DE3206265C2 - Free-flowing, spray-dried hollow beads for producing detergent particles containing builders, process for producing the same and use of the same for forming detergents with non-ionic detergent active substances - Google Patents

Abstract

The invention relates to free-flowing hollow spheres into which nonionic detergent active in liquid form can be absorbed to form a free-flowing, particulate, builder-containing synthetic nonionic organic detergent having improved detergency properties. These detergents contain 15 to 30% sodium carbonate, 10 to 22% sodium bicarbonate, 10 to 50% water-softening aluminum silicate (zeolite), 0 to 18% sodium silicate, 1 to 20% bentonite and/or 0.05 to 2% polyacrylate having a molecular weight of 1000 to 5000, and 1 to 15% moisture together with suitable auxiliaries and processing-facilitating substances in small amounts, normally less than 10% in total and preferably less than 5%.

Description

p However, it evaporates during spray drying, which leads to losses of surfactant and also to environmental pollution &

|? The invention has set itself the task of free-flying

K; suffix spray-dried hollow beads,

&xgr;&khgr; which are suitable for the formation of particulate detergent products containing builders and non - ionic surfactants and can absorb the latter to ultimately form particulate builder-containing

' ^y and free-flowing detergents containing

&rgr; non-ionic surfactants, which leave less deposits on the textile.
To solve this problem, free-flowing spray-dried hollow beads are therefore proposed which are composed according to the main claim, with further advantageous embodiments being explained in more detail in the subclaims.
};'; Furthermore, the invention has the object of proposing a |· process for producing such hollow beads p , wherein to solve this problem a p| crutcher mixture with a solids content of 40 to 11 75% is dissolved in an aqueous medium with transfer &psgr; of a portion of the sodium bicarbonate is spray dried in sodium carbonate, which preferably consists to 100% of 15 to 30% by weight of sodium bicarbonate _, 10 to 25% by weight of sodium carbonate, 10 to 50% by weight of zeolite, 0 to 18% by weight of sodium silicate and 1 to 20% by weight of bentonite and/or 0.05 to 2% by weight of polyacrylate with a molecular weight of 1000 to 5000. This gives the spray dried particles a hollow spherical shape which is particularly suitable for the absorption of non-ionic detergents.

. Ultimately, the object of the present invention is

. the use of the hollow spheres according to the invention

: - to propose a detergent for the formation of a detergent,

^: to achieve this object, the hollow beads mentioned are used to absorb non-ionic detergent active substance in an amount of 8 to 30% by weight.

Surprisingly, it has been shown that the spray-dried hollow beads according to the invention

not only have excellent flow properties, but can also absorb non-ionic surfactants particularly well, and that the detergents obtained from these hollow beads deposit less residue on the washed materials despite the presence of zeolite and silicate, and that the addition of bentonite unexpectedly does not cause any deposit problems, whereby the known properties of zeolite, silicate and bentonite in the detergent, such as binding of calcium ions, softening effect and corrosion prevention with excellent dispersibility,

ity of solids can be fully exploited.
: The formation of hollow beads and their good

; absorption capacity for non-ionic surfactants

Surprisingly, it also shows that during spray drying of the crutcher mixture, part of the sodium bicarbonate is converted into sodium carbonate with the release of carbonic acid.

L?'S SI«&iacgr;&Pgr;&ngr;&idiagr;&Agr;&idiagr;&idiagr;&idiagr;&Igr;&Ggr;5>&idiagr;&ngr;&Ggr;&Ggr;&idiagr;«!3£&Ggr;&idiagr; iiohliCli^fiiC. ^" ^ntholtAn 1 &tgr;

up to 30 wt.% sodium carbonate, 10 to 22 wt.% sodium bicarbonate, 10 to 50 wt.% zeolite, 0 to 18 wt.% sodium silicate and 1 to 20 wt.% bentonite and/or 0.05 to 2 wt.% polyacrylate with a molecular weight of 1000 to 5000. The moisture content is 1 to 15 wt.%.
When these hollow beads are used to make a detergent, enough non-ionic detergent actives are applied and absorbed in the liquid state to form a free-flowing product containing about 8 to 30% detergent active by weight. The polyacrylate in the hollow beads not only increases the absorbency for the non-ionic surfactants but also improves spray drying by reducing the amount of material sticking to the walls of the dryer, thereby increasing the throughput rate through the spray drying tower.

The various components for the hollow beads of the invention are normally solid, although they can be added to the crutcher dissolved or dispersed in an aqueous medium.

Sodium bicarbonate is anhydrous and the sodium carbonate is generally used in the form of soda ash. However, if desired, the carbonate hydrates such as the monohydrate may also be used and in some cases other carbonates and bicarbonates such as potassium salts may be used in place of some of the sodium salt, although the sodium salts are preferred. The silicate is usually added to the crutcher as an aqueous solution having a solids content of 40 to 50%, e.g. 47.5%, preferably towards the end of the mixing process. The silicate used usually has a Na ₂ OiSiO ₂ ratio of 1:1.4 to 1-3, preferably 1:1.6 to 1:2.4 or 1-2.6 and especially 1:2 to 1:2.4. Part of the sodium silicate may be replaced by potassium silicate or another suitable soluble alkali silicate salt.

The zeolites used include both natural and synthetic crystalline, amorphous and mixed crystalline amorphous zeolites having a calcium ion exchange capacity of about 200 to 400 or more mg equivalents of calcium carbonate hardness per g of aluminum silicate and a softening rate to a residual hardness of 0.02 to 0.05 mg CaCCVl in one minute, preferably 0.02 to 0.03 mg/l and less than 0.01 mg/l in 10 minutes.

The finely divided synthetic zeolite builders normally used for the purposes of the invention have the formula

(Na ₂ O), &khgr; (Al ₂ O ₃ ), x (SiO ₂ );. &khgr; wh ₂ 0,

in which &khgr; = 1, y - 0.8 - 1.2, preferably about 1, &zgr; = 1.5 - 3.5, preferably 2 - 3 or about 2 and w = 0 - 9, preferably 2.5 - 6.

These zeolites are described, for example, in US Pat. No. 2,882,243 and are referred to as zeolite A.

The zeolite molecular sieves can be used in a dehydrated or calcined form containing about 0 or about 1.5 to 3% moisture, or in a hydrated or water-loaded form containing additional bound water in an amount of from about 4% to about 36% of the total zeolite weight. The water-containing hydrated form of the zeolite molecular sieve, which is preferably about 15 to 70% hydrated, is preferred.

The zeolite should preferably be in a finely divided state and have a maximum particle diameter of up to 20 μιη, e.g. from 0.005 or 0.01 to 20 μιη, preferably from 0.01 to 15 μιη and in particular from 0.01 to 8 μιη, average particle size, e.g. from 3 to 7 or 12 μιη in the crystalline state and from 0.01 to 0.1 μιη, e.g. from 0.01 to 0.05 μιη in the amorphous state. Although the extreme particle sizes are much smaller

the zeolite particles usually have particle sizes corresponding to a mesh size of 0.149 to 0.037 mm, preferably 0.105 to 0.044 mm. Zeolites with smaller particle sizes often undesirably form dust and those with larger particle sizes cannot sufficiently and satisfactorily coat the carbonate-bicarbonate particles onto which they may be deposited during spray drying of a crutcher mixture to form the hollow spheres.

The bentonite used consists of a colloidal clay-containing montmorillonite, preferably sodium bentonite, which normally consists of a light to cream-colored impalpable powder and forms a colloidal suspension in water with strongly thixotropic properties. In water, the swelling power of the clay is usually 3 to 15 ml/g, preferably 7 to 15 ml/g, and its viscosity in 6% concentration in water is usually 3 to 30, preferably 8 to 30 mPa.s. Preferred swelling bentonites in 6% concentration in water have a pH in the range 8 to 9.4, a maximum free moisture content of about 8% and a specific gravity of about 2.6. In powdered form, about 85% passes through a sieve with a clear mesh size of 0.074 mm. In these materials, the percentage of exchangeable calcium oxide is approximately 1 to 1.8% and that of magnesium oxide is typically 0.04 to 0.41%. Typical chemical analyses of these materials give 64.8 to 73.0% SiO ₂ , 1.4 to 1.8% Al ₂ O ₃ , 1.6 to 2.7% MgO, U to 3.1% CaO, 2.3 to 3.4% Fe ₂ O ₃ , 0.8 to 2.8% Na ₂ O and 0.4 to 7.0% K ₂ O. Although these bentonites are preferred, they can be replaced by equivalent materials from other sources.

The polyacrylate contained in the preferred hollow beads of the invention is a low molecular weight polyacrylate, usually in the range of about 1000 to 5000, preferably 1000 to 3000, and more preferably 1000 to 2000 or about 2000. The polyacrylate may be partially or fully neutralized, e.g. about half or one third as the sodium salt. Although modified polyacrylates may be used in place of the sodium polyacrylate described, including some other alkali metal polyacrylates and hydroxylated polyacrylates, it is preferred that such substitution be limited to a minor proportion and preferably the polyacrylate is an unsubstituted sodium polyacrylate. The sodium polyacrylates are in the form of a clear amber liquid or powder, with a solution solids content of about 25 to 40%, e.g. B. 30% and a pH of the solutions or a 30% aqueous solution of the powder of about 7.5 to 9.5, e.g. about 9. These materials are completely soluble in water and are used as dispersants. They have the ability to bind calcium ions and are used to prevent the deposition of insoluble calcium compounds from aqueous solutions

The presence of the polyacrylate, even in a very small amount, promotes the mixing of the various components of the crutcher mixture, including the ultramarine blue used in preferred formulations, which, if poorly distributed, can discolor laundry washed with the detergent made from the hollow beads. The polyacrylate also promotes the even distribution of fluorescent brighteners in the crutcher mixture and in the detergent composition so that uniformly white laundry is obtained. In addition, the polyacrylate makes the entire end product more homogeneous. Any aids present to prevent gel formation and settling of inorganic material in the crutcher mixture during the mixing process and while the mixture is standing are more evenly dispersed in the crutcher mixture so that their effectiveness is improved. Finally, the polyacrylate makes the hollow beads formed by spray drying more absorbent for the non-ionic detergent active sprayed onto the hollow beads in liquid state. In some cases, the beads' absorption capacity for the detergent active is increased. material while still remaining free-flowing. The spray drying process is also improved as less sprayed material sticks to the walls of the dryer, increasing the throughput rate through the spray drying process. increased and the number of cleanings required is reduced.

The only other component required for the production of the hollow beads is water; during the drying of the hollow beads, their moisture content can be reduced so that the product is almost to water-free. Desalinated water is preferred

Since concentrated aqueous crutcher mixtures of silicate, carbonate, bicarbonate, zeolite as well as bentonite and/or polyacrylate in the crutcher due to changes interactions between the components can "freeze out" if they are kept in this state for a permissible time, when using silicate and therefore also in the finished hollow beads and in the detergent composition, preferably auxiliary agents tel that prevent premature solidification or gel formation of the mixture, such as citric acid and magnesium sulfate. Instead of citric acid, soluble citrates such as sodium citrate can also be used. Although anhydrous magne sium sulfate is used, but various hydrates of magnesium sulfate, such as Epsom salts, can also be used. Magnesium citrate can also be used. Instead of the preferred system that prevents gel formation, other suitable systems can be used. used to keep the crutcher mixture in a flowable state, such as sodium sesquicarbonate which can replace part of the sodium carbonate and sodium bicarbonate. After the hollow beads have been made, together with the non-ionic detergent or separately from it, various auxiliary substances such as perfumes, enzymes, dyes, bleaches and flow-enhancing substances are sprayed onto them so that these substances do not drying process and do not inhibit the absorption of the non-ionic detergent by their presence in the spray-dried hollow beads. If the auxiliary substances used are stable, they can also be mixed with the non-ionic detergents. organic salts of the crutcher slurry. Thus, dyes and fluorescent brighteners can normally be included in the crutcher mixture from which the hollow beads are formed. The preferred dye is ultramarine blue, but other permanent pigments and dyes may also be used together with it or in its place. Of the materials that are subsequently applied to the spray-

&iacgr;&ogr;

dried hollow beads, the most important is the nonionic detergent active. Although various nonionic detergent actives with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide and with hydroxyl-containing bases such as nonylphenol and oxo-type alcohols, the preferred nonionic detergent active is usually a condensation product of ethylene oxide and higher petrochemical alcohols containing 10 to 20 and preferably 12 to 16 carbon atoms and about 3 to 20 ethylene oxide groups per mole, preferably 6 to 12.

Enzyme preparations that are also normally subsequently applied to the hollow beads are alkaline proteases, but also amylolytic enzymes, such as β-amylase and proteolytic enzymes, usually together with an inert powdered carrier, such as sodium or calcium sulfate. Furthermore, perfumes, which are usually heat-sensitive and contain volatile solvents, can be added.

The proportions of the various components in the hollow beads are such that the latter are free-flowing and sufficiently absorb the non-ionic detergent applied in liquid form, so that the detergent ultimately formed by incorporating this detergent is also satisfactorily free-flowing.

In the presence of silicate, satisfactory hollow beads contain 15 to 30% by weight of sodium carbonate, 10 to 22% by weight of sodium bicarbonate, 20 to 40% by weight of water-softening aluminum silicate (zeolite), 3 or 4 to 12% by weight of sodium silicate and 1 to 15% by weight of bentonite as active components, and 1 to 15% by weight of water. In these hollow beads, the aluminum silicate is preferably present as sodium zeolite with 15 to 25% by weight of water of hydration. Preferably, this zeolite is a zeolite A. The preferred weight ratio of sodium carbonate:sodium bicarbonate is about 1 to 3, the hollow spheres having a bulk density of 0.6 to 0.9 g/cm ³ , preferably 0.7 to 0.8/cm ³ , and the particle sizes of the hollow spheres corresponding to clear mesh sizes of 2.00 to 0.149 mm, ie passing through a sieve with a clear mesh size of 2.00 mm and remaining on a sieve with a clear mesh size of 0.149 mm, preferably clear mesh sizes of 2.00 mm to 0.25 mm. Other preferred proportions of the components are 20 to 25% sodium carbonate, 13 to 19% sodium bicarbonate, 30 to 37% hydrated zeolite, 5 to 8 or 10% sodium silicate, 5 to 8% bentonite and 4 to 10% water, excluding the hydration water of the zeolite. In these preferred products, the weight ratio of sodium carbonate to sodium bicarbonate is in the range of 1 to 2.

If a polyacrylate is present in the composition for the hollow beads together with the zeolite, its proportion is normally 0.1 to 2%, preferably 0.2 to 1.6% and in particular 0.8 to 1.4%. The proportions of the auxiliary substances and the processing-facilitating agents as well as the fillers, if they are contained in the hollow beads, are normally limited to 20% and preferably to 1 to 10%, in particular to 3 to 7%. The proportions of the processing-facilitating substances when using magnesium sulfate and citric acid are normally 1 to 3% magnesium sulfate, in particular 1.5 to 2.5% and 0.2 to 1% sodium citrate, in particular 0.2 to 0.5%. The amount of pigments and fluorescent brighteners is preferably 0.05 to 0.6% pigments, such as ultramarine blue, in particular 0.2 to 0.4%, and 0.1 to 4% fluorescent brighteners, in particular 1 or 1.5 to 3%. These proportions of the substances and auxiliaries that facilitate processing relate to different types of hollow beads according to the invention, provided that auxiliaries and substances that promote processing are used.

The proportions of the various components in the crutcher mixture and the hollow beads made from it, which contain polyacrylate but no bentonite, are such that a uniform or nearly uniform mixture is obtained and the hollow beads are free-flowing and sufficiently absorbent for the non-ionic detergent active applied in liquid state, so that the detergent obtained by incorporating the detergent active is also satisfactorily free-flowing. It has been found that satisfactory hollow beads for this purpose contain 15 to 30% by weight of sodium carbonate, 10 to 22% by weight of sodium bicarbonate, 20 to 40% by weight of aluminum silicate (zeolite) as a water softening agent, 3 or 4 to 18% by weight of sodium silicate and 0.1 to 2% by weight of polyacrylate as active components, and 1 to 12 or 15% by weight of water. The preferred weight ratio of sodium carbonate:sodium bicarbonate in the product is about 1 to 3, the hollow spheres having a bulk density of 0.5 to 0.8 g/cm ³ , preferably 0.7 to 0.8 g/cm ³ and their particle sizes corresponding to a clear mesh size of 2.00 to 0.149 mm, ie they pass through a sieve with a clear mesh size of 2.00 mm and remain on a sieve with a clear mesh size of 0.149 mm. They preferably correspond to clear mesh sizes of 2.00 to 0.25 mm. Other preferred proportions of the components are 20 to 25% sodium carbonate, 13 to 19% sodium bicarbonate, 30 to 37% hydrated zeolite, 7 to 15% sodium silicate, 0.5 to 1.5% sodium polyacrylate and 3 to 10% water, excluding the hydration water of the zeolite. In particularly preferred products of this type, the weight ratio of sodium carbonate to sodium bicarbonate is in the range of 1 to 2.

If the hollow beads contain little or no water-soluble silicate, the proportions of the various components are also selected so that the hollow beads are free-flowing and sufficiently absorbent for the liquid non-ionic detergent active ingredient, so that the detergent formed by incorporating this detergent active ingredient is also satisfactorily free-flowing. In order that the product formed does not lead to an undesirable deposit of zeolite particles, possibly together with other substances, on the washed materials, and the hollow beads have an appropriate bulk density and color, the hollow beads should contain 15 to 30% by weight of sodium carbonate, 10 to 22% by weight of sodium bicarbonate, 10 to 50% by weight of aluminum silicate (zeolite) as a water softening agent, 0 to 3% by weight of sodium silicate and 3 to 20% by weight of bentonite as active ingredients, and also 1 to 15% by weight of water. The percentage of water indicated means free water and does not include the hydration water of the zeolite.

Accordingly, the percentage given for the zeolite includes the water of hydration. In some cases, the free moisture content

11 12

the product must be water-free, but these cases are rare the product must be incorporated,

and it is desirable that the hollow beads have at least According to the invention, the hollow beads are used for the

contain a small amount of water to avoid any unpleasant odors.

desired to prevent dust formation, which otherwise occurs with compositions based solely on a non-ionic

anhydrous formulations. The above-mentioned detergent active ingredient is used. Sometimes it can

preferred weight ratio sodium carbonate:sodium carbonate, however, it may be desirable that the final product also contains a

umbicarbonate in the product is in the range of about 1 anionic detergent is included to the

to 3, wherein the hollow beads have a bulk density of foam properties and the cleaning

0.6 to 0.9 g/cm ³ , preferably 0.6 or 0.7 to 0.8 g/ effect. Normally, preference is given to

cm ³ and their particle sizes are thin meshes, it is not possible to add such anionic detergent to the

widths from 2.00 mm to 0.149 mm, i.e. to incorporate a Crutcher mixture so that if one or

Sieve with a mesh size of 2.00 mm fits - use several such anionic detergents

and sieve with a thin mesh, preferably subsequently to the

te of 0.49 mm. Preferably spray-dried hollow beads are added,

They have a mesh size of 2.00 to 0.25 mm. 15 normally after absorption of the liquid

Further preferred proportions of the components are 20 state present non-ic-nic detergent active substances

to 27% sodium carbonate, 14 to 21% sodium bicarbo- through the hollow beads. Although different types

nat, 20 to 50% hydrated zeolite, 0% sodium silane- anionic detergents can be used

kat, 5 to 20% bentonite and 1 to 5% water, the hydra- nes, preferably in powder form or mixed with

tation water of the zeolite. In these 20 builders, linear higher alkylbenzene sulphonates are

preferred products, the weight ratio is nate, higher fatty alcohol sulfates and polyethoxylated

Sodium carbonate: Sodium bicarbonate in the range of 1 higher fatty alcohol sulfates with 8 to 20, preferably 12

to 2. If silicate is contained in the hollow beads, up to 16 carbon atoms are preferred, preferably

its amount is preferably limited to 2% and in particular as sodium salts. The ethoxylated alcohol sulfate

limited to 0.5 to 1%. Other preferred 25 normally contains 3 to 20 moles of ethylene oxide per mole

Quantities of the important grain fatty alcohols according to the invention.

components are 35 to 45% hydrated zeolite and 5 The proportions of the various components

bhsl5%, especiallyl0to 15% bentonite in the final detergent composition las-

If a polyacrylate is used in the composition for the hollow beads, it is easy to determine the

the hollow beads, its proportion makes normal 30 calculate if one calculates the proportions of subsequently

usually 0.05 to 0.5%, preferably 0.05 to 0.3% of the hollow beads added washing active agent and

and in particular 0.1 to 0.2%. The proportion of auxiliary and other materials is deducted. If, for example, in the final

substances and processing-promoting substances detergent composition only 20% non-ionic

and fillers, provided that such substances are contained in the detergent, which is subsequently

Hollow beads are included, normally added to 20% 35, the individual proportions can

limited, preferably to 1 to 10% and in particular of the components by calculating

to 3 to 7%, with the remaining parts being the same as the amounts given for the hollow beads with 0.8,

are as previously stated. i.e. (100—20)/100 multiplied. If the proportion of

Although in the hollow moulds according to the invention non-ionic detergent in formulations,

gel-based detergent compositions 40 to which only this additive is added to the hollow beads

no corrosion inhibitor additive was present, 8 to 25% of the detergent composition

which replaces the silicate, such additives can be used, the multiplier is similarly

Corrosion-preventing agents are preferred. 0.75 to 0.92. Usually the final percentage

additives which, under the conditions in the Crutcher set of non-ionic detergent in product 8

and are stable in the spray drying tower and these 45 to 25%, preferably 15 to 22% and especially

do not affect the corrosion. The corrosion-preventing agents make up about 20%. In some cases, a proportion of 8 to

the additives or antioxidants can be organic 13% preferred Normally the percentage is

nic or inorganic, with inorganic materials containing 0.1 to 1% of perfume in the final product, preferably

materials are preferred. They are particularly limited to 0.2 to 0.4%; the percentage of enzyme 0.5 to 3%,

their ability to prevent corrosion of the aluminium 50 preferably 1 or 1.5 to 2.5% and the percentage of

minium parts in washing machines selected If a flowability improving agent, which is subsequently

Silicate is used, powdered silicates are added, less than 2%, preferably

preferred, e.g. hydrous sodium silicates less than 1%. When calculating the quantity

(Na ₂ OiSiO ₂ = 1:2.4) or solid soluble silicates. proportions of the components in the final composition

If the product is to have fabric softening properties, softeners, such as cationic compounds, can be added subsequently as a dry powder to the hollow beads. The percentages of other subsequently added compounds, in particular quaternary ammonium halides, must also be taken into account. If these subsequent additions were made in the form of aqueous solutions, this also affects the moisture content, which can often be in the range of 1 to 12% but also up to 15%.
and arylalkyl ^: lower alkyl groups such as distearyl-dime- If polyacrylate is used, but not bentonite, the proportions of the various

These compounds also have antistatic and 65 components 13 to 28% sodium carbonate, 8 to 18%

antibacterial properties. If desired, sodium bicarbonate, 15 to 35% aluminum silicate as

but also use other antibacterial additives - water softening agent, 3 to 40% sodium silicate, 0.1

which are preferably also subsequently diluted with up to 1.6% polyacrylate, 8 to 30% non-ionic washing agent

13 14

agent and 1 to 10% water. The preferred areas for spray drying do not decompose. However, it is known that

16 to 21% sodium carbonate, 10 to 15% sodium that part of the bicarbonate is released during drying at increased

umbicarbonate, 22 to 32% hydrated zeolite, 8 to ten temperatures in a spray tower in carbonate

13% sodium silicate, 0.5 to 1.5% sodium polyacrylate, 3. Therefore, if one considers the characteristics of the

to 6% and sometimes 3 to 10% moisture and 10 5 tower and the drying conditions, so that

up to 22 or 25% non-ionic detergent. The degree of bicarbonate decomposition can be predicted

Percentages of processing aids, the required proportion of carbonate can be

optical brighteners and dyes in the final mixture and bicarbonate in the crutcher mixture.

Detergent composition is about the same For example, if you take a product with about 22% sodium car-

as in the hollow spheres on which they are based. 10 bonate and about 16% sodium bicarbonate,

Preferably they are 0.2 to 0.6% sodium citrate should be added if in the spray tower about 1/3 of the bicarbonate is

and 1 to 2% magnesium sulfate, 0.1 to 03% ultramarine carbonate, with two parts of carbonate from

blue, and 1.5 to 2% fluorescent brightener. The En- three parts of decomposed bicarbonate, 24% bicar-

Enzyme content is 0.5 to 3%, usually 1 to 2% and bonate and 17% carbonate (on dry basis) in the

the perfume content is 0.1 to 1%, preferably 0.2 to 0.4%. 15 crutches are given.

The proportions of the various components in the spray-dried portion of the final washing crutcher mixture and in the spray-dried hollow agent composition can, if there is no or little silicate present, be calculated in the manner described above. With regard to the subsequently added components, the percentages of the non-ionic washing active ingredient are the same as above, however, a constant degree of hydration is assumed.
The percentage of perfume in the final product is 0.1 to 1%, preferably 0.2 to 0.4%, of the percentage of enzyme 0.5 to 3%, preferably 1 to 2%, and if hydrous silicate is subsequently added, its proportion is normally limited to 2 to 10%, usually 10%, preferably 7% and in particular 3 to 8%, e.g. about 5%. When a softener is used, the percentage of enzyme is 0.5 to 3%, preferably 1 to 2%, based on the solids. These organic materials which may be present in the final product include citric acid and soluble citrates, fluorescein brighteners, polyacrylates, dyes and pigments, chelating agents and polyelectrolytes. However, the total weight of anionic and nonionic detergent active in the final product is primarily comprised of inorganic materials and water.

the non-ionic detergent only For products containing polyacrylate but not bentonite

If anionic detergent is used, the Crutcher mixture contains hollow beads on a

is applied, its amount normally makes the 0.2 solid basis of 100% normally about 10 to

up to 0.8 times the weight of the non-ionic washing agent 40 25% sodium carbonate, 15 to 30% sodium bicarbonate

Of course, when calculating the weight ratio of sodium bicarbonate to sodium

The proportions in the final composition of tricarbonate from 0.5 to 2.20 to 40% water softening

composition except the percentage of post-added aluminium silicate, 4 to 18% sodium silicate and

added non-ionic washing active ingredient the percentage 0.1 to 2% polyacrylate If the processing promotes-

ze of the other subsequently added aids are present, their proportions are

be taken into account. If these subsequent additions are made, on the same basis usually 1 to 3% mag-

ze in the form of aqueous solutions, this affects sium sulfate and 0.2 to 1 % sodium citrate Preferably

also the moisture content This amounts to the final in these Crutcher slurries the content

product usually 1 to 12%, but can sometimes contain 0.5 to 1.5% sodium polyacrylate, and if the

can also make up to 15%. 50 processing aids and dyes

The hollow beads according to the invention for the Her- are available, their amount is 1.5 to 2.5% mag-

Preparation of washing machine compositions sium sulfate, 0.2 to 0.5% sodium citrate 0.2 to 0.4% ul-

is maintained by spray drying an aqueous Crut- tramarine blue and 13 to 3% fluorescent brightener on

cher mixture, which is normally about 40 to about 70 solids basis.

or 75% solids, preferably 50 to 65% and as 55 The crutcher mixture is preferably prepared by sequential addition of the various compocher mixtures so that a miscible, easily pumpable and non-settling slurry is obtained, taking into account the moisture content of the hollow beads. and the crutcher mixture from the composition of the hollow beads. The sequence for spray drying is calculated. If, for example, For example, if a crutcher mixture is to contain 50% moisture and if hollow spheres are to be prepared with a moisture content of 5%, the silicate solution should be added last, and if not last at least after the addition of the zeolite, the materials or substances hindering processing should be added. Normally, the percentages of the components in the hollow spheres should be multiplied by 10/19, i.e. (100/2 [100-5]). Preferably, all or nearly all of the water is added to the crutcher first, preferably at about the processing temperature, whereupon all or nearly all of the water is added to the crutcher first.

if used, the processing aids and other components used in minor quantities including pigments and fluorescent brighteners and, if used, polyacrylates are added, followed by the bentonite, zeolite, bicarbonate, carbonite and, if used, silicate. Usually in these additions each component is thoroughly mixed in before the next is added, but the rate of addition can be varied so that they can be added together. Sometimes the components, such as the silicate, may be added in two or more parts. Different components may be premixed before they are added to speed up the mixing process. Normally the mixing speed and force are increased as materials are added. For example, low speeds may be used until after the last bentonite or zeolite is added and these speeds may then be increased to medium speed and then to high speed before, during and after the addition of the silicate solution .

The temperature of the aqueous medium in the crutcher is usually at room temperature or higher, normally in the range of 20 to 80 ⁰ C, preferably 30 to ?5°C and especially 40 to 70° C. The use of processing aids in the mixture ensures that desirable non-gelling slurries are obtained at both lower and higher temperatures. Temperatures above 80° C are usually avoided since at these temperatures one or more crutcher components may decompose, e.g. the sodium bicarbonate

Crutcher mixing times to achieve good slurries can vary from as little as 5 minutes in small crutchers and up to 4 hours for higher moisture slurries. The mixing time required to homogeneously mix all the crutcher components can be from 10 to 60 minutes, although 30 minutes is the preferred upper limit. Including initial mixing times, normal times in the crutcher are 15 minutes to 2 hours, e.g. 20 minutes to 1 hour, however, the crutcher mix should be mobile without gelling or settling for at least 1 hour, preferably 2 hours and especially 4 hours or more after mixing is complete. It can even be mobile for 10 to 30 hours before being pumped into the spray drying tower.

The crutcher slurry is fed from the bottom of the crutcher at high pressure through spray cans at the top of a conventional spray drying tower operated in countercurrent or cocurrent flow, causing the slurry droplets to fall through a hot drying gas in which the droplets are dried to the desired absorbent hollow beads. During the drying stage, a portion of the bicarbonate, often 1/4 to 1/2, e.g. 1/3, is converted to carbonate, releasing carbon dioxide which, in conjunction with the polyacrylate content, if any, in the spray dried mixture, improves the physical properties of the hollow beads so that they exhibit greater absorbent capacity for the liquid nonionic detergent actives which can then be sprayed on. The zeolite and bentonite contained in the hollow beads also appear to enhance liquid absorption capacity, and the polyacrylate promotes faster drying, thereby increasing throughput through the tower.

After drying, the product is sieved to the desired particle size, e.g. to a particle size corresponding to a mesh size of 2.00 to 0.25 or 0.149 mm, after which it is ready for spraying on the non-ionic detergent

&iacgr;&ogr; The hollow beads can be warm or cooled to room temperature. However, the non-ionic detergent usually has an elevated temperature, such as 30 to 60° C, e.g. 50° C, in order to be liquid. When cooled to room temperature

However, it solidifies and forms a waxy solid. Even at room temperature, the non-ionic detergent is somewhat sticky. However, this property does not affect the flowability of the final composition because the detergent is in or ter penetrates the surface of the hollow beads The non-ionic detergent, which is sprayed onto the moving or circulating hollow beads or applied in the form of droplets, is preferably a condensation product of ethylene oxide and higher ^fatty alcohol, but other non-ionic detergents can also be used. The enzyme preparation, hydrous silicate and any other powdery additives that may be added later can then be dusted onto the particles. Perfume and Any other liquids can be sprayed at a suitable time before or after the addition of the powdery substances.

The spray-dried hollow beads and the detergents made from them can have little or no Silicate from the Crutcher mixture; in this case solid silicate can be added subsequently. The subsequently added powdered silicate, if used, does not appear to react with the zeolite, so that zeolite-silicate agglomerates that settle on the washed materials. Although, if bentonite is not present, silicate is normally used, at least for its anti-corrosive effect, it has not been found that the detergents according to the invention compositions, aluminum objects will not corrode, even in the absence of silicate. The bentonite does not affect the durability of the product and actually seems to help hold the hollow beads together so that they resistant to breakage and powder formation during transport and use. The bentonite and/or polyacrylate improve the properties of the final detergent composition, with the bentonite leading to a stronger bond of calcium ions, so that less zeolite is deposited on the washed fabrics. When polyacrylate with a low molecular weight is included, the hollow beads are more porous and better absorb the non-ionic detergent without unduly reducing the bulk density of the product. Considering that bentonite is a clay, one might expect problems with scaling and gelling, so the reduced zeolite scaling and lack of gelling are surprising.

The following examples illustrate the invention. Unless otherwise stated, all temperatures are ⁰ C and all parts in the examples and in the

17 18

Description refer to the weight for fum, 0.2% ultramarine blue, 5.0% bentonite The obtained

The zeolite specified weights and ratios detergent is an excellent all-purpose detergent

refer to the normal hydrate and is particularly suitable for washing household linen in automatic washing machinesa It is

Example 1 5 physically and aesthetically pleasing, as it is not

dusty and extremely free-flowing so that it can be used in glass

A crutcher mix of 4536 kg of deionized water at a temperature of about 27° C. was prepared for the spray drying of hollow spheres according to the invention by adding 1832 kg of demineralized water at a temperature of about 27° C. and then adding 513 kg of anhydrous magnesium sulfate to the crutcher at a low mixing speed, the difference being even more pronounced when the washing water has a high degree of hardness, e.g. B. 200 ppm lighter than calcium carbonate, 68 kg ultramarine blue powder, 169.6 kg bentonite, 914 kg hydrated zeolite AA with 20% crystallization water, 6363 kg sodium bicarbonate and 4563 kg sodium carbonate are added so that the total material added equalized the weight of the bentonite omitted. Then, at a higher mixing speed, _189.6 kg sodium silicate was added at a ratio of 1:2.4 (399.2 kg sodium carbonate and sodium bicarbonate). The entire batch is mixed for about 1 hour so that the total material added equalized the weight of the bentonite omitted. The crutcher mixture was spray dried and converted to the same manner as above. During mixing, the crutcher slurry is constantly mobile. No gel formation, settling or caking occurs. Since the bicarbonate is partially converted to carbonate during drying, the amounts of the inventive product and bound calcium into calcium can be varied according to the conditions in the spray drying tower. When the silicate content was increased to 10.7%, the increased silicate content was compensated by a reduced carbonate and sodium bicarbonate content.

About 5 minutes after the addition of all components, the mixture is fed into the upper end of a spray drying tower operated in countercurrent, in which the initial temperature is about 430° C and the final temperature is about 105 ⁰ C. The hollow spheres formed are usually prepared quickly and emptied from the crutcher just as quickly. Sometimes they are made in just 5 minutes and pumped out of the crutcher in just 10 minutes, have a bulk density of 0.6 to 0.7 g/ml, an initial adhesion of about 40%, and a fines fraction that passes through a sieve with a mesh size of 0.297 mm described. It is often important, however, that the mixes are stable in the crutcher for at least 1 hour without forming gels or solidifying, as production can sometimes be disrupted by such time periods. The crutcher mixing width of 0.297 mm described is about 15%. The moisture content of the hollow spheres is about 45%. The crutcher mixing width can even be kept in the crutcher for 4 hours or longer without gel formation. The hollow spheres formed are free-flowing or non-sticky, satisfactorily porous but firmer than their surface and are able to easily absorb substantial amounts of liquid non-ionic detergent without becoming undesirably sticky. However, other agents which facilitate processing and prevent gel formation and settling may also be used. 50

From the spray-dried hollow spheres, hindering agents will be used, and under certain Detergent products manufactured by applying the right conditions can reduce their proportions Surfaces of the tumbled hollow spheres one and one or both components can be omitted

normally waxy non-ionic detergents. Other detergents can also be used in smaller quantities

active substance in heated liquid state in such a 55 used components of the Crutcher mixture, such as

amount that the final product contains 20% non-ionic, the fluorescent brighteners and pigments are omitted

contains a proteolytic enzyme and perfume, although it is preferred

zym is applied in powder form in an amount that ensures that all materials are present. The

that its concentration in the product is 1.99%. Mixing temperature in the crutcher can be modified, e.g. to

Perfume is sprayed in an amount that increases in the pro- 60 52° C and the proportions of the various components

product 0.25%. The detergent components obtained can be used within the above-mentioned

has a bulk density of about 0.7 or 0.8 g/ml and can be varied by ±10%, ±20% and ±30%,

contains 27.3% zeolite, 20.1% non-ionic detergent, whereby processable crutcher mixtures are obtained.

tive, 17.8 sodium carbonate, which is partly formed by cerium, which leads to the desired hollow spheres and

decomposition of sodium bicarbonate, 12.7% 65 detergent compositions.

Sodium bicarbonate, 5.6% sodium silicate, 5.45% water. Instead of the anhydrous magnesium sulfate, a

2.0% enzyme, 1.7% fluorescent brightener, 1.5% magnet equivalent amount of Epsom salts are used,

sium sulfate, 0.4% citric acid (as citrate), 0.25% par- and various other components can be used as

19 20

aqueous solutions, provided that the zeolite, the carbonate, the bicarbonate, the

The amount of moisture introduced with them is absorbed by silicate and the bentonite together with the polyacrylate

of the amount added to the crutcher. Others in the indicated amounts in the hollow balls are also

Order of addition can be applied, as well as the non-ionic detergent in the

However, it is normally desirable that the final detergent composition, which is like the

The processing agent containing no phosphates should be added at an early stage of the manufacturing process, and the silicate should be added last or towards the end. Instead of zeolite AA Example 3 Zeolite A" and V can also be used, furthermore

other zeolite A types. During the present example, hydrated zeolite AA is preferred for detergent compositions which are used in anhydrous crystalline zeolites or amorphous zeolites (Na2O:SiO2 ratio 1:2.4), 0.26% ultramarine blue , 13.64% sodium silicate, 0.23% sodium carbonate, 16.60% sodium bicarbonate, 15 2£0% brightener, 135% magnesium sulfate, 0.32% lemon. B. on 3 and 10% sodium citrate, 1.29% sodium polyacrylate, 1.29% and 5.64% moisture. They were prepared by spray drying a pilot crutcher approach which contained 50% solids and 50% water, including the water added in the aqueous solution with the polyacrylate and with any desired reduction in zeolite residue. The proportion used commercially depends on a variety of factors and is normally introduced halfway between the products containing bentcnite and 5.64% moisture. They were prepared by spray drying a pilot crutcher approach which contained 50% solids and 50% water, including the Epsom salts used. The other solid components make up the other 50% of the properties of the other components of the detergent mixture and are present in the same relative amounts as indicated with respect to the hollow beads, the sodium carbonate and sodium hydroxide.

Example 2 umbicarbonai excepted. In these cases,

if one considers a 1/3 decomposition of the bicarbonate to car-

A product was prepared analogously to Example 1, in which a polyacrylate with a low molecular weight of 1000 to 2000 was added to the crutcher mixture before the addition of the bentonite in order to obtain a comparable product containing 1% polyacrylate. The magnesium sulfate added is anhydrous, 35 The water introduced into the crutcher consists of demineralized water and has a temperature of 27° C. The sodium bicarbonate content of the crutcher was adjusted to compensate for the addition of the polyacrylate. The sodium bicarbonate content of the crutcher was adjusted to compensate for the addition of the polyacrylate. After addition of the detergent mixture, the magnesium sulfate, citric acid, brightener, ultramarine blue powder and polyacrylate were transferred to the crutcher by spray drying as in Example 1, with the exception that polyacrylate was added. An excellent free-flowing detergent was obtained which left less zeolite on the washed laundry than the comparative product Au. The hydrated zeolite AA, sodium bicarbonate and sodium carbonate can then be added, with the mixer running at low or medium speed. The mixing rate is then adjusted to a high value and the absorbency of the hollow beads was noticeably improved so that they absorbed the liquid nonionic detergent active more easily. The bulk weight of the hollow beads and the detergent product was not noticeably reduced, which is essential if a concentrated detergent of relatively high bulk density is to be produced. It was also found that no gelling, settling or baking with the polyacrylate in the crutcher mix occurs.

Spray drying runs better and less material is lost due to deposits on the walls of the spray tower 55 Since the bicarbonate decomposition can vary depending on the spray drying conditions, the amounts of bicarbonate and carbonate added can also be varied accordingly in order to maintain the desired composition of the hollow beads within the specified limits; larger amounts of polyacrylate lead to greater porosity 60.

of the hollow cucurbits. In some cases, poly- About 5 minutes after all components of the

acrylates with higher molecular weights of 4000 to Crutcher mixture were added, the mixture

5000 can be used, but in most cases the Crutcher is equipped with a pump under a

In some cases the lower part of this range is preferred. As in Example 1, the processing can be carried out using a pressure of about 21 kg/cm ² in the upper end of a countercurrent spray drying tower.

tune facilitating agent, the perfume, the enzyme, which leads to the initial temperature of about 430°C and

Fluorescence curing agent and the pigment are omitted, the final temperature is about 105 ⁰ C. The formed, I

or exchanged, but in all of these, consisting essentially of inorganic material,

;; 21 22

The hollow beads have a bulk density of about also excellent effect against re-deposition

0.6 to 0.7 g/ml, low adhesion, particle size enlargement and inhibit soiling of laundry

- Ben in an area which is essentially a clearing due to redeposition of removed dirt.

Mesh size of 2.00 to 0.149 mm and the manufacturing process can be the same as

do not contain any objectionable amount of fines 5 in Example 1, and various processing

The moisture content of the hollow beads is enhancing agents and auxiliary materials are used.

about 5.6%. The hollow beads are free-flowing, not the ones indicated in this example.

;' adhesive, satisfactorily porous and yet of ge- also certain auxiliary materials can be omitted. The

desired physical strength They can easily be modified by mixing temperature in the crutcher and e.g.

increased amounts of e.g. 2 to 5% or more of liquid io can be increased to 52°C. The proportions of the various

with non-ionic detergent, which components can be used within the specified

■:. is sprayed onto them without becoming undesirably sticky. Ranges varied by ±10%, ±20% and ±30%

den., whereby still processable Crutchermi-

The formed hollow beads not only have the loops that lead to the desired

desired properties, but also solid- 15 hollow beads and detergent compositions

v, provided that the accumulation of product on the in- lead. The various compounds can be in

inner wall of the spray drying tower often by 20 to form aqueous solutions are added, pre-

■·'" 50% less than if no polyacrylate is included, the amount of moisture added with them

The throughput rate through the tower is determined by the amount in the crutcher formulation.

.v increases and it seems that the content of fines in the 20 pulled. The variation of the polyacrylate amount within

i» Product is reduced The reduction of the specified range, e.g. to 1.0 and 1.7% in the

■ · Collections on the tower wall and the formation of fines still results in usable products , but the products with a higher proportion of sodium polyacrylate usually have a better

■ From the spray-dried hollow beads, 25 effects in terms of cleaning, absorption of the detergent products are produced by using the non-ionic detergent active ingredient and improving

> Surface of the circulated hollow beads has a normal spray drying process. Usually it is

'ö usually waxy non-ionic detergents, it is not desirable to use more than about 2% polyacrylate.

& sprayed on either heated or liquid, as its effectiveness increases with higher concentrations.

H. Condition in such an amount that in the finished product 30 decreases and the benefits achieved are not economically

5s product contains 20.7% non-ionic detergent. I; are. A proteolytic enzyme is added in such quantity

i: applied in powder form, that its concentration in Example 4 f, product is 132% Perfume is applied in an amount

;: sprayed so that its concentration is 0.25% 35 A product was prepared analogously to Example 3,

;5 The detergent obtained has a bulk density of, however, using a sodium polyacrylate solution

■% about 0.7 g/ml and contains 27.0% zeolite (hydrate), 20.7% solution in which the polyacrylate has a molecular weight of

^; non-ionic detergent, 18.17% sodium carbonate, about 1000 or from 1000 to 2000. It is a

nat, part of which is formed by decomposition of the sodium bi- clear amber liquid with a solid

carbonate is formed, 12.9% sodium bicarbonate, 10.6% 40 content of 30%.

Sodium silicate, 4.39% moisture, 1.32% enzyme, 1.51% magnesium sulfate, 1.71% fluorescent brightener, 0.25% citric acid (as citrate), 0.25% perfume, 0.2% The detergent active ingredient is converted into a finished detergent by the process described using non-ionic ultramarine blue and 1.0% sodium polyacrylate. The detergent of this formulation is an excellent all-purpose detergent and is particularly suitable for washing household laundry in automatic washing machines. It is physically and aesthetically pleasing as it is non-dusty and extremely free-flowing so that it can be filled into narrow-necked glass and plastic bottles from which it is easily dispensed. 50 and synthetic sebum. A test group of people preferred such a product as compared to one that did not contain polyacrylate. Similarly, in comparative tests using similar compositions that did not contain polyacrylate, instrument measurements of washed materials showed better performance for the compositions of the invention. 55 The tests described were carried out on cotton, ; Removal of soil and stains when different types of soil and stains were examined on a wide variety of test fabrics, including cotton, polyester-cotton blends, polyester fabrics, and other synthetic fabrics. The test conditions included machine washing using water with a hardness of 150 ppm, a detergent concentration of 0.07 wt.% and water at a temperature of 49°C. Regarding stain removal, it was found that:

The same process advantages as in Example 3 were observed, including excellent dispersion of the materials in the crutcher and a clean spraying of the product. The hollow bead stains, as found in many loads of laundry, have a measurably greater porosity than the bulk compositions of the invention without polyacrylate. The weight is not as much as a few percent lower.

ger, ζ. B. by 3%, which is important for such concentrated products. Similar results are obtained by varying the content of the various other essential components in the formulation by ±15% and ±30% within the ranges given. These results are also obtained when other zeolite A types with different degrees of hydration, e.g. 15 and 22%, and polyacrylates with a molecular weight range of 1000 to 5000 are used. Preferably these polyacrylates are neutralized with sodium, either completely or at least to about 50%. However, less neutralized ones can also be used.

Similar results are also achieved if the fluorescent brightener, perfume, enzyme and processing-enhancing substances such as citric acid and magnesium sulfate are omitted. In these cases, however, care should be taken to ensure that spray drying is carried out soon after the crutch mix has been produced.

nevertheless have a solid surface and can easily absorb significant amounts of liquid non-ionic detergent without becoming undesirably sticky.

Detergents are made from the spray-dried hollow beads by spraying a normally waxy non-ionic detergent onto the surface of the circulating beads. The non-ionic detergent is warmed state at a temperature of about 45° C in such an amount that the final product contains 20% of the non-ionic detergent. Proteolytic enzyme is applied in powder form in such an amount that its concentration in the pro product is about 1.5%. Perfume is also sprayed on in an amount that its concentration is 0.25%. The detergent obtained has a bulk density of about 0.7 to 0.8 g/ml and contains 32.45% zeolite (hydrated), 19.7% non-ionic detergent

g g (y)

so that the mixture in the Crutcher 20 substance, 18.5% sodium carbonate, part of which is

does not settle

Example 5

decomposition of sodium bicarbonate, 13.5% sodium bicarbonate, 1.3% free water, 1.4% enzyme, 1.6% fluorescent brightener, 0.25% perfume, 0.2% ultramarine blue, 9.6% bentonite, 0.1% sodium polyacrylate and 1.4% titanium dioxide. This detergent is an excellent all-purpose detergent suitable for washing household linen in automatic washing machines. It does not produce dust and is extremely free-flowing. It has been found that detergent compositions

A 4536 kg crutcher batch for the production of 25 spray-dried hollow beads according to the invention which do not contain any water-soluble silicate was obtained by mixing 2132 kg of demineralized water at a temperature of about 27 ⁰ C and then initially at a low mixing speed 47.2 kg brightener, 30 calcium ions much better than the above-containing bentonite, 5.9 kg ultramarine blue powder, 3.2 kg sodium polyacrylate, 957^ kg hydrated zeolite AA, (20% crystallizer) 2834 kg bentonite, 714.4 kg sodium bicarbonate, technical grade, 351.1 kg sodium carbonate, zeolite residues, particularly when the washing machine is washed with them in an automated washing machine, especially when the washing machine is in an automatic washing machine. Titanium dioxide in 35 ppm is dried on the line than comparable compositions which contain less bentonite and sodium silicate in the spray dried hollow spheres, which takes about 15 minutes. The difference is particularly pronounced when the wash water is very hard, e.g. 200 ppm than calcium carbonate, which takes about 15 minutes. The wash water is cold and mixing is continued for about 1 hour. During this time some of the water, e.g. about 90.7 to 272.2 kg, may be lost through evaporation and, if desired, replaced. During mixing some of the auxiliary materials as mentioned therein may be omitted. The crutcher slurry is constantly moving and there is no gelling, settling or caking inside. As the bicarbonate is partially decomposed to carbonate during spray drying, workable crutcher mixtures can be obtained which can be converted to the desired amount of bicarbonate and carbonate in the crutcher shapes. The solids content in the crutcher mixture can be varied above the specified ranges, depending on the conditions in the spray drying tower.

Approximately 5 minutes after all components of the crutcher mixture have been added, the mixture is introduced from the crutcher at a pressure of about 21 kg/cm ² into the upper end of a countercurrent spray tower in which the initial temperature is about 430 ⁰ C and the final temperature is about 105 ⁰ C. The hollow spheres formed, consisting essentially of inorganic material, have

can be varied widely, e.g. to 45 and 65%, whereby good mixing and spray drying is achieved. Instead of zeolite 4A, zeolites X and Y can be used, as well as other zeolite A types. Although the hydrated zeolite 4�L used in this example is preferred, other zeolite hydration levels are also acceptable and in some cases almost anhydrous crystalline zeolites can be used.

However, varying the amount of bentonite within the specified range, e.g. to 10 and 17%, still results in usable products. Those with a larger mesh size of 0.297 mm of about 65 to 15%. The moisture content of the hollow beads is 1 to 10%. The hollow beads are free-flowing ( flow rate 80%), non-sticky, satisfactorily porous, contain little soluble silicate or no silicate, achieve improvements in the deposition of

25 26

less residue on the washed laundry, a lower content of non-ionic detergent

by examining the described product in the substance of e.g. 17%, to determine the flowability and

Compared to a control product, it has been shown that it achieves non-adhesive properties, yet still has a

was essentially formulated in the same way, but represented a usable product.
no bentonite and about 8% sodium silicate contained 5

In such an evaluation in a washing machine Example 7
The washing periods in a gentle cycle were 8 minutes.
The detergent concentration was 0.06%, Example 5 was repeated using 2% sodium silicate with a wash water had a combined calcium:magnesium carbonate Na ₂ O=SiO ₂ ratio of 1:2.4, which was added to the crutcher as a 47.5% aqueous solution and the water temperature was 24° C. The crutcher mix did not form a gel during the normal manufacturing process, however it is more desirable than the cotton. The laundry was wet and after line drying no residue was observed in either case 15 When using the control detergent, a moderate residue was observed in all test samples. The detergent composition also leaves more residue behind in the washed laundry, which

The practical results described above are more noticeable when the colors of this laundry are dark

The test was carried out by weighing the residue. 20
which was left on a denim test sample

In this test, the inventive example 8
Detergent filtered through a sample of the denim material,
Example 5 was repeated using 5% hydrous sodium silicate powder at a concentration of 0.12% in water at ₂₅ °C, which was subsequently added together with the enzyme powder. This subsequent addition of silicate does not appear to have a significantly adverse effect on the zeolite deposits on the fabrics. It was found that the residue was only about 75% compared to the control sample, which is a significant improvement.

In the adhesion test given above, which measures the stickiness
of the detergent is measured, 10 g of Example 9
Hollow beads or detergent composition 35

evenly between two watch glasses, each of which The procedure of Example 5 was only carried out with water,

because they have a diameter of about 23 cm. On zeolite, bentonite sodium carbonate, sodium bicarbonate

the upper glass is placed a weight of 500 g After and sodium polyacrylate in the crutcher mixture and in

about 5 minutes the weight of the upper glass is repeated with the hollow beads made from it,

removed and the lower glass was turned over and 40 Subsequently, only the non-ionic detergent was

The product adhering to this glass weighs The percentage of substance applied The product obtained has satisfactory

tual adhesion represents the number of grams of product the cleaning properties, but is

which remains on the glass divided by 10 and is not commercially acceptable for aesthetic reasons,

multiplied by 100. because it does not contain perfume. It also does not clean as well

The flow index is the value obtained from a flow test 45 due to the absence of enzymes and it also has

results in the volumetric flow rate not the bluing and brightening effect of the ultra-

properties of the hollow beads and the final product and marine blue and fluorescent agents in other

of standardized Ottawa sand, formulations,
by measuring the time required for complete emptying
of a 1.91 vessel through a hole with a 50
Diameter of 2.2 cm in a nozzle on its lid
required. The index is the time the sand
required divided by the time the test product
required expressed as a percentage.

55
Example 6

Example 5 was produced on a smaller scale without polyacrylate
in the Crutcher mixture repeated The throughput speed
through the spray drying tower 60
is noticeably reduced and the absorption capacity
the hollow beads for the non-ionic detergent
is lower or the product obtained is
slightly stickier if the same amount of non-ionic
washing agent is used. The Crutcher- 65
mixture is not solid in the Crutcher, the hollow beads
can be produced by spray drying
and the detergent formed, although it is

Claims (24)

Patent claims 1. Free-flowing spray-dried hollow beads useful for forming particulate detergent products containing builders and nonionic surfactant, characterized in that they contain 15 to 30 wt.% sodium carbonate, 10 to 22 wt.% sodium bicarbonate, 10 to 50 wt.% zeolite, 0 to 18 wt.% sodium silicate and 1 to 20 wt.% bentonite and/or 0.05 to 2 wt.% polyacrylate having a MW of 1000 to 5000. 2. Hollow spheres according to claim 1, characterized in that they contain 0 to 3% by weight of sodium silicate and 1 to 20% by weight of bentonite. 3. Hollow beads according to claim 2, characterized in that their bulk density is 0.6 to 0.9 g/cm ³ , their particle sizes are in a range corresponding to a clear mesh size of 2.00 mm to 0.149 mm, the zeolite is sodium zeolite with 15 to 25 wt.% water of hydration and an ion exchange capacity for calcium ions of 200 to 400 milligram equivalents of calcium carbonate hardness per g of anhydrous zeolite, the sodium silicate has a Na:;0:SiO ₂ ratio of 1:1.4 to 1:3 and the weight ratio of sodium carbonate:sodium bicarbonate is about 1 to 3. 4. Hollow beads according to claim 3, characterized in that they contain 20 to 30 wt.% sodium carbonate, 13 to 22 wt.% sodium bicarbonate, 35 to 45 wt.% hydrated zeolite, 0% sodium silicate, 5 to 20 wt.% bentonite and 1 to 15 wt.% water, excluding the hydration water of the zeolite, the zeolite consisting of zeolite A with an ultimate average particle size in the range of 3 to 12 μm. and a calcium ion exchange capacity of 250 to 350 milligram equivalents/g and a softening rate to a residual hardness of less than 0.01 mg/l in 10 minutes, the bentonite is a swelling clay with a swelling capacity in water of 3 to 15 ml/g and a viscosity of 3 to 30 mPa s at 6% concentration in water and the weight ratio sodium carbonate:sodium bicarbonate is in the range of 1 to 2. 5. Hollow beads according to claim 4, characterized in that their bulk density is 0.6 to 0.8 g/cm ³ , they contain 0.05 to 0.5% by weight of sodium polyacrylate with a molecular weight of 1000 to 5000 and the bentonite consists of a processed Wyoming bentonite with a swelling capacity of 7 to 15 ml/g and a viscosity of 8 to 30 mPa · s at 6% concentration in water. 6. Hollow beads according to claim 1, characterized in that they contain 20 to 40% by weight of zeolite, 4 to 12% by weight of sodium silicate and 1 to 15% by weight of bentonite. 7. Hollow beads according to claim 6, characterized in that they have a bulk density of 0.6 to 0.9 g/cm ^J and particle sizes in the range corresponding to a clear mesh size of 2.00 mm to 0.149 mm, the zeolite has 15 to 25 wt. % hydration water and an ion exchange capacity for calcium ions of 200 to 400 milligram equivalents of calcium carbonate hardness per g of anhydrous zeolite, the sodium silicate has a Na ₂ O=SiO ₂ ratio of 1:1.4 to 1:3 and the weight ratio of sodium carbonate to sodium bicarbonate is in the range of about 1 to 3. 8. Hollow beads according to claim 1, characterized in that they contain 20 to 25% by weight of sodium carbonate, 13 to 19% by weight of sodium bicarbonate, 30 to 37% by weight of hydrated zeolite, 5 to 8% by weight of sodium silicate, 5 to 8% by weight of bentonite and 4 to 10% by weight of water, excluding the hydration water of the zeolite, the zeolite consisting of zeolite A with an extreme average particle size of 3 to 12μπα, a calcium ion exchange capacity of 250 to 350 milligram equivalents/g and a softening rate to a residual hardness of less than 0.01 mg/l in 10 minutes, the sodium silicate has a Na ₂ OSiO^ ratio of 11 to 1 -2A , the bentonite consists of a swelling clay with a swelling capacity in water of 3 to 15 ml/g and a viscosity of 3 to 30 mPas at 6% concentration in water and the weight ratio sodium carbonate:sodium bicarbonate is in the range of 1 to 2 9. Hollow beads according to claims, characterized in that their bulk density is 0.6 to 0.8 g/cm ³ , they contain 0.1 to 2 wt.% sodium polyacrylate with a MW of 1000 to 5000 and the bentonite consists of processed Wyoming bentonite with a swelling capacity of 7 to 15 ml/g and a viscosity of 8 to 30 mPa.s at 6% concentration in water 10. Hollow beads according to claim 1, characterized in that they contain 20 to 40 wt.% zeolite, 4 to 18 wt.% sodium silicate and 0.1 to 2 wt.% polyacrylate with a MW of 1000 to 5000. 11. Hollow beads according to claim 10, characterized in that they have a bulk density of 0.5 to 0.8 g/cm ³ and particle sizes in the range corresponding to a clear mesh size of 2.00 to 0.149 mm, the zeolite is sodium zeolite with 15 to 25% by weight of hydration water and an ion exchange capacity for calcium ions of 200 to 40 milligram equivalents of calcium carbonate hardness per g of anhydrous zeolite, the sodium silicate has a Na ₂ O=SiO ₂ ratio of 1:1.4 to 1:3 and the weight ratio of sodium carbonate to sodium bicarbonate is in the range of about 1 to 3. 12. Hollow beads according to claim 11, characterized in that they contain 20 to 25% by weight of sodium carbonate, 13 to 19% by weight of sodium bicarbonate, 30 to 37% by weight of hydrated zeolite, 7 to 15% by weight of sodium silicate, 0.5 to 1.5% by weight of sodium polyacrylate and 3 to 10% by weight of water, excluding the hydration water of the zeolite, the zeolite consisting of zeolite A with an extreme average particle size of 3 to 12 μηι, a calcium ion exchange capacity of 250 to 350 milligram equivalents/g and a softening rate to a residual hardness of less than 0.01 mg/l of 10 minutes, the sodium silicate has a Na ₂ O:SiO ₂ ratio of 1:2 to 1:2.4, the polyacrylate consisting of sodium polyacrylate with a MG of 1000 to 3000 and the weight ratio sodium carbonate:sodium bicarbonate is in the range of 1 to 2. 13. Process for the preparation of hollow beads according to claim 1, characterized in that a crutcher mixture containing 40 to 75% solids 3 4 substances according to claim 1 in an aqueous medium Na2O:SiOr ratio of 1:1.4 to 1 -3 , the po- to contain, with conversion of a portion of the Na- lyacrylate from sodium polyacrylate with a MG triumbicarbonate in sodium carbonate spray-dried from 1000 to 3000, the weight ratio net Sodium carbonaterSodium bicarbonate in the range 14. Process according to claim 13, characterized in that a crutcher mixture which consists of a condensation product of 50 to 12 moles of ethylene oxide and one mole of higher fatty alcohols having 12 to 16 carbon atoms is spray dried and 15. A process according to claim 13, characterized in that a crutcher mixture containing 50 to 65% of solids according to claim 9 is spray dried in an aqueous medium. the amount of sodium carbonate is 16 to 21%, the amount of sodium bicarbonate is 10 to 15%, the amount of hydration water of the zeolite is 10 to 15%. 16. Process according to claim 13, characterized in that a crutcher mixture is prepared from 40 to 70% by weight of solids and 60 to 30% by weight of sodium polyacrylate, the moisture content is 3 to 6% and the water, the solids, based on the amount of non-ionic detergent, being 10 to 100%, about 10 to 25% of sodium carbonate, to 22%. 15 to 30% of sodium bicarbonate at a weight ratio Sodium carbonate:sodium bicarbonate Description of 0.5 to 2, 20 to 40% of zeolite, 5 20 up to 18% sodium silicate and 0.1 to 2% The invention relates to free-flowing spray-dried Polyacrylate with a molecular weight of 1000 to 5000 best hollow beads that are used to form particulate and the Crutcher mixture spray dries detergent products containing builders 17. Use of the hollow beads according to claim 1 for forming a detergent by absorption of a non-ionic detergent active substance in spray-dried hollow beads for forming a detergent which absorbs non-ionic detergent active substances. 18. Use according to claim 17, characterized in that sorbed contains indicates that the non-ionic detergent particulate detergent containing substance from a condensation product of 6 to 30 aluminium silicates such as zeolites as sequestering agents 12 moles of ethylene oxide and a higher fatty acid for calcium ions and as insoluble builders alcohol with 12 to 16 carbon atoms is generally known. These detergents can also be sodium The proportion of non-ionic detergent active ingredient in trium silicates, which can cause corrosion of detergents Detergent is 15 to 22% and the detergent machine parts and the adverse effect tel also contains 0.5 to 3% of an enzyme 35 to eliminate magnesium ions in the wash water. 19. Use according to claim 17, characterized in that the hollow beads according to claim 5 absorb non-ionic washing agent in amounts of 8 to 25%. Polyacrylates of usually relatively high 20. Use according to claim 17, characterized in that hollow beads are used in amounts of 8 to 25% according to their dispersing and deposition-inhibiting effect of insoluble non-ionic detergents in claim 7 calcium compounds. 21. Use according to claim 20, characterized in that the non-ionic washing agent consists of a condensation product of 6 to 12 moles of ethylene oxide and a higher fatty alcohol with 12 to 16 carbon atoms and that the detergent also contains 0.5 to 3% of an enzyme together with zeolites. 50 22. Use according to claim 17, characterized in that hollow beads according to claim 9 are used to deposit bentonites on the washed textiles and are practically regarded as clay soil. Quantities of 8 to 25% are absorbed. Detergents containing insoluble 23. Use according to claim 17, characterized in that the detergent formed contains 13 to 35 wt. % sodium phosphate, zeolite, bentonite or polyacrylate, which have the advantage that they are environmentally friendly because the use of soluble detergents can be avoided. However, it was long believed that the presence of phosphate with a molecular weight of 1000 to 5000 and 8 to 60 wt. % non-ionic detergent active ingredient is obligatory when a silicate together with zeolite is present in the detergent. 24. Use according to claim 23, characterized in that the detergent formed has a bulk density of 0.6 to 0.9 g/cm ³ and particle sizes in the range corresponding to a clear width of 2.00 to 0.149 mm, the crutcher containing bentonite together with a phosphate builder or kaolinite with another builder and a non-ionic surfactant homogeneously distributed in the crutcher mixture. The non-ionic surfactant is present in the zeolite A and the zeolite is a non-ionic surfactant homogeneously distributed ...