DE2432523A1 - PROCESS FOR IMPROVING THE PROPERTIES OF GRILLY DETERGENTS AND CLEANING AGENTS - Google Patents

Description

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HENKEL— KERN - FEILER - HÄNZEL — MÜLLER

DR. PHIL. DIPL.-ING. DR. RER. NAT. DIPL.-ING. DIPL.-ING.

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TMLKFON: (OS ID 613T97. 66 .1O 91- ·): HiOMr-UCMQn WtCHSELBANK MUNICH NO. 318-85

ThLlCiRAMMK: ILLIPSOID MONCH! -N D-8000 MUNCHtN VU POSTAL CHECK: MCHN 1621 47-809

Lion Fat & Oil Co., Ltd.

Tokyo, Japan ^ 4. Juti 1974

Process for improving the properties of granular detergents and cleaning agents

The invention relates to a process for improving the properties of a conventional spray-drying process granular detergents and cleaning agents produced. This process aims to make the concerned grainy Detergents and cleaning agents have excellent flowability and resistance to Consolidation due to hygroscopicity and (stable) durability. At the same time, this should perfume added to such detergents and cleaning agents is stabilized will.

The majority of commercially available granular detergents and cleaning agents are produced using a spray-drying process suitable for mass production, i.e. a process in which sprayed particles of a slurried The material is dried into granules by briefly bringing it into contact with a parallel or counter-rotating stream of hot air are produced. Of these granular laundry detergents and cleaning products, those are for household use after their preparation by spray drying mixed with a little liquid perfume by spraying. That kind of manufactured detergents and cleaning agents for household use

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need suffer from the fact that the odorous substances or fragrances added to them largely in a relatively short time until disappear completely.

The usual granular detergents and cleaning agents of the described Although type are sufficiently soluble in water, they do not have sufficient stability against a hygroscopic solidification, i.e. they cannot be stored in a stable manner over long periods of time. Under "Stability against hygroscopic solidification "the property of the detergent granules is not to be understood solidify by absorbing moisture from the air or · to bake together. In other words, anti-hygroscopic solidification absorbs excellently stable, granular detergent and cleaning agent hardly or never moisture from the air and retains its granular Form without caking over a long period of time. The usual granular detergents and cleaning agents have one of these poor stability against hygroscopic solidification, that they are already in one pretty soon after packaging Cardboard box or a cardboard drum caking due to moisture absorption. Even in the event that such a Solidification is controlled somewhat, the flowability of the detergent granules is poor per se, making the removal from the storage container or packing in a cardboard box or a cardboard drum difficult will.

To eliminate these disadvantages, it is known, for example, from US Pat. No. 3,472,748, to use a granular detergent and cleaning agent by adding a surface-active agent and from water to inorganic builders that can be used in detergents and cleaning agents, such as sodium tripolyphosphate, soda ash and the like, and blending them

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Manufacture components in a ribbon (screw) mixer. According to the teachings given above, the washing and Detergent granules evenly on their surface with tripolyphosphate, soda ash or sodium sulfate be coated. Even with this known method, however, it is not possible to obtain sufficiently granulated detergents. and manufacture detergents. In addition, this known method does not contribute to the long-term Improving the fragrance of granular detergents and cleaning agents for household use.

The invention was based on the object of providing a method for producing an improved one over a longer period of time Flowability, stability against hygroscopic solidification and odorous or fragrance-containing granular To create detergents and cleaning agents.

The invention thus relates to a method for improving the properties of granular detergents and cleaning agents, which is characterized in that the surface of each granule of a conventional granular detergent and cleaning agent which has been prepared by spray drying with (continually) turning the granular material is, moistened with a short-chain alcohol or a liquid perfume as a binder and that one the as a result, detergent granules made sufficiently sticky on their surface with a special, powdery metal soap applied, whereby the powdery metal soap on the surface of the detergent granules is made to stick.

More precisely, the (mainly by spraying subsequent) application of the short-chain alcohol to the granular

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-in detergents and cleaning agents to make the surface of the washing and cleaning agent granules so sticky that sufficient adhesion of the powdered metal soap to the granule surface is made possible. The application of the liquid perfume to the granular detergent and cleaning agent (also by spraying) also serves on the one hand to enable the powdered metal soap to adhere sufficiently to the granule surface and on the other hand to stabilize the odor and fragrance of the granular detergent and cleaning agent. If water were used instead of the short-chain alcohol or the liquid perfume to coat the detergent granules with the powdered metal soap as a binder, the desired success could not be achieved because the metal soap has such a poor affinity for water that a uniform coating of the Surface of the detergent granules of the powdered metal soap could not be reached. Replacing the powdered metal soap with inorganic builders that can be used in detergents and cleaning agents, such as sodium tripolyphosphate and sodium sulfate, would also not lead to the desired success. A wide variety of attempts have already been made to ensure the fragrance or odor of granular detergents and cleaning agents, but none of these attempts was carried out in the context of rolling granulation for film coating, as is carried out according to the invention. Furthermore, none of these attempts has proven to be suitable for eliminating the disadvantages outlined at the same time.

The success of the method according to the invention is based on the use of a short-chain alcohol or of liquid Perfume as a binder and the use of a powder

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deform metal soap as a coating agent. The reason why these two measures lead to the desired success remains to be clarified. Presumably, however, the success of the method according to the invention is based on a synergistic interaction of the water insolubility and the water repellency of the powdered metal soap and a suitable affinity of the short-chain alcohol or liquid perfume for the metal soap. This synergistic interaction makes it possible for the powdered metal soap to adhere uniformly with the formation of a coating on the surface of the detergent granules. In particular when a liquid perfume is used as a binder, the perfume in question is distributed inside the product, while at the same time ensuring the desired scent or smell of the product for a long time due to the surface coating. If the detergent and cleaning agent in question then disintegrates during use, its scent or smell becomes even stronger. Since the surface of each washing and cleaning agent granule is uniformly coated with a metal soap, the granular washing and cleaning agent that can be produced according to the invention has improved flowability and stability against hygroscopic solidification.

According to the invention, monohydric and polyhydric alcohols having 1 to 4 carbon atoms can be used as short-chain alcohols be used. Such alcohols can be used either individually or in combination with one another. Per 100 parts by weight of granular detergent and cleaning agent should advantageously be 0.1 to 1 part by weight of short-chain alcohol be used. If less than 0.1 part by weight of short-chain alcohol is used, the surface of the Detergent and cleaning agent granules not enough

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moisturizes. The use of more than 1 part by weight is shorter Alcohol is therefore not desired, as additional measures, such as drying and recovering the alcohol, will be required. According to the invention, any liquid perfume can usually be used for granular detergents and cleaning agents Home perfume can be used as long as there is a suitable affinity to it which has metallic soap to be applied to the layer of perfume adhering to the granular detergent and cleaning agent. Suitable perfumes belong, for example, to the terpene series (linalool, terpineol, geraniol), to the phenol series (eugenol) or to the series of aromatic perfume alcohols (phenylethyl alcohol, Benzyl alcohol). Such liquid perfumes can either be used alone or in combination with one another be used. Expediently 0.05 to 1 part by weight is used per 100 parts by weight of granular detergent * and cleaning agent used liquid perfume.

In the case of the powdered metal soap which can be used according to the invention it is a calcium or magnesium salt of a saturated fatty acid with an average particle diameter of less than 100 u. In the event that a short-chain alcohol is used as a binder, it is required to use a fatty acid salt of a fatty acid having 16 to 20 carbon atoms. Using a Powdered metal soap with an average particle diameter of over 100 ii is not advisable, as this is used for To guarantee the desired success, not only would larger quantities of powdered metal soap have to be used, but also the appearance of the product obtained would be impaired. The aforementioned powdered metal soaps can be used either alone or in combination with each other. Per 100 parts by weight of granular detergent

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and detergent should preferably be 0.3 to (η) 15 part (s) by weight, preferably 0.5 "to 10 part (s) by weight powdered metal soap can be used. Using the surface of the detergent granules can be reduced by less than 0.3 part by weight of powdered metal soap do not cover evenly. If more than 15 parts by weight of powdered metal soap is used this occurs in excess and goes on dissolving the granular detergent and cleaning agent product obtained - because it is insoluble - turns into an undesirable white emulsion.

That is the starting material for the process according to the invention Formative granular detergents and cleaning agents do not have to consist of a very specific detergent and cleaning agent exist as long as it is only in the form of conventional hollow granules, as they are by spraying and drying a washing and Cleaning agent composition are obtained. In other words, there is a starting material at Granular detergent and cleaning agent used in accordance with the invention and composed of a surface-active agent, an inorganic or organic builder, an optical brightener and other additives.

Any known rolling devices can be used within the scope of the method according to the invention. So can For example, the tumbler commonly used in the detergent and cleaning agent industry for adding perfumes can be used. The addition of the short-chain alcohol or liquid perfume can be in any Manner, as long as an even addition is guaranteed. Regardless, is particularly suitable good a spray process, especially an atomization process, with a solid cone nozzle, a hollow

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cone nozzle and the like works. Also applying the powdered metal soap can be done in the usual known manner, provided that a uniform coating of the washing and detergent granules is guaranteed. The powdered metal soap can be applied, for example, by Sprinkling the granules done.

The following are the individual measures for the invention Production of improved granular detergents and cleaning agents explained in more detail. Of course leave the individual measures change in the most varied of ways.

When carrying out the method according to the invention, the hollow-grain detergent and cleaning agent starting material is first used filled in a roller drum. The granular detergent and cleaning agent in the drum is then removed atomize while rotating the drum in a suitable manner, for example by spraying with a suitable amount short-chain alcohol or liquid perfumes. When all the detergent and cleaning agent granules are on the surface so much short-chain alcohol or liquid perfume has stuck to it that the individual granules have become damp, the damp detergent granules are suitably, for example by sprinkling, evenly applied with a predetermined amount of a powdery metal soap. The internal temperature Of course, the roller drum must not be so high that the short-chain alcohol or the liquid Perfume boil or evaporate. If one consequently to carry out the method according to the invention as The starting material is a granular detergent and cleaning agent immediately after its manufacture by spray drying

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used and this is still so warm that the short-chain alcohol to be applied or the alcohol to be applied to it liquid perfume could boil or evaporate, it must be done before the short-chain alcohol is applied or the liquid perfume.

The method according to the invention can be extremely simple Continuously, so it is good for mass production.

The following examples are intended to illustrate the process according to the invention in more detail.

example 1

100 parts by weight of a hollow-grain detergent and cleaning agent, that by spray drying a mixture of the following composition:

linear sodium alkylbenzenesulfonate 17 g

Sodium tripolyphosphate 25 g

Sodium silicate 10 g

Sodium sulfate 38 g whitening agent 0.4 g

Carboxymethyl cellulose 0.6 g

Water 9 g

had been made were placed in a rolling drum. While the drum was being turned, the in detergents and cleaning agents located in the drum are treated with 0.5 part by weight of atomized ethanol in such a way that that the individual detergent granules were moistened evenly. After the washing and

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Detergent granules with the specified amount of ethanol were sufficiently moistened, the individual laundry and cleaning agent granules were sprinkled with 1 part by weight Calcium stearate with a mean particle diameter of less than 20 u with an adhesive layer (the Metal soap). The internal temperature of the roller drum was 35 ° C. in this case.

A review of the flowability and stability against hygroscopic solidification of the granular obtained Detergent and cleaning agent product after standing for 24 hours gave the results given in Table I below Results.

Example 2

In the manner described in Example 1, a granular detergent and cleaning agent product was produced, wherein however, the ethanol has been replaced by a perfume, geraniol.

A check of the flowability and the stability against hygroscopic solidification of the washing and washing machine obtained Detergent product gave the results given in Table I below.

Example 5

In the manner described in Example 1, 100 parts by weight of a hollow-grain detergent and cleaning agent were used of the following composition:

Sodium olefin sulfonate containing 13 to 18 carbon atoms 17 g

Sodium tripolyphosphate 20 g

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Sodium silicate 10 g

Sodium sulfate 43 g whitening agent 0.4 g

Carboxymethyl cellulose 0.6 g

Water 9 g

using 1 part by weight of ethanol as a binder coated with 2 parts by weight of calcium stearate with an average particle diameter of less than 20 μ _{or the like}

Find the results of an investigation of various properties of the detergent product obtained Table I.

Example 4

In the manner described in Example 1, 100 parts by weight of a hollow-grain detergent and cleaning agent were used following composition:

Sodium olefin sulfonate with 15 to 18 carbon atoms 18 g

Sodium tripolyphosphate 20 g

Sodium silicate 10 g

Sodium sulfate 42 g

Brightener 0.4 g

Carboxymethyl cellulose 0.6 g

Water 9 g

using 0.2 part by weight of a perfume, viz a mixture of geraniol and linalool in a weight ratio of 1: 1, as a binder with 2 parts by weight of calcium stearate a mean particle diameter of less than 20 ti coated.

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The results of an investigation of certain properties of the detergent and cleaning agent product obtained can be found in Table I below.

Example 5

In the described in Example 1, 100 parts by weight of a hollow granular detergent and cleaning agent of the composition indicated in Example 1 using 1 part by weight of ethanol as a binder with 3 parts by weight of calcium stearate, one of which 20 wt -.% An average particle diameter 50-30 u and 80 wt .-% an average particle diameter of less than 30 had u, coated. The internal temperature of the roller drum was 40 ° C. in the present case.

The results of an investigation of certain properties of the detergent product obtained are compiled in Table I below.

Example 6

In the manner described in Example 1, 100 parts by weight of a hollow-grain detergent and cleaning agent were used Composition given in Example 1 using 0.3 part by weight of ethylene glycol instead of 0.5 part by weight Ethanol (cf. Example 1) as a binder with 1 part by weight of magnesium stearate with an average particle diameter below 10 η (instead of calcium stearate) coated.

The results of an investigation of certain properties of the detergent product obtained are compiled in Table I below.

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Example 7

In the manner described in Example 1, 100 parts by weight were added a hollow-grain detergent and cleaning agent of the following composition:

linear sodium alkylbenzenesulfonate 30 g Sodium sulfate 65 g

Water 5 g

using 0.5 part by weight of methanol as a binder with 2 parts by weight of calcium stearate of a medium Particle diameter of less than 10 u coated.

The results of an investigation of certain properties of the detergent and cleaning agent product obtained are compiled in Table I below.

Example 8

In the manner described in Example 1, 100 parts by weight of a hollow-grain detergent and cleaning agent were used of the following composition:

linear sodium alkylbenzenesulfonate 20 g

Sodium tripolyphosphate 22 g

Sodium silicate 10 g

Sodium sulfate 38 g whitening agent 0.4 g

Carboxymethyl cellulose 0.6 g

Water 9g

using 0.15 part by weight of a perfume, namely a mixture of geraniol and linalool by weight

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ratio 1: 1, as a binder with 3 parts by weight of calcium stearate a mean particle diameter of less than 20 ti coated.

The results of an investigation of certain properties of the detergent and cleaning agent product obtained are in Table I below is compiled.

Example 9

In the manner described in Example 2, the calcium stearate was replaced by magnesium stearate Detergent and cleaning product manufactured. The results of an investigation into certain properties of the obtained detergent and cleaning agent products are in the Table I below compiled.

Example 10

In the manner described in Example 1, 100 parts by weight were the hollow-grain detergent and cleaning agent starting material used in Example 1 using of 0.2 part by weight of a perfume, namely of eugenol, as a binder with 3 parts by weight of calcium stearate an average particle diameter of less than 20 u coated.

The results of an investigation of certain properties of the detergent and cleaning agent product obtained are summarized in the following Table I:

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Table I. Example no.

8 9 10

Flowability *

(Angle of repose) 37 ° 36 ° 35 °. 35 ° 34 ° 38 ° 35 ° 35 ° 37 ° Stability against
hygroscopic

Solidification ** 55342653 Fragrance or odor content *** - 38 - 45 - - 47 38

Remarks:

* The measurement of the flowability took place at a temperature of the sample, ie of the examined detergent and cleaning agent, of 35 ^° C.

** The stability against hygroscopic solidification was determined in such a way that the sample (ie the detergent and cleaning agent product) was ^{left to lie for 24 hours at a temperature of 30 °} C. and a relative humidity of 95%, then through a sieve of one mesh size sieved by 4.7 mm and finally the amount by weight of the sample retained on the sieve was determined.

*** The fragrance or odor content was determined in such a way that the sample (i.e. the detergent and cleaning agent product) was packed in a cardboard box which was packed After cutting open the pouring opening of the cardboard box, stand the sample in a room at normal temperature left and the number of days after packing the sample to reduce the odor and Scent intensity required to half were counted.

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The determination and measurement methods mentioned also apply to the following comparative examples.

Comparative example 1

The hollow-grain detergent and cleaning agent starting material used in Example 1 was left for 24 hours without treatment according to the invention and then examined for its flowability and stability against hygroscopic solidification. The Results are summarized in Table II below.

Comparative example 2

Example 1 was repeated, except that the amount of CAI ciumstearat of 1 part by weight to 2 parts by weight increased, the particle diameter of the calcium stearate to below 10 η lowered and was used instead of the ethanol water. The results of an investigation of certain properties of the hollow-grain detergent and cleaning agent product obtained are compiled in Table II below.

Comparative example 3

Example 1 was repeated, but the calcium stearate by 2 parts by weight of sodium sulfate of a medium Particle diameter of less than 100 u was replaced. The results of an investigation of certain properties of the hollow-grain detergent and cleaning agent product obtained are compiled in Table II below.

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Comparative example 4

Example 1 was repeated, but with the calcium stearate replaced by 2 parts by weight of sodium sulfate and instead of 0.5 part by weight of ethanol 0.2 part by weight of geraniol was used.

The results of an investigation of certain properties of the hollow-grain detergent and cleaning agent product obtained are compiled in Table II below.

Comparative example 5

0.2 part by weight of geraniol became 100 parts by weight of the hollow-grain detergent and cleaning agent raw material used in Example 1 added.

The results of an investigation of certain properties of the detergent and cleaning agent product obtained are in compiled in the following table II:

Table II

Comparative example No.

Flowability * (angle of repose)

Stability against hygroscopic solidification ** Fragrance or odor content ***

42 ° 40 ° 38 ° 40 ° 42 ⁽ 25 27 30 20 25

32 30

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Claims (8)

Claims Process for improving the properties of granular Detergents and cleaning agents, characterized in that a conventional one obtained by spray drying is used Hollow-grained detergent and cleaning agent raw material with agitation of the granules of the washing and cleaning agent raw material mixed with a short-chain alcohol or a liquid perfume and that the surface of the detergent granules, which has been made sufficiently tacky as a result, with a powdered metal soap with an average particle diameter of less than 100 u. 2. The method according to claim 1, characterized in that there is at least one monohydric alcohol as the short-chain alcohol Alcohol with 1 to 4 carbon atoms and / or at least one dihydric alcohol with 2 to 3 carbon atoms used. 3. The method according to claims 1 and / or 2, characterized in that that one per 100 parts by weight of detergent and cleaning agent starting material 0.1 to 1 part by weight short chain alcohol used. 4. The method according to claim 1, characterized in that The liquid perfume is at least one from the terpene series, the phenol series or the aromatic series Used perfume alcohols. 5. The method according to claim 4, characterized in that the liquid perfume linalool, terpineol, geraniol, Eugenol, phenylethyl alcohol and / or benzyl alcohol are used. -19- 409885 / U09 6. The method according to one or more of claims 1, 4 and 5f, characterized in that one per 100 parts by weight of detergent and cleaning agent starting material 0.5 to 1 part by weight of liquid perfume is used. 7. The method of claim 1, .dadurch in that when using a short-chain alcohol ls _a metal soap is a calcium and / or Magnesi.umsalz a saturated fatty acid having 16 to 20 carbon atoms, and when using a liquid perfume, a calcium and / or Magnesium salt of a saturated fatty acid with 16 to 22 carbon atoms is used. 8. The method according to claim 7, characterized in that one per 100 parts by weight of detergent and cleaning agent starting material 0.3 to 15 part (s) by weight of metal soap is used. A 098 8 5 / U 0 9