JPH046760B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to free-flowing, spray-dried substrate beads useful in the production of built, particulate synthetic nonionic organic detergent compositions. Also relates to free-flowing spray-dried detergent compositions. More particularly, it relates to such beads, compositions containing specified proportions (within specified ranges) of a water softener aluminosilicate (e.g., zeolite), bentonite, water-soluble builder for detergents. The product exhibits lower zeolite adhesion than conventional products containing similar proportions of water softener aluminosilicate.
Such conventional products usually also contain significant proportions of water-soluble silicates and are usually free of bentonite.

In recent years, water softener insoluble aluminosilicates such as hydrated zeolites have been used as builder components in laundry detergent compositions. Initially, the renewed interest in zeolites appears to have been stimulated by the need to produce phosphorus-free detergent formulations. The trisodium salt of nitrilotriacetic acid and other salts (NTA) have been proposed as powerful substitutes for phosphates (particularly pentasodium tripolyphosphate) and have been extensively used in built laundry detergent compositions. However, NTA-containing compositions have long been suspected of being harmful and are no longer sold in the United States. There have never been any serious questions about the safety of phosphates for humans, and US authorities' disapproval of the use of NTA in detergents has recently been rescinded. Therefore, certain phosphate-free detergent formulations are manufactured for use in areas close to lakes and rivers, where phosphates can provide a necessary nutrient source for algae growth and cause eutrophication of lakes and rivers. However, detergent compositions containing phosphates and/or NTA are once again available for sale.

Zeolite (zeolite A is preferred, hydrated zeolite A is particularly preferred) is phosphorus-free and NTA-free.
Although previously a builder salt in detergent compositions, it has now been found that it is also a useful ingredient in improved detergent, base bead compositions containing phosphate and/or NTA. Water-soluble sodium silicate, typically about 6-12%, has been used in clutch materials (from which spray-dried substrate beads and detergent compositions were made). This silicate is used for its binding effect on other components of the bead (binding results in stable beads) and has been found to aid in the production of reticulated internal bead structures. It also acts as an anti-corrosion additive that prevents chemical attack on the Al parts of the washing machine and other items that the detergent solution may come into contact with. However, previously used proportions (e.g. 8% of the final product)
~10%), the combination of water-soluble silicates and zeolites in the crutcher produces aggregates of such materials in the spray-dried beads, which adhere undesirably to the laundry and negatively affect its color. It has been recorded that there is a tendency to By using specific proportions of zeolite, bentonite, water-soluble builders, and little or no water-soluble silicates, the present invention provides spray-dried beads with sufficient physical stability to be commercially acceptable. and its zeolite adhesion is low (ie the adhesion of zeolite-silicate aggregates is low). Even when small proportions of silicates are present, bentonite helps neutralize the tendency of zeolites and silicates to react to form particles of larger size than the zeolites normally present, and this Undesirable adhesion of zeolite or zeolite-silicate particles to laundry fabrics is thereby prevented or reduced. Furthermore, bentonite-containing compositions disintegrate and distribute in the wash water much more easily, which is also clearly due to the presence of bentonite. Another advantage of the present invention when using little or no silicates is that formulations containing carbonates and/or bicarbonates prevent excessive concentration of clutter materials even in the absence of anti-gelling agents. It is possible to prevent thickening. Such additives are usually unnecessary when the detergent's primary builder is phosphate or when little or no carbonate and/or bicarbonate is present, but phosphorus-free compositions (often with significant amounts of carbonate and/or bicarbonate) (containing bicarbonate), the absence of anti-gelling agents is of decisive advantage from both processing and economical points of view.

The prior art relating to detergent compositions, softener compositions, detergent/softener compositions, includes one of zeolites, bentonites, silicates, phosphates, NTA, quaternary ammonium compounds (softeners) and other ingredients.
It teaches that a variety of detergent compositions can be made that include more than one species, usually along with synthetic organic detergents. However, while there is extensive and detailed disclosure of almost every material that has been used for some purpose in detergent/softener compositions (sometimes referred to as a "laundry list"), there is no clear disclosure for the detergent compositions of the present invention. There is no teaching or suggestion, and this is especially true for compositions containing little to no soluble silicates. The prior art disclosures do not seem to recognize the importance of bentonite containing sufficient "lubricating" water between the layers, and do not appreciate the combination of bonding and disintegration effects due to "hydrated" bentonite. Not yet. Also, although many of the "reference" formulations contain significant proportions of sodium sulfate (filler) (presumably to improve the physical properties of the product particles), this is not necessary for the production of the compositions of the present invention and therefore The amount of active ingredients (including builders) can be increased.

The free-flowing spray-dried beads of the present invention, which are useful as detergents and in the preparation of granular synthetic nonionic detergent compositions with builders, are characterized by the presence of bentonite in the spray-dried beads, low content to absence of water-soluble silicic acid. (because of this, particle adhesion is low) is 5 by weight.
~60% water softener aluminosilicate, 2-40%
of bentonite (with sufficient water to aid in the dispersion of the bentonite and prevent aluminosilicate buildup on the laundry), 5 to 60% water-soluble builders or mixtures thereof, 0 to 30% Water-soluble synthetic organic detergent, consisting of 0-3% water-soluble silicate. The aluminosilicate may be a zeolite with a significant Ca ion exchange capacity, and the bentonite has a significant swelling capacity in water, facilitating the breakdown of interlayer bonds when detergent beads are placed in water, either alone or in combination with other detergent ingredients. The water-soluble builder or builder mixture is a polyphosphate, nitrilotriacetate or carbonate, and no water-soluble silicates are present. By spray-drying the described bead formulations with anionic detergents present in clutch materials, or by spray-drying liquid nonionic detergents containing no detergent or only a relatively small proportion of anionic detergents or mixtures thereof. Also included in the invention are detergent compositions made by spraying onto rocking beads. Mixtures of such compositions, anionic and nonionic detergent hybrid compositions, are also useful and have excellent cleaning properties.

The zeolite used has hardness ions in the washing water.
Natural or synthetic crystalline or amorphous zeolites and mixtures thereof that can satisfactorily and quickly and effectively antagonize Ca. Such materials
reacts with Ca ions sufficiently rapidly so that the wash water, alone or in conjunction with other water softener compounds in the detergent, can react with Ca ions before undesirable reactions with other components of the synthetic organic detergent composition occur. Preferably, it can be softened. The zeolite used is characterized by a high Ca ion exchange capacity, and its value is usually about 200 to 400 mg or more of Ca carbonate hardness equivalent per gram of aluminosilicate, preferably 250 to more.
350 mg equivalent/g. Furthermore, preferably 0.02 to 0.05 mg CaCO ₃ /l, preferably 0.02 to 0.05 mg CaCO 3 /l after 1 minute.
It has a residual hardness of 0.03 mg/l and a hardness reduction rate of less than 0.01 mg/l after 10 minutes (all based on anhydrous zeolite).

Other ion exchange zeolites can also be used, but
The finely synthesized zeolite builder particles typically used in the practice of the present invention are represented by the following formula.

( _Na2O )x・( _Al2O3 ) _y・( _SiO2 ) _z・_WH2O ) (x is 1; y is 0.8 to 1.2, _preferably about 1, z
1.5-3.5, preferably 2-3 to about 2; W 0-9, preferably 2.5-6) The zeolite must be a monovalent cation-exchangeable zeolite, i.e. b) Other alkali metals, ammonium,
It must be an aluminosilicate of a monovalent cation such as H (sometimes). The monovalent cations of zeolite molecular sieves are alkali metal cations, especially Na, K,
is preferred, and most preferred is Na.

Crystalline zeolites which can be used at least in part as good ion exchangers in the present invention are zeolites of the secondary crystal structure groups: A, X, Y, L, mordenite, erionite (where A, X, Y are preferable). Mixtures of such molecular sieve zeolites are also useful, especially when Type A zeolites are present. These crystalline zeolites are well known in the industry;
It is described in detail in "Zeolite Molocular Sieves" by Donald W. Breck, published by Tohn Wiley & Sons. Representative commercially available zeolites having the above structural type are listed in Tables 9 and 6 on pages 747-749 of the article.
Such zeolites are known in the art. Other such suitable zeolites for use as builders in detergent compositions are described in a number of recent patent documents.

The zeolites used in the present invention are typically synthetic and are often characterized by a network of substantially uniformly sized pores of about 3 to 10 Å, often about 4 Å (typically). This size is uniquely determined by the unit structure of the zeolite crystal. Type A or a structure similar thereto, particularly the one described on page 133 of the article, is preferred. When using 4A type molecular sieve zeolite (its monovalent cation is Na and the pore size is approximately 4 Å)
good results have been obtained and such zeolites are preferred. Such a zeolite molecular sieve is patented in the United States.
Zeolite A is described in Publication No. 2882243.

Molecular sieve zeolites with ion exchange and water softening properties can be produced either as dehydrated or calcined bodies containing about 0-1.5 to 3% water or as hydrated or water-carrying bodies containing additional bound water of about 4-36%. (The values are based on the total amount of zeolite and vary depending on the type of zeolite used). When using such crystalline products, a hydrated form of molecular sieve zeolite (approximately 15 to 70%
(preferably hydrated) are preferred for the practice of this invention. The manufacture of such crystals is well known in the art. For example, in the production of zeolite A, the crystallization medium (e.g. hydrated amorphous aluminosilicate
Hydrated zeolite crystals formed in Na gel)
The use as a catalyst (eg cracking distillation catalyst) is used without the high temperature dehydration (calcination to a water content of less than 3%) normally carried out in the production of such crystals.
Crystalline zeolites, whether fully hydrated or partially hydrated, are obtained by removing the crystals from the crystallization medium and drying in air at ambient temperature to reduce the water content to about 10 to 15 to 25
For example, 17-22% (eg 20%) can be recovered.
However, the water content of the molecular sieve zeolite used may be much lower, as mentioned above, in which case the zeolite is typically hydrated during crutching or other processing.

Preferably, the zeolite is in a finely divided state, with an ultimate particle size of less than 20 microns (e.g. 0.005 to 0.01 to 20 microns), more preferably 0.01 to 15 microns (e.g. 3 to 12 microns), particularly preferably an average particle size of The diameter of the crystal is 0.01 to 8 microns (e.g. 3 to 7
micron), amorphous and 0.01 to 0.1 micron (e.g.
0.01-0.05 microns). The size of the zeolite particles is between 100 and 400 mesh, preferably between 140 and 325 mesh, although the ultimate particle size is much smaller. Smaller sized zeolites are often too powdery, and larger ones are distributed with bentonite during spray drying of clutter materials to form substrate beads. Carbonate, bicarbonate, phosphate and/or NTA substrate particle cores may not be adequately coated.

The bentonite used is colloidal clay (Al silicate) containing montmorillonite. Montmorillonite may have approximately 1/6 of its Al atoms substituted with Mg atoms, and various amounts of H, Na,
It is a hydrous Al silicate to which K, Ca, Mg and other metals may be loosely bonded. The type of bentonite clay specified herein for the production of the substrate beads of the present invention is bentonite
Na (Wyoming or Western Bentonite)
It is usually a pale to cream-colored, intangible powder that forms a highly thixotropic colloidal suspension in water. Its swelling capacity in water is usually 3-15ml/
g, preferably 7-15 ml/g, and its viscosity is usually 3-30 cps, preferably 8-30 cps at 6% concentration in water.
It is 30cps. A preferred swellable bentonite of this type is manufactured by Georgia Kaolin Co., Ltd.
Trademarked mineral colloid (Mineral Colloid) as industrial bentonite from Bentonclay Company, a subsidiary of Kaolin Co.
Colloid). Yizen is the trademark THIXO
- These materials sold at JEL are bentonite that has been selectively mined and commercialized, and the most useful ones are available as mineral colloid No. 101 (THIXO-JEL No. 1, 2,
3 and 4). This material has a PH (at 6% concentration in water) of 8 to 9.4, a large free water content of about 8%, and a specific gravity of about 2.6, and is a fine powder product and about 85% of it passes through a 200 mesh sieve according to the American sieve standard. do. Although beneficent bentonite is preferred as a component of the composition, other bentonites are also useful (especially when they make up a small proportion of the bentonite used).

Although, as mentioned above, limiting the maximum free water content is desirable, the bentonite employed contains sufficient free water (the majority of which is believed to be present between adjacent layers of bentonite) and the concentration of bentonite and other adjacent materials in the particles It is even more important that detergent compositions containing them be capable of promoting rapid disintegration when in contact with water, such as wash water. at least about 2%, preferably about 3%, more preferably about 4%
It has been discovered that at least % of water should be present before mixing with other ingredients in the clutcher (ie, initially) and that this proportion should be maintained after spray drying. In other words, overdrying the bentonite to the point where it loses its "initial" moisture can significantly reduce the usefulness of the composition. If the water content of the bentonite is too low, the bentonite will not prevent the formation of silicate-zeolite agglomerates and will not support the disintegration of the beads in the wash water.
When the moisture content of bentonite is satisfactory, it exhibits an exchangeable Ca oxide percentage of about 1 to 1.8;
For Mg oxides this percentage is usually between 0.04 and 0.41. Typical chemical analysis values for such materials are as follows.

64.8~73.0% ( _SiO2 ), 1.4 _~ 1.8% ( _Al2O3 ),
1.6-2.7% (MgO), 1.3-3.1% (CaO) 2.3-3.4
% ( _Fe2O3 ), 0.8~ _2.8 % ( _Na2O ), 0.4~7.0%
( _K2O ).

The water-soluble builder or mixture thereof used may be any conventional material used as a builder or presented for such purpose. Inorganic, organic builders, and mixtures thereof. Preferred among the inorganic builders are various phosphates, preferably polyphosphates,
For example, tripolyphosphates, pyrophosphates such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Nitrilotriacetic acid trisodium salt (preferably used as the monohydrate) and other nitrilotriacetic acid salts (eg, disodium nitrilotriacetic acid) are preferred water-soluble builders. Although sodium tripolyphosphate, sodium pyrophosphate, and NTA can be used in hydrated form, bentonite and zeolite appear to prevent agglomeration due to subsequent hydration even when anhydrous compounds are used. Naturally, carbonates such as sodium carbonate are useful builders, preferably used alone or in conjunction with bicarbonates such as sodium bicarbonate. When using polyphosphate, replace sodium pyrophosphate with sodium tripolyphosphate.
and 1:10 to 10:1, preferably 1:5 to
Preferably, they are present in a 5:1 ratio, with the total proportion of both builders being approximately the same as mentioned for tripolyphosphate. Other water-soluble builders that may be useful include various other inorganic and organic phosphates, borates (eg, borax), citrates, gluconates, EDTA, iminodiacetic acid. These builders are preferably in the form of alkali metal salts (Na or K salts) or mixtures thereof, with Na salts usually being preferred. Generally, the salts may be neutral or basic, although in some cases (eg, when producing neutral to slightly acidic detergent compositions) acid type builders (particularly of organic builders) are preferred. Silicates ( _Na2O :
_SiO2 ratio is 1:1.6~1:3.0, preferably 1:2~
1:2.8, e.g. 1:2.35 or 1:2.4 Na silicate
(preferably) also serves as a builder salt, but because of its strong binding properties and its ability to promote agglomeration or agglomeration with zeolite particles, it is a special builder and is preferably not included in the composition. However, due to its anti-corrosion properties, it may sometimes be present in very small proportions, which is especially important when detergent solutions are used in contact with Al parts in washing machines and other equipment. In such cases, it is preferable to post-add the hydrated sodium silicate particles so that they do not react with, or agglomerate, the zeolite particles during the crutching and spray drying operations. Although sodium sulfate, NaCl, and other filler salts do not have builder properties, they are sometimes used in detergent compositions because of their filling properties. In addition to increasing product volume and weight to facilitate metering, they may also improve the stability of the beads and the physical properties of the detergent composition beads in which they are incorporated. However, the present compositions may be satisfactory without the presence of fillers and it is preferred that fillers be completely absent or used in minimal proportions (usually the lowest practical amount).

Typically, the detergents used are usually nonionic or anionic, although amphoteric detergents can also be used in the present compositions, especially in combination with nonionic and/or anionic detergents. Cationic detergents serve as fabric softeners in these products, but are usually not spray dried with anionic detergents because of possible undesirable interactions. These groups of materials are well known and have been repeatedly described in the detergent industry. Since it is not a preferred component of the composition, it will not be described further.

Various nonionic detergents with favorable physical properties (e.g. nonylphenol, oxo-type alcohol, etc.)
Although condensation products of ethylene oxide and propylene oxide with each other and with hydroxy-bearing bases can be used, it is highly preferred that the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohols. In such products, the higher fatty alcohols are _C10-12 , preferably _C12-16 , and the nonionic detergents contain about 3 to 20 to 30 (preferably 6 to 12) ethylene oxide groups/mol. The nonionic detergent has a higher fatty alcohol having about 12 to 13 to 15 carbon atoms, and 6 to 7 to 11 carbon atoms.
The most preferred is one containing double the mole of ethylene oxide. Such detergents are manufactured by Shell Chemical Company (Shell Chemical Company).
Chemical Company), trade name Neodol (registered trademark) 23-6.5, 25.7
You can get it using the . Their particularly attractive properties are that, in addition to their good cleaning properties against oily laundry stains, their melting point is relatively low, but significantly above room temperature, and therefore they can be sprayed onto substrate beads as a solidifying liquid. .

A variety of anionic detergents (usually Na salts) can be used, but the most preferred are linear higher alkyl benzene sulfonates, higher alkyl sulfates, and higher fatty alcohol polyethoxylate sulfates.
Preferably, the higher alkyl of the higher alkylbenzene sulfonate is linear and the number of C atoms is from 12 to
15, for example 13, and the salt is the Na salt. The alkyl sulfate has a C atom number of 10 to 18, preferably 12.
Higher fatty alkyl sulfates of ~16, for example 12, are preferred and are also used as Na salts. Similarly, higher alkyl ethoxamer sulfates (preferably fatty alkyls)
The number of C atoms is 10 to 12 to 18, for example 12, and the amount of ethoxy groups is usually 3 to 30 (preferably 3
5 to 20 pieces)/mol. Na salt is still preferable. Therefore, the alkyl is preferably a C _10-18 linear or fatty higher alkyl, the cation is preferably Na, and when a polyethoxy chain is present, the sulfate group is terminal. Other useful anionic detergents are higher olefin sulfonates and paraffin sulfonates, such as the Na salt (the olefin or paraffin group is _C10-18 ). Specific examples of preferred detergents are sodium tridecylbenzene sulfonate, sodium tallow alcohol polyethoxy (3EtO) sulfate, and sodium tallow alcohol sulfate. In addition to the preferred anionic detergents mentioned above, other detergents belonging to this well-known group may also be present, especially in small proportions relative to those mentioned above. Mixtures thereof may also be used, and in some cases such mixtures may be superior to single detergents. Various anionic detergents are well known in the industry and were first published in 1958 by Interscience Publishers, lnc.
It is described in detail in "Surface Active Agents and Detergents" by Schwartz, Perry, and Berch, Volume 25-138, published by Schwartz, Perry, and Berch.

Various adjuvants may be present or post-added in the clutcher mix (from which base beads and detergent compositions can be spray-dried), and the method of addition depends on the adjuvant's physical properties, heat resistance, and aqueous clutcher medium. It is often determined by its resistance to decomposition and volatility. Of relative importance among the adjuvants are polyacrylates, which are known to help control bead properties and bulk density, and which have dispersing, anti-fouling, and anti-redeposition effects in the composition, Helps maintain fluidity and homogeneity of mixes.

The polyacrylates present in the preferred substrate beads of the present invention are low molecular weight polyacrylates, the molecular weight of which is usually between about 1000 and 5000, preferably
1000-3000, most preferably 1000-2000 or approx.
It is 2000. The polyacrylate may be partially or fully neutralized (eg, about 1/2 or 1/3 Na polyacrylate). The aforementioned sodium polyacrylate may be substituted with some other chemically modified polyacrylates such as alkali metal polyacrylates and hydroxylated polyacrylates, but this substitution is preferably limited to a small proportion. , the polyacrylate is preferably red-substituted polyacrylic acid Na. Such materials are manufactured by Alco Chemi-cal.
Alcosperse from Corporation
(registered trademark). The sodium polyacrylates are available as a clear amber liquid powder, and the solids content of the solution is approximately 25-40%.
For example, 30%, the pH of a 30% aqueous solution of the powder is about 7.5 ~
9.5, for example about 9. Such materials are completely soluble in water and used as dispersions. They have the ability to bind Ca ions and are used to prevent insoluble Ca compounds from being deposited from aqueous solutions.
The small amount (i.e., proportion) in the present spray drying process facilitates creating beads with improved porosity.

If the clutch material contains carbonates and/or bicarbonates and silicates, even small amounts of silicate will tend to cause the mixture to gel or "freeze" in the clutcher (particularly if processing delays cause the clutch to freeze). (If you hold Yamitsu for longer than the normal 30 minutes). In such cases, if a silicate is present, a processing aid is also preferably present in the mix (and thus the final base beads, detergent composition) to prevent premature setting or gelling. Citric acid and Mg sulfate are most preferred. Soluble citrate salts such as sodium citrate can also be used in place of citric acid. Although the use of anhydrous Mg sulfate is preferred, its various hydrates (eg, Epsom salts) can also be used. Also, Mg citrate can be used instead. Sodium sesquicarbonate instead of the preferred anti-gel system
Other means to maintain the clutch system in a fluid state, such as sodium carbonate, bicarbonate, etc., are also suitable systems.
Can be used in place of some of the Na. However, it is a feature of the present invention that such processing aids, while useful in many cases, are unnecessary for the production of the preferred silicate-free substrate beads.

Some adjuvants such as fluorescent brighteners, pigments (e.g. ultramarine blue), titanium dioxide, inorganic filler salts can be added to the clutcher, but fragrances,
Other substances such as enzyme bleaches, some colorants, bactericides, fungicides, fabric softeners, glidants, etc. may be sprayed or otherwise applied with the nonionic detergent and/or separately with the base beads or the spray-dried detergent composition. If they are mixed and are adversely affected by the high temperatures of the spray drying operation,
It is often possible to ensure that their presence in the spray-dried beads (post-sprayed onto the beads) does not prevent absorption of nonionic detergents. However, adjuvants that are stable and solid at room temperature can also be mixed with the starting slurry in the clutcher. For example, when pigments and fluorescent brighteners are used, they are typically present in a clutter mix from which the substrate beads of the present invention are spray-formed. The preferred colorant is ultramarine blue, but other stable pigments and dyes may be used as substitutes therewith. The spray-dried substrate beads of the present invention typically may be dull in color due to the use of natural minerals, so that the hue of such colorants may be adversely affected. Incorporation of a small percentage of titanium dioxide into the clutch material mixture helps to maintain the desired hue of the colorant, and the presence of titanium dioxide also improves the appearance of laundry washed with detergent compositions made from base beads containing titanium dioxide. It was found that it does not seem to have any negative effect on

The most preferred fluorescent brightener is Tinopal 5BM (especially in ultraconcentrate form). However, a variety of other cotton brighteners (such as those sometimes referred to as CC/DAS brighteners) derived from the reaction products of cyanuric chloride and diaminostilbennysulfonic acid disodium salt (triazine rings, aromatic (This also applies to derivatives with ring substitutions).
This group of brighteners is known in the detergent industry and is most often used when no bleaching ingredients are present in the final product. When it is desirable to include a bleaching agent, such as sodium perborate or other oxidizing bleach, in a detergent composition, a bleach-stable brightener is typically incorporated into the bleaching mix. Examples include benzidine sulfone sulfonic acid, naphthotriazolyl stilbenesulfonic acid, and benzimidazolyl derivatives. Polyamide brighteners can also be present, such as aminocoumarins and diphenylpyrazoline derivatives, and polyester brighteners can also be used, such as naphthotriazolylstilbenes. Such brighteners are typically used as soluble salts, but may also be loaded as the corresponding acids. Cotton brighteners usually make up the majority of the brightener systems used.

Since it is heat sensitive, the enzyme agent that is usually added to the substrate beads may be any of a variety of commercially available products, such as Alcalase and Maxatase manufactured by Novo Industri (A/S). Both are alkaline proteases (subtilisins). Maxazyme
375 is sometimes preferred. Although these alkaline proteases are most often preferred, starch-degrading enzymes such as 2-amylase can also be used. The compositions typically contain the active enzyme together with an inert powder vehicle such as Na sulfate or Ca sulfate, and the percentage of active oxygen varies, typically from 2 to 80% in commercial formulations. The percentages herein refer to the enzymatic agent and not only to its active portion. The fragrances used (usually heat-sensitive and may contain volatile substances such as alcohol (also solvents)) are usually synthetic fragrances, sometimes mixed with natural ingredients, and generally contain alcohol, aldehydes, terpenes, retention agents, and other common aroma ingredients. Glidants, such as special clays (sometimes added to detergent products, but often useful to improve flow, reduce viscosity of various compositions), are probably in part bentonite and/or polyacrylates. is unnecessary in this case due to the absence or very small amount of silicate. but,
In addition, fluidity can be further increased if desired. Although anti-corrosion additives do not need to be present in detergent compositions made from the present substrate beads to replace the unused silicates, the use of suitable such materials is within the scope of this invention, and It is preferred to use materials that are stable under clutching and spray drying conditions and do not adversely affect such operations. Such anti-corrosion additives and antioxidants may be organic or inorganic, but inorganic substances are generally preferred, and selection of those suitable for preventing corrosion of the Al parts of washing machines is preferred. Continued use of silicates for such purposes and their Mg
Powdered silicates are usually preferred if the use of silicates is desired because of their ionic hardness treatment effects. An example is hydrated sodium silicate, which is commercially available under the name Britesil® and manufactured by Piladelphia Quartz Co. (Na ₂ O:SiO ₂ = 1:2.4), post-addition is preferred. However, other room temperature solid soluble silicates (preferably alkali metal salts) can also be post-added (preferably after absorption of the nonionic detergent) to the beads of the invention.

If it is desired that the product has fiber flexibility, a softener (preferably in dry powder form) can also be post-added to the base beads by any suitable method. This group of materials is well known, most commonly cationic compounds,
Especially quaternary ammonium compounds, such as quaternary ammonium halides. Particularly preferred are higher alkyl-, alkylaryl-, arylalkyl-lower alkyl quaternary ammonium chlorides, bromides, such as distearyldimethylammonium chloride. The most preferred commercially available softener is sold under the trade name Arosurf AT-100 (manufactured by Sherax Chemical Company). Such compounds also have antistatic and antibacterial properties, although other antibacterial adjuvants can be used if desired (preferably post-added to the product).

Naturally, water will be present in the clutcher to serve as a medium for dispersing the various other bead components. Some water is present in the product, both free and hydrated. During bead drying its initial moisture content (approximately 25
~60%) drops to about 5-15%. Such water content is sufficient, with the bentonite in the dried beads containing at least 2% water, preferably at least 4% water. The use of deionized water is preferred as it has a very low hard water ion content and minimal metal ions that can promote the decomposition of organic matter that may be present in clutch materials, substrate beads, and detergents. , usually tap water can be used instead. The hardness of such water is typically less than 150 ppm as _CaCO3 , but
More preferably less than 100 ppm, most preferably less than 50 ppm.

The proportions of the various components in the base beads and spray-dried detergent composition beads are such that the nonionic detergent to which they are added in liquid form is free-flowing and, in the case of the base beads, sufficiently absorbent and the detergent composition The material is also satisfactorily free-flowing. It will also be appreciated that the detergent composition is an effective detergent (the builder present aids in the detergency of the organic detergent in the aqueous solution of the composition) and the product is a zeolite particle (i.e. zeolite-silicate aggregate) onto the laundry. It is important that the material does not cause undesirable adhesion of particles (aggregates). Zeolite particles and bentonite particles are insoluble but small in size, so they do not cause undesirable discoloration or fading of the laundry, but they are retained in the fibers and
Such discoloration can occur when zeolite aggregates that are large enough to be easily visible are formed, especially when a significant proportion of them are not removed from the laundry by dissipating with the drying air during free drying. It is also desirable that the substrate beads and detergent composition beads have appropriate bulk density and color.

Preferable beads for achieving the above purpose are from 5 to 50% by weight.
It was found to consist of 60% water softener aluminosilicate (zeolite), 2-40% bentonite (with desired water content), 5-60% water soluble builder or mixtures thereof. 0-30% water-soluble synthetic organic detergents and/or 0-3% water-soluble silicates may also be present, but in many cases it is preferred to exclude them. Preferably, the spray dried beads are between 3 and 15
%, more preferably 5-12%, usually 7-10%
% of water (including water of hydration). Such water of hydration may be present in addition to the interlayers of bentonite when zeolites, NTA, phosphates, carbonates, bicarbonates, and Mg sulfate are included in the formulation.
The above water content also includes strongly retained water of hydration, such as is retained in the zeolite even after several hours of distillation of the dispersion in toluene. If the product has a high zeolite concentration and up to about 12-15% water is present in the zeolite as hydration water, the water content of the spray-dried beads can be as high as 20%, and sometimes reach about 25%. . However, improving the fluidity of the product,
Typically such an upper limit is about 15% to minimize viscosity and agglomeration (particularly when the final detergent composition contains a significant proportion of nonionic detergent). The displayed percentage of zeolite includes its hydration water. For the reasons mentioned above, it is possible to make useful spray-dried beads with less than 3% water content if the bentonite contains sufficient bound water, but due to the strong water absorption of zeolites and other Due to the action of the hydratable substances, a minimum of 3% water is normally required to "lubricate" the bentonite's desired internal water (layers) and aid in their separation when products containing them are dispersed in water. We have found what is necessary to avoid losses (which are thought to be Furthermore, when making anhydrous products, even if sufficient moisture is retained in bentonite, it is physically unstable and easily powders, assrition, and disintegrates.

The bulk density of the spray dried beads is 0.2-0.9 g/cc. Bulk densities in the lower half of this range are readily obtained when no silicate is present in the clutch mixture to be spray dried and when little or no nonionic detergent is absorbed by the beads. High bulk densities are obtained when nonionic detergents are applied to porous beads or when some silicate is present in the beads. Light products have a bulk density of 0.2-0.5 g/cc, often 0.3-0.4 g/cc, and heavier particles have a bulk density of 0.6-0.9 g/cc, usually 0.6-0.8 g/cc. Bead particle size is normal, American standard sieve No.10
~100 (passing through No. 10; moored at No. 100), more preferably within the range of No. 10 to 60. In preferred formulations, the ratio of bentonite to zeolite is from 1:4 to
The ratio of water-soluble builder to zeolite is 1:2 to 3:1, and the ratio of bentonite to water-soluble builder is 1:10 to 1:1. Such ratios are 1:3 to 2:3, 2:3 to 2:1, 1:6 to
1:2 is more preferred. Expressed in %, the composition contains 10-40% of partially hydrated zeolite Na (15-25% by weight of water of hydration) and Ca ions with a hardness equivalent to Ca carbonate of 200-400 mg equivalent per 1 g of anhydrous zeolite. 2-35% bentonite swelling capacity is 7-15 ml/g, and the viscosity is 8-30 cps at 6% concentration in water), 10-35%
50% water-soluble alkali metal builder salt or mixture thereof, 0-25% water-soluble synthetic anionic organic detergent,
Preferably it consists of 0-3% water-soluble silicates. Silicates present are alkali metal oxides:
It is an alkali metal silicate having a silicon dioxide ratio of 1:1.6 to 1:3 (more preferably 1:2 to 1:2.8). A more preferred bead formulation is 15-35%
Zeolite A, 5-20% beneficent Wyoming bentonite, 20-50% water-soluble Na builder salt or mixture thereof, 0-20% water-soluble synthetic anionic organic detergent, 0% Na silicate.

Although carbonate, bicarbonate builders are useful in the production of substrate beads within the present invention (particularly those to be spray dried with nonionic detergents), whether or not anionic detergents are included, and nonionic detergents are also used. Whether or not polyphosphate and/or nitrilotriacetate builders are often preferred for spray-dried beads. Preferred formulations of base beads based on NTA as the sole or major soluble builder include 15-35 to 40% hydrated zeolite;
5 to 10 to 20% bentonite, 20 to 50 to
Contains 60% NTA. When using a phosphate such as sodium tripolyphosphate as the primary or basic water-soluble builder, equal proportions of zeolite and bentonite can be used, but more phosphate than NTA is usually present. In substrate beads sprayed with nonionic detergents and corresponding compositions based on carbonates or mixtures of bicarbonate and carbonate (carbonate:bicarbonate ratio in the spray-dried substrate beads is within about 1 to 3) Preferably, no water-soluble synthetic organic detergents are present, and little or no water-soluble silicates are present.
When bicarbonate and carbonate are used together in such formulations, the total amount is 20-40% of the base beads, and when carbonate alone is used, it is usually 10-30%.

When anionic detergents or other suitable organic detergents are included in the clutcher to produce a spray-dried detergent product, the proportion thereof is from 3 to 5 to 30%, more preferably from 5 to 25%, most preferably from 10 to 25% of the product. For example, 10%, 15%), detergents are linear alkylbenzene sulfonic acid Na (alkyl _C10-18 ) fatty alcohol sulfate Na (alcohol is _C10-18 ) fatty alcohol ethoxylate sulfate (fatty alcohol is
_C10-18 ; having 3 to 30 ethylene oxide groups/mol) and mixtures thereof. Among these, currently the most preferred is linear tridecylbenzenesulfonic acid.
Na (alkyl is preferably _C12-16 ).

When the nonionic detergent is absorbed into the spray-dried substrate beads (sometimes a small proportion can be absorbed into the spray-dried detergent beads), the proportion is usually 5 to 8-30%, preferably 10-25%, such as 15%, 20%. . In such a case, a preferred nonionic detergent is a condensation product of a _C12-16 higher fatty alcohol and 6 to 12 times the molar amount of ethylene oxide.

When polyacrylate is present in any detergent composition or base beads, it is usually 0.05 to 1%, and preferably has a molecular weight of 1000 to 5000.

The presence of anionic detergents in spray-dried detergent beads can prevent the formation of a bead structure capable of absorbing the desired proportion of non-ionic detergent, so spray-dried detergent beads of the type within the scope of the present invention are not produced. It may be preferred to have a high proportion of nonionic detergent present in the final product by mixing with the substrate beads of the invention (previously sprayed with nonionic detergent). Various ratios can therefore be used depending on the properties desired in the final product (e.g., for the above components, 1:10-10:1, 1:5-5:1,
1:2-2:). It is desirable that the bulk densities of the beads before mixing are approximately the same, preferably each
0.1 g/cc, and the particle size should be approximately uniform (usually within the range of US Standard Sieve No. 10-100) to prevent migration and separation of the final mix.

The proportion of substrate beads, adjuvants and processing aids in the spray-dried detergent is usually limited to 20%, preferably 1-10%, more preferably 3-7%.
When using Mg sulfate and citric acid, the processing aid ratio is usually 0.5 to 2% (preferably 1 to 1.5%).
%), Na citrate 0.1-0.5% (preferably 0.1-0.5%)
0.3%). When color pigments and fluorescent brighteners are present, the proportion is usually 0.05 to 0.6%, preferably 0.2 to 0.4% of color pigments such as ultramarine blue.
%, 0.1-4% with fluorescent whitening agent, preferably 1-3
%. The proportion of titanium dioxide (white pigment) is usually 1 to 3%, preferably 1.5 to 2.5%. If colored dyes are used in place of colored pigments, the proportion is usually 1 to 50%, especially 5 to 20% of the colored pigments.

Suitable spray-dried beads within the scope of the invention that contain NTA or a polyphosphate builder and may or may not contain a synthetic organic detergent, or may contain such a detergent together with any of the suitable water-soluble builder salts listed above. In the case of , the bulk density is 0.2-0.8g/cc,
The aluminosilicate is Japanese Zeolite A and the bentonite is at least 3% on an anhydrous bentonite basis.
Contains water-soluble silicates (if present)
is Na silicate with Na ₂ O:SiO ₂ of 1:2 to 1:2.8, and the water content of the beads is 3 to 12%. When the beads contain NTA or nitrilotriacetic acid or other Na salts (synthetic organic detergents may or may not be included)
The bentonite:zeolite ratio is 1:6 to 1:
2. NTA:zeolite ratio is 1:2 to 2:1, bentonite:NTA ratio is 1:6 to 1:2,
Hydrated zeolite, bentonite, nitrilotriacetic acid
The percentages of Na and silicate are 10-40% and 2-40%, respectively.
25%, 10-40%, and 0-3%.

When the preferred NTA-containing beads include the zeolite A, bentonite, and water as well as a synthetic anionic organic detergent (with or without the presence of soluble silicate), 5 to 30% of the synthetic anionic organic detergent is included.
% is preferable. Here, the synthetic anionic organic detergents are linear alkylbenzene sulfonic acid Na (alkyl is _C10-18 ), fatty alcohol sodium sulfate (alcohol is _C10-18 ), fatty alcohol ethoxylate sodium sulfate (fatty alcohol is _C10-18 ; 3-30 pieces/
mol of ethylene oxide groups) or a mixture of two or more thereof, the water-soluble builder is Na salt of nitrilotriacetic acid (NTA), the bentonite:zeolite ratio is 1:6 to 1:1,
NTA:zeolite is 1:3-3:1, bentonite:NTA is 1:10-1:1, synthetic anionic organic detergent:zeolite is 1:1-1:
4, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent, and silicate are 10-40%, 2-25%, 10-40%, respectively.
10-25% (more preferred range) 0-3%.

In the case of phosphate-containing beads, apart from the presence or absence of synthetic detergent, the materials and ratios are the same as for the corresponding NTA-containing beads, except that pentasodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof is used. It is used in place of NTA, and the percentages are 15-35%, 5-20%, 15-40%, and 0-3%, respectively.
It is. Similarly, for phosphate-containing beads where anionic detergent is also present, the materials and ratios are the same as the corresponding NTA-containing beads, with total polyphosphates ranging from 10 to 50
The % range is also the same except that it is %.

The proportions of the various base bead components in the final detergent composition can be adjusted from the proportion of base beads by reducing the proportion of detergent or other materials post-added to the beads when nonionic detergent (possibly with other materials) is post-added. On the contrary, the bead component part (also,
From this, the final product formulation can be calculated backwards from the final product formulation. So, for example, to calculate the range in the final product formulation from the range in the beads, if only nonionic detergent is added to the final detergent composition and the final product contains 20% nonionic detergent, then the base material For various percentage fluctuation ranges of bead components
The percentage in the final detergent composition product can be calculated by multiplying by 0.8 ( ^100-20 ₁₀₀ ). Similarly, when the proportion of nonionic detergent (in formulations that are the only additive to Biz) is between 8 and 25% of the detergent composition, the multiplier is
It is 0.92-0.75. The final percentage of nonionic detergent in the product is between 8 and 30%, preferably between 10 and 25%, more preferably between 15 and 22%, such as about 20%, but for certain types of products, in some cases between 8 and 13%. may be preferred. Usually the % of fragrance in the final product is
0.1-1, preferably 0.2-0.4, and the enzyme is 0.5
-3%, preferably 1 to 1-2%, and when the hydrated silicate is added afterwards, the proportion is usually 1.
%, preferably about 5%, but in some cases as much as 10% can be used. When the softener compound is present in the final product, the proportion is usually between 3 and 12
%, preferably 5-10%.

The substrate beads and spray-dried detergent beads of the present invention are aqueous clutch materials (usually about 40-70 to 75
% solids, preferably from 50 to 65%, with the remainder being spray dried from water, preferably deionized as described above, but tap water can also be used).

Crutcher mixes are preferably made by sequentially adding the various ingredients in a manner that produces a most miscible, pumpable, non-settling slurry that is spray dried. The order of addition of materials can vary depending on the conditions, but the silicate solution (if used) should be added last, and if not last then at least the gel or antifreeze material or processing aid ( e.g., citric acid, Mg sulfate). Typically, all or nearly all of the water (at about processing temperature is preferred) is first added to the clutcher, followed by processing aids (if present).
Other minor ingredients (such as pigments, fluorescent brighteners, polyacrylates (if present), etc.) are added, followed by zeolites, water-soluble builders, anionic detergents (if present), bentonite, silicates ( (if present). Normally, during such addition, each component is thoroughly mixed before addition of the next component, but the method of addition can be varied depending on the conditions to allow for co-addition. Sometimes the ingredients can be added in portions, or different ingredients can be premixed before addition to speed up mixing. Typically, the speed and power of mixing increases as materials are added. For example, use low speed until you have incorporated the slower of the zeolite and water-soluble builder, then increase the speed to medium, then high, and keep this high speed before, during, and after the silicate solution. It is preferable.

The temperature of the aqueous medium in the clutcher is usually about room temperature or above, usually 20-80°C, preferably 30-75°C.
℃, more preferably 40 to 70℃. Heating the clutcher medium promotes dissolution of water-soluble salts in the mix and increases miscibility, but when the heating operation is performed in the clutcher, the production rate is slow and may accelerate hardening of the mix. The advantage of having a processing aid present in the mix (particularly when soluble silicates are present) is that the desired non-gelled slurry is ensured at both low and high temperatures. One or more clutch materials ingredients (e.g. bicarbonate)
80℃ (sometimes 70℃) as there is a risk of decomposition of Na)
Higher temperatures are generally avoided. Also, in some cases, lowering the clutcher temperature increases the upper limit of the clutcher solids content, possibly due to insoluble cold gelling or curable components.

The crutcher mixing time to obtain a good slurry ranges from as short as 5 minutes for a slurry with a high water content using a small crutcher, to as little as 4 minutes in some cases.
It can vary widely over long periods of time. Although the mixing time required to substantially homogenize all of the Crutcheromics ingredients in one medium is as short as 10 minutes,
In some cases it can take up to an hour, but 30 minutes is the preferred upper limit. Taking into account such initial mixing time, a normal clutching period is 15 minutes to 2 hours (e.g. 20 minutes to 1 hour), but if clutching materials are used at least 1 hour after their manufacture, preferably 2 hours.
It must be fluid, i.e. not gel or harden, for a period of time, more preferably 4 hours or more, and 10 hours before pumping to the spray tower where other manufacturing problems may occur. May be fluid for ~30 hours.

Crutcher mixes (with various salts and other ingredients dissolved or homogeneously dispersed in granular form) are conventionally fed to a spray drying tower (usually located near the crutcher). The slurry is allowed to fall from the bottom of the crutcher into a forced displacement pump and is forced under high pressure (countercurrent or cocurrent) through a spray nozzle at the top of a conventional spray tower. The slurry droplets fall through a hot drying gas (usually a combustion product of fuel oil or natural gas) and the droplets are dried into the desired absorbent bead bodies. Bicarbonate (if present) during drying
A portion of the carbonate may be converted to carbonate with the release of CO ₂ , which, together with the polyacrylate that may be present in the mix to be spray dried, improves the physical properties of the beads produced. , thus the beads become more absorbent of liquids (eg, liquid nonionic detergents, which can then be post-sprayed onto the beads).
However, the zeolite, bentonite, and polyphosphate (when present) components in the base beads produced also appear to aid in liquid absorption and production of strong beads.
Polyacrylates also improve bead properties, speed drying and increase tower throughput.

After drying, the product is sized to the desired size (e.g.
Use American standard sieves No. 10 to 60 to 100), and nonionic detergent can be sprayed onto them. For base bead formulations, the beads can be in warm or cooled (to room temperature) conditions. However, nonionic detergents are usually heated to a high temperature such as 30 to 60°C (for example, 50°C) to ensure that they become liquid. Moreover, it is desirable that the material becomes a solid (often resembling a wax-like solid) when cooled to room temperature. Even at room temperature, nonionic detergents are somewhat viscous, which impairs the flowability of the final composition as the detergent penetrates below the surface of the beads. Nonionic detergents used as sprays or droplets on moving or oscillating beads in a known manner include ethylene oxide and higher fatty alcohols (such as those mentioned above).
The condensation product with is preferred, but other nonions can also be used. Enzymes (herein referred to as enzymes, but also include carrier materials), hydrous silicates, and other powdered adjuvants can be powdered onto the surface of detergent particles, and fragrances and other liquids to be added later can be applied before and after powder addition. It can be sprayed at any suitable time.

Spray-dried detergents, spray-dried beads, and detergents made therefrom may contain little or no silicates from Clatcheromics. However, silicates in solid form can be added later. The use of powdered silicate added after this is not expected to react appreciably with the zeolite, and therefore the zeolite-silicate agglomerates that tend to stick to the laundry are the result of the silicate being in the clutter. Decreased compared to deposits from added products. Although silicates are commonly used in the absence of bentonite, at least for their bead control anti-corrosion effects, this detergent composition provided acceptable beads and did not corrode Al products. Additionally, bentonite does not adversely affect product stability and in fact helps to hold the beads together, making them resistant to crushing and powdering during shipping, use. The presence of bentonite significantly improves the properties of the final detergent composition, increasing the Ca ion binding rate and
Reduces zeolite adhesion to laundry fabrics. The presence of the low molecular weight polyacrylate makes the substrate beads more porous and better absorbs liquid nonionic detergent without unduly lowering the bulk density of the product. Given that bentonite is a clay and acts as a binder, it would be expected to cause its own adhesion and gelation problems. Therefore, low adhesion,
The absence of gelation and the easy dispersibility of the product are surprising and important results of the present invention. Furthermore, an important consequence of the presence of a small proportion of polyacrylate in the spray-dried beads is that the improved spray-drying of the substrate beads and detergent compositions of the present invention and the liquid nonionic detergents with substrate beads. This is an improvement in the absorption of

The following examples are illustrative of the invention and are not intended to be limiting. In this specification, unless otherwise specified, all temperatures are in degrees Celsius and all parts are parts by weight. The weights and proportions of zeolite are based on the usual hydrates used. This is because the water of hydration of the zeolite does not leave the zeolite and is not considered to become part of the aqueous solvent in the clutcher operation of the present invention, and is also present in the substrate beads and detergent composition. This is because some of the water exists as zeolite hydration water. Also, part of the water present in the base beads and detergent composition exists as zeolite hydration water. Similarly, water bound to bentonite can also be considered not free water, but the proportion is so low that in practice this difference can often be ignored.

Example 1 (Comparative Example) A 100-part batch of Clutch Mixtures was placed in a clutch at about 27° C. for spray drying onto the substrate beads which were then considered suitable for conversion into a detergent composition by the addition of a synthetic nonionic organic detergent. 47
1 part of deionized water, then 1.04 parts of Tinopal 5BM Extra Conc (manufactured by Ciba Geigy), 0.13 parts of Ultramarine Blue Powder, while first mixing at low speed with a crutcher.
0.7 parts sodium polyacrylate (Alcosperse 107D)
21.11 parts Linde hydrated zeolite 4A (20% water of crystallization), 6.25 parts mineral colloid No. 1 (bentonite), 15.75 parts sodium bicarbonate (industrial grade), 7.74 parts sodium carbonate (natural soda ash) ) was made by mixing it with 0.91 parts of titanium dioxide (anatase).

Increase the mixer speed to medium while mixing the various ingredients,
Finally turn on high and add all ingredients (took about 15 minutes)
Afterwards, mixing continued for approximately 1 hour (sometimes 4 hours). During this time some water, for example about 2 to 6 parts, is lost by evaporation (which can be replenished if desired). During mixing, the clutcher slurry remained fluid and did not gel, harden, or clump; the bicarbonate, carbonate in the clutcher formulation was partially decomposed to carbonate during spray drying. The amount of was varied depending on the spray tower operating conditions.

Approximately 5 minutes after all components of the clutcher were added, the mixture was dropped from the clutcher to the pump and pumped to the head of the countercurrent spray tower at a pressure of approximately 21 kg/cm ² (initial temperature was approximately 430°C). , final temperature approximately 105℃). The essentially inorganic substrate beads obtained have a bulk density of approximately 0.6-0.7 g/ml and an initial adhesion rate of 10%.
The particle size range was substantially 10 to 60 mesh using a US standard sieve (the particles were sized to fall within this range), and the fineness (passing a US standard sieve No. 50) was about 15%. The moisture content of the beads was usually close to 10%, for example 8-10%. It was free-flowing (80% flow rate), non-viscous, moderately porous, and had a hard surface. They were able to easily absorb a significant proportion of liquid nonionic detergent without becoming excessively viscous.

A detergent product was made by spraying a wax-like nonionic detergent onto the surface of oscillating spray-dried beads at room temperature. I used Neodol 23-6.5, but you could substitute Neodol 23-7 or Neodol 25-7 (sometimes Neodol 45-11). The nonionic detergent was in a heated state (approximately 45°C). Sprayed in an amount such that the final product contained 20% nonionic detergent. Proteolytic enzyme (Alcalase 1.7T or Maxa Tweet)
375) was used in powder form to give a concentration of 1.5% in the product, and fragrance was sprayed onto the product to give a concentration of 0.25%. The resulting detergent product has a bulk density of approximately 0.7 to 0.8 g/ml
and 32.45% zeolite (hydrate), 19.7%
of nonionic detergent, 18.5% sodium carbonate (some of which is produced by decomposition of sodium bicarbonate), 13.5% bicarbonate
Na, 1.3% water, 1.4% enzyme, 1.6% fluorescent brightener, 0.25% fragrance, 0.2% ultramarine blue, 5.0% bentonite (Thixo-Jel), 0.1%
of sodium polyacrylate and 1.4% titanium dioxide.

The detergents of the above formulation made are excellent heavy-duty laundry detergents, non-dusting and extremely free-flowing (hence the narrow-necked glass bottles) that are particularly useful for washing household laundry in automatic washing machines. It is physically and aesthetically advantageous and attractive because it can be easily packaged in plastic bottles and dispensed from it. As mentioned above, the resulting detergent composition containing bentonite contains Ca.
The rate of ionic bonding was significantly improved, but more importantly, the deposits on laundry washed (at normal concentrations for such products and in an index washer at normal wash temperatures) were reduced to bentonite. in particular, compared to similar compositions containing Na silicate in the spray-dried base beads.
Such laundry was rarely line-dried.
This difference is due to the high hardness of the washing water (for example, as Ca carbonate)
200 ppm), increased when the wash water was cold and a mild agitation cycle was used.

The substrate beads and detergent compositions produced were of an acceptable standard, whereas the latter were superior when compared to other beads and detergent compositions mentioned above (Examples below). Also, the manufacturing method was essentially the same and seemed to be satisfactory.

The clutching mixture can be made rapidly in conventional manner, discharged from the clutcher rapidly (sometimes in as little as 5 minutes), and pumped out of the clutcher in as little as 10 minutes. However, it is often important that the mixes of the present invention be able to withstand at least one hour in a clutcher without gelling or solidifying. This is because commercial production sometimes involves downtimes of such length. The described clatschiamics can be used for up to 4 hours (in many cases can be retained (considerably more). Other minor components of the clutter-mixture may also be excluded, such as fluorescent brighteners and pigments, and enzymes and fragrances may also be excluded from the final product, although it is highly preferred that all such materials be present. The clutch temperature is 52℃, for example.
The percentage of various components can be changed by increasing up to ±10%, ±20%, ±30% within the above range.
The desired bead and detergent compositions can be modified to provide usable clutch mechanics. The clutter mix solids content can be varied within the above range, for example from 45% to 65%, with good mixing and spray drying. Although other orders of addition of ingredients to the clutcher can be used, it is generally preferable to add the silicate at or near the end, and the bentonite to be added late in the process, preferably just before the silicate. and preferable. Zeolite X and Y can be used instead of zeolite 4A, and other types of zeolite A may also be used. Almost 80% hydrated zeolite 4A (water content about 20%) in this example
Although the use of zeolites to varying degrees of hydration can be used, in some cases anhydrous crystalline zeolites and amorphous zeolites can also be used. The amount of zeolite within the above range is, for example, 7% in the base beads, 13
%, 19% still yields a useful product, but those containing higher percentages of bentonite are usually more effective in helping to prevent zeolite from sticking to laundry. In some cases, it may be desirable to use higher percentages of bentonite within the above range, but care must be taken to ensure that the other components of the base beads act in a way that renders the beads free-flowing and effective detergents. Should. The proportion of bentonite suitable for commercial use depends on a number of factors and is typically
It represents a balance between a reduction in zeolite loading and the desired builder effect and other functional effects of other detergent composition ingredients that are included at the expense of a reduction in bentonite.

The improvement noted in the detergent compositions of this example, in terms of reduced laundry deposits, is that the product was compared to a control product of essentially the same formulation (no bentonite present in the final product, about 80% % Sodium silicate)
This was demonstrated by testing against In this evaluation, Whirlpool Satsuzu Save (Whirl−
A washing machine (pool Suds Save) was used, and the washing period was 8 minutes on a gentle wash cycle. The detergent composition concentration was 0.06%, the (Ca+Mg) mixed hardness of the wash water was 200 ppm in terms of Ca carbonate, and the water temperature was 24°C. The laundry items were as follows:

100% wood line; 100% polyester; Acetate 85
% + nylon 15%; polyester 65% + wood line 35
%.

The laundry was observed when wet and after line drying (line drying usually results in more visible build-up than automatic dryer drying). No deposits were observed in any case. Moderate deposits were observed in all laundry specimens when the control formulation detergent composition was tested.

The results of the practical adhesion test described above were verified by measuring the amount of adhesion to the test material denim. In such tests, detergent compositions of the invention were filtered through denim wood samples (detergents were placed in hard water (200 ppm as _CaCO3 ) at 24 DEG C. as a 0.12% solution-suspension). The amount of adhesion to the cloth was recorded and compared. In such tests, the control adhesion rate was approximately 75%, which is considered to represent a significant improvement in the appearance of the laundry.

In the adhesion test, which measures the tackiness of detergent products, 10 g of substrate beads (and optionally detergent composition) were placed evenly between two watch glasses. Both watch glasses are approximately 23 cm in diameter, and the top surface of the upper watch glass is
A 500g weight was placed (both watch glasses were concave with raised sides). After leaving it for about 5 minutes, the weight and upper watch glass were removed, the lower watch glass was turned over, and the weight of the product still attached thereto was measured. The adhesion rate is the number of grams of product remaining on the watch glass multiplied by 10.

Flow index is a flow test [volume flow rate of substrate beads (sometimes the final product) and standard Ottawa sand (-20 + 60, American standard sieve), measured at a 2.2 cm nozzle attached to the cap of a 1.9 Mason jar.
Comparison was made by measuring the time required for complete ejection from the jar through the diameter hole. This flow index % is the sand flow time divided by the test product flow time and multiplied by 100.

Example 2 Substrate beads identical to Example 1, but containing NTA in place of some of the carbonate and bicarbonate, were made in essentially the same manner as that Example. The formula is 5 times the amount of zeolite, 12 parts of sodium bicarbonate, and 3 parts of sodium carbonate as the trisodium salt-hydrate in the crutcher.
It was only changed to NTA of the department. NTA was added after Na carbonate during the mixing operation. The resulting substrate beads were not as crisp as the substrate beads of Example 1, but were sufficiently free-flowing. Instead of a final detergent composition containing 19.7% nonionic detergent, it was also sufficient to keep the percentage at 12% and increase the final percentages of other ingredients accordingly. The product was a preferred heavy duty granular detergent.

As an improvement to this formulation, it has anti-corrosive properties and
2.5% hydrated Na silicate was added to the product to capture Mg ions in the wash water. Because the silicate had nearly identical particle size and density, it was not sieved or separated from other detergent bead components during transportation and storage, and the product met commercial heavy-duty detergent specifications. However, small proportions of zeolite-silicate aggregates may be found on the laundry surface.

Another formulation has a _Na2O : _SiO2 ratio of approximately 1:2.43
% Na silicate was included in the final product by adding its aqueous solution into the clutcher along with 1.5% Mg sulfate and 0.4% citric acid to prevent gelation and solidification in the clutcher. Although the final product was a good heavy-duty detergent, more zeolite-silicate aggregates were deposited on the line-dried laundry than the corresponding formulation with post-added hydrated sodium silicate.

Example 3 The method of Example 2 was repeated. However, NTA was changed to pentasodium tripolyphosphate. The product is a good detergent, with a bulk density of about 0.8g/cc (same as example 2)
However, this density could be varied from 0.7 to 0.9 by adjusting the spray tower conditions and formulation, and in some cases could be reduced to 0.3. In the case of post-added silicates, the density may be slightly higher.
(especially the density within the lower part of the range). The product was more free-flowing than that of Example 2, but the cleaning power was about the same.

In the formulations above and in Examples 1-2, bentonite could be added to the clutcher to provide 15% (or more) bentonite in the product.
Such products had better binding effects, dispersibility and other desired properties attributed to bentonite, and were good detergents (base beads). Furthermore,
Similar good products were obtained by replacing all or part (eg 1/2) of the tripolyphosphate with tetrasodium pyrophosphate.

Example 4 A final detergent product containing 30 parts zeolite, 30 parts NTA, 20 parts nonionic agent, 10 parts bentonite, 5 parts sodium carbonate, 5 parts water, 1.3 parts enzyme was prepared essentially as Example 1. I made it using two methods. The product is approx.
It had a density of 0.5g/cc and was a satisfactory detergent.
However, it was desirable to reduce the nonionic detergent content to 15%, preferably 12%, to improve the flowability of the product. To increase the bulk density to approximately 0.7, half of the bentonite is mixed with Na silicate, which is added as a 47.5% aqueous solution as the last ingredient in the clutcher.
(Na ₂ O:SiO ₂ ratio = 1:2.4) and correspondingly 1.5 parts of Mg sulfate and 0.4 parts of citric acid were added as anti-gelation agents early in the production of the clutter mix. The bulk density of the product was approximately 0.7 g/cc, and it was able to absorb approximately 20 parts of nonionic detergent without becoming viscous or reducing fluidity. The addition of the clutter resulted in less deposits of zeolite-silicate agglomerates than in formulations with higher amounts of silicate than usual, but the agglomerates were washed with the product and line-dried. was detected.

Example 5 Instead of spraying a detergent to form substrate beads to form a detergent composition, the composition was spray dried directly from a clutcher with a suitable synthetic organic detergent contained in the clutcher mixer. Example 1
The clatcher mixture was made using essentially the same method as described and spray dried to contain 16 parts linear tridecylbenzene sulfonate, 20 parts zeolite, 12.5 parts bentonite, 15 parts NTA, The detergent beads contained 10 parts of sodium carbonate and the usual adjuvants (colorants, brighteners). The bulk density of spray dried products is between 0.3 and 0.8, usually within the lower half of this range, but sometimes as low as 0.2 g/cc. In manufacturing, organic detergents are usually added after water. After drying, the moisture content was approximately 8-12%. Preferably, the product contains about 3 parts of post-added hydrated sodium silicate along with other conventional adjuvants such as enzymes, fragrances, etc. It was a preferred heavy-duty detergent that did not deposit inadequate amounts of zeolite or zeolite-silicate agglomerates on the laundry fabric. Due to the presence of bentonite, the detergent dispersed very quickly when added to the wash water. It is believed that this rapid dispersion, combined with the presence of bentonite, tends to inhibit zeolite deposition, at least in part.

Example 6 The method of Example 5 was repeated. However, an equal amount of soda ash was used instead of NTA. This product was also a satisfying heavy duty detergent.

Example 7 The method of Example 5 was repeated. However, pentasodium tripolyphosphate was included in place of NTA. The product was particularly free-flowing and was a good heavy synthetic organic detergent composition. When silicate is present, it is preferably post-added as hydrous sodium silicate, but up to 5 parts of silicate may be added in the clutcher with appropriate proportions of Mg sulfate and citric acid as described in the previous example. Useful detergent compositions can be produced. However, some zeolite-silicate will adhere.

In addition to the usual materials that can be post-applied, the product of this example (and the products of other examples) contains a softening percentage of cationic substances (e.g. 8% dimethyl distearyl ammonium chloride), amphoteric detergents [e.g. 5% Milano-
Miranol C ₂ M (1-carboxymethyl-1
-carboxyethoxyethyl-2-coco-imidazolinium betaine)] or bleaching agent [e.g. (5
% Na perborate (preferably activated)]
can also be added. Naturally, the addition of such materials reduces the proportion of other ingredients in the final composition and therefore changes the properties of the composition slightly, sometimes requiring the use of more product in the wash to obtain the same cleaning effect. This is necessary.

In Examples 5 to 7, the linear tridecylbenzene sulfonate can be substituted with an equal amount of sodium lauryl sulfate or sodium lauryl polyethoxy sulfate (3 to 10 Eto), or a mixture of equal parts of these, and the resulting products are also It is useful as a detergent composition. Similarly, carbonate, carbonate and bicarbonate, polyphosphate, Na citrate and/or
Alternatively, it could be replaced with sodium gluconate, and a good detergent was obtained.

Example 8 The products of Examples 1 and 7 (the main products mentioned at the beginning) were mixed in equal proportions to obtain a final product having the properties of both components. Before mixing, the bulk densities of both mixed materials are almost the same (approximately
0.5g/cc), particle size is the same (US standard sieve No. 10-60)
This prevents separation during transportation and storage. This hybrid product was particularly useful in removing oily and clay stains from laundry and was free-flowing, stable and attractive. In some cases, one particulate starting material was colored while others were left in their natural color to obtain special appearance effects. In addition to having approximately the same particle size and density, it is also preferred that the water content be approximately the same, for example about 10%, so that there is little moisture transfer between the beads.

A mixture made by replacing the material used as an anionic detergent in Example 7 with sodium alkylbenzenesulfonate and sodium α-olefin sulfonate (olefin is C _14-15 ) or sodium paraffin sulfonate (paraffin is C _12-15 ) is also useful. It was a detergent.

EXAMPLE 9 The method described in Example 1 was substantially followed to prepare Clutchyarmix: 36.9 parts water, 1.2 parts fluorescent brightener (Tinopal 5BM, super concentrate), 0.1 part ultramarine blue, 2.1 parts of Mg sulfate (hexahydrate), 0.3 parts of Na citrate, 22.4 parts of Zeolite 4A powder (partially hydrated, water content approximately 20%), 20.9 parts of trisodium nitrilotriacetate monohydrate. 7.4 parts of sodium silicate (Na ₂ O: SO ₂ = 1:2.4) solid content 47.5%
solution, 3.7 parts Na bentonite (formerly THIXO−
sold as JEL No. 2), 2.8 parts natural soda, 2.1 parts mineral type compound (increases bead porosity,
He also worked as a builder. This clutch material mixture was spray dried as described above. The moisture loss during drying was approximately 45.2%.

78.4 parts of spray-dried substrate beads with particle sizes ranging from US Standard Sieve No. 10 to 100 (after sieving) were sprayed with 20 parts of Neodol 23-6.5, and then the beads were mixed with 1.3 parts of highly active protein. It was mixed with a degrading enzyme and sprayed with 0.3 parts of detergent fragrance. The final product has a zeolite content of 25
%, NTA content is 30%, bentonite Na content is 5
%, and the water-soluble sodium silicate solid content was 5%. . The water content was 5% and the active cleaning ingredient (polyethoxylated higher fatty alcohol) content was 20%. The bulk density is approximately 0.7g/cc, and the pH of its 1% solution is approximately
It was 10.

The detergent compositions made by this method are satisfactory heavy nonionic detergents, but contain slightly more zeolite in the line-dried wash cloth than corresponding compositions made without water-soluble silicate solids. - deposited silicate aggregates. Preferably, about 0.1 to 0.5% of low molecular weight sodium polyacrylate of the type described above is also present in such corresponding compositions. Both products clean laundry well and are especially effective in cold water washes.
This fact is at least partly due to the bentonite content and the almost instantaneous dispersion that can be observed when detergents are added to the wash water (this dispersion is a combination of soluble silicates and zeolites that form undesirable agglomerates). (It also shortens the reaction time during the process.)

Claims (1)

[Claims] 1. Free-flowing spray-dried beads useful for the production of granular compositions of synthetic nonionic detergents with builders as detergents, which detergents are characterized by the presence of bentonite in the spray-dried beads, the presence of water-soluble silicate 5-60% water softener aluminosilicate by weight; 5 to 60% water-soluble builder or a mixture of such builders;
Consisting of 30% water-soluble synthetic organic detergent, 0-5% water-soluble silicate; beads. 2. When a water-soluble synthetic detergent is not present, the water-soluble builder is a polyphosphate, a pyrophosphate, an orthophosphate, a borate, a nitrilotriacetate, a gluconate, a citrate, or two or more thereof. Beads according to claim 1, consisting of a mixture. 3. The beads according to claim 2 have a bulk density of 0.2 to 0.9 g/cc; a particle size in the range of US Standard Sieve No. 10 to 100; It is a hydrated zeolite that is a water softener containing 15 to 25% by weight of hydration water, and has a Ca ion exchange capacity equivalent to 200 to 400 mg of Ca carbonate equivalent hardness per 1 g of anhydrous zeolite; When bentonite swells in water 3~15ml/
g, a swelling viscosity of 3 to 30 cps at 6% concentration in water and containing at least 2% water on an anhydrous bentonite basis; polyphosphates, pyrophosphates, orthophosphates, borates, nitrilophosphates. triacetate, citrate,
Gluconate, carbonate, bicarbonate or two thereof
There are water-soluble builders that are _a mixture of more _than one species;
1:3 alkali metal (M) silicate; beads. 4 In the beads described in paragraph 3 of the scope of the patent request,
The ratio of bentonite to zeolite is 1:4 to 1:1
and the ratio of water-soluble builder and zeolite is 1:2 ~
The ratio of bentonite to water-soluble builder is 1:10 to 3:1;
1:1; beads. 5. Beads according to claim 4, comprising 10-40% hydrated zeolite Na2-35% bentonite (having a swelling capacity of 7-15 ml/g and a viscosity of 8-30 cps at a 6% concentration in water) type), 10-50% water-soluble alkali metal builder salts or mixtures thereof, 0
~25% water-soluble synthetic anionic organic detergent, 0-3%
Beads made of water-soluble silicate. 6. In the beads described in claim 5,
15-35% Zeolite A, 5-20% beneficent Wyoming bentonite, 20-50% water-soluble Na builder salt or mixture thereof, 0-20% water-soluble synthetic anionic organic detergent, 0% Na silicate. Consists of bentonite:zeolite ratio of 1:3 to 2:
3, the water-soluble builder:zeolite ratio is from 2:3 to 2:1, and the bentonite:water-soluble builder ratio is from 1:6 to 1:2; beads. 7. Beads according to claim 2, in which the water-soluble builder is selected from the group consisting of carbonates, bicarbonates, polyphosphates, nitrilotriacetates or mixtures thereof; the bentonite is low on an anhydrous bentonite basis; Both contain 3% water; beads. 8. Beads according to claim 7, wherein the bentonite contains at least 4% water; the water-soluble builder consists of nitrilotriacetate; neither water-soluble synthetic organic detergents nor water-soluble silicates are present; beads. 9 In the beads set forth in claim 8, 15
~40%, contains 15~25% of hydration water by weight, and has a hardness of ~200 in terms of Ca carbonate per gram of anhydrous zeolite.
Hydrated zeolite A with a Ca ion exchange capacity of 400 ml equivalent; 10-20% bentonite, a beneficent Wyoming bentonite with a swelling capacity of 7-15 ml/g and a viscosity of 3-30 cps at a 6% concentration in water; 20 ~60%
beads consisting of NTA; 10. Beads according to claim 7, wherein the bentonite contains at least 4% water; the water-soluble builder consists of a polyphosphate; neither water-soluble synthetic organic detergents nor water-soluble silicates are present; . 11. The beads according to claim 10, which contain 20 to 40% of hydration water and 15 to 25% by weight of hydration water, and have a Ca ion exchange capacity of 200 to 400 mg equivalent hardness in terms of Ca carbonate per 1 g of anhydrous zeolite. Hydrated zeolite A with 10-20%, swelling capacity 7-15
ml/g, bead consisting of bentonite, a beneficent Wyoming bentonite with a viscosity of 3-30 cps at 6% concentration in water; 20-60% Na tripolyphosphate; 12. The beads according to claim 2, comprising 5 to 30% of a water-soluble synthetic organic detergent. 13. The beads according to claim 12, wherein the water-soluble synthetic organic detergent is an anionic detergent. 14. The beads according to claim 13, wherein the anionic detergent is linear alkylbenzene sulfonic acid Na (alkyl is _C10-18 ), fatty alcohol sulfuric acid,
Na (alcohol is C _10-18 ), fatty alcohol ethoxylate Na sulfate (fatty alcohol is C _10-18 and has 3-30 ethylene oxide groups per mole), or a mixture of two or more thereof. ;
The proportion of such detergent in the beads is from 5 to 25%; beads. 15. Beads according to claim 7, comprising 3 to 30% of a water-soluble synthetic anionic organic detergent. 16. The beads according to claim 15, wherein the anionic detergent is linear alkylbenzene sulfonic acid Na (alkyl is _C10-18 ), fatty alcohol sulfuric acid,
Na (alcohol is _C10-18 ), fatty alcohol ethoxylate Na sulfate (fatty alcohol is _C10-18 and has 3 to 30 ethylene oxides per mole), or a mixture of two or more thereof;
The proportion of such anionic detergent in beads is 5-25%
Beads. 17. The beads of claim 7, which contain neither soluble synthetic organic detergents nor water-soluble silicates. 18. The beads according to claim 2, which are made of 0.05 to 1% polyacrylate and have a molecular weight of 1000 to 5000. 19. The beads according to claim 3, wherein the bulk density is from 0.2 to 0.8 g/cc; the aluminosilicate is hydrated zeolite A; and the bentonite contains at least 3% water on an anhydrous bentonite basis. ; if the water-soluble builder is Na nitrilotriacetate; if a water-soluble silicate is present, Na ₂ O: SiO ₂
It is sodium silicate with a ratio of 1:2 to 1:2.8; a water content of 3 to 12%; a bentonite:zeolite ratio of 1:6 to 1:2.
the NTA:zeolite ratio is 1:2 to 2:1; the bentonite:NTA ratio is 1:6 to 1:2; the percentage of hydrated zeolite, bentonite, sodium nitrilotriacetate, and silicate is 10-40%, respectively.
2-25%, 10-40%, 0-5%; Beads. 20. The beads according to claim 3, which have a bulk density of 0.2 to 0.8 g/cc; contain 5 to 30% of a synthetic anionic organic detergent; and the aluminosilicate is hydrated zeolite A; The bentonite contains at least 3% water on an anhydrous bentonite basis; the water-soluble builder is Na nitrilotriacetate; the synthetic anionic organic detergent is Na linear alkylbenzene sulfonate (alkyl is _C10-18 ), fatty alcohol Na sulfate. (alcohol is _C10-18 ), fatty alcohol ethoxylate sodium sulfate (fatty alcohol is
_C10-18 and having 3-30 ethylene oxide groups per mole) or a mixture of two or more thereof; if a water-soluble silicate is present, the _Na2O : _SiO2 ratio is 1: It is sodium silicate with a ratio of 2 to 1:2.8; water content is 3 to 12%; bentonite:zeolite ratio is 1:6 to 1:1
the NTA:zeolite ratio is 1:3 to 3:1; the bentonite:NTA ratio is 1:10 to 1:1; the synthetic anionic organic detergent:zeolite ratio is 1:1
~1:4; the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent, and silicate are 10-40%, 2-25%, 10-40%, and 10, respectively.
~25%, 0-5%; Beads. 21. The beads according to claim 3, wherein the bulk density is 0.2 to 0.8 g/cc; the aluminosilicate is hydrated zeolite A; and the bentonite contains at least 3% water on an anhydrous bentonite basis. ; the water-soluble builder is pentasodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof; if the water-soluble silicate is present, Na silicate with a Na ₂ O:SiO ₂ ratio of 1:2 to 1:2.8; water content is 3-12%; bentonite:zeolite ratio is 1:6-1:2
Total polyphosphate:zeolite ratio is 1:2 to 2:1
Bentonite:total polyphosphate ratio is 1:6 to 1:
2; the percentages of hydrated zeolite, bentonite, total polyphosphate, and silicate are 15-35% and 5-35%, respectively.
20%, 15-40%, 0-5%; Beads. 22. The beads according to claim 3, which have a bulk density of 0.2 to 0.8 g/cc; contain 5 to 30% of a synthetic anionic detergent; the aluminosilicate is hydrated zeolite A; and the bentonite is contains at least 3% water on an anhydrous bentonite basis; the water-soluble builder is pentasodium tripolyphosphate or tetrasodium pyrophosphate, or a mixture thereof; the synthetic anionic organic detergent is sodium linear alkylbenzene sulfonate (alkyl is C _{10 to 18} ), fatty alcohol sodium sulfate (alcohol is _C10-18 ), fatty alcohol ethoxylate sodium sulfate (fatty alcohol is
_C10-18 and having 3-30 ethylene oxide groups per mole) or a mixture of two or more thereof; if a water-soluble silicate is present, the _Na2O : _SiO2 ratio is 1: It is sodium silicate with a ratio of 2 to 1:2.8; water content is 3 to 12%; bentonite:zeolite ratio is 1:6 to 1:1
Total polyphosphate:zeolite ratio is 1:3 to 3:1
Bentonite:total polyphosphate ratio is 1:10 to 1:
1. Synthetic anionic organic detergent:zeolite ratio is 1:
1 to 1:4; the percentages of hydrated zeolite, bentonite, total polyphosphate, synthetic anionic organic detergent, and silicate are 10 to 40%, 2 to 25%, 10 to 50%, and 10 to 25%, respectively.
%, 0-5%; Beads. 23. A detergent composition comprising beads according to claim 1, which absorbs and retains nonionic detergent at a percentage of 8 to 30% of the composition. 24. A detergent composition according to claim 23, comprising beads according to claim 2, which absorb and retain nonionic detergent at a percentage of 8 to 30% of the composition. . 25. The detergent composition according to claim 24, wherein the nonionic detergent is a condensation product of 6 to 12 times the mole of ethylene oxide and _C12-16 higher fatty alcohol; the proportion of such nonionic detergent in the composition is 10
~25%; composition. 26. A detergent composition according to claim 23, comprising beads according to claim 17, which absorb and retain nonionic detergent in a proportion of 8 to 30% of the composition. . 27 In the detergent composition according to claim 26, the nonionic detergent contains 6 to 12 times the mole of ethylene oxide.
It is a condensation product with a C _12-16 higher fatty alcohol; the proportion of such nonionic detergent in the composition is 10-16 _.
25%; composition. 28 The detergent composition according to claim 23, comprising a mixture of the beads according to claim 17 and the composition according to claim 26; the particle size is within the range of 100 and the ratio by weight is within the range of 1:10 to 10:1; the bulk density of the beads of the mixture is 0.1 g/cc or less; the bulk density of the final composition is 0.2 to 0.9 g/cc;
Composition.