DE2536594A1 - CARRIER CORES FOR NON-ionic DETERGENTS - Google Patents

Description

DR. JUR. DIM-CHEM. WALTER SE !!. ,. _JOT "

ALFRto HOoTiINbR R Aug. 1975

DR. JUR. DIK.-CHiM. H.-J. WOLFF DR. JUk. HANS ChK. AX

623 FRANKFURT AM MAIN-HOCHS7

AOElONSIRASSt 58

Our no. 20 O83 Ka / La

Procter & Gamble ETC Strombeek-Bever / Belgium

Carrier grains for nonionic detergents

The present invention relates to spray-dried carrier granules suitable for containing organic detergents as well as processes for their production. In particular, the invention relates to the production of spray-dried Carrier granules, which have a regulated density and which are capable of being an organic nonionic To hold detergent.

Detergent compositions intended for cleaning soiled Laundry intended are generally referred to as heavy duty detergent compositions. Typically, such mixtures contain soap or a organic synthetic detergent, a builder for complex binding or other removal of hardness ions, such as they occur in the water and, if desired, other components, e.g. alkali metal silicate, sodium sulfate, bleach etc. Most builder-containing ash compositions v / earth produced in solid granular form. A process used in the detergent industry to produce such granular builder-containing Y / ash compositions are good known, provides to form an aqueous slurry of most or all of the components of the composition and then spray-dry the sludge to form grains.

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Builder detergent compositions; wio them currently widely used, generally contain a water-soluble organic anionic detergent as Main component for dirt removal. Such detergent compositions v / earth applied in removing various types of stains. Your ability to remove However, grease and oil stains are somewhat limited. Such a deficiency is particularly evident when using polyester fabrics with various grease and oil stains in aqueous washing baths getting washed.

Organic nonionic detergents are known to be particularly effective at removing grease and oil stains. Although these nonionic detergents have considerable performance in this regard, detergent compositions are the latter than the larger dirt-removing one Component included, has not become commercially available to a significant extent. Various disadvantages regarding Processing and performance have the introduction of a composition based on non-ionic detergents. For example, certain organic nonionic detergents are composed of relatively volatile components; aqueous slurries containing such components in a contain significant amounts, lead to unacceptable emission problems during spray drying.

To solve the problems associated with incorporating a nonionic detergent in a laundry detergent composition Tests have been carried out using various process techniques. A field of processing technology, Considerable attention has been paid to the use of carrier granules for nonionics Detergents. Various carrier grains have been proposed which are said to be suitable for placing an organic on it Spray on nonionic detergent. Incorporation of the nonionic detergent in the

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ORIGINAL INSPECTED.

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Detergent composition eliminates the need to have the nonionic detergent present as part of the aqueous sludge which is then spray dried. While such a method eliminates the undesirable emissions problems, there are still several disadvantages. This is because, even after a carrier loaded with nonionic detergent has been formed, it is still necessary to mix other conventional components of detergent compositions with this carrier. Obviously, additional processing steps are necessary as a result. In addition, various carriers have been proposed for such use which, in turn, add undesirable loads to the detergent composition. Y / ährorA η? - !? " ¹ If the carrier material performs the necessary function of serving as a means of incorporating the nonionic detergent into the composition, in many cases it does not act as a soil removing agent.

It would be desirable to form a carrier granule composed of the various components of a spray dried detergent composition. If it is possible to use an aqueous sludge containing the basic components of a detergent composition (excluding the detergent), i.e. a matrix of a detergent composition, sprühzutrock- nen and then spraying the nonionic detergent onto the spray-dried matrix would avoid the above mentioned problems v / ground. Unfortunately, the formation of a spray-dried support matrix in this way has created processing difficulties. It has been found that the density of such spray dried grains is unacceptably high. If one takes into account the fact that a non-ionic dopant has to be sprayed onto such grains, it is found that the loaded material finally obtained will have a particularly high density and is therefore unusable.

A relatively low and even density is achieved by

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ORIGINAL INSPECTEC

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Housewives preferred. The appropriate density of spray-dried Detergent composition is made up of the following Reasons necessary: The consumer usually receives a Product measured by volume based on instructions; there is a potential segregation problem if components of different density are mixed with the spray-dried composition; further is a correct filling of standardized packs depending on volume controls.

It has now been found that the addition of a phosphate ester, as defined below, to the aqueous slurry is essentially free of organic detergent Composition prior to spray drying has a significant effect on the density of the resulting spray dried granules having. The spray-dried grains obtained have a low density and are suitable as carrier granules for spraying a nonionic detergent.

The aim of the invention is therefore to produce spray-dried carrier grains.

Another object of the invention is to produce spray-dried carrier granules of controlled density.

These and other goals are identified by the following description and the examples obvious.

In the context of the present invention, unless otherwise stated, all statements refer to Percentages and ratios% by weight and ratios by weight.

The carrier granules according to the present invention are obtained by a spray drying process. The spray drying aqueous slurries is a well known drying method. It becomes an aqueous slurry with a temperature

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of 4Ό to 100 ^J C of the whole or part of the Waschmittelzusaimncnsetzung formed and atomized in the head of a spray drying "· .. turmes. According to a spray drying procedure, hot air, ie air with a temperature in the range from 180 to 380 ° 0, is introduced at the base of the tower. As the hot air rises, it comes into contact with the deaf droplets, expelling essentially all of the free water. The resulting carrier grains are collected at the base of the tower, while the air laden with tea leaves the upper end. Another method of spray drying is to introduce the hot air together with the sprayed droplets at the same end of the tower. Optionally, an inert gas is injected into the aqueous slurry to aid in reducing the density of the grains. All of these known spray drying processes can utilize the advantages of the present invention as described below.

The spray-dried carrier grains according to the present invention. Invention contain 0.05 % to 1.5 % of a phosphate ester, 30 ^f ; up to 70 % of an alkaline inorganic builder salt, 2> · to 10 % of an alkali metal silicate and 10 % to 50 % of an alkali metal sulfate. A conventional spray drying process as described above is used to form carrier granules which have a density of 300 g / l to 500 g / l.

Phosphate esters according to the present invention have the following general formula

0
EO-P-OH,

Or

R is hydrogen or R. (OC ₂ H ^) OH, wherein

R. a straight or branched chain alkyl or Alkenyl group with 8 to 22 carbon atoms, if " η - 0, and from 2 to 22 carbon atoms,

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if η = 1 to 50 means, symbolizes, with with the proviso that no more than one radical R is hydrogen.

The phosphate ester can be a mixture of different esters and can be formed with a base such as sodium hydroxide the corresponding salts must be neutralized, which are also useful. In the context of the present invention, the Term "phosphate ester" to denote acidic mono- and dialkyl, mono- and dialkenyl, ethoxylated mono- and Dialkyl and ethoxylated mono- and dialkenyl phosphates, their alkali metal salts including sodium and potassium salts or ammonium and substituted ammonium salts are used.

Commercially available forms of the phosphate esters can contain small amounts of condensed phosphate such as pyrophosphates, polyphosphates, and mono- and dialkyl orthophosphates. Smaller amounts, for example up to 5 %, of the trialkyl phosphate esters can also be formed during the preparation of the mono- and dialkyl phosphate esters.

Typical acidic alkyl phosphates used in Suitable for the purposes of the invention are acidic mono- or dipalmityl phosphate, acidic dis te aryl phosphate and the Mono- or disodium salts thereof. Certain alkenyl acid phosphates and their salts can also be used, e.g., dioleyl acid phosphate.

The acidic alkyl phosphates are made by reacting a primary aliphatic alcohol with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and phosphoric acid manufactured. Such reactions are known per se. Unsaturated aliphatic alcohols, which have the same number of carbon atoms as oleyl alcohol, with a phosphoric acid to form an acidic one

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Alkenylphospliats implemented. Secondary saturated or unsaturated Aliphatic ^ alcohols with the required number of carbon atoms are formed with a phosphoric acid branched chain phosphate ester brought to implementation.

Acid, ethoxylated alkyl or alkenyl phosphates are made by phosphate removal, carried out in a known manner, of compounds of the formula R ^ OG ^^ OH, in which R ^ has 2 to 22 carbon atoms, preferably 12 to 16 carbon atoms, and η = 1 to 30, 'preferably 1 to 10, means prepared Examples of such materials are the coconut fatty alcohol adducts with 6 to 10 moles of ethylene oxide, oleyl alcohol adducts with 10 to 20 moles of ethylene oxide, tridecyl alcohol adducts with 10 to 20 moles of ethylene oxide and stearyl alcohol adducts with up to 30 moles of ethylene oxide. Preferably, each R group of the phosphate ester is R ₁ (OC ₂ H ^ X

Examples of phosphating agents used in the manufacture The phosphate esters used are polyphosphoric acid and orthophosphoric acid. Other means and mixtures of funds can be used. In GB-PS No. 1,159,6 ^ Corresponding processes for the preparation of the phosphate esters according to the present invention are described.

The phosphate esters are incorporated into the aqueous slurry in an amount ranging from 0.05 % to 1.5%, preferably 0.25 % to 0.6 %, on a dry weight basis. An amount of phosphate ester below 0.05 % has no noticeable effect on the density of the spray-dried carrier grains. An amount greater than 1.5% has no further effect on reducing the density of the spray-dried carrier granules and is therefore avoided.

The alkaline inorganic detergent builder is added to the aqueous slurry in an amount ranging from 30 % to 70 ^c / j, preferably from 40 % to 65%, on dry weight

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basis incorporated. Examples of suitable water-soluble, inorganic alkaline detergent builder salts which are useful in the context of the invention are the alkali metal carbonates, phosphates, polyphosphates and bicarbonates. Specific examples of such salts are sodium and potassium bicarbonate, carbonate, tripolyphosphate and pyrophosphate. A particularly preferred detergent builder is sodium tripolyphosphate.

Alkali metal silicate, which has an SiOo: M ₂ O ratio of 3.2: 1 to 1: 1, preferably 1.5: 1 "to 2.5; 1, is added to the aqueous slurry in a proportion of 2 % to 10% %, preferably 3 % to 7 %, on a dry weight basis, incorporated. A particularly preferred alkali metal silicate is sodium silicate.

10% to 50%, preferably 12 % to 40%, on a dry weight basis, of an alkali metal sulfate is also incorporated into the slurry of the present invention. Examples of such sulfates are sodium and potassium sulfate.

The remainder of the slurry contains water. The amount of water contained in the aqueous slurry is primarily determined by the amount required to form a slurry which has a viscosity low enough to facilitate pumping and atomization. As little water as possible is used because it is necessary to remove the latter with drying effort later. However, there must still be enough water to make a slurry that can be pumped and atomized. Generally the water of the slurry will constitute 25 % to 60 % .

Optionally, commonly used components of detergent compositions can be incorporated into the slurry will. For example, foam suppressors,

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lighter, dyes, anti-flocculants and dirt suspending agents can be added in smaller proportions. Such usually added components can also be loaded with, spray dried grains as discussed later.

Small proportions, e.g. below 5%, on a dry weight basis, Organic detergents can be incorporated into the aqueous slurry without departing from the scope of the invention is left. Preferably the slurry is detergent free. This ensures that there will be no emission problems, as with certain nonionics Detergents occurs, and that no other organic detergent is present xSt which would improve the soil removal performance of the nonionic detergent.

The aqueous slurry described above is then spray dried by known techniques to form carrier granules. Spray dried carrier granules according to the invention are substantially dry, ie, they contain less than 15 ° / o water, preferably between 5% and 15% water.

The spray-dried carrier granules described above have a density of 500 g / l to 500 g / l, preferably 350 g / l to 450 g / l. The lower density values are shown with Achieved using an inert gas injection stage. Gas injection is commonly used in the spray drying of detergent compositions applied. It consists of injecting an inert gas, usually air, into the aqueous slurry up to the saturation point, i.e. the point above which the physical stability of the slurry is no longer given. The addition of the phosphate esters according to the invention reduces the density of the grains regardless of whether an inert gas is used aqueous slurry or not. The support matrix given above typically has, if so, a phosphate ester has been omitted, a density of about 600 g / l,

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if they are formed by a spray drying process, which does not use gas injection; the carrier matrix has a density of about 500 g / l if it is gas-injected is formed, and no phosphate ester addition takes place.

The spray-dried carrier granules described above are then loaded with an organic nonionic detergent. An amount of 5 % to 25%, preferably 10 % to 20 %, based on the total loaded grain, of the nonionic detergent is sprayed onto the carrier grains in the usual way.

Water soluble organic nonionic detergents useful in the present invention can to be defined as compounds produced by condensation of alkylene oxide groups (hydrophilic type) with an organic hydrophobic compound, which is more aliphatic or alkyl aromatic Nature can be educated /. The length of the polyoxyalkylene group that will condense with any particular hydrophobic group can easily be tailored to obtain a water-soluble compound which is the desired Has relationship between hydrophilic and hydrophobic elements.

For example, one known class of nonionic organic detergents is on the market under the trade name PLURONIO available. The compounds are formed by the condensation of ethylene oxide with a hydrophobic base, which is formed during the condensation of propylene oxide with propylene glycol. Other suitable nonionic organic Detergents include the polyethylene oxide condensates of alkyl phenols, e.g. the condensation products of alkyl phenols with an alkyl group containing about 6 to 12 carbon atoms more straight-chain or has a branched-chain configuration, with Ethylene oxide, the ethylene oxide being present in amounts corresponding to 5 to 25 moles of ethylene oxide per mole of alkylphenol.

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The water-soluble condensation products aliphatic Alcohols with 8 to 22 carbon atoms in either straight chain or branched chain configuration with ethylene oxide, e.g., coconut alcohol / ethylene oxide condensate of 5 "to 30 moles of ethylene oxide per mole of coconut alcohol, with the coconut Nut alcohol fraction having 10 to 14 carbon atoms are also useful nonionic detergents and will be preferred within the scope of the invention.

V / as ser-insoluble organic nonionic detergents, ■ as described in the Luxembourg patent ITr. 69 256 described v / earth, can also be used v / earth. These detergents have the general formula R (OG H ~) OH, wherein R is an alkyl or alkenyl group with 8 to 22 carbon atoms or an alkylated or alkenylated phenyl group with 6 to 12 carbon atoms in the alkyl or alkenyl group represents, symbolizes χ = 2 or 3 and η = 1 to 8 means. The hydrophile-lipophile ratio (HIiB), calculated in the von Becker, "Emulsions Theory and Practice", Reinhold Publishing Co., pp. 233 and 248, referenced 7, 'iron is less than 10.0 for such detergents.

Commonly used components of detergent compositions are either added to an aqueous slurry as described above, or with the loaded carrier grains dry mixed. Certain components that cannot tolerate spray-drying treatment, e.g. sodium perborate, are dry mixed with the loaded carrier grains.

The following examples illustrate the invention.

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Example 1: It becomes an aqueous slurry of the following composition on a dry weight basis puts;

Sodium Tripolyphosphate (STPP) 61.5 Sodium Silicate (SiO ₂ : Na ₅ O = 2.0) 6.3

"Sodium sulfate 25,4-phosphate ester * 0.36

Sodium carboxymethyl cellulose (CMC) 0.9. Sodium ethylenediaminetetraacetate 0.3

Miscellaneous Eest.

* = The phosphate ester is a mixture of 80 % acid, ethoxylated ivionoalkyl phosphate and 20 % acid, ethoxylated dialkyl phosphate, in which each compound has 16 carbon atoms in its alkyl groups and an average of 2 ethylene oxide groups.

The slurry contains 4-5 ° / o V / ater. Before atomization in the upper part of a spray drying tower, air is sprayed into the slurry. Hot air is introduced at the bottom of the tower and exits at the top. The resulting spray-dried grains contain 12 % water and have a density of around 350 g / l. Grains formed under the same conditions, apart from the addition of the phosphate ester, have a density of about 525 g / l

A nonionic detergent (a 50:50 mixture of C ^ and CLc alcohols ethoxylated with an average of 4 moles of ethylene oxide) is then sprayed onto the carrier granules, with loaded carrier granules being obtained which contain 18 % contain non-ionic detergent.

When used under typical washing conditions, the Mixture excellent cleaning performance and is particularly capable of removing grease and oil stains,

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ORIGINAL f ^ SPECTEp

Example 2: Example 1 is repeated using acid monostearyl phosphate, acid monooleyl phosphate, acid monostearyl (EO) ^, - phosphate, acid monostearyl (EO ^ rs-phosphate, acid monopropyl (EO) ^ phosphate and acid distearyl phosphate using the same amounts, essentially the same results are obtained.

Example 2: It becomes example 1 without the air injection stage repeated; the resulting spray-dried grains have a density of around 470 g / l.

Example 4-: Replaced in the context of the example the sodium tripolyphosphate by sodium carbonate, so be obtained essentially the same results.

Example 5: The effect of different amounts of Phosphate ester on density is illustrated below. Example 1 is repeated using different amounts of phosphate ester. The densities of the emerging Grains are as follows:

Phosphate ester %: Density (g / l):

0 525

0.15 380

0.25 "360

0.36 350

0.70 355 1.00

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Claims (14)

Patent claims: E 89 • Λύ carrier grains with a density of 300 g / l to 500 g / l, which are produced by a spray-drying process and • are suitable for holding an organic detergent, characterized in that they essentially consist of: (a) 30 % to 70 % of a water-soluble alkaline inorganic builder salt, (b) 2 % to 10 % of an alkali metal silicate with a SiOp: MpO ratio of 3.2: 1 to 1: 1, (c) 10% to 50 ° / o of an alkali metal sulfate, and (d) 0.05 % to 1.5 % of a phosphate ester having the formula 0
RO-P-OH, OR wherein
R is hydrogen or R ₁ (OC ₂ H ^) _n OH, where R ^ a straight or branched chain alkyl or Alkenyl group with 8 to 22 carbon atoms, if η = 0, and with 2 to 22 carbon atoms, if η = 1 to 30, symbolizes with the proviso that no more than one radical R is hydrogen,
exist. 2. Carrier grains according to claim 1, characterized in that they contain 0.25% ^ is 0 _} 6 % of the phosphate ester. 3 · - carrier grains according to claim 2, characterized in that each radical R of the phosphate ester is R ₁ (OC ₂ H ^) _n OH and η = Ί to 30. 4-. Carrier grains according to Claim 3, characterized in that that η = 1 to 10 and R. contains 12 to 16 carbon atoms . G-O 98 10/0991 E 89 5. Carrier grains according to claim 4, characterized in that they contain 40% to 65 % of the alkaline inorganic framework salt, 3 % to 7 # of the alkali metal silicate and 12% to 40% of the alkali metal sulfate. 6. carrier grains according to claim 5, characterized in that that the alkaline inorganic builder salt sodium tripolyphosxjhas is. 7. carrier grains according to claim 6, characterized in that the density is 350 g / l to 450 g / l. 8. Carrier grains according to claim 1, characterized in that the carrier grain additionally contains 5. % To 25%, based on the total l'ori, "ines organic nonionic detergent. 9. Carrier grains according to claim 7, characterized in that the carrier grain additionally contains 5 % to 25%, based on the total grain, of an organic nonionic detergent. 10. Process for the production of spray-dried carrier grains, which have a density of 300 g / l to 500 g / l, characterized in that one (a) forms an aqueous slurry? consisting essentially, on a dry weight basis, of (1) 30% to 70 % of a water-soluble alkaline inorganic builder salt, (2) 2 % to 10 % of an alkali metal silicate with an SiO ₂ : MgO ratio of 3.2: 1 to 1: 1, (3) 10 % to 50% of an alkali metal sulfate, (4) 0.05 % to 1.5 % of a phosphate ester of the formula 0
EO-P-OH, Or where R is hydrogen or R. (OCpH ^) OH, where R ^ - 15 - GG98 10/0931 E 89 a straight or branched chain alkyl or alkenyl group with 8 to 22 carbon atoms, if η = 0, and 2 to 22 carbon atoms, if η = 1 to 30, means, with the proviso that no more than one R is hydrogen and (5) the remainder is water, and (b) spray drying the slurry to form the carrier granules. 11. The method according to claim 10, characterized in that an additional 5 % to 25 %, based on the total weight of organic nonionic detergent, is sprayed onto the spray-dried carrier grains. 12. The method according to claim 11, characterized in that a phosphate ester is used means and η = 1 to 30. a phosphate ester is used in which each residue is RR ₁ (OC ₂ Hj,) OH 13. The method according to claim 12, characterized in that a phosphate ester is used in which η = 1 to 10 and R _{1 contains} 12 to 16 carbon atoms. 14. The method according to claim 13, characterized in that in addition to the aqueous slurry prior to spray drying Injected gas. For: Procter & Gamble ETC. St rombeek-Bever // Belgium Dr. H. J. VJdIf f lawyer - 16 - 0 9 810 / Π 9 91 60 98 10/099 1