DE2345115B2 - LIQUID DETERGENT - Google Patents

Description

The invention relates to a liquid, clear, aqueous cleaning agent, in particular for dishes containing a surfactant detergent, a protein derivative and conventional additives characterized by is that, based on the total weight of the agent,

(A) about 2 to about 40 weight percent of a water soluble organic nonionic surfactant Means in the form of

(1) tertiary oxides of the general formula

R ₁ R ₂₁ R ₃ Y ^ O (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, R _s and R ₃ each represent a methyl, ethyl, hydroxymethyl or hydroxyethyl radical and Y a nitrogen or phosphorus atom ,

(2) Amides of the general formula

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

where R _{4 is} a saturated or unsaturated aliphatic hydrocarbon radical with 7 to 21 carbon atoms, R _{5 is} a methylene or ethylene group and m is the number 1, 2 or 3,

(3) Condensation products of from about 3 to about 25 moles of ethylene oxide and 1 mole of an organic hydrophobic compound of aliphatic or alkyl aromatic nature with about 8 to about 24 carbon atoms, or a mixture thereof,

(B) about 0.1 to about 5% by weight of a water soluble Gelatin with a molecular weight of at least 12,500, an isoelectric Point between pH 4.5 and about 9.2 and a gel strength between 25 and 300 bloom grams and the remainder contains water.

The liquid, clear aqueous cleaning agent according to the invention is used in particular for cleaning glass, porcelain and glazed or enameled objects and is characterized by a particularly good drainage behavior, so that you do not have to dry off with a cloth; the formation of films, streaks, or stains on washed, rinsed, and air-dried items is minimized. The detergent contains a nonionic detergent surfactant and a water soluble gelatin having a molecular weight between 12,500 and,000 and preferably between about 25,000 and 80,000, a gel strength of 25 to 300 and preferably 8Π to 200 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 objects with a glazed surface is usually rated by the consumer in terms of gloss, lack of film formation, lack of spots and streaks. The liquid dishwashing detergents on the market today are primarily formulated to remove dirt from glass, dishes and windows, but whereupon residues of the detergent solution and redeposited dirt are removed by rinsing and / or rubbing the wet items with the towel have to. If you do not rinse immediately or rub off with a towel, these residues dry on the surface of the washed items and leave stains, films or streaks that are difficult to remove

ao back.

If the items are washed and / or rinsed with clean water and not immediately with the After the water has evaporated, stains and streaks remain on the towel after drying the water hardness decrease, visible on the surface.

That dries! the washed items such as glasses and dishes immediately after removal the rinsing and rinsing bath with the towel is uneconomical (you need a lot of towels) and not always possible (too frequent interruption of the flushing process). Hence, many housewives make the washed and rinsed dishes for draining and drying in the air only to the side. the Cleaning effect of the product used «which is visually satisfactory after rinsing and rinsing can then be lost due to being difficult to remove, unsightly, clinging or renewed Deposited detergent residues, dirt and / or water hardness from the rinsing or rinsing water.

Even when cleaning larger glazed surfaces such as tiled walls, e.g. B. in shower stalls, or Ceramic bathtubs, sinks or the like with a glass-like surface must be cleaned after cleaning surfaces that are still damp must be rubbed down to avoid the formation of stains, films and streaks. Rubbed dry immediately after cleaning is not always possible and requires frequent Interruption of cleaning work. It may therefore appear that the detergents are not work well, although the dirt is removed first, as streaks, films and stains will later appear on the treated areas remain.

Numerous attempts have been made to prevent redeposition of detergent, To minimize dirt and / or water hardness residues when drying in the air, in order to although by means of various additives for the rinsing or rinsing process, through complex formation of the Water hardness salts, the addition of improved dirt-suspending agents or by formulating special ones Rinse aid. The incorporation of complexing and / or dirt-suspending agents in liquid detergents creates difficulties in the formulation, while special rinsing agents must be packed separately and used separately.

5 6

Surprisingly, it has now been found that the combination (A) about 2 to about 40 wt .-% of a water-soluble

nation from a small amount of a gelatin with borrowed, organic, nonionic surfactants

a gel strength of at least 25 bloom grams, detergent in the form of

a molecular weight of at least 12,500 and (1) tertiary oxides of the general formula
an isoelectric point between pH 4.5 and 5 ^ r R ₃ Y- ^ O (])
9.2 and one of the specified light-ionic surface-active detergents, where where R _{1 is} a straight-chain or branched, as well as other specific surface-active agents, saturated or unsaturated, aliphatic carbon and / or skeletal salts in precisely defined amounts of hydrogen, hydroxy hydrocarbon or alkyl can be, leads to excellent washing jo oxykohlenwasserstoffrest mii 8 to 24 carbon and cleaning agents, which are in particular atoms, R, and R ₃ each a methyl, ethyl, for cleaning glass, porcelain, glazed or hydruxymethyl or hydroxyethyl radical and Y are glass-like objects and represent a marked nitrogen or phosphorus atom,
Show run-off behavior, so that drying with the (2) amides of the general formula

Towel avoided and the formation of films, 15 ^ qq N (H) mi (R ₅ OH) ₃ _ _m (II)

Streaks or stains on the washed, ⁴

rinsed and air-dried glass, porcelain wherein R _{4 is} a saturated or unsaturated aliod. Like. Is kept minimal. Phatic hydrocarbon residue with 7 to 21 carbon detergents, soft gelatine or hydrolyzate atoms, R ₅ contain a methylene or ethylene group-based proteins and surface-active agents, 30 and m represent the number 1, 2 or 3,
are for example from GB-PS 1160 485 or (3) condensation products from about 3 to about DT-OS 16 17 062 and from IT-PS 8 62 247 25 mol of ethylene oxide and 1 mol of an organic one or from DT-AS 19 29040 known. DT-OS1617 062 hydrophobic compound of aliphatic or alkyl describes lotions or detergent mixtures, aromatic type with about 8 to about 24 carbon atoms, in addition to a surface-active detergent, or a mixture thereof,
partially degraded protein with a gel strength .'B) contain about 0.1 to about 5% by weight of a water solution of 0 bloom grams. A gelatin with borrowed gelatin with a molecular weight of a gel strength of 0 bloom grams is completely unsuitable for the at least 12,500, a gel strength between 25 purposes of the present invention, since and 300 bloom grams and an isoelectric them - as shown in Test C below - 30 point between pH 4.5 and about 9.2 and the remainder does not cause the desired drainage effect. The ones in water.

The cleaning agents according to the above Italian The non-ionic surface-active gelatins mentioned to be used in the cleaning agents according to the invention or the German patent application cannot be incorporated into the detergents of the invention, the gelatin and the other liquid cleaning agents according to the invention are described in more detail below. While the detergent surfactant is being used in describing additional surfactant systems and other mandatory components, the detergents and other ingredients will prevent the detergents and other ingredients from dripping off on a salt. Reference is made, so it is either in addition to a constant need for detergents and cleaning agents, a sodium, potassium, ammonium, trimethyl, gungsmittel, especially dishwashing detergents, the 40 triethyl, dimethyl, diethyl, trimethanol , Remove tri-dirt residues and improve the appearance of the dry ethanol, dimethanol or diethanol ammonium objects, there is also steady salt, unless otherwise stated.
Need for an acceptable combination of Since gelatin is a typical protein (obtained from materials that simultaneously cleanse, improve the appearance of collagen by boiling the skin, tendons, bones of the cleaned objects in the end 45 and the like with water) are The gelatin and towel towel drying or rubbing molecules like the molecules of other proteins largely make superfluous. The aim of the present invention, and therefore complex with average molecular, is to provide a liquid, clear, weighted between about 5000 and up to 200,000 and permanent, aqueous cleaning agent for glazed more. The gelatin molecules, which are charged in alkaline or glass-like objects with excellent 5 ° acidic solution and are thus amphoteric cleaning properties and improved drainage, have a specific isoelectric point, properties after rinsing, which stains mainly from the process conditions the washed and rinsed depends on the manufacturing process. Air-dried surfaces are prevented by acid treatment and gelatin obtained has an isoelectric point. Drying with a towel or rubbing over- 55 generally between pH 7 and 9, while making it liquid. After alkali treatment, gelatine obtained an isoelectronic The comfort, effectiveness and economic point of usually pH 4.6 to 5 of the agents according to the invention can still be referred to. Gelatins can be improved by special treatments, adapted to specific requirements and tailored to with isoelectric points from only pH 4.5 and up to certain conditions, in 60 to pH 9.2, and by mixing additional, water-soluble organic anions Gelatins with various isoelectric niche surface-active detergents, water-soluble points, any gelatin mixtures with borrowed organic acids or their salts, emul-isoelectric points between pH 4.5 and 9.2 gators, bactericides, dyes, perfumes, corrosion agents can be put together.

inhibitors and / or soil suspending agents 65 The amount of water-soluble gelatin in the

of the kind explained later. inventive liquid cleaning agent can

The cleaning agent according to the invention contains between 0.1 and about 5% by weight and preferably

calculated on the total weight of the agent between 0.2 and about 2 wt .-%, calculated

7 8

on the total weight of the agent. The very low methyl-dodecyl-amine oxide, diethyl-tetradecyl-amine lower Limit of 0.1 wt .-% is required to oxidize, bis (2-hydroxyethyl) dodecyl amine oxide, biseinen still noticeable drainage effect to be achieved, while ^ -hydroxyäthyO-S-dodecoxy-l-hydroxypropyl-amine-

rend the limitation to a maximum value of about oxide, dimethyl-2-hydroxydodecylamine oxide and di-

5 wt .-% on requirements of the formulation to 5 ethyl-eicosyl-amine oxide;

declines, d. H. the requirement for a pourable (2) water-soluble, nonionic tertiary phosphine

liquid mixture that is easy to handle, dissolve oxides of the general formula

and is to be applied. R R R -> O CII

To achieve the desired cleaning effect, ι * 3 ()
ie the removal of dirt by simply io where Y represents a phosphorus atom and R “R ₈ and rinsing and the removal of dirt, detergent R _{3 have} the above meanings. These compounds and water hardness residues from the runoff are obtained by alkylating an alkylphosphine after additional rinsing, but without removing waste and oxidation of the reaction product or drying with a towel, as is the case, for example, in FR-PS 13 17 586, the molecular weight must have an effect der wasserlös- 15 described. Specific examples of tertiary phosphinous gelatine more than 12,500 and preferably oxides are: dimethyl-dodecyl-phosphine oxide, diethyl more than 15,000, particularly preferably 25,000 to tetradecylphosphine oxide, bis- (2-hydroxyethyl) -dode-80,000 and in particular 35,000 to 50 000, cyl-phosphine oxide, tetradecyl-methyl-2-hydroxyethyl, while the isoelectric point of gelatin is between phosphine oxide, oleyl-dimethylphosphine oxide and pH 4.5 and 9.2, preferably above 6 and 20, 2-hydroxydodecyl-dimethyl-phosphine oxide;
particularly preferably between pH 7 and 9 (3) water-soluble amides of the general formula and the gel strength of the gelatin must be more than _R ^ r \ wmi ro nm m \
25 bloom grams, preferably more than 50 and R ₄ -CO-N (IV ₁ (R ₅ OHU (II)
particularly preferably between 80 and 200 blooms, in which R _{4 has to be} a saturated or unsaturated ali-grain. The gel strength in Bloom-25 phatic hydrocarbon radicals with 7 to 21 and grams or the Bloom strength is the required - preferably 11 to 17 carbon atoms, R ₅ a liehe force (in grams), which one on a cylinder methylene or ethylene group and m must use the number 1, 12.7 mm in diameter, so that 2 or 3, preferably 1, represent. Special beers in the surface of a gel made of 6.67 % gelatin such amides are the monoethanol coconut with 15% moisture penetrates 4 mm (compare 30 nut fatty acid amide, diethanol dodecyl fatty acid amide British Standard Method for Sampling and Testing and dimethanol oleylamide;
Gelatins). (4) water-soluble condensation products that

By adding some synthetic anionic holdings, condensation is known per se surface-active detergents in certain Men- from 3 to about 25 moles of ethylene oxide with 1 mole of one gen is the rinsing time required to achieve an organic hydrophobic compound aliphatic good drainage is required. These or alkylaromatic in nature with 8 to 24 carbons detection allows the formulation of liquid pure substance atoms and at least one reactive watering agent, the additional anionic surface material atom, preferably a reactive hyactive Detergents (in amounts up to 40% by weight) hydroxyl, amino, amido or carboxyl group. All included, Common examples specifically for use in water 40 are:

medium to high ionic strength are suitable (ion- (a) the condensates of ethylene oxide and aliphatic

strength = concentration of the washing liquid in metallic alcohols with more than 8 carbon atoms,

Metal cations such as Ca ⁺ +, Mg ⁺ +, mainly due to the The alcohols can be made from naturally occurring

Decreasing water hardness, Na ⁺ , K ⁺ and the like. Originate from fatty acids, but also from different ones

Builders). 45 branched chain higher alcohols. To the

For use in the preferred liquid alcohol-ethylene oxide condensation products according to the invention Water-soluble non-products suitable for cleaning agents include those made from alcohols made from sebum and sebum Ionic surfactant detergents are products made from coconut fatty acids. Special

(1) water-soluble, nonionic tertiary amine oxides are DERS preferably atoms condensation products of the general formula 5 ° about 4 to about 12 moles of ethylene oxide per mole of ali-RRR Y- "· O (B phatic alcohol having 10 to about 18 carbon ^113, especially from a coconut fatty alcohol where Y is a nitrogen atom, R _{1 is} a high molecular weight, medium fraction and 6 mols of ethylene oxide;
Straight-chain or branched, saturated or mn- (b) condensates of ethylene oxide and alkylphenolsaturated aliphatic hydrocarbons, hydroxy- 55 nols, where the phenols can be mono- or polyalkylated hydrocarbons or alkyloxy hydrocarbons and the total number of carbon radicals, preferably an alkyl radical, with 8 to 24 and atoms in the side chains is 5 to 18 The aromatic 12 carbon atoms carrying preferably 12 to 18 and particularly preferably phenolic hydroxyl groups, or a mixture of Dode ring can be a benzene, naphthalene or diphenyl, decyl and tetradecyir residues, in a soft nanometer residue and preferably a benzene residue. Special at least 50% of the radicals consist of dodecyl radicals, examples are the condensation products of 1 mol and R ₄ and R ₃ , be the same or different nonylphenol and 9 to 15 mol of ethylene oxide; can each represent a methyl, ethyl, hydroxy (c) condensate of ethylene oxide and fatty methyl or hydroxyethyl radical. esters, preferably monofatty acid esters of the gambler

The above amine oxides are generally alcohols sorbitol and mannitol and, although less because of direct oxidation of the corresponding tertiary preference, the di- and polysaccharides. Special binary amines, prepared in a manner known per se, are the polyoxyethylene sorbitol monolaunn specs. Examples of tertiary amine oxides are: diacid esters with 20 or more ethylene oxide units

and the polyoxyethylene derivatives of fatty acid partial esters of hexitol anhydrides, generally under the Trade name "TWEENS" are known;

(d) esters obtainable by reacting ethylene oxide with carboxylic acids. The acids can come from natural fatty acids or from fatty acids from oxidized paraffin wax, mono- or polyalkylated Benzoic or naphthenic acids be produced. Preference is given to aliphatic fatty acids with 10 to 20 carbon atoms and benzoic acids with 5 to 18 carbon atoms in the alkyl radical. Specific examples and preferred condensation products are the tall oil / ethylene oxide condensation products and oleic acid / ethylene oxide having 9 to 15 ethylene oxide units;

(e) Condensation products from fatty acid alkanolamides of the type

C ₇ _ ₁₇ alkyl - CO - NHC ₂ H ₄ OH,
C ₇ _ ₁₇ alkyl - CO - N - (C ₂ H ₄ OH) ₂

and ethylene oxide. Condensation products of 1 mol of coconut-CO-NH-C ₂ H ₄ OH and 5 to 20 mol of ethylene oxide are preferred. Specific examples of such polyethyleneoxyalkanolamides of fatty acids are the products known under the trade name "ETHOMID";

(f) condensation products of C ₈ _i ₈ alkyl, C ₈ _ ₁₈ alkenyl and C ₅ -, ₈ alkylaryl amines and ethylene oxide. A specific and preferred example is the condensation product of 1 mole of a dodecyiamine and 9 to 12 moles of ethylene oxide. Another specific example corresponds to the formula

C "_ ₁₃ alkyl - CO - NH - C ₆ II ₄ -

per mole of fatty alcohol are implemented. Specific examples are the connections:

C ₁₂ _ ₁₄ alkyl - O - (C ₂ H ₄ O) ₃ - SO ₃ N (C ₂ H ₄ OH) _3;
Coconut - O - (C ₂ H ₄ ) - SO ₃ Na;
C ₁₄ alkyl - O - (C ₂ H ₄ O) ₃ SO ₃ NH ₄ ;
C ₁₂ _ ₁₆ alkyl - O - (C ₂ H ₄ O) ₆ - SO ₂ K;
and tallow - O - (C ₂ H ₄ O) ₉ - SO ₃ N (H) (C ₂ H ₄ OH) ₂ .

Important examples of hydrocarbon sulfates of the general formula III, in which η denotes the 2 [ahl O, are compounds which, by sulfating hydrocarbons containing hydroxyl groups, preferably fatty alcohols having 8 to 18 and particularly preferably 12 to 16 carbon atoms, with sulfur trioxide, sulfuric acid or the like. subsequent hydrolysis and / or bleaching are obtained;
(6) water-soluble salts of organic sulfuric acid reaction products represented by the general formula

R ₇ - SO ₃ M

(IV)

The amount of nonionic detergent surfactant in the liquid detergent compositions of the invention should preferably be no more than 40% by weight.

As already mentioned, the convenience, effectiveness and economy of the invention Cleaning agents can be improved and adapted to special needs by adding water-soluble organic anionic surface-active detergents, water-soluble organic acids or salts and the like are admixed. As already described, there is a special advantage of adding one anionic surface-active detergent in the reduction of the post-rinse time, which is optimal for achieving Expiration is required.

Organic synthetic suitable as additive to the liquid cleaning agents according to the invention are anionic detergent surfactants

(S) water-soluble hydrocarbon sulfates of the general formula

R ₄ O (C ₈ H ₄ O ^ SO ₄ M

(HD

wherein Rß is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 22 carbon atoms, η is a number tob O to about IS and M is a cation, preferably the sodium or potassium ion. Important examples of such additives are the salts of an organic reaction product from Schwefelräüre and a saturated or unsaturated Fettdköhol with S to 18 carbon atoms, preferably tallow or KokosnnBalkobol, with 1.5 to iS and preferably 3 to 12 mol of ethylene oxide wherein R ₇ is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical with 8 to 24 and preferably 12 to 18 carbon atoms or an alkylbenzene radical with 8 to 18 and preferably 12 to 16 carbon atoms in the alkyl radical and M represents a cation. Important examples of synthetic detergents that

Suitable components of cleaning agents according to the invention are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series including the iso-, neo-, meso- and η-paraffins with 8 to 24 and preferably 12 to 18 carbon atoms or of a hydrocarbon of the ethylene series with 8 to 20 and preferably 12 to 18 carbon atoms and 1 to 4 double bonds and a sulfonating agent such as SO ₃ , H ₂ SO ₄ , oleum or the like

Sulphonation can be obtained in a manner known per se, including bleaching and hydrolysis. The sulfonated C _I2 _ ₁₈ n-paraffins, individually or in a mixture with sulfonated a-OIefinen with an average of 14 carbon atoms are preferred. Important

Examples of alkylbenzenesulfonates with alkyl radicals with about 9 to 18 carbon atoms are the dodecyl, Tetradecyl and hexadecyl benzene sulfonates and the products described in U.S. Patents 2,220,099 and 2,477,383.

The maximum amount of the water-soluble anionic surface-active detergent in the liquid cleaning agents according to the invention results from the amount of nonionic surface-active detergent and also the gel present

amount of tin. The maximum total amount of nonionic and anionic surfactant detergents is about 48% by weight, based on the Total weight of the agent. Preferred amonic surface-active detef Gentien are water-soluble hydrocarbon sulfates the general formula

R ₆ O (C ₁ H ₄ O) ^ SO ₈ M <P§

wherein R, preferably a straight-chain, saturated aliphatic hydrocarbon radical with 8 to 20, preferably 12 to 16 carbon atoms, η rtiaa ^ ß as a number from 1.5 to 12 and particularly preferably from 3 to 9 and M preferably sodium or KaEtm

3

23 4b 1 lö ι

11 12

is. These preferred ethoxylated hydrochloric acid - maleic acid, lactic acid, tartaric acid, propionic acid,

Substance sulfates can be used in amounts up to 40% and preferred butyric acid, malonic acid, polymaleic acid, polyita-wise between 5 and 20% by weight, based on the consic acid, glutaric acid, citraconic acid, benzene penta-

Total weight of the agent. carboxylic acid and hexacarboxylic acid, succinic acid,

Are in the inventive liquid purifying 5 ethylenediamine-tetraacetic acid, nitrilotriacetic acid, agents water-soluble salts of organic sulfur- These organic acids and / or their salts are acid reaction products of the general formula added to improve the cleaning R, SO ₃ M (IV), in which R ₇ a straight-chain or action of the liquid cleaning agent, also branched, saturated or unsaturated aliphatic - they can serve as an ion source that keeps the pH value of the hydrocarbon residue at 8 to 24 and the preferred io of the agent at a predetermined level,
wise 12 to 18 carbon atoms or an alkyl The maximum amount of citrate, monopotassium tartrate, disodium succinate, tetra should be less than 30% by weight, based on the total sodium mellitate C ₆ (COONa) ₄ - (COOH) ₂ .
weight of the agent, and preferably 20 Do not exceed the maximum amount of water-soluble, organic% by weight. Preferred additives are acid and / or salts thereof _lt not only by the sulfonated C .. ₁₈ n-paraffins, either individually or in the amount of surface-active detergents premixed with sulfonated Cjj_ ₁₈ "-01efinen. given, but mainly through the presence

When using combinations of water resistance of the gelatine. She should. 15% by weight, based on

soluble, ethoxylated hydrocarbon sulfates which do not exceed the total weight of the mixture

Formula R ₆ O (CjH ₄ O) _n SO ₃ M (III) and water-soluble and preferably below 5% by weight. Some

Salts of organic sulfuric acid reaction products Organic acid salts can be replaced by inorganic

of the formula R ₇ SO ₃ M (IV), in which R ₆ , R ₇ , M and η framework salts are replaced. The amount of inorganic

Have the above meaning, the weight should 25 niche framework salts, z. B. sodium phosphates or

ratio between the water-soluble salt of the organic sodium carbonate, should preferably be 5% by weight

niche sulfuric acid reaction product and not to exceed.

Sum of non-ionic surface-active detergent Suitable further components or additional

gens and ethoxylated hydrocarbon sulfate pre-components that are appreciated by the consumer,

preferably, depending on the concentration and 30 are perfumes, dyes, fluorescent substances, that

Type of metal tarnish-inhibiting substances such as benzotriazole or

Cations (i.e. the ionic strength) at most 3: 1 and ethylene thiourea, gloss improvers such as boric acid

preferably less than 1.5: 1. Particularly or boric acid salts in amounts up to 3% by weight,

agents that are used as water-soluble bactericides such as 2-bromo-2-nitro-l, 3-propanediol, sub-

ethoxylated hydrocarbon sulfates compounds 35 substituted benziodolium compounds, by chlorine,

of the formula C _u _ _ie alkyl - O - (C ₂ H ₄ O) ₃ _ "SO ₃ M, diphenyl substituted as bromine and / or trifluoromethyl

water-soluble salts of organic sulfur reaction ethers such as B. S. ^ dichloro - ^ '- trifluoromethyldiphenyl-

products C ₁ j_ ₁₈ -paraffin sulfonates and as non-ioether, and organic solvents in amounts up to

Niche surfactant detergent a mixture of 15 wt .-%, which the pourability of the agent

from C _li _i ₄ alkyl dimethylamine oxide and coconut 4 ° and improve the compatibility of the individual

contain fatty acid diethanolamide, increasing the Ge components. Suitable solvents are

weight ratio of paraffin sulfonates to the sum z. B. the C._ ₈ mono and dialcohols, e.g. B. butanol,

from C ₁₂ _ ₁₆ -alkyl - O - (C, H ₄ O) ₃ _ ₆ SO ₃ M plus amine- methyl-propanol- (1) and - (2), amylol or pentanol,

oxide and fatty acid diethanolamide at most 2: 1 and butanediol as 1,2-, 1,3- and 1,4-butanediol, toluene,

is preferably 1: 1. 45 Benzylcarbinol, ethylene glycol monobutyl ether, pro

To improve the emulsification of fatty pylene glycol propyl ether and diethylene glycol dimethyl

Dirt can other non-ionic surface ethers. The excellent cleaning effect and

active means such as B. polyethylene glycol condensate the improved drainage of the invention

Sation products with a molecular weight of liquid detergents are made by the following

about 160 to about 1200 and / or fatty acid esters, previously demonstrated by tests:

preferably fatty acid monoesters of sugar alcohols, test A
Sorbitol and mannitol, the agents according to the invention

be added. The amount of polyethylene glycol- 4 rows A, B, C and D with 5 rinsing liquids each

Condensation products can contain up to 15% by weight, which are described in more detail below,

, preferred amounts are 2 to 8 55 and 3 rows A ', B' and C each with 5 rinsing

Wt%. The maximum amount of fatty acid esters of liquids are made. Any rinsing liquid Sugar alcohols are because of their solubility in front of a series contains 0.2 wt .-% per liter of a da

given, it should preferably be 3% by weight, based on the detergent described in more detail below. the

on the total weight of the MhIeIs. Rinsing fluids consist of pure loosening

Another component that makes the invention 60 water. The water for detergents and rinsing liquids can be added, has a hardness of about 3.4 Mfllhnol Calchmiis a water-soluble, low-molecular organic carbonate per liter. Every rinsing and rinsing bath Acid or the water-soluble alkali metal, Ainmo contains about 101 water, the temperature all egg mom or substituted ammonium salts thereof. Use of washing liquids or baths is at the beginning Suitable water-soluble, low molecular weight organic 65-52 ° C and generally between 42xmd35 ° C Acids and their salts including some of them and completely neutralized salts are e.g. B. the 17 and 19.5 ° C Acetic acid, citric acid, malic acid, (muconic acid, in each of the 5 liquid fluids of the 4 test series

13 5711

10 soiled glasses (from a cafeteria) are immersed for 2 minutes, removed one after the other, rinsed one after the other for 1 minute with the final rinsing liquid and removed from them for draining and drying in the air (room temperature) at about 23 ^° C.

As soon as the glasses are dry, four experienced evaluators individually compare the appearance of the glasses, taking the 10 glasses that were rinsed in the first rinsing liquid of series A and in the first rinsing liquid of series A 'were rinsed, compare with the 10 glasses that were in the first rinsing liquid of series B and rinsed with the first rinsing liquid of B ', then it is

were the same with the 10 glasses that came with the first rinsing liquid Series C rinsed and rinsed with the first series C rinse fluid and so on, with the 10 glasses in the second

5 rinsing and rinsing liquid of row A and A 'treated, the 10 glasses, which in the second rinsing and rinsing liquid of series B or B 'have been rinsed and rinsed and so on. The 10 Giäser, which was rinsed in the 5 rinsing liquids of the D series

ο are not rinsed, only on air dried. The evaluation of the evaluators is expressed as follows: equal (0), worse (-), better (+), much better (++). The results are summarized in Table I:

Table I.

Cf. 1. Rinsing / post-series rinsing liquid AB AC

AD ⁺

2. Rinsing / rinsing liquid AB AC

AD ⁺

3. Rinsing / rinsing liquid AB AC AD ⁺

4. Rinsing / rinsing liquid AB AC AD ⁺

5. Rinsing / rinsing liquid

AB AC AD *

Evaluator

1 + + + 0 2 + + + - 3 + + + + 0 4th + + +

Rows without rinsing.

0 0 0

0 0

0 0

The liquid dishwashing detergents used in rows A through D were as follows composed:

component line C. D. AWAY 10 10 Paraffin sulfonate ammonium
salt (average mole
gross weight of the coal
hydrogen residues = 196) 10 - 10 10 Coconut alcohol ethylene
oxide (3) sulfate ammonium
salt 10 - 4th 4th Dimethyldodecylamm 4 4 7th 7th Coconut alcohol ethylene 7 20

oxide (6) condensate

Coconut fatty acid diethanolamide

Gelatin ( avg

Weight 25000; isoelectric Point approx. PH 8; Bloom strength approx. 100)

water

pH of the washing liquid

- 2 - -

rest

The detergent of series A is representative of an effective dishwashing agent. It is noticeable that the glasses rinsed in the detergent of series D (same composition as the washing fluids of grater A, but with 1% by weight of gelatine) are not cleaner than the groove the rinsing and rinsing liquids of rows A and A ', although the overall appearance of the glasses rinsed with rinsing and rinsing liquids B and C or B' and C are much better than those with rinsing and rinsing liquids A and A ' treated glasses.

Test B

Four more rows E, F, G and H are prepared with ffol r dishwashing liquids which contain ^{rT c, 2 '"" ^ of a dishwashing detergent.} The rinsing liquids in series E contain the detergent from series A, the liquids in series F contain the detergent from series B, the rinsing liquids in series G contain the detergent from series C and the rinsing fluids in series H contain the detergent from series D. Furthermore, three rows of rinsing agents E ', F' and G 'are provided. The water used has the same hardness as in test A. Each rinsing and rinsing bath contains about 51 water, the water in each bath is 10 cm high. The temperature of the rinsing fr ^ ata is maintained at about 42 ° C, the temperature of Tempe Nachspülbäder Hegt between 30 and 35 ⁰ C. groups of 4 flat plates soiled nut ghnslcr surface (from a Cafeterria) of each of the 5 m each Spülflnssigkeften Row E, F, G and H rinsed (a total of 80 plates), removed from the SpÜlnusagtaat and then rinsed in the next wash baths of each row, (5 χ successively in the bath immersed and removed from it) ^ Ai! Siahmeder5Grai _T enY0njeweils4Tellän, iL ^{m 4} S- ⁵ SpHHfluyaSteft of the H series can be flushed. The plates are removed from the Hachspüffiad, allowed to drain and dried on the IMt.

L3 571I

The rinsing water drips from the rinsing and rinsing liquids in rows F and G or F 'and G' treated plates within 60 seconds, while the water on the dish with the rinsing and Rinsing liquids E or E 'or H treated plates only slowly disappears through evaporation (10 to 12 minutes until dry plates are obtained).

If groups of 4 soiled plates are washed as described above, but with a final AbSpU ¹ Sn under running tap water at approx. 16 ° C instead of immersing them in the final rinse, the bleaching dripping phenomenon is observed in the case of the rinsing liquids of series F. and G rinsed plates, while the dividers rinsed in the rinsing liquids of row E take 10 to 12 minutes to dry after rinsing under running tap water.

TestC

3 rows of 5 rinsing liquids K, L and M each containing 0.2% by weight per liter of a rinsing agent according to the following information are produced. The detergent used for rinsing and rinsing has the same hardness as in test A, the temperature of all rinsing liquids is kept at 47 ° C, the temperature of the rinsing baths is between 30 and 36 ^C C. Each bath contains 51 water, the water height is 10 cm .

In each of the 5 washing liquids of the series K, L and M, soiled dishes are washed as described in test B, removed from the washing liquid and then, as also described in test B, rinsed in the respective rinsing bath.
The detergent of the K series is composed

ίο like the A series dishwashing detergent from test A, that L series detergent corresponds to the B series detergent of test A, and the detergent to the Row M is identical to the detergent in row B of test A, with the difference that 1% gelatin with an average molecular weight of about 5000 (Bloom strength 0) is used.

The rinsing water runs from the one with the rinsing and rinsing liquids of rows K. or K 'and M and M 'washed dishes not off, but

ao only disappears later, mainly through evaporation, while the plates treated with the washing and rinsing liquids of the L or U series run off the water within 60 seconds of being removed from the rinsing bath.

In the following examples, all percentages relate to weight.

Examples (wt%) I. II III IV V VI VII Dimethyl dodecyl amine oxide
Coconut Alcohol Ethylene Oxide (6>
condensate 8th
15th 4th
7th 2
6th 4th
7th 2
2 4th
7th 3
6th Diethanol-C _u - _W fatty acid amide,
Coconut Alcohol Ethylene Oxide (3>
sulfate sodium salt 2 10 3
9 14th 2
10 12th 2
14th C _u - ₁₈ paraffin sulfonate,
Na-SaIz - 10 9 - 9 10 12th C "- ₁₄ α-olefin sulfonate
Ammonium salt - - - 12th - - - Triethanolamine - - - - - - - Boric acid - - - - - 2 1.5 Gelatin·) 1 1 1 1 0.75 1 1 water rest

·) Gelatin: Mol.wt. 40,000; isoelectric point 8.4; Bloom strength about 100.

Example VIII

Dishwashing detergent is made by mixing this mixture is suitable when used in First, the surfactants are mixed in water 0.2% aqueous solution for cleaning Ge and then the gelatine dishes and glass while stirring. When used, this conveys adds, using the following formulation: detergent, dishes and glass after

Rinse off with shine water and it diminishes

Cj, -alkyl-ethylene oxide (12) -sulphate K-salt 18.6% stain and film formation. The agent possesses accept-

Dodecyl sulfate K-Salz 10% foam properties and skin-friendly

Dodecyl dimethyl amine oxide 5% speed.

Gelatine (Mol.gew. About 60,000; isoelek- similar rinsing effect is achieved if you

tric point approx. 4.6; Bloom strength 65 gelatin in the mixture of Example VIII by 1.2

150) 1.8% wt% gelatin having a molecular weight of about 80,000,

Potassium toluenesulfonate 8% with an isoelectric point of about 4.8 and

Water rest of a bloom strength of 220 replaced.

609530/458

Example IX

Coconut ethylene oxide (6) sulfate Na salt ... 16%

Coconut alcohol sulfate Na-Salz 11%

Coconut alkyl dimethyl amine oxide 4.5%

Gelatin (mol. Wt. About 70,000; isoelectric Point approx. 6; Bloom strength

about 200) 1%

Potassium toluenesulfonate 8%

Water and minor additives remainder

Such a mixture is physically stable and is suitable for cleaning porcelain and glazed tiles when used in 0.2% aqueous solution. The agent gives the objects treated with it shine and keeps film and flake formation to a minimum. The foaming power and the skin tolerance are acceptable for the market.

Essentially the same rinsing effect is achieved if the sodium coconut ethylene oxide (6) sulfate is used the mixture of Example IX with an equivalent amount of potassium coconut ethylene oxide (12) sulfate, Ammonium coconut ethylene oxide (12) sulfate, ammonium coconut ethylene oxide (6) sulfate, Triethanolamine coconut ethylene oxide (6) sulfate or triethanolamine coconut ethylene oxide (12) sulfate replaced.

Furthermore, essentially the same dish-washing effect is achieved if the coconut alcohol su'fat sodium salt is used of Example IX replaced with an equivalent amount of coconut alcohol potassium or ammonium salt.

Essentially a similar cleaning effect is achieved when using the coconut alkyl dimethylamine oxide in the mixture of Example IX by an equivalent amount of dimethyl-dodecyl-amine oxide, dimethyl-tetradecyl-amine oxide or cetyl dimethyl amine oxide replaced.

In addition, essentially the same cleaning effect is obtained if the mixture of Example IX the gelatin by 1.8% by weight of a gelatin with a molecular weight of about 45,000, with an isoelectric Point of 4.6 and a Bloom strength of about 120, or by 0.8% by weight of a gelatin of molecular weight about 60,000 with an isoelectric point of about 8.2 and a Bloom strength replaced by about 180.

Example X

Dimethyl dodecyl amine oxide 4%

Coconut Alcohol Ethylene Oxide (6) Condensate 5%

Coconut alcohol ethylene oxide (3) sulfate,

K-SaIz 10%

C ₁₃ -18 paraffin sulphonate Na salt 8%

Coconut alcohol sulfate K-SaIz 4%

Boric acid 1.5%

Triethanolamine 5%

Ethanol 3%

Gelatin (Mol.wt. 40,000 - isoelectric

Point 8.4; Bloom strength approx. 100) 1%

Water rest

Example XI

Dimethyl dodecyl amine oxide 4%

Coconut Alcohol Ethylene Oxide (6) Condensate 5% Coconut Alcohol Ethylene Oxide (3) Sulphate,

K-SaIz 10%

C ₁₃ -, fl-paraffin sulfonate sodium salt 8%

J ₀ coconut alcohol sulfate K-salt 4%

Sodium citrate 1%

Boric acid 1.5%

Triethanolamine 5%

Ethanol 5%

Gelatin (Mol.wt. 40,000 - isoelectric

Point 8.4; Bloom strength approx. 100) 1%

Water rest

Example XII

Dimethyl dodecyl amine oxide 4%

Polyethylene glycol, Mol.gew. 400 7%

Coconut Alcohol Ethylene Oxide (3) Sulphate

NH ₄ salt 12%

C for ₁₂ - ₁₄ - * - olefin sulfonate, NH ₄ -SaIz 10%

Sodium acetate 0.5%

Gelatin (Mol.wt. 40,000 - isoelectric

Point 8.4; Bloom strength approx. 100) 1%

Water rest

Example XIII

Dimethyl dodecyl amine oxide 4%

Coconut Alcohol Ethylene Oxide (6) Condensate 10%

Tallow alcohol-ethylene oxide (ll) condensate ... 6%

Diethanoi Ciä-ij fatty acid amide 2%

Polyethylene glycol condensate, Mol.gew. 400 4%

. _o Gelatin (mol. wt. 25000 - isoelectric

Point 8; Bloom strength approx. 60) 1%

Water rest

Example XIV

Dimethyl dodecyl amine oxide 2%

Diet hanoi C ₁₂ fatty acid amide 2%

Coconut Alcohol Ethylene Oxide (6) Condensate 2%

Polyethylene glycol condensate, Mol.gew. 400 2% r ₀ coconut alcohol ethylene oxide (6) sulfate,

Na salt 7.5%

Cuj-14-alkyl sulfate, Na salt 2.5%

C ₁₃ -I e-paraffin sulfonate, sodium salt 10%

Gelatin (Mol.wt. 60000 - isoelectric

Point 7; Bloom strength approx. 200) 0.75%

Water rest

In order to show that known cleaning agents which contain a gelatin with a gel strength of Og Bloom do not produce the run-off effect of the cleaning agents according to the invention, 4 series T ₁ , T ₂ , T ₈ and T ₄ of three wash liquors each were produced. Each wash liquor in each series contained about 0.25% by weight of a cleaning agent described below per liter. The hardness of the water used to make the detergents

19 20

was about 3.4 mmol CaCO ₃ per for series T ,: detergent of the above case liter. Two plates and a game of X, but without boric acid, were placed in each wash liquor, two glasses being immersed in the gelatin. While the plates and glasses were dipped through 1% by weight of the _{gelatin glasses used for Series T 1} , the temperature was replaced;
each washing solution about 42 ° C. The plates and glasses 5

were taken out after about 3 minutes. for series T ₄ : cleaning agent as for series T ₃ , but the plates and glasses dipped into the first and second wash liquor of each series with a content of 3% by weight of the specified plates and glasses were about 1 minute gelatin,
long with gentle agitation in rinsing water (temperature: about 21 ⁰ C; hardness: as with the washing liquor) io As a result of the experiments it was observed that neither the plates nor the glasses, which were in the washing of the air, were immersed and allowed to drip off and dry posed. The plates and glasses immersed in the third wash liquor from series T ₁ , T, and T _{s of} each series showed a noticeable run-off effect within 60 seconds after rinsing for about 20 seconds with the pipe running. The according to water (temperature: about 16 ° C; hardness: as with the 15 series T ₄ washed plates and glasses showed inner wash liquor) rinsed and then set aside to drain and half of 60 seconds after rinsing, set aside to dry in the air. wrestling, irregular and slow draining effect

For the individual series, the following stains and after complete drying were stains.

Detergents used: Detergents were also used in their

ao composition of example 1 of DT-OS 16 17 062

for series T ₁ : cleaning agent according to example 1 that corresponded to, but no opacifier and perfume,

DT-OS 1617 062, without opacifiers and without instead but additionally 0.5% by weight or 3% by weight

Perfume, but with 1% by weight of a gelatin with a gelatin with a molecular weight of about

an average molecular weight of 10,000,500, a gel strength of 0 g Bloom and a

(determined by membrane osmometry at a material isoelectric point at around pH 5.2 to 5.8

lien kept deionized to remove salts under approximately the same conditions as in

had been), a gel strength of 0 g Bloom test C above (washing dirty plates

and an isoelectric point between pH 5.2 and subsequent rinsing, with only two

and 5.8; Wash liquors instead of five liquors

30 were; Temperature of the washing solutions approx. 42 ° C,

for series T _2: T detergent as for Series _1, but the temperature Nachspülbäder about 21 ⁰ C) were tested, the indicated with a content of 3 wt .-% being within 60 seconds after the NachGelatine; rinse hardly any runoff was observed.

Claims (11)

Patent claims: 1. Liquid, clear aqueous cleaning agent, especially for <"- eschin, containing a surface-active one Detergent, a protein derivative and common additives, characterized in that it, based on the total weight of the agent, (A) about 2 to about 40 weight percent of a water soluble organic nonionic surface active agent in the form of (1) tertiary oxides of the general formula R ₁ R ₁ R ₃ Y- ^ O (I) in which 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, R ₂ and R ₃ each have a methyl, ethyl, hydroxymethyl or hydroxyethyl radical and Y is a nitrogen or phosphorus atom represent, (2) amides of the general formula R ₄ -CO- N (H) _m _j (R, OH),., »(II) wherein R _{4 is} a saturated or unsaturated aliphatic hydrocarbon res; l: with 7 to 21 carbon atoms, R _{5 is} a methylene or ethylene group and m is the number 1, 2 "of 3, (3) Condensation products of from about 3 to about 25 moles of ethylene oxide and 1 mole of pure organic hydrophobic compound aliphatic or alkyl aromatic Nature with from about 8 to about 24 carbon atoms, or a mixture thereof, (B) about 0.1 to about 5% by weight of a water soluble Gelatin with a molecular weight of at least 12,500, one isoelectric point between pH 4.5 and about 9.2 and a gel strength between 25 and 300 bloom grams and than The remainder contains water. 2. Cleaning agent according to claim 1, characterized in that it contains about 0.2 to about 2% by weight a water-soluble gelatin having a molecular weight of more than 15,000 and preferably between 25,000 and 80,000, in particular between J5 000 and 50 000. 3. Cleaning agent according to claim 1 or 2, characterized in that it is a water-soluble Gelatin with an isoelectric point above 6, preferably between pH 7 and 9, and a gel strength above 50, preferably between 80 and 200 Bloom-Granum. 4. Cleaning agent according to claim 1 to 3, characterized in that it is aiii water-soluble Organic nonionic surfactant • in a 5: 1 to 1: 2 mixture of tertiary amino oxides and Cjj - ^ - Alkyl-CO-diethanolamiden decolded. 5. Cleaning agent according to claim 1 to 4, characterized in that it bi · to 40 wt ⁰ ,, a water-soluble hydrocarbon sulphate salt of the general formula R ₆ O (C ₂ H ₁ O) _n SO ₃ Ni (III) contains, wherein R _{6 is} a straight or branched, saturated or unsaturated aliphatic hydrocarbon radical with 8 to 22 un ( ^J preferably 12 to 16 carbon atoms. η is a number between 1.5 and about 15 and M is a potassium ion, preferably a sodium or potassium ion make, the total amount of non-ionic surfactant detergent and hydrochloric sulfate salt is at most 48% by weight, based on the total weight of the agent. 6. Cleaning agent according to claim 5, characterized in that it contains 5 to 20% by weight of a water-soluble hydrocarbon sulfate salt of the general formula R ₈ O (CsH ₄ O) _n SO ₃ M (III), wherein R _{8 is} a straight-chain, saturated aliphatic Hydrocarbon radical with 12 bi> 16 carbon atoms, η a number between 3 and ί and M represent a sodium or potassium ion. 7. Cleaning agent according to claim 5 or 6, characterized in that it contains up to 40 wt .-% of a mixture of a water-soluble hydrocarbon sulfate salt of the general formula R _e O (C _s H ₄ O) _B SO ₃ M (III), wherein R ₆ , M and η have the above meaning, and a water-soluble organic sulfuric acid reaction product of the general formula R ₇ SO ₃ M, in which M has the above meaning and R _{7 is} a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical with 12 to 18 Represents carbon atoms, wherein the total amount of nonionic detergent surfactant, hydrocarbon sulfate salt and organic sulfuric acid reaction product is not more than 48 wt .-% and wherein the weight ratio of organic sulfuric acid reaction product to the sum of nonionic surfactant detergent and hydrocarbon sulfate salt is less than 1.5: 1. 8. Cleaning agent according to claim 7, characterized in that it contains 0.5 to 2% by weight of a gelatin with an isoelectric point between pH 7 and 8.5, an average molecular weight between 35,000 and 50,000 and a gel strength of 80 to 200 Bloom gram, 4 to 16% of a water-soluble nonionic surfactant detergent consisting of a mixture of C, s- ₁₄ -alkyldimethylamine oxide and coconut fatty acid diethanolamide, 5 to 20% by weight of a water-soluble hydrocarbon sulfate salt of the formula C ₁₂ _ _ie alkyl-O- (C ₂ H ₄ O) ₃ -SO ₃ M _ _e and 3 to 15% by weight of a paraffin _{sulfonate of the formula C 12} _ _ls -paraffin-SO ₃ M, wherein M has the above meaning, the weight ratio of paraffin sulfonate to nonionic surfactant detergent being below 2.5: 1 , while the weight ratio of paraffin sulfonate to the sum of nonionic detergent surfactant and hydrocarbon sulfate salt is less than 1: 1. 9. Cleaning agent according to claim 1 to 8, characterized in that it contains up to 15% by weight, based on the total weight of the agent, a water-soluble low molecular weight organic Acid or a water-soluble alkali metal, ammonium or substituted ammonium salt contains a low molecular weight organic acid. 10. Cleaning agent according to claim 9, characterized in that it is about 2 to about 10 and preferably 2 to 4% by weight of an alkali metal salt citric acid, tartaric acid, succinic acid, benzene hexacarboxylic acid or ethylene diminetetraacetic acid contains. 11. Cleaning agent according to claim 1 to 10, characterized in that there are 2 to about 10 % By weight of an emulsifier in the form of triethanolamine or a polyethylene oxide condensation product having a molecular weight between about 160 and about 1200 contains.