DE1767228A1 - Liquid detergent - Google Patents

Description

DR. ΙΝΘ. A. VAN DER WERTH DR. FRANZ LEDERER

21HAMBUR3 9O 8 MONKS 8

WILSTORFER STR. 32 -TEL. (Ο411) 7ΤΟΩ61 LUCILE-GRAHN-SFR. 22 TEL. CO8 11) 44 Ο846

O 184

YOUR SIGNS: 1 H R E N ACH R I CH Γ VO M: M E I N E Z E I C H E N: H AM BU RG - HA R B U R Q. D E N

NS. 11 April 1968

UNILEVER KV
Museum Park 1, Rotterdam / Holland

Liquid detergent.

Priority: British Patent Application No. 17 028/67 v. April 13, 1967

The invention relates to highly active cleaning agents

in the form of liquids The means are for yerwen- " application for cleaning hard surfaces by hand or using machines, e.g. of dishes, silver and

Cooking devices suitable for ₉

The invention relates to liquid cleaning agents, which contain an ammonium salt of an alkylbenzenes ⁰⁰ sulfonic acid, the alkyl group of which has 8-16 carbon atoms,

^ preferably contains 11-13 carbon atoms, one close »So far these agents contained an ammonium -" - ^a salt, produced by neutralizing the, LLkylbynfcoJ

ihydrexyd.

TBLEFONI8CHE AGREEMENTS REQUIRE WRITTEN BESTATI (SUNa

BATH ORIGINAL

-2- 176722Π

The product of the neutralization had a high water content and a high content of inorganic pollution (namely ammonium sulphate), which in total made up at least 25 % of the product. If paste-like products are used in liquid cleaning agents, they cause difficulties in terms of phase stability under the usual storage conditions for the agents, 2> ß. but is a c temperature to -20 ⁰ C, and also on the different required by the consumer viscosity which varies from country to country 50-1500 Qentistokes. These difficulties in the phase stability have been overcome by the incorporation of a hydrotrope, but this is a costly material _for which little or nothing to add to the Heini narrowing property of the agent "Kin liquid detergent with a high content of active detergent and a minimum content of impurities is significantly advantageous in terms of selling and the economics of the packaging, as well as being a phase stable3 agent with an acceptable viscosity for consumption.

It has now been found that an ammonium salt of an alkylbenzenesulfonic acid with a high active detergent content (ie a high percentage by weight of pure ο surface-active substance), namely 80 # active ingredient, co as an anionic surface-active constituent in connection with a liquid nonionic surface ; jj active * component with a high active detergent content (in -J follows η i called anionic and nonionic). ue. in liquid detergent, which the

BATH ORIGINAL

νorerwähnto ^ has advantages of yielding »such I-funds not only have a considerably higher rate ii AJ: tive content than was previously possible using the ammonium alkylbenzenesulfonate paste mentioned above

result
proved}: has, but also surprisingly, no phase stability problems over a wide range of compositions. It is also surprising that this ammonium salt, which is in gel form, can be easily incorporated into a liquid lionionic of high activity to become an agent of clearer -

to produce phase-stable liquid por in »

The invention provides a clear, homogeneous liquid detergent of an activity level of at least 8O5 *>, which both satis α ens dividing Reinigungsvermö- gene has for sc] inut :: i'eller strength as well as satisfactory foaming power.

Accordingly, the invention relates to a liquid cleaning agent in terms of weight with regard to its composition 80-10O ^ of a mixture of ammonium alkylbenzene- J sulfonate in which the alkyl group has 8-16 carbon atoms and a water-soluble synthetic nonionic Detergent which is liquid at room temperature, the weight ratio of the sulfonate to the lionionic is between 4 ί 1 and 2: 3,

c The fluids according to the invention preferably have fluids cc

^ at least $ 90 active detergent _e in such agents which

- ^ 80 $ active detergent, the rest exist

³ ^ 20 $ essentially from water, v / which is usually present in no more than 7 $, and is derived from either the ammonium salt or the nonicnic, or both, and *

BATH ORIGINAL

~ ^A J 767228

from a viscosity-reducing substance, e.g. an aliphatic alcohol, which in an amount of no more than $ 15 is present.

An ammonium alkylbenzenesulfonate with at least 80 $ active detergent content can conveniently be prepared by neutralizing a liquid alkylbenzenesulfonic acid using gaseous anhydrous ammonia *. The neutralization reaction takes place at atmospheric pressure and temperatures between 10 and 90 C _1, preferably 15-3O ⁰ C, and is continued until the pH of the reaction mixture exceeds 7. Excess ammonia can be removed from the product by bubbling nitrogen gas through the reaction product. The product is a gel which contains at least 80% active detergent and is essentially free of water and ionic by-products such as ammonium sulfate. Substantially 100% conversion of the sulfonic acid can be achieved. A further reduction in the already low content of contamination by by-products (ammonium sulfate) can be brought about by blowing an inert flushing gas, 2 _β Ι3 _β nitrogen gas, through the alkylarylsulfonic acid before neutralization.

Suitable sulfonic acids for neutralization with gaseous v / an scr for eggs ammonia are decyl toluene, Dodecylxylene, octylbenzene, nonylbenzene, decylbenzene, Undecylbenzene, dodecylbenzene, tridecylbenzene, tetradecylbenzene, Pentadecylbenzene and hexadecylbenzene · The preferred Acid is dodecyl benzenesulfonic acid

109834/1577

BATH ORIGINAL

Suitable nonionics are ethylene oxide adducts of alkylphenols, such as _e iithxlenoxyd a condensate of octyl or Honylphenol with 3-15 Get; a condensate of C ^ -G ^, or C ^ .- C ^ ₁ - or C. λ -CLe secondary alcohol with 3-12 moles of ethylene oxide, a condensate of oleyl alcohol with 3-15-ethylene oxide or an ethoxylated ethanolamido

The above process can be used with commercially available technical grade alkylbenzenesulfonic acids. If these are very dark in color, the resulting ammonium salt may be too dark to be incorporated into be the liquid detergents. Color enhancement is preferably done by bleaching the commercially available Acid obtained before the production of the salt with hydrogen peroxide solution, because this bleaching process that requires the least amount of water and also because it introduces smaller amounts of inorganic contaminants »One optimal concentration of aqueous hydrogen peroxide, in which essentially no foam is formed during neutralization, there is around 5-7% of aqueous ^ Hydrogen peroxide with a strength of 50 volumes and enables the production of a bleached ammonium alkylbenzenesulfonate, which only contains 4-6 $ water »If This sulfonate is used as a major ingredient in a liquid detergent, it leads only 2-3? s water in the compilation.

In agents which contain a HTcnionic which is inert to ammonia it contains two components, the ammonia neutxalifla-

tion of the Alkvlbenzenesulfonsäure in AriwK ^ en (. t on

3W1577

kvlbenzolsulfon 1Ö983W1577

BATH ORIGINAL

water-soluble nonionic to be used in the batch. The honionic is not affected by the ammonia, and does the useful puncture of keeping the viscosity of the reaction liquid at a reasonably low level, from 100 to 500 oentistokes. If the liquid cleaning agent made from ammonium alkylbenzenesulfonate and the lionioriic is somewhat too viscous, then a viscosity-reducing agent is expediently present in the neutralization process of the sulfonic acid, provided that the agent is inert to anhydrous ammonia and is present in amounts which are not those caused by the system exceed the tolerated amount. Suitable substances are methyl, ethyl or isopropyl alcohol. If the neutralization is carried out in the presence of an aromatic solvent, e.g. BeMzol, this should be removed before the liquid cleaning agent is used.

So far, liquid detergents with «iraatxhohen Active detergent content, ζ, B. 80-955 * »» water soluble Nonionics as a basis, which are commercially available as 100? 6 Active detergents are available either as their main ingredient (e.g. used in combination with inorganic G-builders, such as sodium tripolyphosphate) or as a sole component. But these water-soluble

or as a main component Hon ± on ± c8 Bind used alone / unsuitable for

liquid dishwashing detergent yfr »TTfr ¥ because of their proportionate poor foaming power in the presence of an iet ^ 'flour / protein soiling · this is viz

a ^ k η te the fohaumjverni ent pollution. 109834 / 1E77

BATH ORIGINAL

If the agents according to the invention, dna are a highly active ammonium alkylbenzenesulfonate in connection with a water-soluble honionic, are used, it turns out that the volume generated under o-standard conditions (as described in the following test method) and its stability against fat / flour / Protein soiling is comparatively advantageous with essentially the same: active detergent content compared to the foam volume and the stability of a known, customary liquid dishwasher with a low active detergent contenta, i «B. a mixture of sodium dodecylbenzenesulfonate and tert. ~ oct; ylphenol-11,5-ethylene oxide condensate. (Such a mixture is unstable at high active detergent content), Table 1 shows the improved "foam index" of the nonionic / anionic system given in the table at a concentration of 0.1 $ active detergent compared to each substance alone, and also the improvement in the Dirt removal index (test method 3), as it is achieved by iie coordination with the Kcnionic alone. ^^ g ;! is «A is AramoniumdodecyVDerzoloulfonat ^r nit 95 ^ .-i (11, ρ is the average Athoxylatl-ctte)

from 100 ^ Aj uivdetorgens «

Table 1

Kj. I iel " Foam number " S chmuta removal index σ 4 H cA U

⁰⁰ 1009 & ii 14 21 10

^w "^ " 106 124 20

5096

124 124 23

_L 143 143 31 A 74 28 26

ORIGINAL

The invention also relates to liquid high-quality cleaning agents of at least $ 80 active detergent content, which in addition to the ammonium alkylbenzenesulfonate and the water-soluble lionionic include a sulfate of an ethoxylated alcohol, in which the alcohol has 11-15 carbon atoms and the ethoxylation is on average 5 parts of ethylene oxide per mole of alcohol »The cation of the sulfate can be ammonium, alkali or amine. The preferred ternary compositions for the liquid dishwashing agents according to the invention are those in which the ammonium alkylbenzene sulfonate $ 40-65, preferably $ 45-55, the alkyl ether sulfate $ 1.8-15 , preferably $ 3-13, and the water-soluble nonionic is $ 20-60, preferably $ 25-40 of the agent, all expressed as $ 100 active detergent Foaming power, plate washing power and viscosity as discussed below t, were found ₀ Additions of solution alcohol can be made up to $ 10 while maintaining the ratio of alkyl benzene sulfonate to alkyl ether sulfate to nonionic within the limits set above. good foaming by a high Nonionicgehalt and, -jute dispersing be increased by Anionic which you Vielcsitat affected. The addition of AlKyether sulfate modifies the dense foam, un: habilitiert the foam against contamination, even if ■. ■ incorporated into me as a minor be ^ lairited 1

^{1096? 4} ' ¹⁵⁷⁷ BADOMGINAL

will. The foam values for the agent: (a) highly active ammonium dodecylbene sulfonate, (b) tert-octylphenol-11,5-ethylene oxide condensate, (c) sodium-O-j -j-O j ^ -alkyl ether sulfate (3-ethylene oxide) show synergistic foaming power ο The sodium C 1-6 alkyl ether sulfate (3-ethylene oxide) used here contained only $ 60 active detergent. This level of activity is currently the most available for commercial products _o The remaining $ 40 consists of $ 25 alcohol and $ 75 water.

Particularly useful remedies in this (a), (b), (c) -3 / star are those which 40-7O $ (a), 20-40 $ (b) and 1-2 ^ c) Λ

by weight of the whole mean, expressed as $ 100 active salary, $ 100 active salary and $ 60 active salary, »Use of sulfates with a low water content is desirable, e.g. use of the amine salt, which by neutralization of the alkyl ether sulfuric acid with an organic base such as morpholine, triethanolamine or isopropylamine instead of the sodium salt can be produced.

The foaming power of this jtüf. (a), (b), (c) systems J.

in the presence of soil was further carried out using one described below as Test Method 2 ! Deller's wash test investigates “Remedies with $ 40-90 (a), $ 1-60 (b) and $ 1-30 (c) develop aynergistic properties Effective properties and means with 50-65 $, 25-40 $ and 3-18 $ (a), (b) and (c) are preferred when foaming ability in the liquid detergent is desired is.

To be useful in aqueous media, 3-n. liquid cleaning agent good water-dispersibility:

10983A / 1B77 * _Ar

«Ιοί 7 6 7? 2 8

have.) a property which is directly related to the viscosity of the agent. The viscosities of agents within the aforementioned preferred ternary system, determined using an Ostwald "yiskometer tube at 25 C, indicate that an optimal area of low viscosity, i.e. 80-500 centistokes, mean at 20-55 ^C A (a), 20 -6C # (b) and 5-3O (c) covers.

Agents made from the ranges given above for the preferred (a), (b), (c) core system

proved to be phase stable and did not require any other

the
hydrobropen additive as / reducing the viscosity

Alcohol.

Although the specified nonionic, tert.-octylphenol-i1,5-ethylene oxide, was used in the ternary system investigated, other nonionics can be used instead. The effect on the foam number through the replacement of terto-octylphenol-11,5-ethylene oxide (b) by another ethylene oxide adduct in a product with the composition 45 $ aramonium dodecylbenzenesulfonate, 30 # (b) and 15 $ sodium C ₁₂ -JUkyläthersulfat (3 -Ethylene oxide) and 5 ^ ethylene alcohol is shown in Table 2.

109834/1577

6AD ORIGINAL

gabeile 2

'.D

Gruone

O . ~ ΰ., ^ s eKundlir gr ^{11 Ί} - alcohol

.-C., .- 3sJau; dti.ror ¹ ° alcohol

x-secondary-rx '"Alc ^ ol

Oleylalkonol Octylphenol * Zaiii of the atxixlenoxide groups (average)

7 8

304
360
206

198

246

437

127 104

10 12

105

463 500 96

204

159

JL

14th

123

* is a condensate called (b) above tert-octylphenol ~ 11.5-ethylene oxide »Der Ein. aehiieit; for the sake of this result is in the 12 ethylene oxide

■ palte / u ^ egecen *

The agents according to the invention can be more than one Honionic include. The anti-pollution remover can be replaced without loss of phase stability by replacing part of the water-soluble honionics by one

less water-soluble nonionic, e.g. "a! fat or an acid mono- or diethajnolajnid, BtK" g / 3 fatty acid amine. such as, for example, lauric isopropylamine, can be enlarged. In hard surface cleaners, it is customary perfume, a bacteriostat, such as _e formalin, and if possible add a coloring _e These additions may be made to the above-mentioned ternary system for their usual purposes. However, the addition of a bacteriostat is not an essential requirement of stable products when water is absent from the composition. The amount of active detergent in cleaning agents for hard surfaces is usually between 0.05-0.25% active detergent in an aqueous solution.

The invention will now be explained by way of example. Example 1 describes a highly active detergent wherein the active ingredient ammonium dodecylbenzenesulfonate una is an ethoxylated octylphenol made by Neutralization of the sulfonic acid with anhydrous gaseous ammonia in the presence of the ethoxylated Octylphenols.

example 1

300 g of dodecylbenzenesulfonic acid were poured into a 500 ml Reaction time see introduced, 21 g 50 percent by volume Hydroxide solution was added and the Mixture 1C λ ':.: -: ·; ^ oj long stirred at Rauniteiuperntur.

ORIGINAL

40 ml tert * 0etylphe: iol-11,5-ethylene oxide was added as the viscosity decreased to about 1000 Cebtistokes, the mixture was stirred and anhydrous Anunoniakgas at 20-30 ⁰ O passed, was until the pH of the mixture over 7 " Excess ammonia was removed by bubbling nitrogen through it for about 15 minutes. The product was a golden yellow free flowing liquid with a total active detergent content of $ 94 ($ 83 in terms of the sulfonate component). This product can be used in any of the compositions of Examples 2-5 by adjusting the ionic content, expediently by simple addition, _e

Examples 2-5 describe liquid dishwashing detergents

according to the invention »(The ammonium dodecylbenzenesulfonate had an active

detergent content of

Example 2 Part of example 2

Ammonium dodecylbenzenesulfonate

(expressed as $ 100 active detergent content) $ 60 Octylphenol-11.5 ~ ethylene oxide ($ 100 4 active detergent content) . $ 40

Water content in $ 0

Foam number 4 ° H water 124

Foam number 24 ° H ~ water ■ 124

Dirt removal index water hardness Cr (demineralized j 23

109834/1577

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Examples 3-5

Component Examples 3 4 5

Ammonium dodecylbenzenesulfonate
(expressed as 1000 active detergent content) 550 5Ο? έ 650

Octylphenol-11,5-ethylene oxide

(1ΟΟ5έ active detergent content) 300 250 300

0 j 2 ~ * -A-alcohol 3-ethylene oxide sulfate

(Sodium salt) (600 active detergent content) 150 150 50 Octyl phosphate (1000 active detergent content) - Coconut monoethanolamide (1OO0 Active detergent content - 50 -

Ethyl alcohol

7.50 70 50 -35 +3 -55 458 278 3000 207 207 208 205 216 205 112
101 88
90 107
94

Water content Clear point ( ⁰ O) Viscosity (Oentistokes) "Foam number" 4 ° H water "Sohaumzahl" 24 ° H ~ water

Wash number of soiled plates 4 ° H water

24 ° H- ¥ ater

Dirt removal index, water hardness 0 °

(demineralized) 25 29 26

In Examples 2-5, the alcohol content can be freely adjusted to produce any desired viscosity without any noticeable effect on the cleaning fluid the means, provided the proportions of other components are kept constant »

lestme th oda 1 cylinder foam test.

100 ml of a solution containing 0.10 detergent, were placed in a graduated 250 ml measuring cylinder, held in a bath at 45 °, which was then

aohle ΐί ^Λ ^ d was reversed 10 times, and the foam height 109834/1577

BATH ORIGINAL

was visually "determined ₀ 0.1 g of dirt (fat / ilehl / protein dirt) was gradually added." After each addition, the cylinder was inverted five times and foam height was measured until all foam was destroyed. All recordings from SchaumhÖhcn were added and expressed as foam ζ aiii

Test method 2 washing dishes

5 1 rinsing solution was prepared in a plastic bowl of 30 ciu diameter at 45 G · It had a reproducible foam volume as a result of a standardized process, the addition of 4 »5 1 hot water to 0.5 1 water with a content of the total amount of cleaning agent by pouring it into a reproducible """'ice from a height of 208 cm. Dinner plates, each soiled with 2.4 g of a fat / flour / olein SCiJiUtSeS ₁ , were then washed individually in the bowl with liquid until the foam layer on the liquid surface was broken to leave was noted and the average was calculated. The agents according to the invention were used with 0.02 and Q _t QA active detergent content.

TestmetliO -l · 't> -Schmutζentfrrnun.y; jnd ex «

The öchnuir \ tf firi.un ^ sverinögcn of Ji: / igungsmittelr became du; -fv -iu ^ expression Su. ^ Ut. ^ Intl'eraiungsindex b ^ ... "- .. hi-.t;

Di (? R? Er ir.n : wjrd bessim Oi-r ::: V- r ,, l »i 1c-s G: ⁱ s ir 109834/15 7 * ^

Removal of thin layers of dried egg yolks from glass surfaces using a 0.1% active detergent solution of the detergent in demineralized water with the degree of removal by means of a 0.1 # igen Active detergent solution of octylphenol-11.5 ~ ethylene oxide, both degrees being determined at 45 C and a solution pH of. The ratio becomes with the factor multiplied to get clear numbers. Common anionic nonionoc liquid dishwashing detergents have dirt removal indexes of 22,

The liquid cleaning agents according to the invention are clear, homogeneous, low viscosity and good agents Phase stability, which very little water, one

salary
high active detergent TS ¥ Ktyirä "fcifür contain and none

other hydrotrope than a viscosity adjusting one Requires water-miscible solvents · Another advantage of the small amount of water present in these agents is that substances can be added either dissolved, suspended or encapsulated, which can react with water if the agent is used to produce beneficial effects such as bleaching, Chafing, effervescence, surrendering.

BATH ORIGINAL

Claims (2)

. 1. Liquid cleaning agent, consisting essentially of in percent by weight of the agent from $ 80-100 of a mixture of ammonium alkylbenzenesulfonate in which the alkyl group has 8-16 carbon atoms and a water-soluble one nonionic synthetic detergent which is liquid at ambient temperature, the weight ratio being of the sulfonate to the honionic between 4 * 1 to 2: 3 lies. 2. Means according to claim 1, characterized in that that the sulfonate is ammonium dodecylbenzenesulfonate and the Ifonionic an ethylene oxide condensate of an alkylphenol, preferably octyl- or ifonylphenol, condensed with 3-15 moles of ethylene oxide. 3 »Means according to claim 1 or 2, characterized geke η η - records that there is also a sulfate of an alcohol with 11-15 carbon atoms, ethoxylated with up to 5 moles of ethylene oxide per mole of alcohol, present - in an amount of 1.8-15% by weight of the composition. 4- * means according to claim 3, characterized in that that the sulfonate in an amount of $ 40-65 and the lionionic is present in an amount of $ 20-60 from the weight of the entire compound. 5. Agent according to claim 3 or 4, characterized in that the sulfate is liatrium-O ^ -alkyl ethersulfate (3-ethylene oxide), present in amounts of 3-12 $ based on the weight of the total agent ,! 09834/1677 _M 6β means after. the. preceding claims, thereby characterized in that the nonionic is a less water-soluble nonionic, preferably one Fatty acid alkanolamide, includes » 7 «A method for producing an agent according to claim 1 or 2, characterized in that an alkylarylsulfonic acid with gaseous anhydrous Ammonia is neutralized in the presence of the water-soluble nonionics. 8, method according to claim 7 »characterized in that the sulfonic acid before neutralizing using 5-7 $ aqueous 50 $ solutions Hydrogen peroxide is bleached. 109834/1577 BAD ORiGiNAL