DE1617184A1 - cleaning supplies - Google Patents

Description

Dr. Walter Beil ig. Dec. 196S

Alired Koepp bull . - ·

Dr, Kaiis Joidi ^ Wolff 1617184 Dr, Hans Chr. Beil

Rectiisarian lawyers

Frankfurt a. M, - maximum

AdeionstxaBe 58 - TeL 3126 4?

- Our No. 13 252 -

The Procter & Gamble Company Cincinnati, Ohio, V.St.A.

cleaning supplies

The invention relates to cleaning agents with superior properties, in particular those containing builders, liquid cleaning agents in the form of permanent oil-in-water emulsions.

Looking for liquid detergents with superior properties in a wide variety of conditions, such as e.g. when using cold water, there is lively demand. Many components are necessary for this and the production of liquid detergents is very difficult when they contain many different materials, contain both organic and inorganic. For example, if the liquid detergent contains inorganic builders contains, it tends to form a second phase with some of the organic materials. Also can individual components react with one another, thereby impairing one or both components.

109809/1880

The aim of the present invention is a builder containing liquid cleaning agent with superior properties that are also found e.g. in make cold water usable. This detergent is a well-tolerated one made up of several components existing, liquid, permanent emulsion; it is superior in whiteness retention Properties. For this purpose detergents are mixed appropriately.

These and other objects can be achieved by using a liquid containing builders Detergent composition in the form of a permanent oil-in-water emulsion which essentially consists of the following components:

. 1) about 1 to about 15 wt%, preferably about 3 to about 12 weight% of a nonionic detergent having the following formula.:

R (-OCH ₂ CH) _Y (-CH ₃

in which R is alkyl radicals having from about 8 to about 18 carbon atoms or alkylphenyl radicals, the alkyl groups from about 9 to about 15 carbon atoms Y is an integer from 0 to about 7, and Z is an integer from about 5 to about 45.

2) About 1 to about 10 weight percent of any of the following Detergents

109809/1886

a. A sultain detergent having the following formula: R ²

R ¹ _ N * - CH ₂ - R ⁴ - SO ₃ ^θ

in which R is an alkyl radical with about 1o to about

2 represents 3 carbon atoms; R and R respectively

a methyl, ethyl or hydroxyethyl radical be ™

interpret; R is a methylene, ethylene or propylene radical and X is hydrogen or a hydroxyl group, the hydroxyl group on one secondary carbon atom.

b. A detergent of the following formula:

R ⁶

R ⁵ - Q - 0

: t ⁷ -

in which R is an alkyl or monohydroxyalkyl radical means with about 10 to about 24 carbon atoms, with a content of 0 to about 3 ether bonds and a molecular fraction that is about 10 to about 18 Contains carbon atoms and no ether bonds. R and R each represent a methyl, ethyl, Hydroxyethyl, propyl or hydroxylpropyl group and Q is a phosphorus or nitrogen atom.

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1 BI 7184

c. Mixtures of these detergents

3) About 10 to about 36 weight percent builders from alkali (e.g. Sodium or potassium pyrophosphate, alkali salt,

Ammonium or substituted ammonium salts of nitrilotriacetic acid, ethane-1-hydroxy-1,1-diphosphonic acid or ethylenediaminetetraacetic acid, potassium tripolyphosphate or mixtures of these materials, with no more than about 10 weight percent potassium tripolyphosphate are present.

4) An emulsion stabilizer, namely ethylene-maleic anhydride copolymers with a specific viscosity of about 0.5 to about 1, which was determined with a 1 percent solution of the copolymer in dimethylformamide at 25 ^° C. or methyl vinyl ether-maleic anhydride copolymers whose specific viscosity is about o, o 1 to about 6, wherein the specific viscosity was determined with a 1 percent solution of the copolymer in methyl ethyl ketone at 25 ⁰ C. If the first-mentioned emulsion stabilizer is used, then it is present in amounts of 1 to about 2 % by weight, and when the last-mentioned emulsion stabilizer is used, its amount is about 0.3 to about 1.5% by weight. Mixtures of the stabilizers mentioned can also be used.

5) Water as the remainder, the pH of the composition being between about 11.7 and about 13

When combined in the specified proportions, these constituents lead to the desired one Product durability and the high quality properties in its use.

109809/1880

The pH of the above composition is, if necessary, by adding e.g. potassium hydroxide, Sodium hydroxide, lithium hydroxide or the corresponding oxides brought to about 11.7 to about 13, ο. All Unless otherwise stated, percentages, parts and ratios are based on weight.

Numerous other ingredients can optionally be added to the above mixture to achieve specific effects without significantly departing from the basic laundry properties desired. This includes about 0.1 to about 0.5% of a germicide with the following formula:

13th

R ¹² -

NO

12th
in which R is an alkyl radical with about 8 to about 18 carbon

13 14 substance atoms means, R and R are each a methyl,

15 * ethyl or propyl group, R a methyl, Represents ethyl or benzyl group and X is a bromide, Is fluoride or chloride anion. ·

The discontinuous phase, i.e. the oily phase of the oil-in-water emulsions according to the invention the non-ionic detergents, at least the majority of the other detergents (2) and, it is believed, the majority of the other organic components present in small amounts, such as a.B, optical brighteners

PAD OHiGINAL

109809 / 1ö80

and pigments. To achieve an oily "phase must be
the non-ionic detergent may be oily, although it need not be a liquid oil. examples for
suitable non-ionic detergents from the general group given above are:

(1) Tetrapropylene phenol, which contains about 11 moles of ethylene oxide is condensed per mole of tetrapropylene phenol,

(2) Coconut alcohol containing from about 5 to about 8 moles
Propylene oxide condensed per mole of coconut alcohol

w is and the resulting reaction mixture

then with about 7 to about 10 moles of ethylene oxide is condensed per mole of the reaction mixture.

The function of the non-ionic detergents is
twofold. On the one hand, as described above, non-ionic detergents represent the main component of the oily phase. On the other hand, they do not impart
ionic detergents give the compositions when they are used for laundry the desired properties leading to the retention of the whiteness.

ψ Specific examples of group (2) detergents are:

a. Sultain detergents

Of particular interest are those where the long alkyl chain (R) is a specific
C ₁ -C. "- alkyl or a mixture of alkyl cats derived from naturally occurring hydrogenated or
non-hydrogenated substances and in which the short alkyl chains are methyl groups * ijtammt ζ , Β. R of tall oil or coconut oil, iat ίΓ an ethylene radical in which a hydroxyl group -λ-u : a.? ^; ; ; -t «reu coal-

BATH ORIGINAL

10 9 8 0 9/1880

Substance atom of the CH ₉ -R group is substituted

2 3
and R and R are methyl groups. The Sultaindeter- gene is particularly preferred "Other specific examples of preferred Sultaindetergentien are 3- (N, N-Oimethyl-N-hexadecylammonio) propane-1-sulfonate, 2- (N-methyl-N-ethyl-N-decyl) - Ethane-1-sulfonate, ^ - (NjN-diethyl-N-tetradecylJ-butane-isulfonate, k- / ß, N-di- (2-hydroxyethyl) -N-octadecyl / ^ - hydroxy-butane-1-sulfonate, Z- / W, N-di (2-hydroxyethyl) -N-dodecyl7 ~ ethane-1-sulfonate, 4- / N-methyl-N- (2-hydroxyethyl) -N-hexadecyl / rS-hydroxybutane-1-sulfonate and 3- (N, N-dimethyl-N-hexadecylammonium) -2-hydroxy-propane-1-sulfonate Other specific examples are compounds in which alkyl chains of different lengths are used to give the corresponding decyl, dodecyl, tetradecyl -, hexadecyl and octadecyl homologues of the above compounds, such as a-CNjN-dimethyl-N-tetradecylammonium) propane-1-sulfonate, 3- (N, N-dimethyl-N-octadecylammonium) ethane-1-sulfonate, etc. Still other specific examples include compounds in which those on the nitrogen atom are the foremost Current compounds substituted short chains are replaced by the corresponding methyl, ethyl and hydroxyethyl groups to give the corresponding homologues of the above compounds .

b. Specific examples of phosphine oxide detergents are!

Dimethyldodecylphosphine oxide Dimethyl tetradecyl phosphine oxide Ethylnethyltetradecylphosphinoxyd Cetyldimethylphoaphinoxide Dimethylst arylphosphine oxide Cetylethylpropylphomphinoxyd

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Piäthyldodecylphosphinoxyd Diethyltetradecylphosphinoxyd Dipropyldodecylphosphine oxide bis (2-hydroxyethyl) dodecylphosphine oxide bis- (2-hydroxyethyl) 3-dodecoxy-2-hydroxypropyl-

phosphine oxide

(2-hydroxypropyl) methyl tetradecylphosphine oxide

Dimethylpleylphosphine oxide and dimethyl (2-hydroxydodecyl) phosphine oxide

The C ₁₂ -C ₁ dimethyl homologues of the above compounds are preferred. Other examples include those compounds in which the short alkyl chains of the above compounds are replaced with methyl, ethyl, hydroxyethyl, propyl and hydroxypropyl radicals, respectively, to give homologues of the above compounds. Still other examples are compounds in which decyl, dodecyl, tetradecyl, hexadecyl and octadecyl hydrocarbon groups replace the long alkyl chains of the above compounds to give the corresponding homologues.

c. Specific examples of the amine oxide detergents are:

Dirnethy1dodecylamine oxide
Dimethyltetradecylamine oxide
Ethylmethyltetradecylamine oxide
Cetyldimethylamine oxide
Dimethylstearylamine oxide
Cetylethylpropylamine oxide
Diethyldodecylamine oxide

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Diethyl tetradecylamine oxide Dipropyldodecylamine Oxide

bis (2-hydroxyethyl) dodecylamine oxide bis- (2-hydroxyethyl) -3-dodecoxy-2-hydroxypropyl-

amine oxide

(2-hydroxypropyl) methyltetradecylamine oxide

Dimethyloleylamine oxide Dimethyl (2-hydroxydodecyl) amine oxide

The C. ₂ -Cj, dimethyl or bis (2-hydroxyethyl) homologues of the above compounds are preferred. Other examples include the compounds in which the short alkyl chains of the above compounds are replaced with methyl, ethyl, hydroxyethyl, propyl and hydroxypropyl radicals, respectively, to give homologues of the compounds provided. Nooh's other examples include those compounds in which the decyl, dodecyl, tetradecyl, hexadecyl and octadecyl carbon hydrogen groups replace the long alkyl chains of the above compounds to give the corresponding homologues.

The suitain, phosphine oxide and amine oxide detergents impart superior bottle properties to the compounds of the invention. In particular, the preferred suitain, amine oxide and phosphine oxide detergents impart detergency to the compositions in both cold and hot water. Surprisingly affect these surfactant compositions do not respect the whiteness maintenance _f when used along with the nonionic obeiA £ chenaktiv> s agents · sultaine Detergentlen the excellent properties of nonionic surfactant detergents are

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Oi «Alkali pyrophosphates, which can form a Τ · 11 of the compositions according to the invention, are di · builders conventionally used in liquid detergent compositions. The preferred one Pyrophosphate is a tetrakaiium pyrophosphate.

The preferred organic builders are alkali salts, e.g. sodium or potassium salts, ammonium or substituted ammonium salts of nitrilotriacetic acid or xthane-1-hydroxy-1,1-diphoephonic acid, preferably the potassium salts. The organic framework substances, together with the pyrophosphate, lead to superior properties with regard to the retention of the Whiteness of the detergent composition. Xthyiendiamlntetreessigs & uresalse are effective, however must Care should be taken that the compositions must be used with a sufficient amount of a corrosion inhibitor to prevent that this organic builder creates corrosion problems.

The above expression "substituted Aamoniu *" - see s.B · on MonoMthanolaseioniu *! Diethanolaeeoaiu * and TrUthanola — Bnium Salse.

The foregoing organic plastics and pyrophosphates tend to corrode aluminum. the end For this reason, a corrosion inhibitor should be incorporated if the washing solution comes into contact with aluminum. Sodium and Potassium Silicates with a ratio from SiO ₂ to M ₂ O ("M" refers to sodium or potassium) from about 1.0 to about 2.6, preferably about 1.6 to about 2.6 are effective when used in a concentration of about Z. to be incorporated up to approx. 4 sew.%

109809/1880

Less than 2 % silicate solids * do not lead to adequate protection under extreme conditions and more than k% have a disadvantageous effect on the product resistance.

The emulsion is kept constant by the presence of the aforementioned specific emulsion stabilizers. Obviously, the specific compositions described above and in particular the compositions containing the sultainic detergents mentioned above are extremely sensitive to changes in the stabilizer. For this reason - the choice of stabilizers is critical. The stabilizers are described in U.S. Patent No. 2.ο47.398. Preferably these copolymers are linear and the molar ratio of the monomers present in these materials is preferably about Isi. The copolymers are characterized in the foregoing by their specific viscosity, which is an accepted parameter for characterizing this type of compound. Wherever specific viscosities are given, they have been determined by the experiments mentioned.

The presence of these stabilizers appears to be essential for the i

Production of the stable emulsions according to the invention to be critical. The specific emulsion stabilizers are particularly valuable where the transport conditions are such that the compositions are subjected to continuous jolts and agitation.

The pH of the composition must be between 11.7 and 13, ο be held. If the pH is not in this If this is kept within a range, the effects on product durability can be extremely worrying. As above has already been mentioned, the pH value can be, for example

109809/1880

by adding sodium hydroxide, potassium hydroxide, lithium hydroxide or the corresponding sodium, Lithium and potassium oxides can be adjusted.

Optionally, other components such as optical whiteners (brighteners) can be added. It it has been found that only a limited number of optical whitening agents can be used in the compounds according to the invention is compatible, especially when the preferred sultain detergents are used. Suitable optical brighteners include at least one optical whitening agent of the following type:

(1) The reaction product of about 1 mole of ethylene oxide and 1 mole of 1,2-bis (benzimidazolyl) ethylene, e.g. N- (2-hydroxyethyl) -1,2-bis (benzimidazolyl) -ethylene.

(2) Tetrasodium-4, k '-bis- / J "4" -bis- (2 "" -hydroxyethyl) amino-6 "- (3""- sulfophenyl) -amino-1", 3 ", 5 ^u -triazin-2 "-yl) amino7" -2,2 · stilbene disulfonate.

(3) N- (2-hydroxyethyl-4,4'-bis (benzimidazolyl) stilbene.

(4) Disodium 4- (6 ^l -sulfonaphtho- / T ', 2'-dT-triazol-2-yl) -2-stilbene sulfonate.

(5) Disodium-4,4'-bis- / j4 ^{! L} - (2 " ^l -hydroxyethylamine) -6" -anilino-1 ", 3", 5 "-triazine-2 ^ll -yl) amine p7" -2 , 2 · -stilbene disulfonate.

(6) Disodium-4,4 ^l -bis- / j4 ^ll - (2 "Xhydroxyäthoxy) -6 ¹¹ -anilino-1", 3 ", 5" -triazin-2 ^ll -yl) aminp / -2,2 ' -stilbene disulfonate.

(7) 1,2-bis (5'-methyl-2 ^l -benzoxazolyl) -ethylene.

(8) A-methyl-T-dimethylaminocoumarin.

ORIGIMAL INSPECTED

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I BI 7184

(9) 2-styrylnaphth- / T _s 2-d / -Qxazole

(10) The reflection product of 1 mole of 4,4'-bis (benzimidazolyl) -stilbene and about 0.5 moles of ethylene oxide and 0.5 moles of propylene oxide

(11) Mixtures of these »materials

When the compositions of the invention contain a quaternary ammonium salt, such as a quaternary one Ammonium germicide, then non-ionic optical whiteners are preferred. However, it can also the other mentioned ionic optical whitening agents can be used. They are particular together with non-ionic optical whiteners preferred

These optical whitening agents are preferred in a concentration of about o.o3 to about o, 8 wt.%, Preferably about o, k wt.%. They are normally added to and are present in the discontinuous phase, for example the oily phase of the composition.

Bin particular advantage of the present invention resides in that the above optical brighteners (optical whiteners) (if they are present, as well as cationic materials) in the oily phase of the composition significantly more compatible with the SuItain-, Phosphinoxyd- and Aminoxyddetergentien, when diejZusammensetzung is in the form of the oil-in-water emulsion described above instead of a homogeneous aqueous solution.

The compositions can also contain about 0.2 to 1.5% dirt-repellent agents, such as alkali, ammonium and substituted ammonium carbon

IbI / 184

methyl cellulose or alkali, ammonium and substituted Ammonium carboxymethyl hydroxyethyl cellulose. An advantage of the liquid according to the invention Detergent is that the more readily available carboxymethyl cellulose salts can be used. The carboxymethyl cellulose salts are less soluble than the carboxymethylhydroxyethyl cellulose salts and normally it is very difficult to use carboxymethyl cellulose salts in liquid detergent compositions to use. By suspending the carboxymethyl cellulose salts in the discontinuous phase however, the solubility problem is solved. The carboxymethyl cellulose can also be dissolved in a Silicate-water solution before adding to the composition can be added.

Other possible components are the above is led germicides. Specific examples of such germicides are pentadecylbenzyldimethylammonium chloride and tetradecyldiethylmethylammonium bromide.

The compositions of the invention can be obtained by the following process steps:

1.Bs a premix is prepared that the non-ionic surface-active detergent, at least about \ / k of the sultain, phosphine oxide or amine oxide detergent, the optical whitening agents, dyes, carboxymethyl cellulose and any alkali required to prepare an alkaline solution. These ingredients are mixed thoroughly.

ORUsHmAL INSFeGTEO

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2. The emulsion stabilizer is obtained by hydrolyzing the above-described copolymer. A small amount of the nonionic detergent, about 2 to 80 weight percent based on the amount of the unhydrolyzed emulsion stabilizer, is dissolved in water and then mixed with the emulsion stabilizer. The mixture is heated from about 65 ⁰ C to about 95 ° C, so that the emulsion stabilizer hydrolyzed, is brought whereby the pH value to below. 7 It is believed that the nonionic detergent surfactant is Λ

with the emulsion stabilizer to form a Esters converts. The amount of non-ionic detergent which is used in the hydrolysis of the emulsion stabilizer is very essential as it is proportionate small variations in the amounts of non-ionic detergent result in very large changes the viscosity of the final product. The use of larger amounts of the non-ionic Detergent increases viscosity.

3. The hydrolyzed resin is preferably made alkaline by means of sodium hydroxide or potassium hydroxide

made. . |

4. The premix and the aqueous solution containing the hydrolyzed emulsion stabilizer Preferably at least a portion of the builder becomes that of the emulsion stabilizer containing aqueous solution given before the premix of the aqueous Solution is added.

5. If available, the remainder of the sultain, phosphine oxide or amine oxide detergent is added to the mixture.

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6. Optionally, additional builder is added to the mixture.

7. If used, the silicate is added to the composition.

8. At each of the above steps, the composition mixed very thoroughly after each addition. While the temperature of the composition at this Place is relatively high, the composition is mixed with high shear force. E.g. will

a stirrer was used with a speed at the ends in excess of 12.7 m / s. Mixing with high Shear strength improves the persistence of the emulsion while reducing the size of the droplets discontinuous phase.

9. The composition is cooled and perfume is added. The compositions according to the invention can also by mixing an optical brightener, a Dirt suspending agent, e.g. Sodium carboxymethyl cellulose, the non-ionic, surface-active detergent, the SuItain-, Phosphinoxyd- or Amine oxide detergent and, if used, the pigment. This mixture forms the dispersed one (oily) phase of the emulsion. This dispersed phase becomes a solution of the, as described above, obtained emulsion stabilizer and sodium acid pyrophosphate (or potassium acid pyrophosphate) in Added water and mixed thoroughly.

Potassium or sodium hydroxide is then added as needed added to neutralize the acidic sodium pyrophosphate. The other components, e.g. Potassium nitrilotriacetate, potassium or sodium pyrophosphate, sodium silicate, etc. then become the Mixture given.

109809/1880 originally inspected

16171

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The compositions of the invention are extremely effective detergents. The term "detergency" as used herein refers to the ability of a solution of a detergent ₃ to remove dirt from clothes. ^{The term "whiteness retention cs"} refers to the ability of a detergent solution to prevent suspended soil from settling on clothing during the washing process. ^{As used herein, "detergency w"} encompasses both detergency and retention the whiteness. The detergents according to the invention are particularly effective in terms of maintaining the degree of whiteness

The compositions of the invention are particularly effective when washing with cold Water, e.g. at about 2? up to 38 ° C, is carried out « This is especially the case when using the sultain detergents are present in the compositions according to the invention *

Practice of the present invention will be the following example © explains "

example 1

Liquid detergents were used as permanent oil-in-water emulsions with 2 »use dsp naohfolsnäsn component = part © (all © numbers are. 6 © wiotitsps © s © ato ) fee ^ gostsilt s

You wuj? Den dadu ^ efe © 5pfealtoa _D that jtaa doa optissfioa

the && kmnt8 & uQp®ndiQT®naQ means _s clso not and dos on & @ & ® D © t © i »gons s © wio that

Solution of the emulsion stabilizer and acidic sodium pyrophosphate given and mixed carefully. The potassium hydroxide was then added to adjust the pH to bring to 12, and the remaining ingredients were then added while mixing.

Compositions t

Dodecylphenol ί ethylene oxide condensate,

the average 11 moles of ethylene oxide

contains 5.4 per mole of phenol

_ LN, N-dimethylammonium 7-2-hydroxypropane-1-sulfonate; the
Alkyl is derived from coconut alcohol and contains 2 % C,, 66 % C ₁₉ , 23 % C ₁₄ , 9 % C ₁₆ ^{lo 12} 5.4 6

Potassium pyrophosphate
Potassium nitrilotriacetate
Sodium silicate (2.45: 1; Si0 ₂ «Na ₂ 0) N- (2 · hydroxyethyl) -1,2-bis-

(benzimidazolyl) ethylene ο, οοί> ο, οο5

Tetrasodium 4,4'-bis-Zp'-bis- (2 '- hydroxyethyl) amino-6 "- C 3" ^t3 -sulf ophenyl,) amino-1 ¹¹ -I ", 5 ^H -ti" iazin -2 "-yl) -amino / -2.2 ^l -

o, 15 o, 15

27 3 2o, 2 8th, 8th 6, 25th 2, 2, 82

Dye traces traces

ethyl

specific viscosity of about 0.6

("DX Ö4o - 2? - Resin") 1.4 1, 4

Paj ?? niii ο »3 o,

Water = remaining amount remaining amount

ORIGINAL 5HSPECTED

These compositions were excellent detergents and exhibited good whiteness retention baim washing textiles,

If a roconut alcohol-ethylene oxide condensate with an average of 15 moles of ethylene oxide per mole of coconut alcohol is used either wholly or in part instead of the dodecylphenol-ethylene oxide condensate in the above composition, essentially similar results are obtained in that the compositions still maintain good retention of the whiteness and excellent comprise detergents, etc.

Become coconut alkyldimethylphosphine oxide, coconut alkyldimethylamine oxide or any specific detergent listed above or mixtures the same either in whole or in part instead of 3- (N-alkyl-N, N-dimethylamonnium) -2-hydroxypropane-1-sulfonate When used in the above formulas, the results are essentially similar in this respect obtained as stable emulsion products with good washing properties.

If a linear methyl vinyl ether / maleic anhydride copolymer with a specific viscosity of g

about 0.2 instead of the ethylene / maleic anhydride copolymer of the above formulas either in whole or in part are used in this respect Results obtained when the emulsion is persistent.

If potassium acid pyrophosphate is used in whole or in part of the sodium acid pyrophosphate in the above Example are used to this extent essentially

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equivalent results obtained as the compositions are stable.

In the above formulas, most of the potassium pyrophosphate is, potassium nitrilotriacetate and sodium silicate in the aqueous phase and most of the other ingredients in the oil phase. It is believed that the carboxymethyl cellulose and the ethylene / maleic anhydride copolymers are concentrated at the oil-water interface.

Example 2

The following liquid detergent compositions, when prepared according to the procedure of Example 1 in Produced in the form of permanent oil-in-water emulsions excellent detergent compositions.

Compositions,

Dodecylphenolί propylene oxide;

Ethylene oxide condensate, which is an average of 3 moles of propylene oxide and 12 moles of ethylene oxide per mole of phenol contains 4 6

3- (N, N-dihydroxyethyl-N-hexadecylammonium) propane-1-sulfonate 8th

Coconut alkyl di- (2-hydroxyethyl) -

phosphine oxide 6

Coconut alkyl di- (2-hydroxyethyl) -

amine oxide *

Potassium pyrophosphate 18 24 3ο

Potassium ethylenediamine tetraacetate 8 4

Potassium nitrilotriacetate 2

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1.5 1.5 1.5 0.05 0.05 U, 05 0.7 0.7 0.7 traces traces traces

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0 D E

Linear methyl vinyl ether / maleic acid anhydride mixed polymer \, 1s1) with a specific viscosity of about 0.3 ("Gantrez ΑΈ 119")

K- (2-hydroxyethyl-4,4-bis (benzimidazolyl) -stilbene

Sodium urboxymethylhydroxyabhy1 "cellulose

Pigments

Water remaining amount remaining amount remaining amount

The pü value is set to 12 with potassium hydroxide

The above examples include the potassium pyrophosphate and potassium ethylenediamine tetraacetate predominantly in the aqueous phase and the predominant part of the rest Components in the oil phase. It is believed that the carboxymethyl cellulose and the methyl vinyl ether / maleic anhydride copolymer are concentrated at the oil-water interface «,

If, in the above examples, the following brighteners are added in amounts of about 0.4 ^c ß> and / or used in whole or in part instead of the above brighteners, then essentially equivalent results are obtained insofar as the compositions are excellent detergents and have good whitening power have

(1) The reaction product of about one mole of ethyleneoxy and one mole of 1,2 «b ± s ~ (benzimidazolyl)» ethylene, Z ₀ B ₄₁ (N- (2'-hydroxyethyl) -1,3 ~ bis ~ (benzimidazolyl) -äthylenj

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(2) ^{Tetrasodium 4.4 l} -bis / j4 "-bis- (2"'- hydroxyethyl) -amino-6 "- (3""-sulfophenyl)-amino-1", 3 ", 5" -triazine -2 "ryl) -amino7-2,2'-stilbene disulfonate;

(3) N- (2-hydroxyethyl-4,4'-bis (benzimidazolyl) -stubes;

(4) disodium-4- (6 ^I sulfonaphtho- / T ^l, 2 ^l -d7-triazol-2-yl) 2-stilbensulfonat;

(5) Disodium-4,4'-bis- / fCV ^l -2 ¹¹ '-hydroxyethylamine) -6 "-anilino-1", 3 ", 5 ^H -triazine - 2"-ylKaminp7-2,2' - stilbendisul fonat;

{6) _ Disodium-4,4'-bis-ZJV'-C 2 «· -hydroxyethoxy) -6" -anilino-1 ", 3", 5 "-triazine-2" -yl) -amino / -2 , 2'-stilbene

"disulfonate;

(7) 1,2-bis (5'-methyl-2-benzoxazolyl) -ethylene;

(8) 4-methyl-7-dimethylaminocoumarin;

(9) 2-styrylnaphth- / T, 2-d7-oxazolJ

(10) The reaction product of one mole of 4,4'-bis (benzimidazolyl) stilbene with about 0.5 moles of ethylene oxide and 0.5 moles of propylene oxide and

(1-1) mixtures of the same,

in a weight ratio of e.g. 1: 1.

If in the above examples either the sodium, ammonium, ethanolammonium, diethanoiammonium or triethanolammonium salts of ethane-1-hydroxy-1,1 -diphosphonic acid, nitrilotriacetic acid, pyrophosphoric acid, ethylenediaminetetraacetic acid or Mixtures thereof or potassium ethane 1-hydroxy-1,1-diphosphonate or tripolyphosphate (^ 1 ο #) or mixture the same either entirely or partially instead of the Kallurnäthylendiamintetraecetats and / or Kaliumnitrilotri acetate used in the above compositions,

Claims (1)

thus substantially equivalent results are obtained in that the calcium ions, etc. are withdrawn. If pentadecylbenzyldimethylammonium chloride and / or tetradecyldiethylmethylammonium bromide are added to the compositions of the preceding examples are added in an amount of about 0.3%, so to that extent are essentially equivalent results obtained when the compositions are oil-in-water persistent emulsions and have excellent detergent properties. The compositions also have germicidal properties. In the previous examples, sodium pyrophosphate is used instead of potassium pyrophosphate and / or ammonium, Monoethanolammonium, diethanolammonium, triethanolammonium or potassium carboxymethylhydroxyethyl cellulose and / or carboxymethyl cellulose either whole or used in part, results substantially equivalent to those above are obtained Compositions are excellent detergents. Example 3 The following liquid cleaning agents are, when used according to Example 1 in the form of stable oil-in-water emulsions are made excellent detergents; Coconut alcohol (middle fraction): ethylene oxide condensate with a Content of 25 moles of ethylene oxide per Moles of alcohol 13% by weight 3- (N-coconut-alkyl-N, N-dimethyl- ammonium) -2-hydroxypropane-1- sulfonate 5% by weight Potassium Pyrophosphate 2 ο Gew _e $> Potassium nitrilotriacetate 5% by weight Sodium silicate (2, ^ 5: 15 SiO ₂ SNaO) 3, ο wt.% Gantrez AN 119 (see example Z) o.7% by weight Haters rest The pH is adjusted to 12 with potassium hydroxide. 10 9809/1880 LOCAL SUSPECTED - 2k - Claims 1.Liquid cleaning agent containing build-up substances in the form of a permanent oil-in-water emulsion, characterized by the following components: 1) about 1 to about 15 weight percent of a non-ionic Detergent with the following formula: R (-OCH ₂ CH) _y (-OC ₂ H ₄ -) _z 0H CH ₃ in which R is an alkyl radical with 8 to 18 carbon atoms or alkylphenyl radical, its alkyl groups contain about 9 to about 15 carbon atoms, represents, Y is an integer from 0 to about 7 and Z is an integer from about 5 to about 45, 2) about 2 to about 10% by weight of at least one of the fol "Gentle surface-active detergents: a) a sultain detergent of the following formula: R ^{2 CH} 2 ~ R ³ in which R is an alkyl radical with about 1o to about 2 3 18 carbon atoms, R and R each denote methyl, ethyl or hydroxyethyl radicals, R denotes a methylene, ethylene or propylene radical and X denotes hydrogen or a Represents hydroxyl group, where the hydroxyl group is only on a secondary carbon atom, 109809/1880 originally inspected b) a detergent of the following formula R ⁶ R ⁵ - Q - 0 R ⁷ in which R represents alkyl or monohydroxyalkyl radicals with about 10 to about 2k carbon atoms, which contain 0 to about 3 ether bonds and a molecular fraction with about 10 to about 18 carbon atoms without ether bonds, and R and R each contain methyl, ethyl, Mean hydroxyethyl, propyl or hydroxypropyl radicals and Q is a phosphorus or nitrogen atom, c) Mixtures of these detergents 3) about 10 to about 36% by weight of a builder, which can be an alkali metal pyrophosphate, alkali metal, ammonium and substituted ammonium salt of nitrilotriacetic acid, ethane \ -hydroxy-1,1-diphosphonic acid or ethylenediaminetetraacetic acid, potassium tripolyphosphate or a mixture of these materials in which no more than about 10% by weight potassium tripolyphosphate is present, k) an emulsion stabilizer consisting of ethylene-maleic anhydride copolymers with specific viscosities of about 0.5 to about 1.0 or methyl vinyl ether-maleic anhydride copolymers with a specific viscosity of about 0.1 to about 0.6, the former • 1OS809 / 1880 16 V / 184 Emulsion stabilizer in an amount of about 1 to about 2% by weight and the latter emulsion stabilizer in an amount of about 0.3 to about 1.5% by weight is used or from mixtures of these materials, 5) the balance of water, the pH of the composition being between about 11.7 and about 13. o. 2. Cleaning agent according to claim 1, characterized in that it contains about 0.1 to about 0.5% of a germicide of the following formula as a further component! 13th R ¹² - i -R ^15th · _Χ β in which R is an alkyl radical with about 8 to about 18 carbon 13 Ui. represents material atoms, R and R each methyl, Ethyl or propyl radicals, R a methyl, ethyl or benzyl radical and X a bromide, Is fluoride or chloride anion. 3. Cleaning agent according to claim 1, characterized in that as a further component, which is present in the oily phase in an amount of about 0.03 to about 0.8%, contains at least one of the following compatible, optically whitening agents ORIGINAL INSPECTED 109809 / 188Q (1) the reaction product of about 1 mole of ethylene oxide and 1 mole of 1,2 bis (benzimidazolyl) ethylene, e.g. N- (2'-hydroxyethyl) -1,2-bis (benzimidazolyl) ethylene, (2) Tetrasodium-4, if -b ± s- / Jk ⁿ -bis- (2 "'-hydroxyethyl) -amino-6 ^II - (3 ^llll -sulfophenyl) -amino-1", 3 ", 5" -triazin-2 "-yl) -amino / ⁱ '-2,2' -stilbene disulfonate (3) N- (2-Hydroxyethyl-4 , k ' -bis- (benzimidazolyl) - Stilbene. G (4) Disodium 4- (6'-sulfonaphtho / T ¹ , 2'-dT-triazol-2-yl) -2-stilbene sulfonate (5) Dinatriura-4,4 ^t -bis- / j4 ^ll - (2 " ⁱ -hydroxya-thylamine) -6" -anilino-1 ", 3", 5 "-triazin-2" -yl) -aminp7- 2,2'-stilbene disulfonate (6) disodium 4,4 -bis- ^l / j4 '- (2 ^Ifl -hydroxyathoxy) -6 "-anilino-1", 3 ", 5 ^H ™ triazin-2" -yl) -amino7-2,2 · -. Stilbene disulfonate (7) 1,2-bis (5 ^l methyl-2'-benzoxazolyl) ethylene (8) 4-methyl-7-dimethylaminocoumarin (9) 2-styrylnaphth- / T, 2-d7 ^ - (10) The reaction product of 1 mole of 4,4'-bis- (benzinide azolyl) stilbene and about 0.5 moles of ethylene oxide and 0.5 moles of propylene oxide, or (11) Mixtures of the above compounds, e.g. in a weight ratio of 1: 1. 109809/1880 4. Liquid detergent containing GerUststoffe according to claim 1 to 3, characterized in that it contains the following ingredients: (1) about 5% of a _f 4-dodecyl phenol ethylene oxide condensate with a content of about 11 moles of ethylene oxide per mole of phenol (2) about 5.4% 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate, the alkyl group of which contains from about 10 to about 16 carbon atoms and at least about 50% of the groups contain 12 carbon atoms (3) about 27% potassium pyrophosphate (4) about 8.3 1 »potassium nitrilotriacetate (5) about 2.8 % sodium silicate with a ratio of SiO ₂ : Na ₂ O of about 2.45: -1 (6) about 0.7 % sodium carboxymethyl cellulose (7) about 0.2% of a compatible brightener that comes from 1-Benzimidazolyl-2- (N-hydroxyethyl) benzimidazolylethylene or tetrasodium 4,4'-bis- / j4-diethanolamino-6- (3-3ulfo) -anilino-1,3,5-triazin-2-yl) -amino7-2,2-stilbene disulfonate consists (8) about 1. k% ethylene-maleic anhydride copolymer with its own specific viscosity of about 0.7 (9) about 0.3 % dyes and perfumes and (lo) water as the rest, the pH being adjusted to 12. ORtQINAL INSPECTED 10980 9/1880 5. detergent containing builders according to claim 1, characterized in that it contains 4 to Gsw,% of a non-ionic detergent (1). ό. GerUststoffe containing cleaning agent according to claim 1 characterized by t 4 to 8 wt.% Of a detergent surfactant (2). For: The Procter & Gamble Company Cincinnati, Ohio, V.St.A. Right sftiwalt 109809/1890