was 539 microns. The dynamic flow rate was 81.1 ml / s and the compressibility was 9.2% v / v.

This powder exhibits a fast dissolution rate comparable to the highest bulk bulk powder currently on the market.

A sample was taken and examined by scanning electron microscopy, showing that the initial solid mixture had a much porous surface than the powder prepared without the addition of dicamole 424, a flow aid.

Example 12-14

This example illustrates the advantage of adding a flow aid (calcite, in this case calcite U) during the first stage of the process, i.

Three batches of 60Kg of high bulk density detergent powder having the following composition were prepared using a high-speed mixer / granulator Sapphire (R) RMG-100.

This powder is prepared by the process described in Example 1, but with the following differences with respect to the addition of the flow aid.

In this example the ratio of liquid to solid material after completion of the neutralization step was 0.55, 0.57 and 0.60, respectively.

All three powders had no fluidity, exhibited a homogeneous blue color, and had a bulk density of 700 g / L or more. Other powder characteristics are as follows.

The results show that when added continuously as in Example 12, excellent powder having a smaller average particle size and faster dissolution rate can be obtained.

Example 15-19

This example illustrates the effect of the type of flow aid added before the neutralization step.

A 60 kg powder batch was prepared by the general procedure used in the previous examples. However, different types of flow aids were added in different amounts as follows.

Powder characteristics are shown in the following table. It can be seen that the powder of Example 19 has the best overall properties.

Example 20-22

The general procedure of the previous example was repeated, except that a powder was prepared containing a mixed surfactant system of alkylbenzenesulfonate (produced by neutralization) and alpha-olefinsulfonate salt (post-added as a 4% by weight aqueous solution). The composition is as follows.

1 added before neutralization

2 added after neutralization

As shown in the following table, the powder characteristics of Examples 20 and 21 are not significantly different from those of Example 19. The powder of Example 22 has higher bulk density but poor flow characteristics.

Example 23-25

The general process of the previous example was carried out to prepare a detergent powder made of sodium tripolyphosphate having the following composition.

1 added before neutralization

2 added after neutralization

Powder characteristics are as follows.

Example 26-29

The general process of the previous example was carried out to prepare a 600Kg detergent powder made of sodium carbonate having the following composition. In Examples 27 and 28, the alpha-olefin sulfonate was post-added in the form of 70% by weight paste. In Example 29, after the neutralization step, the calcite was added in the form of an aqueous solution before much was added.

Powder characteristics are as follows.

It was found that the poor flow characteristics of the powder of Example 26 could be improved by post addition of small amounts of sodium tripolyphosphate. 7.5 wt% STP improves the dynamic flow rate to 55.3 ml / s. The 15.0 weight percent STP improves the dynamic flow rate to 60.0 ml / s.

Claims (27)

A method for producing a granular detergent composition or ingredient having a bulk density of 650 g / l or more, comprising: (i) a water-soluble alkaline inorganic agent in the form of a particulate solid in an amount of at least the amount required for neutralization in a high speed mixer / granule having both agitation and cutting operations Optionally allowing the material to optionally flow and mix with one or more other particulate solids, and (ii) adding acid precursors gradually into the high speed mixer / granulator while maintaining a temperature below 55 ° C. At least 650 g / l by a process comprising the step of neutralizing the material with a water-soluble alkaline inorganic material and maintaining the mixture in particulate form, and (iii) granulating the mixture in a high speed mixer / granulator in the presence of a liquid binder. A method for producing a granular detergent composition or component having a bulk density. The method according to claim 1, wherein the particulate water-soluble alkaline inorganic material is composed of sodium carbonate. The process according to claim 2, wherein the particulate water-soluble alkaline inorganic material is composed of sodium carbonate together with sodium bicarbonate and / or sodium silicate. The method of claim 1, wherein the acid precursor is a linear alkylbenzenesulfonic acid. The process of claim 1 wherein the ratio of liquid to solid at the completion of step (ii) is no greater than 0.60. The method of claim 1, wherein in step (ii), the acid precursor is added over 2-12 minutes. The method of claim 1, wherein water is added in an amount of 0.5-2.0% by weight of the total solids present in steps (i) and (ii), simultaneously with or prior to the addition of the acid precursor of step (ii). Manufacturing method characterized in that. The solid material of step (i) is characterized in that it contains sodium carbonate with at least one detergent builder selected from crystalline and amorphous alkali metal aluminosilicates, alkali metal phosphates, and mixtures thereof. Manufacturing method. The process according to claim 1, wherein the solid material present in step (i) further contains a surfactant in powder form. The method according to claim 1, wherein the solid substance present in step (i) contains a spray drying base powder. The method according to claim 1, wherein the particulate solid material present in step (i) contains a microparticulate flow aid. 12. The process of claim 11 wherein the flow aid is selected from zeolites, amorphous alkali metal aluminosilicates, heat treated pearlite, calcite, diatomaceous earth, or combinations thereof, and is prepared in an amount of 2-8% by weight of the final composition. Way. The method of claim 1, wherein the total amount of solids present in step (i) is at least 60% by weight of the total composition present in step (ii). The method according to claim 1, wherein the total amount of free water present in steps (i), (ii) and (iii) is 8% by weight or less of the total composition. A process according to claim 1, wherein the temperature in the high speed mixer / granulator is maintained at 47 ° C or lower during step (ii). The method of claim 1 wherein the high speed mixer / granulator is in the form of a bowl and has a vertical stirring axis. The method according to claim 1, wherein (iii) mixing the granular detergent composition or component with 0.2-12.0% by weight of the particulate flow aid after the granulation step is completed. 18. The method of claim 17, wherein the flow aid is microparticulate amorphous sodium aluminosilicate, heat treated pearlite, calcite, diatomaceous earth, or a combination thereof, and the amount of the additive is 0.2-5.0% by weight of the total composition. 18. The process according to claim 17, wherein the flow aid is microparticulate crystalline sodium aluminosilicate and the amount added is 3.0-12.0% by weight of the total composition. (i) fluidizing by mixing, together with one or more other particulate solid materials, water-soluble alkaline inorganic materials in the form of particulate solids or more necessary for neutralization in a high speed mixer / granulator having both stirring and cutting operations. (Ii) gradually adding an acid precursor to the high speed mixer / granulator while maintaining the temperature below 55 ° C, whereby the acid precursor is neutralized by the water-soluble alkaline inorganic material and the mixture is maintained in the form of particles. (iii) granules having a bulk density of at least 650 g / l and containing at least 50% by weight of particles of at most 1700 microns, prepared by a process comprising granulating the mixture in a high speed mixer / granulator in the presence of a liquid binder. Mold detergent composition or ingredient. 21. The detergent composition or component according to claim 20, which contains 5-45% by weight of anionic surfactant. 21. The non-satellite active substance of claim 20, wherein (a) at least a portion of the equatorial composition consists of anionic surfactants, (b) 15-45 weight percent (based on anhydrides) and optionally other crystalline or amorphous alkali metal aluminosilicates A detergent composition or component, wherein the ratio of (b) to (a) is at least 0.9: 1. The method of claim 20, wherein (a) 17-35% by weight of a soap-free detergent active material, at least a portion of which is composed of anionic surfactants, (b) 28-45% by weight of crystalline or amorphous alkali metal aluminosilicates and optionally other Comprising a detergent component, wherein the weight ratio of (b) to (a) is 0.9: 1-2.6: 1 detergent composition or component. 21. The composition of claim 20, comprising (x) at least 12-70% by weight of a soap-free detergent active material, (y) at least 15% by weight of a water soluble crystalline inorganic salt including sodium tripolyphosphate and / or sodium carbonate and optionally other detergent components. Wherein the weight ratio of (y) to (x) is 0.4: 1 or greater. 21. An inorganic builder salt according to claim 20, selected from (a) 5-45% by weight of anionic surfactant, (b) crystalline or amorphous alkali metal aluminosilicate, sodium tripolyphosphate, sodium carbonate, sodium silicate or combinations thereof. 70% by weight, (c) 0-20% by weight of a filler and / or udon aid selected from diatomaceous earth, silica, calcite, sodium sulfate, bentonite, kaolin or combinations thereof and optionally other detergent ingredients Detergent composition or ingredient. 21. The filler and / or flow of Claim 20 selected from (a) anionic surfactants, (b1) sodium tripolyphosphate, (b2) sodium carbonate, (c) diatomaceous earth silica, calcite, sodium sulfate, bentonite, kaolin or combinations thereof A detergent composition or component, comprising 0-20% by weight of an adjuvant and optionally other detergent components. The filler according to claim 20, which is selected from (a) 15-30% by weight of anionic surfactant, (b) 20-70% by weight of sodium carbonate, (c) diatomaceous earth, silica, calcite, sodium sulfate, bentonite, kaolin or combinations thereof And / or 0-20% by weight of a flow aid and optionally other detergent components.