DE69721287T2 - METHOD FOR PRODUCING A DETERGENT COMPOSITION BY A NO-TOWER PROCESS - Google Patents

Description

Field of the Invention

The present invention relates to generally a non-tower process for making a particulate detergent composition. More specifically, the invention is directed to a continuous one Procedure while which detergent agglomerate by adding a surfactant and Coating materials can be made in a number of mixers. The process produces free-flowing Detergent compositions, their density for a wide range Consumer requirements can be set, and soft commercially can be distributed.

Background of the Invention

Within the detergent industry existed in recent Time a considerable Interest in laundry detergents which are "compact" and therefore have low dosage volumes. For the production of these so-called low-dose detergents Many attempts have been made to facilitate detergents high bulk density to produce, for example with a density of 600 g / l or higher. The Low dose detergents are currently highly desired because they conserve resources and are sold in small packages can, which for consumers are more comfortable. However, the extent to which modern detergent products are "compact" in nature have to indefinite. Indeed prefer many consumers, especially in developing countries, to continue higher Dosage levels in their respective laundry procedures.

Generally there are two main ones Types of process by which detergent granules or powder can be produced. The first type of process involves spray drying an aqueous detergent slurry in a spray drying tower, around highly porous Manufacture detergent granules (e.g. tower process for low density Detergent compositions). In the second type of procedure, the different Detergent components dry-mixed, after which they are mixed with a binder such as a non-ionic or anionic surfactant, to produce high density detergent compositions (e.g. agglomeration processes for high density Detergent compositions). In the two procedures above are the main factors affecting the density of the resulting Master detergent granules, the shape, porosity and particle size distribution the granulate, the density of the different raw materials, the shape of the various starting materials and their respective chemical composition.

There have been many attempts in the art to provide methods that increase the density of detergent granules or powders. Particular attention has been paid to the compression of spray-dried granules by "post-tower" treatments. For example, one approach involves a batch process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulfate are densified in a Marumerizer ^® and are made spherical. This device comprises a substantially horizontal roughened, rotatable table positioned within and at the base of a substantially vertical smooth-walled cylinder. However, this process is essentially a batch process and is therefore less suitable for the large scale production of detergent powders. More recently, other attempts have been made to provide a continuous process for increasing the density of "post tower" or spray dried detergent granules. Typically, such methods require a first device which pulverizes or crushes the granules and a second device which increases the density of the pulverized granules by agglomeration. Although these processes achieve the desired increase in density by treating or densifying "post-tower" or spray-dried granules, they are limited in their ability to achieve higher surfactant levels without a subsequent coating step. In addition, the treatment or compression using the "post tower" is not favorable in terms of economy (high capital costs) and the complexity of the procedure. Furthermore, all of the above-mentioned processes are mainly aimed at the compression or other processing of spray-dried granules. Currently, the relative amounts and types of materials that are subjected to spray drying processes in the manufacture of detergent granules have been limited. For example, it has been difficult to achieve high levels of surfactant in the resulting detergent composition, a feature that simplifies the manufacture of detergents in a more efficient manner. Thus, it would be desirable to have a method at hand that can make detergent compositions without the limitations imposed by conventional spray drying techniques.

For this reason, the art is also rich in disclosures of processes involving agglomerating detergent compositions. For example, attempts have been made Agglomerate detergent builders by mixing zeolite and / or layered silicates in a mixer to form free-flowing agglomerates. While such attempts suggest that their methods can be used to make detergent agglomerates, they do not provide a mechanism by which starting detergent materials in the form of pastes, liquids and dry materials can be effectively agglomerated into tough, free-flowing detergent agglomerates.

Consequently, remains in the field There is a need for an agglomeration (non-tower) process for continuous Preparation of a high density detergent composition directly from starting detergent ingredients and preferably the density can be adjusted by adjusting the process conditions be achieved. Likewise, there remains a need for such a method, which is more efficient, flexible and economical to manufacture in the large scale of detergents (1) with regard to flexibility in the final density the final composition and (2) flexibility in terms of Introduction of several different types of detergent components (especially liquid Ingredients) to facilitate the process.

Set the following references on the compression of spray-dried Granules: Appel et al., U.S. Patent No. 5,133,924 (Lever); Bortolotti et al., U.S. Patent No. 5,160,657 (Lever); Johnson et al., British Patent No. 1,517,713 (Unilever) and Curtis, European patent application 451 894.

Set the following references focus on the production of detergents by agglomeration: Beujean et al., Publication No. WO 93/23523 (Henkel), Lutz et al., U.S. Patent No. 4,992,079 (FMC Corporation); Porasik et al., U.S. Patent No. 4,427,417 (Korex); Beerse et al., U.S. Patent No. 5,108,646 (Procter &Gamble); Capeci et al., U.S. Patent No. 5,366,652 (Procter &Gamble); Hollingsworth et al., European patent application 351,937 (Unilever); Swatling et al., U.S. Patent No. 5,205,958; Dhalewadikar et al., Disclosure No. WO 96/04359 (Unilever).

For example, describes the disclosure No. WO 93/23523 (Henkel) the process comprising the pre-agglomeration through a low speed mixer and the further agglomeration step a high speed mixer to obtain a high density Detergent composition in which less than 25% by weight of the granules a diameter over Have 2 mm. U.S. Patent No. 4,427,417 (Korex) describes a continuous agglomeration process that prevents clumping and oversized agglomerates reduced.

The US 5,554,587 discloses a method of making detergent compositions comprising introducing air into a mixer during agglomeration of a surfactant paste and other detergent ingredients so that at least a minor amount of water from the surfactant paste is absorbed by the air.

WO 96 09370 discloses a method for the manufacture of high density detergent compositions comprising the steps of mixing a surfactant paste and dry detergent ingredients in a mixer to form the first agglomerates, the conditioning of the first agglomerates to obtain second agglomerates with a specific particle size, the Recycling of any agglomerates that do not have the desired particle size, for another Agglomeration to obtain second agglomerates with the desired one Particle size, and adding detergent ingredients to the second agglomerates to form a high density detergent composition.

The EP 663 439 discloses a method of making a detergent composition comprising the steps of making a detergent paste comprising water-soluble silicate salt and surfactant or water-soluble polymer, and dispersing the paste with a builder powder under pressure.

WO 93 25378 discloses a method for the preparation of detergent compositions comprising the steps the dispersing of a surfactant paste via a powder stream, the Agglomeration of the paste and powder in a mixer and the Drying or cooling of agglomerates.

WO 95 12659 stands up the problem of producing detergents with low relative humidity at elevated Process temperatures and dissolves this problem by using a preconditioned gas in the procedural conditions.

The US 5,489,392 discloses a method of making high density detergents comprising the steps of mixing a surfactant paste in a mixer to form agglomerates, sieving the agglomerates to form a first agglomerate mixture, separating the agglomerates by particle size, and either grinding or recycling the agglomerates for one further agglomeration to obtain a final agglomerate mixture with the desired particle size and admixing detergent ingredients to the final agglomerate mixture to obtain a high density detergent composition.

WO 92 01036 discloses a method for the production of surfactant granules, comprising the steps of Mixing an aqueous surfactant with a solid to form of granules, the drying of the granules and the recycling of the dried granules as a portion of the solid.

It is also known to use a fluidized bed for other purposes when making particulate detergents. For example, GB-A-2 209 172 proposes a liquid material on fluidi Sprayed or swirled particulate material comprising a builder, and it is particularly proposed to achieve this in order to achieve an in situ reaction in the fluidized bed between fluidized particulate material comprising at least one alkaline builder carrier and liquid material based on the bed is sprayed and which comprises at least one acid precursor of an anionic detergent-active compound.

The process does not use the usual Spray drying towers, which currently in the manufacture of high composition Restricted surfactant load are. About that in addition, the method of the present invention is more efficient more economical and flexible with regard to the variety of detergent compositions, which can be produced in the process. Furthermore, the procedure better for environmental concerns in that it doesn't use spray drying towers, which are typically particulates and volatile organic compounds into the atmosphere submit.

As used herein, the term "agglomerates" refers to particles formed by agglomerating raw materials with binders such as surfactants and / or inorganic solutions / organic solvents and polymer solutions. As used herein, the term "granulate" refers to the thorough fluidization of agglomerates to produce free-flowing, round-shaped granular agglomerates. As used herein, the term "mean residence time" refers to the following definition:
mean residence time (h) = mass (kg) / flow rate (kg / h)

All percentages used herein are expressed as "weight percent" unless otherwise stated. All conditions here are weight ratios, unless otherwise stated. As used herein "Comprehensive" means that other steps and other components, which do not affect the result can be added. That term includes the expressions "consisting of" and "consisting essentially of".

According to a first aspect of Invention becomes a method of making a granular detergent composition provided with a density of at least about 600 g / l.

The process includes the following Steps:

• (a) dispersing a surfactant, and coating the surfactant with fine powder with a diameter of 0.1 to 500 micrometers in a mixer, conditions of the mixer including (i) 2 to 50 seconds average residence time, (ii) 4 to 25 m / s top speed and (iii) 0.15 to 7 kJ / kg energy state, forming agglomerates become; and
• (b) granulating the agglomerates in a fluid bed drying device, while Drops of liquid Detergent material is sprayed into the bed in an amount of up to 20%, wherein conditions of the vortex device include (i) 1 to 10 minutes mean residence time, (ii) 100 to 300 mm depth of non-fluidized Bed, (iii) no more than 50 micron drop spray size, (iv) 175 to 250 mm spray height, (v) 0.2 to 1.4 m / s vortex speed and (vi) 12 to 100 ° C bed temperature.

The invention leads to the production of granular detergent compositions with a high density of at least about 600 g / l.

First cut [step (A)]

In the first step of the process become surfactant, d. H. one or more aqueous and / or non-aqueous surfactant (s), which) in the form of powder, paste and / or liquid is present, and fine powder with a diameter of 0.1 to 500 Microns, preferably about 1 to about 100 microns, into one Mixer fed, so that agglomerates are made (The definition of surfactants and fine powder are described in detail hereinafter). If necessary, an internal circuit flow of powder with a Diameters from about 0.1 to about 300 microns produced from the Fluidized bed device, which hereinafter in the second step is described, in addition to the fine powder are fed into the mixer. The amount of such an internal circuit flow of powder can be 0 to about 60% by weight of the final product from the process of the present invention be.

In another embodiment of the invention the surfactants) initially into a mixer or pre-mixer (e.g. a conventional Screw extruder or other similar mixer) before the above are fed, after which the mixed detergent materials in the mixer of the first step, as described herein for the agglomeration, supplied become.

The average residence time of the mixer is in the range of about 2 to about 50 seconds, and the top speed of the mixer is in the range of about 4 m / s to about 25 m / s, the energy per unit mass of the mixer (energy state) is in the range of about 0.15 kJ / kg to about 7 kJ / kg, more preferably the average residence time of the mixer is in the range of about 5 to about 30 seconds, and the top speed of the mixer is in the range of about 6 m / s to about 18 m / s, the energy per unit mass of the mixer (energy state) is in the range of about 0.3 kJ / kg to about 4 kJ / kg, and most preferably the average residence time of the mixer is in the range of about 5 to about 20 seconds, and the spit Zen speed of the mixer is in the range of about 8 m / s to about 18 m / s, and the energy per unit mass of the mixer (energy state) is in the range of about 0.3 kJ / kg to about 4 kJ / kg.

The examples of mixers for the first Can step any type of mixer known to those skilled in the art, as long as the mixer has the above-mentioned condition for the first Can keep pace. An example can be a Lodige CB mixer, manufactured by Lodige (Germany). As a result The first step is the resulting product (agglomerates with fine powder on the surface the agglomerates) obtained.

Second step

In the second step of the process the resulting product of the first step (the agglomerates) fed into a fluidized bed device while droplets of liquid Detergent material can be sprayed in an amount of up to 20%, granulation to produce free-flowing, high-density granules to reinforce. In the second step, the resulting product becomes the first Step so thoroughly fluidized that the Granules from the second step have a round shape. If necessary, you can about 0 to about 10%, more preferably about 2-5% of the powder detergent materials the type used in the first step and / or others Detergent ingredients are added in the second step. The sprayed into the bed liquid Detergent materials can be of the type used in the first step, and / or other detergent ingredients can added to the step of granulation and coating on the surface to reinforce the granules.

In order to achieve the density of at least about 600 g / l, preferably more than 650 g / l, the conditions of a fluidized bed device are as follows:
Average residence time: about 1 to about 10 minutes
Non-fluidized bed depth: about 100 to about 300 mm
Drop spray size: no more than about 50 microns
Spray height: about 175 to about 250 mm
Vortex speed: about 0.2 to about 1.4 m / s
Bed temperature: about 12 to about 100 ° C,
more preferred
Average residence time: about 2 to about 6 minutes
Non-fluidized bed depth: about 100 to about 250 mm
Drop spray size: less than about 50 microns
Spray height: about 175 to about 200 mm
Vortex speed: about 0.3 to about 1.0 m / s
Bed temperature: about 12 to about 80 ° C.

The second step can do more than use a fluidized bed device (e.g. the combination of different Types of fluid bed devices such as fluid bed dryers and Fluidized bed cooler). If there is more than one fluidized bed device, each under the same scope of conditions, but the atomized liquid can be in only one of the beds. If two different Types of fluidized bed device can be used, the middle Total time of the second step about 2 to about 20 minutes, more preferably about 2 to 12 minutes.

A coating agent for improvement the fluidity and / or minimizing over-agglomeration the detergent composition can be on one or more of the following Places of the present process are added: (1) The coating agent can be placed right after the fluidized bed cooler or fluidized bed dryer are added, and / or (2) the coating agent can be between be added to the fluid bed dryer and the fluid bed cooler. The Coating agent is preferably selected from the group consisting of from aluminosilicates, silicates, carbonates and a mixture thereof. The coating agent not only improves the flow properties the resulting detergent composition, which is used by consumers therefore desired will that she a simple pouring or spoons of detergent during allowed to use, but also serves to control the agglomeration by preventing or minimizing over-agglomeration. Like the professional may well recognize over-agglomeration too undesirable flow properties and aesthetic Characteristics of the final detergent product lead.

Starting detergent materials

The total amount of surfactants in the products made by the present invention, which are included in the following detergent materials, of finely atomized liquid and additional detergent ingredients is generally about 5% to about 60%, more preferably about 12% to about 40%, more preferably about 15 to about 35% in percentage ranges. The surfactants, which are in the above standing may form any part of the method of the present invention, e.g. B. from one of the first step and / or the second step of the present invention.

Detergent surfactant (aqueous / non-aqueous)

The amount of the surfactant of the present Process can be about 5% to about 60%, more preferably about 12% to about 40%, more preferably about 15 to about 35% of the total of the final product obtained by the process of the present invention be.

The surfactant of the present process which in the above mentioned Starting detergent materials used in the first step is in the form of powdered, pasty or liquid Raw materials.

The surfactant itself is preferred chosen from anionic, nonionic, zwitterionic, ampholytic and canonical classes and compatible mixtures thereof. Here in useful Detergent surfactants are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972 and U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975. Useful canonical surfactants conclude also those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980 and U.S. Patent 4,239,659 to Murphy, issued on December 16, 1980. The surfactants become anionic and nonionic are preferred, and the anionic are most preferred.

Nonlimiting examples of the preferred anionic surfactants useful in the present invention include the conventional C ₁₁ -C ₁₈ alkylbenzenesulfonates ("LAS"), primary, branched and statistical C ₁₀ -C ₂₀ alkyl sulfates ("AS"), the secondary C ₁₀ -C ₁₈ - (2,3) -alkyl sulfates of the formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ ) CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ ) CH ₂ CH ₃ , where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate and the C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AE _x S"; specifically EO 1-7 ethoxysulfates).

helpful close anionic surfactants also water soluble Salts of 2-acyloxyalkane isulfonic acids with about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane residue; water soluble salts olefin sulfonates of about 12 to 24 carbon atoms; and beta-alkyloxyalkanesulfonates, containing about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane unit.

Optionally, other exemplary surfactants useful in the paste of the invention include C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxy carboxylates), the C _10-18 glycerol ethers, the C ₁₀ -C ₁₈ alkyl polyglycosides, and the corresponding sulfated ones Polyglycosides and alpha-sulfonated C ₁₂ -C ₁₈ fatty acid _esters . If desired, the conventional nonionic and amphoteric surfactants, such as the C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including the so-called narrow peak alkyl ethoxylates, and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and ethoxy / propoxy) can be mixed ), C ₁₀ -C ₁₈ amine oxides and the like may also be included in the overall compositions. The C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ₁₂ -C ₁₈ -N-methylglucamides; see WO 92 06154. Other sugar-derived surfactants include the N-alkoxypolyhydroxy fatty acid amides, such as C ₁₀ -C ₁₈ -N- (3-methoxypropyl) glucamide. The N-propyl to N-hexyl-C ₁₂ -C ₁₈ glucamides can be used for low foaming. Conventional C ₁₀ -C ₂₀ soaps can also be used. If high foaming is desired, the branched chain C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional surfactants that can be used are listed in standard texts.

Cationic surfactants can also be used as a detergent surfactant herein, and suitable quaternary ammonium surfactants are selected from mono-C ₆ -C ₁₆ , preferably -C ₆ -C ₁₀ -N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Ampholytic surfactants can also be used as a detergent surfactant herein, where they are aliphatic derivatives of heterocyclic secondary and tertiary amines; zwitterionic surfactants, which include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; water-soluble salts of esters of alpha-sulfonated fatty acids; alkyl ether; water soluble salts of olefin sulfonates; beta-alkyl-oxyalkansulfonate; Betaines having the formula R (R ¹ ) ₂ N ⁺ R ² COO ^- , wherein R is a C ₆ -C ₁₈ hydrocarbyl group, preferably a C ₁₀ -C ₁₆ alkyl group or C ₁₀ -C ₁₆ acylamidoalkyl group, each R ¹ typically C ₁ -C ₃ alkyl, preferably methyl, and R _{2 is} a C ₁ -C ₅ hydrocarbyl group, preferably a C ₁ -C ₃ alkylene group, more preferably a C ₁ -C ₂ alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethylbetaine; Hexadecyldimethylbetain; C _12-14 acylamidopropyl betaine; C _8-14 acylamidohexyl diethyl betaine; 4 [C _14-16 acylmethylamidodiethylammonio] -1-carboxybutane; C _16-18 acylamidodimethylbetaine; C _12-16 acylamidopentanediethyl betaine; and C _12-16 acylmethylamidodimethylbetaine. Preferred betaines are C _12-18 dimethylammonio hexanoate and the C _10-18 aclala midopropane (or ethane) dimethyl (or diethyl) betaine; and the sulatins with the formula R (R ¹ ) ₂ N ⁺ R ² SO ₃ -, wherein R is a C ₆ -C ₁₈ hydrocarbyl group, preferably a C ₁₀ -C ₁₆ alkyl group, more preferably a C ₁₂ -C ₁₃ - Is alkyl group, each R ^{1 is} typically C ₁ -C ₃ alkyl, preferably methyl, and R ^{2 is} a C ₁ -C ₆ hydrocarbyl group, preferably a C ₁ -C ₃ alkylene or preferably hydroxyalkylene group. Examples of suitable sultaines include C ₁₂ -C ₁₄ dimethylammonio-2-hydroxypropyl sulfonate, C ₁₂ -C ₁₄ amidopropylammonio-2-hydroxypropyl sulfate, C ₁₂ -C ₁₄ dihydroxyethylammoniopropane sulfonate and C _16-18 dimethylammoniohexane sulfonate, where C _12-14 -Amidopropylammonio-2-hydroxypropylsultain is preferred.

Fine powder

The amount of fine powder of the present method, which is used in the first step about 94% to 30%, preferably 86% to 54% in the total Starting material for be the first step. The starting fine powder of the present The preferred method is chosen from the group consisting of ground soda ash, pulverized sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulfates, Aluminosilicates, crystalline layered silicates, nitrilotriacetates (NTA), phosphates, precipitated Silicates, polymers, carbonates, citrates, powdered surfactants (such as pul-verisierten alkane sulfonic acids) and an internal recycle stream of powder obtained from the process of the present invention occurs where the average Diameter of the powder 0.1 to 500 microns, preferably 1 to 300 microns, more preferably 5 to 100 microns. In the event of the use of hydrated STPP as the fine powder of present invention, STPP becomes a mirror of not less than 50% hydrated is preferred. The here as Detergent builders preferably use aluminosilicate ion exchange materials both a high calcium ion exchange capacity and a high exchange rate on. Without intention is bound by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several related factors, which derived from the process by which the aluminosilicate ion exchange material will be produced. In this regard, those used herein Aluminosilicate ion exchange materials preferably according to Corkill et al., U.S. Patent No. 4,605,509 (Procter & Gamble).

The aluminosilicate ion exchange material is preferably located in "sodium" form because the potassium and hydrogen forms of the present aluminosilicate not so high exchange rate and capacity show how they are provided by the sodium form. Furthermore the aluminosilicate ion exchange material is preferably in one over-dried Form before so that the Preparation of snap-resistant detergent agglomerates as described herein is facilitated. The aluminosilicate ion exchange materials used herein preferably have particle size diameters, what their effectiveness optimize as a detergent builder. The term "particle size diameter", as used herein the average particle size diameter of a given Aluminosilicate ion exchange material as determined by conventional ones analytical techniques such as microscopic determination and scanning electron microscope (SEM). The preferred particle size diameter of the aluminosilicate from about 0.1 microns to about 10 microns, more preferred from about 0.5 microns to about 9 microns. Most preferred amounts the particle size diameter to about 1 micron to about 8 microns.

Preferably the aluminosilicate ion exchange material has the formula Na _z [(AlO ₂ ) _z · (SiO ₂ ) _y ] × H ₂ O wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5, and x is from about 10 to about 264. The aluminosilicate more preferably has the formula Na ₁₂ [(AlO ₂ ) ₁₂ · (SiO ₂ ) ₁₂ ] × H ₂ O wherein x is from about 20 to about 30, preferably about 27. These preferred aluminosilicates are commercially available, for example under the designations Zeolite A, Zeolite B and Zeolite X. Alternatively, naturally occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be prepared as described in Krummel et al., U.S. - Patent No. 3,985,669, the description of which is incorporated herein by reference.

The aluminosilicates used herein are further characterized by their ion exchange capacity, which is at least about 200 mg equivalent of CaCO ₃ hardness / gram calculated on an anhydrous basis, and which preferably ranges from about 300 to 352 mg equivalent of CaCO ₃ -Hardness / gram.

Finely atomized liquid

The amount of finely atomized liquid sprayed into the fluidized bed of the present method can be about 1% to about 10% (active ingredient basis), preferably 2% to about 6% (active ingredient basis) in the total amount of the final product obtained by the method of the present Invention. The finely atomized liquid of the present process can be chosen are from the group consisting of liquid silicate, anionic or cationic surfactants, which are in liquid form, aqueous or non-aqueous polymer solutions and Mixtures of these. Other optional examples of the finely atomized liquid of the present invention Sodium carboxymethyl cellulose solution, Polyethylene glycol (PEG), and solutions of dimethylene triamine pentamethylphosphonic acid (DETMP).

The preferred examples of the anionic surfactant solutions, which as the finely atomized Liquid in about 88-97% active can be used in the present invention HLAS, about 30-50% active NaLAS, about 28% active AE3S solution, about 40-50% active liquid Silicate, and so on.

Cationic surfactants can also be used as the finely atomized liquid herein, and suitable quaternary ammonium surfactants are selected from mono-C ₆ -C ₁₆ , preferably -C ₆ -C ₁₀ -N-alkyl or alkenylammonium surfactants, in which the remaining N- Positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

mit einem modifizierten Polyamin der Formel V_(n+1)W_mY_nZ, oder ein Polyamingrundgerüst, entsprechend der Formel:

mit einer modifzierten Polyamin-Formel V_(n–k+1)W_mY_nY'_kZ, worin k kleiner als oder gleich n ist, wobei das Polyamingrundgerüst vor der Modifikation ein Molekulargewicht von größer als etwa 200 Daltons aufweist, worinPreferred examples of the aqueous or non-aqueous polymer solutions which can be used as the atomized liquid in the present invention are modified polyamines comprising a polyamine backbone, according to the formula:

with a modified polyamine of the formula V _{(n + 1)} W _m Y _n Z, or a polyamine backbone, corresponding to the formula:

with a modified polyamine formula V _{(n-k + 1)} W _m Y _n Y ' _k Z, wherein k is less than or equal to n, wherein the polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein

• i) V units end units are of the formula:
  
  wherein backbone compound R units are selected from the group consisting of C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, - (R ¹ O) _x R ¹ -, - (R ¹ O) _x R ⁵ (OR ¹ ) _x -, - (CH ₂ CH (OR ² ) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH (OR ² ) CH ₂ ) _w -, -C (O) (R ⁴ ) _r C (O) -, -CH ₂ CH (OR ² ) CH ₂ - and mixtures thereof; wherein R ^{1 is} C ₂ -C ₆ alkylene and mixtures thereof; R ^{2 is} hydrogen, - (R ¹ O) _x B and mixtures thereof; R ^{3 is} C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkyl, C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl, and mixtures thereof; R ^{4 is} C ₁ -C ₁₂ alkylene, C4-C12 alkenylene, C ₈ -C ₁₂ aryl alkylene, C ₆ -C ₁₀ arylene and mixtures thereof; R ⁵ C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C4-C12 dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene, -C (O) -, -C (O) NHR ⁶ NHC (O) -, -R ¹ (OR ¹ ) -, -C (O) (R ⁴ ) _r C (O) -, -CH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) CH ₂ O (R ¹ O) _y R ¹ OCH ₂ CH (OH) CH ₂ - and mixtures thereof; R ^{6 is} C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene; E units are selected from the group consisting of hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, - (CH ₂ ) _p CO ₂ M, - (CH ₂ ) _q SO ₃ M, -CH (CH ₂ CO ₂ M) CO ₂ M, - (CH ₂ ) _p PO ₃ M, - (R ¹ O) _x B, -C ( O) R ³ and mixtures thereof; Oxide; B hydrogen, C ₁ -C ₆ alkyl, - (CH ₂ ) _q SO ₃ M, - (CH ₂ ) _p CO ₂ M, - (CH ₂ ) _q (CHSO ₃ M) CH ₂ SO ₃ M, - ( CH ₂ ) _q - (CHSO ₂ M) CH ₂ SO ₃ M, - (CH ₂ ) _p PO ₃ M, -PO ₃ M and mixtures thereof; M is hydrogen or a water-soluble cation in an amount sufficient to satisfy charge balance; X is a water soluble anion; m is from 4 to about 400; n is from 0 to about 200; p has the value 1 to 6; q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1. An example of the most preferred polyethyleneimines would be a 1800 molecular weight polyethyleneimine further modified by ethoxylation to a level of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E7). For the above polymer solution, it is preferred to be pre-complexed with anionic surfactant such as NaLAS.

Other preferred examples of the aqueous or non-aqueous polymer solutions which can be used as the finely atomized liquid in the present invention are polymeric polycarboxylate dispersants which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomer acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene malonic acid. The presence of monomeric segments containing no carboxylate residues, such as vinyl methyl ether, styrene, ethylene etc., in the polymeric polycarboxylates described herein is suitable provided that such segments make up no more than about 40% by weight of the polymer.

Homopolymeric polycarboxylates, which Molecular weights above 4000, as will be described next prefers. Particularly suitable homopolymeric polycarboxylates can be made from acrylic acid be derived. Such acrylic acid-based polymers, which useful herein are the most water soluble Salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably in the range from over 4,000 to 10,000 preferred from over 4000 to 7000, and the strongest preferred from over 4000 to 5000. Water soluble Salts of such acrylic acid polymers can for example the alkali metal, ammonium and substituted ammonium salts lock in.

Co-polymeric polycarboxylates such as Acrylic / maleic copolymers can also be used. Such materials close the water soluble Salts of copolymers of acrylic acid and maleic acid on. The average molecular weight of such copolymers in the acid form is preferably in the range of about 2,000 to 100,000, more preferably about 5000 to 75000, the strongest preferably about 7000 to 65000. The ratio of acrylate to maleate segments in such copolymers is generally in the range of about 30: 1 to about 1: 1, more preferably about 10: 1 to 2: 1. Water soluble salts such acrylic acid / maleic acid copolymers can for example the alkali metal, ammonium and substituted ammonium salts lock in. For the polymer solution above it is preferable to precomplex with anionic surfactant such as LAS to be.

Additional detergent ingredients

The detergent starting material in present procedures may be additional Include detergent ingredients and / or any number of additional components into the detergent composition during the subsequent steps of the present procedure. These additional Close ingredients other cleaning builders, bleaches, bleach activators, foam boosters or Suds suppressors, Anti-Trübungsund Anti-corrosion agents, dirt suspending agents, dirt releasing agents, Germicides, pH adjusters, non-builder alkalinity sources, Chelating agents, smectite clays, enzymes, enzyme stabilizing agents Agents and perfumes on; see U.S. Patent 3,936,537, issued February 3, 1976 Baskerville, Jr. et al., Which is incorporated herein by reference is.

Other builders can generally be selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxysulfonates, polyacetates, carboxylates and polycarboxylates. The alkali metal, especially sodium salts of the above are preferred. Preferred for use herein are the phosphates, carbonates, C _10-18 fatty acids, polycarboxylates, and mixtures thereof. Further preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate, mono- and disuccinates and mixtures thereof (see below).

Compared to amorphous sodium silicates, crystalline layered sodium silicates show a significantly increased calcium and magnesium ion exchange capacity. In addition, prefer the layered sodium silicates Magnesium ions opposite Calcium ions, a necessary trait to ensure that essentially the whole "hardness" is removed from the wash water. These are crystalline layered sodium silicates however, generally more expensive than amorphous silicates and others Builder. Therefore, in order to provide an economically feasible laundry detergent the proportion of crystalline layered sodium silicates used expertly be determined. Such crystalline layered sodium silicates are discussed in Corkill et al., U.S. Patent No. 4,605,509, earlier herein was included by reference to it.

Specific examples of inorganic Phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate with a degree of polymerization of about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, which Sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Other phosphorus builder compounds are described in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148; all of which are incorporated herein by reference.

Examples of non-phosphorus inorganic builders are tetraborate decahydrate and silicates with a weight ratio of SiO ₂ to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Water-soluble, non-phosphorus-containing organic builders useful herein include the various alkali metal, ammonium, and substituted ammonium polyacetates, carboxylates, polycarboxylates, and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid.

Polymeric polycarboxylate builders are shown in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the description of which is incorporated herein by reference. Such materials close what serially soluble salts of homo- and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid. Some of these materials are useful as the water-soluble anionic polymer, as described hereinafter, but only when in intimate admixture with the non-soap anionic surfactant.

Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and U.S. patent 4,246,495, issued March 27 1979 to Crutchfield et al., Both of which are herein incorporated by reference are involved. These polyacetal carboxylates can by Bringing together an ester of glyoxylic acid and a polymerization initiator be produced under polymerization conditions. The resulting one Polyacetal carboxylate ester is then attached to chemically stable end groups attached to the polyacetal carboxylate against rapid depolymerization in alkaline solution to stabilize, converted to the appropriate salt and to a detergent composition added. Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions, comprising a combination of tartrate monosuccinate and tartrate disuccinate, described in U.S. Patent 4,663,071, Bush et al., issued May 5. May 1987, the disclosure of which is incorporated herein by reference is.

Bleach and activators will be described in U.S. Patent 4,412,934, Chung et al., issued November 1 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20 1984, both of which are incorporated herein by reference. Chelating agents are also described in the U.S. patent 4,663,071, Bush et al., From column 17, line 54 to column 18, line 68, which is incorporated herein by reference. Foam modifiers are also optional components and are described in U.S. Patent 3,933,672 issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both of which are incorporated herein by reference.

Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al. issued on August 9, 1988, column 6, line 3, to column 7, line 24, which is incorporated herein by reference. suitable additional Detergent builders for use herein are enumerated in that Baskerville patent, column 13, line 54, through column 16, line 16, and in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, both of which are incorporated herein by reference.

Optional procedural steps

Optionally, the process can Spraying step an additional Binder in the mixer for encompass the present invention. A binder is used for the purpose improving agglomeration by providing a "binding" or "adhesive" means for added the detergent components. The binder is preferred chosen from the group, consisting of water, anionic surfactants, nonionic surfactants, liquid Silicates, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof. Other suitable binder materials including those listed herein are described in Beerse et al., U.S. Patent No. 5,108,646 (Procter & Gamble Co.), the description of which is incorporated herein by reference is.

Other optional, in the present Processes contemplated include sieving the oversized detergent agglomerates in a screening or classifying device, which a variety of Can take forms, including but not limited to conventional Sieves which for the desired Particle size of the finished Detergent product selected become. Other optional steps include conditioning the detergent agglomerates by subjecting the agglomerates to an additional Drying using the earlier discussed Contraption.

Another optional step of the The present process entails the finishing of the resulting Detergent agglomerates by a variety of processes, including spray on and / or admixing other conventional detergent ingredients. For example, the finishing step involves spraying on Fragrances, brighteners and enzymes on the finished agglomerates, for a more complete To provide detergent composition. Such techniques and components are well known in the art.

Another optional step in the process includes a process structuring the surfactant paste, z. B. hardening an aqueous anionic Surfactant paste by introducing a paste-hardening material using an extruder, before the process of the present invention.

To make the present invention easier understandable to make reference to the following examples, which are intended to be illustrative only and not for the Restricting scope are intended.

Examples

Example 1:

The following is an example of getting high density agglomerates using a Lödige CB mixer (CB-30) followed by a fluid bed device for others Granulations.

[Step 1] 250-270 kg / h of an aqueous coconut fatty alcohol sulfate surfactant paste (C ₁₂ -C ₁₈ , 71.5% active) is mixed with the pencil tools of a CB-30 mixer together with 220 kg / h of pulverized STPP (medium Particle size of 40-75 microns), 160-200 kg / h of ground solo ash (average particle size 15 micrometers), 80-120 kg / h of ground sodium sulfate (average particle size 15 micrometers) and the 200 kg / h of the internal circulating stream of powder. The surfactant paste is added at about 40 to 52 ° C and the powders are fed in at room temperature. The conditions of the CB-30 mixer are as follows:
Average residence time: 10-18 seconds
Top speed: 7.5–14 m / s
Energy status: 0.5–4 kJ / kg
Mixer speed: 550-900 rpm
Jacket temperature: 30 ° C

[Step 2] The agglomerates from the CB mixer are fed into a fluid bed drying device for drying, rounding off and for the growth of the agglomerates. 20-120 kg / h liquid silicate (43% solids, 2.0 R) are added to the fluidized bed dryer at 35 ° C. The condition of the fluid bed drying device is as follows:
Average residence time: 2-4 minutes
Non-fluidized bed depth: 200 mm
Drop spray size: less than 50 microns
Spray height: 175-250 mm (above the distributor plate)
Vortex speed: 0.4-0.8 m / s
Bed temperature: 40-70 ° C

The resulting granules step 2 have a density of about 600 g / l and can optionally the optional method of cooling, Classifying or sieving and / or grinding.

Example 2:

The following is an example of Obtaining high density agglomerates using a Lödige CB mixer (CB-30) followed by a fluid bed device for others Granulations.

[Step 1] 15 kg / h - 30 kg / h HLAS (an acid precursor of C ₁₁ -C ₁₈ allcylbenzenesulfonate; 95% active) at about 50 ° C and 20 kg / h AE ₃ S liquid (C ₁₀ -C _18- alkyl alkoxysulfates, EO-3; 28 active) are made using the pencil tools of a CB-30 mixer together with 220 kg / h powdered STPP (average particle size of 40-75 micrometers), 160-200 kg / h ground soda ash ( average particle size of 15 micrometers), 80-120 kg / h of ground sodium sulfate (average particle size of 15 micrometers) and the 200 kg / h of the internal circulating stream from powder. The surfactant paste is added at about 40 to 52 ° C and the powders are fed in at room temperature. The conditions of the CB-30 mixer are as follows:
Average residence time: 10-18 seconds
Top speed: 7.5–14 m / s
Energy status: 0.5–4 kJ / kg
Mixer speed: 550-900 rpm
Jacket temperature: 30 ° C

[Step 2] The agglomerates from the CB-30 mixer are fed into a fluid bed dryer for drying, rounding and for the growth of the agglomerates. 20-80 kg / h of liquid silicate (43% solids, 2.0 R) are added to the fluidized bed drying device at 35 ° C. The condition of the fluid bed drying device is as follows:
Average residence time: 2-4 minutes
Non-fluidized bed depth: 200 mm
Drop spray size: less than 50 microns
Spray height: 175-250 mm (above the distributor plate)
Vortex speed: 0.4-0.8 m / s
Bed temperature: 40-70 ° C

The resulting granules step 2 have a density of about 600 g / l and can optionally the optional method of cooling, Classifying or sieving and / or grinding.

Example 3:

The following is an example of Obtaining high density agglomerates using a Lödige CB mixer (CB-30) followed by a fluid bed device for others Granulations.

[Step 1] 15 kg / h - 30 kg / h HLAS (an acid precursor of C ₁₁ -C ₁₈ alkylbenzenesulfonate; 95% active) at about 50 ° C and 250-270 kg / h of an aqueous coconut fatty alcohol sulfate surfactant paste (C ₁₂ -C ₁₈ 71.5% active) are made using the pencil tools of a CB-30 mixer together with 220 kg / h of pulverized STPP (average particle size of 40-75 micrometers), 160-200 kg / h of crushed soda ash (average particle size of 15 Micrometers), 80-120 kg / h of ground sodium sulfate (average particle size of 15 micrometers) and the 200 kg / h of the internal circulating stream from powder. The surfactant paste is added at about 40 to 52 ° C and the powders are fed in at room temperature. The conditions of the CB-30 mixer are as follows:
Average residence time: 10-18 seconds
Top speed: 7.5–14 m / s
Energy status: 0.5–4 kJ / kg
Mixer speed: 550-900 rpm
Jacket temperature: 30 ° C

[Step 2] The agglomerates from the CB-30 mixer are fed into a fluid bed dryer for drying, rounding and for the growth of the agglomerates. 20-80 kg / h of liquid silicate (43% solids, 2.0 R) are added to the fluidized bed drying device at 35 ° C. The condition of the fluid bed drying device is as follows:
Average residence time: 2-4 minutes
Non-fluidized bed depth: 200 mm
Drop spray size: less than 50 microns
Spray height: 175-250 mm (above the distributor plate)
Vortex speed: 0.4-0.8 m / s
Bed temperature: 40-70 ° C

The result from the fluidized bed drying device is fed into a fluidized bed cooling device. The conditions for the fluidized bed cooling device are as follows:
Average residence time: 2-4 minutes
Non-fluidized bed depth: 200 mm
Vortex speed: 0.4-0.8 m / s
Bed temperature: 12–60 ° C

The resulting granules step 2 have a density of about 600 g / l and can optionally the further process of classifying or screening and / or grinding be subjected.

Claims (10)

Agglomeration process for making a granular detergent composition with a density of at least about 600 g / l, comprising the steps: (A) Dispersing a surfactant, and coating the surfactant with fine Powder with a diameter of 0.1 to 500 μm in a mixer, subject to conditions of the mixer include (i) an average residence time of 2 to 50 seconds, (ii) 4 to 25 m / s top speed and (iii) 0.15 to 7 kj / kg Energy state, whereby agglomerates are formed; and (B) Granulating the agglomerates in a fluidized bed drying device, while Drops of liquid Detergent material is sprayed into the bed in an amount of up to 20%, wherein conditions of the vortex device include (i) 1 to 10 minutes mean residence time, (ii) 100 to 300 mm depth of non-fluidized Bed, (iii) not more than 50 μm Drop spray size, (iv) 175 to 250 mm spray height, (v) 0.2 to 1.4 m / s vortex speed and (vi) 12 to 100 ° C bed temperature. The method of claim 1, wherein 2 to 10% (active ingredient basis) liquid Detergent material can be sprayed into the bed. A method according to claim 1 or claim 2, wherein the sprayed liquid detergent material is selected from solutions of silicate, anionic surfactant, cationic surfactant and polymer. Method according to at least one of the preceding claims, wherein a coating agent immediately after the fluid bed dryer is added to the fluidity improve or overgranulation to minimize. A method according to at least one of claims 1 to 3, wherein the fluid bed drying device is followed is from a fluidized bed cooler. The method of claim 5, wherein a coating agent between the fluidized bed drying device and the fluid bed cooler or right after the fluidized bed cooler is added to make it flowable to improve, or overgranulation to minimize. The method of claim 1, wherein an aqueous or non-aqueous polymer solution with the surfactant is dispersed in step (a). The method of claim 1, wherein an internal recycle stream from powder from the fluidized bed device further step (a) is added. The method of claim 1, wherein the fine powder is selected from the group chosen consisting of soda ash, powdered sodium tripolyphosphate, hydrated tripolyphosphate, sodium sulfates, aluminosilicates, crystalline layered silicates, phosphates, precipitated silicates, Polymers, carbonates, citrates, nitrilotriacetates, powdered surfactants and mixtures thereof. The method of claim 1, wherein the total amount of surfactants for the The method of claim 1 from about 5% to about 60% of the total amount Composition as obtained by the method of claim 1 is.