JP3299984B2 - Method for producing detergent composition by non-tower process - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates generally to non-tower processes for producing granular detergent compositions. More particularly, the present invention relates to a continuous process in which detergent agglomerates are produced by feeding surfactants and coating materials into a series of mixers. In that process, the density can be marketed to meet a wide range of consumer needs,
Produce a free flowing detergent composition.

BACKGROUND OF THE INVENTION In recent years, there has been considerable interest in the detergent industry for laundry detergents that are "compact" and require low usage. In order to facilitate the production of these so-called low usage detergents, many attempts have been made to produce high bulk density detergents, for example of 600 g / or more. Low usage detergents are currently in high demand because they conserve resources and can be sold in smaller packages that are more convenient for consumers. However, in fact, the degree to which current detergent products need to be "compact" remains to be determined. In fact, many consumers continue to prefer higher usage levels in their washing operations, especially in developing countries.

Generally, there are two main types of processes in which detergent granules or powders are manufactured. In the first type of process,
The aqueous detergent slurry is spray dried in a spray drying tower to produce highly porous detergent granules (eg, a low density detergent composition tower process). In a second type of process, the various detergent components are dry-mixed and then they are agglomerated with a binder such as a nonionic or anionic surfactant to produce a high-density detergent composition (e.g., Agglomeration process of high-density detergent composition). In the above two processes, the important factors that determine the density of the resulting detergent granules are the shape, porosity and particle size distribution of the granules, the density of the different starting materials, the shapes of the different starting materials and their respective chemical properties. The composition.

 Provide a process to increase the density of detergent granules or powder
Many attempts have been made in the art above. Special attention
For densification of spray-dried granules by post tower treatment
Have been paid. For example, one attempt is to use tripolyphosphate
Spray containing sodium and sodium sulfate
Rye or granule detergent powder is Marumerizer Densification and
And a batch process to be spheroidized. This device is
The interior and base of a substantially vertical, smooth-walled cylinder
A substantially horizontal, coarse turntable located at the base
Become. However, this process is inherently batch
Process, so large-scale production of detergent powder
Not suitable. More recently, other attempts have been made
-"Or continuous to increase the density of spray-dried detergent granules
Made to serve the process. Typically, like this
First process to grind or pulverize granules
And a second device that increases the density of the pulverized granules by agglomeration
I do. These processes involve a “post tower” or
Processing or densifying play-dried granules to increase density
Can achieve the desired increase, but they will
Limited ability to increase surfactant levels without steps
is there. In addition, "post tower" processing or dense
Is economical (high capital cost) and operational complexity
Is not preferred. In addition, all of the above processes are spray
ー Dry granulation or other processing
It is about the Lord. Currently, spray granules are produced
-Relative amounts and types of substances subjected to the dry process
Is restricted. For example, the resulting detergent composition may
It was difficult to make Bell surfactant, but its characteristics
Signs make detergent production more efficient. These
Therefore, the detergent composition can be manufactured by the conventional spray drying technology.
Have a process that can be produced without restrictions
Is desired.

To that end, the art is also rich in disclosing processes involving agglomeration of detergent compositions. For example, attempts have been made to agglomerate detergent builders by mixing zeolites and / or laminated silicates in a mixer to form free flowing agglomerates. While such attempts suggest that the processes can be used to produce detergent agglomerates, the starting detergent material in the form of pastes, liquids and dry matter is converted into a crisp free flowing detergent agglomerate. They do not provide a mechanism that can be effectively aggregated.

Accordingly, there remains a need in the art to have an agglomerated (non-tower process) process for continuously producing a detergent composition and densifying directly from the starting detergent components, preferably reducing the dense process conditions. This can be achieved by adjustment. Moreover, the large scale of detergents in terms of (1) flexibility in terms of final density of the final composition and (2) flexibility in incorporating several different types of detergent components (especially liquid components) into the process. There remains a need for more efficient, flexible and economical such processes to facilitate production.

The following references relate to densifying spray-dried granules: Appel et al., US Pat. No. 5,133,924 (Leve
r), Bortolotti et al., US Patent No. 5,160,657 (Leve
r), Johnson et al., UK Patent No. 1,517,713 (Unilever)
And Curtis European Patent Application No. 451,894.

The following references relate to producing detergents by flocculation: Beujean et al., Publication No. WO 93 / 23,523 (Henkel), Lutz
U.S. Pat. No. 4,992,079 (FMC Corporation); Pora
US Patent No. 4,427,417 to Sik et al. (Korex), US Patent No. 5,108,646 to Beerse et al. (Procter & Gamble), Capeci.
No. 5,366,652 (Procter & Gamble), Ho.
llingsworth et al., European Patent Application No. 351,937 (Unileve
r), Swatling et al., U.S. Patent No. 5,205,958, Dhalewadik
WO 96/04359 (Unilever), ar et al.

For example, WO 93 / 23,523 (Henkel) describes:
It describes the process of pre-agglomeration with a low speed mixer and another agglomeration step with a high speed mixer to obtain a high density detergent composition of less than 25 wt% granules having a diameter of 2 mm or more. U.S. Pat. No. 4,427,417 (Korex) describes a continuous process for agglomeration that reduces caking and excessive agglomerates.

None of the current technologies have demonstrated all of the advantages and effects of the present invention.

SUMMARY OF THE INVENTION The present invention satisfies the needs in the art by providing a process for producing a high-density granular detergent composition. The present invention also meets the aforementioned needs in the art by providing a process for producing a granular detergent composition that is flexible in terms of final density of the final composition from an agglomerated (eg, non-tower) process. I have. The process does not use a conventional spray-dry tower limited in producing high surfactant content compositions. In addition, the process of the present invention is more efficient, economical and flexible for the various detergent compositions that can be produced in the process. In addition, the process is amenable to environmental issues in that it does not typically employ a spray-dry tower that releases particles and volatile organic compounds into the atmosphere.

The term "aggregate" as used herein relates to particles formed by agglomerating raw materials with surfactants and / or binders such as inorganic / organic solvents and polymer solutions. The term "average residence time" as used herein relates to the following definition: average residence time (hr) = mass (kg) / throughput (kg / hr) All percentages used herein are ,
Unless otherwise noted, they are shown as "% by weight".
All ratios are by weight unless otherwise indicated. As used herein, "comprising" means that other steps and other ingredients which do not affect the result can be added. This term encompasses the terms “consisting of” and “consisting essentially of”.

According to one aspect of the present invention, there is provided a method of producing a granular detergent composition having a density of at least about 600 g /.

The method is as follows: (a) In a mixer, disperse the surfactant and add
Coat the surfactant with a fine powder having a diameter of 1-500 microns (mixer conditions include (i) about 2
(B) an average residence time of about 50 seconds, (ii) a tip speed of about 4 to about 25 m / s and (iii) an energy condition of about 0.15 to about 7 kj / kg, where aggregates are formed); Spray the microspray onto the agglomerate with a mixer (mixer conditions include (i) an average residence time of about 0.2 to about 5 seconds, (ii) a tip speed of about 10 to about 30 m / s, and (ii)
i) including energy conditions from about 0.15 to about 5 kj / kg).

Also provided is a method for producing a granular detergent composition having a density of at least about 600 g /, comprising the steps of: (a) dispersing a surfactant in a mixer,
Coat the surfactant with a fine powder having a diameter of 1-500 microns (mixer conditions include (i) about 2
An average residence time of about 50 seconds, (ii) a tip speed of about 4 to about 25 m / s, and (iii) an energy condition of about 0.15 to about 7 kj / kg, wherein a first aggregate is formed); b) spraying the fine spray onto the first agglomerate with a mixer (mixer conditions include (i) an average residence time of about 0.2 to about 5 seconds, (ii) a tip speed of about 10 to about 30 m / s and (I
ii) containing energy conditions of about 0.15 to about 5 kj / kg, forming a second agglomerate); and (c) thoroughly mixing the second agglomerate in a mixer (mixer conditions include (i) Average residence time of about 0.5 to about 15 minutes and (ii) energy conditions of about 0.15 to about 7 kj / kg).

Also provided is a granular detergent composition having a high density of at least about 600 g / produced by any one of the process embodiments described herein.

Accordingly, it is an object of the present invention to provide a method for continuously producing detergent compositions that is flexible in terms of final product density by controlling energy input, residence time conditions and chip speed conditions in a mixer. It is to provide. It is also an object of the present invention to provide a more efficient, flexible, and economical way to facilitate large-scale production. These and other objects, features and additional advantages of the present invention will become apparent to those skilled in the art from a reading of the following specific description of the preferred embodiments and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a method of producing a free-flowing granular detergent agglomerate having a density of at least 600 g /. In that way,
To produce low-density granules, after producing granule detergent agglomerates from aqueous and / or non-aqueous surfactants, 0.1-500
Coat with a fine powder having a micron diameter.

Process First Step (Step a) In the first step of the process, one or more aqueous and / or non-aqueous surfactants in powder, paste and / or liquid form are combined with 0.1 to 500 microns, preferably about Fine powder having a diameter of 1 to about 100 microns is fed into the first mixer to create agglomerates (the definitions of surfactant and fine powder are described in detail below). Optionally, an internal recycle stream of powder, typically having a diameter of about 0.1 to about 300 microns, coming from an additional step after the process of the present invention, an "optional conditioning process (i.e., a drying and / or cooling step)". Can also be supplied to the mixer in addition to the fine powder. The amount of such an internal recycle stream of powder is 0 to about 60 wt% of the end product.

In another embodiment of the present invention, the surfactant is first fed into a mixer or premixer (eg, a conventional screw extruder or other similar mixer) prior to the above and then mixed detergent The material is fed into a first step mixer as described herein for agglomeration.

Generally speaking, preferably, the average residence time of the first mixer is in the range of about 2 to about 50 seconds, and the tip speed of the first mixer is in the range of about 4 to about 25 m / s; Energy per unit mass of one mixer (energy conditions)
Is in the range of about 0.15 to about 7 kj / kg, more preferably
The average residence time of the first mixer is in the range of about 5 to about 30 seconds, the tip speed of the first mixer is in the range of about 6 to about 18 m / s, and the energy per unit mass of the first mixer (energy Conditions) are in the range of about 0.3 to about 4 kj / kg, most preferably, the average residence time of the first mixer is in the range of about 5 to about 20 seconds, and the tip speed of the first mixer is about 8 to Within the range of about 18 m / s, the energy per unit mass of the first mixer (energy condition) is about 0.3 to
It is in the range of about 4kj / kg.

The example of the first mixer in the first step may be any type of mixer known to a person skilled in the art, as long as the mixer can maintain the above conditions for the first step. For example, Lodge company (Germany)
There is a Lodige CB mixer manufactured by: As a result of the first step, an aggregate having a fine powder on the surface of the aggregate (first aggregate) is obtained.

Second step (step b) obtained from the first step (ie first aggregate)
Is supplied to a second mixer. The fine spray is sprayed onto the agglomerates in a second mixer. Spraying the microspray liquid binds the excess fines on the agglomerates from the first step, if the excess fines from the first step are optionally contained in the product added to the second step It is useful in making About 0 to 10 powdered detergent components and / or other detergent components of the type used in the first step
%, More preferably about 2-5%, may be added to the second mixer.

Generally speaking, preferably, the average residence time of the second mixer is in the range of about 0.2 to about 5 seconds, and the tip speed of the second mixer is in the range of about 10 to about 30 m / s; The energy per unit mass of the three mixers (energy conditions) is in the range of about 0.15 to about 5 kj / kg; more preferably, the average residence time of the second mixer is in the range of about 0.2 to about 5 seconds; The tip speed of the two mixers is about 10 to about 30
m / s, the energy per unit mass of the second mixer (energy conditions) is in the range of about 0.15 to about 5 kj / kg, and most preferably, the average residence time of the second mixer is about 0.2 to The tip speed of the second mixer is in the range of about 15 to about 26 m / s, and the energy per unit mass (energy condition) of the second mixer is in the range of about 0.15 to about 2 kj / kg. Within range.

An example of a second mixer may be any type of mixer known to those skilled in the art, as long as the mixer can maintain the above conditions for the second step. As an example, F manufactured by the Schugi company (Netherlands)
There is a lexomic model. As a result of the second step, a second aggregate is obtained.

Third step [step (c)] If the second agglomerate is less than 600 g /, or if further agglomeration is chosen to meet the optimal conditions as the end product according to the process of the invention, then from the second step (Second aggregate) is supplied to a third mixer. That is,
The second agglomerate is mixed in a third mixer for spheroidization and growth of the agglomerate and sheared well. Optionally, about 0-10%, more preferably about 2-5% of a powdered detergent component and / or other detergent components of the type used in the first and second steps may be added to the third step. Preferably, a chopper that can be connected to a third mixer can be used to break up unwanted excessive agglomerates. Thus, a process involving a third mixer with a chopper is useful for reducing the amount of excessive agglomerates as a final product, and such a process is one preferred embodiment of the present invention.

Generally speaking, preferably, the average residence time of the third mixer is in the range of about 0.5 to about 15 minutes, and the energy per unit mass of the third mixer (energy conditions) is about
More preferably, the average residence time of the third mixer is in the range of about 3 to about 6 minutes, and the energy per unit mass of the third mixer (energy conditions) is about 0.15 to about 7 kj / kg. It is in the range of 0.15 to about 4 kj / kg.

An example of a third mixer may be any type of mixer known to those skilled in the art, as long as the mixer can maintain the above conditions for the third step. As an example, Lodig manufactured by the Lodge company (Germany)
There is e KM Mixer.

As a result of the second (or third) step,
A product having a density of at least 600 g / is obtained. Optionally, the result may be further dried, cooled and / or milled.

The process of the present invention comprises: (1) a CB mixer having flexibility in injecting at least two liquid components; and (2) a Schugi having flexibility in injecting at least two liquid components.
Mixer, (3) When using a KM mixer with flexibility in injecting at least one liquid component, the process can incorporate five different liquid components into the process. Thus, the process presented is useful for incorporating into the granulation process starting detergent materials that are in liquid form, are rather expensive, and are sometimes more cumbersome to handle and / or store than solid materials. Beneficial to those skilled in the art.

Starting Detergent Substances The total amount of surfactants in the products made according to the invention, contained in the following detergent substances, microsprays and auxiliary detergent components, is usually about the total amount of end products obtained by the process of the invention. 5 to about 60%, more preferably about 12 to about 40%,
More preferably, it is about 15 to about 35%. The surfactant contained above is from any part of the process of the present invention, for example, any of the first, second and / or third steps of the present invention.

Detergent Surfactant (Aqueous / Non-Aqueous) The amount of surfactant in the present process is from about 5 to about 60%, more preferably from about 12 to about 40%, of the total amount of end product obtained by the process of the present invention. , More preferably about 15 to about 35
%.

The surfactant of the present process used as the starting detergent material in the first step is in the form of a raw material as a powder, paste or liquid.

The surfactants themselves are preferably selected from the anionic, nonionic, zwitterionic, amphoteric and cationic classes and compatible mixtures thereof. Detergent surfactants useful in the present invention are described in Norris U.S. Pat.No. 3,664,961 issued May 23, 1972 and Laughlin et al. U.S. Pat.No. 3,929,678 issued Dec. 30, 1975. Are described, both of which are incorporated herein by reference. Useful cationic surfactants include September 16, 1980
Cockrell U.S. Pat.No. 4,222,905, issued on Dec. 16, and Murphy U.S. Pat.
Some are described in 4,239,659, both of which are incorporated herein by reference. Among the surfactants, anionic and nonionic are preferred, and anionic is most preferred.

Non-limiting examples of preferred anionic surfactants useful in the present invention, conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates ( "LAS"), branched primary and random C ₁₀ -C ₂₀
Alkyl sulfate (“AS”), formula CH ₃ (CH ₂ ) _x (CHO
SO ₃ ^- M ⁺⁾ CH ₃ and _{CH 3 (CH 2) y (} CHOSO 3 - M +) of the CH ₂ CH ₃
C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates (x and (y + 1) is at least about 7, preferably at least about 9 integer, M is a water-soluble cation, especially sodium), not Saturated sulfates such as oleyl sulfate, C ₁₀ -C ₁₈ alkylalkoxy sulfate (“AEx
S "; especially EO1-7 ethoxysulfate).

Useful anionic surfactants include about 2 to about 20 acyl groups.
Water-soluble salts of 2-acyloxyalkane-1-sulfonic acids having 9 carbon atoms and about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates having about 12 to 24 carbon atoms; There are also β-alkyloxyalkanesulfonates having about 1-3 carbon atoms in the alkyl group and about 8-20 carbon atoms in the alkane moiety.

Optionally, the surfactant to be useful other exemplary paste of the present invention, C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially EO1-5 ethoxycarboxylates), C ₁₀ -C ₁₈ glycerol ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and the corresponding sulfated polyglycosides, and there is a C ₁₂ -C ₁₈ alpha-sulfonated fatty acid esters. If desired, conventional nonionic and amphoteric surfactants, for example C ₁₂ -C ₁₈ alkyl ethoxylates (“AE”), including so-called narrow peak alkyl ethoxylates, C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), well as C ₁₀ -C ₁₈ amine oxides, can be included in the overall composition. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. A typical example is C
There are ₁₂ -C ₁₈ N-methyl glucamides. See WO 9,206,154. Other sugar-derived surfactants, it is N- alkoxy polyhydroxy fatty acid amides, such as C ₁₀ -C ₁₈ N- (3- methoxypropyl) glucamide. N-propyl to N-
Hexyl C ₁₂ -C ₁₈ glucamide can be used for its low foaming properties. C ₁₀ -C ₂₀ conventional soaps may also be used. If high sudsing is desired, it may also be used branched chain C ₁₀ -C ₁₆ soaps. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional and useful surfactants are listed in the standard text.

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

Amphoteric surfactants, including aliphatic derivatives of heterocyclic secondary and tertiary amines; Bipolar surfactants, including derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds; esters of esters of α-sulfonated fatty acids Water-soluble salts; alkyl ether sulfates; water-soluble salts of olefin sulfonates; β-alkyloxyalkane sulfonates; betaines having the formula R (R ¹ ) ₂ N ⁺ R ² COO ⁻
The C ₆ -C ₁₈ hydrocarbyl group, preferably a C ₁₀ -C ₁₆ alkyl or C ₁₀ -C ₁₆ acylamido alkyl group,
Each R ¹ is typically a 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 groups, more preferably C ₁ -C ₂ alkylene groups) can also be used as the detergent surfactant. Examples of suitable betaines, coconut acyl amidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C _12-14 acyl amidopropyl betaine, C _8-14 acyl amides hexyl diethyl betaines, 4- [C _14-16 acyl methylamide diethyl Ammonio] -1-carboxybutane, C _16-18
Amides dimethyl betaine, there are C _12-16 acylamido pentane diethyl betaine and C _12-16 acyl methylamide dimethyl betaine. Preferred betaines are C
_12-18 dimethyl ammonium hexanoate and C _10-18
Acylamidopropane (or ethane) dimethyl (or diethyl) betaine; sultaine having the formula R (R ¹ ) ₂ N ⁺ R ² SO ₃ ^— (R is a C ₆ -C ₁₈ hydrocarbyl group, preferably C ₁₀ -C ₁₆ alkyl group, more preferably a C ₁₂ -C ₁₃ alkyl group, each R ¹ is typically C ₁ -C ₃ alkyl, preferably methyl, R ² is C ₁ -C ₆ hydrocarbyl group, preferably a C ₁ -C ₃ alkylene group, or preferably a hydroxy alkylene group). Examples of suitable sultaines, C ₁₂ -C ₁₄ dimethylammonio-2-hydroxypropyl sulfonate, C ₁₂ -C ₁₄ amido propyl ammonio-2-hydroxypropyl sultaine, C ₁₂ -C ₁₄ dihydroxyethyl ammonio propane Sulfonate and
C _16-18 have dimethylammonio hexane sulfonate, C _12-14 amido propyl ammonio-2-hydroxypropyl sultaine being preferred.

Fines The amount of fines of the process used in the first step is about 94-30 of the total amount of starting materials in the first step.
%, Preferably 86 to 54%. The starting fine powder of this process is ground soda ash, powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulfate, aluminosilicate, crystal-laminated silicate, nitrilotriasate (NTA), phosphate, precipitated silicate, polymer, Selected from the group consisting of carbonates, citrates, powdered surfactants (eg, powdered alkane sulfonic acids) and internal recycle streams of powders resulting from the process of the present invention, wherein the average diameter of the powders is
It is 0.1 to 500 microns, preferably 1 to 300 microns, more preferably 5 to 100 microns. When hydrated STPP is used as the fine powder of the present invention, STPP hydrated to a level of 50% or more is preferred. The aluminosilicate ion exchange material used in the present invention as a detergent builder preferably has both a high calcium ion exchange capacity and a high exchange rate. Without being bound by theory, it is believed that such high calcium ion exchange rates and capacities are a function of several correlation factors based on how the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange material used in the present invention is disclosed in Corkill et al., U.S. Pat.
It is preferably produced according to No. 09 (Procter & Gamble), the disclosure of which is incorporated herein by reference.

Preferably, the aluminosilicate ion exchange material is in the "sodium" form because the potassium and hydrogen forms of the aluminosilicate do not exhibit exchange rates and capacities as high as those provided by the sodium form. In addition, the aluminosilicate ion exchange material is preferably in an over-dried form to facilitate the production of crisp detergent agglomerates as described herein. Preferably, the aluminosilicate ion exchange materials used in the present invention have a particle size that optimizes their effectiveness as detergent builders. The term "particle size" as used herein refers to the average particle size of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, for example, microscopy and scanning electron microscopy (SEM). The preferred particle size of the aluminosilicate is from about 0.1 to about 10 microns, more preferably from about 0.5 to about 9 microns. Most preferably, the particle size is from about 1 to about 8 microns.

Preferably, the aluminosilicate ion exchange material has the formula: Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] xH ₂ O, wherein z and y are at least integers of 6; z vs. y
Is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O where x is from about 20 to about 30, preferably about 27. . These preferred aluminosilicates are commercially available, for example, under the names zeolite A, zeolite B and zeolite X. Alternatively, natural or synthetic aluminosilicate ion exchange materials suitable for use in the present invention may be made as described in U.S. Pat.No. 3,985,669 to Krummel et al., The disclosure of which is incorporated herein by reference. It is.

Aluminosilicate used in the present invention, calculated on a dry basis, a CaCO ₃ hardness / g to about 200mg equivalent at least, ion exchange is preferably in the range of about 300~352mg equivalent CaCO ₃ hardness / g It is further characterized by its capacity. In addition, the aluminosilicate ion exchange material may have at least about 2 grains Ca ⁺⁺ / gallon / min / -g / gallon, more preferably about 2 to about 6 grains Ca ⁺⁺ / gallon / min / -g / gallon. Is further characterized by a calcium ion exchange rate in the range of

Fine Spray Liquid The amount of fine spray liquid in the present process is about 1 to about 10% (active basis), preferably 2 to about 6% (active basis) of the total amount of end product obtained by the process of the present invention. is there. The microspray of the present process can be selected from the group consisting of liquid silicates, anionic or cationic surfactants in liquid form, aqueous or non-aqueous polymer solutions, water and mixtures thereof. Other optional microsprays of the present invention include sodium carboxymethyl cellulose solution, a solution of polyethylene glycol (PEG) and dimethylenetriaminepentamethylphosphonic acid (DETMP).

Preferred examples of anionic surfactant solutions that can be used as microsprays in the present invention include about 88-97% active HLAS, about 30-
50% active NaLAS, about 28% active AE3S solution, about 40-50% active liquid silicate and the like.

Cationic surfactants can also be used as the fine spray liquid,
Suitable quaternary ammonium surfactants are the mono C ₆ -C _16, preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants (remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups Selected).

Preferred examples of aqueous or non-aqueous polymer solutions that can be used as microsprays in the present invention are polyamine backbones corresponding to the following formula: And a polyamine backbone having the modified polyamine formula V _{(n + 1)} W _m Y _n Z or corresponding to the following formula: And modified polyamine formula V _{(n-k + 1)} W _m Y _n Y ′ _k Z (k is n
Wherein the unmodified polyamine backbone has a molecular weight of about 200 daltons or more. Wherein i) the V unit is a terminal unit having the formula: ii) W units are backbone units having the formula: iii) Y units are branch units having the formula: iv) Z units are terminal units having the formula: In the above formula, the main chain connecting R unit is 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 -,-(C
^{_{H 2 OH (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 (O) -, - CH 2 CH (OR 2) CH
Selected from the group consisting of _2- and mixtures thereof; 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, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₆ -C ₁₀ arylene and mixtures thereof; R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C
₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy alkylene, C ₈ -C ₁₂ dialkyl arylene, -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) C
^{_{H 2 O (R 1 O)}} y R 1 OCH 2 CH (OH) CH 2 - and is a mixture thereof; R ⁶ is a C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene; E units are 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) is selected from the group consisting of R ^3, and mixtures thereof; oxides; B is 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 is M, and mixtures thereof; M is a sufficient amount of water-soluble cationic in meeting hydrogen or charge balance; X
Is a water-soluble anion; m has a value of 4 to about 400; n
Has a value of 0 to about 200; p has a value of 1 to 6; q has a value of 0 to 6; r has a value of 0 or 1;
Or has a value of 1; x has a value of 1-100; y is 0
Has a value of 100100; z has a value of 0 or 1; One example of a most preferred polyethyleneimine is about 7 per nitrogen.
Polyethyleneimine having a molecular weight of 1800 (PEI 1800, E7), further modified by ethoxylation to the extent of two ethyleneoxy residues. Pre-complexing with an anionic surfactant such as NaLAS is preferred for the polymer solution.

Another preferred example of an aqueous or non-aqueous polymer solution that can be used as a microspray in the present invention is a polymeric polycarboxylate dispersant, which can be prepared by polymerizing or copolymerizing a suitable unsaturated monomer, preferably in the acid form. is there. Unsaturated monomeric acids that 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 There is malonic acid. The presence of monomer segments without carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., in the polymer polycarboxylates is suitable, provided that such segments represent more than about 40% by weight of the polymer. Not be.

Homopolymer polycarboxylates having a molecular weight of 4000 or more as described below are preferred. Particularly suitable homopolymer polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably between 4000 and 10,000, preferably between 4000 and 7000, most preferably between 4000 and 5000. Such water-soluble salts of acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts.

Copolymer polycarboxylates, such as acrylic acid / maleic acid based copolymers, may also be used. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably from about 2000 to 100,000, more preferably from about 5000 to 75,000, and most preferably from about 7000 to 65,000.
It is. The acrylate / maleate segment ratio in such copolymers is usually from about 30: 1 to about 1:
1, more preferably about 10: 1 to 2: 1. Such water-soluble salts of acrylic / maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Pre-complexing with an anionic surfactant such as LAS is preferred for the polymer solution.

Supplementary Detergent Components The starting detergent material of the process can include additional detergent components, and / or some additional components can also be incorporated into the detergent composition during later steps in the process. These auxiliary ingredients include other cleaning builders, bleach, bleach activators, foam enhancers or suppressors, fade inhibitors, and corrosion inhibitors, soil suspending agents, soil releasing agents, disinfectants, pH There are regulators, non-builder alkali sources, chelating agents, smectite clays, enzymes, enzyme stabilizers and fragrances. Baskervill, published February 3, 1976, incorporated herein by reference.
See U.S. Pat. No. 3,936,537 to e, Jr. et al.

Other builders usually use various water-soluble alkali metals,
Ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxysulfonates,
It can be selected from polyacetate, carboxylate, and polycarboxylate. Alkali metals, especially sodium, the salts mentioned above are preferred. Preferred for use in the present invention are phosphates, carbonates, _C10-18 fatty acids, polycarboxylates and mixtures thereof. Even more preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono and disuccinate, and mixtures thereof (see below).

Compared to amorphous sodium silicate, crystalline layered sodium silicate clearly shows increased calcium and magnesium ion exchange capacity. In addition, laminated sodium silicate favors magnesium ions over calcium ions, which is virtually all "hardness"
Is a necessary feature to ensure removal from the wash water.
However, these crystalline layered sodium silicates are usually more expensive than amorphous silicates and other builders. Therefore, in order to provide an economically feasible laundry detergent, the proportion of crystal-laminated sodium silicate used must be determined in consideration. Such crystal-laminated sodium silicates are described in U.S. Pat. No. 4,605,509 to Corkill et al., Which is already incorporated herein by reference.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphates, pyrophosphates, polymeric metaphosphates having 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, the sodium and potassium salts of ethane 1-hydroxy-1,1 diphosphonic acid, and ethane 1,1,2.
-The sodium and potassium salts of triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Pat.
No. 3,213,030, 3,422,021, 3,422,137,
Nos. 3,400,176 and 3,400,148, all of which are incorporated herein by reference.

Examples of non-phosphorous inorganic builders are tetraborate decahydrate and silicates having a weight ratio of SiO ₂ to alkali metal oxide of about 0.5 to about 4.0, preferably about 1.0 to about 2.4.
Water soluble non-phosphorus organic builders useful in the present invention include various alkali metal, ammonium and substituted ammonium polyacetates, carboxylate, polycarboxylate and polyhydroxysulfonate. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzenepolycarboxylic acid and citric acid.

Polymer polycarboxylate builder, March 1967
No. 3,308,067 to Diehl, issued on Dec. 7, the disclosure of which is incorporated herein by reference. Such materials include the water-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 methylenemalonic acid. Some of these materials are useful as water-soluble anionic polymers, as described below, but only in complete mixtures with non-soap anionic surfactants.

Other polycarboxylates suitable for use in the present invention include:
U.S. Pat. No. 4,144,226 issued to Crutchfield et al. On Mar. 13, 1979 and C issued on Mar. 27, 1979.
No. 4,246,495 to Rutchfield et al., which is a polyacetal carboxylate, both of which are incorporated herein by reference. These polyacetal carboxylates can be prepared by combining the ester of glyoxylic acid and the polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is then attached to a chemically stable end group and converted to the corresponding salt to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution. , Added to the detergent composition. A particularly preferred polycarboxylate builder is an ether carboxylate comprising a combination of tartrate monosuccinate and tartrate disuccinate described in Bush et al., U.S. Pat. No. 4,663,071, issued May 5, 1987. A builder composition, the disclosure of which is incorporated herein by reference.

Bleaches and activators are disclosed in Chung et al., US Pat. Nos. 4,412,934 and 1984, issued Nov. 1, 1983.
Hartman U.S. Patent No. 4,483,7, issued November 20,
No. 81, both of which are incorporated herein by reference. Chelating agents are also described in U.S. Patent No. 4,663,07 to Bush et al., Which is incorporated herein by reference.
It is described in the specification 1, column 17, line 54 to column 18, line 68. The foam control agent is also an optional ingredient and is disclosed in U.S. Pat. No. 3,933,672 to Bartoletta et al., Issued Jan. 20, 1976 and Gault et al., U.S. Pat.
No. 45, both of which are incorporated herein by reference.

Smectite clays suitable for use in the present invention are described in U.S. Pat. No. 4,762,645 to Tucker et al., Issued Sep. 9, 1988, which is incorporated herein by reference.
It is described from column 3 line to column 7 line 24. Additional cleaning builders suitable for use in the present invention are described in Baskerville Patent Specification, column 13, line 54 to column 16, line 16, and U.S. Patent No. 4,663,071 issued May 5, 1987 to Bush et al. They are listed in the specification, both of which are incorporated herein by reference.

Optional Process Steps Optionally, the process may include spraying an additional binder in one or more of the first, second and / or third mixers for the present invention. Binders are added to increase cohesion by providing a "binding" or "sticking" agent for the detergent components.
The binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, liquid silicates, polyethylene glycol, polyvinylpyrrolidone polyacrylate, citric acid and mixtures thereof. Other suitable binder materials, including those listed herein, are described in Beerse et al., US Pat. No. 5,108,646 (Procter
& Gamble Co.), the disclosure of which is incorporated herein by reference.

Other optional steps that can be considered by this process include:
Excessive detergent agglomerates are screened with a screening device, which can take a variety of forms, including but not limited to conventional screens selected for the desired particle size of the final detergent product Can be. Another optional step involves conditioning the detergent agglomerates by subjecting the agglomerates to additional drying in the equipment already described.

In another optional step of the process, the resulting detergent agglomerates are finished by various processes, including spraying and / or mixing other conventional detergent ingredients. For example, in the finishing step, perfumes, brighteners and enzymes are sprayed on the final agglomerates to provide a more complete detergent composition. Such techniques and components are well-known in the art.

Another optional step in the process involves a surfactant paste building process, for example, curing the aqueous anionic surfactant paste by compounding the paste curing material using an extruder prior to the process of the present invention. Details of the surfactant paste construction process are disclosed in co-pending application PCT / US96 / 15960, filed October 4, 1996.

To better understand the invention, reference is made to the following examples, which are for purposes of illustration only and are not intended to be limiting.

Examples Example 1 The following is a Lodige CB mixer (CB-30), then Schug
This is an example for obtaining an aggregate having high density using an iFX-160 mixer.

[Step 1] Aqueous CFAS (coconut fatty alcohol sulfate surfactant) paste (C ₁₂ -C _18, 71.5% active) was 250~270kg / hr, (the average particle size of 40-75 microns) powder STPP 220 kg / hr, CB-30 mixer with ground soda ash (average particle size of 15 microns) 160-200kg / hr, ground sodium sulfate (average particle size of 15 microns) 80-120kg / hr and internal recycle stream of powder 200kg / hr Disperse with a pin tool. The surfactant paste is supplied at about 40-52 ° C and the powder is supplied at room temperature. The conditions of the CB-30 mixer are as follows: Average residence time: 10-18 seconds Chip speed: 7.5-14 m / s Energy condition: 0.5-4 kj / kg Mixer speed: 550-900 rpm Jacket temperature: 30 ° C [Step 2] The aggregates from the CB-30 mixer were
Feed to X-160 mixer. HLAS (acid precursor of C ₁₁ -C ₁₈ alkylbenzene sulfonate; 94-97% activity) 30 kg / hr
At about 50-60 ° C as a fine spray in a Schugi mixer. Soda ash (average particle size of about 10-20 microns) 20-80
Add kg / hr to the Schugi mixer. The conditions of the Schugi mixer are as follows: Average residence time: 0.2-5 seconds Chip speed: 16-26 m / s Energy condition: 0.15-2 kj / kg Mixer speed: 2000-3200 rpm The granules obtained from step 2 are approximately It has a density of 600 g / and can optionally be subjected to any process of drying, cooling, sizing and / or grinding.

Example 2 Below is a Lodige CB mixer (CB-30) followed by Schug
i FX-160 mixer, then Lodige KM mixer (KM-60
0) is an example for obtaining an aggregate having a high density.

[Step 1] HLAS (acid precursor of C ₁₁ -C ₁₈ alkylbenzene sulfonate; 95% activity) 15-30 kg / hr and aqueous CFAS (coconut fatty alcohol sulfate surfactant) paste (C ₁₂ -C ₁₈ ) at about 50 ° C. , 70% activity) 250-270kg / h
r, powder STPP (average particle size of 40-75 microns) 220kg / h
r, ground soda ash (15 micron average particle size) 160-220kg /
hr, pulverized sodium sulfate (15 micron average particle size) 80 ~
Along with 120 kg / hr and an internal recycle stream of powder of 200 kg / hr, they are dispersed with the pin tool of the CB-30 mixer. The surfactant paste is supplied at about 40-52 ° C and the powder is supplied at room temperature. The conditions of the CB-30 mixer are as follows: Average residence time: 10-18 seconds Chip speed: 7.5-14 m / s Energy condition: 0.5-4 kj / kg Mixer speed: 550-900 rpm Jacket temperature: 30 ° C [Step 2] The aggregates from the CB-30 mixer were
Feed to X-160 mixer. Neutralized AE ₃ S liquid (28%
Activity) 35 kg / hr is dispersed as fine spray in a Schugi mixer at about 30-40 ° C. Add 20-80 kg / hr of soda ash to the Schugi mixer. The conditions of the Schugi mixer are as follows: Average residence time: 0.2-5 seconds Chip speed: 16-26 m / s Energy condition: 0.15-2 kj / kg Mixer speed: 2000-3200 rpm [Step 3] Aggregation from Schugi mixer The feed is fed to a KM-600 mixer for further agglomeration, spheroidization and growth of the agglomerate. 60 kg / hr of ground soda ash (15 micron average particle size) is also added to the KM mixer. Serrated plows are used as mixing elements in a KM mixer. A KM mixer chopper may be used to reduce the amount of excessive agglomerates. The conditions of the KM mixer are as follows: Average residence time: 3-6 minutes Energy condition: 0.15-2 kj / kg Mixer speed: 100-150 rpm Jacket temperature: 30-40 ° C Approximately 700 g of the granules obtained from step 3 It has a density of / and can optionally be subjected to any process of cooling, drying, sizing and / or grinding.

Having thus described the invention in detail, it will be apparent to those skilled in the art that various changes can be made without departing from the scope of the invention and the invention is not limited to what is described herein. Will.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References Special Table Hei 5-508431 (JP, A) Special Table Hei 7-503750 (JP, A) US Patent 5,554,587 (US, A) International Publication No. 96/9370 (WO, A1) WO 95/10595 (WO, A1) WO 95/12659 (WO, A1) WO 96/9369 (WO, A1) WO 95/19421 (WO, A1) WO 93/25378 (WO, A1) A1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C11D 11/00-11/02 C11D 17/06

Claims (8)

(57) [Claims] (1) In a first mixer, a surfactant is dispersed and the surfactant is coated with a fine powder having a diameter of 0.1 to 500 microns (the conditions of the mixer are (i) 2 Average residence time of ~ 50 seconds, (ii) 4-25
(ii) containing a tip speed of m / s and (ii) an energy condition of 0.15-7 kj / kg, forming a first agglomerate); Spray (mixer conditions include (i) an average residence time of 0.2-5 seconds, (ii) a tip speed of 10-30 m / s, and (ii)
i) containing 0.15-5 kj / kg of energy conditions to form a second aggregate); and (c) thoroughly mixing the second aggregate with a third mixer (mixer conditions include (i A) a non-tower method for producing a granular detergent composition having a density of at least 600 g /, comprising an average residence time of 0.5 to 15 minutes and (ii) an energy condition of 0.15 to 7 kj / kg). 2. The method of claim 1, wherein the surfactant is selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, zwitterionic, amphoteric and mixtures thereof. . 3. The method according to claim 2, wherein the surfactant is selected from the group consisting of alkyl benzene sulfonates, alkyl alkoxy sulfates, alkyl ethoxylates, alkyl sulfates, coconut fatty alcohol sulfates and mixtures thereof. 4. The method of claim 2, wherein excess fines are formed in step (a) and excess fines are added to step (b). 5. The method of claim 2, wherein the aqueous or non-aqueous polymer solution is dispersed with a surfactant in step (a). 6. The fine powder is soda ash, powdered sodium tripolyphosphate, hydrated tripolyphosphate, sodium sulfate, aluminosilicate, crystal-laminated silicate, phosphate, precipitated silicate, polymer, carbonate, citrate, nitrilotriate, powder surface activity 3. The method of claim 2, wherein the method is selected from the group consisting of agents and mixtures thereof. 7. The microspray liquid according to claim 2, wherein the liquid silicate, anionic surfactant, cationic surfactant, aqueous polymer solution, non-aqueous polymer solution, water and mixtures thereof are selected. The method described in. 8. The method of claim 1, wherein the method is a continuous method, wherein step (c) is performed.
2. The method according to claim 1, wherein the product obtained from the above is further subjected to a cooling and / or drying step, which produces an internal recycle stream of powder, the internal recycle stream of powder being further added to step (a). Method.