DE2345115A1 - LIQUID DETERGENT - Google Patents

Description

LAWYERS

ÄS ™ "' ¹ ' - Sep 6, 1973

At SS-Ae ^ ^wol "2345115

FRANKFURTAM MAIN-HOCHSf

Our no. 18 361

Procter & Gamble
European Technical Center otrombeek-Bever / Belgium

Liquid detergent

The present invention relates to a liquid, clear, aqueous cleaning agent, which is a non-ionic surfactant detergent and a gelatin with an Iklolekulargevicht of at least 12,5oo and a gel strength contains at least 25 bloom grams. The invention relates in particular to a liquid, clear aqueous cleaning agent for cleaning glass, porcelain, glazed or enamelled objects, which runs perfectly, so that you do not have to dry it with a cloth.

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Formation of a PiIm3, from stripes or blanks on the washed, rinsed, and air-dried items is kept to a minimum. The detergent contains a nonionic detergent surfactant and a water-soluble gelatin having a molecular weight between 12,500 and 2oo,000 and preferably between about 25,000 and 80,000, a gel strength of 25 to 300 and preferably from 5 to 2oo bloom grams and an isoelectric point between pH 4.5 and 9 »2.

The quality of a detergent for cleaning Glass, dishes, windows and other items with a glazed surface are commonly used by consumers regarding gloss, lack of filiculation, missing Stains and streaks rated. The liquid dishwashing detergents on the market today are first Line formulated in such a way that it removes dirt from glass, dishes and windows, but leaves residue on it the detergent solution and redeposited dirt by rinsing and / or rubbing the wet objects must be removed with the towel. It is not immediately rinsed or rubbed with a towel, so these residues dry on the surface of the washed items and leave them difficult to remove Stains, films or streaks.

r / ground the items washed with clean water and / or rinsed and not towel dried immediately, so In addition, after the water has evaporated, streaks and streaks that are due to the hardness of the water remain visible on the surface.

Drying the washed items such as glasses and dishes immediately after removing them from the washing machine

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Rinsing with a dec towel is uneconomical (you need lots of towels) and not always possible (too often Interrupting the rinsing process). Hence, many housewives make the washed and unwound dishes to drain and drying in air only to the side, the cleaning action of the product used, which can be visually satisfactory after rinsing and rinsing, then goes lost due to the difficult to remove, unsightly, clinging or otherwise deposited detergent residues, Dirt and / or '. "/ Water hardness from the dishwashing or Rinsing water.

Also when cleaning larger glazed surfaces such as tile walls, e.g. in shower cubicles or ceramic bathtubs, sink or the like with a glass-like surface, the surface that is still damp after cleaning must be rubbed off, so that r'leck-, jj'ilm- and streaking are avoided.

The 'rubbing dry immediately after cleaning is not always possible and requires frequent interruptions in cleaning work. It can therefore appear that the detergents do not work well, although the dirt is removed first, as later streaks Film and bruise remain on the treated surfaces.

Numerous attempts have been made to reduce the deposition of detergent, dirt and / or «Water hardness residues when drying in the air are minimal to design, namely by means of various additives for the rinsing or rinsing process, through complex formation the water hardness salts, addition of improved sehmutz-suspending Agents or by formulating special rinsing agents. The incorporation of complex-forming and / or dirt-suspending gowns in liquid detergents creates difficulties in the formulation while

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special rinse aid must be packed separately and used separately.

It has now surprisingly been found that the combination au3 a small amount of a gelatin kit of a liquidity of at least 25 bioom grams, one molecular weight of at least 12,5oo and an isoelectric point between pH 4.5 and 9.2 and a non-ionic, surface-active Detergent, with optionally other specific surface-active agents and / or framework salts can be present in precisely defined! «! narrow ranges, leads to excellent detergents and cleaning agents that are particularly suitable for cleaning glass, porcelain, glazed or glass-like objects and excellent Show run-off behavior, so that towel drying is avoided and the formation of films, Strip or if'lick on the washed, rinsed and Air-dried glass, porcelain or the like is kept to a minimum.

Detergents containing gelatin or hydrolyzed proteins and surfactants are for example from GB-PS 1 16o 435, IT-Pa 862 or the DAiS 1 929 o4o known. The said British Patent specification describes lotions or detergent mixtures, which contain a partially degraded protein with a gel strength of 0 blomgrams. A gelatin with a gel strength of 0 bloom grams is for the Purposes of the present invention completely unsuitable. The ones in the detergents according to the above Italian patent specification or the German patent application mentioned gelatins cannot be used in the liquid according to the invention Cleaning agents are incorporated, while the surface-active detergent system and other compulsory ones

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Co-components prevent dripping.

In addition to a constant need for detergents and cleaning agents, in particular dishwashing detergents, which remove dirt residues and improve the appearance of the dry articles, there is also a constant need for a compatible combination of materials - which clean at the same time, improve the appearance of the cleaned objects in the end and eliminate the need for towel drying or rubbing. It is therefore an object of the present invention to provide a liquid, clear, permanent, aqueous cleaning agent for glazed or glass-like objects with excellent cleaning properties and improved Drainage properties after rinsing, what kind of leakage on the washed, rinsed, air-dried surfaces and drying with eliminates the need for a towel or rubbing.

The comfort, the effectiveness and the economy of the Agents according to the invention can still be improved, certain Adapted to requirements and tailored to specific conditions by adding additional, water-soluble organic anionic surface-active detergents, water-soluble organic acids or their salts, emulsifiers, bactericides, dyes, perfumes, corrosion inhibitors and / or dirt-suspending agents of the type explained in more detail below are admixed.

The cleaning agent according to the invention contains calculated on the total weight of the agent

(a) about 2 to about 40 wt .- ^ S of a water-soluble, organic, non-ionic surfactant detergent in the form of

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-G-

(1) tertiary oxides of the general formula

O (I)

in which R _{1 is} a straight-chain or branched, saturated or unsaturated, aliphatic hydrocarbon, hydroxy-hydrocarbon or alkyloxy-hydrocarbon radical having S to 24 carbon atoms, Up and R are each a methyl, ethyl, hydroxymethyl or hydroxyethyl radical and Y is a nitrogen or phosphorus atom ,

(2) Amides of the general formula

R ₄ -CO-N (H) _1n-1 (R ₅ OH) ₃ _ _m (II)

wherein R. is a saturated or unsaturated aliphatic Hydrocarbon radical with 7 to 21 carbon atoms, R-one Methylene or ethylene group and m represents the number 1, 2 or,

(3) Condensation products from about 3 to about 25 KoI ethylene oxide and 1 iviol of an organic hydrophobic compound of an aliphatic or alkyl aromatic type with about 8 to about 24 carbon atoms.

or a mixture thereof,

(B) from about 0.1 to about 5 percent by weight of a water-soluble gelatin having a molecular weight of at least 12,5oo, a liquidity between 25 and 300 bubbles and an isoelectric point between pH 4.5 and about 9.2 , and

the rest of the water.

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The nonionic surface-active detergents to be used in the emulsifiers according to the invention, the gelatin and the other ingredients are described in more detail below. If in the description of additional surface-active detergents and other ingredients reference is made to a dalz, it is either a sodium, potassium, ammonium, trimethyl, i'riäthyl-, dimethyl, diethyl, i'rimethanol- , triethanol, dimethanol or diethanolaminonium salt, unless otherwise stated.

There. ίGelatin is a typical protein (made from collagen obtained by boiling skin, tendons, bones and the like with water), the G-elatin molecules are like that molecules of other proteins large and complex with average molecular weights between about 5,000 and up to 2oo ooo and more. The gelatine molecules that are charged in alkaline or acidic solution and are therefore amphoteric have a specific isoelectric point, which depends mainly on the process conditions of manufacture depends. Gelatin obtained by acid treatment has an isoelectric point generally between pH 7 and 9> while gelatin obtained by alkali treatment has an isoelectric point of usually pH 4.6 to 5. Gelatins with isoelectric points as low as pH 4.5 and up to pH 9> 2, and by blending gelatins with different isoelectric points one can choose any gelatin mixture with isoelectric points between Combine pH 4> 5 and 9> 2.

The amount of water-soluble gelatin in the inventive liquid cleaning agent can be between 0.1 and about 5 wt .-> j and preferably between 0.2 and about 2 wt .- />

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calculated on the total weight of the putty ice. The very low lower limit of 0.1% by weight is required uir. to achieve a noticeable process effect, while the limitation to a maximum value of about 5% by weight is based on the requirements of the formulation declines, i.e. the requirement for a pourable liquid genic that is easy to handle, to solve and is to be applied.

In order to achieve the desired settlement effect, i.e. the Removal of dirt by simple rinsing and the removal of dirt, detergent and water hardness residues by running down after additional I-washing, but without To effect rubbing or drying with the towel, ffiuij the lolefcular weight of the water-soluble gelatin more than 12,5oo and preferably more than 15,000, particularly preferably 25,000 bx3,500 and in particular 35,000 bx3 50,000 be, while the isoelectric point of gelatin between pH 4.5 and 9 * 2, preferably above 6 and especially preferably between pH 7 and 9 and the gel strength of the gelatin more than 25 Bloca-Gracxi, preferably ir.more than 5o and particularly preferably between 3o and 2oo BioODi-Graam (the gel strength in Bloom-Graam or the Bloom-iPestigkeit is the required one Force (in grams) that nan on a cylinder of 12.7 mm Diameter, must be used so that it can be inserted into the surface of a gel made of 6.67? " Gelatin with 15'jj moisture 4 mm penetrates (compare British standard l.; ethod for Sampling and Testing Gelatins).

By adding some synthetic anionic surfactants Detergents in starry Jkengen will die ^ .washing time required to achieve good drainage is decreased. This finding allows the formulation of liquid detergents that in addition anionic surfactant detergents (in kengen

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up to 40 wt. ys), which are especially suitable for use in water, medium to high ionic strength (ionic strength = concentration of the washing liquid in ivalications such as Ca ⁺⁺ , kg ⁺ , mainly due to the hardness of the water, Na, K and the like . from builders).

For use in the liquid cleaning agents according to the invention are suitable water soluble nonionic detergent surfactants

(1) Water-soluble, non-ionic tertiary amine oxides general terms

R ₁ R ₂ R ₃ Y- * 0 (I)

wherein Y is a nitrogen atom, R _{1 is} a high molecular weight, straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon, hydroxy or alkyloxy hydrocarbon radical, preferably an alkyl radical, with 3 to 24 and preferably 12 to 18 and particularly preferably 12 carbon atoms, or a mixture of dodecyl -, iteyl and ietradecyl radicals, in which at least 5a,.> of the radicals consist of dodecyl radicals, and Rp ^{un (} 3 R- *> which can be identical or different each represent a methyl, ethyl, hydroxymethyl or hydroxyethyl radical.

The above amine oxides are generally by direct Oxidation of the corresponding tertiary amines produced in a manner known per se. Special .examples of tertiary Amine oxides: dimethyl dodecyl amine oxide, diethyl tetradecyl amine oxide, Bis (2-hydroxyethyl) dodecyl-a single oxide, bis (2-hydroxyethyl) -3-dodecoxy-1-hydroxypropyl amine oxide, Di-

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methj / l-2-hj ^r droxydodecjrl-an: inoxicl and diethyl-eicosyl-ariine oxide;

(2) water-soluble, non-ionic tertiary phosphine oxides of the general formula

R ₁ H ₂ R ₅ X— f O (I)

wherein Ϊ represents a phosphorus atom and H ₁ , Hp and Ji have the above meanings. These compounds are prepared by alkylation of an alkylphosphine derivative and oxidation of the reaction product, as described, for example, in J ¹ R-PS 1,317,586. Specific examples of tertiary phosphine oxides are: dimethyl dodecyl phosphine oxide, ethyl tetradecyl phosphine oxide, bis (2-hydroxyethyl) dodeeyl phosphine oxide, tetradecyl ethyl 2-hydroxyethyl phosphine oxide, oleyl dimethylphosphine oxide and 2-hydroxydodeeyl phosphine oxide;

(3) water-soluble amides of the general formula

A ₄ -CO-S (K) _n-1 (H ₅ OII) ₃ _ _m (II)

v / orin R. a saturated or unsaturated aliphatic Hydrocarbon radical with 7 to 21 and preferably 11 to 17 carbon atoms, RV a kethylene or ethylene group and m the number 1, 2, or 3 », preferably 1, represent. Specific examples of such amides are lonoethanol coconut fatty acid amide and diethanol dodecyl fatty acid amide and dinethanol-oleylamide;

(4) water-soluble condensation products obtained by condensation known per se from 3 to about 25 Iv.ol ethylene oxide with 1 LoI of an organic hydrophobic Compound of aliphatic or alkyl aromatic nature init

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3 to 24 carbon atoms and at least one reactive hydrogen atom, preferably a reactive hydroxyl, Amino, amido or carboxyl group. General examples are:

(a) the condensates of ethylene oxide and aliphatic alcohols with more than 8 carbon atoms. The alcohols can be made from naturally occurring fatty acids, but also from various branched-chain higher alcohols. The preferred alcohol-ethylene oxide condensation products belong to the alcohols from algae and coconut fatty acids manufactured products »Condensation products are particularly preferred from about 4 to about 12 Iviol ethylene oxide per Get aliphatic alcohol with 10 to about 13 carbon atoms, especially from a coconut fatty alcohol middle eleven raction and 6 i; ol ethylene oxide ';

(b) Condensates of ethylene oxide and alkylphenols, where the phenols can be mono- or poly-alkylated and the total number of the carbon atoms in side chains 5 to 18 amounts to. The aromatic king bearing the phenolic hydroxyl group can be a benzene, naphthalene or diphenyl radical and preferably a benzene residue se.in. Specific examples are the condensation products from 1 mole of ilonylphenol and 9 to 15 moles of ethylene oxide;

(c) Condensates of ethylene oxide and fatty acid esters, preferably conofatty acid esters of the sugar alcohols sorbitol and cannitol and, but less preferably, the di- and polysaccharides. Specific examples are the polyoxyethylene sorbitol monolauric acid esters with 20 or more ethylene oxide units and the polyoxyethylene derivatives of fatty acid partial esters of hexitol anhydrides, which are generally known under the trade name "ΪwjciäKS ^H ;

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■ ι *

(d) obtainable by reacting ethylene oxide with carboxylic acids Ester. The acids can be made from natural fatty acids or from i'atty acids from oxidized paraffin wax, mono- or polyalkylated benzoic or naphthenic acids be prepared. Preference is given to aliphatic fatty acids with 1o to 2o Carbon atoms and benzoic acids with 5 to 18 carbon atoms in the alkyl radical. Specific examples and preferred condensation products are the condensation products from I'all oil / ethylene oxide and oleic acid / ethylene oxide with 9 to 15 Ethylene oxide units}

(e) Condensation products from fatty acid alkanolamides of the type C _7-17 AIkVl-CO-NHC ₂ H ₄ OH, C _7-17 AIk ₁ Yl-CO-IT- (C ₂ H ₄ OH) ₂ and ethylene oxide. Condensation products from 1 KoI KOkOSnUS-CO-NH-C ₂ H ₄ OH and 5 to 20 moles of ethylene oxide.Special examples of such polyethyleneoxyalkanolamides of fatty acids are the products known ^{under the trade name Β 11;}

. (f) Condensation products of Cg ^ o-alkyl, Cq_ ^ alkenyl and Cp-ig-alkylarylainins and ethylene oxide. A specific and preferred example is the condensation product of 1 mol of a dodecylamine and 9 to 12% ethylene oxide. Another special example corresponds to the formula C .., .alkyl-CO-NH-C ₆ H ₄ -N- ^ f (OC ₂ H ₄ ) ₆ 0H7 ₂ .

Me amount of non-ionic detergent surfactant in the liquid detergents according to the invention should preferably not more than 4o Gev /.--^.

As mentioned earlier, this can be convenience, effectiveness and economy the cleaning means according to the invention improved and adapted to special needs by adding water-soluble organic anionic surface

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surface-active detergents, water-soluble organic acids or courtship and the like mixed, v / ie already described, consists a special advantage of adding an anionic surface-active detergent in reducing the post-rinse time, necessary to achieve optimal drainage is.

Organic synthetic anionic agents suitable as an additive to the liquid cleaning agents according to the invention
are surface-active detergents

(5) water-soluble hydrocarbon sulfates of the general Ji ¹ O sleeves

K ₆ O (O ₂ H ₄ O) _n SO ₃ M (III)

wherein Rg is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical
with 3 to 22 carbon atoms, η a number ', from 0 to
about 15 and ii a cation, preferably da3 sodium or
Potassium ion 'represent' vain examples of such
Additives are the salts of an organic reaction product of sulfuric acid and a saturated or unsaturated fatty alcohol with S to 18 carbon atoms. preferably
Tallow or coconut alcohol, which are reacted with 1.5 to 15 and preferably with 3 to 12 Ι, ίοΐ ethylene oxide per KoI Ji'ettalkohol. Specific examples are the connections:

^C 12-14 A ¹ ^ yI-O- (C ₂ H ₄ O) ₃ -SO ₃ N (C ₂ H ₄ OK) ₃ ; Coconut-0- (C ₂ H ₄ J ₄ -SO ₃ Na; C ₁₄ AIkVl-O- (C ₂ H ₄ O) ₃ SO ₃ NH ₄ ; C _l2 _ _i6 alkyl-O- (C ₂ H ₄ O) ₆ -SO ₂ K; and TaIg-O- (C ₂ H ₄ OJ ₉ -SO ₃ N (H) (C ₂ H ₄ OH) ₂ .

void examples of hydrocarbon sulfates of the general Formula III, where η denotes the number ü, are compounds that contain hydroxyl groups by sulfation

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Hydrocarbons, preferably from fatty alcohols with 3 up to 13 and particularly preferably 12 to 16 carbon atoms with sulfur trioxide, sulfuric acid or the like., then Hydrolysis and / or bleaching are obtained;

(6) water-soluble mats of organic sulfuric acid reaction products of the general formula

B, -SO-LI (IV)

wherein R _{7 is} a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 24 and preferably 12 to 18 carbon atoms or an alkylbenzene radical having 3 to 13 and preferably 12 to 16 carbon atoms in the alkyl radical and K is a cation. Important examples of synthetic detergents which can be used as components of cleaning agents according to the invention are the salts of an organic sulfuric acid reaction product from a hydrocarbon of the oil series including the iso-, iieo-, meso- and n-paraffins with 3 to 24 and preferably 12 to 13 carbon atoms or a hydrocarbon of the ethylene series having 3 to 2o and preferably 12 to 13 carbon atoms and 1 to 4 double bonds and a sulfonating agent such as S0 ~, HpSO., oleum or the like. Which by sulfonation in a manner known per se, including. Bleaching and hydrolysis. The sulfonated 12-18 ⁿ ~ - ^ ^ara ^^ i ^ne »are preferred individually or in a mixture with sulfonated C <-olefins with an average of 14 carbon atoms. Important examples of alkylbenzenesulfonates having alkyl radicals of about 9 to 13 carbon atoms are the dodecyl, tetradecyl and hexadecylbenzenesulfonates and the products described in US Pat. Nos. 3,322,099 and 2,477,335.

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The maximum amount of the water-soluble anionic surfactant Detergent in the liquid cleaning agents according to the invention results from the amount of non-ionic surface-active detergent and also the amount of gelatin present. The maximum total amount of nonionic and anionic detergent surfactants is about Ί8 Qew .- #, based on the total weight of the Means.

Preferred anionic surface-active detergents are water-soluble hydrocarbon sulfates of the general iOrrcel Kgü (O "Ii.u) JOJL (III), where Rr is preferably a tertiary, saturated aliphatic hydrocarbon test with 3 to 20 and preferably 12 to 16 carbon atoms, η preferably a number from 1.5 to 12 and particularly preferably from 3 to 9 and fr is preferably liatrium or potassium. These preferred ethoxylated hydrocarbon sulfates can be present in up to 40% and preferably between 5 and 2o uev ..- ·; ', based on the total weight of the cement.

.. earth in the liquid according to the invention. cleaning agents water-soluble salts of organic sulfuric acid reaction products of the a .igeirieinen iorrrel 1 \ ~ -3ϋΛ: (IV), v _t orin H ₇ a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical with 3 to 24 and preferably 12 to 13 carbon atoms or an alkylbenzene radical with β up to 13 and preferably 12 to 16 carbon

/ a ^ eacbei atoms in the alkyl radical and I.- represent a cation, so should the maximum amount less than 30 wt .- ^, based on the üessir.t weight of the putty ice and preferably 2o Weight .-; .. do not exceed, .preferred additives are the

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sulfonated C _? _ „N-paraffins, individually or in a mixture with sulfonated C _{0 s} ^ -olefins.

When using combinations of water-soluble, ethoxylated hydrocarbon sulfates of the formula HgO (O ₂ HO) Sü ^ Li (III) and water-soluble organic sulfuric acid reaction products of the formula R ₇ SO ^ H (IV), in which Hg, K ₇ , Id and η Have the above meaning, the weight ratio between the water-soluble salt of the organic sulfuric acid reaction product and the SuEime of non-ionic surface-active detergent and ethoxylated hydrocarbon sulfate should preferably, depending on the concentration and type of the metal cations present in the .Spüliquid (ie the ionic strength) at most J5 / 1 and preferably less than 1.5 / i. Particularly preferred are agents which, as water-soluble, ethoxylated hydrocarbon sulfates / compounds of the formula ^ ₁₂ -16 ⁱ ^ ^k yl ~ ^ü ~ ( ^ü 2 ^ 4 ^ H ~ 6 ^^ 3 ^il '"' ^a ^ ^{s was3e} soluble salts of organic sulfur reaction products 0 2_ ο Paraffinsulfonate and as a non-ionic surface-active i) detergent a mixture of U-, _A ülkyl-diraethylamin.-

I d ~ I "-f

oxide and coconut fatty acid diethanol ^ jside, the weight ratio of paraffin sulfonates aui * üUEine -from C ρ, - alkyl-Ü- (Ü2H.0) _a _gaÜ, M plus amine oxide and ett acid diethanolamide at most 2 / 1 and preferably l / l.

To improve the emulsification of greasy dirt other non-ionic surfactants can be used such as polyethylene glycol condensation products with a molecular weight of from about 160 to about 1200 and / or fatty acid esters, preferably fatty acid esters of sugar alcohols, iiorbit and Lannit the smocks according to the invention be added. jJie length of polyethylene glycol condensate

sprodüktep
tion _ can be up to 15 wt. - · ρ , preferred L> narrow

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bend at 2 to S weight £>. The Köehstmenge to ü'ettsäureestern of sugar alcohols is dictated by the solubility thereof, it should preferably not exceed 3 wt ¹ ^, based on da3 total weight of the composition.

Another component that the cleaning agents according to the invention can be added is a water-soluble low molecular weight organic acid or the water solvent Alkali metal, ammonium or substituted aismonium salt of that. Suitable water-soluble low molecular weight organic acids and their salts including the partial and Completely 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, Poly maleic acid, polyitaconic acid, glutaric acid, citraconic acid, Benzene pentacarboxylic acid ^ and hexacarboxylic acid, succinic acid, Eth / lenediamine-tetraacetic acid, nitrilotriacetic acid. These organic acids and / or their salts are added in order to improve the cleaning effect of the liquid detergents, they can also be used as Serve ion source, which means the pH value of the means to a predetermined Height holds.

Specific examples of suitable water-soluble partially or fully neutralized acid salts are; Cono-, di- and i'rin sodium citrate, diammonium citrate, iconopotassium tartrate, disodium succinate, tetrasodium mellitate G ^ ( COONa) ₄ -

(COOH) ₂ .

The maximum amount of water-soluble, organic acid and / or their salts is not only dictated by the tightness of the surface-active detergents, but mainly by the presence of the gelatin. It should be 15 wt .- ^ i, based on the total weight of the mixture, not exceeding

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.then and preferably below 5 wt .-> S are linear organic Inorganic acid salts can be replaced by inorganic acid salts will. The amount of inorganic skeleton salts, e.g. Sodium phosphates, or liatrium carbonates, should be preferred Do not exceed 5% by weight.

Suitable further ingredients or additional components that are valued by the consumer are perfumes, dyes, fluorescent substances, tarnishing-inhibiting substances such as benzotriazole or ethylene thiourea, gloss improvers such as boric acid or boric acid salts in lengths of up to 3 wt 2-3rom-2-nitro-1,3-propanediol, substituted benziodolium compounds, diphenyl ethers substituted by chlorine, bromine and / or trifluoromethyl, such as, for example, 3,4-dichloro-4 ^f -trifluoromethyldiphenyl ether, and organic solvents in amounts up to 15 Gev /.-> i, which improve the pourability of the agent and increase the compatibility of the individual components. Suitable solvents are, for example, the '^? α Mono- and Malcohols, e.g. butanol, methyl-propanol- (1) and - (2), amylol or pentanol, butanediol as 1,2-, 1,3- and 1,4-butanediol, toluene, benzylcarbinol, ethylene glycol monobutyl ether, propylene glycol propyl ether and diethylene glycol dimethyl ether. The excellent cleaning effect and the improved drainage of the liquid cleaning agents according to the invention are demonstrated by the following tests:

Test A

4 rows A, B, G and D each with 5 rinsing fluids, which are referred to in more detail below, and 3 rows A ', B ¹ and C ¹ with 5 rinsing fluids each are produced. Each rinsing liquid contains a No o 2 wt ^c /> per liter of the detergent more fully described below. the

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Rinse fluids consist of pure tap water. The water used for rinsing and rinsing liquids has a hardness of around 3.4 idilliinol calcium carbonate per liter. Each rinse and final rinse contains about 1o 1 wetter, asehflüssigkeiten the i'emperatur all "or -bäder is at the beginning 52 ⁰ U and falls to the end at 42-35 ° C. The 'temperature of the rinsing baths fluctuates between 17 and 19.5 ⁰ G.

In each of the 5 rinsing liquids in the 4 test series io soiled glasses (from a cafeteria) soaked for 2 minutes, removed one after the other, rinsed one minute after the other with the rinsing liquid and removed from it for Drain and dry in the air (room temperature) about 23 ° U.

As soon as the glasses are dry, four experienced judges individually compare the appearance of the glasses, comparing the 1o glasses that were rinsed in the first "washing liquid of series A" and rinsed in the first rinsing liquid of series A "with the 1o glasses, which were rinsed in the first rinsing liquid of the series B 'and rinsed with the first rinsing liquid of the B', then compared to the 10 glasses that were rinsed with the first rinsing liquid of series 0 and rinsed with the first rinsing liquid of series C and so forth, have been and with the 1o glasses treated in the second washing and final washing of the series A and A ^1, rinsed 1o the glasses in the second washing and final washing of the series B or B ¹ and rinsed so Further. The 10 glasses that were rinsed in the 5 rinsing liquids of the Jerie D are not rinsed, but only dried in the air. x) The evaluation of the evaluators is expressed as follows: equal (0), worse (-),

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better (+), much better (++). The results are in Table I. summarized:

Table I.

Cf. 1. 5pül- / NachspU.lflü.saigk: eit 2. upül- / Haehspüli'lüssig] i: eit rows AB AG. AJ) AB AO AD ⁺

Evaluator
1 + n- O + + + + 2 + -ι l + - ++ 3 ++ η n- O ⁺ ++ O 4 + h + - lapül- 5. Rinsing / rinsing
liquid 3. Rinse / rinse
liquid 4. Rinse / Na et
liquid . AD ⁺ AB AG AD ⁺ AB AG AD AB AG

iy + ■ ++ o ++ ++ ο

oeihen without rinsing.

The liquid dishwashing detergents that were used in the series α to Ώ were composed as follows:

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i3 constituent series

A BGD

Paraff insulfonate anuaonium salt
(average molecular weight of the hydrocarbon radical = 196) 1o - 1o 1o

Coconut Alcohol Ethylene Oxide (3) -

sulfate-aminonium salt 1o - 1o 1o

Dimethyldodecylamine 444 4

Coconut Alcohol Ethylene Oxide (6) -

Condensate 7 2o 7 7

Coconut fatty acid diethanolamide - 2 - - -

Gelatine (average MoI-

Weight 25,000; isoelectric

Point approx. PH 8; Bloom-iPestig-

loo) - 1 1 1

Vvasser rest

pH of the washing liquid 7 7 7 7

The dishwashing detergent from series A is representative of an effective dishwashing detergent. It is noticeable that the glasses rinsed in the washing liquids of row D (same composition as the washing liquids of row A, but with 1 wt .- / j of gelatine) are not cleaner than those with the washing and rinsing liquids of rows A or A ¹ , although the glasses rinsed with the rinsing and rinsing liquids B and C or B 'and C ¹ are significantly better in overall appearance than the glasses treated with the rinsing and rinsing liquids A and A ^1.

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Test B

Ea 4 more borrow E, a \ G and H π it every 5 Geschirrspülflüsaigkeiten prepared, o, ⁱ 25 wt;! I included a Gesctiirrspülmittels. The liquids in series E contain the detergent from series A, the liquids from series ü ¹ contain detergent from series B, the detergent from series G contains detergent from series C and the detergent from series D contains detergent from series D In addition, three types of rinsing agents K ¹ , i · "and G ¹ are provided. The wet one used has the same hardness as in test A. Each rinsing and rinsing bath contains about 5 liters of water, there is 10 water in each bath cm high. Me temperature of the rinsing liquids is maintained at about 42 ⁰ C, the temperature of the Nachspülbäder between 3o and 35 ° C. groups of 4 polluted flat plates with a glazed surface (from a Cafeterria) are in each of the 5 äpülflüssigkeiten each Keihe ü, ü ¹ , G and H rinsed (a total of 80 plates), removed from the washing liquid and then rinsed in each row in the rinsing baths (5 times in succession in the bath egg submerged and removed from it) with the exception of the 5 groups of 4 plates each, which are rinsed in the 5 rinsing liquids of the LJerie H. The i'ellers are removed from the final rinsing bath, allowed to drain and air-dried.

The rinsing water drips off the dishes treated with the rinsing and rinsing liquids of no F and G or and G * within 60 seconds, while the water drips off the dishes with the rinsing and rinsing liquids E or E ¹ or H treated plates only slowly disappears through evaporation (10 to 12 minutes until dry

409812/1133

i'eller can be obtained).

'' you wash groups of 4 mischievous plates as described above, however, with subsequent rinsing under running tap water at approx. 16 C ansteile des Dipping in the washing up liquid, so observed aaa The same dripping phenomenon occurs with the rinsing liquids of the no F and G rinsed ropes, while those rinsed in the rinsing liquids of series E are dry after 10 to 12 minutes after rinsing under running tap water.

l'est G

iis are 3 -none out of 5 flushing liquids K, L and L produced, the o, 2 wt .- ^ - i · per liter of a detergent according to the following information contained, that for rinsing Ivjittel used and rinsing has the same hardness in most A, the 'temperature of all opaque liquids

is maintained at 47 ° C, the 'temperature of between Nachopülbäder J> o ^ and 36 ° ·· Each bath containing 5 1 of water, which is liasserhöhe Io cm.

In each of the 5 washing liquids of the series K, L and M, soiled dishes are washed as described in read B, taken from the rinsing liquid and then, as also described in test B, in the respective liach rinsing bath rinsed.

Heihe K's detergent is made up like that Detergent series A from test A, detergent series' L corresponds to detergent series ß from test A and that Dishwashing detergent, item 1.-: is identical to washing-up liquid of "Row B of" Test A, with the exception that 1 $ 5 gelatin

409812/1133

.24 _

having an average molecular weight of about 5,000 (Bloom-i'estigkeit ü) is used.

The rinsing water runs from dernF.it for the rinsing and after.

jgewasclieiie dishes * Rinsing liquids with no K or K 'and K and k' / not but disappears later, mainly through evaporation, during the with the detergent and rinse fluids the rows L or L 'treated plates, the water within 60 seconds after removal from the post-washing bath expires.

In the following examples, all percentages are based on weight.

409812/1133

2345115 I. II III IV V VI VII Examples (wt .- ^ ά) 8th 4th 2 4th 2 4th 3 Dimethyl-dodecyl-amine oxide 15th 7th 6th 7th 2 7th 6th Coconut Alcohol Ethylene
oxide (6) condensate 2 - * 3 2 _ 2 Diethanol-Cj2_-i6 fatty acid
amide ~ - 1o 9 .14 1 ο 12 14th Coconut Alcohol Ethylene
oxide (3) sulfate sodium salt 1o 9 9 1o 12th I! 13-18 paraffin sulfonate 12th mm. C _12-14 oil olefin sulfonate
Ammonium salt ■ - - - - 5 - '-triethanolamine ·' - - - - - 2 1.5 Boric acid 1 1 1 1 O , 75 1 1 gelatin Heat V / ater

Gelatine: liol.gew. 40,000; isoelectric point 3,4j Bloom- x ^ estigkeit about loo.

Example VIII

Dishwashing detergent is made by first mixing the surfactants in water then add the gelatin while stirring, using the following formulation:

C ₁₂ alkyl ethylene oxide (i2) sulfate K salt 18,65 b

Dodecyl sulfate K-SaIz #

Dodecyl dimethyl amine oxide

Gelatin (mol. Wt. About 60,000; isoelectric

Point approx. 4.6; Bloom -! Strength about 15o) 1.3 $ »

KaliuEi-toluenesulfonate Qfi

Water reads

409812/1133

this mixture is suitable when used in o, 2, iiger aqueous ^ -usurig 2un; ^ some of dishes and glass. Jei eggs using conveys he was in FINISH tt el the dishes and Ulcss by dec rinse with water shine and it reduces ^ ¹ ^ Ieck- and transformation. The agent has acceptable properties and skin tolerance.

A similar effect is achieved if the gelatine is used in the mixture of Example VIII by 1.2% by weight gelatin of molecular weight about 80,000, with an isoelectric Point of about 4 »3 and a bloom strength of 22o replaced.

Example IX

iCoko3nuü-Äth ^ lenoxid (6) -sulfat Ka-o Coconut alcohol sulfate ija-üalz 11 '; j

KokosnutJalkyl-dimethyl-aciinoxid 4 _t 5 "/ ·>

Gelatine (LoI.gev /. About 7o 000; iaoelektriacher

Point approx. 6; Bloom resistance about 2oo) 1> ί

Potassium toluenesulfonate 3> j

water and minor additives Heat

Such a mixture is physically stable and suitable to none of the porcelain and glazed ones contributed Use in o, 2 ^ jiger aqueous solution. The Littel gives the objects treated with it gloss and keeps film and leakage to a minimum. The ochaumkraft and the skin tolerance are acceptable for the ark.

In; substantially the same julling effect is achieved if one

409812/1133

the sodium coconut ethylene oxide (6) sulfate of genius of Example IX by an equivalent amount of potassium coconut ethylene oxide ( i2) -sulphate, ammonium-coconut-äthj-lenoxi (12) sulfate, ammonium coconut ether oxide (6) sulfate, x'riätha nolumin-coconut-ethylene oxide (6) -sulphate or i'riethanolaminicokosnuJi-ethylene oxide ( 12) sulfate replaced.

becomes essentially the same. Effect is achieved when using the coconut alcohol sulfate sodium salt of Example Ia by an equivalent iienge coconut alcohol-potassium or. aiunonium salt replaced.

A substantially similar cleaning effect is achieved if the coconut alkyl dinethyl amine oxide in the example of Example IX is replaced by an equivalent amount of dimethyl dodecyl amine oxide, dimethyl tetradecyl amine oxide or ethyl diciethyl arcine oxide

t.

In addition, essentially the same cleaning effect is obtained, v.enn the gel-elatine in the mixture of Example IX 1.8% by weight of a gelatin with a molecular weight of about 45,000, with an isoelectric point of 4 »6 and an ΒΪοοικ-i'estigkeit of about 12o, or 0.8% by weight of a gelatin of molecular weight about 60,000 with an isoelectric i'punkt of about 8.2 and a .Bloon; -. strength of about 1So replaced.

409812/1133

Example X

Dimethyl-dodecyl-arriine oxide
Coconut alcohol-ethylene oxide 6) condensate
Coconut alcohol £ 'üh, ylene oxide (3) sulfate, K-SaIz 1ο) ί

ϋ -, - ζ -, ο Paraff insulfonat Na-3alz ßft

ι j— ίο

. Coconut alcohol sulfate K-oalz 4 ^

uric acid 1 »5 '; j

Ethanol

gelatine (LoI. weight. 4o ooo - isoelectric
Point 3,4; -uloom-resistance approx. 100)

water hest

Example XI

iiimethyl-dodecyl-aciine oxide 4 / »

Coconut alcohol iith / lenoxide (6) condensate 5/3

i: oko3nubalkohol-Ethylenoxid (3) -sulfat, K-üalz 1o; 3

^ i 3-1 β -Pa raff insulphonate [ia-ualz BS ^

Kokosnutfa lko hol sulfate E-3aliz 4 ^ 0

Sodium citrate 1 ^

13oric acid 1, 5>

■ jjriethanolamine 5 ^

Ethanol 5> j

ü-elatine (LoI.gew. - _r o ooo - isoelectric point

3.4; j31oorr.-i ^'l estigkeit about 1oo) 1.4

./asser

A09812 / 1133

Example XII

Dimethyl-dodecyl-amine oxide 45 °

Polyethylene Glycol, Mol.wt. 400
Coconut Alcohol Ethylene Oxide (3) Sulphate NH Salt

_{i214 4}

Sodium acetate o, 5? J

Gelatin (KoI.gew. 40,000 -isolelectric point
8.4; Bloom strength approx. Loo) 1 $ S

Water heat

Example XIII

Dimethyl dodecyl amine oxide
Coconut alcohol-ethylene oxide (6) condensate
i'algalkohol-ÄthylenoxidC 11) -Condensate ξφ

Diethanoi ^ ₁ O-Ig i'atty acid amide 2 / j

Polyethylene glycol condensate, Biol.gew. 400 4 />

Gelatin (molar weight 25,000 isoelectric point

8th; Blooni j? Est about 60) £ 1

• Yasser Hest

Example XIY

Dimethyl-dodecyl-amine oxide 2rf>

Diethanoi C. _o "^ -Jiettsäureamid 2%

Coconut Alcohol Ethylene Oxide (6) Condensate 2fj

Polyethylene glycol condensate, KoI.gew. 400 2 ^c />

Coconut alcohol-ethylene oxide (6) sulfate, calcium salt 7

C ₁₂ alkyl sulfate, sodium salt 2.5 $

^C 11-18 ^{Para ± f} insulfonat, ITa-öalz 1o ^

Gelatin (oil weight 60,000 - isoelectric point

7; BlooB-Pestigkeit approx. 2oo) o, 75

409812/1133

Claims (1)

Patent claims 1. Containing liquid clear aqueous detergent a surfactant detergent and conventional additives, characterized in that it, based on the total weight of the means, (A) about 2 to about 4o wt .- ^ 'ό of a water-soluble organic non-ionic surfactant in ίΌπη of (1) tertiary oxides of the general formula H ₁ H ₂ R ₃ Y— > 0 (I) wherein R _{1 is} a straight-chain "or branched, saturated or unsaturated aliphatic hydrocarbon, hydroxy-hydrocarbon or alkyloxy-hydrocarbon radical having 8 to 24 carbon atoms, Kp and H are each a methyl, ethyl, hydroxymethyl or kydroxyethyl radical and Y is a nitrogen or phosphorus atom , (2) Amides of the general i'Onr.el R ₄ -OO-N (H) _1n-1 (R ₅ OH) ₃ _ _m (II) where R. is a saturated or unsaturated aliphatic hydrocarbon _{radical with 7 to 21 carbon atoms, R 1} - a methylene or ethylene group and π represents the number 1, 2 or, (3) Condensation products made from about 3 to about 25 ftoles of ethylene oxide and 1 liol of an organic hydrophobic compound ali- phatic or alkyl aromatic nature with about 3 to about 24 carbon atoms, or 409812/1133 of a Geiriseh, (B) from about o, 1 to etv "a 5 wt .- ^ o a water-soluble gelatin having an L olekulargewicht of at least 12 5o.o, an isoelectric point between pH 4.5 and about 9» 2 and a GeIfestigkeijs between 25 and 300 blooni grams and as xiest contains water. 2. iieinigungsffiittel according to claim 1, characterized in that there is about 0.2 to about 2 wt .- ^ of a water-soluble gelatin with a molecular weight of more than 15,000 and preferably between 25,000 and Bo, in particular about 35,000 and 50,000. 3. I-.eini ^ mittel according to claim 1 or 2, characterized in that ciaii it a water-soluble gelatin with a; isoelectrical Point above 6, preferably between pii 7 and y, and a gel strength above 5o, preferably vf'eiae between Bo and 200-ßloom-Grarjn. 4 «cleaning agent according to claim 1 to 3» characterized in that it contains a 5: 1 to 1: 2 mixture of tertiary amine oxides and O ₁ I ₁₇ alkylene copper diethanol amides as the water-soluble organic non-ionic surface-active agent. A09812 / 1 133 5. Cleaning agent according to claims 1 to 1, characterized in that it up to 4o ü-ew.-v> of a water-soluble hydrocarbon sulfate acid of the general formula U ₆ O (C ₂ H ₄ U) _n Su ₃ UL (III) " contains, in which Hg is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical with 3 to 22 and preferably 12 to 16 carbon atoms, η is a number from Ü to about 15 and M is a cation, preferably a sodium or potassium ion. 3tellen, wherein the total amount of nonionic surfactant detergent and hydrocarbon sulfate salt is at most 43 wt .- ^, based on the total weight of the iiittele. 6. No cleaning agent according to claim 5, characterized in that it contains 2 to 30% by weight of a water-soluble hydrocarbon salt of the general formula H ₆ O (C ₂ H ₄ O) _n SO ₃ Iu (III) contains, where H ₅ and K have the above meaning and η is a number between. 1.5 and about 15, and preferably between 3 and 12. 7. it cleaning agent according to claim 5, characterized in that it contains 2 big 15 wt .-> j of a water-soluble hydrocarbon sulfate salt of _{the general formula U 6 U (CpH 4} O) iJü, k (III), where R ^ and L have the above meaning and η represents the number υ. 409812/1133 _ 33 _ . iieinigungsniittel according to claim 1 bivS **, characterized in that da ^ it up to 3o wt .- ;. i of a water-soluble organic rich sulfuric acid reaction product of the general U ₇ SO ₃ BL (IV) contains, wherein R _{7 is} a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical with 3 to 24 and preferably 12 to 18 carbon atoms, or an alkylbenzene radical with 3 to 13 and preferably 12 to 16 carbon atoms in the alkyl portion and L. a cation, preferably the ^ represent atriuij- or potassium ion, the total amount of non-ionic surfactant detergent and organic sulfuric acid reaction product at most 43 wt .- ^, based on the total amount by weight of the cement. 9. iieinigungsmittei according napruch ^ 8, characterized in that there ii up to 2o and preferably 3 bi3 15 parts by weight of an organic Ji uchwefelsäurereaktionsprodukts the general i ^'l o rniel contains, in which H ₇ and M have the above meaning, the weight ratio of organic iichvef els acid reaction product (IV) to nonionic surfactant detergent being less than 5: 1 and preferably less than 3: 1. 10. cleaning agent according to claim 8 and 9, characterized in that it _{contains a G 2} _ _ig n-paraffin sulfonate as the organic sulfuric acid reaction product IV. 409812/1133 ¹ ^. iteinigungsir.it t el according to claims 1 to 10, characterized in that>;> s up to 40 wt. - >> of an excess of a water-soluble hydrocarbon sulfate salt of the general formula II / -U (C, _% H.. u) Ju -.l. (III) and a water-soluble organic sulfuric acid reaction product of the general -u'orniel R "üü ^ L (IV), where Rg, K ₇ , L. and η have the above meaning, the Ge3ac: t amount of non-ionic K. surfactant detergent, hydrocarbon sulfate salt and organic öchwefelsäurereai. tion3 product than 48 wt - / ■> and wherein daa Gewichtsverhältnia organic ochv / efeisäurereaktionaprodukt to ijumine of nonionic surfactant Detergena and hydrocarbon sulfate salt at most 3: 1. 12. Cleaning agent according to claim 11, characterized in that that the weight ratio of organic sulfuric acid reaction product to the human being made from non-ionic surface-active substances Detergent and hydrocarbon sulfate salt less than 1.5: 1. 13th Cleaning agent according to claims 1 to 12, characterized in that it contains 0.5 to 2 degrees of gelatin with an isoelectric point between pH 7 and 3.5, an average molecular weight between 35,000 and 5o,000 and a gel strength of 3o to 2oo Bloom-Gramci, 4 to 16 '/) of a water-soluble non-ionic surfactant detergent, 2 to 3o ^ of a water-soluble hydrocarbon sulfate salt of the general formula R ^ O (O ₂ Pi-O) ίΐΟ, Μ, wherein iw- and ii the above Have meaning and η represents a number from 6 to 12, and 3 to 15 wt .-; of an organic sulfuric acid reaction product of the general formula π ^ ΜΛ. (i · /), in which U ₇ and k have the same meaning as above, contains v. where the weight ratio of sulfuric acid reaction product to non-ionic ^409812/1133 BADQR ₁ G ₁ NAL surface-active detergent is below 2.5: 1, • ..during the weight ratio of sulfuric acid reaction product to ourime from non-ionic, surface-active x / detergent and hydrocarbon sulfate is less than 1: 1. 14th .Cleaning agent according to claim 1 to 13, characterized in that that it is up to 15% by weight, based on that Total weight of the putty, a water-soluble low molecular weight organic acid or a water-soluble alkali metal, ammonium or substituted amnoniucealz contains a low molecular weight organic acid. 15th Cleaning agent according to claim 14>, characterized by Daourch, that it is about 2 to about 1o and preferably 2 to 4 yo by weight of an alkali metal salt of citric acid, «one acid, Succinic acid, uenzene hexacarboxylic acid or ethylenediaminetetraacetic acid contains. ± 6 · iteinigungsmittel according to claim 1 to 15, characterized in that it äaü 2 to about 1o wt .- ί a iicrulgiermittels in ü ^l onr. of triethanolamine or a polyethylene oxide condenation product with a molecular weight of between about 16o and about 12o. Procter & Gamble european technical center Jt roinbeek-Uever / Belgium Br.H.J.WoUi lawyer ^ s 409812/1133 "