DE2162673A1 - DETERGENTS, DETERGENTS AND CLEANING AGENTS - Google Patents

Description

Patent application

D.4395
"Detergents, dishwashing detergents and cleaning agents"

The effect of the well-known detergents, dishwashing detergents and cleaning agents is largely based on the presence of inorganic or organic complexing agents for alkaline earth metal ions. These complexing agents support the effect of other, non-complexing, inorganic or organic, cleaning agents Substances. Such complexing agents include, for example, sodium tripolyphosphate or various organic ones Complexing agents of the type of the 'Phösphonate or the aminopolycarboxylic acids. The use of these complexing agents in detergents, dishwashing detergents and cleaning agents in public is related criticized with questions of environmental protection; it will still strongly controversial view that the eutrophication of the waters and the associated excessive growth largely due to the phosphorus or nitrogen compounds that get into the water through such detergents and cleaning agents. The requirement for washing, Dishwashing detergents and cleaning agents that contain biologically harmless components.

It is an object of the invention to provide the known inorganic or organic complexing agents containing phosphorus and / or nitrogen completely or partially to be replaced by complexing agents that do not contain such elements and, moreover, a have good washing and cleaning properties.

309829/0971

Henkel & Cie GmbH S · ». 2 »r Paunfcmmtldung D 4 ^ 595 O 1 R 9 P * 7 * 3

The invention relates to detergents, dishwashing detergents and cleaning agents that are in solid form, as pastes, dispersions or solutions, that have a content of complexing agents for alkaline earth metal ions, and those that are water- and / or solvent-free Products related are composed as follows:

5-95 -.% Of the built-up of approximately equal molar amounts of maleic acid and furan polymers having molecular weights from 300 to 20,000, preferably 500 to 5000,

r where the polymers are preferably in the form of their water

soluble salts capable of complexing with alkaline earths are present, and

95-5 Gew .- ^ o other common additives of detergents, dishwashing and cleaning agents, in particular organic or inorganic substances with a cleaning effect.

If the compositions according to the invention are solid, they are usually in the form of fine to granular powders, agglomerates or granules. Such agents can be practically anhydrous; but they can also contain crystal water or water of hydration. The agents according to the invention can, however, also be used as pastes, dispersions or solutions; they then contain lesser or greater amounts of liquid solvents, such as, for example, water or organic water-soluble solvents in which the other constituents are partially or completely dissolved. For certain cleaning purposes, for example, solutions can be used which contain up to 1% by weight, preferably up to 4 % by weight, of the solid agent. The solutions, dispersions or pastes can also be much more concentrated, so that the amount of the solvent up to JJO wt .- ^, preferably up to 50 wt -.% Makes. Hydrotropes can also be incorporated into the solutions, dispersions or pastes.

309829/0971

Henkel & CIe GmbH S.lt. yy for Pal.oMndung D 4j95 9 1 R 9 R 7 3

The polymers of the above definition which can be used according to the invention, in particular their salts, hereinafter referred to as "copolymers" referred to are in the "Journal of Macromolecular Science Chemistry", Vol. A4 (1), pp. 52-54. The products can by copolymerization of furan and maleic anhydride or by polymerization of the Diels-Aider adduct from furan and maleic anhydride are prepared, for example by reaction in benzene solution with azobisisobutyronitrile as Catalyst. The polymers obtained in this way are converted into their salts by saponification with inorganic or organic bases.

The copolymers which can be used according to the invention are preferred used as sodium salts; they can also be present as potassium or ammonium salts, as well as water-soluble salts of aliphatic amines or alkylolamines with a maximum of 6 carbon atoms in the molecule, e.g. as salts of di- or trimethylamines, of mono-, di- or triethylamine, of mono-, di- or triethanolamine, of mono- or di-hydroxypropylamine, etc.

309829 / Π971

Henkel & Cie GmbH su 4 * »<■ Pat.monm.idune ο 4395 O 1 COC Π Ο

The detergents, dishwashing detergents or cleaning agents according to the invention can be used in numerous areas of technology and household for a wide variety of cleaning tasks. Examples of such areas of application are the cleaning of devices, apparatus, pipes and vessels made of wood, Plastic, metal, ceramics, glass, etc. in industry or in commercial operations, cleaning furniture, walls, Floors, objects made of ceramic, glass, metal, wood, plastic, cleaning of polished or painted surfaces in the household, etc. A particularly important area of application is the washing and bleaching of textiles of all kinds and that Machine washing of dishes in industry, in commercial operations and in the household. With all of these cleaning tasks the copolymers defined above are characterized by a good ability to form complexes for alkaline earth metal ions and by a good cleaning and washing power.

The composition of the preparations according to the invention can depending can be very different according to their field of application. For the industrial cleaning of surfaces of solid materials with With the exception of textiles, for example, products with the following composition are suitable:

5-30 wt .- ^ copolymers,
10 - 30 wt .- ^ alkali silicates,
10 - 80 wt .- ^ caustic alkalis,

0-10% by weight surfactants.

309829/0971

Henkel & de GmbH

2 Ί DZD / J

These agents can also contain alkaline or neutral salts, corrosion inhibitors, disinfectants, complexing agents, in particular those for heavy metals, contain and other common components of such agents. As a cleaning agent for the manufacturing sector of the metal industry, for example, products with the following composition are suitable:

10 - Jio wt -.% Copolymers, 10 - J> 0 wt .- ^ alkali metal silicates, 10-40 .- $ caustic, 0-10 wt .- ^ surfactants.

Preparations of the following composition are suitable as cleaners for the food industry:

5-30 wt -.% Copolymer, 10 - 20 wt .- ^ alkali metal silicates, 40 - 80 wt .- ^ caustic alkalis, 0-5 wt -.% Surfactants.

Preparations are used as cleaning agents for automatic dishwashing in commercial and household dishwashing machines the following composition usable:

5-90 wt .- ^ copolymers, 95-5 -.% Water-soluble alkali metal silicates, 0-20 wt -.% Alkali metal hydroxides or alkali metal carbonates, 0-10 wt -.% Low-foaming nonionic surfactants, 0-25 wt -.% Other Common components of dishwashing detergents such as active chlorine compounds, enzymes, complexing agents for heavy metals, dyes and fragrances.

309829/0971

Henkel & Cie GmbH s «». 6 zur Pai.manm.idun _e d ^ 395 9 1 R 9 R 7 3

While the caustic alkali-containing preparations are mostly only for cleaning of surfaces of solid materials used in industry or in commercial operations and for machine dishwashing are used as a household cleaner or as a laundry detergent for soaking, washing and bleaching in the In industry, in commercial laundries or in the household, caustic alkali-free agents whose 1 # aqueous solutions have a pH value of at most 11.5.

The inventive, the copolymers containing one " Softeners, pre-wash detergents, painstaking detergents, detergents or bleaching agents can be used with textiles made from a wide variety of natural fibers or of synthetic origin. These include, for example, cotton, regenerated cellulose or linen as well Textiles, the highly refined cotton or synthetic man-made fibers, such as polyamide, polyester, polyacrylonitrile, polyurethane, Contain polyvinyl chloride or polyvinylidene chloride fibers. The detergents according to the invention can also be used for Washing of textiles made of synthetic fiber / cotton blended fabrics, which are referred to as "easy-care", sometimes also as "non-iron" use.

309829/0971

Henkel & Cie GmbH -s.it. J _{Iur Pot.nionm.} Attire d 4J95 216 267 3

The composition of this one in Ijoiger aqueous solution Agent with a pH value of at most 11.5 is in the range of the following formulation:

0-80, preferably 5-40 wt .- ^ of a surfactant component consisting of anionic and / or zwitterionic and / or nonionic surfactants 5 - 95 * preferably 10 - 80 wt -.% Serving as builders copolymers,

95-0 * preferably 90 - 20 wt -.% Of other inorganic and / or organic builders and optionally a bleach component,

0-50, preferably 1 - 25 wt. - ^! t other common ingredients of detergents and cleaning agents.

To the other usual detergent and cleaning agent ingredients include e.g. foam stabilizers, non-surfactant foam inhibitors, brighteners, antimicrobials, enzymes, color and fragrances. The bleaching component consists of bleaching active chlorine or active oxygen compounds and possibly from activators and / or stabilizers for this.

By using the copolymers defined above, which contain no phosphorus or nitrogen and which are not toxic to fish, the previously used or in the Some or all of the phosphorus- and / or nitrogen-containing complex-forming builder substances proposed in the literature substitute. When the condensed phosphates such as sodium tripolyphosphate as well as organic, phosphorus and / or nitrogen containing complexing agents in the previous commercially available agents e.g. half through the copolymers and optionally are replaced by other customary P- and / or N-free structural substances, then this leads to the application in the the usual washing, rinsing and cleaning liquors considerable reduction in the P and / or Η concentration in the wastewater.

309829/0971. " ⁸ "

Hang! & CiQ GmbH s.it. 8 _Iur Pai.ntcnmoiduna ο 4395

The ability of the copolymers to form complexes is at the
Alkaline earths are particularly pronounced, so that they are able to support washing and cleaning processes; on the other hand, their ability to form complexes for heavy metals - as is the case with other known complex-forming framework substances - ■ is only slight. It is therefore advisable to add such complexing agents to the agents according to the invention in small amounts of, for example, 0.1-5 *, preferably 0.1-2% by weight. As a complexing agent for
Heavy metals, especially for copper, are, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid or aminotriäthylidenediphosphonic acid or theirs. Salts. ·

In the detergents according to the invention, including in particular the pre-wash detergents, cleansing detergents and high-temperature detergents, the surfactant component preferably contains at least 50 percent by weight of anionic surfactants, with essentially anionic surfactants
capillary-active sulfates and / or sulfonates and / or soaps are understood. The amount of the builder substances including the copolymers is preferably 0.5 to 7 times
and in particular 1 to 5 times the total surfactant component. If the preparations according to the invention contain more than 40 percent by weight of surfactant component, then they will mostly
used for commercial purposes, for example in the ashes and in the textile industry, where they are used less often on their own, more often in combination with the usual additives.

309829/0971

BATH ORIGINAL

Henkel ■ & Cie GmbH su - O, igrFOtenianm.iduna ο 4395 O 1 Q OCT ^

The composition of powdered preparations according to the invention, especially used as a detergent or cleaning agent is generally in the range of the following recipe:

5 - 50 * preferably 8 - 40 wt .- ^ of a surfactant component, consisting essentially of anionic and / or zwitterionic and / or nonionic surfactants and optionally from one or more of the following substances:

0-10, preferably 0.5-8 wt .-; 4 foam stabilizers,
0-10, preferably 0.5-8 wt .-; ^ non-surfactant

like foam inhibitors,

95-5 * preferably 92-10 wt .- ^ copolymers, 0 -. 9Oj preferably 5-82 wt ~% of inorganic and / or other organic builders and optionally bleaching components and
0 - 30, preferably -1 - 15% by weight; i other detergent ingredients, such as dirt carriers, fabric softeners, antimicrobials, enzymes, brighteners, parboil and fragrance substances, water.

The surfactant component is preferably at least $ 0 % by weight. from anionic surfactants from the group of alkylbenzenes sulfonates, alkanesulfonates, fatty acid ester sulfonates, olefin sulfonates, fatty alcohol or fatty alcohol glycol ether sulfates and soaps. Low-foam detergents suitable for use in drum washing machines according to the above recipe contain either a combination of surfactants of the sulfonate and / or sulfate type and soap in a ratio of 30: 1 to 1: 5, preferably 20: 1 to 1: 2, and / or a non-surfactant foam inhibitor. The foam suppression is particularly pronounced, the soap content contains at least 5 and preferably at least 10% by weight of soaps of saturated fatty acids with 20-24, preferably 20-22, carbon atoms.

309829/0971 - 10 -

BATH ORIGINAL

2,62673

Henkel & Cie GmbH S.it. 10 x for patent application D 4395

The bleaching component makes mostly 5 - ^ 0, preferably 7-35 wt -.% Of the total detergent from.

The powdered detergents, dishwashing detergents and cleaning agents according to the invention can be produced by various methods known per se. For example, the more or mix less fine powders or individual components in the form of granules. According to the technically at the moment preferred manufacturing method for detergents, dishwashing detergents and cleaning agents an aqueous approach of the components insensitive to water and heat) is used in a manner known per se, e.g. dried on hot surfaces or in a stream of hot air. The powder obtained are then further components that are used in such processing could lose their effect in whole or in part. These include e.g. foam inhibitors, Bleaches, enzymes, antimicrobials, dyes and fragrances etc. It may be of advantage, especially for the gentle incorporation of smaller amounts of substances through them Mixing it with some of the structural substances first converts it into a dry, powdery preliminary product, which is then converted to the usual Way is added to the washing powder, dishwashing detergent or cleaning agent powder.

In the following, in the washing, rinsing according to the invention and cleaning agents are described in more detail sorted by substance class.

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303829/0 971

BAD ORIGSNAL

Henkel & Cie GmbH s.it. \ \ zur Pot.n »anm.id _U n _B D 4395

The surfactants contain at least one hydrophobic radical of mostly 8-26, preferably 10-22 and in particular in the molecule 12-18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated hydrophobic residue is mostly aliphatic, possibly also of an alicyclic nature; he can with the water-solubilizing Groups can be linked directly or via intermediate links, e.g. via benzene rings, carboxylic acid ester, carbonamide or sulfonic acid amide groups as well as residues of polyhydric alcohols bonded in the manner of ethers or esters.

As an anionic active washing substance, soaps are made from natural ones or synthetic fatty acids, possibly also from resin or naphthenic acids, especially if these acids have iodine numbers of at most 30 and preferably less than 10 exhibit.

Of the synthetic anionic surfactants, the sulfonates have and sulphates of particular practical importance,

The sulfonates include, for example, the alkylbenzenesulfonates with preferably straight-chain Cq_-1 -, in particular C-jQ - ^ - alkyl radicals, the alkanesulfonates, obtainable from preferably saturated aliphatic Co_- | g- »in particular ^C 12-18 ~ ^{hydrocarbons. er} sulfochlorination or sulfoxydation, the mixtures of alkene sulfonates, hydroxyalkane sulfonates and disulfonates known under the name "olefin sulfonates", which, in the case of acidic or alkaline hydrolysis, of terminal or intermediate Cq_ _1q - and preferably ^c -] 2-18 ~ olefins by sulfonation with sulfur trioxide sulfonation products initially formed arise. The sulfonates which can be used according to the invention also include salts, preferably alkali salts, of CO sulfo fatty acids and salts of esters of these acids with mono- or polyhydric alcohols containing 1-4 and preferably 1-2 carbon atoms.

- 12 30 9 829/0971

Henkel & CIe GmbH st ».12 *» r Pc.n.onm.idun, d 4 ^ 95

Other useful sulfonates are salts of fatty acid esters the oxethanesulfonic acid or the dioxypropanesulfonic acid, the Salts of the fatty alcohol esters of lower, 1-8 carbon atoms containing aliphatic or aromatic sulfomono- or -dicarboxylic acids, the alkyl glyceryl ether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Suitable surfactants of the sulfate type, fatty alcohol sulfates may be mentioned are, in particular from coconut fatty alcohols, tallow or W of oleyl alcohol produced, further sulfated fatty acid alkylolamides or fatty acid monoglycerides and suifatierte alkoxylation products of alkylphenols (Cg _-1, - alkyl), fatty alcohols, Fettsäureamideη or fatty acid alkylolamides with 0.5 - 20, preferably 1-8 and especially 2-4 ethylene and / or propylene glycol residues in the molecule.

Suitable anionic surfactants of the carboxylate type are e.g. the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the amide-like condensation products of Fatty acids or sulfonic acids with aminocarboxylic acids, e.g. with - • Glycocoll, Sarcosine or with protein hydrolysates.

The anionic surfactants are usually lower than the salts of the alkali metals, especially sodium and ammonium aliphatic amines or alkylolamines.

309829/0971

Henkel & CIe GmbH s.it. \ J> iur p _a t.ntanm.idun _e 4

To the non-ionic surfactants, here for the sake of simplicity referred to as "Nonionics" belong to those created by attachments 4-100, preferably 6-40 and especially 8-20 mol of ethylene oxide in fatty alcohols, alkylphenols, fatty acids, fatty amines, Fatty acid or sulfonic acid amides available polyethylene glycol ether, also the addition products of propylene or butylene oxide, which are still water-soluble, with them. to the nonionics also include those known under the trade names "PIuronics" or "Tetronics", from which are water-insoluble per se Polypropylene glycols or from water-insoluble propoxylated lower. 1-8, preferably 5-6, aliphatic alcohols containing carbon atoms or from water-insoluble alcohols propoxylated alkylenediamines by Äthoxyleren up to Products obtained solubility in water. Finally, nonionics are also known as "Ucon-Fluid", partly still to use water-soluble reaction products of the above-mentioned aliphatic alcohols with propylene oxide.

As nonionics are also mono- or diethanolamine, dihydroxypropylamine or other polyhydroxyalkylamines, e.g. fatty acid or sulfonic acid alkylolamides derived from glycamines, useful. Furthermore, the oxides of higher tertiary amines with a hydrophobic can be used as nonionics Alkyl radical and two shorter alkyl and / or alkylol radicals containing up to 4 carbon atoms each.

Zwitterionic surfactants contain both acidic groups in the molecule, such as carboxyl, sulfonic acid, sulfuric acid half-ester, Phosphonic acid and phosphoric acid partial ester groups, as well as basic groups such as primary, secondary, tertiary and quaternary ammonium moieties. Zwitterionic compounds with quaternary ammonium groups belong to the type the betaine. Have carboxy, sulfate, and gulfonate betaines of particular practical interest because of their good compatibility with other surfactants.

3 0 * 98 29/0971

Henkel & CIa GmbH stt »l4 i _U r Pot.ntonm.idun _e ο 4395

The foaming power of the surfactants can be achieved by combining them Increase or decrease suitable surfactant types, as well as by adding non-surfactant organic substances can be changed.

Suitable foam stabilizers are, especially in the case of surfactants of the sulfonate or sulfate type, capillary-active carboxy or Sulfobetaines as well as the above-mentioned nonionics of the alkylolamide type; in addition, fatty alcohols or higher terminal diols have been proposed for this purpose.

A reduced foaming capacity, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates and / or nonionics on the one hand with soaps on the other. In soaps, the foam inhibition increases with the degree of saturation and the number of carbon atoms of the fatty acid radical anj as foam suppressants have soaps οδ of saturated Cp _0th "· ^^ '^ ¹¹¹ proven" * ^611th

The non-surfactant-like foam inhibitors include, if appropriate, chlorine-containing N-alkylated aminotriazines, which can be passed through Reacting 1 mole of cyanuric acid chloride with 2-3 moles of a mono- and / or dialkylamine with 6-20, preferably 8-18 C atoms in the alkyl radical. Propoxylated and / or butoxylated aminotriazines, e.g. products that can be used, have a similar effect by adding 5-10 moles of propylene oxide to 1 mole of melamine and further adding 10-50 moles of butylene oxide to this Propylene oxide derivative obtained.

Other non-surfactant foam inhibitors are water-insoluble organic compounds such as paraffins or haloparaffins with melting points below 100 ° C, aliphatic CjQ to C.Q ketones and aliphatic carboxylic acid esters,

"309829/0971

Henkel & Cie GmbH s.it. ir to Ponnianm.idun _B d

which contain at least 18 carbon atoms in the acid or alcohol radical, possibly also in each of these two radicals (e.g. triglycerides or fatty acid fatty alcohol esters); They can be used especially with combinations of sulfate and / or surfactants Use sulfonate type with soaps to steam the foam.

As a particularly low-foaming nonionics, both alone as well as in combination with anionic, zwitterionic and nonionic surfactants. and the foaming capacity lower foaming surfactants, adducts of propylene oxide to those described above are suitable capillary-active polyethylene glycol ether and the Pluronic, Tetronic and Ucon fluid types also described above.

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0 * 9 829/0971

O 1 Ρ »OP 1

Henkel & Cie GmbH. Seullß to Pafenlanmelduno D 4395

Suitable builders, which can optionally be used together with the copolymers defined above, are inorganic or organic salts, in particular inorganic or organic complexing agents, with a weak acidic, neutral and alkaline reaction. Usable, weakly acidic, neutral or alkaline reacting salts are, for example, the bicarbonates, carbonates, borates or silicates of alkalis, furthermore mono-, di- or tri-alkali metal orthophosphates, di- or tetraalkali metal pyrophosphates, metaphosphates known as complexing agents, alkali metal sulfates and the alkali salts of organic, not capillary-active, 1 - 8 carbon atoms containing sulfonic acids, carboxylic acids and sulfocarboxylic. These include, for example, water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfo. dicarboxylic acids and the salts of acetic acid, lactic acid, citric acid and tartaric acid.

The water-soluble salts of higher molecular weight polycarboxylic acids, in particular polymers, can also be used as builder substances of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Also copolymers of these acids with one another or with other polymerizable substances, such as ethylene, propylene, Acrylic acid, methacrylic acid, crotonic acid, 3-butene carboxylic acid, 3-methyl-3-butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, Isobutylene, acrylamide and styrene are useful. The alkaline substances are also suitable as complex-forming structural substances reactive polyphosphates, especially tripolyphosphate.

- 17 -

3 09829/0971

Henkel & Cie GmbH

Sail · 1 "J lur Potonianmelduno D

The organic complexing agents include, for example Nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, Polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, combinations of different complexing agents also being used can be. To the other known complexing agents ^! also include di- and polyphosphonic acids of the following constitutions:

OH X

I I

O = P - C

I i

OH H

OH

- P = O

OH

OH X

I I

o-p - c

I I

OH Z

OH

P = O OH

R-Nc

X OH

ι ι

c - p = o II

Y OH

X
C.

OH

- P = O

I I

OH

HO

O = P

HO

I y

- R ^f - N-

i I

OH

P = O

OH

wherein R is alkyl and ^{-R 1 is} alkylene radicals with 1-8, preferably with 1-4 carbon atoms, X and Y represent hydrogen atoms or alkyl radicals with 1-4 carbon atoms and Z represents the groups -OH, -NH ₂ or -NXR . The following compounds are particularly suitable for practical use: methylenediphosphonic acid, l-hydroxyä'i, han ~ l, l-diphosphonic acid, l-aminoethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), methylamino or Ethylamine-di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid). All of these complexing agents can be present as free acids, preferably as alkali salts.

- 18th

309829/0971

BATH ORIGINAL

Henkel & Cie GmbH since. L ^ iur roi.Manmeidune ο 4 ^ 95 9 1 C η C "1 O

The higher molecular weight polycarboxylic acids which can be used as builder substances also include the practically uncrosslinked polyhydroxycarboxylic acids and polyformylcarboxylic acids which contain predominantly CC bonds in the main chain and which are composed essentially of ethylene units each with a carboxyl, formyl, hydroxymethyl or hydroxyl group. The polyhydroxycarboxylic acids have a ratio of carboxyl groups to hydroxyl groups of 1.1-15 *, preferably 2-9 * ^and a degree of polymerization of preferably 5-600; they can be prepared, for example, by copolymerization of acrolein and acrylic acid ψ in the presence of hydrogen peroxide and subsequent reaction according to Cannizzaro (DOS 1 90 ^J t 9 ^ 1).

Orniylcarbonsäuren the Polyf have a ratio of the Carboxylzu B ⁿ ormylgruppen of at least 1 and a degree of polymerization of preferably 5-100; if appropriate, the polymers have terminal hydroxyl groups. They can be produced, for example, by oxidative polymerization of acrolein with hydrogen peroxide (DOS 19 ^ 2 256). .

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30 ^ 829/0 971 BAD

Henkel & Cie GmbH s., T. JkJ ™ po _te manm.idun _g d ^ 595 ^ · Ό ZO / O

The preparations according to the invention can also contain dirt carriers, the dirt detached from the fiber keep them suspended in the fleet and thus prevent graying. Water-soluble colloids of mostly organic nature are suitable for this, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Even water-soluble polyamides containing acidic groups are suitable for this purpose. Soluble starch preparations can also be used and use other starch products than those mentioned above, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

The components of the laundry detergents and auxiliary agents according to the invention, In particular, the structural substances are usually selected in such a way that that the preparations react neutral to clearly alkaline, so that the pH value of a 1 ^ igen solution of the preparation usually in the range from 7 to at most 11.5. Detergents for mild detergents usually have a neutral to slightly alkaline reaction (pH value = 7 - 9 * 5), during soaking, prewash and cooking detergents set more alkaline (pH = 9 * 5 - Hj5)

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30'9829 / 0971 BAD ORIGINAL

Henkel & CIe GmbH su ^ φ for patent registration d 43Q5

Among the compounds which serve as bleaching agents and yield IUCU in water, sodium perborate tetrahydrate (NaBO ₂ · H ₂ O _2. 3 H ₂ O) and monohydrate (NaBO _2. H ₂ O ₃ ) are of particular practical importance. However, other _{borates which produce H 2} O _{2 can also} be used, for example the> Perborax Na ₂ B ^ O ₇ . 4 H ₂ O. These compounds can be partially or completely replaced by other active oxygen carriers, in particular by peroxohydrates such as percarbonates (Na ₂ CO ^ 1.5 H ₂ O ₂ ), perpyrophosphates, citrate perhydrates, percarbamide or melamine H ₂ 0 ₂ - Compounds and ψ can be replaced by HgO _2- supplying peracid salts such as caroates (KHSO ₁ -), perbenzoates or perphthalates.

It is advisable to incorporate customary water-soluble and / or water-insoluble stabilizers for per compounds in amounts of 0.25-10% by weight. _{The magnesium silicates MgO: SiO 2} = 4: 1 to 1: 4, preferably 2: 1, usually obtained by precipitation from aqueous solutions, are suitable as water-insoluble perstabilizers, which make up, for example, 1-8, preferably 2-7 % of the weight of the total preparation up to 1: 2 and in particular 1: 1. Other alkaline earth metal, cadmium or tin silicates of corresponding composition can be used instead. Hydrous oxides of tin are also suitable as stabilizers. Water-soluble stabilizers, which can be present together with water-insoluble ones, are the organic complexing agents, the amount of which can make up 0.25-5 », preferably 0.5-2.5% of the weight of the entire preparation.

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30 * 9829/0971

ί {

Henkel & Cie GmbH since. 2 ¹ ^ r patentonm.idong d 4j595 ^ JOZO / J

The active chlorine compounds serving as bleaching agents can be inorganic or organic in nature.

The inorganic active chlorine compounds include alkali hypochlorite, which condensed in particular in the form of their mixed salts or addition compounds to orthophosphates or to Phosphates such as pyro- and polyphosphates or alkali silicates can be used. Contain the washing and cleaning agents monopersulphates and chlorides, active chlorine is formed in aqueous solution.

Particularly suitable organic active chlorine compounds are the N-chlorine compounds in which one or two chlorine atoms are bonded to a nitrogen atom, the third valence of the nitrogen atoms preferably leading to an electron-withdrawing group, in particular to a CO or SO ₂ group. These compounds include dichloro and trichlorocyanuric acid or their salts, chlorinated alkylguanides or alkyl biguanides, chlorinated hydantoins and chlorinated melamines.

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3 098? 9 / nfl71 BAD ORIGINAL

Henkel & CIe GmbH 'S.lltJ ^ _Iur Pat.nianm.liiune D 4395

Certain serve as activators for per compounds HPOP delivered in water, with this H ₂ Op form organic peracids N-acyl, O-Aeyl compounds and carbonic or pyrocarbonic esters, their activation value for the j-compounds (= titre) at least 3 preferably at least 4.5 is. This activation value is determined in the following way:

Solutions containing 0.615 g / l NaBO ₂ · HgO ₃ x 3 HgO (4 mmol / 1) and 2.5 g / l Na ^ P ₂ O ₇ · 10 contain HPO, after heating to 60 ⁰ C and 4 mmol / l added activator and kept at the specified temperature for 5 minutes while stirring. 100 ml of this liquid are then added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and, immediately after the addition of 0.35 g of potassium iodide, titration is carried out with 0.1 η sodium thiosulphate solution and starch as an indicator; the amount of thiosulfate solution consumed in ml is the activation value (= titer); with a 100% activation of the peroxide used, it would amount to 8.0 ml.

From the bottom to be described types of activators are especially compounds having a melting point of at least 70 ⁰ C, preferably at least 100 ⁰ C and is furthermore in particular of at least I50 ⁰ C., the equivalent weight of these compounds (under Ä'ouivalentgewicht is here the Cuotient from the molecular weight and the number of acyl residues or carbonic acid or pyrocarbonic acid residues present in the molecule) be at most 170, preferably at most 130 and in particular at most 110. Activators which can be used according to the invention include

a) the N-diacylated and N, N ^! -tetraacylated amines such as Ν, Ν, Ν ¹ , N'-tetraacetyl-methylenediamine or -ethylenediamine, N, N-diacetylaniline and Ν, Ν-diacetyl-p-toluidine or 1,3-diacylated hydantoins, such as the Compounds 1,3-diacetyl-5,5-difnethylhydantoin and 1,3-dipropionylhydantoin;

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b) the N-alkyl-N-sulfonyl-carbonamides known from British patent specification 1 003 JlO, for example the compounds N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide;

c) those described in Swiss patent specification 407 387 N-acylated cyclic hydrazides, acylated triazoles or urazoles such as the monoacetyl maleic acid hydrazide;

d) the Ο, Ν, Ν-trisubstituted hydroxylamines described in DP application P 17 1 "9 574.3-43, such as, for example, O-benzoyl-N ^ N-succinylhydroxylamine, O-acetyl-NiN-succinyl-hydroxylamine, Op-methoxybenzoyl -N, N-succiny! -Hydroxylamine, Op-nitrobenzoyl-NjN-succinylhydroxylamine and O ₁ N, N-triacetyl-hydroxylarain;

e) the N, N ¹ -diacyl-sulfurylamides known from DOS 1 801 713, for example N, N ¹ -dimethyl-N, N ¹ -diacetyl-sulfurylamide, and N, N ¹ -diethyl-N, N ^f -dipropionyl -sulfurylamide;

f) the triacyl cyanurates, for example triacetyl cyanurate and Tribenzoyl cyanurate from DAS 1,294,919;

g) those from Swiss patent specification 347 930 or the DBP publication 893 049 or the DOS 1 444 001 known carboxylic acid anhydrides such as benzoic anhydride, m-chlorobenzoic anhydride, Phthalic anhydride, 4-chlorophthalic anhydride;

h) those known from Swiss patent specification 348 682 Sugar esters, for example glucosepentaacetate;

i) the 1,3-diacyl-4,5-diacylöxy-imidazolidines of DOS 1 801 141, for example the compounds 1,3-diformyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine;

j) the compounds tetraacetylglycoluril known from DOS 1 594 865 and tetrapropionyl glycoluril;

k) the diacylated described in DP application P 20 38 106.0 2,5-diketopiperazines such as l ^ -diacetyl ^^ - diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine; 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine;

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Henkel & Cio GmbH

see below 25 ", p.,. ni", ™ w. "g d ^ 395 ^

1} the Äeylierungsprodukte described in the DP application P 21 12 557.5 of propylenediurea or 2,2-dimethylpropylenediurea (2,4,6,8-Tetraaza-bicyclo- (3.3 * 1) -nonan- ' 3,7-dione or its 9j9-dimethyl derivative) in particular the Tetraacetyl or the tetrapropionyl propylene diurea. or their dimethyl derivatives

ra) the carbonic acid esters of DOS 1 444 024, for example the sodium salts of p- (ethoxycarbonyloxy) -benzoic acid and p- (propoxycarbonyloxy) -benzenesulfonic acid.

Of particular practical interest are those under j), k) and l) the types of activators mentioned.

When the per compounds are activated by the aforementioned N-acyl and 0-acyl compounds, carboxylic acids such as e.g. Acetic acid, propionic acid, benzoic acid, free and it is advisable to use appropriate amounts of alkali to bind these carboxylic acids to add. In the case of effective activators, activation is already possible when using amounts of 0 ^ 05 mol of activator per Detect g-atom active oxygen. It is preferred to work with 0.1-1 mol of activator; however, the amount can also be up to 2 moles of activator per g-atom of active oxygen can be increased.

309829/0971

Henkel & Cie GmbH s.it. ^ g ^ on the patent application d 4j595

The brighteners that can be used are mostly, if not exclusively, Derivatives of aminostilbene sulfonic acid or diaminostilbene disulfonic acid, diarylpyrazolines, carbostyrils, of 1,2-di- (2-benzoxazolyl) - or 1,2-di- (2-benzimidazolyl) -ethylene, of benzoxazolyl thiophene and coumarin.

Examples of brighteners from the class of the diaminostilbene disulfonic acid derivatives are compounds according to formula I:

-CH

In the formula, R ^ and Rp can denote alkoxyl groups, the amino group or residues of aliphatic, aromatic or heterocyclic! ", Primary or secondary amines and residues of aminosulfonic acids, aliphatic residues present in the above groups preferably 1-4 and in particular 2-4 C -Atoms, while the heterocyclic ring systems are usually 5- or 6-membered rings. The aromatic amines are preferably the residues of aniline, anthranilic acid or anilinesulfonic acid. Brighteners derived from diaminostilbene disulfonic acid are mostly used as cotton whitening agents. The following products derived from formula I are commercially available, where R .. represents the radical -NHCgH ₁ - and Rp can represent the following radicals: -NH ₂ , -NHCH ₅ , -NHCH ₂ CH ₂ OH, -NHCH ₂ CH ₂ OCH ₅ , -NHCH ₂ CH ₂ CH ₂ OCH ₅ , -N (CH ₅ ) CH ₂ CH ₂ OH, -N (CH ₂ CH ₂ OH) ₂₁ MOrPhOlInO-, -NHC ₅ H ₅ , -NHC ₆ H ^ SO ₅ H, -OCH _5. Some of these brighteners are deliberate h the fiber affinity to be regarded as transition types to the polyamide brighteners, eg the brightener with R ₂ = -NHCgH ₁ -. The compound 4,4'-bis- (4-phenyl-1,2,3-triazol-2-yl) -

2,2 · stilbene disulfonic acid.

- 27 309829/0971

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Henkel & Cie GmbH S.It. ~! &<for patent application D 4395

The polyamide brighteners include diarylpyrazolines of the formulas II and III:

- C Cn 'CH ₉ CH

^b III:

In formula II, FU and R, - hydrogen atoms, optionally substituted by carboxyl, carbonamide or ester groups, alkyl or aryl radicals, R ^ and Rg hydrogen or short-chain alkyl radicals, Ar ^ and Ar ₂ aryl radicals, such as phenyl, diphenyl or may carry naphthalene w methyl, the other substituents _t such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic ester, SuIfonsäure-, sulfonamide and SuIfongruppen or halogen atoms. Commercially available brighteners of this type are derived from the formula III, where the radical R _{7 can represent} the groups Cl, -SO ₂ NH ₂ , -SO ₂ CH = CH ₂ and -COOCH ₂ CH ₂ OCH ₅ , while the remainder Rq usually means a chlorine atom. 9-cyanoanthracene is also one of the polyamide brighteners.

The polyamide brighteners also include aliphatic or aromatic substituted aminocoumarins, e.g. 4-methyl-7- ^ dimethylamine- or the ^ methyl-T-diethylaminocoumarin. Further- ^ the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene are used as polyamide brighteners and 1-ethyl-3-phenyl-7-diethylamino-carbostyril useful. The compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-Benzoxazolyl) naphtho {j2,3-bj thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable.

If the brighteners are used together with other components of the invention Products are in the form of an aqueous solution or paste and are converted into a solid state by hot drying, it is recommended to stabilize the brighteners organic complexing agents in amounts of at least 0.1, preferably 0.2 -

Incorporate 1 wt .-? O of the solid products. _

- 2o - · ».». '. ·. "" 30 98 29/097 1

Hang! & Cie GmbH sen »^ 2 ^ ^{Iur Po} " ^nl ° ^nmeldun o ^D ^ 595 ^ - ^ ^ -

The enzyme preparations to be used are usually a mixture of enzymes with different effects, e.g. proteases, carbohydrases, Esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases. Of particular interest are the ones from Bacterial strains or fungi such as Bacillus subtilis or · Streptomyces griseus obtained enzymes, in particular proteases or anylases, which react to alkali, per compounds and anionic surfactants are relatively stable and still effective at temperatures of up to 70 C.

Enzyme preparations are mostly used by the manufacturers as aqueous Solutions of the active ingredients or as powder, granules or as cold-atomized products on the market. They contain A.as co-solvents often sodium sulfate, sodium chloride, alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. Particular importance is attached to dust-free preparations; they are obtained in a manner known per se by incorporating them of oily or pasty nonionics or by granulating with the help of molten salts containing crystalline water in your own crystalline water.

Enzymes can be incorporated for a specific Soil type are specific, for example proteases or amylases or lipases; combinations are preferred from enzymes with different effects, especially combinations of proteases and anylases "

3 0 9 8 7 9/0 9 7 1 _B AD ORIGINAL

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Examples

The following examples describe compositions of some inventive laundry detergents, detergents , dishwashing detergents and cleaning agents. The percentage amounts of the constituents were converted to anhydrous agents in accordance with the patent claim, with the exception of the constituents borax and perborate, for which the water of crystallization content is specified. But since most of them are prepared by hot-drying an aqueous batch, these agents generally contain 5-20% by weight of water of crystallization and / or water of hydration. If the agents contain borax or perborate, these are added to the hot-dried powder. Synthetic surfactants of the sulfate or sulfonate type generally contain small amounts of sodium sulfate as an accompanying substance, which are insignificant for the formulation. The presence of this sodium sulfate is indicated in the NapSCk lines of the example tables with the, sign +.

The salt-like constituents contained in the agents in the examples - · Salt-like surfactants, other organic salts and inorganic salts - are in the form of sodium salts, provided that nothing else is expressly stated. The relatives Designations or abbreviations mean:

"" ABS "the salt of a condensing straight chain terminal olefins with benzene and sulfonating the resulting Alkylbenzenes obtained alkylbenzenesulfonic acid with 10-15, essentially 11-13> C atoms in the alkyl chain j

"Alkanesulfonate" consists of paraffins with 12-16 carbon atoms sulfonate obtained by way of sulfoxidation;

Tallow fatty acid sulfonate obtained by sulfonation with SO ₇ ;

"Ps-ester sulfonate" is a hardened one from the methyl ester

at;

98 29/0 971 _{ΛΒΙΛ1ΚΙΛ} .

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■ "Olefinsulfonat" a from 0 Ie f ingerni see with 12 - 18 C-atoms by sulfonating with SO-. and hydrolyzing the sulfonation product sulfonate obtained with lye, which is essentially However, alkene sulfonate and hydroxyalkane sulfonate also consist of small amounts of disulfonates contains;

"KA-SuIfat" or "TA-Sulfat" are the salts of sulfated, through Reduction of coconut fatty acid or tallow fatty acid produced, essentially saturated fatty alcohols

"KA-A'O-sulfate" or "TA-A" 0-sulfate "or" OA-ÄO-sulfate "the sulfated addition products of 2 mol of ethylene oxide 1 mol of coconut fatty alcohol or of 3 mol of ethylene oxide to 1 mol of partial fatty alcohol or of 2 mol of ethylene oxide to 1 mol of oleyl alcohol;

the "soap" was derived from fatty acid mixtures with an iodine number of at most 7 j, the composition of which was within the following formulation: 0-20 wt .-; i C ₁₃ , 0-15 wt .- / 'C ₁ ^, 5 - 40 wt .- ^ "C _16, 5 - '/ Ό wt .-; ^ ₁ Q C, 0 - 20 parts by weight tf C _30, 0-80 Gev /.-; ^v j C ^ p, wherein the ends schaumdämpf effect of this soap with increasing mean C number increases;

"OA + 5 ÄO", "OA + 10 XO" and "KA + 20 A'0" are the addition products of ethylene oxide (A'0) with technical oleyl alcohol (OA) or coconut alcohol (KA), the numbers denoting the molar amount of ethylene oxide added to 1 mol of alcohol;

"KA + 9 ÄO + 12 PO" a by converting 1 mole of "KA + 9 ΆΌ" Nonionici obtained with 12 moles of propylene oxide -

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"NTA", "EDTA" and "HEDP" the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid and hydroxyethane diphosphonic acid;

“Perborate” a product containing about 10% active oxygen with the approximate composition NaBOg · HgOg · 5 HgO;

"CMC" the salt of carboxymethyl cellulose;

As "copolymer" was a was converted by polymerization of l, 2,3,6-tetrahydro-3J6-epoxy-anhydride obtained polymer with a molecular weight of about 000 H, and the hydrolyzed to the disodium salt, is used, "Copolymerisat- Mixture "in Table I means the abovementioned polymer in a mixture with other builder substances (further details before Table I).

The means, the composition of which is described in Examples 1-7 are primarily intended for the following purposes:

Example 1: Example 2:

Example J>: Example H:

Example 5: Example 6:

Example 7:

Detergents for the metal industry; Detergents for the food industry (both made by mixing the powdery ingredients);
low-foam kitchen detergent; high-foaming product that can also be used as a mild detergent;
Soaking agent

(all made by hot atomization); Soaking agent

(produced by spraying the nonionics onto the mixture of powdery ingredients); Cleaning agent that can also be used in the household for materials other than textile (hot-dried).

309829/0971 "

BATH ORIGINAL

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Henkel & Cie GmbH S.it. ^ 2 for patent application lduns O ^ 395

In the case of the agents according to Examples 1, 2 and 5-.7 of the following Table I, the quantities given relate to the Copolymers on the technically pure product; in the case of the agents according to Examples j5 and 4, the quantities given relate to the copolymers both on the technically pure copolymer as well as mixtures of equal parts by weight of this copolymer isats with the following structural substances:

a) a polymerized according to the specifications of DOS 1 9C4 941 Acrolein by treatment with alkali hydroxides according to Cannizzaro, optionally in the presence of formaldehyde, obtainable salt of a polyhydroxypolycarboxylic acid with an average degree of polymerization of 40 and a molar ratio COOH: OH = 7

b) Na ₂ SiO ;;

c) sodium citrate;

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Henkel & Cie GmbH si ·. ftf for patent application D 4395 216 267 3

Table I.

■ '' ■ 5 G 1 2 2 Part of 8th 4th 5 middle 6th - - β. example component , 0 , 0 20.0 4th 7th 7, 5 , 0 after 20th SECTION 6th 3 KA -XO-SuIfat 3, 4, soap 30th 25th 2, OA + 10 XO , 0 , 0 40.0 33 60, Copolymer 42, 3 , 0 10, 0 10. (Mixture) Na ₅ P ₃ O ₁₀ 0, 2 0, 0 SDTA 30th 48 30.0 0 HEDP 20th , 0 15th , 0 26, 8th Perborate , 0 j , 0 3, 6, 3 NaOH 3, 0 _Well? 0.3,3Si02 15th 10 1 0 Ha ₂ CO ₃ , Oj , 0 10.0 15, 18 0 5, _Well? 3 ₄ 0 .10 H ₂ O 12, 2 0 • 62, Na ₂ SO ;. 5.0 1, 1,
5 CMC 2
, 0 , 0 , 0 0 0

The agents described in Examples 8-20 - except for that according to Example 11, produced by spray drying are primarily intended for the following purposes:

Example 8: Soaking or pre-wash medication; Examples 9-11 and 1j5-17: All purpose detergents, in particular bleaching cooking agents Examples 12 and 18: Colored detergents; Examples 19 and 20: mild detergent »

309829/0971

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4395 Z I 0 Z D / O

The cooking detergents on the one hand and the colored or mild detergents on the other hand differ - not recognizable from the above recipes - in the presence or absence of cotton and / or polyamide and / or polyester brighteners.

As a foam inhibitor is a mixture of about ^ 5 ^c ß> a di- (alkylamino) -monochlortriazins and about 55 ^C was added p of an N-N'-N "-Trialkylmularnins used in all of these triazine derivatives of the alkyl radicals to be as a mixture of homologs. 8-18 carbon atoms. The monochior triazine derivative or the trialkyl melamine could be used with similar success. If the products described contained synthetic sulfates or sulfonates together with soap, the other non-surfactant-like foam inhibitors mentioned in the description could be used In the manufacture of the preparations, the foam inhibitor used was dissolved in a suitable organic solvent or, in a molten state, sprayed onto the moving powdery preparation using a nozzle.

'BAD ORIGINAL

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Henkel & Cio GmbH

Vf

for patent application

Table II

component Ge w. - j component of the means 10 11 according to example I. 12.4 13th 8th 9 13.2 12th SECTION 10.8 1.6 Olefin sulfonate 6.1 14.3 15.2 soap 2.4 11.2 2.2 OA + 5 AO 7.2 6.2 4.3 OA + 10 AO 9.6 13.6 KA + 20 ÄO 9.3 KA + 9 ÄO + 12 PO 3.7 0.6 - Foam inhibitor 0.4 40.7 32.0 1.0 38.0 Copolymer 73.7 28.7 49.6 ^Na 5 ^P 3 ° 10 20.3 9.9 NTA 0.9 2.2 EDTA 1.8 0.7 0.9 3.7 HSDP 22.8 19.8 21.8 Perborate 19.1 4.8 5.6 Na ₂ 0.3.3 SiO ₂ 5.4 6.2 Na ₄ P ₂ O ₇ 7.2 13.0 Na ₂ CO ₃ 11.1 "1,2 2.2 MgSiO ₃ 1.2 1.9 1.6 1.8 1.1 CMC 2.0 1.8

- 36 -

309829/0971

BATH ORIGINAL

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* - <"P ° lonlanmel <! Us 0

Table III

component Gev /. -γ 4th } Component 0 Ϊ
«Ι 8th . 16 at the Means by example 18th ■ 2.8 19th 20th 1 , 4 15th 9 17th SECTION 9 4th 7.0 6.7 Alkanesulfonate 7.9 Fs-ester sulfonate 8th, 3 7.9 18.5 Olefin sulfonate ,8th 1.2 9 , 4 1.7 3.9 KA sulfate 1 , 6 3, 1.7 TA sulfate 0 , 2 4th 3 , 5 36.8 9.2 KA-Ä0 sulfate 2 8.6 TA -A'O -Sulfate OA-SO sulfate , 4 6.8 1.2 4.7 soap 6th 11 7th 10, 8th 24.5 OA + 5 A'O 3, 2.7 4.3- OA + 10 Ä'O - 0.6 4, 9 0.9 1.1 Foam inhibitor ,1 40.0 35.5 40.6 Copolymer 32 35, 30, 5 1.8 13.5 Na _n P ₃ O ₁₀ ,1 6.1 NTA 11 0.5 EDTA 0 , 6 0, 27.0 0, 5 Per; borate 26th , 5 .30, 6.0 30, 4th 4.2 Na _p 0.3.3 SiO ₂ 5 4, 5.0 4, 9. Na ₂ CO , 2 MgSiO ₃ 2 ,8th 1.2 3, 5 1.5 2.1 CMC 1 2, 2.0 1, 6th 41.2 11.1 Na ₂ SO ₄ H ₂ O

309829/0971

BATH ORIGINAL

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Henkel & CIo GmbH. s _o ; ie ^ fz _ur Paionto ^ eUtme d 4395 ZlU ZD /

Examples 21 and 22

Pre-wash detergents that enable extensive, if not complete, disinfection even at temperatures of up to 6 "0 ° C.

Example 21 Example 22

13.7 10.0 wt .- ^ ABS, alkanesulfonate or

Olefin sulfonate,

7.0 5.0% by weight soap, 0.5 0.5% by weight foam inhibitor, 60.0 20.0% by weight copolymers 0.0 24.5% by weight Na _? C0, 4.0 9.0 wt .-; 5 NaOH (to neutralize the

Phenol),

! 13.8 30.0 wt .- # o-phenyl-phenol, pentachlorophenol or mixtures thereof, from 1.0 1.0 wt -.%

B oisplel 23 / ■ '

Antimicrobial bleaching rinse aid for washed VJasche, at the same time fiber incrustations, in particular calcareous fiber incrustations, dissolves.

30.0 wt .- # perborate,

30.0 wt .-, i copolymer ,.

15 ^ 0 wt .- ^ Na ₂ CO ₅ ,

2.6 wt .- ^ 2-hydroxy-2 ', 4.4 "-trichlorodiphenyl ether,

8.0. Wt .- ^ MgSiO ₅ ,

14.4 wt .-; i Na ₂ SO ^.

Example 24. ■

Dishwashing detergents for commercial and household dishwashers:

55j0 wt -.% Copolpjerisat,

42.0 wt -.% Of the composition of sodium metasilicate Na ₂ Q · 2.75 SiO _2,

1.0% by weight Jβ OA + 5 ÄO,

2.0 wt .- / a potassium dichloro cyanurate. _ 38 -

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Example 25

A 25% solution of a mixture serves as a disinfectant surface cleaning agent

40.0 wt. Ji ABS,

48.0 wt.% Copolymers

12.0 wt -.% 2-hydroxy-2 ', 4,4'-trichloro-diphenyl ether,

in a mixture of 0.2% of perfume oil, 10% isopropanol and 89.8 fo v / ater.

The inventive washing, described in the examples, Dishwashing detergents and cleaning agents have good washing and cleaning power that is as good or better than the corresponding one Preparations based on tripolyphosphate. Because of the excellent complex binding capacity of the copolymers Alkaline earth metal ions show the advantageous properties of the preparations according to the invention especially during washing and Clean 'in hard water. Those which can be used according to the invention Copolymers are also practically not hygroscopic, which is important for the storage stability and the bulk behavior of the powdery Preparations is of great importance.

If the disodium salt of is replaced in these preparations Polymerization of the furan- ^ faleinic anhydride adduct available Polymers by the salt of a by direct copolymerization of maleic anhydride and furan in a molar ratio of 1: 1 manufactured product with a molecular weight of approx.; 5,000, this leads to similar results.

Is added to the perborathaligen means, in particular to be applied at temperatures below 80 ⁰ C (rinsing) with activators for per compounds, for example with tetraacetylglycoluril, Tetraacetylmethylen- or-ethylenediamine,: are obtained even at temperatures of 20 to 70 ⁰ C a good bleaching effect .

-309829/0971

SAD ORiGiNAL

Claims (6)

91R9R7 Henkel & Cie GmbH 'Since ·, ^ 9 * iur Pat.ntanm.Idune D 4 ^ 95 _. Claims 1. Detergents, dishwashing detergents and cleaning agents that are in solid form, as pastes, dispersions or solutions - which have a content of complexing agents for alkaline earth metal ions,., and those, based on the water- and / or solvent-free products, by the following composition are characterized: 5-95% by weight of the ^{polymers built up from approximately equal molar amounts of N} maleic acid and furan Molecular weights of 300-20,000, preferably 500 - 5,000, wherein the polymers are preferably in the form of their water-soluble, capable of complexing with alkaline earths Salts are present, and 95 - 5 wt .- ^ other common additives of detergents, Dishwashing and cleaning agents, in particular organic or inorganic substances with a cleaning effect. 2. Cleaning agents, preferably for industrial cleaning of the surfaces of solid materials with the exception of textiles, according to claim 1, characterized by the following composition: 5-30 wt .- # copolymers according to claim 1, 10-30 wt -.% Alkali metal silicates, ^ 10-80 wt .- ^ caustic alkalis, * 0-10% by weight surfactants. 3. Detergents and cleaning agents, their 1 ^ ige aqueous solutions have a pH value of at most 11.5, characterized by the following composition: 0-80, preferably 5 - ho wt -.% Of a surfactant consisting of anionic and / or zwitterionic and / or nonionic surfactants, / 5 - 95 * preferably 10 - 80 wt -.% As builders serving copolymers according to claim 1, 309329/0971 * ^BAD Henkel & Cie GmbH s * n.) Tf5- _Iur Pat.manmeidune d 4 ^ 95 ZIDZD / J -. ■ - O, preferably 90-20% by weight of other inorganic and / or organic builders and optionally a bleach component,. - 50, preferably 1-25 wt .- ^ other common ingredients of detergents and cleaning agents 4. Washing and cleaning agents, preferably for use for textiles, according to claim 3, characterized by the following composition: - 50, preferably - 8 - 40 wt .- ^ of a surfactant component, consisting essentially of anionic and / or zwitterionic and / or nonionic surfactants and optionally from one or more of the following substances: 0 - 10, preferably 0.5 - 8 wt -.% Foam stabilizers,
■ 0 - 10, preferably 0.5 - 8 wt -.% Non-surfactant -like foam inhibitors, - 5j preferably 92 to 10 wt -.% copolymer as claimed in claim 1. . O - 90 * preferably 5 - 82 wt -.% Of inorganic and / or other organic builders and optionally bleaching components and - JO, preferably 1 - 15 wt -.% Of other detergent ingredients, such as soil suspending agents, fabric softeners, antimicrobial agents, enzymes, brighteners, dyes and fragrances, water. 5. Agent according to claim 3 and 4, characterized by the presence of a bleaching component in amounts of 5-40, preferably 7-35% by weight . BATH ORIGINAL -309829/0971 Henkel & Cie GmbH S »lt · ^ / ζ xur Pal.ntanm.ldung D 4395 6. Means for machine washing dishes according to claim 1, characterized by the following composition: 5-90 wt .- ^ copolymers according to claim 1, 95-5 -.% Water-soluble alkali metal silicates, 0-20 wt -.% Alkali metal hydroxides or alkali metal carbonates, 0-10 wt .- ^ low-foaming nonionic surfactants, 0-25 wt. -% of other common ingredients of dishwashing detergents such as active chlorine compounds, enzymes, complexing agents for heavy metals, parbohydrates and fragrances, 309879/0971