DE1617047A1 - Dishwashing detergent - Google Patents

Description

(U.S. 450,509 - Ρ ** ίο April 23, 1965 4079)

Colgate-Palmolive Company New York, N.Y./V.St.A.

Hamburg, 23 "

Dr. Expl.

The present invention day relates to new ones middle

Washing

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BATHROOM 0RfΘ! ^ 4ÄL

With the present invention, a new biodegradable liquid dishwashing detergent has now been found which, moreover, has an improved cleaning effect and is relatively inexpensive. The type which, together with the other components of the mixture, results in a particularly effective dishwasher detergent.In this Alfeylbenölsilfonat. The Ällqrlphenylteil on a molecular level of S30 to 240 and the alkyl groups consist of mixsdeefe © ssg 80 HoI ^ «us Oro | spea old 10 to 2.2 carbonatesi®z & vssu tti ^ Mu9B% ^ B zur SSlL £ 1 && this ßwippßß, ait IG to IS EeMcsaafeoffstooMrn and »in.d« st © ns 1 ^ -45 % of the Qesanstau Qruppmi with 10 to II EoStlesefeoffatomen,

& üpp§U- mit, l4 imä sGftr Xehleaet ^ f t «

2 ^ from βκϋΐρβΒ Kit 9

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The molecular weight of the alkylphenyl part and the distribution of alkyl groups as well as the proportion of as * alkyl groups with deia benzolrast in the various positions can easily be determined by conventional mass spectrometry using pure fractions as reference standards. By means of such a mass spectral analysis it can be determined that the alkyl groups mentioned are at least 95 % linear. Since the alkylbenzenesulfonate generally does not contain any alkyl groups with the benzene group on the carbon atom in the 1-position, essentially all alkyl groups are secondary alkyls.

The higher alkyl ether sulfate used is a sulfate of an ethoxyated higher alcohol of the formula HCOCHgCHg ^ SOijM, in which R is a preferably primMre ®fi @ p sskundMr © long-chain alkyl group with 10 to 15 carbon atoms, η a © number from 1 to 5, e.g. 3, and M a cation such as ammonium, sodium, potassium or mono-, di- or triethanolamine or the like is. In order to achieve maximum biodegradability, the alkyl groups are unbranched or branched as little as possible, for example with a methyl or ethyl branch.

The higher fatty acid aonoethanolamides contain beneficial a fatty acid residue with an average chain length of 11 to 1 ^ carbon atoms. It has been found that

BAD OFiSGIMAL 109812/1548

the washing tools according to the invention give the best results with an average chain length of 12 carbon atoms (e.g. 11.4-12.6} can be achieved.

The Qeeumtkonz & ntration of Alkylbenzolsulfcnat and Alkyläthersulfafc in the river strength Gesebfcrrwaschmlfcteln fcatrUgt least JQ #, preferably 35 - HQ% _t and the ratio of ASkyl & fchersulfat to Alkylbenzolsulfoiiat 0.4: 1 to. 1: 1, Since the alkyl ether sulfate is more expensive than the alkyl benzene sulfonate, the economically optimal composition is achieved with a ratio of 0.4: 1 to 0.7: 1. The proportion of fatty murcimonoethanol araid is expediently at least 5 % _{, for example 5-7% s,} and is preferably in the range from 1/8 to 1/5, preferably 1/6, of the total weight of alkyl ether sulfate and alkyl benzene sulfonate.

The dishwashing detergents according to the invention can also contain hydrotropic compounds such as the known alkali (sodium or potassium) or ammonium salts of benzene, toluene or xylene sulfonic acid. These serve to improve the mutual solubility of the components and to achieve further advantageous physical properties such as low viscosity, and can be used in amounts of up to 20 % . A similar effect is obtained by using a water-soluble lower alkanol such as ethanol or isopropanol instead of part or all of the amount

109812/1548 bath

The hydrotrope compounds mentioned above are replaced by alcohol. In addition, alcohol can serve as a coloring agent or coloring agent. Furthermore, TrÜfowKgsroittel such as polystyrene © or other substances in the invention substances and small compounds were added, for example © in amounts up to 5 %

In addition, in ü @ n © rfintongsgeasllßen \ i & B®hm & tt®ln neutral salts ^ such as d ^ j In general with the alkyl feeniol sulfate ^ for example © la! Teig® "up to 5 ^ be present"

lcasm las sllgeEe @ ia © m isa © © goaue ^ ig © ä®QS

BATHROOM OBl

other readily soluble salts such as ammonium salts and salts of lower alkanolamines such as mono- and triethanol amines can also be used. The corresponding calcium and magnesium acid salts are prepared in a similar manner. The product can also contain various amounts of water-soluble inorganic sulfates, which are formed by neutralization of excess sulfuric acid used in the sulfonation process.

The proportion of alkylbenzenes is with alkyl groups which contain the benzene residue on the carbon dioxide in the S position (ie S-Fhsnylalkasieii) can be reduced by modification of the alkylation group. Thus kSnnsn the desired 3 "· 4 -, 5- mid-6-f & 9nylalkane the residue hölwm Qehftlfe by fractional distillation in the least-illa'5 ices®®atri®pt M" gestures _# v $ HRMD aa 2-BN® ayIalteßii eat the AlSgyllsru & gsgefäfi

isa lcacB ^ s © at the exi ^ e & lieSeaden Oleich-Sss "Äikyli®" ^ is ia @ sgf * ß ^T ^ aFfe ^ eri Aluminiuni "od®2? © lass g & äftpean Frled "l" Cr & fts-Xäteljsators eise

The! Rfiafes® IdLrS cfciHfc -Si® fslgenöe ^ 3eie ^ i © l @ closer

1 * - ^ ^:: c ^ VsälZu & s & g & lgQ ^ dia, · ^ (ΚΓΐ, ϊ ^ Ι EC ^ 5S-3E ^ | «rS'i * liH _k5 wherein

BATH

R a mixture before primary. straight branch tere alkyl radicals _s was 65 Qew.f) of residues with Ik carbon atoms and 35% aue top 12 Kehleststoffatc-RAEN, stock, and 6% FettsSm-eH-ftionoärfiemclaKiäii wherein the FEFC fcsäurereste 70% Laurlnse'ure - and about 30 $ should consisted of myrstic acid, mixed in water. "In addition," 7% sodium hydroxylene sulfate was added as a hydrotropic compound

The alkylbenzenesulfonate consisted of a mixture of straight-chain monoalkylbenzenesulfonates in which all straight chains were attached to the banzole ring in the 4-, 5-, 6- position of the alkyl chain and the alkyl chains were each 32 1/3 öew. % consisted of chains with 10, 11 and 12 carbon atoms * The allsylphenyl part of the sulfonate had a molecular weight of 231.

With dit-sera oil washing agent - but without the di © hydrotrop © compound - Telleu wash tests were carried out with the usual concentrations of 0.15 % of the product in water of 100 ppm and 250 ppm hardness (calcium and magnesium salts in the washing water, expressed as calcium carbonate) at a Initial temperature of 49 ° C carried out. In these tests, glass plates soiled with a layer of hardened vegetable oil of a certain weight were placed one after the other in the washing water and this was used for washing until the foam collapsed; the number of this

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109812/1548

washed taller was determined repeatedly. Both in the hard and in the relatively soft water, the product showed a very good practical value. When using an alkylbeaaolsulfonate with an alkyl group distribution of 50 Ji! C ₁ ^ and 50 & C ₁ * instead of the above-mentioned alkylbenzenesulphonate, significantly fewer plates could be washed under the same conditions in both hard and water. When using alkylbenzenesulfonates in which the benzene radical was bonded to the carbon atom in the 2-position of the alkyl group, comparisons in products with alkyl group distributions of 33 1/3 % C ₁₀ , 33 1/3 # C ₁₁ , 33 1/3 * C ₁₂ or 20 % C ₁₀ , 60 % C ₁₁ , 20 % C ₁₂ or 30 %. C ₁₀ , 40 % C ₁₁ , 30 % C ₁₂ also received significantly poorer results, especially in those water.

Example 2. .

Example 1 was repeated, but instead of the 6 % lauric acid monoethanolamide, 6 % lauric acid fflonoethanolamide was used.

Example 3

Example 1 was repeated, except that alkylbenzenesulfonates were used with the benzene length of carbon atoms in 4-, 5- and 6-position of the alkyl chain and alkyl group distributions of

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109ai2 / 1548

1817047

(a) 20 $ C ₁ Qi βθ% C _n and / 20 tf

50 ^ C ₁₁ imd 50 ^ C _12,.

e) 30 # C ₁₀ ,

and " ^:

used.

It has a biological, abbatsbares liquid medium Gasehirrwaseh- din'ch-Vermischen'yon 24% wsiter below nJähsr beschrie benem NatriumaJicjrlbengolsulfonat _t Ik% Alkyläthersülfat according to Example 1, ö f> Monoäthanolajöid na © h Example -1, 7 ^{^:} iatriumxylolsulfonafc , 3 ^ 'ethanol, @ about 3 ^' balances ('i iilkylbenzenesulfonate

were'in her®m

on

BATHROOM OBlQIMAL

of linear alkylbenzene sul foraatea with one? not in the frame the structure covered by the invention are made, both in relatively soft (100 ppm hardness) ria as well EXTREMELY EFFECTIVE IN HARD WATER (£ 50 pps).

If, in the product manufactured according to this example, the fatty acid aonoethai oil was exchanged for a fatty acid & irediäthanolaißid of the same fatty acids, there was a substantial decrease in the washing effect by increasing the dietary oil content to 8 % However erbesservang the effect © rzislt ₉ was the Frod & kt iisuaer still much less effective than the Prodölsfe 6% Moaoäthanolamid.

When testing with the standard amount currently in use of 1.5 S S @ s © hirrwasohsitt @ I «üf 1 liter ¥ ess« r was over-

found «dsf di @ in

Products ¥ nd © th MonoIfchanolÄmid® eise besmidere effect on%? Ice «ffis ^ wesm si © at Kcmsentrati ^ no ^ the mentioned alkylb @ ns © lsulfenatea® € Al ^ rlätfeersiilf at® vea a total of 33 % ..

or more ®sjg®w ©? aä © i5 »For these, Product® ^ rnsrd © diia5? @Li Srhifötmg des

from 3 tmt 6% 'min® & @ hi? strong Zunana » φ & ρ aims (sB 38 fell.®! ³ .feet .6-Ji compared to 30 plates at Dies® WivkuiQS is obosE ^ aacHeaa ^ fe when the quantities MStäanolfuaäu © la® i3®s © sfelieH /" lower improvement with irfeÄ ^ sg ü © r Ami ^ unzmntwmtlQn achieved hurdle

^N - BAD Of ^ QlNAL

(· Η · 35 plates at £ 8 and 33 plates at 6 % versus 30 plates at $ 3} * Ia Geg © nsatK da & a was with a lower total concentration of the alkylbenxol sulfonate and alkyliibhersuliats used according to the invention (see example, a total concentration of 28 % Application of 0.5 g of Ctesehirrwaechruittel to 1 liter of water) this big difference in the effect of the two aaids was not observed.The above-mentioned concentration of 33 % corresponds to a total concentration in the washing water of 0.5 g of benzene sulfonate plus alfcyther sulfate in 1 liter of solution.

Another embodiment of the invention can be used instead of fat & ireiononanolamide is also a long-chain one Alkylamine oxide can be used in equal amounts. Pearly Aaiine oxides are for example Lauryl & imethylarainoxyd, LatiryldihydroxyäthylaJBinoxyd, Myristyldimetliylaminosyd and ■ Btyristyldihydroxyätbylaminoxid.

According to a further embodiment of the invention can also a mixture of, alkyl fenzenesulfonate and alkyl ether sulfate of the types mentioned without the addition of amide or amine oxide or can be used in combination with other foam stabilizers or other additives. Such mixtures, in which the ratio of alkylbenzenesulphonate to alkylstheresulphate for example the same as described in the » A three-component system can be advantageous

BATH

for. the same purposes as the «three-component system, if can also be used with somewhat less effect to achieve advantages of the invention. For example, those described in Examples 1, 3 and 4 are suitable Products also without the addition of mono-kthanolamide for> the purposes of the invention.

The products of the invention come also instead of in liquid form 'in solid, dry form, such as Manufactured as deep or powdered products will.

1098-12 / 1648

Claims (1)

(U-S. -4-50,509 -prio 25.4 * 1965 4079) Golgate-Falmoli \ »e Cosspsny Hew York. N.Y./V.&fc. A, • Hamburg * March 23, 1966 1. detergents, in particular dishwashing detergents, characterized in that daJ. ®s © in linear alkylbenzenesulfonate, in which the mole © kul ^ gewielit of the alkylphenyl part ■; 23O to 240 and - ± m alkyl groups of at least 80 mol from groups with 10 to "12 -C atoms and at least half of" groups "with 10 to 3.2 -C Atoms and mlndest®sss 45
old 10 to 11
with 14 C ~ Ätoiieii _ß % n
, 9 G-At © m. © n and to h8 @ föst «ss" 15 S ^. ®> us 13 Si a sulfate
with. 10 rock ■■ '... "■■' ■ ■ '..- ■" BAD ORlG *. Sol. 11 2 / ti6i ^: 3 «. Detergent according to Claim 1 and 2, characterized in that that ea also contains a foam stabilizer. 4 detergent according to claims 1-3 * characterized in that that it is a MonoHthanolamld of a fatty acid with 11 to IjJ contains .C atoms. 5 «Detergent according to claim 1 - 4, characterized» that, as an aqueous solution, it affects the entire product related content of sulfonate plus sulfate of at least 30 # is present. 6 · detergent according to Anapruog. 1-5, characterized in that ee in aqueous solution, based on the total product Jr, contains up to 40 % sulfonate plus sulfate and at least 5 % Pett's and iremonoethanolamide, the amount of Pett's monoethanolamide 1/8 to 1/5 = the total amount of sulfonate plus Sulfate. 7 »Geschlrrwa® © hmitt <ai according to claims 1 - 6, characterized by the fact that @ @@ in aqueous solution, based on the Qesaiatprmlukfe 55 to 40 % sislphonate plus sulfate and at least. @ Tm 5 $ to at most 1/5 of the Siilf © aat plMs SMifat an FettsguremonoSthanolasiid whereby the Stilfat 1 to 5 O-xyäthylgruppaß ,. the aiaid. in the Fatty acid part contains 11.4 to 12.6 carbon atoms and the sulfate in the alkyl part contains at most 10 % groups with 13 carbon atoms and the ratio sulfate to sulfonate is 0.4: 1 to 0 * 7. S. Process for washing dishes, characterized in that that in the washing water a detergent according to claims 1 to 7 in an amount of 0.5 g of sulfonate plus Sulphate used per liter of water. '.- ■ -. " : * ' BAD ORIGINAL 1 OSSi 2 / tS4S