DE2060762A1 - Preparations for the production of cold bleach liquors, in particular washing liquors with a cold bleaching effect - Google Patents

Description

"Means for the production of cold bleaching liquors, in particular washing liquors with active bleaching properties"

It is known to use aqueous solutions of hydrogen peroxide or hydrogen peroxide-yielding per compounds as oxidation and to use bleach baths, especially for fibers and preferably for textiles. At those bleach baths it can also be solutions of bleaching auxiliary washing agents or detergents. In such aqueous solutions the Active oxygen is generally only effective at temperatures from 80 to 100 ° C.

It has already been proposed to use organic substances belonging to certain types of N-acyl or 0-acyl compounds, to be used in such treatment baths as activators for the per compounds. These activators convert that into The hydrogen peroxide present in the wash liquor is converted into an organic peracid, which means that the active oxygen is much lower Temperatures of, for example, 20 to 70 ° C., preferably ^ 0 to 60 ° C is delivered in a bleaching state. Agents intended for the production of such treatment baths for textiles can contain brighteners.

209826/1012

Henkel & Cie GmbH S.it. 2 iur Poienlan registration D 41 60

The invention "relates to activator-containing preparations for production of cold bleach liquors, in particular of washing liquors with a cold bleaching effect. These funds are characterized by that they contain:

- 100, preferably 5-90 wt .-% of a bleaching component consisting of:

a) 99.99-95, preferably 99.98-97.5% by weight of a per-compound which delivers HpOp in aqueous solution and of an N-acyl or O-acyl compound which serves as an activator for HpOp, which is a test method described below has a certain activation value for the per compounds of at least 3, preferably of at least 4.5, the per compound and the activator being present in such amounts that per g atom of active oxygen at least 0.01 and at most 4, preferably at least 0.05 and at most 2 moles of activator are present,

b) 0.01-5, preferably 0.02-2.5% by weight at least a brightener of the following types: 4,4'-bis (azolyl-) stilbene-2,2'-disulfonic acids, Stilbyl naphtotriazole, bis (benzoxazolyl) derivatives and / or 2-benzoxazolyl-4,5-naphtothiophene compounds, said Brighteners, insofar as they represent acids, in particular sulfonic acids, also in the form of their Salts may be present,

- 0, preferably 95-10% by weight of other common ingredients of bleaching agents or bleaching detergents.

For the sake of simplicity, the N-acyl or O-acyl compounds defined above and used as activators for H _{3 O 3} are referred to as "activators" with the activation value given there. //^

- 3 209826/1012

Henkel & Cie GmbH su 3 w Poi. «Ta« m.id _U n _e d 4160

The products according to the invention can be used naturally for bleaching and for bleaching a wide variety of fibers or of synthetic origin. These include, for example, cotton, regenerated cellulose or linen and especially the so-called "easy-care" textiles made from highly refined cotton or synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers exist or contain them. To the as "easy to care for", occasionally Textiles also referred to as "non-iron" also include those made of synthetic fiber-cotton blended fabrics, which can be specially equipped.

The products according to the invention are particularly well suited for the bleaching and bleaching of these easy-care textiles because the degree of whiteness achieved without the presence of bleach activation means that at temperatures of 20-70 ° C., preferably 30-60 ° C. Activators can only be achieved at temperatures of 70-100 ° C, preferably 80-95 ° C. The high degree of whiteness that can be achieved with active oxygen and activators even at lower temperatures is advantageous above all for the effect of the brighteners.

However, internal, ie not previously published, tests by the applicant have shown that the effect of optical brighteners can be impaired by the presence of the activators. This impairment can be observed to a greater extent in the presence of traces of heavy metals, for example copper, which can get into the washing liquor from the copper heating rods of the washing machines, for example. These disadvantages and their causes were not known; It is therefore a particular merit of the inventors to have found products in the abovementioned brighteners whose effect is not reduced by the presence of activators. y ^

- 4 -209826/1012

Henkel & Cie GmbH s. »E 4 w patemanm.idun _g d 4160

Although the effect of the brighteners to be used according to the invention is not or is not even in the presence of heavy metal ions but is impaired to a much lesser extent than is the case with other brighteners, it recommends nevertheless, the products according to the invention are up to 25% by weight of corrosion inhibitors and up to 10% by weight, preferably 0.1-7% by weight of organic complexing agents for such ions to be added. The agents according to the invention can be used as Corrosion inhibitors contain the following substances in the amounts specified there:

0-5, preferably 0.1-2% by weight corrosion inhibitors of the type of triazoles and / or tetrazoles which contain a group = NMe or = N0Me, in which Me represents a metal or a hydrogen atom that can be replaced by metal,

0-20, preferably 1-10% by weight corrosion inhibitors of the type of salts of partial esters from fatty alcohols with 10-22, preferably 16-18, carbon atoms or their 1 - 10, preferably 1-4 glycol ether groups in the molecule containing ethoxylation and / or propoxylation products with ortho-, pyro- or polyphosphoric acid.

During the bleaching process, the acyl residues of the activators are released as carboxylic acids. It is therefore advisable to add so much alkali metal salts of weak acids to the agents according to the invention that at least a quarter of those formed Carboxylic acids are bound as salts. Such salts are, for example, the alkali metal carbonates and alkali metal silicates and alkali borates. Accordingly, the formulation of the products according to the invention is advantageously in the following range:

5-90, preferably 10-70 % by weight of the above-described bleaching component consisting of per compound, activator and brightener,

0-25, preferably 0.1-20% by weight of those described above Corrosion inhibitors and complexing agents for heavy metals, especially copper, Va

209826/1012 ~ ⁵ "

Henkel & Cie GmbH Sail. 5 for patent application Ο

95-10, preferably 89.9-10 wt .- $ in laundry and

VJaschhilfsmifcteln common, neutrally, preferably alkali-reacting builder substances and optionally surfactants, such amounts of alkali metal salts Weak acids are present that the acyl groups contained in the activators at least a quarter can be bound in the form of salts.

Bleaching textile treatment agents composed according to the above information can be used as special products for the textile industry or for commercial laundries or as preferred in the Soaking, prewash and laundry detergents for household use have been brought onto the market.

The former contain mostly more than 5O wt -.% Of bleaching component, this quantity refers to the pure activator, the pure peroxy compound and the pure brightener, sets _u without other Z. However, such products can also be used in the household for special purposes, for example as soaking agents or detergents with an increased bleaching effect, which can also be of interest as cold detergents, or as bleaching rinsing agents for washed laundry.

The products to be used as soaking agents, prewash agents or detergents usually contain lower amounts of per-compounds, Activators and brighteners; these are therein in amounts of, for example 5 to 50, preferably from 10 to 55 wt .- ^ present. In addition, such agents contain alkaline-reacting, non-complexing structural substances as further essential components, complex-forming structural substances and, in most cases, surfactants. The corrosion inhibitors described above of the ortho-, pyro- or polyphosphoric acid ester type are at the same time surfactants and can for this reason also

209826/1012

Henkel & Cie GmbH page 6 for patent application D 416O

larger quantities than specified in the above recipe. The same applies to the complexing agents for copper too. For this reason, the following recipe information for the soaking, prewash and laundry detergents the esters of ortho-, pyro- and polyphosphoric acid the surfactants and the complexing agents for heavy metals the complexing agents Assigned structural substances.

The products according to the invention can also be used with advantage as soaking agents, especially when washing remains in the solution of the soaking agent for a long time. Such soaking agents have approximately the following composition:

0 '- 5 wt .-% surfactants including the optionally

existing ortho-, pyro- or polyphosphoric acid esters
95-45% by weight, preferably 90-60% by weight, preferably

alkaline-reacting builder substances and possibly non-surfactant anti-corrosion agents and / or any complexing agents present for heavy metals

5-50% by weight, preferably 10-35% by weight of the bleaching component according to the definition above

In addition, those described below, usually to be used in smaller quantities, can be used in such soaking agents Detergent ingredients are present, such as antimicrobial substances, dirt carriers, brighteners, Enzymes, perfumes, dyes, etc.

Since the action of the activators is associated with the consumption of alkali, the builder substances should contain sufficient quantities of strongly alkaline salts, such as alkali carbonates, to prevent the pH of the bleaching or washing liquor from falling below the desired value. K ±

- 7 209826/1012

Henkel & Cie GmbH see _{below 7 »Γ} Paiutcnnwnung d 4160

A preferred field of application of the invention are the bleaching prewash detergents and detergents, their composition is generally in the range of the following recipe:

- 40, preferably 7-30% by weight of a surfactant component, Containing at least one surfactant of the sulfonate, sulfate, soaps, nonionics and / or the Ortho, pyro or polyphosphoric acid partial esters and optionally one or more of the following Substances:

0-10, preferably 0.5-8 wt. 96 foam stabilizers,
0-10, preferably 0.5-8% by weight 96 non-surfactant i

like foam inhibitors,

10-90, preferably 30-55% by weight of 96 complex-forming and / or non-complex-forming structural substances, including the alkali salts of weak acids determined to bind the acids released by the activator effect and, if appropriate, corrosion inhibitors and / or complexing agents for heavy metals, at least some of these structural substances , preferably the predominant amount reacts alkaline and wherein the amount of the alkaline to neutral reacting builder substances is preferably 0.5 to 7 times and in particular | makes up 1 to 5 times the total surfactant combination,
5-50, preferably 10-35% by weight of the bleaching component as defined above,

0-20, preferably 2-15% by weight of other detergent ingredients, such as fabric softeners, antimicrobial effective substances, dirt carriers, brighteners, enzymes, perfume, dyes, water./^

209826/1012

Henkel & Cie GmbH Since. 8 for patent application D M-160

This general recipe also includes temperatures

ο
up to 70 bleaching mild detergents to be used, the surfactant content of which is usually in the range from 8-40, preferably from 12-40 wt. If these mild detergents are not intended for use in washing machines, in particular in drum washing machines, they do not need to contain any foam inhibitors either.

Of particular practical importance are those for use in washing machines, preferably in drum washing machines, certain detergents in which the surfactant component is mostly 7-5O wt .- ^ makes up; this usually contains at least one of the following three types of surfactants in the amounts specified there:

15-99 »preferably 35 - 90 wt -.% Sulfonates and / or sulfates having preferably 8 - 18 carbon atoms in the hydrophobic radical,

10-60, preferably 10-50 wt .- ^ nonionics, 1 - 60, preferably J5 - 50 wt .- ^ Ortho-, Pyro- or Polyphosphoric acid partial esters

and optionally one or more of the following

Substances:

5-70, preferably 10 - 60 wt .- ^ soap, 0 - 10, preferably 0.5-8 wt -.% Foam stabilizers,
0 - 10, preferably 0.5 - 8 wt .- ^ not tensld-

like foam inhibitors,

but the foaming capacity of the surfactant component is either due to the simultaneous presence of different, the foaming power of mutually reducing surfactants and / or foam-suppressing soap and / or non-surfactant foam inhibitors is reduced ./,,'^

209826/1012

Henkel & Cie GmbH S »» * -7 to Palenlanitulduna D M-IDU

_{Among the preferably inorganic per-compounds which supply HgO 2} in aqueous solution, sodium perborate tetrahydrate (NaBOp. HpOp. 3 HpO) is of particular practical importance. In its place you can partially or completely, ie up to the NaBOp. HpO ₂ dehydrated perborates can be used. They are also the NaBOp borates described in DBP 901 287 and USP 2,491,789. HpOp useful in which the ratio Na ₂ O: B ₂ O- is less than 0.5 '· 1 and preferably in the range of 0.4-0.15' · 1, while the ratio HpO ₂ : Na in falls within the range of 0.5-4: 1. All these perborates may be fully or partially by other inorganic perverted (bonds, in particular by peroxohydrates be replaced, such as the peroxohydrates the ortho, pyro or polyphosphates, especially the Tripolyphosphates, and carbonates.

It is recommended that in the products for stabilizing the peroxy customary water-soluble or water-insoluble and or stabilizers in amounts of 0.25 - incorporate% - 10 wt.. As water-insoluble perstabilizers, which make up, for example, 1-8, preferably 2-7 % of the weight of the entire preparation. make, the magnesium silicates usually obtained by precipitation from aqueous solutions, MgO: SiOp = 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1, are suitable. g Other alkaline earth metal, cadmium or tin silicates of the appropriate composition can be used instead. As . Water-soluble stabilizers are the already mentioned complexing agents for copper./4.

- 10 -

209826/1012

: <4 Cie GmbH * ;. 10 ™ p _a i ^ < _an mn ^ ₃ ο 4160

The activators to be used according to the invention should as defined above, have an activation value of at least 3, preferably of at least 4.5. This Activation value (= titer) is determined as follows: '

Solutions containing 0.615 g / l NaBO ₂ . H ₃ O ₂ . 3 H ₂ O (4 ml / l) land 2.5 g / l Na / PpOr,. 10 H ₂ O contain, after heating to 60 ° C., 4 millimoles / l of activator are added and the mixture is kept at the specified temperature for 5 minutes with 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. Under the stated test conditions, a 100% activation of the peroxide used consumes 8.0 ml of thiosulfate solution, ie the titer is 8.0. However, this maximum value is not always reached; good activators have a titre of at least 4.5 and preferably from 5 to 7.

Activators of the N-acyl or O-acyl compound type contain an acyl radical R-CO-, in which R represents optionally substituted hydrocarbon radicals with 1-8 carbon atoms. Are the radicals R of aliphatic nature, they preferably have 1-3 carbon atoms; If they are aromatic residues, they can contain up to 8 carbon atoms. Accordingly, the following are preferred as radicals R: methyl, ethyl, n or i-propyl, phenyl, toluyl or xylyl radicals. As substituents there are Cj, alkoxyl groups, halogen atoms, nitro or Nitrile groups in question; especially in the area of aromatic radicals are chlorine-substituted and / or nitro-substituted, in particular m-chlorine or m- or p-nitro-substituted Residues R usable./ ;.

- 11 -

209828/1012

Henkel & CIe GmbH

StHt

11

»R F

4160

20S0782

Of the types of activators to be described below, compounds with a melting point of at least 70 ° C., preferably at least 100 ° C. and in particular of at least 150 ° C. are particularly suitable Molecular weight and the number of R-CO- radicals present in the molecule) be at most 170, preferably at most 130 and in particular at most 110 .

The activators which can be used according to the invention include the Connection types listed under a - 1. In the formulas the numbered radicals R have the meaning given above for R j if several radicals R are present in a molecule they can be the same or different.

R ₁₁ -

(D (Ia)

R ₁₂ -CO

-X

-CH ₂ -N

/ ^C0 - ^R 13

CO-R

(Ib) ^
-CH ₂ -CH ₂ -N
^N C

14th

^N CO-R.

(Ic)

-N

N CO-R

a) N-diacylated amines of the formula I, in which X is a radical R or one of the radicals Ia, Ib or Ic is. From the class of these compounds are examples of Ν, Ν, Ν'Ν'-tetraacetyl methylenediamine (F = 92 - 95 ° C) or ethylenediamine, the Ν, Ν-diacetylanlline and the Ν, Ν-diacetyl-p-toluidine too call.//^

- 12 -

209826/1012

Hor.kGl & Cio GmbH

b) N-alkyl-II-rmlXonyl-crr: '. oxamides of the formula "JI, in dor R preferably ₀ ~ a C ₁ - Alfcylrcst means activator cn this.'y.yr>r> are: 3, B. dan M'-ilothyl-ri-i / iosyl-aootylamide (F =, 73 - 79 ° C), the KM ^ etixyl-ri-Tacßyl-benaoyn.nnicl (F = 116 - 118.3 ° C), diio N-KGthyl-N-raoüyl-p-nitrobenzoylamide (F = 159-160 ° C) and the MlI
amide (F = 117-117.5 ° C).

(II)

OC-R ₂₁

co - c - υ

(HI)

X ₃₂ - Il

N - X

32 31

'C

Il

c) N-Acy! hydantoine of Forraol III, in which at least one of the radicals X ^ ₁ and X ^ _{2 represents} a radical R-CO-, while the other also represents a radical R or an optionally esterified !! Can represent carboxyethyl radical; Y -, - or Y ^ ₂ denote hydrogen or alkyl radicals with 1 or 2 carbon atoms. Suitable compounds are, for example, 1,3-diacetyl-5, 5-di-diethyl-hydantoin, 1,3-dipropionyl-hydantoin (melting point 104.5-106 ° C.) and 3-benzoyl-hydantoin-1-acetic acid ethyl ester.

d) Cyclic N-acyl hydrazides of the formula IV, in which the two nitrogen atoms are part of one

5- or 6-membered hetero ring from the vj \ j - cuR / group of Kaleincäurehydrazids, Phthalic acid hydrazide, Triazoles or Urajsols are. Monoacetyl maleic acid hydrazide may be mentioned as an example. j _a

2 0 9826/1012 BATH ORIGINAL

Henkel U CiQ GmbH

S'i · \ J iur Palenlanmsldung D HI 60

(VI)

O-CO-R j 61

R ^ ₀ -CO-OC

⁶² \

C-O-CO-R,

R ₇₁ -CO

X.

(VII)
NO-CO- (CH ₂ ) ^ - R ₇₃

(Vila)

OC-R,

-CO-ON
X

72

e) triacyl cyanurates of the formula VI; e.g. triacetyl or ' Tribenzoyl cyanurates.

f ) Possibly substituted anhydrides of benzoic acid or phthalic acid, in particular benzoic anhydride itself or m-chloro-benzoic anhydride (P = 95 ° C).

g) 0 ", N, N-trisubstituted hydroxylamines of the formula VII, in which R ₇ , a radical R, preferably a methyl or ethyl radical, an optionally substituted aryl radical or the group VIIa, while X ₇₁ or X ₇ ^ is a 4 R-CO-, R- ^ SO ₂ - or one of the aromatic radicals R described above, or each can be linked to the corresponding R ₇₁ or R ₇₂ radical to form a succinyl or phthalyl radical, η denotes an integer from 0 to 2./^

Si «

- 14 ~

209828/1012

BATH ORIGINAL

Henkel & Cie GmbH like this ». 14 »r PoicMonraeidune d 4160

Activators of this type include, for example, 0-benaoyl-N, N-succinyl-hydroxylamine (F = 137-139 ° C), O-acetyl-N.N-guccinyl-hydroxylamine (P = 132 - 134 ° C), O-p-Methoxybenzoyl-NjN-succinyl-hydroxylamine (F = 142 145 C, 0 ~ p-Nitroben3oyl-N, N ~ succinyl ~ hydroxylamine (F = 212 - 215 ° C) and 0, N, N-triacetyl-hydroxylamine.

h) Ν, Ν'-diacyl-sulfurylamides of the formula VIII, in which R _Q1 and Rg-Z are preferably C, »-alkyl radicals or aryl radicals, while Rg ₂ and R _Q ^ are preferably Cj ^ -alkyl radicals, in particular C,., - Mean alkyl radicals. Examples are N, N'-dimethyl-N ^ I'-diacetyl-sulfurylamide (F = 58-60 ° C) and N, N'-diethyl "N, N'-dipropionyl-sulfurylamide (F = 95-97 ° C) .

^R 81 / ^R 83 (VIII) ^ N-SO-N ^X

R ₈₂ -CO

i) 1,3-Diacyl-4,5-diacyloxy-imidazolidines of the formula IX, in which Xg _{0 is} hydrogen or R 2. These include: i ^ -Diformyl ^^ - diacetoxy-iniidazolidine (F = 160 - 165.5 ° C), i ^ -Diacetyl ^^ - diacetoxy-imidazolidine (F = 139 - 140.5 ° C), 1.3 -Diacetyl-4,5-dipropionyloxy-imidazolidine (F = 85 - 07 ° C).

OC-R ™ R, ^ h-CO X

(IX) X ₉₀ -CH

^{) C} ~ ^R 90 ^R 101

, N. . N-CH-N.

-CH-O-CO-R ₉₁ O = CIC = O

(X) N-CH-IT

^{V J} Il

CH-O-CO-R ₉₂ ^R 102 " ^{CO 0C} ~ ^R 103

OC-R ₉₅

k) Acylated glycolurils of the general formula X in which X..Q .. represents one of the radicals R or R-CO, ^ i

209826/1012 - 15 -

BATH ORIGINAL

HenkelÄ Cie GmbH si »15 x» r jO! .Nft> nn. _e idimg ο 416O

Tetraacylated glycolurils are preferably used and especially tetraacetylglycoluril (F = 233 240 C); in addition to this are the following acylated glycolurils suitable: di- (chloroacetyl) ~ diacetyl-glycoluril (F = 267 - 269 ° C), tetrapropionyl-glycoluril (F = 144 - 146 ° C), 1-methyl-3,4,6-triacetylglycoluril (F = 179-180 ° C), Diacotyl-dipropionyl-glycoluril (F = 144 - 146 ° C) and Diacetyl-dibonzoyl-glycoluril (F = 244-249 ° C). the Acylated glycolurils are not only special because of their excellent properties as activators practical importance; Because of their high melting point, they are more storable and powdery for production Products well suited.

It is often sufficient to activate only part of the available active oxygen! for this purpose, activator additives of at least 0.01, preferably of at least 0.05 mol of activator per g atom of active oxygen are sufficient. If the activation of the active oxygen Viert is as extensive as possible, the addition of activator can be increased by up to 4 mol, preferably up to 3 mol. However, it is preferred to use 0.3-2 Kol of activator per g-atom of active oxygen. However, these amounts can be changed according to the activity of the activator used.

The activators can be provided with a shell made of substances inert to the activators; this prevents the activators from coming into contact with the alkaline-reacting builder substances and possibly with the per-compounds, which contributes to the storage stability of the products according to the invention.

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2 0 9826/1012
BATH ORIGINAL

Henkel & Cie GmbH

Page 1 D iur patent application D Μ · J DU

The types of brighteners mentioned in the definition of the invention include the following substances:

4,4'-bis (azolyl) stilbene-2,2 ^l -disulfonic acids of the general formula

Azolyl

Azolyl

where naphtotriazolyl, triazolyl or pyrazolyl radicals of the following structures are present as azole radicals can,

where A is hydrogen or the sulfonic acid radical and R is hydrogen or C ^ c -alkyl radicals,

Stilbyl-naphtotriazoles of the general formula

HC-CH- (Q / - N

R;

where R- is hydrogen or halogen atoms, Rp is the groups -CN, -SO ₅ H, -SO ₂ IiHR (meaning of R, see definition above), R, hydrogen or the sulfonic acid radical.

- 17 -

19828/1012

BATH ORIGINAL

Henkel & Cie GmbH

S «» · 17 for patent application D H-1 60

Bis (benzoxazolyl) derivatives of the general formula

where R ^ denotes the following radicals O- ^{Hc =}

^cit

SX /

and A V / water, C. __, - alkyl or aryl radicals, in particular Denotes phenyl radicals, while X stands for -NH, -S- or -0-,

2-Benzoxazolyl-4,5-naphtothiophene of the general formula

The products according to the invention can also contain combinations of brighteners of the types mentioned above. As far as in the products of this invention by soaking or washing in which the bleach component in accordance with definition of the invention in amounts of 5 - 50, preferably from 10-35 wt -.% Is present, the fluorescent whitening agent of these compositions is preferably in the range of 0.002 - 1.5 ^

- 18 -

■ 209.826 / 1012

Henkel & Cie GmbH s. ». 18 ™ r patent application d 4160

To those known as anti-corrosion agents mentioned above Triazoles or tetrazoles with the group = NMe or = N0Me include, for example, benzotriazole, methylbenzotriazole, 1,2- and 1,8-naphtotriazole, nitrobenzotriazole, tetrazole, 5-amino ~ tetrazole, alkylene-5,5'-ditetrazole, 5-alkylenetetrazole, 5-dialkyl-aminotetrazole and 5-alkyl-4-oxytetrazoles, in which the alkyl or alkylene radicals can contain 1 to 5 carbon atoms.

Triazoles containing an aromatic nucleus such as a benzene or naphthalene nucleus are particularly effective. the end For this reason, the benzotriazole and the naphthotriazoles are preferred for practical use.

The organic complexing agents for heavy metals include the salts of iminotriacetic acid, ethy ^ lendiamine tetraacetic acid, diethylenetriaminopentaacetic acid and amino-tri-ethylidene diphosphonic acid. In their place you can other complexing agents can also be used, provided that their complexing capacity is not essential, especially for copper is below that of the substances mentioned.

The complexing agents mentioned are already recommended as builders for soaking agents, prewash agents and detergents been. Therefore, the amounts used above for these complexing agents only apply in the event that they have not already been used larger amounts of such complexing agents are present as builder substances. / ^

- 19 -

2 0 98 267 10 12

Henkel & Cie GmbH S.ile I 9 to the Patenlenm «Idun _B D 4160

The for the production of the above-mentioned Ortho, Pyro or Polyphosphoric acid partial esters serving fatty alcohols or their Ethoxylation products are essentially the same as those used in the manufacture of other surfactants; in this context, reference is made to the list below of the synthetic surfactants optionally contained in the products according to the invention.

This gives these T _e ilester for example, by direct esterification of the alcohol component with the corresponding acids of phosphorus, with the halogen derivative of phosphorus or with the corresponding Phosphorsäureanhydriden, in particular with (phosphorus pentoxide. In particular, the latter reaction provides a practically useful method of preparation of such esters is In addition to the partial esters of orthophosphoric acid, partial esters of anhydric acids of phosphorus, in particular of pyro- and polyphosphoric acids, are obtained, although the esters of orthophosphoric acid, optionally also the esters of orthophosphoric and pyrophosphoric acid, represent the main product Salts of partial esters of the acids of phosphorus mentioned can contain one or two fatty alcohol radicals bonded like an ester to a phosphorus atom t two alcohol residues per phosphorus atom.

These esters of acids of phosphorus also have surfactant properties and therefore can be used as such in larger amounts than from the viewpoint of the anti-corrosive effect seems necessary -. ^

- 20 -

209826/1012

Henkel & Cie GmbH sosts 20 to patemanmiiduna D 41o0

The products according to the invention can be added to all the manufacture of oxidizing, bleaching, washing auxiliaries and Manufacture detergents using the usual methods. So you can, for example, the individual components in dry, powdery or mix together in a granular state. These mixtures can be granulated or agglomerate by spraying them while agitating with water or with aqueous solutions of substances contained therein. This method is particularly recommended when the mixtures contain anhydrous salts that bind crystallize from water of crystallization.

In all of these processes, it is advisable to have the activators and the per compounds in direct contact in the presence to avoid of water, because then the activator effect already sets in and some of the activators or des Active oxygen is consumed.

This applies above all to the hot drying processes customary in the manufacture of detergents and detergents. Usually only those constituents are incorporated into the aqueous, hot-dried mixture which are not changed by water and / or heat, in order then to mix the other constituents into the prepowder obtained in this way. For the effect of the combination according to the invention, it is irrelevant in which partial powder the individual constituents are present. For example, the anti-corrosion agents of the phosphoric acid ester type, optionally ethoxylated fatty alcohols, and the complexing agents, together with the other components of the product, in particular the washing aid or detergent, can be processed into an aqueous batch and then incorporated into a conventional method, preferably by hot drying Transfer powder. This powder is then used with the other moisture and / or a / ^

- 21 -

209826/1012 BAD ORJGfNAL

Henkel & Cie GmbH s «u« 21 for puttntanm «idung d 410

heat-sensitive ingredients mixed, in particular the activator, the per compound and possibly other, Components to be incorporated separately for the same reasons, such as enzymes.

The following is a list of the other constituents present in the products according to the invention, in particular in the washing auxiliaries and detergents according to the invention, such as surfactants, structural substances, dirt carriers, enzymes, etc.

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2 0 9826/1012 BAD

Henkel & Cie GmbH . Page 22 for Poland registration D 416O

The anionic, zwitterionic or nonionic surfactants contain at least one hydrophobic radical in the molecule of mostly 8-26, preferably 10-22 and in particular 10-18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated hydrophobic residue is usually more aliphatic, possibly also of an alicyclic nature; it can work with the water-soluble groups directly or via intermediate links be connected. As intermediate links come z. B. benzene rings, carboxylic acid ester or carbonamide groups, ethereal or residues of polyhydric alcohols bonded like esters, such as. B. that of ethylene glycol, propylene glycol, des Glycerine or corresponding polyether residues are possible.

The hydrophobic group is preferably an aliphatic hydrocarbon group with about 10-18, preferably 12-18, carbon atoms, but depending on the nature of the respective surfactant Deviations from this preferred range of numbers are possible.

Soaps made from natural or synthetic fatty acids, possibly also from resinous or synthetic fatty acids, are anionic active washing substances Naphthenic acids can be used, 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 sulfates of particular practical importance.

15, in particular 10 - - to the sulfonates such as the alkyl aryl sulphonates, especially the alkyl benzene sulfonates used, inter alia from vorzugsv / else ^ eradkcttigen al.LpIiatischen hydrocarbons having 9 includes I ^ C-atoms by chlorination and Alkyliercn from benzene or from corresponding terminal or inner wall olefins obtained by alkylating benzene and gulfonating the resulting alkylbenzenes. Furthermore bind aliphatic ^ sulfonates from Interecse, as they ^

209826/1012 - 23 -

BATH ORIGINAL

9 Π β Π 7 CO

Honker & de GmbH ropes 23 to rofentonmeldur.g D 4160

ζ. B. from preferably saturated, 8-18 and preferably 12-18 carbon atoms in the molecule containing hydrocarbons by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and conversion of the products obtained in the sulfonates are accessible. As aliphatic sulfonates alkene sulfonates, Hydroxyalkansülfonate and disulfonate-containing mixtures are also useful, which are z. For example, from a terminal or pendent Co _-1 O- and "C preferably _12" - olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of Sulfanierungsprodukte obtained The thus prepared aliphatic sulfonates, the sulfonate group is often at a secondary carbon atom. but you can also use sulfonates with a terminal sulfonate group obtained by reacting terminal olefins with bisulfite.

The sulfonates to be used according to the invention include furthermore salts, preferably dialkali salts, of cC-sulfofatty acids as well as salts of esters of these acids with mono- or polyvalent, 1-4 and preferably 1-2 carbon atoms Alcohols

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or dioxypropanesulfonic acid, the Salts of the fatty alcohol esters of lower aliphatic or aromatic sulfomono- or sulfonate containing 1-8 carbon atoms -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. ,.

209826/1012

BATH ORIGINAL

Honkel & CIe GmbH

J Π R Π 7 R 0

Page 2A- to the patent application D H-160

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular those produced from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Useful sulfonation products of the sulfate type can also be obtained from terminal or internal Co jiQ olefins. This group of surfactants also includes sulfated fatty acid alkylamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (Co_ _{1 (} -alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides, which have 0.5-20, preferably 1-8 and especially 2-4 may contain ethylene and / or propylene glycol * residues. _χ

Suitable anionic surfactants of the carboxylate type are, for. B. 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. B. with Glycocolla, sarcosine or with protein hydrolysates.

■ To the non-ionic surfactants, here for the sake of simplicity Known as "Nonlcnics", products include their water solubility the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups as well as an accumulation of hydroxyl groups in general.

Of particular practical interest are obtained by addition of ethylene oxide and / or glycidol with fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides products available, these nonionics h - 100, preferably 6 - hö and especially 8-20 ether radicals, especially May contain ethylene glycol ether residues per molecule. In addition, propylene or butylene glycolate residues or polyether chains can be present in these polyether chains or at their ends. m-

- 25 -

209826/1012

BATH ORIGINAL

Henkel & Cie GmbH su 25 zur Po., N.anmoid _U n _a ο 4160

The nonionics also include those under the handsl name "Pluronics" or "Tetronics" known products. They are obtained from water-insoluble polypropylene glycols or from water-insoluble ones propoxylated lower, 1-8, preferably 3-6 Aliphatic alcohols containing carbon atoms or from water-insoluble propoxylated A1Icy lend! amines. These water-insoluble Propylene oxide (i.e., hydrophobic) derivatives are ethoxylated converted into the nonionics mentioned until they are water-soluble. Finally, nonionics are also those known as "Ucon-Fluid" known, partly still water-soluble reaction products of the above mentioned aliphatic alcohols with propylene oxide usable.

The nonionics also include fatty acid or sulfonic acid * alkylolamides, see e.g. B. from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g. B-. derive the glycamines. You leave yourself out by amides higher primary or secondary alkyl amines and polyhydroxycarboxylic acids substitute,

The capillary-active amine oxides include, for. B. those of higher tertiary, one hydrophobic alkyl radical and two shorter ones, Products derived from amines containing up to 4 carbon atoms each containing alkyl and / or alkylol radicals.

Zwitterionic surfactants contain both acidic and <| in the molecule also basic hydrophilic groups. The acidic groups include carboxyl, sulfonic acid, sulfuric acid half-ester, phosphonic acid, and Partial phosphoric ester groups. The basic groups are primary, secondary, tertiary and quaternary Ammonium groupings in question. Zwitterionic compounds with quaternary ammonium groups belong to the betaines type.

Carboxy, sulfate, and sulfonate betaines have good properties because of their good properties Compatibility with other surfactants of particular practical interest. Suitable sulfobetaines are obtained, for example by reacting tertiary amines containing at least one hydrophobic alkyl radical with sultones, for example Propane or butane sultone, corresponding Carboxybetalne receives ^

209826/1012 -26-

BAD ORIGINAL , '<* <:

Henkel & CiQ GmbH page 26 for Poland registration D A-I 60

by reacting the tertiary amines mentioned with chloroacetic acid, their salts or with chloroacetic acid esters and cleavage of the ester bond.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants, as can it can be changed by adding non-surfactant organic substances.

Particularly suitable foam stabilizers for surfactants * of the sulfonate or sulfate type are 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.

Products with reduced foaming power are primarily intended for use in washing machines and dishwashers, with limited foam dampening sometimes being sufficient, while in other cases more foam dampening may be desirable. Of particular practical importance are products that are still foaming in the medium temperature range up to about 65 ⁰ C, but with the transition to higher temperatures (70 to 100 ⁰ C) import ^ mer produce less foam.

A reduced foaming power is often obtained with combinations of different types of surfactants, in particular with combinations of synthetic anionic surfactants, especially of (1) sulfates and / or sulfonates or of (2) nonionics on the one hand and (3) soaps on the other. In the case of combinations of components (1) and (2) or (1), (2) and (j>), the foaming behavior can be influenced by the soaps used: in soaps preferably made from saturated fatty acids with 12-18 carbon atoms the foam attenuation is lower, while soaps made from saturated fatty acid mixtures with 20 - ^

- 27 -

209826/1012 ORIGINAL BATHROOM

Honkel &. Cte GmbH

Soap.

27 χ

at POOH * »

4160

26, preferably 20-22 carbon atoms, the amount of which can make up 5-10% by weight of the total soap content present in the surfactant combination, achieves greater foam suppression, especially in the higher temperature range.

The skin ability of the surfactants can also be increased by additives known, non-surfactant foam inhibitors reduce. These include optionally chlorine-containing N-alkylated aminotriazines, which are obtained by reacting 1 mol of cyanuric acid chloride with 2-3 moles of a mono- and / or dialkylamine with 6-20, preferably 8-18, carbon atoms in the alkyl radical receives. Aminotriazine and melaraine derivatives have a similar effect, which contain propylene glycol or butylene glycol ether chains, with 10-100 such glycol residues in the molecule could be. Such compounds are obtained, for example, by adding appropriate amounts of propylene and / or Butylene oxide on aminotriazines, in particular on melamine. Preferred For example, the decomposition products of 1 mole of melamine are included at least 20 moles of propylene oxide or at least 10 moles of butylene oxide Usable · Products have proven to be particularly effective that are obtained by adding 5-10 moles of propylene oxide on 1 mole of melamine and further addition of 10-50 moles of butylene oxide to this propylene oxide derivative.

Other, non-surfactant, water-insoluble organic compounds, such as paraffins or haloparaffins with melting points below 10O ⁰ C, aliphatic ^ C ^ g- to C ^ ₀ ketones and aliphatic carboxylic acid esters, which are in the acid or alcohol radical, possibly also in each of these Both residues, containing at least 18 carbon atoms (e.g. triglycerides or fatty acid fatty alcohol esters), can be used as eye inhibitors, especially in combination with anionic synthetic surfactants and soaps.

- 28 -

209828/1012 BATH

28 to PotentoamriJuno D 4 1 60 2060762

Henkel & Cie GmbH Sciio 28 zur Pulenlonrr.eUung D

The non-surfactant foam inhibitors are often only being used fully effective at temperatures at which they are in the liquid state, so that the foam behavior of the products through the choice of suitable foam inhibitors can be controlled in a similar manner as through the choice of soaps made from fatty acids suitable chain lengths.

Combine foam stabilizers with temperature-dependent ones Foam inhibitors are obtained well at low temperatures, and always as the temperature approaches the boiling point weaker foaming products.

Addition products of propylene oxide to the capillary-active polyethylene glycol ethers described above as well as the Pluronic-, Tetronic and Ucon fluid types. ,. ,,

209826/1012
BATH ORIGiMAL

Henkel & Cio GmbH

SJ ₁₅ 29 iur patent application D 41 60 206 07 62

Suitable structural substances are weakly acidic, neutral and alkaline reacting inorganic or organic salts, especially inorganic or organic complexing agents.

According to the invention, weakly acidic, neutral or alkaline Reacting salts are, for example, the bicarbonates, carbonates, borates or silicates of alkalis, furthermore mono-, di- or Trialkali orthophosphates, di- or tetraalkali pyrophosphates, as Complexing agents known metaphosphates, alkali sulfates and the Alkali salts of organic, non-capillary-active, 1 - 8 carbon atoms containing sulfonic acids, carboxylic acids and sulfocarboxylic acids. These include, for example, water-soluble salts of benzene, toluene or xylene sulfonic acid, and water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids as well as the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Furthermore, the water-soluble salts are of higher molecular weight as structural substances Polycarboxylic acids can be used, in particular polymers 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, jJ-butene carboxylic acid, ji-flethyl - ^ - butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, Isobutylene, acrylamide and styrene are useful.

Also suitable as complex-forming structural substances are the metaphosphates with a weakly acidic reaction and the polyphosphates with an alkaline reaction, in particular tripolyphosphate; they can be completely or partially replaced by organic complexing agents, i ^ y

- 30 -

2 0 98 26/1012 BATH

Henkel & Cie GmbH

Since"

iur Potonluiimoldung D

^ t I OU

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 various complexing agents are also used can be. 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 OH

I I I

O = P-C-P = O

1 I I

OH Z OH

R-Nc

X OH

ι ι

c - p = o I I

Y OH

X OH

I I

C-P = O

I I

Y OH

HO X

I I

o = p -σ Ι I

HO Y

• N - R ¹ -

OH

- C

I I

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, 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, amino-tri- (methylenephosphonic acid), methylamino- or ethylamino- di- (methylenephosphonic acid) and ethylenediamine-tetra- (methylenephosphonic acid). All of these complexing agents can be present as free acids, preferably as alkali salts

- 31 -

209 8 26/1012

BATH ORIGINAL

Henkel & CIe GmbH ropes 31 for Palent registration D H-1 60

The preparations according to the invention can also contain dirt carriers which have become detached from the fiber Keep dirt suspended in the liquor and prevent it from turning gray. For this purpose, water-soluble colloids are usually more organic Naturally suitable, 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 acid sulfuric acid esters of cellulose or starch. Also containing water-soluble acidic groups Polyamides are suitable for this purpose. Furthermore, soluble starch preparations and other than the above use the starch products mentioned, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

The constituents of the laundry detergents and auxiliary agents according to the invention, in particular the skeleton subs dance, are usually selected so that the preparations react neutrally to clearly alkaline, so that the pH value of a 1 solution of the preparation is usually in the range of 7-12. Detergents for mild detergents · mostly have a neutral to slightly alkaline reaction | (pH value = 7 - 9, b), while canning, prewash and cooking detergents are more alkaline (pH value = 9 * 5 ~ 12, preferably ^, 5 - 10.5). It has already been recommended to incorporate strongly alkaline salts, such as alkali metal carbonates, in order to either completely bind the acid formed during the action of the activators or to buffer it to such an extent that the pH does not drop below the desired value will.

- 32 -

209826/10 12 ORIGINAL BATHROOM

2 O 6 O 7 ß

Henkel & CIO GmbH S «i! E 32 rur Pofcntanmciciung D 4160

The enzymes to be used are usually a mixture of different enzymatic active ingredients. Depending on their effect, they are called proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases. Of particular interest are the enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis and Streptomyces griseus, in particular proteases or amylases. From Bacillus subtilis obtained preparations loading ^ i sit opposite each other has the advantage that up to 70 ⁰ C / irksam are compared with alkali compounds and anionic detersive active ingredients and relatively stable even at temperatures v.

Manufacturers usually supply enzyme preparations as aqueous solutions of the active ingredients or with the addition of diluents marketed as a powder. Sodium sulphate, sodium chloride, Alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. In many cases, the still moist enzyme preparations are combined with calcined salts, which may then be used. while the particles present agglomerate to form larger P particles, the water of crystallization present and the enzymatic ones Bind active substance.

If the enzymatic active ingredients are in the form of a dry powder, liquid, pasty and possibly also solid, nonionic, preferably capillary-active, organic pre-bonds, in particular Use the nonionics described above to add the enzymes to the powder of the detergent or auxiliary laundry detergent

- 33 -

2090 2G / 1Ü12 BATH ORIGINAL

Henkel & CIÖ GmbH S «il» 33 i »r Polentannnltlune D 4160

tie. For this purpose, a mixture of the respective product and the enzymatic agent is preferably sprayed Active ingredient with the above-mentioned non-ionic substances, or the enzyme preparation is dispersed in the nonionic substance mentioned and this dispersion is combined with it the other components of the product. If these rest Solids can also be part of the product the dispersion of the enzymatic active ingredients in the nonionic component on the other solid constituents spray on. The enzymes can also be used as granules or as cold-atomized products can be incorporated. Such enzyme preparations are enveloped and so too fast in front of you Loss of activity protected. '

The enzymes, or combinations of enzymes with different effects, are generally used in amounts that the finished products have protease activities of 50-5,000, preferably 100-2,500 IiVE / g and / or amylase activities from 20-5,000, preferably from 50-2,000 SKBE / g and / or lipase activities from 2-1,000, preferably 5-500 IU / g exhibit.

These details about the enzyme activities result from the activities of those enzyme preparations which on the day of registration for use in detergent area I

appear justifiable from an economic point of view. From a chemical-technical point of view, the enzyme activities of the preparations can be increased as required so that the activities with proteases and amylases e.g. up to 5 times, with lipases e.g. up to 10 times the above specified maximum values can be increased. Therefore, preparations with high activities should be available in the future which also appear to be suitable from an economic point of view for use in the detergent sector, so can the enzyme activities can be increased as required. ^

- 34 20 9 826/1012

t I>

Henkel & de GmbH s »», 34 _w w. «..« m .. | D * HbU

Regarding the determination of the enzyme activities, see the following references are referenced:

Determination of the activity of proteases according to Löhlein-Volhard:

A. Künzel: "Gerbereiehemisches Taschenbuch", 6th edition, Dresden and ¹ Leipzig 1955;

Determination of the activity of amylases: "J. Wohlgemuth:" Biochemische Zeitschrift ", * Volume 9, (1908), pages 1-9, as well as

RM Sandstedt, E. Kheen, and MJ Blish t

"Cereal Chemistry ¹¹ , Volume 16 (1939), pages 712-723;

Determination of the activity of the lipases: R. Willstätter, E. Waldschraidt - Leitz and Pr. Memmen: "Hoppe-Seyler ¹ S magazine for physiological chemistry", Volume 125 (1923), pages 110-117;

R. Boissonas: "Helvetica Chimlca Acta", Volume 31 (19 ^ 8), pages 1571-1576. ψ

The products according to the invention can also contain antimicrobial substances; as such, the 2-hydroxy-2 ^l , 4,4 ^f -trichloro-diphenyl ether has proven itself. ^

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20382S71012

Day

'ienkel A CIe GmbH $. ». 35 «r« itin «> iMM.n · ο 4160

Examples

The following examples describe compositions of some preparations according to the invention. The salty ones it contains Components - salt-like surfactants, other organic salts and inorganic salts - are present as sodium salts, unless expressly stated otherwise. The related terms and abbreviations mean:

"ABS" the salt of a straight-chain condensation Olefins with benzene and sulfonating the resulting Alkylbenzenes obtained alkylbenzenesulfonic acid with 10-15, preferably 11-13 carbon atoms in the alkyl chain,

"Alkanesulfonate" consists of paraffins with 12-16 carbon atoms sulfonate obtained by way of sulfonation,

"HPK-SuIfonat" or "HT-SuIfonat" those from the methyl esters a hardened palm kernel or a hardened tallow fatty acid obtained by sulfonating with SO, αί_ permanent Sulfonates,

"Olefin sulfonate" is a sulfonate obtained from olefin mixtures with 12-18 carbon atoms by sulfonating with SO2 and hydrolyzing the sulfonation product with lye, which consists essentially of alkene sulfonate and oxyalkane sulfonate, but also contains small amounts of disulfonates. There are products useful, the constant of ~ οί or produced from internal olefins · // "

- 36 -

209826/1012
BAD ORl (SfNAt.

& CiG GmbH S ₁ -. 36 »ir Prlenranm.ldimg O 4160

"ΚΑ-sulfate" or "TA-sulfate" are the salts of sulfated, by reducing coconut fatty acid or tallow fatty acid, essentially saturated fatty alcohols,

"KA-ÄO-Sulphate" the sulphated addition product of 2 moles of ethylene oxide in 1 mole of fatty alcohol,

"KA-ÄO-Phosphat" or "TA-ÄO-Phosphat" the orthophosphorus * acid monoesters of ethoxylated coconut or tallow alcohols; if these surfactants are diethanolamine or triethanolamine salts have been used, the percentages in the table are marked with a (D) or (T),

¹¹ OA + 10 ÄO "," KA + 20 ÄO "or" Fs-amide + 8 AO "the addition products of ethylene oxide (ÄO) with technical oleyl alcohol (OA) or coconut alcohol (KA) or coconut fatty acid amide, where the numbers denote the molar amounts of ethylene oxide added to 1 mole of the starting compound,

"KA + 9 ÄO + 12 PO" is a nonionic obtained by reacting 1 mole of "KA + 9 ÄO" with 12 moles of propylene oxide,

"Carboxybetain" or /. "Sulfobetaine" is obtained by reacting 1 mole of cocoalkyldimethylamine with 1 mole of chloroacetic acid or betaines obtained with 1 mole of propanesulfone,

"CMC" the salt of carboxymethyl cellulose,

"NTA", "EDTA", "DETP", "HEDP" and "ATMP" are the salts of the Nitrilotriacetic acid, ethylenediarn: nletraacetic acid, diethylenetriamine pntaacetic acid, Iydroxyethane diphosphonic acid or aminotrimethylene phosphomic acid, / ^

- Yl ~

-09Ü2Ö / 1Q12 ORIGINAL BATHROOM

Henkel & Cie GmbH page 37 2Ur patent application D 41 60

"Perborate" sodium perborate monohydrate of the approximate Composition NaBOp.HpO or sodium perborate tetrahydrate the approximate composition NaBOp.HpOp.3 HgO, where the former is denoted by a (m) and the latter by a (t) after the quantity,

"TAGU" the tetraacetylglycoluril.

The composition of the fatty acid mixtures that make up the soaps -B, C, and D are from the table below refer to. The table also contains the composition of the fatty acid mixture in a soap G. If you replace the soaps B, C and D mentioned in the examples by the same Amount of soap G, so the foaming power of this Viaschmitteis be significantly stronger than the corresponding Viaschmitteis with the soap C, but slightly less than the corresponding Viaschmitteis with the soap B. ^

- 38 -

^ 098 267
BATH-

Henkel & Cie GmbH

5 «il» * 8 iur Potenl'jnn * ldun9 D H-I 60

Composition of the fatty acid mixtures corresponding to the soaps

Weight% fatty acid component in the soap

C number of
fatty acid B. C. D. G _: <= c ₁₀ CVJ 2 4th 1 C ₁₂ 19th 21 16 6 ' ^C 14. 8th 6th 10 5 ^C 16 4th 16 25th 28 ^C 18 22nd 33 45 60 ^C 20 8th 4th - - ^C 22 37 18th - - JZ of the fat
sour cream 4th 8th 6th 4th

The foam inhibitor used was a mixture of about 45 % of a di (alkylamino) monochlorotria3ine and about 55 % of an NN ¹ -N "~ trialkylmelamine. In all of these triazine derivatives, the alkyl radicals were a mixture of homologues with 8-18 carbon atoms A similar success could also be achieved; Honochlorotriazine derivative or trialkylmelamine.If the products described contained synthetic sulfates or sulfonates together with soap, the other non-surfactant foam inhibitors mentioned in the description could be used, such as, for example, paraffin oil or paraffin During the preparation of the preparations, the foam inhibitor used is dissolved in a suitable organic solvent ^ ..- dissolves odor in ^ /, u:; tiv'iid by means of a nozzle aiii 'the agitated idiLvo iVciparufc - sprayed on ^.: \ _T

- '59 -

BATH ORIGINAL

Henkel & Cie GmbH

Sail · Jj iur Palenlannnldune D Η-Ί DO

The products described in the examples contained the following brighteners:

Brightener I:

Sodium salt of 4,4, ^f -Bis- (4-phenyl-vic-triazol-2-yl-) stilbene-S ^ '- disulfonic acid of the structure

N-

HC-CH- / O / -N

0, Na SO ₃ Na

Brightener II:

Sodium salt of 4- (4,5-naphtotriazol-2-yl-) stilbene-2

sulfonic acid

-HC = ^ CH

SO ₃ Na

Brightener III:

2,5-bis (benzoxazol-2-yl) thiophene

Brighteners _IV:;

1,2-bis (5-methylbenzoxazol-2-yl) ethylene

H ₅ C

-N,

2Q982671012? BAD ORfGINAU

Henkel & Cie GmbH Since MO to Pot «nlanm« ldun _e D 41 60

Brightener V:

2-benzoxazolyl-4,5-naphtothiophene

The composition of some bleaches according to the invention, which are preferably used as bleaching components in the textile industry or in commercial laundries, can be found in the following examples B1-B10.

component
of
Preparation Weight
B1 .-i> Bestar
B2 id part at
example
B3 preparation
B4 after
B5 Perborate 4i, 0 (t) 36.1 (t) 4i, 0 (m) 42.6 (m) 38.1 (m) TAGU 23.0 19.7 21.3 43.5 16.5 KA -KO phosphate 5.8 TA-ÄO-Phosphate 12.0 EDTA 2.0 2.9 0.2 ATMP 1.6 Benzotriazole 0.1 Na ₄ P ₂ O ₇ 23.1 21.4 Na ₂ CO ₃ 33.2 12.6 34.6 13.4 11.8 Brightener I 0.8 Brightener II 1.0 Brightener III 0.2 Brightener IV 0.3 Brightener V 0.2

- 41 -

209826/1012 ORIGINAL BATHROOM

Henkel & Cie GmbH

Sa,

iite H-Ί for patent application

g D

component
of
1 preparation B6 Weight B7 Bests indteil be:
Ex
B8 , 0 (m) Lm preparation
al
B9 it after
B10 Perborate 43 * 5 (t) 44 , 8cm) 38 ,8th 47.1 (m) 32.2 (m) TAGU 23 , 3 46 , 3 22nd 10.1 24.8 KA-SO phosphate , 7 23.6 (T) 3.5 (D) EDTA 0 DETPA 0 , 5 Methylbenzene
triazole , 7 0.7 1,8-naphtho-
triazole 0 ,8th Na ₄ P ₂ O ₇ 10, 45 11.8 4.5 Na ₂ CO 32, 5 7, 45 26, 4th 6.15 34.0 Brightener I 0, 6th O, 0.7 Brightener II 0, 8th 0.5 Brightener III 0, 1 0.2 Brightener IV 0, 05 15th Brightener V 0, 1 0, 0.05 0.1

The composition of some detergents according to the invention is can be found in the examples W1 .- W10. ^

- 42 - '

20982.6 / 1012

Henkel & Cie GmbH

Rope » HrC. for patent application D 4 1 OU

component Weight % Part of I. , 0 ¥ 3 Preparation according to the example ¥ 5 of the preparation ¥ 1 ¥ 2 IN THE 4.9 W4 _ SECTION 6.1 , 2 1.2 5.1 - HPK sulfonate - - - Olefin sulfonate - 3.1 1.5 - Soap B 3.6 , 0 - _ Soap D - - 4.1 _ KA-SO phosphate - 4th - 5.0 TA-KO phosphate - , 5 1.9 - - OA + 10 AO 2.0 1 , 5 - _ 7.0 KA + 20 KO - , 2 _ KA + 9 KO + , 3 6.6 12 PO - 2 - _ Fs-amide + 8 KO _ - 3.1 - Foam inhibitor - 38.5 0.2 40.2 Na ₅ P ₅ O ₁₀ 31.0 36 1 4.8 30.2 4.5 Na ₂ O.3,3SiO ₂ 5.4 1 0 8.2 2.9 5.0 Na ₂ CO ₃ 14.4 14th 4th 3.4 18.7 Well-SO ,. 0.3 0 0 « - 0.5 - NTA - 7th 0.5 - - EDTA 0.2 1 - 0.1 HEDP - - - _ ATMP - 1, 3 0.3 - 1.5 CMC 0.6 1. 2.2 0.5 1.0 MgSiO 1.1 2, 08 17.4 (m) 1.0 16.0 (π) Perborate 21.4 (t) 25, 9.0 16.3 (m) 0.7 TAGU 11.8 7, - 15.0 Benzotriazole - 0, 0.3 - 0.2 Brightener I 0.2 - - __ Brightener II - 0, - 0.20 0.05 Brightener III - - 0.15 - Brightener IV - 0, 0.1 - 0.08 Brightener V- -. ■ M _ Remainder V / ater

- 43 -

209826/1012

Henkel & Cie GmbH

- «> 4160

Part of the preparation

Wt .- ^ component of the preparation according to example W6 Wl \ tQ W9 V10

SECTION

Alkanesulfonate HT-sulfonate KA-SuIf at TA-Sulphate

5.3

1.4
0.5

5.0

1.2 0.3

5.0

KA-EO sulfate - - - 1.5 5.0 6th * mm *. 2 • 6 (m) Soap C 7.6 - - - _ 1 14th , 2 6th KA-ΆΌ phosphate - 0.35 - - 7.0 2 0 > 5 OA + 10 AO 5.0 - - - _ • ι , 5 KA + 9 ÄO + 0.16 • 12 PO 1.8 - - - - _ MM 25th Carboxy betaine - - 0.5 _ em • a SuIfobetain 0.7 _ 0.6 0 em ■■ · 009 Foam inhibitor - 0.5 0.5 0.6 36 0, , 4 Na ₅ P ₃ O ₁₀ - 32.6 34.2 41.1 mm ,1 03 Na ₀ O.>, 3 SiO « 5.5 3.4 4.0 4.5 15, Na ₂ CO ₅ 14.8 " 16.2 - - 15, "1 Na ₂ SO ₄ 0.4 0.2 2.5 - mm , 4 CMG - 1.6 1.3 1.7 , 0 NTA 15.0 - 15.0 _ «Μ m EDTA - --- 0.2 ο, m DETP - 0.2 - m HEDP 14.0 4.0 7.0 9.0 ο, m ATMP - - _ _ MgSiO ₅ - 2.5 2.0 - 0, Perborate 19.0 (t) 14.0 Od] > 10.0 (m) 14.0 (m) TAGU 10.2 14.0 6.0 3.0 Methylbenzotriazole - - - 0.2 1,8-naphthotri- aaol - 0.2 Brightener I 0.31 - - Brightener II - - 0.29 Brightener IH 0.12 - - Brightener IW - Brightener V - 0.13 Rest water

209826/1012

-44

Henkel & Cie GmbH Rope 44 iur Pctentnnmaldung D 4 1 60

You wash or bleach textiles made of cotton or folyaiiiid using the bleaching agent or detergent described in the examples, one also achieves below the boiling temperature an excellent degree of whiteness, which is the prerequisite for a satisfactory effect of the brighteners. Included v / the brighteners to be used according to the invention are not damaged, although there is damage to other types of brightener can be determined by per compounds and activators. This advantage of the products according to the invention is particularly important observe if there are traces of heavy metal in the liquor and / or if the liquors a certain time before the addition of the to be treated Textile goods are set. The advantages described are also available when the pH value is affected by the The carboxylic acid formed in the activator decreases somewhat. But since there is no drop in the pH value, especially with white laundry estimates, the products according to the invention can contain the alkaline-reacting intended to scavenge the carboxylic acids formed Contain salts.

If the tetraacetylglycoluril contained in the agents of Examples B1-B10 and W1-W10 is replaced by the corresponding one Amounts of tetrapropionylglycoluril, methyl-triacetylglycoluril, diacetyl-dibenzoyl-glycoluril, diacetylaniline, Diacetyl toluidine, diacetyl dimethyl hydantoin, tetraacetyl methylenediamine or tetraacetyl-ethylenediamine, one comes to similar results, but the perborate is by the acylated glycolurils are better activated than by the other activators.

The products according to the above examples B1-B10 and W1-W10 partly contain insufficient amounts of activator, ie not all of the active oxygen contained in the perborate is activated. Working with such preparations is advantageous if you want to use the action of the activators at low temperatures in order to continue the bleaching at higher temperatures with the active oxygen still present. With such a procedure, the amount of activator can, for example, be up to 5 % of the amount of the active oxygen carrier present., ^ 20982G / 1O1?

Claims (1)

Godfather tansp rüche 1. Means for the production of cold bleaching liquors, in particular of cold bleaching detergents, consisting essentially of the end: - 100, preferably 5-90% by weight of a bleaching coraponent. consisting of ί a) from 99.99 to 95, preferably \ / ice 99.98 -.!% a-providing in aqueous solution HNO ^ percompound and an activator for serving as HgO ^ N-acyl or 0-Acy compound - 97.5 wt which has an activation value determined by the test method described above for the per compounds of at least 3, preferably of at least 4.5, the per compound and the activator being present in such amounts that per g-atom of active oxygen at least 0.01 and at most 4, preferably at least 0.05 and at most 2 mol of activator are present, b) 0.01-5, preferably 0.02-2.5% by weight at least a brightener of the following types: 4,4'-bis (azolyl) stilbene-2,2'-disulfonic acids, Stilbyl naphtotriazoles, bis (benzoxazolyl) derivatives and / or 2-benzoxazolyl-4,5-naphtothiophene compounds, where the abovementioned brighteners, insofar as they are acids, in particular sulfonic acids, also in the form of their Salts may be present, - 0, preferably 95-10 wt .-? <> other common ingredients of bleaching agents or bleaching detergents. ^ - 46 - 209826 / 10-2 Henkel & Cie GmbH Page M-O for patent application D 4160 - 0, preferably 95-10 wt .- ^ other common ingredients of bleaching agents or bleaching detergents. 2. Means according to claim 1, characterized by a content at - 5, preferably 0.1-2 wt .- ^ corrosion inhibitors of the triazole and / or tetrazole type which contain a group = MMe or = N0Me, in which Me represents a metal or a hydrogen atom which can be replaced by metal, and / or - 20, preferably 1 to 10 wt .- ^ corrosion inhibitors of the type of salts of partial esters from fatty alcohols with 10-22, preferably 16-18, carbon atoms or their 1 - 10, preferably 1-4 glycol ether groups in the molecule containing ethoxylation and / or Propoxylation products with ortho-, pyro- or polyphosphoric acid, and / or - 10, preferably 0.1-7 wt .- ^ organic complexing agents for heavy metals, ~ *>. Agents according to Claims 1 and 2, characterized in that they contain acylated glycolurils of the general formula as activators N-CH-N C = O N-CH-N
R ₁₀₂ -CO OC , wherein R ₁₀₁ j ^r io2 ^{and R} 103 * ^GSF substituted hydrocarbon radicals having 1-8, preferably with 1-3 C-atoms and X is one of the ₁₀₁ R _e R ste-jq-j * ^R 1O2 ° ^ ^he ^ 103 or R ₁ ^ -CO represent. i, 105 / ViV- - 47 209828/1012 BATH ORIGINAL & C ie GmbH Sail «4? to FolenlaninelAiilg D 41 60 4. Means according to claim 1 - 3 »that the compounds as an activator Tetraacetylglycoluril, tetrapropionylglycoluril, methyltriacetylglycoluril or diacetyl-dibenzoyl-glycoluril be used. 5. Means according to claim 1-4, consisting essentially of 5 - 90, preferably 10 - 70% by weight of the above-described, bleaching component consisting of per compound, activator and brightener, 0-25 »preferably 0.1-20% by weight of the corrosion inhibitors and complexing agents for heavy metals according to claim 2, 95-10, preferably 89.9-10 wt .- ^ in detergents and washing auxiliaries Customary, neutrally, preferably alkaline-reacting builder substances and optionally Surfactants, such amounts of alkali salts of weak acids being present that the at least a quarter of the acyl groups contained in the activators are bound in the form of salts can be. 6 «Preferred as soaking, prewash and laundry detergent using products according to patent claims 1-5, characterized in that the amount of per compounds and activators makes up a total of 3 - 50, preferably 10-35% by weight. 7. Products to be used preferably as soaking agents according to Claim 6, characterized in that they contain Q - 5% by weight of surfactants including any existing ortho-, pyro- or polyphosphoric acid esters, y, ^ - 48 - 209826/1012 Henkel & Cie GmbH S «it · 48 iur Potentanm» ldung D 4160 4-5 % by weight, preferably 90-60% by weight, preferably alkaline-reacting builder substances as well as possibly non-surfactant-like corrosion protection agents and / or optionally present complexing agents for heavy metals according to claim 2,
5-50% by weight, preferably 10-35% by weight of the bleaching components Component according to claim 1 as well as detergent ingredients that are usually to be used in smaller quantities, e.g. antimicrobial agents Substances, dirt carriers, brighteners, enzymes, etc. P 8. Preferred as Yorwasch- and detergent to be used products according to claim 6, characterized in that they contain 5-40 % by weight, preferably 7-30% by weight, of a surfactant component component containing at least one surfactant of the sulfonate, sulfate, soap type, Nonionics and / or the ortho-, pyro- or polyphosphoric acid partial esters and optionally one or more of the following substances: 0-10, preferably 0.5-8% by weight foam stabilizers,
% Not - 0-10, preferably 0.5-8 wt. surfactant-like foam inhibitors, 10-90% by weight, preferably 30-55% by weight, of complexing agents and / or non-complexing structural substances including those for binding the Alkali salts of weak acids, determined by the acids released by the activator effect including any complexing agents present for heavy metal ^, v / obei at least some of these structural substances, - 49 2 0 9826/1012 BATH ORIGINAL Henkel & Cie GmbH s »u» ^ S to the Pat.nionm.idune d A-160 Preferably the predominant amount reacts alkaline with the amount of the alkaline to neutrally reacting builder substances, preferably 0.5 to 7 times and in particular makes up 1 to 5 times the total surfactant combination, - 50% by weight, preferably 10 - 35% by weight of the bleaching component according to claim 1, - 20% by weight, preferably 2-15% by weight, of other detergents medium ingredients, such as fabric softeners, Corrosion inhibitors, antimicrobial substances, dirt carriers, brighteners, enzymes, Perfume, dyes, water. 9. Products according to patent claims 6 and 8 which can preferably be used as machine detergents, characterized by a content of 7-30% by weight of a surfactant component which usually contains at least one of the following three types of surfactant in the amounts specified there 15-99% by weight, preferably 35-90% by weight sulfonates and / or sulfates with preferably 8 -. 18 carbon atoms in the hydrophobic residue, - 60% by weight , preferably 10 - 50 % by weight nonionics, - 60% by weight, preferably 3 - 50% by weight ortho-, pyro- or polyphosphoric acid partial esters and, if applicable, one or more of the following substances: 5-70 -.%, Preferably 10 - 60 wt .-% soap, 0-10 wt .-%, preferably 0.5-8 wt .-% foam stabilizers,
0-10% by weight, preferably 0.5-8% by weight non-surfactant like foam inhibitors, but the foaming power of the surfactant component is either due to the simultaneous presence of different, the foaming power Mutually reducing surfactants and / or foam-suppressing soap and / or non-surfactant-like foam inhibitors is decreased. 2 0 9826/10 12 "50 ^ Henkel & Cie GmbH Soite 50 iur Polentanmsldung D H-160 10. To be used as soaking, prewash or yi detergent Products according to claim 6-9, characterized in that they contain 0.002-1.5% by weight of the brighteners according to claim 1 included. ^ ι
ι 209826/1012