DE2737409A1 - FREE FLOWING PARTICULAR AGENT AS ADDITIVE TO DETERGENT FORMULATIONS - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT HOE 77 / H

Free flowing, particulate agent as an additive to detergent formulations

The invention relates to a free-flowing, particulate Agents as an additive to particulate detergent formulations, which, despite its content of orthophosphoric acid esters, has a good flowability and shelf life.

Due to their chemical constitution, orthophosphoric acid esters have various specific properties that make them effective additives for detergents and cleaning agents do. For the purpose of use are above all: the mono- and diesters, e.g. weighed their tennid effect, üchauiiiroguUorung, antistatic effect and Avivagec-ff ekle really important.

Diο processing dicr.cr ester in Rainigungrjioitte7Lfoi muli ·: - rungrn in amounts of about 0.1-10 Gc.-v; ^ be] η · .Ί let however considerable Ji '. hv ochv / icidgl'citen since the esters are wachsortig or pnstenföi-mig often and d (-Fl; r.lb djo lücr.olfäljigkeit de · ncinigungr.mittolforinulliei'nng becinträclrtigen Auflorder] tend such Rei?..)) igungf; When dissolved, the esters tend to form yerbiickone due to the stickiness of the esters.

The aforementioned disadvantages of the Orthophosphoriiäuvcc-ster liat by preparing the alkali · or alkaline earth salts Tried to overcome acidic orthophosphoric acid ester. A method for the production of such Phosphorsüureectersnlze is described in DT-OS 2 o22 807. He. has however shown that by the conversion of the acidic Orthophosphorsöureor.ter the original properties of the esters are not always retained in their ester salts. aside from that

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BATH ORIGINAL

the production of the ester salts requires an additional process step compared to the free esters, which leads to an increase in the cost of the ester.

Another possibility for improving the flowability of mixtures containing orthophosphoric acid esters is shown in DT-OS 2,337,262.

The subject of DT-OS 2 337 262 is a free-flowing, particulate phosphate ester mixture as an additive to particulate washing machine mixers, which is characterized by a) a content of a homogeneous mixture of compounds of the general form] η R ¹ O (CH ₂ CH ₂ O) _1n PO (OM) ₂

and Z ~ ^Ri ° C ^CII 2 ^CH 2 ⁰ ^ m ^ 2 ^POCM ' ^{in the r1 a} higher alkyl group with 14 to 20 carbon atoms, in 1 to 6 and II an alkali metal or ammonium, the mixture of phosphate esters being a Has a melting and / or softening point of below A5 ° C, and by b) a content of finely divided silicas in amounts of about 5 to 1 per cent, based on the total amount of the phosphate ester.

The production of the above-mentioned mixture can beirpie.lnweir-e done in this way, doO a powdered Ileutraliciei-ungsmlttel and finely divided silica are mixed, and that liquid on the surfaces of the moving mixture acidic mono- and diesters of orthophosphoric acid with neutralization and simultaneous homogeneous distribution in the finely divided silicas are sprayed on.

The disadvantage of the means according to DT-GS 2 337 262 is that that through the use of finely divided silica as a carrier substance for the phosphoric acid ester when using this agent as an additive to 'washing and cleaning agents in the aqueous cleaning liquor or a water-insoluble one in the washing process Component is introduced that is known to have no washing and cleaning effect, but

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on the contrary, it contributes to increased incrustation in the fabric by depositing it on the laundry.

It has now been found, surprisingly, that the disadvantages of the known agents containing orthophosphoric acid esters are eliminated can be overcome when you put the orthophosphoric acid ester on the surface of a powdery prepared in a certain way and anhydrous sodium sulfate or sodium tripolyphosphate or mixtures thereof.

Thus, the invention relates to a free flowing, particulate Agent as an additive to particulate detergent formulations, consisting of components a) and b) im Weight ratio of about 0.05-1: 1, with component a) being a primary and / or secondary and / or tertiary Orthophosphoric acid ester, the alcoholic component of which is an aliphatic alcohol with 1-24 C atoms, is the reaction product of a fatty alcohol with 2-3o mol of ethylene oxide, phenol or the reaction product of a mono-, di- or trialkylphenol, containing 7-2o carbon atoms, with A-2o mol of ethylene oxide and v / obei component b) is a powdery, anhydrous sodium sulfate or sodium tripolyphosphate or mixtures of these salts with a bulk density of not more than 500 g / liter, the particles of which are sprayed on the surface with the liquid or molten component a).

According to a preferred embodiment of the invention, the weight ratio of component a) to component b) is 0.1 to 1 and the weight ratio of sodium sulfate to sodium tripolyphosphate in the mixture 1 to 99.

Orthophosphoric acid esters suitable as component a) for the purposes of the invention in particular a mixture of primary and secondary orthophosphoric acid esters of straight chain

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gene fatty alcohols with 10 -24 carbon atoms or straight-chain fatty alcohol ethoxylates with 2-5 mol of ethylene oxide and 1o-24 carbon atoms or a mixture of primary orthophosphoric acid esters of straight-chain fatty alcohols with 1o-24 carbon atoms or straight-chain fatty alcohol ethoxylates with 2-5 moles of ethylene oxide and 1o-24 carbon atoms.

Further preferred features of the agent according to the invention are that the bulk weights of the sodium sulfate, of sodium tripolyphosphate or the corresponding mixtures 2oo to 6oo g / liter and the particle size distribution of the aforementioned salts or their mixtures according to the Tyler Standard Sieve Analysis Scale corresponds to the following values:

Sieve residue 0 until 1 Gew? O on 12th Mesh η 1 until 2 Ge \ i% on 16 Mesh η 2 until 3 Gew $ 6 on 2o Mesh η 15th until 35 Weight% on 35 Mesh η 75 until 95 Gew? 4 on 1oo Mesh η 95 until 1oo Weight% on <1oo Mesh

Sodium sulfate or sodium tripolyphosphate, which is the required in terms of bulk density and grain size distribution Values can be met in a known manner, e.g. by atomizing the molten salt hydrates and drying in the hot gas stream can be obtained.

Finally, the invention relates to detergent compositions which essentially contain organic surfactants and builder salts and by adding the above-described free-flowing, particulate agent in an amount of about 0.1 to 50% by weight are marked.

The preparation of the agent according to the invention can, for example take place in such a way that component b) is equipped with rotating mixing tools or in mixing units

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a rotating mixing drum, for example the free-fall mixer, and the liquid or liquefied orthophosphoric acid ester is sprayed onto component b). It is also possible to use mixing units that work according to the eddy current method. If the phosphoric acid esters are not liquid under normal conditions, it is necessary to liquefy them in a melting vessel before spraying. Technical mixtures of orthophosphoric acid esters, such as those obtained in the esterification of polyphosphoric acids with alcohols or in the reaction of P ₂ ⁰ C ro with alcohols, are also suitable as component a).

The advantages of the agents according to the invention compared to Relevant known means are on the one hand in the simpler manufacturing process and on the other hand in the use a carrier salt useful for the washing process for the orthophosphoric acid ester to behold. The good storability and riosafability of the funds is assumed as a matter of course .

Example «play 1-15

In a free-fall mixer, light Na ₀ SO prepared in a hot spray tower. filled with a bulk density of AAo g / liter. According to the Tylor S standard sieve analysis scale, the _{Na 2 SO ^ had the following particle size distribution:}

Sieve residue 0.1 Weight% on 12th Mesh Il 1.0 Cew # on 16 Mesh ti 2.7 Weight% on 2o Mesh Il 17.0 Gew? Ö on 35 Mesh H 78.0 Gew? 4 on 1oo Mesh It

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At the same time, a mixture of the primary and secondary orthophosphoric acid ester of a straight-chain fatty alcohol ethoxylate with 16-20 carbon atoms in the alcohol and 2 moles of ethylene oxide was melted in a melting vessel at a temperature of 75.degree. In the fluidized by the free-fall mixer Na ₂ SO ^, the liquefied pressurized ester was sprayed through a single-fluid nozzle to the Na ₂ SO ^. The quantities of ester and Na ₂ SO ^ used and the bulk weight of the product obtained are shown in Table 1. In each case, a product with good storability and flowability was obtained. Even after a storage time of 2 months, the product did not show any formation of Klurapen «

Example 16

The procedure was analogous to Example 1, _{except that instead of Na 2} SOr, light sodium tripolyphosphate (NTPP) was used. The bulk weight of the NTFP was 300 g / liter. The sieve analysis according to the Tyler standard sieve analysis scale resulted in the following values:

Sieve residue
(GewSO NTPP 4 ester Mesh NTPP 6.3 0.2 12.0 12th 1.0 29.9 16 2.0 01.2 2o 29.3 99.7 35 87.5 1oo, o 1oo 1oo, o <1oo

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Example 17

The procedure was analogous to Example 1, but instead of Na ₂ SO ^ a homogeneous powder of NTPP and Na ₂ SO ^ in a ratio of 1: 1 was used. The bulk density of the homogeneous powder was 400 g / liter and the sieve analysis gave the following values according to the Tyler standard sieve analysis scale:

Sieve residue NTPP / Na ^ O ^ / ester Mesh (Wt%) 5.8 NTPP / Na ₂ S0 ₄ 12.4 0.4 19.2 12th 1.1 79.2 16 2.2 99.8 2o 2o, 5 1oo, o 35 89.3 1oo 1oo, o <1oo

The amounts of salt presented in Examples 1-17 that were sprayed on Amounts of phosphoric acid ester * and the bulk weights of the ester / salt mixtures are shown in Table 1.

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T - 1o - 2737409 submitted A B E L L E 1 Amount of salt sprayed on example Amount of phosphorus Bulk weight No. kg acid ester the ester / 1o kg Salzini schung 1o 0.5 g / l 1 1o 1.0 47o 2 1o 1.5 49o 3 1o 2.0 48o 4th 1o 2.5 49o 5 1o 3.0 46o 6th 1o 3.5 46o 7th 1o 4.0 44o 8th 1o 4.5 45o 9 1o 5.0 44o 1o 1o 5.5 44o 11 1o 6.0 44o 12th 1o 8.0 44o 13th 1o 9.0 46o 14th 5 10.0 46o 15th 5 4.0 46o 16 2.5 51 ο 17th 4oo

The flowability of the products prepared according to Examples 1-17 as a measure of the processability of the starting products To be able to assess, 2oo ml of powder were emptied from a height of 2o cm on a measuring sheet and from the the diameter (D) and height (H) of the cone formed. The following results were obtained in accordance with Table 2: confirm the good flowability of the mixtures obtained.

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TABLE 2

example

Ratio D: H

1-15
16
17th

14.6: 3.2 15: 2.7 15: 2.6

Example 18 (comparative example)

The procedure was analogous to Example 1, but instead of light NapSO »normal Na ₂ SO ^ with a bulk density of 142o g / l was used. The trickle test of this product gave a D: H ratio of 12.5: 4.8. Siebanaly.se of the product according to the Tyler-Standard-Sj.ebanalysen-Scale also showed the following values:

Sieve residue

Il It Il Il Il

O Gew9o on

O Gew? £ on

3.1 Ge \ i%

1o, 5 wt #> on

73.5 QeW) O on

100.0% by weight

12 mesh 16 mesh 2o mesh 35 mesh

1oo mesh 1oo mesh

After spraying 20 % by weight of phosphoric acid ester onto the Na 2 SO 3, a lump-forming mass with a bulk density of 117 g / l was obtained, which turned out to be unsuitable for processing in detergent formulations. In the trickle test, the lump-forming mass gave a D: H ratio of 13: 3.8.

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Claims (8)

HOECHST AKTIENGESELLSCHAFT HOE 77 / H 034 patent claims 1. Free flowing particulate agent as an additive to particulate Y / ash agent formulations, consisting of from components a) and b) in a weight ratio of about 0.05-1: 1, with component a) being a primary and / or secondary and / or tertiary orthophosphoric acid ester, the alcoholic component of which is a aliphatic alcohol with 1-24 carbon atoms, the reaction product of a fatty alcohol with 2-3o mol of ethylene oxide, Phenol or the reaction product of a mono-, di- or trialkylphenol, containing 7-2o C atoms, with 4-2o mol Is ethylene oxide and where component b) is a powdered, anhydrous sodium sulfate or sodium tripolyphosphate or mixtures of these salts with a bulk density of at most 500 g / liter, the particles of which are sprayed on the surface with the liquid or molten component a). 2. Means according to claim 1, characterized in that the weight ratio of components a) and b) is 0.1 to 1. 3. Composition according to claim 1 or 2, characterized in that component a) is a mixture of primary and secondary orthophosphoric acid esters of straight-chain fatty alcohols with 1o-24 carbon atoms or straight-chain fatty alcohol ethoxylates with 2-5 moles of ethylene oxide and 1o-24 carbon atoms or a mixture of primary orthophosphoric acid esters of straight-chain fatty alcohols with 10 -24 carbon atoms or straight-chain fatty alcohol ethoxylates with 2-5. Moles of ethylene oxide and 1o-24 carbon atoms. - 2 909808/0554 ORIGINAL INSPECTED 4. Means according to claim 1-3 » characterized in that the bulk weights of sodium sulfate, sodium tripolyphosphate or the corresponding mixtures are 2oo to 6oo g / liter. 5. Means according to claim 1-4, characterized in that the grain size distribution of the sodium sulfate used as component b), sodium tripolyphosphate or the corresponding mixtures according to the TyIer standard sieve analysis scale corresponds to the following fourth: Sieve residue O until 1 Weight% on 12th Mesh η 1 until 2 Weight% on 16 dd η 2 until 3 Ge \ i% on 2o tr η 15th until 35 Weight% on 35 π π 75 until 95 Weight% on 1oo ti "95 to 100 % by weight on <100" 6. Means according to claim 1-5, characterized in that the sodium sulfate or the sodium tripolyphosphate and the corresponding Geciische were prepared by atomizing the molten salt hydrates and drying in a hot gas stream. 7. Composition according to claim 1-6, characterized in that the weight ratio of sodium sulfate to sodium tripolyphosphate in the mixture is 1 to 99. 8. detergent composition containing essentially organic surfactants and builder salts, characterized by an addition of the agent according to claims 1-7 in an amount of about 0.1 to 50% by weight. - 3 909808/0554