DE1915276A1 - Detergents and cleaning agents - Google Patents

Description

O 274- Rotterdam

U Ή ILEYER ΪΓοΥ.
Rotterdam / Holland, Museum Park: 1

Detergents and cleaning agents

Priority: 29 Mar 1968, Luxembourg, No. ₀ 55 801

The invention relates to detergents and cleaning agents and a Process for their manufacture. In particular, it relates to detergents and cleaning agents which have reduced foaming power in a certain temperature range and one have a high degree of cleaning power.

Powder detergents and cleaning agents are used extensively for laundry purposes, specifically in automatic ones Washing machines * Such means are mostly compositions for coarse washing purposes and generally contain 25 to 55% by weight of the composition of inorganic phosphates and 10 to 30 percent by weight of the composition of organic surface-active substances Substances, usually together with up to 35 wt. ^ Or even more of inorganic or organic bleaching agents Agents, and the usual additives, for example optical brighteners, substances to avoid redeposition cleaning of dirt, chelating substances, dyes, perfumes Uedgl,

With certain types of automatic washing machines, Bioh found that heavy-duty detergents produce an excessive volume of foam during operation. These big ones Amount of foam adversely affects the ability to clean by evaporation of the movement of the wash water.

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which represents a reduction of agitation for]? olge has * The washed laundry will therefore still remaining Schmuta due to this effect have "Raise the reduction of washing efficiency, the foam also the inclination, from the machine to pour out ₆ As a result of this over flowage occurs not only a Loss of the washing liquor on, but the area around the washing machine is flooded with all the associated disadvantages _e

Various detergents and cleaning agents with reduced foaming power are known. Most of them contain known foam depressants, for example solid or liquid hydrocarbons such as paraffin or waxes, silicones and soaps. It was also found that the suds-reducing effect of soaps in detergents and cleaning agents was greater when the soap had a high content of saturated fatty acids with at least 20 carbon atoms. As such, it can be mentioned soap of hardened marine oils or some vegetable oils _e The disadvantages, however, all these Schaumdrüeker containing soaps are that they exert a pronounced foam-suppressing effect on the whole! Temperature range of the washing process, muai which is about! Between 20 to 10O ⁰ O which inappropriately diminishes the washing performance during the first stage of the washing process ο

In contrast, the invention creates detergents and cleaning agents with reduced foam capacity, but of such a type that the foam capacity of the detergent is satisfactory during the first stage of the washing process between about 20 and 60 ⁰ O, while the foaming capacity is satisfactory at the higher temperatures of the washing process is noticeably decreased β

It has been found that the optimal control of the grip strength can be obtained by incorporating an encapsulated Sohaumdrüoker into the detergent and cleaning agent, wherein the material of the capsule wall such

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is temperature dependent that it is the foam pusher in one "released certain temperature range

"Incorporation" is understood here to mean that the encapsulated thickening substance with the other detergent and cleaning agent mixed or added to it, separate from the rest of this agent "

It is therefore an object of the invention to provide detergents and cleaning agents to create with reduced foaming power in a certain temperature range ^ by encapsulated foam suppressing Substances are incorporated into the agent.

The foam pusher is encapsulated in small capsules with walls made of organic material, which ^{responds to temperatures in the range between 55 and 90 0} C of the washing bottle, so that the foam-suppressing substance is released in the specified temperature range.

The washing and cleaning agent consists of an active Detergensanteilj G-erüstsalsen and the usual additives and excipients "The active De'serge & santeil may organic detergents from anionis Chen," k tionischen _P nonionics, ampholytics Eyp or mixtures thereof with one or more G-integrate the the same or one, or more, of these groups of organic detergents include _o

see anionis

anionisehen As organic detergents of the isasgBXubBiskug. lyps can be obtained the alkaline soaps of fatty acids ^ the primary and secondary higher. Alkyl sulfates ₉ the sulfuric acid esters of polyhydric alcohols, some of which are esterified with higher fatty acids, the higher fatty acid alkanolamides & sulfates, the higher alkyl ether sulfates and the various sulfonates, such as the primary and secondary alkyl sulfonates, the olefin, sulfonates, the sulfonated oils or fatty acids, the higher fatty acids and.de. v © n Aminoalkylsulfonsäuren, the Alkylarylsulfone te (one «or polynuclear) mad the Alkylglyceryläthersulfonate, the different phosphoric acid esters and the Alkyl» - or AlkylarylpolyglylcolätherkarTsonsäures as © ©

Organic cationic detergents include the alkylamine, salts, the various quaternary ammonium salts that Acylalkylolamine salts, the sulfonium salts, the phosphonium salts uβdglο

The nonionics organic detergents can be referred to as the condensation products of alkylene oxide groups with an organic hydrophobic group _0. As such, there may be mentioned the reaction products of alkylene oxides with higher fatty alcohols, polyhydric alcohols, alkyl phenols, reaction products of propylene oxide with ethylenediamine, fatty acid amides, Alkylsulfonsäureamiden substituted polyamines tu dglβ The compounds obtained by reacting a condensation product of propylene oxide and a higher fatty alcohol with ethylene oxide, and the higher fatty acid esters of various sugars, can also be named _o

Examples of ampholytic detergents which can be used in the compositions according to the invention are the alkylamine acid salts, the betaines, the sultaines and the imidazoline compounds _e

Useful builder salts include the substantially water soluble organic or inorganic builder salts such as alkali metal phosphates and polyphosphates, alkali salts of Athylendiamintetraessigsäure, the alkali metal salts of nitrilotriacetic acid, the alkali metal silicates, - carbonates, etc. Inorganic or organic bleaching agents, whereby both chlorine bleach (eg _o hypochlorites. ! Trichloroisocyanuric acid) as well as oxygen bleachers (e.g. perborates) ^ can ^ be incorporated ^ "->,

The usual additives and extenders include bactericides or germicides, foam boosters, dyes, perfumes, optical Bleaches, enzymes, dirt preventing redeposition agents, sodium sulfate and also hydrotropes Substances (e.g. alkoxylene sulfonate) and the like

As a foam-suppressing substances may be used those which are normally used for this purpose ₉ s, B · glyceride oils, fatty acids or their derivatives ₉ Z ₀ example, the esters

with lower ali-pb «ti

Sxlikone, charcoal

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Hydrogen, z is ₀ B "paraffin, higher fatty alcohols, Z ₀ B ₀ lauryl or cetyl alcohol, certain katipnische detergents Uodglo

Very suitable foam-suppressing substances are those of the nonionic type, Z ₀ B ₀ the condensation products of alkylene oxides (z _e B _e ethylene oxide, propylene oxide, Uodgl _e ) with a hydrophobic compound ^ with at least one hydrogen atom which can react with the alkylene oxide (e.g. fatty alcohols , Alkylphenols, u «, like ₀ ).

The preferred foam suppressing substances contained in the detergents and cleaning agents according to the invention are used, are the following:

Io compounds of the general formula

R [(O _x H ₂ x O) P (OyH ₂₇ O) ₄ (O ₈ H ₂₈ O) ₁ HJ

wherein R denotes the remainder of an organic compound, which. s- active ·: contains hydrogen atoms, x _s y and ζ are integers from 2 to 4 inclusive, while p, q. and r are integers, the sum of which varies between 6 and 700, where one of these numbers can be NuIl * The organic compound from which R is derived

one

an alcohol, phenol, / carboxylic acid or a nitrogenous compound (e.g. hydrazines, amides, imines, guanidines, Sulfonamides, urea or thiourea), or those containing sulfur Compound ^ e.g. «mercaptans, thiophenols, thiocarboxylic acid or hydrogen sulfide).

II compounds of the general formula

where x, y and ζ have the same meaning as mentioned under I, while the sum of p, q and r varies between 8 and 6 ^c > 0. Examples of these compounds are the products, ¹ A © lohe Lm trade under the VTarenzfii'.jhen "PlutvmLoa" ii / iiilfclioh -iirul, · Ι1ο a ir ui Polyoxypi opy L - in «- Po.iyo'c.yfitiii, yl αϊ--

JU) 8 I 3/1 UM BATH ORIGINAL

HO (0 ₂ H ₄ 0) _p (0 ₃ H ₆ 0) _q (0 ₂ H ₄ 0) _r H

where ρ and r are integers from 2 to 300 and q is an integer A number from about 10 to 45 means “The molecular weights can vary considerably, but are generally in the range between 1000 and 30,000, the percentage being ethylene oxide groups throughout the molecule between $ 10 and $ 90 is β

IIIο compounds of the general formula

Where R ^ and R _{2 are} identical or different alkyl groups with 2-30 carbon atoms, x, y and ζ are integers from 2 to 4 inclusive * and the sum of p, q. and r over a wide range, for example between 4 and 50, varies ₉ wherein one or two of these numbers Nuil may be "Examples of these compounds are the 'products which äind commercially available under the trademark" Ucon ", fluids having average molecular weights between 400 and 5000.

The foam suppressing substances are used in amounts between 0.5 and 10 wt% of the agent, with one preferred The amount varied between 0.5 and 5% by weight of the agent

By "encapsulated" it is meant that a bead the foam pusher is completely surrounded by the shell or capel «By" small "is meant that the capsule a particle size of less than 2 mm, especially from about 0.5 to 1500 microns, with a preferred size in the range of 500-1500 microns.

The Kapselnmit the schaumdrtickenden substance can be produced by known processes, for "B · those using emulsion un ^ Koazervatverfahren bä ₉ spray drying, Fliei3bett-5eohnik, Tauohmathoden u" etc. ·

preferred method for producing the capaels, v! i.j ! πι -jrf Lihlmig; 3. ·! inUaaeii means, botra'tat wt ^ -jii ■, 3.0! L -.--. -., . α, vi, in -uui ¹ J, i -V-! ^ ijti t>: i -. "'· i \ L!:'f,.; ii , '. i \ v) 0 -ii>? ij 04 i --'-. Μ,

η η * i η 11 j 1 a 7 i

BAETt) RIiOlNAL

3,341,466 and 3,190,837.

The choice of encapsulating material is determined by the determines the following requirements:

a) The foam duct or the other components of the Washing and cleaning agents and the capsule wall material should not be mutually unfavorable influence;

b) the organic wall material should respond to temperatures in the temperature range of the wash liquor between 35 and 90 0, preferably between 35 and 70 0, in order to release the contents from the capsule in this temperature range _e

The encapsulating material can be a film-forming hydrophilic colloidal material, e.g. Arabic gummi, Gelatin, agar-agar, an alginate such as sodium alginate, Casein, albumin, pectins, zein, starch, Irish moss or carragheen or commercial extracts from them (carrageenin), Carboxymethyl cellulose and the like.

By a suitable hardening treatment z _e B _e with the aqueous solution of formaldehyde, glutaraldehyde or tannins, the capsule walls can be made harder and more heat-resistant. The heat resistance can therefore also be regulated by the manufacturing conditions of the capsule

will. ^ ₄ .. τ.

synthetic

The encapsulating material can also be a polymer or preferably be a mixed polymer, such as polyethylene-maleic anhydride mixed polymer, polyvinyl methyl ether-maleic anhydride mixed polymer, Styrene-maleic anhydride copolymer, polyethyleneimine, and the like.

Also natural or synthetic waxes or their mixtures can be used, e.g., ozokerite, ceresin, and the like.

The capsules to be used in the agents according to the invention are preferably made from a mixture of pork skin gelatine and gum arabic or a mixture

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Made from pork skin gelatine and Irish moss, on which the capsules are hardened by means of tannin or another hardening substance.

As already stated, the temperature range in which the organic wall material of the capsule should respond to the temperature is between 35 and 90 ⁰ O, preferably between 35 and 70 ⁰ O. At these wash liquor temperatures, the wall material is torn open and the contents of the capsule are released «

The invention is further illustrated by the following examples - without being limited to them.

example 1

Comparative tests were carried out with the following detergents and cleaning agents in dynamic dental foam knives (described in Soap and Ghem.Specialties, y £, No _e 4 »55-57, 104, April 1961) at a concentration of 5 g / l and using water executed with a hardness of 15 ° DH:

A components

Biodegradable dodecylbenzenesulfonate

Tallow fatty acid amide - 11E0 ^ Hardened tallow sodium soap, lauryl alcohol 4,5E0 methyl carboxylate Sodium tripolyphosphate sodium pyrophosphate

Sodium orthophosphate

Sodium metasilicate

Sodium sulfate

Sodium carboxymethyl cellulose

Sodium jumper borate
poly,

Buty3lp * r ^ pylene glycol ethyl diether / 15 PO Water »fluorescent substance, etc.

Weight? 12th 12th 1 1 3 3 3 3 30th 30th 8th 8th -.2 2 10 10 5 VJl 1 1 20th 20th - 1 P. 4th

100

100

EO »ethylene oxide
PO »propylene oxide.

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The dynamic foam meter provides a good simulation of the "wash process in an automatic washing machine ₀ The test results with the dynamic Schäummesser were the first in the curves of figures 2, 3 and 4 applied in these curves and the other will be mentioned curves is the foam height (in cm) plotted on the vertical axis against the temperature (in ⁰ O) on the horizontal axis. FIG. 1 shows the behavior in front of mean A; FIG. 2 shows the behavior of mean B, where di $ Butylpolypropylenglykoläthyldiäther / 15 PO was not encapsulated "in the Figo 3 and 4 was the foam-suppressing substance in encapsulated form with a wall material which responded at about 40 ^Q 0 and 95 0 to the temperature, present _e

The effect of the addition of the encapsulated foam suppressor, wherein the organisehe wall material consisting of a cured mixture of spoke Sohweinehautgelatine and gum arabic, at a wash liquor temperature of about 40 ⁰ C, is obviously "

Example 2

In the same manner as in Example 1, the following two agents were compared;

Components "",

Biodegradable dodecylbenzenesulfonate

Ealgfettalkohol-25B0 Talgfatty acid amicl-11EO

Sodium soap made from hardened sebum Sodium tripolyphosphate

Sodium metasilicate

Sodium sulfate ^ atrium carboxymethyl ^ <C-7 cellulose

Sodium perborate

Butyl polypropylene glycol ethyl • diet / 15 PO

Water, fluorescent material, etc.

100 100

12th 12th 2 2 2 2 3 3 40
5 40
5 5
1 5
1 22nd 22nd - 5 8th 3

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-ΙΟ-The ester results mil; The dynamic foam knife is shown in FIGS. 5, 6 and 7. FIG. 5 shows the behavior of agent O, and Pig. 6 shows the behavior of agent D, in which the foam-releasing substance was not encapsulated. The behavior of agent D with encapsulated foam pusher is shown in FIG. The effect of this agent is pronounced. The capsule wall material was the same as in Example ₁₀

Example 5

In the same way and under the same conditions as described in example .1, the following means were compared

Components E F

Biodegradable dodecylbenzenesulfonate

lalgfettalkohol-25EO Sodium soap from hardened IaIg If atriumtr ipolypho sphat U Sodium Metasilicate Sodium Sulphate Sodium Carboxymethyl Cellulose Sodium perborate

Butyl polypropylene glycol ethyl diether / iSPO

Water, fluorescent material, etc.

Gew.Sfc 12th 12th 2 2 . 4th 4th 40 40 5 5 5 5 1 1 22nd 22nd - ■ 5 4th

100

The Sestergebnisse with the dynamic foam meter are shown in Figures 8,9 and 10, wherein Fig. 8 shows the results obtained with medium E and FIG. 9 shows the results obtained with ¥ means, said di £ butyl polypropylenglykoitftfcytttäthyldiäther / 15P0 nioht was encapsulated ,. In Fig. 10 the results with the encapsulated foam pusher (wall material as in Example 2) are shown. Here too the effect was very noticeable.

Example 4

I & the same way and under the same conditions as in Example 1, means E and a means S were used

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were similar to which the latter was the same as the agent F, but with the modification that 3 wt. ^ butyl-polypropylene glycol ethyl diether / 15PO were used instead of 5 wt. "$" The test results with the dynamic foam knife are shown in FIGS and reproduced 13, wherein Fig. · 11 12 the result obtained with Composition G reproduces the same with FIG. 8 and FIG _c, where OCS of butyl polypropylenglykoläthyldiäther / was not encapsulated 15 PO "In Fig. is the result with encapsulated foam suppressor reproduced (wall material the same as in example 1). The result is striking and needs no explanation *

Example 5

In the same way and under the same conditions as in example 1, means E of example 3 was compared with the following other means:

Components -5— fS & S.

Biodegradable dodecyl

benzenesulfonate 12 12 12 12 12

Tallow alcohol, condensed

with 25 moles of ethylene oxide 2 2 2 2 2

Sodium soap made from hydrogenated tallow fatty acids

Sodium tripolyphosphate sodium metasilicate sodium sulfate

Sodium carboxymethyl cellulose sodium perborate

Polybutylene glycol (1)

Monobutyl ether of polybutylene glycol (2) 3

Dirnethyl ether of polypropylene

glycol (3) '- ■ ■ - 3

Propylene oxide adduct of monobutyl ether of polybutylene glycol (4) - ■ -

Silicones (5). -

Water, fluorescent fabric,

etc. to 100-

4th 4th 4th 4th 4th 40 40 40 40 40 VJl 5 5 5 5 5 5 vn 5 VJi 1 1 1 1 1 22nd 22nd 22nd 22nd 22nd 3 t_ _-

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(1) Molecular weight, 704

(2) Molecular weight 698

(3) n | ° «1.4488

(4) Molecular weight 96S

(5) General formula *

₅ ) 2-S iO - Si-O - Si- (CH ₅ )

OH,

SAa-470 (Union Carbide Corp.)

In all cases, the remedies were examined with the, dynamic show mesmerizing in the following order, the "remedy with non-encapsulated foam pusher and then the same remedy with the same, but encapsulated eye pusher in a capsule * the other material made of a hardened mixture of pig skin

consisted of gelatine and xrish moss with a melting point between 45 and 50 C,
f verified The results for each agent are. ± n reproduced in the same order; di agent for H in Figures 14 and 15 "for medium K in the figures 16 and 17 for middle L in Figures 18 and .19" for medium M in the figures 20 and 21 and for means E in Figures 22 and 25th

The regulated foam behavior in the required temperature range is evident. The advantage of encapsulating the foam-suppressing substance is from the related Figures clearly recognizable »

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Claims (1)

-13-Pa.tent a η Proverbs 1. Washing and cleaning agents with reduced foaming power, in a certain temperature range with a content of an encapsulated foam-suppressing substance, the capsule wall material of which is an organic material which is temperature-sensitive ^{to a Vaschflottentemperatur between 35 and 90 0 O is.} 2. Means according to claim 1, characterized in that the foam pusher is encapsulated in an organic material which is temperature-sensitive ^{to a tank temperature between 35 and 70 0 O.} 3. Agent according to claim 1 or 2, characterized in that the organic material is a hydrophilic is colloidal material or a mixture of hydrophilic colloidal materials. 4. Agent according to one of claims 1-3, characterized in that that the organic material consists of a mixture of gelatin and Arabic gum. 5. Agent according to one of claims 1-3, characterized in that that the ■> organic material consists of a Mixture of gelatine and Irish moss, 6. Agent according to one of claims 1-5, characterized in that the foam pusher is a nonionic Connection is » 7 · Agent according to one of claims 1-6, characterized in that the foam fluid is a nonionic Connection of the general formula where R is the residue of an organic compound containing s active hydrogen atom ^, x, J and ζ are numbers from 2 to 4, while p _f q and r are numbers, the sum of which varies from 6 and 700 , where one of them can be zero. 009833/1873 -Mr 8, means according to any one of claims 1-6, characterized in, that the foam pusher is a nonionic compound of the general formula • H0 (0 _x H _2x 0) _p (C _y H _2y 0) _a (0 _z H _2z 0) _r H is where x, y and ζ numbers from 2 Ms including 4 are, while p, q. and r are numbers, of which the Sum fluctuates between 8 and 650 9ο means according to one of claims 1-6, characterized g e k e η nz ei chnet that the foam depressor is a nonionic compound of the general formula where Ru and E _{2 are} the same or different alkyl groups with from 2 to 30 carbon atoms, x, y and ζ are numbers from 2 to 4 inclusive, and the sum of p, q and r varies between 4 and 50-where one or two of these numbers can be zero 10 »Agent according to one of Claims 1 to 9, characterized by a content of 0.5 to 10% by weight of the agent on an encapsulated foam-suppressing substance » 11. Agent according to one of claims 1-10, marked cib.net by a content of 0.5 bid 5 wt. 56 of the agent to an encapsulated foam suppressing substance. 12. Means according to one of claims 1-11, characterized marked that the foam pressing Substance in capsules with a particle size of less encapsulated as 2 mm 13 · Means according to one of claims 1-12, characterized marked that the foam-suppressing substance is in capsules with an I-part size of 500 to 1500 microns encapsulated, 14 »Method for washing dirty laundry, which the Washing dirty laundry in an aqueous solution 009833- / 1873 of a detergent and cleaning agent according to one of the comprises preceding claims. 009833/1873 Empty eHe