CH626915A5 - Detergent and cleaner - Google Patents

Description

The present invention relates to detergents and cleaning agents which have controlled foaming properties, in particular for use in automatic dishwashing.

Detergents and cleaners typically contain surfactants that tend to foam when moved in aqueous solution. For many applications, particularly in automatic washing machines and dishwashers, excessive foaming in detergents and cleaning agents is a serious problem, and with many effective surface-active agents it is necessary to add foam-inhibiting compounds, hereinafter called foam suppressants, in order to achieve acceptable foaming properties.

Unfortunately, it has been found that adding foam suppressors can create new problems. For example, acidic monostearyl phosphate, which is a common suds suppressor, is very effective and useful at low levels in the product, but if the amount of suds suppressor is increased to handle, for example, increased amounts of surfactant, the suds suppressor becomes incompletely soluble and falls in a washing solution from the solution, where it deposits on the surfaces of the objects and machine and remains there in the form of unsightly streaks and deposits.

Another type of foam suppressor that has often been proposed is that based on silicone, especially polydimethylsiloxane. These materials, commonly referred to below as silicone-based foam suppressants, are known to be very useful in industrial applications where the silicone-based foam suppressant is immediately aqueous, surface-active

Solution containing agent is added. However, they could not live up to the expectations placed on them if detergents and cleaning agents were incorporated; often they are e.g. inactivated in the presence of other detergent components 5 and require special protective measures.

It has now been found that stable detergents and cleaning agents can be produced with braked foam by incorporating silicone materials into the agents in a special way.

Accordingly, it is an object of the invention to provide washing and cleaning agents which are stable in storage and contain silicone-based foam suppressants.

Another object of the invention is to provide a method for incorporating silicone-based foam suppressors into detergents and cleaning agents in order to obtain storage-stable agents with suppressed foam formation.

Another problem that arises with conventional silicone-based foam suppressors, such as polydimethylsiloxane, is that they are either completely inactivated in the spray drying process or that they lose their activity very quickly after the spray-dried granules have been produced.

In the manufacture of spray-dried detergent and cleaning agent granules, an aqueous mixture of the various components of the granules (the detergent or "crutcher" mixture) is sprayed or otherwise introduced into a device which is essentially a drying tower. As the droplets of the “crut-cher” mixture pass through the drying tower, the water is evaporated and solid or semi-porous detergent and cleaning agent grains are formed. The advantage of spray-dried detergent and cleaning agent granules over granules which have been obtained by simply dry mixing the individual components is their homogeneity. This means that each grain contains the different 35 ingredients in the same proportions as in the original "crutcher" mixture that was introduced. This has obvious advantages over simple, dry-mixed detergent and cleaning agent formulations, since the dry mixing can lead to a lack of homogeneity 40 in the finally obtained washing and cleaning agent formulations, so that the user is never sure whether the formulation contains a given proportion of the product.

In order to obtain a homogeneous spray-dried grain, it is necessary that the "crutcher" mixture itself is essentially homogeneous. In some cases, a "crutcher" mixture can be a homogeneous solution. However, to create a "crut-cher" solution, excessive amounts of water are required to dissolve all of the components. However, the use of excessive amounts of water requires additional drying capacity in the spray drying tower and is not economically attractive. In most cases, the «crutcher» mixtures used in the production of spray-dried detergent and cleaning agent formulations are semi-dissolved aqueous solutions

Slurries of the various components that are desired in the spray-dried granules ultimately obtained.

Although the batch blending and spray drying process has the above advantages, it does create a problem with the incorporation of relatively sensitive components, such as the conventional silicone based foam suppressors, into the granules, which is at least in part due to the high alkalinity and Temperatures that are present during the mixing stage. Such constituents can indeed be incorporated into the formulation after the spray drying, for example by dry mixing or spraying. However, the need for such an additional step is undesirable in the process. In addition, certain components are

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oils, especially those which are present in smaller quantities, are not easily distributed evenly in a spray-dried granular formulation. A very desirable way of incorporating a silicone-based foam suppressant into a detergent and cleaning agent will therefore simply be to add the material directly to the "crutcher" mixture before spray drying.

It is also known that the introduction of alkoxylated, nonionic, surface-active agents into an aqueous washing and cleaning agent / crutcher mixture can lead to an inhomogeneity in the mixture. This is because the non-ionic materials take on an oily character and are in a separate phase. This problem can be remedied by agents such as certain alkyl phosphate esters or, preferably, as described in U.S. Patent Application Ser. No. 589 116 (R.M. Wise) of June 23, 1975 it is proposed to apply kaolinite or bentonite clays. However, this problem of inhomogeneity in the "crutcher" mixture is exacerbated by the addition of conventional silicone-based foam suppressants (such as polydimethylsiloxane), since these materials are themselves oily and do not disperse well in water or in nonionic surfactants.

It is therefore an additional object of the invention to provide spray dried detergent granules which contain a nonionic surfactant and also a silicone based foam suppressor.

Another object of the invention is to provide an improved method for incorporating certain silicone based foam suppressors into spray dried detergent granules containing substantial amounts of nonionic surfactant.

Silicones have become widely known as useful foam suppressants in aqueous systems. For example, U.S. Patent Nos. 3,250,727; 3 383 327 and 3 455 839 on foam suppressants based on polydimethylsiloxane and their use in defoaming aqueous solutions.

U.S. Patent No. 3,235,509 relates to silicone based foam suppressors which are absorbed on a solid silica material to improve their stability against alkaline materials. However, this silicone / silica material has also been found to be unsatisfactory for certain applications, and U.S. Patent No. 3,933,672 relates to the further protection of silicone / silica materials by incorporating them into a solid, substantially non-surface active matrix.

The additional level of encapsulation or other protection of the silicone material in an inert carrier is both expensive and time consuming, and has therefore been proposed in CA Patent No. 525,433 and US Patent No. 3,829,386 a silicone based foam suppressor can be incorporated into a base product (e.g. a carrier grain which may be alkaline) using a normally liquid surfactant as an incorporation medium. Unfortunately, this suggestion has not been fully satisfactory since most common silicone materials, e.g. polydimethylsiloxane itself, do not disperse well in liquid surfactants and tend to migrate from the surfactant, along with other, more harmful ingredients come into contact with the wording.

It has also been suggested (see FR-PS No. 2 279 843) that certain silicone-based foam suppressant materials can be molded into a powder and then mixed together with detergent granules. As above, this process also means an additional step in the detergent manufacturing process.

The washing and cleaning agent according to the invention is defined in claim 1. Self-emulsifying foam suppressants are characterized by the presence of an emulsifying component, are in solid non-ionic surface; active agents are highly dispersible and self-emulsify in liquid nonionic surfactants. The expression "intimate mixture" is intended to express that the silicone-based foam suppressant is dispersed in the nonionic surfactant and is in direct contact with it and that it does not tend to migrate from the surfactant during storage of the formulation.

The silicone-based foam suppressor of the agents according to the invention is used in an "foam-suppressing amount". “Foam suppressing amount” means that when the formulations are added, an amount of suppressant can be selected that regulates the foam to the desired extent. For example, a foam height of zero or almost zero is desired for use in automatic dishwashing machines, so relatively more of the foam suppressor will be used. Relatively few foam suppressors are used for manual dishwashing. 25 For laundry washing machines, the amount of foam that can be approved can vary widely depending on the particular application, and accordingly, the foam suppressor will be used more or less. The amount of foam control agent will also vary depending on the detergent component selected. For example, in the case of strongly foaming surface-active agents, relatively more of the regulator is used to achieve the desired foam control than in the case where low-foaming detergents are selected for use in the agents according to the invention.

The term "nonionic surfactant" is not intended to encompass compounds which, while having certain surfactant properties, give essentially no detergent activity. Typical of 40 such materials that are not encompassed by the present invention are the polyethylene glycols and condensates of more than about 20 moles of ethylene oxide with a long chain alcohol.

Preferred self-emulsifying silicone-45 foam suppressors are those which contain a modified polysiloxane which has polyoxyalkylene radicals in the polymer. If these materials are used, an aqueous non-ionic surfactant "crutcher" mixture can be added to the "crutcher" mixture and the "crutcher" mixture mixed by adding this specific type of silicone foam suppressor a temperature of at least 65 ° C (150 ° F), preferably 65 ° C to 99 ° C (150 0 to 210 ° F), until homogeneous. The "crutcher" mixture can then be dried, preferably spray dried, to provide homogeneous detergent granules.

According to this embodiment, homogeneous granular spray-dried washing and cleaning agents can be produced

60 (a) 2 to 60% by weight (preferably 5 to 35% by weight) of an alkoxylated nonionic surfactant and

(b) contain a foam-suppressing amount of a self-emulsifying silicone-based foam suppressor, containing a modified polysiloxane with at least one polyoxyal-65kylene radical with polymer.

The detergents and cleaning agents can additionally contain a broad spectrum of other materials that are usually found in detergents and cleaning agents, and the

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Agents may also contain additional non-ionic surfactants that are not mixed with the silicone-based foam suppressors.

Silicone-based foam suppressor:

The silicone materials used as foam suppressants in the invention can be alkylated polysiloxane materials of various types, either alone or in combination with various solid materials such as silica aerogels and xerogels and hydrophobic silicas of various types. In industrial practice, the term "silicone" has become a general term that includes a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbon groups of various types. In general, the silicone-based foam regulators can be described as such, the siloxane residues with the general structure

R

I.

_ (_ SiO _) _

I x

R '

contain, where x is about 20 to about 2000 and R and R 'are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl or phenyl.

The polydimethylsiloxanes (R and R 'are methyl) with a molecular weight in the range of about 200 to about 200,000 and above are all useful as foam control agents. Such silicone materials are commercially available from Dow Corning Corporation under the trade name Silicone 200 Fluids.

In addition, other silicone materials where the side chain groups R and R 'are alkyl, aryl, or mixed alkyl and aryl hydrocarbon groups have useful foam control properties. These materials are conveniently prepared by hydrolysis of the corresponding alkyl, aryl or mixed alkylarylsilicon dichlorides with water in a manner known per se. As specific examples of such silicone-based foam control agents useful in the invention, for example, diethylpolysiloxanes, dipropylpolysiloxanes, dibutylpolysiloxanes, methylethylpolysiloxanes, phenylmethylpolysiloxanes, and the like. be mentioned. The dimethyl polysiloxanes are particularly useful in the context of the invention because of their low cost and easy availability.

A second type of silicone based foam control agent useful in the compositions of the invention comprises a mixture of an alkylated siloxane of the type described above and solid silica. Such mixtures of silicone and silica can be prepared by placing the silicone on the surface of silica (SiO 2), for example by means of the catalytic reaction described in US Pat. No. 3,235,509. Foam control agents comprise mixtures of silicone and silica in a silicone: silica ratio of 19: 1 to 1: 2, preferably 10: 1 to 1: 1. The silica can be chemically and / or physically bound to the silicone in an amount that is preferably about 10% to 15% by weight, based on the silicone. The particle size of the silica used in such silica / silicone foam control agents should preferably not be more than 100 nm, in particular from 10 to 20 nm, and the specific surface area of the silica should preferably exceed 50 m2 / g.

Alternatively, foam control agents containing silicone and silica can be prepared by mixing a flowable silicone of the type described above with a hydrophobic silica which has a particle size and a specific surface area in the range given above. Any number of known methods 5 can be used to produce a hydrophobic silica which can be used in the context of the invention in combination with a silicone as a foam-regulating agent. For example, a pyrogenic silica can be reacted with a trialkylchlorosilane for the purpose of attaching hydrophobic trialkylsilane groups to the surface of the silica (i.e. "siliconized"). In a preferred and well known method, fumed silica is contacted with trimethylchlorosilane and a preferred hydrophobic silanized silica useful for the compositions 15 of the invention is obtained.

In another procedure, a hydrophobic silica which can be used in the detergents and cleaning agents and in the process according to the present invention is obtained by contacting silica with any of the following compounds: metal, ammonium and substituted ammonium salts of long-chain fatty acids, such as sodium stearate, aluminum stearate and the like. ; Silyl halides such as ethyltrichlorosilane, butyltrichlorosilane, tricyclohexylchlorosilane 25 and the like. ; and long chain alkyl amines or ammonium salts such as cetyltrimethylamine, cetyltrimethylammonium chloride and the like.

A preferred foam-regulating agent for use in the context of the invention comprises a hydrophobic silanized (particularly preferably trimethyl-silanated) silicic acid which has a particle size in the range from about 10 to 20 nm and a specific surface area above about 50 m2 / g, in an intimate mixture with a flowable dimethylsilicon, which has a molecular weight in the range from about 500 to about 200,000, with a weight ratio of sili-35 kon: silanized silica of about 19: 1 to about 1: 2 Such foam control agents preferably comprise Süikon and the silanized silica in a weight ratio of silicone: silanized silica of 10: 1 to 1: 1. The foam control agents based on a mixture of hydrophobic silanized 40 (in particular trimethyl-silanized) silica silicone result in foam control over a wide range of temperatures, which is presumably due to the controlled release of the silicone from the surface of the silanized silica.

45 Another type of silicone-based foam control agent for use in the invention includes a flowable silicone, a silicone resin, and silica. The flowable silicones which are useful in such foam regulating mixtures are any of the types described above, but preferably dimethyl silicones. The silicone "resins" used in such foam control agents can be any alkylated silicone resins, but are usually those made from methylsilanes. Silicone resins are usually described as "three-dimensional" polymers, which are formed during the hydrolysis of trichlorosilanes, whereas the flowable silicones or silicone fluids are "two-dimensional" polymers that are formed during the hydrolysis of dichlorosilanes. The silica components of such foam control agents are microporous materials, such as the pyrogenic silica aerogels and xerogels with the particle sizes and specific surfaces as stated above.

The flowable silicone / silicone resin / silica mixed materials useful in the present compositions 65 can be prepared in the manner described in U.S. Patent No. 3,455,839. These mixed materials are commercially available from Dow Corning Corporation. According to the information in US Pat. No. 3,455,839, such

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Materials are described as mixtures, which essentially consist of:

(a) about 10 parts by weight to about 100 parts by weight of a flowable polydimethylsiloxane with a viscosity in the range of 20 cSt to 1500 cSt at 25 ° C;

(b) 5 parts by weight to 50 parts by weight of a siloxane resin composed of (CH3) 3Si01 / 2 units and Si02 units, the ratio of the (CH3) 3SiOJ / 2 units to the Si02 units is in the range of 0.6 / 1 to 1.2 / 1; and

(c) 1 part by weight to 10 parts by weight of a silica gel.

Such mixtures can also be sorbed on or in a water-soluble solid, as indicated above.

The silicone based suds suppressors discussed above are generally not readily dispersible in nonionic surfactants, and if dispersed by agitation or stirring they tend to migrate from the surfactant. For the purposes of the present invention, therefore, these relatively non-dispersible (i.e., non-self-emulsifying) silicone-based foam suppressants are used in admixture with nonionic surfactants that are normally solid, i.e. they are solid at room temperature. This will be explained in more detail below.

There is a type of silicone based suds suppressor that is highly dispersible in solid surfactants and that self-emulsifies in liquid surfactants. This type of suds suppressor has little or no tendency to migrate from the surfactant phase, and with this type of silicone material, the present invention encompasses the use of both liquid and solid non-ionic surfactants.

The silicone-based self-emulsifying foam suppressors mentioned above are characterized by the presence of an emulsifying component in the foam suppressor formulations. The preferred self-emulsifying foam suppressants are those which contain emulsifiers which have at least one polyoxyalkylene radical incorporated into a basic polysiloxane structure. The polyoxyalkylene radicals are preferably incorporated as polymer groups which are substituted on silicon atoms and are attached to the polysiloxane base chain. However, if the silicone compound is in an emulsifier, the polyoxyalkylene residues may be in other positions and may, for example, be part of the base polymer chain, i.e. as a block copolymer. The use of these preferred emulsifiers in the silicone-based foam suppressor formulation allows the foam suppressors to be incorporated into an aqueous, alkaline “crutcher” mixture and the formation of a spray-dried granular detergent and cleaning agent which contains the foam suppressors in an active form.

Highly preferred emulsifiers of the type described above are typically represented by the formula

Represents RaSiY4_a, wherein a represents 0 or an integer from 1 to 3; R from (a) alkyl groups with 1 to about 30 carbon atoms, (b) groups of the formula.

-R '- (OR') b ~ OR ",

wherein R 'represents an alkylene group having 1 to about 6, preferably 2 to 4 carbon atoms, b has a value of 1 to about 100; and R "symbolizes a terminating group which consists of hydrogen, alkyl, aryl, alkaryl, aralkyl or al-kenyl groups with up to 20 carbon atoms; acyl groups with up to 20 carbon atoms, sulfate, sulfonate, phosphate, Phosphonate, borate or isocyanate groups or a mixture comprising mixtures thereof can be selected, and Y is a group with the formula

5

R

I.

(-0-Si) c-0SiR3 I

10 rows

symbolizes where R has the formula given above and c represents a value from 1 to 200; and wherein at least one of the groups R in the compound has the formula given above

15

[—R '(OR') b — R "1

in which b is sufficiently large to obtain an emulsifier.

Preferred emulsifiers for the silicone self-emulsifying foam control agents are those described in U.S. Patent Nos. 3,233,986 and 3,511,788, which are incorporated by reference. The agents described in U.S. Patent 3,511,788 are most preferred.

Preferred combinations of these emulsifiers together with silicone-based foam control agents are described in UK Patent No. 1,373,903 and US Patent No. 3,746,653, which are incorporated by reference. The mixtures are preferably at least 50% RaSiY4_a-, about 5% to

30 contain about 45% of a liquid polydimethylsiloxane and 0.05% to about 5% silica. The mixture may additionally contain a minor amount of a polydimethylsiloxane resin.

Other effective self-emulsifying silicone-based foam suppressants contain a high ethoxylate one

35 Fatty acid as an emulsifying component. The condensation products from about 300 to about 2000 moles of ethylene oxide per mole of fatty acid are particularly useful. Fatty acids are straight-chain saturated and unsaturated monocarboxylic acids that usually have an even number of carbon atoms (from about 10 to

40 about 20), preferably around 18. Examples of common fatty acids include palmitic acid, stearic acid and oleic acid.

The emulsifying component can also be a zwitterionic surfactant. Zwitterionic surface

45 surfactants useful in the invention include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic radicals can be straight or branched chain and in which one of the aliphatic substituents has 8 to 18 carbon atoms

50 and one containing an anionic water-solubilizing group. Preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates, which are described in US Pat. Nos. 3 925 262 and 3 939 678 and in US patent application Serial No. 603,837 (Laughlin et al) of August 11, 1975-

55 are written; all of this information is referred to as a disclosure.

Particularly preferred ethoxylated zwitterionic surfactants are those with the general formula

60 ch3

I.

c16h33-n + - (c2h4o) 9c2h4x-,

I.

ch3

65

where X is S03 or S04.

Other preferred zwitterionic surfactants include those having the general formula

7

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CH3

I.

CK) H "-N + - (C, H40) yC2H4S04-,

I.

(C2H40) XH

where the sum of x and y is about 15.

The amount of silicone-based foam suppressing formulation used is typically from about 0.01% to about 5%, preferably from about 0.05% to about 0.5% by weight. % and in particular about 0.1% by weight to about 0.4% by weight of the washing and cleaning agents according to the present invention.

Nonionic surfactant:

The nonionic surfactants useful in the present invention are solid or, when mixed with self-emulsifying silicone materials, also liquid.

Most common are nonionic surfactants compounds obtained by condensing an alkylene oxide (hydrophilic type) with an organic hydrophobic compound, which is usually aliphatic or alkyl aromatic type. The length of the hydrophilic polyoxyalkylene residue condensed with any particular hydrophobic compound can easily be adjusted to provide a water-soluble compound that has the desired degree of equilibrium between hydrophilic and hydrophobic elements.

The balance between the hydrophobic and hydrophilic residues of the nonionic surfactant and, more importantly, the chain length of each of the residues determines whether the surfactant is normally solid (i.e., has a melting point> 18 ° C) or is normally liquid.

Examples of suitable types of nonionic surfactants (without specific reference to their phase here) include:

1. The polyethylene oxide condensates of alkylphenols. These compounds include the condensation products of alkylphenols containing an alkyl group of 6 to 12 carbon atoms in either a straight or branched chain configuration with ethylene oxide, the ethylene oxide being present in amounts corresponding to 5 to 20 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, di-isobutylene, octene or nonene. Examples of compounds of this type include nonylphenol which is condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol, do-decylphenol which is condensed with about 12 moles of ethylene oxide per mole of phenol, dinonylphenol which condenses with about 15 moles of ethylene oxide per mole of phenol is diisooctylphenol which is condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-610, available from GAF Corporation; and Triton X-45, X-14, X-100 and X-102, all of which are available from Rohm and Haas Company.

2. The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol can be either straight or branched and generally contains 8 to 22 carbon atoms. Preferably there are about 3 to about 18 moles of ethylene oxide per mole of alcohol. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide

Coconut fatty alcohol, wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains of 10 to 14 carbon atoms in length, and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the coconut alcohol described above. Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9 available from Union Carbide Corporation, Neodol 23-6-5 available from Shell Chemical Company and Kyro EOB, which is brought onto the market by Procter & Gamble Company.

3. The condensation products of ethylene oxide with a hydrophobic compound, which by condensation of

15 Propylene oxide with propylene glycol is formed. The hydrophobic portion of these compounds has a molecular weight of about 1500 to 1800 and shows water insolubility. The addition of polyoxyethylene residues to this hydrophobic section leads to an increase in the water solubility of the molecule as a whole, 20 and the liquid character of the product is maintained to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product. Examples of the compounds of this type include certain commercially available Pluronic surfactants available from 25 of Wyandotte Chemicals Corporation.

4. The condensation products of ethylene oxide with the product that results from the reaction of propylene oxide and ethylenediamine. The hydrophobic base of these products consists of the reaction product of ethylenediamine and excess

30 sigen propylene oxide, wherein the base has a molecular weight of about 2500 to about 3000. This base is condensed with ethylene oxide to such an extent that the condensation product contains about 40 to about 80% by weight of polyoxyethylene and has a molecular weight of about 5000 to about 11,000. Examples of this type of nonionic surfactant include certain commercially available tetronic compounds available from Wyandotte Chemicals Corporation.

Mixtures of the surfactants listed above are also useful in the present invention.

All of the above-described types of nonionic surfactants, preferably surfactants, which are normally solid, include the condensation product 45 of nonylphenol with about 9.5 moles of ethylene oxide per mole of nonylphenol, the condensation product of tallow fatty alcohol with about 9 moles of ethylene oxide per mole of fatty alcohol, the condensation product a C15-C2o-aliphatic alcohol with about 6 to 20 mol of ethylene oxide and the ethylene oxide / propylene oxide copoly-50 mer, which is commercially available under the name Pluronic 2.5R5. Preferred surfactants, which are normally liquid, include the condensation product of a C12-C13 alcohol with 3 moles of ethylene oxide per mole of alcohol, the condensation product of a Ci4-C15 alcohol with 7 moles of 55 ethylene oxide per mole of alcohol, the condensation product of a C12-C15 - aliphatic alcohol with about 3 to 9 moles of ethylene oxide and the ethylene / propylene oxide condensate, which is marketed by Wyandotte Chemicals Corporation under the trade name Pluradot HA 430. The preferred self-emulsifying suds suppressors, which contain a modified polysiloxane with polyoxyalkylene residues in the polymer, can be combined with any of the detergent alkoxylated surfactants well known in the art and processed into granular, 65 spray-dried detergents and cleaning agents. Generally speaking, these nonionic agents are water-soluble detergent surfactants of the general formula

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R-0- (CyH2yO) a- (CzH2zO) b-CwH2wOH,

wherein R is from the primary, secondary and branched chain alkyl hydrocarbon residues; primary, secondary and branched chain alkenyl hydrocarbon residues; and a group comprising primary, secondary and branched chain alkyl and alkenyl substituted phenolic hydrocarbon radicals, the hydrocarbon radicals having a hydrocarbon chain length of 8 to about 20, preferably 10 to 16 carbon atoms. In the general formula for the alk-oxylated nonionic surfactants, y and z each represent integers from 2 to 3, preferably 2, with either z or y = 2 when the other integer is 3 (ie excluding the total -PO surfactants); w is an integer from 2 to 3, preferably 2, and a and b are each integers from 0 to 8, the sum of a + b being in the range from 6 to 25, preferably 6 to 10. The surfactant formula includes ethylene oxide (EO) and mixed ethylene oxide / propylene oxide (EO-PO) alkoxylates, all of which are useful in the invention. The total PO surface active agents do not give any cleaning advantages in the detergents and cleaning agents and are therefore not intended for use here.

Preferred nonionic surfactants used in the invention are the ethoxylated nonionic surfactants, both from the standpoint of availability and cleaning performance.

Specific examples of alkoxylated nonionic surfactants include, but are not limited to, the di- to hexadecaalkoxylates of C8-C18 straight chain primary alcohols; the di- to hexadecaalkoxylates of QrQo straight chain secondary alcohols; the di- to hexadecaalkoxylates of alkylphenols; the di- to hexadecaalkoxylates of primary and secondary alkenyl alcohols and alkenylphenols; and the di- to hexadecaalkoxylates of branched chain primary and secondary alcohols.

Particularly preferred alkoxylated nonionic surfactants include C8-Clg aliphatic alcohols which are condensed with 3 to about 15 moles of ethylene oxide per mole of alcohol and (C6-C9 alkyl) phenols which are with about 6 to about 16 moles of ethylene oxide per mole Phenol are condensed.

A mixed alkoxylated nonionic system useful in the invention comprises one or more of the above cleaning alkoxylated nonionic surfactants which have an HLB in the range of about 11 to 17 (preferably 12 to 15) and as a "co- surfactant »one or more water-soluble alkoxylates which have an HLB in the range from 7 to 10.5 (preferably 9 to 10.5). The two types of alkoxylated materials can be combined in appropriate weight ratios to set a total HLB in the mixture of about 10 to about 12.5 (preferably 10 to 12; especially 10.5 to 12.0). Such blends of nonionic surfactants and nonionic co-surfactants provide superior textile cleaning performance and are particularly useful for removing greasy dirt from polyester and cotton / polyester blended fabrics. These preferred mixtures of nonionic surface-active plus nonionic “co-surface-active” alkoxylates are described in more detail in BE-PS 149 552, to which reference is made as a disclosure.

Another highly preferred alkoxylated nonionic surfactant system is that disclosed in U.S. Patent Application Serial No. 557,217 (Jerome H. Collins) of March 10, 1975, which is incorporated herein by reference. This surface active system comprises a base catalyzed primary alcohol ethoxylate of the formula Ri-R2-0 (CH2CH20) na> H, where R is a linear alkyl radical and R2 has the formula CHR3-CH2, where R3 is hydrogen and mixtures thereof with C1-C4 alkyl groups means, wherein no more than 70% by weight of the groups are contained in the mixtures 5, in which Rt and R2 together form an alkyl radical which contains on average 9 to 15 carbon atoms and at least 65% by weight of the rest have a chain length within Have ± 1 carbon atom of the mean, where 3.5 <nav <6.5. Such a system is also characterized by a content of <5% by weight of non-ethoxylated alcohol and by at least 63% by weight of ethoxylates which contain 2 to 7 ethylene oxide groups, the HLB of the system being in the range of 9.5 to 11.5. The system is otherwise free from alkoxylated nonionic surfactants. 15 Nonionic surfactant systems of the type described above can be obtained by ethoxylating a suitable alcohol to less than the desired level with a base catalyst and then stripping off non-ethoxylated alcohol and lower ethoxylates to give a product 20 which has the desired ethoxylate distribution.

A preferred material of this type can be made from Neodol 23, a primary C12-C13-OXO alcohol available from Shell Chemical Company and having approximately 20% 2-alkyl (predominantly methyl) branch . To produce the preferred nonionic surfactant, Neodol 23 is ethoxylated with an average of 3 moles of ethylene oxide per mole of alcohol and the ethoxylated material is then stripped to remove non-ethoxylated alcohol and low ethoxylates. Approximately 34% by weight 30 of the ethoxylate is removed and the residue has an HLB of approximately 10.55 and an ethoxylation value of approximately 4.9 moles per mole of alcohol.

Other ingredients.

35

The intimate mixture of the two essential components described above can be incorporated into any of a wide variety of non-liquid detergent and cleaning agent formulations. You can use such a procedure that the physical properties of the intimate mixture are not destroyed. In general, a sufficient amount of the intimate mixture is used to maintain a concentration of from about 0.01% to about 5%, preferably 0.05% to 0.5% by weight of the foam -45 silicone-based pusher in the formulation.

The present invention also encompasses detergent and detergent formulations containing surfactant materials other than the substantially nonionic surfactant. Such other 5t surfactants can be selected from anionic, nonionic, zwitterionic and ampholytic surfactants.

Examples of the above types of surfactants are given in U.S. Patent No. 3,862,058, which is incorporated herein by reference.

Useful anionic surfactants include alkyl sulfates and sulfonates containing from about 8 to about 18 carbon atoms; Alkylbenzenesulfonates with about 9 to about 20 carbon atoms in the alkyl chain, especially sodium 6C or alkanolamine salts of linear straight chain alkylbenzenesulfonates in which the average chain length in the alkyl group is about 10 to about 14, especially about 11.8 carbon atoms (usually abbreviated as NaCll8LAS); Alkyl ether sulfates of the formula

65

R0 (C2H40) nS03M,

wherein R is alkyl or alkenyl with about 10 to about 20 carbons

9

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Substance atoms, n = 1 to 30 and M represent an alkali metal cation; and olefin sulfonates which are derived from the sulfonation of ci2-C24-cx-olefins with sulfur trioxide. Other useful anionic surfactants in combination with the silicone / surfactant mixture that can be used in the present invention are the alkaline earth metal, preferably magnesium or calcium salts of linear alkylbenzenesulfonic acids. Useful nonionic surfactants, besides those already mentioned, include amine oxides, phosphine oxides and sulfoxide. Specific examples of such surfactants include dimethyldodecylamine oxide, dimethylstearylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dimethyldodecylphosphine oxide, dodecylmethyl sulfoxide and octadecylmethyl sulfoxide.

Preferred zwitterionic surfactants include higher alkyl or alkarylammoniopropane sulfonates such as 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate, 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane 1-sulfonate and 3- (N, N-dimethyl-N-alkylammonio) -2-hydroxypropane-l-sulfonate, the alkyl group being derived from the middle cut coconut fatty alcohol, and higher alkyl or alkarylammoniocarboxylates, such as (N-dodecylbenzyl -N, N-dimethylammonio) acetate, (N, N-dimethyl-N-hexadecylammo-nio) acetate and 6- (N-dodecylbenzyl-N, N-dimethylammonio) hexanoate. Other useful zwitterionic materials are the ethoxylated ammoniosulfonates and sulfates described in U.S. Patent 3,929,678.

Detergents and cleaning agents according to the present invention normally contain builder salts, in particular alkaline, polyvalent anionic builder salts. These alkaline salts serve to maintain the pH of the cleaning solution in the range of about 7 to about 12, preferably about 8 to about 11.

If the agents according to the invention are formed by spray drying, such builders can be used in the crutch mixture at concentrations of about 10% by weight to about 80% by weight (preferably 15% by weight to 50% by weight), in order to obtain dry washing and cleaning agents which contain about 15% by weight to about 90% by weight, preferably about 20% by weight to 60% by weight, of these builders.

Suitable detergent builder salts which can be used in the present compositions can be the polyvalent inorganic or polyvalent organic types or mixtures thereof. Non-limiting examples of suitable water-soluble alkaline detergent builder salts include alkali metal phosphates, pyrophosphates, orthophosphates, poly lyophosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and polycarboxylates. Specific examples of such salts include the sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, orthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergent builder salts are: (1) water soluble aminopolyacetates, e.g. Sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N- (2-hydroxyethyl) nitrilodiacetates; (2) water soluble salts of phytic acid, e.g. Sodium and potassium phytates; (3) water soluble polyphosphonates including sodium, potassium and lithium salts of ethane-l-hydroxy-l, l-diphosphonic acid; Sodium, potassium and lithium salts of methylene diphosphonic acid and the like.

Other organic builder salts useful in the instant compositions include the polycarboxylate materials described in U.S. Patent No. 2,264,103, including the water-soluble alkali metal salts of mellitic acid. The water-soluble salts of the polycarboxylate polymers and copolymers as described in U.S. Patent 3,308,067, which is incorporated by reference, are also suitable. Although the alkali metal salts of the above inorganic and organic polyvalent anionic builder salts are preferred for use from an economic point of view, the ammonium, alkanolammonium, e.g. Triethanolammonium-, Diethanoiammonium- and the like. Water soluble salts of any of the above builder anions are also useful.

Another class of detergent builder materials that can be used in the present compositions are the insoluble sodium aluminosilicates, especially those described in BE-PS 814,874. In this patent, detergent and cleaning agent formulations are described, the sodium aluminosilicates of the general formula

15 Naz (A102) z (Si02) yxH20

contain, wherein z and y are integers corresponding to at least 6, the molar ratio of z to y is in the range of 1.0: 1 to about 0.5: 1 and x is an integer from 15 to 264 20, wherein the aluminosilicates have a calcium ion exchange capacity of at least 200 mg equivalents / g and a calcium ion exchange rate of at least about 0.13 g / 3.791 / min / g. A preferred material is Na12 (Si02 • A102) 12 • 27H20.

Mixtures of organic and / or inorganic builders can also be used. Such a mixture of builders is described in CA-PS 755 038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-l-hydroxy-301.1-diphosphonate.

Although any of the above alkaline polyvalent builder materials are useful, sodium tripolyphosphate, sodium nitrilotriacetate, sodium melithate, sodium citrate and sodium carbonate are preferred for use as a builder. Sodium tripolyphosphate is particularly preferred as a builder, because of its detergent builder activity and its ability to keep dirt from illite and kaolinite clay suspended and to prevent the redeposition of this dirt on the textile surface. In the non-spray-dried compositions according to the present invention, the detergent builders are generally used in concentrations of about 10% by weight to about 60% by weight, preferably 20% by weight to 50% by weight.

Bleaching agents 45 can also be incorporated into the agents according to the invention, and examples of typical bleaching agents are chlorinated trisodium phosphate and the sodium and potassium salts of dichloroisocyanuric acid.

The washing and cleaning agents according to the invention can also contain other materials which are usually used in such agents. For example, various dirt suspending agents such as carboxymethyl cellulose, corrosion inhibitors, dyes, fillers such as sodium sulfate and silica, optical brighteners, germicides, anti-clouding agents, pH regulating agents such as mono-, di-55 or triethanolamine, enzymes and the like can also be contained therein. as are well known in the art for use in detergents

Manufacture of washing and cleaning agents. 60 The inventive method is defined in claim 10. The liquid mixture of silicone-based foam suppressor and nonionic surfactant can also be applied to, or coated on, or adsorbed on or absorbed in the carrier grain, 65 the carrier grain containing the other ingredients of the detergent and cleaning agent formulation.

Becomes a self-emulsifying silicone material together with a liquid or melted liquid surface

626 915

10th

active agent used, then the silicone can be easily mixed into the surfactant and a stable emulsion or dispersion is formed. As for the less dispersible silicones, it is appropriate in this context that the mixture of silicone and surface active agent (using melted surface active agent) is subjected to agitation or stirring or shear treatment shortly before incorporation into the product . In this way, the silicone material remains sufficiently dispersed in the molten surfactant so that it does not migrate before the surfactant cools and solidifies after being sprayed onto the product. After the surface active agent has solidified, there is no longer any possibility that the silicone material can escape.

When a normally solid surfactant is used, it is common to heat the surfactant to form a liquid phase, although the use of a solvent to dissolve the surfactant is not excluded. In the heating process, it is important to minimize the time that the silicone material is in contact with the hot surfactant. In certain cases, silicone materials can lose their effectiveness if they are hot, i.e. surfactants having a temperature in the range of 49 to 94 ° C (120-200 ° F) for relatively long periods, e.g. over 30 min.

In a preferred method, therefore, liquid surfactant is continuously sprayed onto carrier granules and the silicone-based foam suppressant is injected into a line leading to the spray nozzles, with mixing devices being provided downstream of the injection site. The mixing devices may include baffle or baffle plates of a line or a perforated plate in the line which causes the silicone material to be effectively dispersed within the surfactant.

To facilitate mixing in the process, the self-emulsifying silicone compounds are preferred both in a mixture with solid and with liquid surface-active agents.

Highly preferred detergents and cleaning agents according to the present invention are those which are intended for use in automatic dishwashing machines. In these formulations, the intimate mixture of nonionic surfactant and silicone-based foam suppressor can be sprayed onto a base grain which contains, for example, sodium tripolyphosphate, chlorinated trisodium phosphate and sodium silicate. Such a base grain can be produced by agglomeration of the sodium tripolyphosphate and the chlorinated trisodium phosphate with a solution of sodium silicate. Examples of useful methods for making such grains are found in U.S. Patent Nos. 3,598,743 and 3,888,781, which are incorporated by reference.

In the case of automatic dishwashing machine products, the formulations preferably contain from about 20% to about 60% sodium tripolyphosphate, from about 10% to about 60% sodium silicate and from about 15% to about 35% chlorinated trisodium phosphate in the base grain. The intimate mixture of nonionic surface-active agent and silicone-based foam suppressant can be incorporated into this base grain, in order to have a proportion of surface-active agent in the formulation of at least 2.5% by weight to preferably 12.5% by weight and a proportion of foam suppressant from about 0.05 to about 0.5% by weight.

The washing and cleaning agents according to the present invention are preferably in granular form, but can also be used in other non-liquid forms, for example as powders, tablets, pastes and gels.

If the particularly preferred self-emulsifying silicone-based foam suppressants containing a modified Po-5 lysiloxane with a polyoxyalkylene in the polymer are used, their preparation can be carried out by producing a detergent-crutcher mixture which contains the various components which are finally obtained Detergent and cleaning agent formulation are present in an io aqueous medium.

The crutcher mixtures used in this process may conveniently comprise an aqueous slurry containing from about 15% to about 50% (preferably from about 25% to about 40% by weight) 15 water, about 1% to about 40% by weight (preferably about 5% to about 20% by weight) of water-soluble organic detergent component having a predominant nonionic surfactant content as described above and about 10% by weight. -% to about 80% by weight (preferably 20 to about 15% by weight to about 50% by weight) of detergent builder and additives as described above.

Use of the above Crutcher blends in combination with an amount of from about 0.005% to about 5% by weight of the Crutcher blend of the preferred self-emulsifying suds suppressors results in the formation of substantially homogeneous blends which are suitable for the manufacture of homogeneous powdered and granular detergents and cleaning agents are suitable.

Such detergents and cleaning agents contain the various components that were originally contained in the crutcher mixture. The final concentrations of such components in the dry washing and cleaning agents can, however, vary somewhat compared to their concentrations in the soap mixer, since a larger part of the water is removed during drying.

The preferred silicone-based self-emulsifying suds suppressors, although generally stable in the presence of nonionic surfactants, can be inactivated if subjected to extreme heat in the presence of surfactants. It is therefore preferred to form and mix the Crutcher mixture as quickly as possible and then spray dry it without causing excessive delays.

In general, the residence time of the silicone-containing mixture in the soap mixer should not exceed about 10 to 15 minutes.

It is preferred to intimately mix the silicone based suds suppressor with the nonionic surfactant before adding to the soap mixer because it is believed that it is important that the silicone material remain in the same phase as the nonionic surfactant.

55 The crutcher mixture is generally prepared at a temperature of 60 to 66 ° C and the hot mixture is introduced into a spray tower and sprayed to obtain a granular detergent and cleaning agent. The spray drying process section can follow in the usual manner.

The following examples are representative of the compositions and methods according to the invention.

example 1

A detergent and cleaning agent formulation is prepared for an automatic dishwasher, which has the following components:

11

626 915

component

Sodium tripolyphosphate (STP)

Sodium silicate (ratio of Si02: Na20 = 2.8)

chlorinated trisodium phosphate (C1TSP)

Tallow alcohol condensed with 9 moles of ethylene oxide per mole of alcohol (TAE9)

Dow Corning DB 544 foam suppressor *)

Moisture and minor components, rest on

% By weight of the composition

43.0

16.0 26.0 7.5 0.4

100

set, but instead of the DB 544 foam suppressor contains 0.4% of the foam suppressor Dow Corning DB 100 (a silicone / silica foam suppressor).

5 Example 4

Using the procedure of Example 1, the following formulation is made:

*) A silicone based foam suppressant containing a siloxane / glycol copolymer.

To prepare the above formulation, the sodium tripolyphosphate and the chlorinated trisodium phosphate are mixed and agglomerated in a granulating pan using a solution of the sodium silicate. After the granulation is complete, the TAE9 is heated above its melting point and the DB 544 foam suppressor is mixed into the TAE9 to form a stable emulsion. The melted emulsion is then sprayed onto the granular material to form the detergent and cleaner formulation.

The above formulation was tested in the following manner:

The formation of foam in an automatic dishwashing machine causes a reduction in the rotational speed of the rotor arm, which is driven by the force of the water or the detergent and cleaning agent solution which is passed through the arm. The speed of the rotor arm with pure water is used as a control value (100% effectiveness). The speed of the rotor in a solution of contaminated surfactant is measured. Generally, using a low-foaming surfactant, together with a foam suppressor, the rotor arm rotates at about 90% of its speed in water. The numerical value of 90% is referred to as "foam effectiveness". The higher this numerical value, the more effective the foam suppressor.

The formulation of Example 1, when freshly prepared, had a foam effectiveness of 90%. After 9 weeks of storage at 32 ° C, the formulation was tested again and found to still have 90% foam effectiveness.

Substantially identical results are obtained when the DB 544 in the above formulation is replaced by DB 31, a silicone / silica foam suppressor which contains a highly ethoxylated fatty acid emulsifying component and is marketed by Dow Corning.

Example 2

A formulation analogous to that of Example 1, but containing 0.3% polydimethylsiloxane in place of the DB 544 foam suppressor, was prepared. After 3 weeks, no significant change in the foam effectiveness of the formulation was found.

Example 3

There is a formulation analogous to that of Example 1 on component

D

Sodium tripolyphosphate

Sodium silicate (ratio of Si02: Na20 = 2.4)

Sodium silicate (ratio of Si02: Na20 = 2.8)

chlorinated trisodium phosphate

5

TAE9 SAG 100 *)

25 moisture and minor components, rest on

20th

Wt% 26.0

5.0

12.0 22.0 5.0 0.2

100

*) A polydimethylsiloxane marketed by Union Carbide.

30th

Using the foam test described above, the above formulation is tested before and after three weeks of storage at 32 ° C. No significant change in foam effectiveness is observed.

35

Example 5

A detergent and cleaning agent formulation is produced which is suitable for use in an automatic dishwasher and a normal liquid

40 has nonionic surfactant, the procedure being analogous to Example 1. It has the following components:

45

50

component

Sodium tripolyphosphate (STP)

Sodium silicate (ratio of Si02: Na20 = 2.8)

)

chlorinated trisodium phosphate (C1TSP)

Coconut fatty alcohol condensed with 55 6 moles of ethylene oxide per mole of alcohol

DB 544

60 moisture and minor components, rest on

% By weight 46.0

17.0

26.0

7.5 0.4

100

This formulation was relatively foaming and, freshly made, had a foam effectiveness of 57%. After three weeks of storage at 32 ° C., the foam effectiveness was measured and found to be 54%, which is not a significant reduction.

626 915

12

Substantially similar results are obtained when the DB 544 in the above formulation is available from DB 31, a silicone / silica foam suppressor that contains a highly ethoxylated (containing about 300 to 2000 ethoxy groups per molecule) fatty acid emulsifying component Dow Corning company.

Comparable results are also obtained when the DB 544 in the above formulation by the foam suppressor DB 100 together with a zwitterionic surfactant as an emulsifying component, such as

CH3

I.

ClftH33-N + - (C2H40) 9C2H4S0r

I.

CH,

is replaced.

Example 6

A formulation similar to that of Example 5 is prepared, but using Pluradot HA 430 (Wyandotte Chemical Corporation) as the only nonionic surfactant (a liquid surfactant). In this case, only 0.1% of DB 544 is used, and the formulation proves to be stable in storage and shows good foam suppression.

After all of the examples above, formulations with good storage stability are obtained, which is evidenced by the continuous activity of the foam suppressor after storage for 3 to 9 weeks at 32 ° C.

A formulation containing a carrier granule based on sodium carbonate and sodium silicate and in which the liquid nonionic surfactant of Example 5 is used together with a polydimethylsiloxane foam suppressor is found to have a foam effectiveness of 89% when fresh has been produced, but this drops rapidly to 80% after 2 weeks and subsequently this value drops further.

Example 7

A spray-dried washing and cleaning agent formulation is produced, the preferred self-emulsifying foam suppressants being used and which is composed as follows:

To prepare the above formulation, all of the constituents of the formulation are slurried in water and mixed at 66 ° C to give a homogeneous Crutcher mixture. The mixture is then introduced into a spray drying tower and spray dried to form homogeneous grains.

The resulting formulation shows controlled foam properties that are maintained for 3 weeks after storage at 32 ° C and 80% relative humidity.

io The same formulation as above, but with the product Dow Corning DB 100 as foam suppressor instead of DB 544, shows no foam suppression after spray drying, even if it is freshly prepared. DB 100 contains no polyoxyalkylene-modified polysiloxane emulsifying component.

Example 8

A granular, high-performance detergent and cleaning agent formulation is produced by spray drying a detergent-2 (gene slurry in the customary manner. The slurry has the following composition:

component

Neodol 23, which is ethoxylated with 3 moles of ethylene oxide and stripped to an HLB of 10.55 *)

Sodium tripolyphosphate

Sodium silicate (ratio of Na20: Si02 = 1.6)

DB 544 **)

Sodium sulfate

Moisture and minor components, rest on

% By weight of the composition

Ingredients parts by weight

2i condensate of a Ci4-C15 mixed

alcohol 1: 1 with 7 moles of ethylene oxide 17.0

4,4'-thiobis (6-tert-butyl-m-cresol) 0.02

3c Berol 525 0.7

Pentasodium tripolyphosphate

(anhydrous) 46.0

35 Saturated C16-C22 fatty acid 0.7

Silicate solids, ratio

Si02: Na20 = 2.0 8.0

40 sodium sulfate 14.0

Lower components 3.0

Water 40.0

45

Foam control agent (Dow

Corning DB 544) 0.3

11.0 32.0

10.0 0.2 38.0

100

*) Neodol 23 is available from Shell Chemical Company.

**) Product from Dow Corning, a silicone foam suppressor that contains a copolymer of polydimethylsiloxane and a polyalkylene oxide.

Substantially similar formulations are produced (a) without the addition of DB 544 as a foam regulator and (b) by replacing the DB 544 regulator with an equal amount of the foam regulator described in BE-PS 803 101.

55 There are 75 parts by weight of the granular base powder obtained after spray drying the above slurry with 25 parts by weight of granular perborate tetrahydrate and 1% additional minor components, including a proteolytic enzyme, a perfume and a polyethylene

60 glycol with a molecular weight of about 400 mixed dry.

The foam control capacity of the granular bleach-containing end product thus prepared was tested, namely (1) in the freshly prepared state; and (2) after an accelerated

61 th storage test, as detailed below.

The foam control capacity is measured with a Miele drum washing machine with front loading under the following conditions:

13

626 915

Laundry loading product concentration temperature program

4 kg

0.65% (weight / volume) main wash until boiling.

The foam height, expressed in cm, is measured at a temperature of 90 ° C through the front window. The results were as follows:

DB 544 foam regulator (incorporated by mixing in a soap mixer) (Crutching)

Mixing in a dry soap mixer (Crutching)

No foam suppressant

Foam according to BE-PS 803 101

pusher incorporated by

Freshly prepared

Storage: 1 week at 35 ° C; 80% relative humidity

Storage: 1 week at 50 ° C

12 6

10 12

4 5

4 5

8 6

On the above scale, 6 cm means a foam height that is acceptable to the consumer under cooking conditions (90 ° C). Foam heights of 8 cm and above are undesirable. Thus, the formulations according to the invention are at least as good as or better than identical formulations in which the foam regulator has been replaced with an equivalent amount of a foam suppressor which is known to be suitable for commercial purposes.

C.

Claims (10)

626 915 1. washing and cleaning agent, characterized in that it contains 2.5 to 100 wt .-%, based on the agent, of an intimate mixture of a nonionic surface-active agent and a foam-suppressing amount of a silicone-based foam suppressor, the intimate mixture (a) a mixture of a normally solid nonionic surfactant with a non-self-emulsifying silicone suppressant and / or (b) is a mixture of a nonionic surfactant with a self-emulsifying silicone-based foam suppressor. 2. washing and cleaning agent according to claim 1, characterized in that the nonionic surface-active agent (a) condensation products of alkylphenols with 5 to 20 moles of ethylene oxide; (b) condensation products of aliphatic alcohols containing 8 to 22 carbon atoms with 3 to 18 moles of ethylene oxide; (c) condensation products of ethylene oxide with a hydrophobic compound formed by condensation of propylene oxide with propylene glycol, the molecular weight of the hydrophobic portion being from 1500 to 1800; (d) condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, the molecular weight of the hydrophobic section being 2500 to 3000 and the condensation product containing 40 to 80% by weight of polyoxyethylene; and (e) mixtures thereof are selected and that the silicone-based foam suppressant is present in an amount of 0.01 to 5% by weight, based on the composition. 2nd PATENT CLAIMS 3rd 626 915 is with 12 to 15 carbon atoms, which is condensed with 3 to 9 moles of ethylene oxide per mole of alcohol. 3. Detergent and cleaning agent according to claim 1, characterized in that it (A) 10 to 60% by weight of a builder salt and (B) an intimate mixture which contains as essential components: (i) 2.5 to 12.5% by weight, based on the agent, of a normally solid nonionic surfactant and (ii) 0.05 to 0.5% by weight, based on the composition, of a non-self-emulsifying silicone-based foam suppressant, the nonionic surfactant being composed of (a) condensation products of alkylphenols with 5 to 20 moles of ethylene oxide; (b) condensation products of aliphatic alcohols containing 8 to 22 carbon atoms with 3 to 18 moles of ethylene oxide; (c) condensation products of ethylene oxide with a hydrophobic compound formed by condensation of propylene oxide with propylene glycol, the molecular weight of the hydrophobic portion being from 1500 to 1800; (d) condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, the molecular weight of the hydrophobic section being 2500 to 3000 and the condensation product containing 40 to 80% by weight of polyoxyethylene, and (e) mixtures thereof is selected. 4. Washing and cleaning agent according to claim 3, characterized in that the foam suppressor is a flowable polydimethylsiloxane. 5 (b) condensation products of aliphatic alcohols containing 8 to 22 carbon atoms with 3 to 18 moles of ethylene oxide; (c) condensation products of ethylene oxide with a hydrophobic compound formed by condensation of propylene oxide with propylene glycol, the molecular weight io of the hydrophobic portion being from 1500 to 1800; (d) condensation products of ethylene oxide with the product formed in the reaction of propylene oxide and ethylenediamine, the molecular weight of the hydrophobic section being 2500 to 3000 and the condensation pro 15 duct contains 40 to 80 wt .-% polyoxyethylene; and (e) mixtures thereof is selected. 5. washing and cleaning agent according to claim 1, characterized in that it (A) 10 to 60% by weight of a builder salt and (B) an intimate mixture which contains as essential components: (i) 2.5 to 12.5% by weight, based on the agent, of a nonionic surfactant and (ii) 0.05 to 0.5% by weight, based on the composition, of a self-emulsifying silicone-based foam suppressant, the nonionic surfactant consisting of (a) condensation products of alkylphenols with 5 to 20 moles of ethylene oxide; 6. washing and cleaning agent according to claim 5, characterized in that the nonionic surfactant is normally liquid and that the self-emulsifying 20 silicone-based foam suppressors containing the condensation product of 300 to 2000 moles of ethylene oxide with a fatty acid. 7. washing and cleaning agent according to claim 5, characterized in that the self-emulsifying foam base 25 silicone-based pusher contains a polysiloxane as emulsifier, which has at least one polyoxyalkylene radical in the polymer. 8. Detergent and cleaning agent according to claim 7, characterized in that the self-emulsifying silicone component is an emulsifier of the formula: 30th RaSiY4_a, where a is 0 or an integer from 1 to 3, R from 35 (a) alkyl groups of 1 to 30 carbon atoms and (b) Groups of the formula: -R '- (OR') b-OR " 40 wherein R 'is an alkylene group having 1 to 6, preferably 2 to 4, carbon atoms, b has a value of 1 to 100 and the symbols R "are each hydrogen, an alkyl, aryl, alkaryl, aralkyl or alkenyl group with up to 20 carbon atoms or a sulfate, sulfonate, phosphate, phospho- 45 nate, borate or isocyanate group or mixtures thereof, is selected and Y is a group of the formula: -OSiR3 55, wherein R has the meaning given above and c has a value from 1 to 200, at least one symbol in the emulsifier of the formula -R '(OR') b-R " 60 where b is large enough to form an emulsifier. 9. washing and cleaning agent according to claim 8, characterized in that the foam suppressant as essential 65 components at least 50 wt .-% of the compound of formula RaSiY4_a, 5 to 45 wt .-% of a polydimethylsiloxane liquid and 0.05 to 5 wt .-% contains silica and that the nonionic surfactant is an aliphatic Alko 10. A method for producing a granular detergent and cleaning agent according to claim 1, characterized in that (A) produces an intimate mixture of a nonionic surfactant and a silicone based foam suppressant in a liquid phase, the intimate mixture (i) a mixture of a normally solid nonionic surfactant with a non-self-emulsifying silicone suppressant and / or (ii) is a mixture of a nonionic surfactant with a self-emulsifying silicone based foam suppressant and the nonionic surfactant is made of (a) condensation products of alkylphenols with 5 to 20 moles of ethylene oxide; (b) condensation products of aliphatic alcohols containing 8 to 22 carbon atoms with 3 to 18 moles of ethylene oxide; (c) condensation products of ethylene oxide with a hydrophobic compound formed by condensation of propylene oxide with propylene glycol, the molecular weight of the hydrophobic portion being from 1500 to 1800; (d) condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, the molecular weight of the hydrophobic section being 2500 to 3000 and the condensation product containing 40 to 80% by weight of polyoxyethylene; and (e) mixtures thereof is selected, and (B) spraying this intimate mixture in the liquid phase onto carrier granules which contain a builder salt, the intimate mixture being present in the agent in an amount of at least 2.5% by weight.