DE2159435A1 - Detergent - Google Patents

Description

UNIIiEVER N.V. Museum Park 1, Rotterdam / Holland

Detergent

Priority: December 4, 1970, UK No. 57647/70

The invention relates to detergents and, more particularly, to those for use in fabric washing.

Detergent for rough washing of textiles in washing machines Nines for textiles comprise active detergent compounds as major components and builders. The most used Builders are condensed phosphates, especially sodium tripolyphosphate, although others are inorganic or organic Materials, e.g. sodium nitrilotriacetate and sodium copolyethylene maeate were proposed.

It has been suggested that the use of condensed phosphates as builders in - ^ etergensraiddle to the appearance of the Eutrophication contributes. Considerable effort has been made to find other builders which do not contain phosphorus and yet are at least as effective as those previously available Materials are, but not asu expensive, one or the other have disadvantageous properties.

In the eohwebenden patent application P 19 39 973.6 are detergent products described which salts of

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DIcarboxy acids of the general formula R.CH (COOH), (CH ₂ ) _n .COOH

contain, wherein η 0 or 1 and R is a primary or secondary straight-chain alkyl or alkenyl group with from 1Q to to 20 carbon atoms.

It has now been found that other water-soluble or water-dispersible salts of dicarboxylic acids are builders and advantageously used in detergents can. Such other dicarboxylic acids have the general formula χ y

, R ₁ -CH- CH- R ₂ - CH (COOH). (CH ₂ ) _n .COOH (I)

wherein R ^ is a hydrogen atom or an alkyl or substituted alkyl group with from 6 to 20, preferably from 10 to 20 carbon atoms, R _{2 is} an alkylene or substituted alkyl; group with from 0 to 4 "preferably from 0 to 1 carbon atoms and optionally with heteroatoms as bonding" groups, the total number of carbon atoms in the groups R 1 and R _{2 being} from 6 to 20, and in which X and / or Y are not -ionizable atoms or groups or otherwise denote a hydrogen atom, and η is 0 or 1.

For the sake of simplicity, the frameworks according to the invention are referred to below as substituted dioarboxylic acid salts.

RJ and R ₂ are preferably linear.

The preferred non-ionizable atoms or groups are Halogen atom ·, in particular chlorine or bromine, and hydroxy groups

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the presence of any additional ionizable groups in the substituted dicarboxylic acids tends to compromise the scaffolding ability to weaken the substituted dicarboxylic acid salts.

A detergent composition according to the invention comprises at least one Active detergent compound and at least one substituted dicarboxylic acid salt as defined above, wherein the weight ratio the active detergent compound to the substituted dicarboxylic acid salt within the range of about 10: 1 up to about 1:10.

The substituted dicarboxylic acid salt is preferably an alkali salt, for example a sodium, potassium or lithium salt, with sodium salts being particularly preferred, but other cations such as ammonium or substituted ammonium can can also be used if desired.

Preferably the weight ratio of the active detergent compound is to the substituted dicarboxylic acid salt in the range of about 2: 1 to about 1: 4.

The substituted dicarboxylic acid salt usually comprises at least about 5, and preferably from about 20 to about 60 Wt% of detergent, although higher levels may also be required can be when the detergent in low concentrations or in a water of particularly high hardness should be applied.

Substituted dicarboxylic acids according to the invention can be prepared are malonic acid or its salt or an alkenylsuccinic acid by addition to the double bond of an alkenyl

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or their salt or anhydride. The addition reaction will "accomplished using standard methods to obtain a '. To give manifold of different groups X and Y in formula (I). X and Y can be the same or different Be groups, and if they are different, it should be noted that each of the different represented by X and Y in the formula (I) groups shown closer to the dicarboxyl head group in the molecule can be. Examples of various reagents. which with the appropriate starting materials, d.s. the Alkenyl succinic or malonic acid or its salts or anhydride can be reacted to give the various additive groups X and Y are shown in Table I below shown.

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reagent -5- * Source material Product group Tabel chlorine I. anhydride Γ T-
-CH - CH - bromine Anhydride ■ ff
-CH-CH- OH Cl
-CH-CH- Chlorinated water acid OH Br
-CH-CH- Bromine water acid Cl
t Hydrogen chloride anhydride - CH ₂ - CH - Br
ι Hydrogen bromide anhydride - CH ₂ - CH - OH OH
I i
-CH-CH- Alkaline potassium
permanganate Sodium salt -CH-CH- Perbenzoic acid anhydride OH
-CH-CH-
OH r
- CH ₂ - CH - Performic acid acid NO ₂
- CH - CH ₂ - hydration (e.g.
IgSO. Addition with after
following hydrolysis acid nitric acid anhydride

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■ -6-

The "preferred starting materials which are used to prepare the substituted dicarboxylic acids of the invention are lkenyl succinic acids or their salts or anhydrides, which can be prepared by the reaction between an olefin and maleic anhydride to give an alkenyl succinic anhydride which is then hydrolyzed to to give the acid, and then neutralized, if desired to give the salts «In the alkenylsuccinic acids or their anhydrides or salts, the double bond in the alkenyl group is predominantly between the 5th and 6th carbon atom, in which case R ₂ in of formula (I) contains no more than 1 carbon atom, but some amount of migration of the double bond along the carbon chain occurs, either during the preparation of the alkenyl compound or during the reactions to form the compounds of the invention, so that R1 contains up to about 4 carbon atoms can _e

Alternatively, the starting material can be an alkenyl malonic acid and its salts or anhydride. These can be prepared using standard malonic acid ester synthesis methods be prepared, wherein a sodium malonic acid diester with an alkenyl halide, for example wise chloride, is converted to the alkenyl malonic acid ester followed by customary treatment to form the acid, anhydride, or salt if desired »In This Pail the position of the double bond will depend on the position of the double bond in the alkenyl halide used. Another way of producing an alkenylmalonic acid and its derivatives is by condensation of one

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in which case the double bond was located directly on the malonic acid group

_R E according to the invention substituted dicarboxylic acids can also be prepared by reaction of a halogen with an alkylsuccinic acid or alkylmalonic acid, in which case the substitution tends to occur in the alpha position on the carbon chain.

A detergent according to the invention will contain at least one active detergent compound. The substituted dicarboxylic acids Salts of the invention themselves have a limited active detergency, but since these salts with Intent to be selected as precipitating builders, for what purpose their substituted starting dicarboxylic acids have to form water-insoluble calcium salts, these will Salts are not considered as active detergent compounds for the purposes of this description «The active detergent content of the Average will generally be from about 5 to about 50, preferably from about 5 to about 35, and especially from about 10 to about 25 percent by weight of the agent. The type of active detergent compound or compounds in the agent is not an essential feature of the invention. Any active detergent compound, which is commonly incorporated into detergents or suggested for this purpose can be used. The specialist in the manufacture of washing and Detergents is made with active detergent compounds familiar with different quantities and combinations; and knows how to use them in an advantageous manner. The active detergent compound or compounds can be anionic, nonionic, amothermic or zwitterionic

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Typical anionic active detergent compounds are water-soluble or water-dispersible salts of various organic acids ". The cations of such salts are generally alkali metals such as sodium and, less preferred, potassium, but other cations, e.g. ammonium and substituted ammonium, can be used if necessary." Examples are suitable Organic acids are: alkylbenzenesulfonic acids, the alkyl chains of which contain from about 8 to about 20 carbon atoms, for example p-dodecylbenzenesulfonic acid and linear alkylCCj _0-15 ) benzenesulfonic acid; the mixtures of sulfonic acids obtained by reacting linear and branched olefins, in particular linear "cracking" or "Ziegler" alpha-olefins, which contain from about 8 to about 22 carbon atoms, with sulfur trioxide; Alky! Sulfonic acids obtained by reacting alkanes having from about 8 to about 22 carbon atoms with sulfur dioxide oxygen or sulfur dioxide / chlorine (followed by hydrolysis in the latter batch) or by addition of bisulfite to olefins, in particular linear "crack wax" - or ^M Ziegler "-alpha-01efine with contents of about 8 to about 22 carbon atoms; alkylsulfuric acids obtained by reacting aliphatic alcohols with from about 8 to about 22 carbon atoms with sulfur trioxide / alkyl ether sulfuric acids obtained by reacting molar amounts of aliphatic alcohols with from about 6 to about 18 carbon atoms with from about 1 to about 15 moles of ethylene oxide or a suitable mixture of ethylene oxide and propylene oxide, and subsequent reaction of the alkoxylated alcohol with sulfur trioxide to form

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the required acid; and natural or synthetic aliphatic carboxylic acids, especially those from natural sources such as tallow, coconut oil, palm oil, palm kernel oil and Peanut oil.

Examples of suitable nonionic active detergent compounds are: condensates of alkylphenols with an alkyl group (derived for example from polymerized propylene, Diisobutylene, octene, dodecene or honing) with from about 6 to 12 carbon atoms in a straight or branched chain with about 5 to 25 moles of ethylene oxide per mole of alkylphenol; Condensates containing from about 40 to about 80% by weight of polyoxyethylene with a molecular weight of about 5000 to about 11000, which results from the reaction of ethylene oxide with the Result of reaction product of ethylenediamine and excess propylene oxide; Condensates of linear or branched chain aliphatic alcohols having from about 8 to 18 carbon atoms with ethylene oxide, e.g. a coconut oil alcohol-ethylene oxide condensate with about 6 to 30 moles of ethylene oxide per mole of coconut oil alcohol; long-chain tertiary amine oxides according to the general

Formula R ₁ R ₂ R ₃ N »0, where R _{1 is} an alkyl radical having from about

8 to 18 carbon atoms and R ₂ and R _{3 are} each methyl, ethyl or hydroxyethyl radicals, such as, for example, dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethylhexadecylamine oxide and N-bis (hydroxyethyl) dodecylamine oxide; long-chain tertiary phosphine

oxides according to the general formula RR "R" P ^ 0, in which

R is an alkyl, alkenyl or monohydroxyalkyl radical with von 10 to 18 carbon atoms and R »and R« are each alkyl or Are monohydroxyalkyl groups of from 1 to 3 carbon atoms

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as ζ.B ₀ Dimethyldodecylphisphinoxyd, Dimethyltetradecylphosphinoxyd, Ithylmethyltetradecylphosphinoxyd, Dimethylstearylphosphinoxyd, Äthylpropylcetylphosphinoxyd, Diäthyldodecylphosphinoxyd, bis- (Hydroxymeth.yl) -dodecylpliosph.inoxyd, 2 bis- (2-hydroxyethyl) -dodecylphosphinoxyd, 2-Hydroxypropylmethyltetradecylphosphinoxyd, Dimethyloleylphosphinoxyd and dimethyl-2- hydroxydodecylphosphine oxide and dialkyl sulfoxides

corresponding to the general formula RR ¹ S> 0, where R

is an alkyl, alkenyl, beta or gamma-monohydroxyalkyl radical or an alkyl or beta or gamma-monohydroxyalkyl radical with one or two oxygen atoms in the chain, the R groups containing from 10 to 18 carbon atoms, and in which R ¹ denotes a methyl, ethyl or alkylol radical, such as dodecylmethylsulphoxide, tetradecylmethylsulphoxide, 3-hydroxytridecylmethylsulphoxide, 2-hydroxydodecylmethylsulphoxide, 3-hydroxy-4-dodecyloxybutyl, dodecyloxybutyl, 2-methylsulphoxyd, 2-methylsulphoxy, 2-methylsulphoxy, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxy, 2-methylsulphoxy, 2-methylsulphoxy, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxyd, 2-methylsulphoxy, tetradecylmethylsulphoxide, tetradecylmethylsulphoxide, 2-de 2-hydroxyethyl sulfoxide.

Examples of amphoteric active detergent compounds are: Derivatives aliphatic secondary and tertiary amines, wherein the aliphatic Radically straight-chain or branched and wherein one of the aliphatic substituents from about 8 to Contains 18 carbon atoms and one an anionic water solubilizer Group, such as sodium 3-dodecylaminopropionate, Sodium 3-dodecylaminopropanesulfonate and Sodium N-2-hydroxydodecyl-li-methyltaurate

Examples of suitable zwitterionic active detergent compounds are: Derivatives of aliphatic quaternary ammonium compounds

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compounds, sulphonium compounds and phosphonium compounds in which the aliphatic radical can be straight chain or branched and wherein one derjaliphatischen substituents contains from about 8 contains up to 18 carbon atoms and containing a einejaliphatische water-solubilizing group, Z ₀ B. 3- (N, N-dimethyl-N-hexadecylammonium ) propane-1-sulfonate betaine, 3- (N, N-dimethyl-N-hexadecylammonium) -2-hydroxypropane-1-sulfonate betaine, 3- (dodecylmethylsulfonium) -propane-1-sulfonate betaine and 3- (cetylmethylphosphonium) ethanesulfonate betaine .

Further examples of suitable active detergent compounds, such as they are commonly used in the art can be found in the book "Surface Active Agents" Volume I of Schwartz and Perry (1949) and in the book "Surface Active Agents" Volume II by Schwartz, Perry and Berch (1958), whose the entire disclosure is incorporated herein by this reference.

The substituted dicarboxylic acid salts according to the invention can make up the total builder content of the detergent according to the invention. However, if desired Mixed from one or more of these salts with one or more several known builders are used «. There one The objects of the invention is to provide an effective detergent agent with either no phosphorous or at most only one In order to create a low phosphorus content, it is preferred that such any other builder does not contain phosphorus Connection should be. Usually the total content of builders in a detergent according to the invention is from about 5 to about 70 percent by weight of the detergent ", Many

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Builders are known and those skilled in the textile detergent are familiar with these materials. Examples of known builders are sodium tripolyphosphate · j sodium orthophosphate; Sodium pyrophosphate; Sodium; lumtrimetaphosphate} NatriuJa ethane-1-hydroxy-1,1-diphosphonate; Sodium carbonate, sodium silicate; Sodium citrate; Sodium oxydiacetate; Sodium nitrilotriacetate; Sodium ethylenediamine tetraacetate; Sodium salts of long-chain dicarboxylic acids, for example straight-chain (C ^ ₀ to Cpo ^ succinic acids and malonic acids; sodium salts of alpha-sulfonated long-chain monoearboxylic acids, sodium salts of polycarboxylic acids - these are acids derived from the polymerization or mixed polymerization, maleic acid, acrylic acid, methacrylic acid, such as methacrylic anhydric acid, such as italic anhydric carboxylic acids, and italic anhydric acid , Crotonic acid and aconitic acid, and the anhydrides of these acids, and also - from the copolymerization these acids and anhydrides with small amounts of other monomers, e.g. vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate and styrene; and modified starches, e.g. starches,

for example
oxidized / using sodium hypochlorite, some

Vßn

ge anhydroglucose units with formation / dicarboxyl units opened.

In addition to the active detergent compounds and builders A detergent according to the invention can be any the usual ingredients of such detergents in any amount, in which such usual additional Components commonly used therein. Example * such additional ingredients are foam boosters, like

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Coconut oil monoethanolamide and palm kernel oil monoethanolamide; Foam regulator; inorganic salts such as sodium sulfate and magnesium sulfate; bleaching agents such as sodium perborate, sodium percarbonate, Trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates; Anti-redeposition agents, such as Sodium arboxymethyl cellulose; and usually only present in smaller quantities perfumes, dyes, fluorescent Substances, corrosion inhibitors, germicides and enzymes.

A detergent according to the invention can be used customary manufacturing processes, as they are generally used for the production of ^ etergensmittel produced be, 55.B. Preparation of a porridge with subsequent spray drying or spray cooling and subsequent addition of drying sensitive components which are not suitable for incorporation before the drying stage. Other common ways of working e.g. noodles, granulating and mixing by fluidizing in a fluidized bed, can be used, as and when required. Such procedures are familiar to those skilled in the manufacture of detergents.

By application of such conventional methods an inventive D _e kana tergensmittel in each etergensmitt for ^ ^ l usual form prepared, for example as powder, flakes, grains, pasta, pieces, bolts and also as liquid preparations.

The invention is further illustrated in the following examples,

as
where parts and percentages are given by weight.

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example 1
Production of disodium dichloro-hexadecyl succinate

Chlorine was slowly passed through a vigorously stirred solution of 250 g of hexadecenyl succinic anhydride in the minimum volume of carbon tetrachloride containing 2% by weight of ferric chloride (based on the alkenyl succinic anhydride) at room temperature until an excess of chlorine was found in the flask head . The ferric chloride and the solvent were then removed and the crude dichloro compound by percolating in light petroleum (bp 60-80 ⁰ C) solution downstream purified in a column of silica "

The product was poured evenly into a

in alcohol

stirred solution of sodium hydroxide / (lO ^ ig) with 10 # molar Excess hydrolyzed. The disodium salt which precipitated was filtered off and washed with a little ethanol Remove excess base and colored by-product, and on drying gave a light brown product (226 g 65 # yield) mainly from disodium sjö-dichloro-hexadeeylsuccinate, where the carbon atoms are counted along the longest chain

Example 2

Manufacture of disodium dihydroxyhexadecyl succinate

Formic acid (850 ml) and 30% hydrogen peroxide (75 ml) were added to a solution of hexadecenylsuccinic acid, prepared by conventional saponification and subsequent acidification of 250 g of the corresponding anhydride. The solution was stirred at 40 ⁰ C for 4 hours and then basified with sodium hydroxide and heated for 1 hour to RIAA Attip-i

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Hydrolyze intermediate. The free acid was precipitated from the solution by acidification with concentrated HCl, filtered off and dried.

The “calculated amount of aqueous Sodium hydroxide was added and the water was then removed by distillation to give 256 g of dry product, which predominantly from disodium stö-trans-dihydroxy-hexadecyl succinate consisted of the numbering of the carbon atoms took place along the longest chain ",

Example 5

Manufacture of mixed disodium hydroxyhexadecyl succinates

To a solution of 65 g hexadecenylsuccinic in 200 ml of 1,4-dioxane 20 g of concentrated HpSO * were slowly added with stirring while the temperature was maintained at 20 ⁰ C. Upon completion of addition the reaction was continued for a further 2 hours and then zugeset a Eösung of 32 g of sodium hydroxide in water for 1/2 hour and the whole stirred solution still for 20 hours at 6O ⁰ C A white solid formed, which was filtered , was washed with dioxane and then with diethyl ether and then dried to give 55 g of product ($ 68) which consisted predominantly of the 5- and 6-hydroxy compounds, wöbe :. the carbon atoms were numbered along the longest chain.

Example 4

Production of disodium epoxy-hexadecyl succinates

150 g of m-chloroperbenzoic acid were in

redeems rmri

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this solution then to a stirred solution of 250 g of hexadeeenyl succinic anhydride in ether / chloroform (1: 3) added so that the "temperature" remained at 25 ° C. The reaction: was continued for 17 hours (overnight), betfor the excess peracid by adding a 10 ^ igen aqueous Solution of sodium bisulfite was destroyed ». The solution was

after another
then quickly washed söwoö & jgigQiKJc with 5 # aqueous sodium carbonate solution, water and brine, before the organic layer is dried with anhydrous sodium sulfate and the. Solvent is removed. The yield was 142 g, mainly from disodium S ^ -epoxy-hexadecylsuceic acid anhydride, which was then hydrolyzed to the disodium salt.

Example 5

Manufacture of disodium bromohydroxyhexadecylsuecinates

The dicarboxylic acid, which was formed by hydrolysis of 50 g of hexadecenylsuccinic anhydride, was dissolved in water and a dilute solution of bromine (12.5 g) in 500 ml of water was added at 20 ^° C. The entire solution was kept at 20 ^° C. for 2 hours and then neutralized with sodium hydroxide and evaporated to dryness. The analysis showed

assumes that the product is $ 70 from bromohydrin and 30 ^ / dibromo-

connections existed.

Example 6

Manufacture of disodium hydroxyhexadecyl malonate

23 g of sodium were dissolved in 600 ml of dry ethanol and 160 g of diethyl malonate at 50 ° was added. The mixture was stirred for 15 minutes, then 240 g of dry hexa-

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decane-1,2-epoxy added. The mixture was made under mild Boiled under reflux for 2 1/2 hours and allowed to cool left »The precipitated product was filtered off and for 1 hour with a slight excess of aqueous Sodium hydroxide heated. The solution was filtered and that Piltrate evaporated to dryness.

Example 7

Production of disodium nitro-hexadecyl succinates.

To a mixture of hexadecenylsuccinic anhydride that is under flood (14.8), nitric acid (13.5 g, 705 & Lg AR grade) and water (18.0 g) were added all at once Solution of sodium nitrite, equivalent to about 0.5 molar $ on the anhydride. Nitration was continued at reflux temperature until browns appeared had stopped loving (1 hour). The solution was cooled to allow two layers to form and the aqueous Layer was separated and with Äthei? extracted. The combined organic layers were washed with water and Washed brine and dried over magnesium sulfate and filtered. The solvent was removed leaving of 13.0 g of a mixture of mainly mitrohexadecyl succinic acid with some of the corresponding anhydride. The mixture was then completely hydrolyzed and neutralized around the disodium salt predominantly of 5- and 6-nitro hexadecylsuccinic acid to build"

Examples 8-14

The scaffolding ability of the seven substituted alkyl succinates and malonates, prepared as in the examples

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1 to 7 was made according to the following procedure certainly.

Disks made of desized cotton batiste were soiled with a radioactive synthetic sebum which was deposited on the disks in an amount of $ 1.5 from a dilute benzene solution. After drying, the soiled disks were placed in the detergent solution which contained 0.05 wt 45 ⁰ C for 2 10 minutes in water of 25 ° H washed at a pH of 10 and a repeatable degree of agitation of 70 rpm. The percent cleaning of each material was determined by counting the radioactivity of each washed cotton disc before and after washing and the detergency was determined according to the equation:

A ₁ - A ₂

Cleaning power $ = 100

^A 1

calculated, where A .. is the corrected radioactivity count before washing and A _{2 is} the corrected radioactivity count after washing.

The results obtained for the novel builders together with a comparison result using sodium tripolyphosphate follow in Table II.

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-19 ·! Dabelle II

Builder

Disodium dihlorhexadecyl succinate from Example 1

Disodium dihydroxylaxadecyl succinate from Example 2

Dinatriteunhydr oxyhexadecylsuccinate from example 3

Disodium epoxyhexadecyl succinate from Example 4

Disodium bromohydroxyhexadecyl succinate from Example 5

Disodium hydroxyhexadecyl malonate from Example 6

Disodium nitrohexadecyl succinate of example 7

Sodium tripolyphosphate cleaning effectiveness * /

57.8 78.5 52.6 74.8 34.4 64.8 . 37.9 37.3 36.3 52.9 59.0 72.9 43.0 61.0 69.3 78.8

These results show that all tested substituted dicarboxylic acid salts according to the invention builder capacity

gen and those of Examples 1, 2 and 6 / ± HÄ especially cheap with the usual builder sodium tripolyphosphate let compare.

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Claims (1)

Sponsorship claims 1. De tergensin means comprising an active de tergent compound and one or more builders, characterized in that at least one of the builders a water-soluble or water-dispersible salt of a dicarboxylic acid of the general formula XY ι ι R ₁ - CH - CH - R ₂ - OH (OOOH). (CH ₂ ) _n .GOOH where R ^ is a hydrogen atom or an alkyl or substituted alkyl group with from 6 to 20 carbon atoms, R _{2 is} an alkylene or substituted alkylene group with from 0 to 4 carbon atoms and optionally with heteroatoms as bonding groups, the total number of carbon atoms in the groups R .. and R _{2 is} from 6 to 20, and wherein X and / or Y are non-ionizable atoms or groups or otherwise a hydrogen atom, and η is 0 or 1, and that the weight ratio of the active detergent compound to the Xj_Bx ± i ± n ± KX ± fiH dicarboxylic acid salt is within the range of about 1:10 to about 10: 1, 2 ο detergent according to claim 1, characterized in that one or both ?? the symbols X and Y are a halogen atom, a hydroxyl group, a nitro group, or X and Y together form an epoxy group of the structure ./ ⁰ p - CH - CH - form. 2 (J 9 8 2 '' / I f ^: 1 2 3 ο detergent composition according to claim 2, characterized ₉ that one or both of X and Y is a Ohloratom, a bromine atom or a hydroxy group. 4 <> detergent according to any one of the preceding claims, characterized in that R ^ from 10 to
Contains 20 carbon atoms 5. Detergent according to one of the preceding claims, characterized in that R _? contains no carbon atom or only 1 carbon atom » 6. Detergent according to one of the preceding claims, characterized in that the weight ratio the active detergent compound to the dicarboxylic acid salt is from about 2: 1 to about 1: 4. T ₉ detergent according to one of the preceding claims, characterized in that the dicarboxylic acid salt is a sodium salt. 8. Detergent according to one of the preceding claims, characterized in that the dicarboxylic acid Salt at least about 5% by weight? » of the detergent, 9. detergent according to claim 8, characterized in that the dicarboxylic acid salt of about 20 to about 60 wt.% of the detergent