DE2648304A1 - LIQUID DETERGENT - Google Patents

Description

BEIL, WOLFF & BEIL

_Dtrr,. ; ^ :: λ; ; ~ ~~ ^m ~ * ° 25 oct. 197s

ADELONri .V: \ .7 J '-: 53

FRANKFURTAM MAIN 80

Our no. 20 739 Ec / m

Procter & Gamble ETC, Strombeek-Bever / Belgium

Liquid detergent

The invention relates to a liquid cleaning agent, a mixture of selected synthetic, anionic, surface-active detergents, an organic, surfactant amine or quaternized amine or a mixture of such amines, a gelatin with a molecular weight of at least 12500 and a gel strength contains at least 25 bloom grams and a liquid carrier. The liquid clear detergent according to the invention is particularly useful for cleaning glassware, porcelain and glazed or glass-like objects, excellent cleaning and outstanding drainage behavior can be achieved, so that drying is possible becomes superfluous with the cloth. In addition, filming, banding and staining will occur the washed, rinsed and air-dried items are significantly reduced. The invention Cleaning agents preferably contain a water-soluble one

709818/111 1

Gelatin with a molecular weight of 12,500 to 200,000, especially from about 25,000 to about 80,000, a gel strength from about 25 to about 300 bloom grams, preferably from about 80 to about 200 bloom grams, and one isoelectric Point from pH 4.5 to pH 9.2, and the liquid carrier consists of water, a lower alcohol with 1 to 5 carbon atoms, or a mixture of water and one lower alcohol with 1 to 5 carbon atoms.

The quality of a cleaning agent to be used for cleaning of glassware, dishes, windows and other objects with glass or shiny surfaces, such as bathtubs (ceramic bathtubs) and tiled walls, usually by the consumer using the gloss and de ^s lack of film formation, Spotting and streaking assessed. The liquid dishwashing detergents currently commercially available are primarily intended to remove dirt from glassware, dishes and window panes, the freshly cleaned items being subsequently rinsed and / or towel dried. Any delay in rinsing and / or drying with the cloth can result in stains, films or streaks that are difficult to remove.

If the items are cleaned and rinsed in tap water and not immediately dried with the cloth, further stains and streaks may appear on the cleaned and rinsed surfaces when the water evaporates, which are due to the hardness of the water. Therefore, the cleaning effect of the agent used is which may have been visibly perceived at the end of the washing or subsequent rinsing process, lost because they are difficult to remove, unpleasant residues of detergents, dirt and / or hardening components of the water the washing liquid or the rinsing water adhere to the objects or are redeposited and dry on.

709818/1 111

Attempts have already been made to determine the effect of the Deposits of detergent residues, dirt and / or hardening components of the water during drying to reduce the air to a minimum by adding various additives. For this purpose, during the Washing or rinsing process a number of additives, e.g. complexing agents for the hardening components of the Water or a suspension agent for the dirt can be used, or a specially formulated rinse aid can be used can be used. However, the incorporation of additional ingredients often leads to difficulties the formulation, while the special rinsing agents must be packaged and used separately.

In the DT-OSs 2 3 ^ 5 ¹¹ ^ ₉ 2 350 008 and 2 350 009 liquid cleaning agents are already described, which are particularly suitable for cleaning glassware, porcelain and other glass-like or glazed objects, with an effective cleaning and in particular an effective Drainage of the final rinse water is obtained by combining a particular gelatin with one or more selected surfactant detergents.

The known cleaning agents, which contain the special gelatin, are effective cleaning agents, but require that the washed items are rinsed for several seconds in a rinsing bath or under running water will. In addition, the draining process, if it is also smooth takes place, requiring a period of several seconds, with an accumulation of a certain amount of drainage water can take place at the bottom of the upright object.

709818/1 1 1 1

26A8304

The present 'invention is therefore based on the object To provide a liquid detergent that is used for glassware, china and window panes as well Glazed or glass-like objects and generally objects with glossy surfaces are excellent Has cleaning effects, requires less rinsing and an improved, i.e. faster, but still allows even and complete drainage, with an accumulation of drainage water on the bottom of an upright object avoided or reduced to a minimum will.

This object is achieved by the cleaning agent described in the claims.

According to the invention it has been found that the cleaning of glazed and glass-like objects with regard to whose final appearance can be improved, in particular effective cleaning and rapid, however, even drainage after washing and rinsing is achieved by using these items washes in an aqueous washing liquid containing a mixture of selected water-soluble organic synthetic anionic surfactants, an organic amine surfactant or quaternized amine or contains a mixture of such amines and a special gelatin.

The liquid cleaning agent according to the present invention contains:

(A) about 4 to about 45 weight percent of a mixture

(1) an organic, synthetic, anionic surface-active detergent of the general formula

R ₁ -O - (C ₂ H ₄ O) _n SO ₃ M (Ia)

709818/1111

wherein R _{1 is} a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 2k carbon atoms, preferably 12 to 18 carbon atoms, an alkylbenzene radical having 8 to 18 carbon atoms in the straight-chain or branched-chain alkyl group or a mixture of such groups; η is a number from about 1.5 to about 15 , preferably from 3 to about 12, and M is an alkali metal, an ammonium radical or a dimethyl, diethyl, trimethyl, triethyl, dimethanol, diethanol, trimethanol or Trxäthanolammonxumrest means;

(2) a water-soluble, organic, synthetic, anionic surface-active detergent of the general formula

R ₂ - SO ₃ M (Ha)

where Rp is a straight or branched chain, saturated or unsaturated aliphatic hydrocarbon radical with 8 to 24 carbon atoms, preferably 12 to 18 carbon atoms, an alkylbenzene radical having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, in the straight or branched chain alkyl group or represents a mixture of such radicals and M has the above meaning;

wherein the weight ratio of (1) to (2) is about : 1 to about 1: 5, preferably about 5: 1 to about 1: 2;

. (B) from about 0.1 to about 5 wt -% of an organic, oberflachenaktxven amine or quaternized amine selected from:

709818/1 1 1 1

(1) a quaternized amine of the general formula:

R.

R ₃ -N- R ₆

(IHa)

wherein R, a hydrocarbon radical with 10 to 22 carbon atoms, which is optionally interrupted by up to 2 ether, -CO-O- or -CONH- bonds, preferably an aliphatic hydrocarbon radical with 14 to 18 carbon atoms or an alkaryl group with 8 to 16 carbon atoms in the alkyl radical, Rj has the meaning of R ^ ₅ or an aliphatic hydrocarbon radical having 1 to 6 carbon atoms or a benzyl radical; R, - and Rg each denote an aliphatic hydrocarbon radical having 1 to 3 carbon atoms, and X denotes an anion, preferably the methyl sulfate, bromide or chloride anion, the total number of carbon atoms of R, and Rj being about 13 to about 32, preferably 15 to 28;

(2) a quaternized amine of the general formula

N-CO I

^R 10

(X ") (IVa)

wherein R- and Rg are each aliphatic hydrocarbon radicals with 6 to 18 carbon atoms mean

709818/1 1 1 1

where R "preferably has at least 12 carbon atoms, Rg is an aliphatic hydrocarbon radical with 1 to 4 carbon atoms, R ^ _{0 is} a hydrogen atom or an aliphatic hydrocarbon radical with 1 to 4 carbon atoms and X is an anion, preferably the methyl sulfate, bromide or chloride anion, the total number of carbon atoms of Rg and Rq being about 10 to 22, preferably about 15 to 20.

(3) an amine of the general formula

^R 11 ^R 12 ^R 13 ^N

(Va)

wherein R _{11 is} an aliphatic hydrocarbon radical with 10 to 24 carbon atoms, preferably 14 to 18 carbon atoms, which can optionally be interrupted by up to 2 ether, -CO-O- or -CONH bonds, R._ is a hydrogen atom, an aliphatic radical having 1 to 22 carbon atoms, a radical of the formula - (alkyl-NH) -H, in which the alkyl group has 1 to 4 carbon atoms and ^{r is} an integer from 1 to 10, preferably from 1 to 3, a group of Formula - (CH ₂ -CH ₂ -O) ₃ -H, in which s is an integer from 1 to 10, preferably from 1 to about 4, and R _{1 is} a hydrogen atom, a methyl, ethyl or benzyl group or a Group of the formula - (CH ₂ -CH ₂ O) ₅ -H, in which s is as defined above,

(4) a polyquaternized amine surfactant formula

11

fl3

-N-

Alkyl

14th

14y

(Via)

709818/1111

ft 264830A

wherein R _{11 is} an aliphatic hydrocarbon radical with 10 to 2k carbon atoms, preferably 14 to 18 carbon atoms, which is optionally interrupted by ether, ester or amide bonds, R ₁ -, a hydrogen atom or a methyl, ethyl or benzyl group or represents a group of the formula - (CH ₀ -CH ₀ O) -H, in which s is an integer from 1 to about 10, preferably from 1 to about 4, the alkyl group has 2 or 3 carbon atoms, R ₁ , preferably the methyl -. or ethyl group, R ₁ J. is a hydrogen atom, an alkyl group with 1 to 3 carbon atoms or a group of the formula (C ₂ H ₁ ^ O) H or (C, HgO) H, where ρ and g are each 0 or a number such that (p + g) do not exceed the number 25, r is an integer from 1 to about 10, preferably from 1 to 3, where R ₁₁ , preferably denotes the methyl or ethyl group and the Substituents R ^ 3 and R ₁ ^ are each identical or different n can, and

(5) mixtures of these surfactants selected organic amines and quaternized amines, wherein the weight ratio of (A) to (B) at 60: 1 to 5: 1,

(C) about 0.1 to about 5 weight percent, preferably about 0.2 to about 2 weight percent, of a water soluble Gelatin having a molecular weight of at least 12,500, preferably from about 25,000 to about 80,000, a gel strength of from about 25 to about 300 bloom grams, preferably from about 80 to about 200 bloom grams, and one isoelectric point at pH ή.5 to pH 9.2 and

(D) the remainder of a liquid carrier consisting of water, a lower alkanol having 1 to 5 carbon atoms or a Mixture of water and a lower alkanol with 1 to 5 carbon atoms.

709818/1111

Contained in a preferred embodiment of the invention the liquid detergents the quaternized amine (purple) or the polyquaternized amine (VIa) in an amount of about 0.5 to about 3 percent by weight, preferably from about 0.7 to about 3 percent by weight, with FU and FL. of the formulas aliphatic hydrocarbon radicals with 14 to 18 carbon atoms mean.

In another preferred embodiment of the invention, the amine (Va) is present in an amount of about 0.5 to about 2 percent by weight, where in this Pall R., - of the formula is an aliphatic hydrocarbon radical having 14 to 18 carbon atoms, R _{2 is} a Represents a radical of the formula - (alkyl-NH-) -H, in which the alkyl group contains 2 or 3 carbon atoms and r is a number from 1 to 3, and R _{1 represents} a hydrogen atom or the methyl or ethyl group.

A mixture of the above preferred quaternized amine (purple) and the above amine (Va) is used in an amount from about 0.5 to about 3 percent by weight, the weight ratio of the amine to the quaternized amine is 10: 1 to 1: 5. The preferred weight ratios of component (A) to component (B) are around 40: 1 to about 10: 1, especially about 20: 1 to about 10: 1. The preferred water-soluble gelatin has a Molecular weight from about 35,000 to about 50,000, a gel strength of at least 50 bloom grams, especially from about 80 to about 200 bloom grams, and an isoelectric point at. : pH 7.0 to pH 9.0 and is used in an amount of about 0.2 to about 2 percent by weight are used.

The preferred mixture of water and alcohol that, as Liquid carrier is used, contains about 3 to about 25 percent by weight, calculated on the total mixture, of an alkanol with 2 to 4 carbon atoms.

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The liquid detergents of the present invention are sufficiently fluid that they can be easily measured and poured and dispersed in water.

The attraction ₃ effectiveness and efficiency of the cleaning compositions of the invention can be further improved, adapted and tailored to specific requirements by other ingredients _s, for example, nonionic surface active detergents, organic or inorganic acids or salts of such organic or inorganic acids, - bactericides, dyes, perfumes , soil suspending agents or anti-corrosive agents, as will be further explained below.

The individual components of the cleaning agents according to the invention are explained in more detail below.

The anionic surface-active detergents which are useful for the cleaning agents according to the invention, represent a mixture of selected, known compounds.

They can be used as water-soluble ethoxylated hydrocarbon sulfates the general formula

R ₁ -O - (- C ^ H ₄ O) _n SO ₃ M (I)

are represented in which R _{1 is} a straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon radical with 8 to 2k carbon atoms, preferably with about 12 to about 18 carbon atoms, or an alkylbenzene radical with 8 to 18 carbon atoms in the straight-chain or branched-chain alkyl radical, η a Number from about 1.5 to about 15, preferably from about 3 to about 12

709818/1111

9t

- N - R,

(III)

wherein R is a hydrocarbon radical with 10 to 22 carbon atoms, which can optionally be interrupted by up to 2 ether, -CO-O or -CONH bonds, preferably an aliphatic hydrocarbon radical with Ik to 18 carbon atoms or an alkylaryl radical with 8 to 16 carbon atoms in the alkyl moiety, means Rj. the meaning of R, which is an aliphatic hydrocarbon radical having 1 to 6 carbon atoms or a benzyl radical, R ₅ and Rg are each aliphatic hydrocarbon radical having 1 to 3 carbon atoms, and X is an anion, preferably a Denotes methyl sulfate, bromide or chloride anion, the total number of carbon atoms of R 1 and Rn being from about 13 to about 32, preferably from 15 to 28;

(2) a quaternized amine of the general formula:

H ₂ C

N N

v /

CH,

N-CO-

^R 10

(IV)

where R ™ and R «each denote an aliphatic hydrocarbon radical with 6 to 18 carbon atoms, where Ry preferably has at least 12 carbon atoms, Rg represents an aliphatic hydrocarbon radical with 1 to k carbon atoms, R ^ ₀ a hydrogen atom or an aliphatic hydrocarbon radical I bis

709818/1111

4 is carbon atoms and X is an anion, preferably a methyl sulfate, bromide or chloride anion, the total number of carbon atoms of Ro and R _{q being} about 10 to 22, preferably about 15 to about 20;

(3) and mixtures thereof.

The organic, surface-active amine is a primary, secondary or tertiary amine of the general formula:

R ₁₁ R ₁₂ R ₁₃ N (V)

wherein R _{11 is} an aliphatic hydrocarbon radical having 10 to 24 carbon atoms, preferably 14 to 18 carbon atoms, which may optionally be interrupted by ether, ester or amide bonds, R _{12 is} a hydrogen atom, an aliphatic radical having 1 to 22 carbon atoms, a group - (Alkyl-NH) -H, in which the alkyl radical has 1 to 4 carbon atoms and r is an integer from 1 to 10, preferably 1 to 3, or represents a group - (CH ₂ CH ₂ O) -H, in which s is an integer from 1 to about 10, preferably from 1 to about 4, and R _{1 represents} a hydrogen atom, the methyl, ethyl or benzyl group or a group of the formula - (CH ₀ -CH ₀ O) -H , wherein s has the preceding meaning.

Useful surface-active amines for use in the cleaning agents according to the invention can be derived by quaternizing compounds of the above general formula V, in which R _{12 represents} a group - (alkyl-NH) _r -H. This class of compounds can conveniently be represented by the following formula:

709818/1111

«6

I.
«13

I alkyl N

14th

(VI)

wherein R .. is an aliphatic hydrocarbon radical with 10 to 24 carbon atoms, preferably 14 to 18 carbon atoms, which may optionally be interrupted by ether, ester or amide bonds, R., a hydrogen atom, the methyl, ethyl or benzyl group or a group of the formula - (CH ₀ -CH ₀ O) -H, in which s is an integer from 1 to about 10, preferably from 1 to about 4, and the alkyl group contains two or three carbon atoms, where R1 is preferably denotes the methyl or ethyl group, R ^ j. a hydrogen atom, an alkyl group with 1 to 3 carbon atoms or a group of the formula (C ₂ Hj ₄ O) H or (C, HgO) H, where ρ and g can each represent 0 or a number such that ( p + g) do not exceed 25, and r is an integer from 1 to about 10, preferably from 1 to 3 ». R ₁ ^ is preferably the methyl or ethyl group. The substituents R ..- Z and R ₁ J can be identical or different. These (polyquaternized) surface-active amines can also be referred to as polyamines, which are optionally substituted.

Quaternized amines of the formula III, which are part of the Forming detergents can be made by known methods, e.g. by addition of an alkyl halide (or sulfate or sulfonate) to a ternary base. The hydrophobic group may originally be a part of the halide or part of the ternary base.

709818/1111

Important examples which form part of the preferred cleaning agents of the present invention are the quaternized amines of the formula III, in which R is an aliphatic hydrocarbon radical with Ik to 18 carbon atoms, e.g. the myristyl, palmityl, stearyl, myristoleyl, palmitoleyl , Oleyl or linoleyl radical, R ^ either has the meaning of R-, or represents the benzyl or methyl group, R ₁ - and Rg each represent a methyl group and X represents any anion.

Among the examples of quaternized amines used in detergents The present invention may include tallow trimethylammonium chloride; Ditallow dimethylammonium chloride; Ditallow dimethylammonium methyl sulfate; Palmity1 trimethylammonium chloride; Laury1-trimethylammonium methyl sulfate; Oleyl benzyl dimethyl ammonium bromide; Stearylhexyldimethylammonium chloride; Dodeey1-triethylammonium methyl sulfate; 7-hexadecinoy1-trimethylammonium bromide; Palmitoley1-trimethylammonium methyl sulfate; and myristoleylbenzyl-dimethylammonium chloride.

The quaternized amines of the formula IV, which can form part of the cleaning agents according to the invention, can according to known processes, e.g. by condensation of fatty acids with N-substituted ethylenediamines and then Quaternization with an alkyl halide.

Examples of imidazolinium compounds of the formula IV which can be used for the cleaning agents according to the invention, are 2-palmityl-l, l-methyl £ (2-stearoylamide) ethyl] imidazolinium methyl sulfate; 2-lauryl-l, l-methyl-C (2-lauroylamide) -ethyl3-imidazolinium chloride; 2-myristyl-l, l-ethyl-C (2-palmitoylämid) -äthyl] -imidazoliniumbroihid; and 2-palmitoleyl, 1-isopropyl-C (2-stearoylamide) -ethyl3-imidazolinium chloride.

709818/1111

* ■

R, - N ⁺ - R,

(III)

wherein R is a hydrocarbon radical with 10 to 22 carbon atoms, which can optionally be interrupted by up to 2 ether, -CO-O or -CONH bonds, preferably an aliphatic hydrocarbon radical with 1H to 18 carbon atoms or an alkylaryl radical with 8 to 16 Carbon atoms in the alkyl moiety, Rh is R-, has an aliphatic hydrocarbon radical having 1 to 6 carbon atoms or a benzyl radical, R ₁ - and Rg are each aliphatic hydrocarbon radical having 1 to 3 carbon atoms, and X is an anion, preferably one Denotes methyl sulfate, bromide or chloride anion, the total number of carbon atoms of R- and Rh being about 13 to about 32, preferably 15 to 28;

(2) a quaternized amine of the general formula:

H ₂ C

NN V /

CH,

N-CO

^R io

- R,

(IV)

where R ~ and Rg each represent an aliphatic hydrocarbon radical having 6 to 18 carbon atoms, where Ry preferably has at least 12 carbon atoms, Rg represents _{an aliphatic hydrocarbon radical having 1 to carbon atoms, R 10 is} a hydrogen atom or an aliphatic hydrocarbon radical I bis

709818/1111

Is 4 carbon atoms and X is an anion, preferably a methyl sulfate, bromide or chloride anion, the total number of carbon atoms of Rg and R _{q being} about 10 to 22, preferably about 15 to about 20;

(3) and mixtures thereof.

The organic, surface-active amine is a primary, secondary or tertiary amine of the general formula:

R ₁₁ R ₁₂ R ₁₃ N (V)

wherein R _{11 is} an aliphatic hydrocarbon radical having 10 to 24 carbon atoms, preferably 14 to 18 carbon atoms, which may optionally be interrupted by ether, ester or amide bonds, R _{12 is} a hydrogen atom, an aliphatic radical having 1 to 22 carbon atoms, a group - (Alkyl-NH) -H, in which the alkyl radical has 1 to 4 carbon atoms and r is an integer from 1 to 10, preferably 1 to 3, or a group - (CHpCHpO) -H, in which s is an integer from 1 to about 10, preferably from 1 to about 4, and R ₁ , a hydrogen atom, the methyl, ethyl or benzyl group or a group of the formula - (CH ₂ -CH ₂ O) -H, in which s is the has the preceding meaning.

Useful surface-active amines for use in the cleaning agents according to the invention can be derived by quaternizing compounds of the above general formula V, in which R _{12 represents} a group - (alkyl-NH) -H. This class of compounds can conveniently be represented by the following formula:

709818/1111

R N R

13th

13th

R.

Alkyl N

i4

(VI)

wherein R _{11 is} an aliphatic hydrocarbon radical having 10 to 24 carbon atoms, preferably 14 to 18 carbon atoms, which may optionally be interrupted by ether, ester or amide bonds, R ₁ - is a hydrogen atom, the methyl, ethyl or benzyl group or a group of the formula - (CHp-CH ₂ O) -H, in which s is an integer from 1 to about 10, preferably from 1 to about 4 and the alkyl group contains two or three carbon atoms, where R ₁ - preferably the Means methyl or ethyl group, R ₁ Ji. denotes a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a group of the formula (C ₂ H ₁₁ O) H or (C, HgO) H, in which ρ and g can each represent 0 or a number such that (p + g) do not exceed 25, and r is an integer from 1 to about 10, preferably from 1 to 3. R ₁₄ is preferably the methyl or ethyl group. The substituents R ₁ -Z and R ₁ ^ can be identical or different. These (polyquaternized) surface-active amines can also be referred to as polyamines, which are optionally substituted.

Quaternized amines of the formula III, which are part of the Forming detergents can be made by known methods, e.g. by addition of an alkyl halide (or sulfate or sulfonate) to a ternary base. The hydrophobic group may originally be a part of the halide or part of the ternary base.

709818/1111

Important examples that are part of the preferred detergents of the present invention are the quaternized Amines of formula III in which R_ is an aliphatic hydrocarbon radical having 14 to 18 carbon atoms, e.g. the myristyl, palmityl, stearyl, myristoleyl, palmitoleyl, Oleyl or linoleyl radical, R ^ either the meaning of R, or represents the benzyl or methyl group, R, - and R / - each represent a methyl group and X represents any anion.

Among the examples of quaternized amines used in detergents The present invention may include tallow trimethylammonium chloride; Ditallow dimethylammonium chloride; Ditallow dimethylammonium methyl sulfate; Palmity1 trimethylammonium chloride; Laury1-trimethylammonium methyl sulfate; Oleyl benzyl dimethyl ammonium bromide; Stearylhexyldimethylammonium chloride; Dodeey1-triethylammonium methyl sulfate; 7-hexadecinoy1-trimethylammonium bromide; Palmitoleyl trimethylammonium methyl sulfate; and myristoleylbenzyl-dimethylammonium chloride.

The quaternized amines of the formula IV, which are part of the Can form cleaning agents according to the invention, can by known methods, for example by condensation of fatty acids with N-substituted ethylenediamines and subsequent quaternization with an alkyl halide.

Examples of imidazolinium compounds of the formula IV which which can be used for the cleaning agents according to the invention are 2-palmityl-l, l-methyl-C (2-stearoylamide) ethyl] imidazolinium methyl sulfate; 2-Laury1-1,1-methy1-C (2-lauroylamide) ethyl / imidazolinium chloride; 2-myristyl-l, l-ethyl-C (2-palmitoylämid) -äthyl3-imidazoliniumbromid; and 2-palmitoleyl, 1-isopropyl-C (2-stearoylamide) ethylU-imidazolinium chloride.

709818/1111

Important examples of organic, surface-active amines which can form part of the preferred cleaning agents of the invention are the primary, secondary or tertiary amines of the formula IV, in which R _{11 is} an aliphatic hydrocarbon radical with 1h to 18 carbon atoms, R _{12 is} a group - (Alkyl-NH) _r -H represents, in which the alkyl group has 1 to 3 carbon atoms and r represents an integer from 1 to 3, and R _ represents a hydrogen atom, or the methyl or ethyl group.

Examples of organic, surface-active amines are laurylamine; Myristylamine; Palmitylamine; Stearylamine; Oleylamine; Linoleylamine; N-methyl-stearylamine; N-propyldipalmitylamine; N-benzyl-N-methyl-myristylamine; N, N-dimethyllaurylamine; N-stearyl-1,3-propanediamine (C ₁ N-myristyl-diethylenetriamine (C ₁₄ H ₂₉ NHCH ₂ CH ₂₂₂ N-i-caproylamidohexyD-triethylenetetramine (C ₇ H ₁₅ CONHC (C ₂ Hj ₄ NH) ₃ C ₂ H ₁₁ NH ₂ ); N, N-diethyl-oleylamine; N, N'-dimethyl-1,12-diaminododeean (CH ₃ NH-CH ₂ - (CHg) ₁₀ CH ₂ -NH-CH ₃ ); and N-polyoxyalkyleneamines such as N -Hexaethoxy-dipalmitylamine

In general, the fastest regular drainage action is obtained with organic, surface active, primary, secondary or tertiary amines containing two to four nitrogen atoms in the molecule. Therefore, preferred examples of such organic surface-active amines which are useful for the cleaning agents according to the invention are the amines of the formula IV, in which R _{11 is} an alkyl group having 14 to 18 carbon atoms, R _{12 is} an ethylenediamine, propylenediamine, diethylenetriamine or triethylenetetraamine group and R _{13 represents} a hydrogen atom or a methyl, ethyl or polyethoxy group.

709818/1111

«9

The organic, surface-active amines can be used as such or in the form of their conjugated acids. The conjugate acid form is preferred when the water solubility of the amines is low. The conjugated Acids of these amines can be prepared by treating them with an organic or inorganic acid, preferably a monobasic acid such as a hydrohalic acid i.e. HCl, HBr, or acetic acid, in the ratio of one equivalent of the acid per nitrogen atom in the amine.

Specific and preferred examples of conjugate acids of the organic surface-active amines used in detergents Particularly useful of the present invention are:

(C ₁₈ H ₃₇ N ⁺ H ₃ ) (CH ₃ COO "); C (C ₁₂ HJ ₂ N ⁺ CH ₃ J (Cl"); LC ₁₆ H ₃₃ N ⁺ H ₂ - (CH ₂ ) ₂ -N ⁺ H- (CH ₂ J ₂ N ^ H ₃ ] (3Cl "); (^ ₈ H ₃₃ N ⁺ H ₃ ) (Br"); (C ₁₈ H ₃₇ NHlCH ₂ CH ₂ CH ₂ N ⁺ H ₃ ) (2CH ₃ COO ").

The preferred polyamines of the general formula VI which can be used in the cleaning agents according to the invention include N-TaIg-N, N, N ¹ , N ', N'-pentamethyl-1,3-propylene-diammonium dichloride; N-tallow-1,3-propylenediamine hydrochloride; N-TaIg-N, N ¹ , N ¹ -triethanol-1,3-propylenediamine hydrochloride; as well as polyamines which are identical to the above except that the tallow alkyl radical is replaced by an alkyl radical having 10 to 24 carbon atoms, preferably up to 18 carbon atoms.

709818/1111

The organic, surface-active amines and quaternized amines listed above can be used in the inventive Cleaning agents can be used individually or in combination. Up to 50 percent by weight of the organic, Surface-active quaternized amines can also be replaced by an equivalent amount of a pyridinium or morpholinium compound, e.g., an alkyl or alkenyl pyridinium chloride having 12 to 22 carbon atoms in the alkyl or alkenyl group or an alkylmethyl, alkylethyl, alkylenemethyl or alkylenethylmorpholinium chloride having 12 to 22 carbon atoms in the alkyl or alkeny group, replaces earth.

The cleaning agents according to the invention contain about 0.1 up to about 5 percent by weight of the organic, surface-active amines, the quaternized amines or mixtures thereof. If more than 5 percent by weight is used, then durability problems can arise, e.g. phase separation and / or the formation of a precipitate. Amounts above 5 percent by weight have no additional effect in the With regard to the speed and regularity of the drainage capacity and are therefore uneconomical. If less are used as 0.1 percent by weight, the concentration of the organic surface-active amines is quaternized Amines or mixtures of such amines in the wash liquor too low, so that the desired speed and Regularity in the process behavior is not achieved if Usual amounts of the liquid detergent are added to the wash liquor.

Within the above range depends on the actual amount of the organic, surface-active amines, quaternized Amines or the mixtures of such amines present in the liquid detergent at the desired use concentration of the detergent in the wash liquor

709818/1111

- 264830A

Vi

and to a lesser extent of the type of the organic amine, the quaternized amine or a mixture thereof Amines. A typical useful concentration of the liquid detergent in the wash liquor is at about 0.1 to about 2 percent by weight. To obtain the optimum benefits of the present invention, included the preferred detergents of the present invention from about 0.5 to about 3 percent by weight of these amines, wherein when only quaternized amines are used, preferably about 0.7 to about 3 percent by weight should be used, and if only amines are used, about 0.5 to about 2 weight percent should be used.

Gelatine is a typical protein that can be obtained from collagen by boiling the skin, tendons, bones etc. with water. The gelatin molecules, like the molecules of other proteins, are large and complex with an average molecular weight of about 5,000 to 200,000 and above. Gelatin molecules, which are charged in alkaline or acidic solution and are therefore amphoteric, have a specific isoelectric point, which mainly depends on the treatment conditions during manufacture. Gelatin obtained by acidic treatment has an isoelectric point which is generally between pH 7 and pH 9. Gelatin obtained by alkaline treatment has an isoelectric point which is usually between pH 4.6 and pH 5.0. By applying special treatments, even gelatins with an isoelectric point as low as pH 4.5 or an isoelectric point as high as pH 9 _S 2 can be obtained, and by mixing gelatins with different isoelectric points, any gelatin mixture with an isoelectric point between pH 4.5 and pH 9.2 can be obtained.

709818/1111

In order to achieve the comprehensive cleaning effect, ie the removal of dirt by simply washing and the removal of residues of dirt ₃ surface-active detergent and hardening components of the water due to the drainage effect after additional rinsing, but without wiping or drying with a cloth, the molecular weight of water-soluble gelatin to be used in the liquid cleaning agent according to the invention is above 12 50O _9, better still above 15 00O _3, preferably between 25,000 and 80,000 and in particular between 35,000 and 50 _s while the isoelectric point of the gelatin is between pH 4.5 and pH 9 * 2, preferably above pH 6 and in particular at pH 7 to pH 9 and the gel strength of the gelatin to be used should be above 25 Bloom grams, preferably above 50 Bloom grams and in particular 80 to 200 Bloom grams. (The gel strength in Bloom grams or Bloom strength is the force in grams that must be applied to a cylinder 12.7 mm in diameter so that it penetrates the surface of a gel made of 6.67 % gelatin with 15 % Moisture penetrates 4 mm deep, compare British Standard Method for Sampling and Testing Gelatins.)

The water-soluble gelatin can be in the liquid detergent of the present invention in an amount of 0.1 to about 5 percent by weight, preferably 0.2 to about 2 Percentage by weight, based on the total weight of the cleaning agent. While the very small amount of 0.1 percent by weight is necessary in order to still achieve a noticeable run-off effect, the upper limit of about 5 percent by weight based on formulation requirements, i.e. on that a liquid composition should be present which is still pourable and consequently easy to handle, dissolve and apply is.

709818/1111

26483QA

The cleaning agents according to the invention can be a simple mixture of the two anionic surface-active detergents, an organic, surface-active amine, quaternized amine or a mixture of these amines and gelatin contain. These cleaning agents can be dispersed or dissolved in an aqueous washing liquor or such Washing liquor can be added to achieve the desired effects. The detergents are in liquid form provided to ensure easy and uniform solubility or dispersibility throughout the wash liquor.

In order to provide the cleaning agents in liquid form, it is necessary to add a liquid carrier. Useful liquid carriers include any toxicologically acceptable liquids that are not compatible with any of the existing Components react, such as the liquid alkanols, preferably alkanols with 1 to 5 carbon atoms, liquid Alkanediols, such as glycols, and the ether derivatives, water, Mixtures of water and alcohol and the like.

Water is the preferred liquid carrier of the invention Cleaning agents, provided that the other components are completely dissolved or suspended therein. If difficult to dissolve organic surface-active amines, quaternized amines or mixtures of such amines are used Mixtures of water and alcohol are preferred as carriers. Particularly preferred alcohols for this purpose are ethanol and isopropanol,

The preferred liquid detergents of the present invention Invention can be formulated as uniform and homogeneous mixtures. In practice, a solution of the organic, Surface-active amines, quaternized amines or mixtures of such amines prepared by adding the compounds to the

709818/1111

264830A

liquid carrier added, whereupon the anionic surface-active Detergents, optionally other optional ingredients and the gelatin, which are separately in one a small amount of the carrier has been dissolved, can be added with stirring to obtain the finished cleaning agent.

The benefits of the cleaning agents according to the invention can improved or the detergents can be tailored to special needs by adding additional surface-active detergents incorporated into the cleaning agent.

The preferred liquid detergents of the present invention preferably contain a nonionic detergent surfactant as an emulsifying, stabilizing and solubilizing agent. Suitable nonionic surface-active detergents which can optionally, but preferably, be used in the cleaning agents according to the invention include the following: about 20 moles of ethylene oxide. Specific examples of these nonionic surface-active detergents are the condensation product of 1 mole of nonylphenol with an average of 9.5 moles of ethylene oxide; the condensation product of 1 mole of decylphenol with an average of 6 moles of ethylene oxide; (2) the condensation product of 1 mole of an aliphatic alcohol having 8 to about 2H carbon atoms in the alkyl chain with about 2 to about 20 moles of ethylene oxide. Specific examples include the condensation product of 1 mole of coconut alkyl alcohol with 7 moles of ethylene oxide; the condensation product of 1 mol of tallow alkyl alcohol with 11 mol

709818/1111

"26A830A

Ethylene oxide; (3) Polyethylene glycols having a molecular weight from about 160 to about 10,000, preferably from about 250 to about 2,500, and (4) mixtures of the foregoing nonionic detergents.

The above nonionic detergent surfactants are compatible with the other ingredients of US Pat Cleaning agents according to the invention and stabilize the liquid agents in that they prevent precipitation and have excellent resistance to freezing and Thaw received. The nonionic detergents also act as stabilizers to improve storage stability and to maintain the desired viscosity. The nonionic detergents can be in the liquid detergents of the invention in amounts up to about 30 percent by weight, preferably in amounts of about up to about 5 weight percent. The use of the above nonionic detergents in the inventive Liquid cleaning agents are particularly preferred because they not only provide the desired resistance and the good properties in freezing and thawing, but also emulsifying and suspending the greasy dirt particles are caused during cleaning.

Detergents according to the invention which are to be used as dishwashing detergents to clean dishes which are mainly soiled with greasy and starchy abrasive particles are preferably adapted to this purpose in that they contain up to about 6% of surface-active amine oxides. Specific examples of such amine oxides include dimethyldodecylamine oxide, dimethyltetradecylamine oxide and dihydroxyethyldodecylamine oxide.

709818/1111

The liquid cleaning agents according to the invention can In addition, various other components, such as low molecular weight organic acids, suspend the dirt Agents, hydrotropic compounds, gloss improvers such as boric acid or water-soluble boric acid salts, bactericides, Dyes, perfumes, anti-tarnish agents and other substances used as ingredients in dishwashing detergents and agents for cleaning hard surfaces are known and those with the constituents of the cleaning agents according to the invention are tolerated, contained in smaller quantities. Preferred hydrotropic compounds are toluene, xylene and cumene sulfonates in amounts up to 8 percent by weight, preferably in amounts of 0.5 to 3 percent by weight, especially when used in combination with lower alkanols, e.g. Ethanol or isopropanol in amounts of 4 to 8 percent by weight, can be used.

Suitable water-soluble, low molecular weight organic acids and their salts including the partially neutralized and the fully neutralized salts are e.g. acetic acid, Citric acid, malic acid, gluconic acid, maleic acid, lactic acid, tartaric acid, propionic acid, butyric acid, malonic acid, Polymaleic acid, polyitaconic acid, glutaric acid, citraconic acid, Benzene pentaarboxylic acid and benzene hexacarboxylic acid, succinic acid, ethylenediamine tetraacetic acid and nitrilotriacetic acid. These organic acids and / or their salts are added to the cleaning effect of the liquid cleaning agent of the present invention, and can also be used as an ion source to improve the Maintain the pH of the detergent at a given pH. The acids can also help make it organic To make surface-active amines soluble by forming conjugated acids with these amines.

709818/1111

The maximum amount of water-soluble, organic acids and / or salts that can be used in liquid detergents can be added to the present invention depends not only on the amount of organic, surface-active amines, quaternized amines or mixtures of these amines that is present but is primarily determined by the present of gelatine is necessary and should not be 5 percent by weight, based on the total weight of the cleaning agent exceed and preferably below 3 percent by weight. Some of the salts of organic acids can be replaced by inorganic acids Builder salts are replaced. The amount of inorganic builder salts, e.g. sodium phosphates or Sodium carbonates, preferably should not exceed 2.5 Be percent by weight.

The excellent cleaning effect and especially that improved drainage behavior of the liquid according to the invention Cleaning agents are explained in more detail by the following examples.

B. e i s ρ i e 1 e

There were four rows A, B, C and D each with 3 rinsing liquids (A ₁ to A 1, B ₁ to B 1, C _± to C, D ₁ to D), which are explained in more detail below, and four rows A !, B ¹ , C ^f and D ^f with three rinse fluids each (A ¹ to A ', B ^ ₁ to B', C ₁ to C 'D ^ to D'). Each flushing liquid in each row contained 0.2 percent by weight of a flushing agent A, B, C or D, as will be explained in more detail below.

That for the production of the 12 rinsing liquids and 12 rinsing liquids The water used had a hardness of about 3.0 mmol CaCO -, / liter. Each rinse bath and each rinse bath contained approximately 10 liters of water. Everyone's temperature

709818/1111

Rinsing liquids amounted to about 50 to 55 ° C at the start of the flushing process, and fell to about 35 to ¹ IO ⁰ C at the end of the flushing process. The temperature of all rinsing liquids fluctuated between about 17 and about 20 ^° C.

4 soiled flat plates (made of dark, glazed ceramic with a Diameter of about 20 cm) immersed for about 1 minute, then gently wiped and wiped one by one then rinsed separately by dipping each plate twice in the rinsing liquid, whereupon they roughly in a vertical position to drain and air dry.

Each plate had previously been soiled with 5 cnr olive oil, evenly with the help of a stream of hot air (around 40 ° C) spread over its inner surface, and for about an hour at room temperature (about 23 ° C) been turned off.

The rinsed and rinsed plates were rated by three experienced evaluators, who worked independently of one another, immediately after the plates had been placed in an approximately vertical position, with regard to the speed and regularity of the drainage. The speed and regularity of the run-off on the set of four plates, which had been _{rinsed in liquid A 1} and rinsed in liquid A * ^, were compared and evaluated, first with the speed and regularity of the run-off on the set of four plates placed in Liquid B ₁ or B ^ had been rinsed or rinsed, then with the speed and regularity of the runoff on the set of four plates that _{had been rinsed or rinsed in liquid C 1} or C ₁ and finally with the speed and Regularity of drainage on the set of four plates _{washed in liquid D 1} and D ^ respectively

709818/1111

or had been rinsed. The same was repeated with the sets of four plates, which were _{rinsed in the second rinsing liquid (A 2} , B ₂ , C ₂ , D ₂ ) and in the second rinsing liquid (A ' ₂ , B' ₂ , C ' ₂ and D' ₂ ) had been rinsed, as well as the sets of four plates that were in the third rinse liquid or rinse liquid (A ,, B ^ ₉ C ^, D, and A ¹ - ,, B ',, C', D ') each Row had been rinsed or rinsed.

The standard of evaluation of the three evaluators can be explained as follows: equal (O), slightly better (+), better (++), much better (+++) in speed and regularity of running on plates, which are classified in B ^ or B ^{1 were} rinsed and rinsed, compared to the speed and regularity of the process en on plates in A ^ and A ^1,. rinsed or rinsed; or in the speed and regularity of the flow on plates that were washed or rinsed in C ^ or C ^, compared to the speed and regularity of ^{the flow on plates that were washed or rinsed in A ^ or A 1} ^; etc. The results are summarized in Table I below:

Table I.

^s Npossible-
^ sRe ihe 1, Rinse / rinse
liquid ...... 2. Rinse / rinse
liquid. 3. Rinse / after
washing liquid 3ewerter ^ v AWAY AC AD AWAY AC AD AB AC AD 1 + ++ +++ ₊ ++ _{+++ + ++ ++} 2 + ++ +++ + _{+++ +++ + ++ +++} 3 O +++ ++ + ♦ _{++ +++}

709818/1111

HO

The liquid dishwashing detergents used in rinsing liquids in rows A to D had the following compositions:

Ingredient (weight?) Example no .: 1 2

ABCD

Paraffin sulfonate, sodium

salt (average ._ ._ _n . _n

Molecular weight of the Koh- ^{ιυ lü}

Hydrogen residues:

about 196)

Coconut alcohol ethylene

oxide (3) sulfate, sodium 10 10 10 10

Gelatin "*") Olli

C ₁₈ H ₃₇ -N ⁺ (-CH ₃ ) y Cl "0 0 1.5 0

^C 1QH ^ ₇ -N ⁺ H ₉ - (CHp), - N ⁺ H ,.

^xo * <* * * * 0 0 0 1

(CH ₃ COO ") ₂

Ethanol 5 .5 5 5 water remainder

Gelatin: average molecular weight about 35,000; Bloom strength about 100 g;
isoeletric point around pH 8.

The dishwashing detergent used in the A series washing liquids is a representative example of a known effective dishwashing detergent. That in the rinsing fluids Dishwashing detergent B used in series B is a representative example of a known effective dishwashing detergent, after rinsing the rinsed glass-like

709818/1111

(μ 264830Α

Objects causes a certain drainage. As can be seen from Table I, the speed and regularity were of running on the plates that are in the the invention Rinsing liquids containing detergent C or D were rinsed and then rinsed, the speed and regularity on the plates, which contain the known detergents A or B. Rinsing fluids had been rinsed and then rinsed, surprisingly superior.

Bs were six further rows E, F, G, H, K and L each with four washing liquids, each containing 0.25 percent by weight per liter of a dishwashing detergent E, P, G, H, K and L, which are explained in more detail below , manufactured. Furthermore, six rows E ¹ , P ¹ , G ¹ , H ¹ , K ¹ and L ¹ with four rinse fluids each were produced. The water used had the same hardness as in the previous experiment. Each rinsing and rinsing bath contained about 12 liters of water. The temperature of the rinsing fluids was maintained at about M5 ° C. The temperature of the rinsing fluids fluctuated between 30 and 35 ° C.

A set of four clean plates (with a glazed surface and a diameter of about 20 cm) was immersed in each of the four rinsing liquids in each row for about 90 seconds (96 plates in total), then the plates were rinsed in the corresponding rinsing liquids in each row (by successive three times immersion for about 10 seconds) and removed from the rinsing liquid> and placed in an approximately vertical position to drip off and air dry.

The speed and regularity of the drainage were assessed by three skilled evaluators using the evaluation method of rated above test. The results are compiled in Table II below «

709818/1111

Table II

26A830A

^ * """" - «- ^^" Compared
Reviewer ^^ ~ \ ^^ 1. Rinse after rinse
liquid 2. Rinse after rinse
liquid 1
2
3 EP EG EH EK EL EP EG EH EK EL ^^ - χ ^^ Compared
Rate it ^ * "^ · ^^ i ζ ii π lii i i ζ zz 1
2
3 3. Rinse / rinse
liquid 4. Rinsing / rinsing
liquid EP EG EH EK EL EF EG EH EK EL I ***** ζ ζ ζ O ++ ++ ++ ++

The liquid dishwashing detergents used in the washing liquids of series E to L had the following compositions:

Component (weight?)

Alkyl sulfonate, sodium salt
(Average molecular weight of the alkyl group: 195)

Coconut alkyl 1- (CH ₉ -CH ₅ -O),
-SO ₃ Na * ds

Gelatin '

Example no: 3

10

10

₃₇
water

- (- NH-CH ₂ -CH ₂ -CH ₂ ) ₂ -NH _{2 O}

1
0
0
0
0

1 1 0 0 0

H 10

10

1 0 1 0 0

rest

K 10

10

1 0 0 1 0

+) Gelatin: average molecular weight 80,000; Bloom weight about 80 g; isoelectric point, for example

^{pH 8i3} 709818/1111

Comparable improvements in speed and regularity of drainage were also obtained when the amines C ^ H ^ NHp;

C. _q H -. "- N - [(CH ₀ CH? 0) ₀ h3 ₀ and C. _O H," - (NH-CH ₀ -CH ₀ -CH ₀ -) ₀ -NH ₀ Io 5i c. c- dd Io 5 (ddddd

have been replaced by the corresponding hydrochloride
C ₁₁₁ H ₂₉ N ⁺ H ₃ -Cl "; C ₁₈ H ₃₇ N ⁺ HC (CH ₂ CH ₂ O) ₂ HJ ₂ -Cl" and

^c i 9 & 1H- (NH ₀ -CH ₀ -CH ₀ -CH ₀ ) _O -N ⁺ H, · 3C1 ~.
Io Ji c. dddd 5

In the next experiment, three rows M, N and D each with three rinsing liquids containing 0.2 percent by weight of the cleaning agents M, N and D, and three rows M ^f , N ¹ and D 'with three rinsing liquids each were produced.

The water hardness, the water temperature of the washing and rinsing liquids and the amount of water were the same as in the first
described experiment. The washing, rinsing, drying and evaluation methods used were also the same as in the experiment described first (for Table I), but using sets of four clean plates each.

The results of this evaluation are as follows
Table III compiled.

Table III

^ "\ _> ^ Compared
^ * \ Rows
Rate he ^ v. 1. Rinse / after
washing liquid 2. Rinse / post
washing liquid 3. Rinse / after
washing liquid 1
2
3 MN MD MN MD MN MD Ϊ4 +++
+ +++
++ +++ ++ +++
+ +++
++ ++ + ++
++ +++
++ +++

709818/1111

The liquid dishwashing detergents used in the washing liquids of the M ₃ N and D series had the following compositions:

Ingredient (Weight-2) Example No .: 7

MND

Paraffin sulfonate, sodium salt

(Average molecular ^ _{0 1Q 1Q} weight of the hydrocarbon residue: 196)

Coconut alkyl-O- (CH ₂ CH ₂ O) ^ - SO ₃ Na 10 10 10

Dodecyldimethylamine oxide 2 2-

Alkyl-O- (CH ₂ CH ₂ O) ₇ H 3 3-

(average number of
C atoms of the alkyl group: 14.7)

_183722223

(CH ₃ COO ") ₂ υυΐ

Gelatine ⁺⁾ 0-1 1

Ethanol 5 5 5

Water rest

+) Gelatin: average molecular weight about 35,000; Bloom strength about 100 g; isoelectric point about pH 8.

The following liquid cleaning agents were also prepared in accordance with the present invention:

709818/1111

Examples: 8th 9 10 11 12th 13th 14th , 0 15th C ₁₂ H ₂₅ -O- (C ₂ H ₁₁ O) ₃ SO ₃ M 8.0 10.0 15.0 12.0 10.0 6.0 9 , 0 16.0 Alkyl-f VsO ₃ M - 5.0 8.0 - - - 2 7.0 (average
Number of carbon atoms
in the alkyl radical:
about 10.8) , 0 Coconut alky1-SO ₃ Na 12.0 5.0 - 12.0 11.0 15.0 8th , 5 4.0 Coconut alkyΙ
Ο- (C ₂ H ₄ ) ₆ -H - 2.0 3.0 - - · - 1 - - - Polyethylene glycol
(Molecular weight
about 400) 3.0 - 1.0 2.5 2.0 - - - Gelatine A ** 1.3 - - 0.6 1.0 1.5 ι, - Gelatin B - 0.9 - - - - - 1 - Gelatine C ⁺⁺⁺⁾ - - 0.5 - - - - - C ₁₈ H ₃₇ -N ⁺ (CH ₃ J ₃ Cl " - - 1.5 - 0.7 - - 0.8 rt υ vT / oil N
Ί (\ "ί" ί »Vyll-r JQ - 1.2 - - - 2.0 , 0 1.2 Cc ₁₈ H ₃₇ -N ⁺ H ₂ -CH ₂ -CH ₂ -
N ⁺ H ₃ J-CCH ₃ COO "3 ₂ 0.6 - - - 0.7 - 1 - (C _l2 H ₂₅ ) ₂ N ⁺ (CH ₃ ) ₂ Br- 0.3 - - 2.5 - -. - - 2-lauryl-1,1-methyl-
C (2-lauroylamido) -
ethyll imidazolinium
methosulfate - - - - - 0.8 - , 5 ■ - Ethanol 5.5 7.0 5.0 6.5 4.0 8.0 5 5.0 Boric acid 0.5 - 2.0 - 0.6 - - 1.5 citric acid - 1.1 - - 0.6 - - Triethanolamine - 0 ,? - - 1.0 - - , 2 - Sodium Cumolsutlfonate 1.4 - -2.0 3.2 2.7 - 1 - water rest

average molecular weight 25,000; isoelectric ... xpoint about pH 8; Bloom pestiness about 100 g.

average molecular weight 45,000; isoelectric jpoint about pH 4.6; Bloom pestiness about 120 g. average molecular weight 60,000; isoelectrical Point about pH 7; Bloom strength about 200 g.

709818/1111

Further homogeneous liquid detergents with the following compositions were also produced, wherein all percentages are by weight:

Examples; l £ Hi ⁸ .

Paraffin sulfonate (Na-Salz) (average content of C atoms: 14.7)

Coconut alkyl 1-0- (C ₂ H ₁₁ O), SO ₅ K coconut alkyl dimethylamine oxide

Stearyl propyl diamine diacetate

N-TaIg-N, N, N ¹ , N ', N ^f -pentamethyl-1,3-propylene-diammonium dichbrid

Triethanolamine

Gelatin**

Ethanol

citric acid

acetic acid

Sodium borate

Cumene sulfonate (potassium salt) perfume

dye

water

Gelatin: average molecular weight 70,000; Bloom strength about 80 g; isoelectric point, for example pH 8.2.

The inventive cleaning agents of Examples 16, 17 and 18 proved to be superior dishwashing detergents in a comparison of their performance against the performance of commercial dishwashing detergents, especially with regard to an improved drainage behavior of glass and vitreous Objects.

7 0 9 818/1111

15.5 9.5 11 10.0 9.5 10 4.2 2.0 3 1.5 0.9 - - - 0.8 5.0 - 2.0 0.75 0.9 0.8 7.0 5.0 5.0 1.2 - - 3.0 - - - 0.7 - 0.5 1.5 1.0 1.0 0.5 0.4 0.4 little little little -Rest-

Practically the same results can be obtained if the N-TaIg-N ₉ N ₉ N ¹ ₉ N ₉ N'-pentamethyl-l ₉ 3 -propylene-diammonium dichloride is replaced by an equivalent amount of N-TaIg-1,3- propylenediamine hydrochloride or N-TaIg-N ₉ N ' ₉ N'-triethanol-l ₉ 3-propylenediamine hydrochloride or replaced on a practically identical compound in which the "TaIg" group by a myristyl, palmityl, stearyl - Or oleyl radical or mixtures of such radicals is replaced.

709818/1111

Claims (1)

Patent claims: ¹ J.} Liquid cleaning agent, containing surface-active detergents, gelatin and common additives, characterized in that it contains the following ingredients in the specified amounts, calculated on the total weight of the cleaning agent: (A) about 4 to about 45 wt -.% Of a mixture of (1) a water-soluble, organic, synthetic, anionic surfactant detergent of the general formula R ₁ -O - (C ₂ H ₄ O) _n SO ₃ M (Ia) wherein R _{1 is} a straight or branched chain, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 24 carbon atoms, an alkylbenzene radical having 8 to 18 carbon atoms in the straight or branched chain alkyl group or a mixture of such groups; η is a number from about 1.5 to about 15 and M is an alkali metal, an ammonium radical or a Dimethyl, diethyl, trimethyl, triethyl, dimethanol, Means diethanol, trimethanol or triethanolammonium radical; (2) a water-soluble, organic, synthetic, anionic surfactant detergent of general formula R ₂ - SO ₃ M (Ha) wherein R _{2 is} a straight-chain or branched-chain, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 24 carbon atoms, an alkylbenzene radical having 8 to 18 carbon atoms in the straight-chain or branched-chain alkyl group or a mixture of such radicals and M has the above meaning; 709818/1111 _r tt, wherein the weight ratio of (1) to (2) is about : 1 to about 1: 5; . (B) from about 0.1 to about 5 wt -% of an organic surface-active amine or quaternized amine selected from: (1) a quaternized amine of the general formula: R ₁ R, - N - (HIa) wherein R ^ is a hydrocarbon radical with 10 to 22 carbon atoms, which is optionally interrupted by up to 2 ether, -CO-O- or -CONH- bonds, or an alkaryl group with 8 to 16 carbon atoms in the alkyl radical, R ₂ , the meaning of Rz or denotes an aliphatic hydrocarbon radical having 1 to 6 carbon atoms or a benzyl radical; R ₁ - and Rg each denote an aliphatic hydrocarbon radical having 1 to 3 carbon atoms, and X denotes an anion, preferably the methyl sulfate, bromide or chloride anion, the total number of carbon atoms of R. and R ₂ being about Is 13 to about 32; (2) a quaternized amine of the general formula N-CO ^R io (X * ") (IVa) 709818/1 11 1 - te - where R ₇ and Rg are each aliphatic hydrocarbon radicals with 6 to 18 carbon atoms, Rq is an aliphatic hydrocarbon radical with 1 to 4 carbon atoms, R._ is a hydrogen atom or an aliphatic hydrocarbon radical with 1 to 4 carbon atoms and X is an anion, preferably the methyl sulfate , Bromide or chloride anion, the total number of carbon atoms of Rg and R ~ being about 10 to 22, (3) an amine of the general formula ^R 11 ^R 12 ^R 13 ^N (Va) where R ^ is an aliphatic hydrocarbon radical with 10 to 24 carbon atoms, which can optionally be interrupted by up to 2 ether, -CO-O- or -CONH bonds, R ^ _{2 is} a hydrogen atom, an aliphatic radical with 1 to 22 Carbon atoms, a radical of the formula - (alkyl-NH) _r -H, in which the alkyl group has 1 to 4 carbon atoms and r is an integer from 1 to 10, a group of the formula - (CH ₂ -CHg-O) ₂ - H, in which s is an integer from 1 to 10, and R ^, a hydrogen atom, a methyl, ethyl or benzyl group or a group of the formula - (CH ₂ -CH ₂ O) -H, in which s has the preceding meaning has, represents, (4) a polyquaternized amine surfactant formula 11 " -N Alkyl -J- IH J (Via) 709818/1111 wherein R _{1 is} an aliphatic hydrocarbon radical having 10 to 24 carbon atoms which is optionally interrupted by ether, ester or amide bonds, R _{1 is} a hydrogen atom or a methyl, ethyl or benzy group or a group of the formula - (CH ₅ -CH ₀ O) ₀ -H, where s is a d is 2 s integer from 1 to about 10 / and the alkyl group has 2 or 3 carbon atoms, R ₁₁ . denotes a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a group of the formula (CoHnO) η or (C, HgO) H, in which ρ and g can each denote 0 or a number such that (p + g) denotes the number 25 do not exceed, and r is an integer from 1 to about 10 and (5) mixtures of these selected organic surface-active amines and quaternized amines, wherein the weight ratio of (A) to (B) is 60: 1 to 5: 1, (C) about 0.1 to about 5 weight percent of a water soluble Gelatin with a molecular weight of at least 500, a gel strength of about 25 to 300 bloom grams and an isoelectric point at pH 4.5 to pH 9.2 and (D) as the remainder, a liquid carrier consisting of water, a lower alkanol having 1 to 5 carbon atoms or a mixture of water and a lower alkanol with 1 to 5 carbon atoms. 709818/1111 2. Cleaning agent according to claim 1, characterized in that it is about 8 to about 25 percent by weight of a mixture the end (1) the water-soluble, organic, synthetic, anionic surface-active detergent of the general formula R ₁ -O - (C ₂ H ₄ O) _n SO ₃ M (Ib) wherein R _{1 is} a saturated or unsaturated, straight-chain hydrocarbon radical having 12 to 18 carbon atoms and η is a number from about 3 to about, and (2) the water-soluble, organic, synthetic, anionic surface-active detergent of the general formula R ₂ - SO ₃ M (lib) wherein R _{2 is} an alkyl group with about 12 to about 18 carbon atoms, an alkylbenzene group with 10 to 16 carbon atoms in the alkyl radical or a mixture of such groups, contains, the weight ratio of (1) to (2) being from about 5: 1 to about 1: 2. 3. Cleaning agent according to claim 1, characterized in that it is about 0.7 to about 3 percent by weight of a quaternized Amine of the general formula ^R 3 ^, ^N - ^R 6 ^R 5 (X "") (HIb) where R _{3 is} an aliphatic hydrocarbon radical with I ¹ I to 18 carbon atoms, Rh is the meaning of R, 709818/1111 or represents a methyl or benzyl group, and R ₁ - and Rg each represent a methyl group, the total number of carbon atoms of IU and R ₁ being about 15 to about 28, contains. 4. Cleaning agent according to claim 1, characterized in that it is about 0.5 to about 3 percent by weight of the polyquaternized contains surfactant amine (B) (4). 5. Cleaning agent according to claim 1, characterized in that that there is about 0.5 to about 2 percent by weight of an amine of the general formula R ₁₁ R ₁₂ R ₁₃ N (Vb) in which R .. denotes an aliphatic hydrocarbon radical with IH to 18 carbon atoms, R ^ ₂ denotes a group - (alkyl-NH-) _r -H, in which the alkyl radical contains 2 or 3 carbon atoms and r denotes a number from 1 to 3, and R ₁ ^ is a hydrogen atom, the methyl or ethyl group or a group - (CH ₂ CH ₂ -O) ₂ -H, in which s is a number from 1 to about 4, contains. 6. Cleaning agent according to claim 3 and 5 _9, characterized in that it contains about 0.5 to about 3 percent by weight of a mixture of the amine of the general formula IHb and the quaternized amine of the general formula Vb in a weight ratio of amine to quaternized amine of 10: 1 to 1: contains. 7. Cleaning agent according to claim 5 and 6, characterized in that it contains an amine of the general formula Vb, wherein R _{11 is} an alkyl group having 14 to 18 carbon atoms, R _{12 is} a radical of ethylenediamine, propylenediamine, diethylenetriamine or triethylenetetramine and R _{1 is} ? represents the methyl or ethyl group or a group - (CH ₅ CH ₀ -O) -Ή, in which s is an integer from 1 to about 4. 709818/1111 26A8304 8. Cleaning agent according to claims 1, 5, 6 and 7, characterized characterized in that the amines contained therein are present in the form of conjugated acids. 9. Cleaning agent according to claim 8, characterized in that the conjugate acids are the reaction product of the amines with hydrohalic acids in the ratio of one equivalent the acid per nitrogen atom present in the amines. 10. Cleaning agent according to claim 8, characterized in that the conjugate acids are the reaction product of the amines with acetic acid in the ratio of one equivalent of acetic acid per nitrogen atom present in the amines. 11. Cleaning agent according to one of the preceding claims, characterized in that the weight ratio of water-soluble organic, synthetic, anionic surface-active detergents to the organic, surface-active Amines, quaternized amines, and mixtures of such amines is about 20: 1 to about 10: 1. 12. Cleaning agent according to claim 4, characterized in that it contains a polyquaternized surface-active amine of the formula Via, wherein R ^ _{1 is} an aliphatic hydrocarbon radical having 14 to 18 carbon atoms, R ^, and R ^ ₁ J is methyl and / or ethyl groups mean .and r is a number from 1 to 3. 13. Cleaning agent according to one of the preceding claims, characterized in that it is about 0.2 to about 2 percent by weight a water-soluble gelatin with a molecular weight of about 25,000 to about 80,000, a gel strength 709818/1111 ability of about 50 to 200 bloom grams and an isoelectric Contains point from pH 6 to pH 9> 2. Ik. Cleaning agent according to claim 13, characterized in that the polyquaternized surface-active amine is an N-alkyl-Ν, Ν, Ν ', N ¹ ₅ N ^I -pentamethyl-1,3-propylene-diammonium dichloride, N-alkyl-1,3 propylenediamine hydrochloride or an N-alkyl-Ν, Ν ¹ , N ^f -triethanol-l, 3-propylenediamine hydrochloride, in which the alkyl group is a myristyl, palmityl, stearyl, oleyl or tallow alkyl group or mixtures of such Represents groups. 15. Cleaning agent according to claim 14, characterized in that it is a gelatin with a molecular weight of about 35,000 to about 50,000, a gel strength of 80 to 200 bloom grams and an isoelectric point of pH 7 to pH 9 contains. 16. Cleaning agent according to claim 15, characterized in that that it contains a polyquaternized amine surfactant according to claim 14, wherein the alkyl group is a tallow alkyl group means. 17. Cleaning agent according to one of the preceding claims, characterized in that it contains a mixture of water and alcohol with a content of about 3 to about 25 %, based on the total mixture, of an alkanol with 2 to k carbon atoms as the liquid carrier. 18. Cleaning agent according to one of the preceding claims, characterized in that it is up to 30 percent by weight, calculated on the total weight of the cleaning agent, of a nonionic surface-active detergent selected from condensation products of 1 mole of an alkylphenol having 8 to 18 carbon atoms in the alkyl chain with about 2 to about 20 moles of ethylene oxide, condensation products of 1 mole of an aliphatic alcohol with 8 to 2k carbon atoms with about 2 to about 20 moles of ethylene oxide, polyethylene glycols 709818/1111 with a molecular weight of ΙβΟ to about 10,000 and Contains mixtures thereof. 19. Cleaning agent according to claim 18, characterized in that that it . 1 to about 5 percent by weight, of a condensation product of one mole of an aliphatic alcohol with up to 18 carbon atoms with 6 to 12 moles of ethylene oxide, a polyethylene glycol with a molecular weight of about up to about 2,500 or a mixture of such compounds. 20. Cleaning agent according to one of the preceding claims, characterized in that it contains up to 3 percent by weight, calculated on the weight of the cleaning agent, water-soluble, low-molecular organic acids or salts contains these acids. 21. Cleaning agent according to one of the preceding claims, characterized in that it contains up to 8 percent by weight, calculated on the total weight of the detergent, a hydrotropic compound selected from sodium or Contains potassium salts of toluene, xylene and cumene sulfonate or mixtures thereof. For: Procter & Gamble ETC. StrombeeJk-BeyWer / Belgium IjI DfIH.JtWoIff Lawyer 7098 18/1 1 11