DE1594864A1 - Process for bleaching and optionally washing textiles and means for carrying out the process - Google Patents

Description

"Process for bleaching and, if necessary, washing textiles / and means for carrying out the process"

Aqueous solutions containing perborates and perborates 31 Calibrating agents or detergents have long been used for bleaching purposes, but above all for simultaneous use Washing and bleaching of textiles related. However, the active oxygen only becomes active at temperatures above 70 ° C and preferably in the range of 80-100 ° C so effective that the bleaching is successful Only use on temperature-insensitive textiles.

PerborathaXtige bleaching - and detergents are used in many cases also for ^ir femperaturempfindliche Textillen, the washed at temperatures of at most 60 ° C. may be. As a result of the low level of active oxygen ♦ development of the perborate at these temperatures, by far the largest part of the active oxygen remains unused in the washing liquors in such cases.

109820 / 19U

There are numerous suggestions in the literature., the active oxygen by adding inorganic or organic catalysts To make activators effective at temperatures below 70 ° C, but these suggestions have not been able to establish themselves in practice.

It is also known to use aqueous solutions of monopersulfates for such purposes, which have an oxidizing effect even at lower temperatures. However, monopersulfate is after References to the literature should not be regarded as an outright bleaching agent with which one can obtain the highest degree of whiteness can achieve, but only as a lightening agent that has a medium degree of whiteness at low temperatures (see K. Dithmar and E. Naujoks: "Melliand Textile Reports" Volume 43 (19Ö2), Page 484, left column, 5th paragraph from the bottom).

U.S. Patent 2,886,534 describes a method for transferring monopersulphates in dry, free-flowing powder, in which an aqueous approach of monopersulfates after the addition of boric acid salts - it can be · perborate * · is atomized. The amounts added

109820/1914 bad owqinai :.

- 3 -A

of boric acid salts are so low that the pH value of the product is below 3.

The English patent specification 1,052,796 describes Oxidizing and cleaning agents which develop gases in aqueous solution, in addition to monopersulphate also contain other per compounds, e.g. * perborate can * These aqueous solutions are primarily used to clean dentures or also for bleaching human hair, wood, melamine ^ '~, molding compounds etc .; they show a vigorous oxygen development that may be desirable in such cleaning agents. With bleach and Washing processes of textiles is quick ·. , ^, Development of gaseous, molecular oxygen - ~ is not wanted because it developed in this way · ■ removes oxygen from the actual bleaching process

- BAD ORiGINAL

109820 / 19U

The invention relates to a process for bleaching textiles by treatment in aqueous liquors containing perborates and monopersulfates. It is characterized in that the liquors containing the usual components of washing and bleaching agents have a pH of 8-11, preferably of. 8.5-10.5 and 0.05-7 g / l, preferably 1.5-3 * 5 g / l, of active oxygen, with 97-50 %, preferably 90-70% of the active oxygen coming from the perborate. '.' To 'Z' ■ aforementioned conventional ingredients of detergents and bleach liquors are especially water-insoluble stabilizers for per compounds, but also etc surfactants, Waschalkälien, complexing agents,. ... .. "The stabilizers are, if any, in Amounts from 0.025 - 10 g / l, preferably 0.7 $ - 7 g / l present

109 820/19 U. ' ^{v / iL}

The invention further relates to solid bleaching, washing and washing auxiliaries ₄ intended for carrying out the claimed method, characterized by a content of.

. a) 5 - 100 weight -% of a bleaching component, comprising:. 1) 80 - 99.5 % of the weight of the component

a of a mixture of perborates and monopersulfates in such amounts that 97-50, preferably 90-70 # of the active oxygen present comes from the perborate, 2) 0.5-20 # by weight of component a of water-insoluble stabilizers for perborate · ■ compounds , """- ^ '"'"■.' - ·· ^:

b) 95-0 wt -.% active oxygen not containing customary, neutral or alkaline reacting constituents "· * share of such agent, said.

1) the type and amount of alkaline reactants Compounds depending on the ratio of perborate: monopersulphate is to be chosen so that liquid aqueous solution. solutions of the entire agent have a pH value in the range of 8-11 and

2) in the case of the presence of sodium perborate tetrahydrate (NaBO, · 4 HgQ), advantageous but also in the presence of perborates with a lower water content, the amount of water in.

BAD ORiQiISLAL

20/1914. ■

soluble stabilizer according to a2 and the amount of any component b together more than that !, Jfold, preferably more than ^ times what is available Make up monopersulfates.

The active oxygen content of such agents is usually in the range from 1 to 7 *, preferably from 1.5 to ² % by weight.

109820 / 19U

Finally, the invention also relates to the practical particularly interesting bleaching detergent; their composition is generally in the range the following recipe!

- 40, preferably 12 - JO wt .- ^ surfactants or Combinations of surfactants consisting of 0-100, preferably 25-65 wt .- ^

Surfactants of the sulfonate and / or * or sulfate type,
O- 100, preferably 5-40% by weight > non-

ionic Terisiden, r 0 - 100, preferably 10 - 50 wt -.% soap, O 6, preferably 0.5 -. 3 wt -.% Foam · *

Stabilizer,
0-8, preferably 0.5 - 5 wt -.% Foam ''.

inhibitor,

- 82, preferably 35 - 75 wt -.% Builder substance, wherein at least a part of this framework substance .... alkaline reaction and the amount of al-- "Kalisz and neutrally reacting Gerustsub * punching preferably 0.5 to 7 times, and in particular makes up 1 to 5 times the total washing active substance,

BAD ORiGiNAL

1 09820 / 19U

ο- - 50, preferably 15-35 wt .- ^ of the invention. proper combination of perborate, monopersulfate and water-insoluble inorganic stabilizers, however, the amount of this combination is preferably so large that the active oxygen content of the entire bleaching Detergent is 1-4, preferably 1.5-3 * wt .- ^,

- 15, preferably 2 - 12 wt -.% Other - · detergent ingredients, for example. Dirt carrier, brightener, perfume, '■■■■; Dyes, water.

109820/1 9U

The finding that aqueous solutions containing both perborate and monopersulfate have proven to be very active textile bleaching agents which can be used both at low temperatures and at temperatures up to 100 ° C. with extensive utilization of the active oxygen must be based on the information contained in the literature on the use of monopersulfate as a bleaching agent should be viewed as very surprising. It could not be derived from the English patent specification 1,052,796 because the gas evolution of aqueous solutions of the perborates described therein is undesirable in textile bleaching. '.> ^R *

According to the American patent 2 886 55 ^ are ·· aqueous Solutions of monopersulphates which contain small amounts of boric acid salts, e.g. perborate, hot -]; * '-. atomized. But if monopersulfate and perborate, as has been found according to the invention, already in the Activate each other's cold, how much more then must Perborate disintegrates when these mixtures are sprayed with hot water Monopersulfate powder practically no more perborate. From the aforementioned American patent is also nothing to be learned about the ability of the monopersulphates, To activate perborate in the alkaline range so that this makes it possible to bleach textile fibers even at temperatures below 70 ° C «_____ .- ■■■; 'ßÄD ORfGINAL

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The following remarks on the per compounds and stabilizers to be used according to the invention and, if applicable, other customary components apply mutatis mutandis to the process and to its Implementation of certain bleaches, detergents and washing aids.

Perborates and monopersulfates are used in the form of their water-soluble salts, preferably as alkali, ammonium or alkali-ammonium salts.

Among the various perborates, sodium perborate tetrahydrate (NaBO, 4 H ₃ O) is of particular practical importance. In its place, partially or completely, ie up to the approximate / approximate composition NaBO,. HgO dehydrated perborates can be used. Finally, borates containing active oxygen are also NaBO ₂ . HgO _{2 can be used} in which the ratio Na ₃ O i BgO, is less than 0.5: 1 and preferably in the range from 0.4-0.15 1 and in which the ratio H ₂ O ₂ : Na is in the range from 0.5-4: 1. These products are described in German Patent 901 287 or, in the US Patent 2,491,789.

109820/1914

As monopersulfate Kaiiummonopersulfat the formula is used KESOc preferred that often as a technical, ca "4.5 percent -.. Containing% active oxygen product usually with potassium sulfate and potassium bisulfate mixed in trading comes ·

The various magnesium silicates are suitable as water-insoluble perstabilizers. In most cases, these are precipitation products that arise when aqueous solutions of alkali silicates are combined with solutions of magnesium salts. The ratio of MgO; SiO ₂ can be in the range of 4: 1 - ■ 1; 4, preferably from 2: 1 to 1: 2 · Usually a product with a ratio ■ .. MgO: SiO ^ = 1: 1 is used. These magnesium silicates can be replaced by the corresponding silicates of other alkaline earth metals, cadmium or tin. Hydrous oxides of tin can also be used as stabilizers

The method according to the invention is applicable to all textiles natural or synthetic Of origin applicable. Except mostly at temperatures from 70 - 100 ° C to be treated

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• · ORIGINAL BATHROOM

According to the invention, textiles made of cotton, regenerated celluloses or linen can be washed and / or bleached, in particular the so-called "easy-care" textiles made from highly refined cotton or from synthetic fibers, such as polyamide, polyester, polyacrylonitrile, polyurethane , Polyvinyl chloride or polyvinyl alcohol fibers or contain at least 50% of them. Particular mention should be made here of the easy-care ₍ light, sometimes also referred to as "non-iron" textiles) made from appropriately finished synthetic fiber / cotton blend fabrics.

Pure bleaching or washing of these easy-care products Textiles can be used at temperatures of 20 - 70 ° C, preferably 30 - 60 ° C. According to the invention The high degree of whiteness achievable at these temperatures is above all at the same time or subsequent treatment of the textiles with optical brighteners is advantageous. According to the invention used bleach liquors can be used immediately before use by adding the necessary and, if necessary, additional ones for bleaching and washing processes common components per se are produced.

10 9820/1914

But you can also get ready-made solid preparations serve, in which already necessary according to the invention and possibly. Further, in such Preparations usual ingredients are present. Therefore, the following statements apply mutatis mutandis to the aqueous treatment liquors or to the preparations for their production apply.

Both perborate and monopersulphate can be used as fine to coarse powders, but also as granules can be used. These granules, in particular the perborate granules, can be used in addition to the perborate still more neutral to alkaline reacting Contain substances.

Because of the in technical potassium monopersulphates the presence of potassium bisulfate drops the alkalinity of perborate monopersulphate mixtures with increasing Content of monopersulphate. Since the monopersulphate also turns into potassium bisulphate when oxygen is released at transformed, it is advisable to work in the presence of alkaline substances, so that the desired pH value is always maintained «

109820/1914

It has been shown that the storage stability of the mixtures according to the invention is influenced by various factors, such as, for example, the water of crystallization content of the constituents, the grain size of the components to be mixed with one another and the presence of additives. The stability of the mixture decreases with increasing water of crystallization content of its constituents and with decreasing grain size. Thus, for example mixtures of industrial monopersulfate are (4.5 wt -.% Of active oxygen) and perborate monohydrate storage-stable even without further additives, while it is recommended when higher perborates crystal water content, add typical solid ingredients of detergents and Bleihmitteln. These improve the storage stability of such mixtures, provided that they are inert to the per compounds.

Of particular practical interest are bleaching detergents which, depending on the surfactants present, as well as any foam stabilizers and / or foam inhibitors, as foaming, as non-foaming and foam-controlled detergents. The powerful foaming detergents are suitable for all washing and bleaching processes,

Bath 109 820/1914

which do not run in drum washing machines. "The Low-foaming detergents and bleaches are primarily intended for use in drum washing machines determined, and the foam controlled detergents evolve at application temperatures up to 60 ° C a certain foam, but the Exceeding this temperature limit becomes more and more unstable, so that this detergent is suitable for both Suitable for washing in tubs as well as for washing in drum washing machines

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BATH ORIGINAL

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According to the invention together with the bleaching components applicable anionic, zwitterionic or nonionic surfactants contain in the molecule at least one hydrophobic radical of 8-30 carbon atoms and an anionic or nonionic water-solubilizing group. The hydrophobic The remainder can be aliphatic or alicyclic, preferably saturated, and with the water-solubilizing Groups can be connected directly or via intermediate links. As intermediate links there are e.g. benzene rings, carboxylic acid ester or carbonamide groups, ethylene glycol or propylene glycol residues in question.

The hydrophobic radical is preferably an aliphatic hydrocarbon radical with about 10-18 carbon atoms, where however, depending on the nature of the respective surfactant, deviations from this preferred C number range possible are.

Soaps which are natural or synthetic can be used as anionic washing active substances Fatty acids, possibly also derived from resin or naphthenic acids.

^109820/1914

Own of the synthetic anionic surfactants the sulfonates and sulfates of particular practical importance.

The Sülfonaten include, for example, the alkyl, aryl sulfonates, in particular the alkylbenzenesulfonates, which are, inter alia, preferably straight-chain aliphatic Hydrocarbons with 9-15, preferably 10-14, carbon atoms by chlorination and condensation with benzene or from corresponding terminal or internal olefins by condensation with Benzene and sulfonating the obtained alkylbenzenes is obtained. There are also aliphatic sulfonates of interest, e.g. from preferably saturated, 8-18 and preferably 10-16 carbon atoms * in the molecule containing hydrocarbons Sulfochlorination with sulfur dioxide and chlorine or SuIfOxydation with sulfur dioxide and oxygen and converting the products obtained thereby into the sulfonates are accessible * As aliphatic Sulphonates are also mixtures of alkene sulphonates, Oxyalkene sulfonates and oxyalkane sulfonates can be used, for example, from terminal or non-terminal Cg to Tf, δ-olefins by sulfonating with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products

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receives. In the case of the aliphatic In sulfonates, the sulfonate group is often located on a secondary carbon atom; But you can also by reacting terminal olefins with bisulfite sulfonates with primary, | i.e. to produce terminal sulfonate group.

The sulfonates to be used according to the invention also include esters of ct-sulfo fatty acids with one or polyhydric alcohols containing 1-4 and preferably 1-2 carbon atoms.

Fatty alcohol sulfates are used as surfactants of the sulfate type to be mentioned, especially those made from coconut fatty alcohols, Tallow fatty alcohols or derived from oleyl alcohol. Also from final or internal C6 to Cj ^ g olefins can be useful Manufacture sulfonation products of the sulfate type. This group of surfactants also includes sulfated fatty acid alkylolamides, sulfated Monoglycerides and sulfation products from ethoxylated and / or propoxylated fatty alcohols, alkylphenols with 8-15 carbon atoms in the Alkyl radical, Fettsäureamiden, FettsäUBalkylolamiden, etc., with one mole of the ethoxylated

109820/1914

and / or propoxylated compounds 0.5

up to 20, preferably 1 - 8, especially 2 - 4 mol

Added on ethylene and / or propylene oxide

could be. .

i Other useful sulfonates are the fatty acid esters

oxethanesulphonic acid and dioxypropanesulphonic acid as well as the condensation products of fatty acids with aminoethanesulfonic acid. The invention Detergents can also contain capillary-active synthetic carboxylates, e.g. the fatty acid esters or fatty alcohol ethers of oxycarboxylic acids and the condensation products of fatty acids with aminocarboxylic acids, e.g. Glycocoll or des sareosin, or with protein hydrolysates.

The foaming power of the detergents according to the invention can be increased or decreased by a suitable combination of different surfactants will. The addition products of propylene oxide are characterized by a low foaming power to the above-described nonionic polyethylene glycol ethers by varying the number im Molecule of existing ethylene glycol and propylene glycol residues can be used with the most varied of products

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^109820/1914 Vo

Establish cloud points. These nonionics work at temperatures above their cloud point to nonionics other than foam inhibitors. They can therefore be used in the inventive Surfactant combinations together with other nonionics, but also in combination "with other surfactants as a nonionic component in the already mentioned combinations of sulfates and / or sulfonates, soaps and use nonioiiies.

The washing and bleaching agents can, however, also contain foam inhibitors known per se / which are not surfactants. These foam inhibitors can be combined with foam stabilizers, which are also known per se, and thus detergents are obtained which foam well in the medium temperature range up to, for example, 65 ^° C., but when this temperature is exceeded, the foaming capacity is reduced.

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109820 / -19U BAD

Similar effects are achieved through the choice of soaps, in particular when these are combined with anionic and / or non-ionic surfactants. Soaps with, for example, 12-18 carbon atoms in the fatty acid residue show a certain degree of foam suppression, which, however, is often insufficient if the detergents are to be used in washing machines at temperatures of 60-100 ° C. In such cases, a strong foam dampening can be achieved with synthetic anionic, zwitterionic and nonionic surfactants by soaps made of fatty acid mixtures, which at least. 50 % of fatty acids with 16 - J30 carbon atoms and at least 3>, preferably more than 5 % of those with 20 or more carbon atoms, preferably the saturated,

Fatty acids containing at least 16 carbon atoms make up at least 50% of the total soap content.

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, BATH

1 09820 / 19H

The bleaching agents according to the invention can be marketed as such in order to e.g. in commercial laundries, with washing alkalis, complexing agents or other common ingredients of washing liquors. One can use the surfactant combinations but also together with these usual detergent additives to a finished detergent, Use detergents or bleaching agents.

Of the usual detergent additives, the water-soluble condensed phosphates, in particular the di- or triphosphates are of particular practical importance. You can through known organic Complexing agents can be replaced or combined with these. .

These include, for example nitrilotriacetic acid, ethylene diamine, N-Oxäthyläthylendiamintriessigsäure, Palyalkylen polyamine-N-polyacetic and other known organic complex, with combinations of various chelating agents can be used · The other known complexing agents include di- and polyphosphonic following Konstitutionenϊ

109820 / 191A - 23 -M _K

J ^ OH

X - t? --H

-OH

, 0H 'OH

HO.

HO- HO-

H0> HO

.OH

OH

OH

.OH

OH

OH

wherein R and R ^{1 are} alkyl or alkylene radicals InIt ₁ I to 8, preferably 1 to ¹ \. C atoms and X and Y represent hydrogen atoms or alkyl radicals with 1 to 4 C atoms. Carboxymethylene phosphonic acid (HOOC-CH ₂ -PO (OH) ₂ ) can also be used according to the invention as a coraplex former. All of these complexing agents can be present as free acids, but preferably as alkali salts.

Instead of the condensed phosphates or complexing agents or in combination with these, alkaline builders such as carbonates and bicarbonates can be present in the detergents according to the invention

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or alkaline silicates. Also neutral, inorganic or organic salts can be incorporated, such as alkali salts of sulfuric acid, benzene, toluene or Naphthalenesulfonic acid or sulfobenzoic acid, Sulfoacetic acid or salts of sulfodicarboxylic acids.

Furthermore, the bleaches and detergents according to the invention can contain dirt carriers, the keep the dirt detached from the fiber suspended in the liquor and thus prevent it from turning gray. Water-soluble colloids of mostly organic nature are suitable for this, such as, for example water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulf acidic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or strength. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, starch and other starch products than those mentioned above can be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

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1 098 20 / 19U

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For example

In the perborate mentioned in the examples. it is sodium perborate tetrahydrate (NaBO,. 4 H ₂ O) with an active oxygen content of 9.6 wt .- ^. A technical mixture of potassium monopersulphate, potassium sulphate and potassium bisulphate which is commercially available under the name "Caroat" (= salt of Carose acid) was used as the monopersulphate. The caroate contained about 4.5% by weight of active oxygen.

example 1

This example demonstrates the differences in the bleaching effect of perborate and caroate compared to mixtures of perborate, caroate and magnesium metasilicate (MgSiO.,), these mixtures also include the unclaimed area in which more than 50 # of the active oxygen from the Caroat comes from.

All experiments were carried out with an active oxygen concentration of 100 mg / 1 and a magnesium silicate concentration νοη · 25ο mg / 1 worked. To all attempts distilled water was used.

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The bleaching effect of these bleaches The aqueous bleach liquors produced were applied to a cotton fabric dyed with black tea (Remission value = 4 ^, 6) in three test series using the following methodology:

In a series of tests, the cotton fabric was treated in a bleaching liquor heated to 30 ° C. and left in it for 45 minutes. In the other series, the cotton fabric was heated to 60 ° or 90 ° C. in the bleaching liquor within 30 minutes and left at these temperatures for 15 minutes. The liquor ratio was 1:25 in all cases.

After the bleaching process, the fabrics were rinsed three times with distilled water, dried and ironed. The reflectance values of the unbleached and the bleached cotton fabric were then measured in the ^{"ELREPHO 11" photoelectric photometer.}

The composition of the bleaching agents, the bleaching conditions and the determined reflectance values are summarized in Table 1. & AD q

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109820/1914

• Table 1 ·

Composition of the bleaching agent or the bleaching liquor and
Remission values of the bleached cotton fabric, dyed with tea

mg / 1, liquor ratio 1:25

OQ

G)

■ BXelohm.
No. ο
co a Contains bleach
Perborate / Caroat / 0 MgSiO, Bl e 1
relation
Perborate c hfl
Act- ^ O from
/ Caroat Ott e
PH value Reflectance values according to
Bleach at _
30 ° C 60 ° C 90 ° C 4th 71.9 76.9 1 OO
NJ 1
° 79.3 20.7 100 0 10.1 55, .Si- b 42.0 4th 74.7 80.7 1 C. 42.3 60.4 15.7 70 30th 9.4 65, 2 74.9 81.0 1 d 26.1 74.3 13.5 50 50 8.9 63, 6th 65.7 70.7 1
Ί ■ · e 13.7 85.3 12.0 30th 70 6.1 57, 2 59.0 65.9 f 4.1 89.9 10.6 10 90 2.8 54, 0 58.4 65.8 0 10.1 0 100 2.6 54,

CD ■ JN · QO cn

Example 2 .

Equal amounts of extracted from the atomizing tower detergent were added after cooling using such amounts of perborate or perborate, caroate and optionally sodium sulfate in that each detergent sample 2 wt -.. Contain% active oxygen and that the individual patterns only by their content of perborate , Caroate and sodium sulphate. They also had the following composition: 6.0 wt .- # technical straight-chain

Dodecylbenzenesulfonate 2.8 wt -.% Nonylphenol + 9 Ä'O 7.5 wt -.% Of soap of a saturated

^C l6 ^"C ^ 22 ~ ^{Pet säureseraiscl1 with} 8% ^of C ₂₀ - and C ₂₂ fatty acids

44.0 wt .- ^ Na ₅ P ^ O ₁₀ + Na ^ P ₂ O ₇ (approx. 2: 1) 6.5 wt .- Jg Na ₂ O. 3.3 SiO ₂ 2.0 wt .- ^ MgSiO, (in the atomization product

-> hold) 1.5 wt -.% CMC

Remainder perborate, caroate, sodium sulfate,

Brightener and water

109820 / 19U

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^8AD

To demonstrate the bleaching effect of the perborate or caroate active oxygen contained in the detergents, normally soiled household laundry was washed using distilled water or v / a at 13 ° dH. The liquors always contained 4 g / l of the detergent, based on the active oxygen-free constituents and sufficient bleaching component that the active oxygen concentration was 100 mg / l. The fleet ¹ ratio was 1; 25,

Sections of raw linen were added to the laundry, the remission value of which was untreated State was 17 * 2. The laundry including the test strips was in the wash liquor inside of 30 min. from room temperature to the desired Bred temperature of 30 ° or 60 ° or 90 ° C and held at this temperature for 15 min. The laundry removed from the wash liquor and the Test strips were then rinsed with running distilled water or water at 13 ° dH. These washing processes were repeated a total of 9 times, with renewed soiling in each wash cycle Household linen was used. The test strips

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BATH ORIGINAL

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however remained the same; So they became Lömal washed under the specified conditions.

The laundry, including the linen test strips, was dried and ironed. Then ." the reflectance values of the linen fabric were measured in the "ELREPHO" photoelectric photometer.

The composition of the detergent, the washing conditions and the reflectance values are summarized in Table 2 below.

The visually "signed off household swas chgut, that at the 90 ° C washes from normal cotton household linen and the 60 ° C or. 30 ° C WMseJhen made of linen made from easy-care material, showed the following degree of purity:

The normally soiled cotton-wool "household had in terms of washing and bleaching effect with increasing Caroat® content an improved degree of cleaning on the optimum was, however, in relation to the active oxygen content of perborate. 80 Caroat® *: 20 or JQ. Reaches 30 When

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Ratio 50: 50 was already an easy one Noticeable decrease in the cleaning effect. When washing easy-care material at 60 ° C, there were also very significant improvements the degree of purification determined by the Caroate addition, which in turn was determined by the relations Active oxygen from perborate: Caroate = 80:20 or 70 s 30 reached their optimum. At the ratio 50:50 there was a noticeable one A decrease in the washing effect can be observed, but the washing result was still better than "with Use of perborate alone. At 30 ° C it was also notice an improved washing effect when the active oxygen is partly off the Caroat came from. However, this washing temperature is preferably used for very sensitive items, for example in woolen goods.

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Table 2

Bleach and active oxygen contents of the used Detergent and reflectance values of the treated raw linen

4 g / l detergent without per compounds (spray product) 100 mg / 1 Akt-O, liquor ratio 1:25

Washing machine
No. 2 a Washing machine contained wt. %
Perborate / caroate O relation
Act-O off
Perborate / caroate 0 Wash in dist. water
Remission values
30 ° c 6o ° C '90 ° c 39.5 55.6 Laundry
30 ° c in water 13 ° dH
Remission values
60 ° G 90 ° C 55, 8th O
(O 19.4 100 32.5 31.1 ■ 38.7 CO
ISJ 2 B 4.4 10 46.1 60.2 60.8 CD
"■". 17.0 90 33.4 34.2 44,, 4 CO 2 c 8.5 20th 48.7 61.3 62, 2 d 14.5 12.6 80 30th - 50.3 63.4 - 48.2 61, 2 e 12.6 19.9 70 50 36.3 48.3 60.8 36.2 49.3 61, 8.6 50 37.0 37.3 50.9 , 2 ,1 .5

ro 'In distilled water, the pH values drop from 9 ^ 9 for detergent 2 a to 9.1 for detergent > 2 e from; In a water / volume of 13 dH, the corresponding pH values drop from 9.6 to 9.0.

Ϊ ',

OO

V> J

Previous year

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Example 3

As described in 'Example 2, a' Detergent powder produced by hot atomization perborate or perborate and caroate and, if necessary, sodium sulfate, two detergents of the following Composition made:

component Wt .- ^ item.
What c hm:
a change part at
Lttel
b Dodecylbenzenesulfonate
(like example l)
Nonylphenol + 9 AO 6.0
2.8 6.0
2.8 saturated C «gC ₂₂ -Na-Seif € 7.5 7.5 Na ₅ P ₅ O ₁₀ + Na ₄ P ₂ O ₇ 44.0 44.0. . Na ₂ O. 3.3 SiO ₂ 6.5 6.5 MgSiO-, (in the atomization
-> product)
CMC 2.0
1.5 2.0
1.5 NaBO,. 4 H ₂ O 20.0 16.0 Caroat - 9.0 Sodium sulfate, brightener,
water 9.7 4.7

Wasohmittel a and b contained the same amount of active oxygen. However, this originated "with the Detergent a completely out of the perborate while he

109820 / 19H

ORIGINAL

80% of the detergent b came from the perborate and 20 % from the caroate _e

With the two washing powders, in a manner similar to that described in Example 2, moderately soiled laundry made of easy-care material was washed 10 times in succession in a long liquor (liquor ratio 1:25) at 60.degree. The laundry of easy-care material consisted of highly refined cotton shirts, shirts made from a mixture of 70 1 ° polyester fiber ^ O% cotton shirts made of fully synthetic polyamide fibers. To control the washing and bleaching effect, sections of. Cotton goods dyed with immediate green (bleach test fabric from laundry research in Krefeld) were added. While the household laundry was changed with each wash, the sections of the bleach test fabric ran without changing during the 10 washes.

It was washed using distilled or moderately hard water of 15 ° dH, with 5 g / l detergent a and b being used. The liquor ratio was 1; 25. After the washes, the items to be washed were rinsed thoroughly with distilled or medium-hard Hasser and then dried, only those

1 098 2Q / 1 9 U ^Bm

1594854

Test strips of the bleach test fabric were ironed, whereupon the reflectance values in the photoelectric photometer "ELREPHO". were measured.

Table 5 shows the washing conditions and the measured reflectance values for the one with immediate green dyed bleach test fabrics summarized. This bleach test fabric had a reflectance value in the unwashed state of 27 * 2 ·.

The visual matching of the laundry from easy-care Material clearly showed an improved washing and bleaching effect in favor of detergent b. The lightening was particularly pronounced in the case of laundry items containing synthetic fibers that had previously yellowed striking.

Working conditions and remission values when renting the Cotton fabric dyed with immediate green after 10 washes

Laundry detergent- a b -. '■ "-. 5 g / l 56/1 concentration 9.90 9.52 pH in dist. water 9.61 9.20 pH in water 15 ° dH 30.2 34.4 Remission values (distilled water) 30.8 36.3 Remission values (water lj5 ° dH)

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example H

The two detergents a and b described in Example 3 were used in an automatic washing machine, who works according to the two-step process.

■ ■ 'J

In the first experiment, 4 kg of table linen (table * towels and napkins made of cotton and half linen), which apart from normal soiling also Stained fruit, vegetables and coffee. In the pre-wash cycle and in the main wash cycle, 100 g each of the washing powder were added used; the liquor ratio was then 1: 5.3. The temperature rose in the main wash to 92 ° C. After completion of the wash cycle, the laundry was rinsed in the usual way in the washing machine and spun, then dried in a drying device with hot air and ironed.

The table linen washed with detergent A. if the result is generally good, there are still remnants of fruit, vegetable and coffee stains. The ones with detergent B washed table linen was completely free of stains «

In the same washing machine, 1 kg of men's shirts made of easy-care material (half made of highly refined cotton fabric, the other half made of a blend of 70 % polyamide and 30 % cotton)

109820 / 19U ⁰ ^ GWGZNAl'-

1694864

with increased liquor level (liquor ratio 1 ί-28) and washed at a temperature of 60 ° C] the amount of detergent was again 100 g. The shirts showed apart from the soiling that normally occurs when wearing coffee, tomato and cherry stains. juice up. The shirts got dripping wet after rinsing hung and air dried, but not ironed, ■

The shirts washed with detergent A were on clean, but the stains were not completely removed. Those treated with detergent B. Shirts, on the other hand, were stain-free.

If these men's shirts were washed several times, Use of detergent B also significantly improves the whiteness, especially with the shirts made of a polyamide-cotton blend. The shirts, which were initially slightly yellowed, were pure white after the fourth wash.

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09 8 20 / .19H

As you can see from the examples, the increases bleaching and stain-removing effect initially to the same extent as active oxygen from perborate is replaced by active oxygen from monopersulphate. At the same time, however, see the reduced Alkalinity of the bleach component. This can be done by combining the bleaching component with Compensate alkaline reacting substances or alkaline reacting detergents, but by doing this the alkali reserve becomes part of the washing and bleaching process withdrawn. Dirt removal suffers due to excessive reduction in the content of alkaline substances, especially with pigment or greasy dirt. From the point of view of the overall washing effect, a combination of dirt removala stains »· distance and bleaching, one can only speak of a technical port step if the The amount of active oxygen from monopersulphate does not exceed the amount of active oxygen from the perborate.

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1O982O / .10U

Claims (11)

1) Process for bleaching and, if necessary, washing textiles by treating them with aqueous, perborates and Liquors containing monopersulphates, characterized in that that to be used at temperatures up to 100 ° C, perborates, monopersulfates and, if necessary. Customary A liquor that contains components of detergents and bleaches and a pH of 8-11 Have active oxygen content of 0.05 - 7 g / l, whereby at least 50 "^ of the active oxygen from the perborate come. ; . 2) Method according to claim 1, characterized in that that the bleach liquors have an active oxygen content of 1 * 5 - 3 * 5 g / l. 3) method nacsii claim 1 and 2, characterized in that that the liquors have a pH value ± m range of 8.5 - 10.5 » 4) method according to claim 1 - 3, characterized in that that the Blej & ie at temperatures of 20 - 70 ° G, preferably carried out at temperatures of 30-60 ° C. 1098 2 0/1914 5) Process according to claims 1-4, characterized in that in the presence of 0., 025-10 g / l, preferably 0.75 -7 g / l water-insoluble stabilizers for per compounds, especially in the presence of magnesium silicates is working. , '■ I' ■ ■ 6) Application of the method according to claims 1-5 on synthetic fibers, such as polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinyl alcohol fibers, or on cotton goods with a "non-iron" or "easy care" finish at temperatures in the range of 20 - 70 " ⁰ C, preferably 30 - βθ ⁰ C. 7) Agents containing perborates and monopersulfates Implementation of the method according to claims 1 - 6, be =, standing from: a) 5-100% by weight ■ of a bleaching component containing? 1) 80 - 99 * 5 % of the weight of component a of a mixture of perborates and monopersulphates in such amounts that 97 50> preferably 90 - 70 % of the active oxygen present comes from the perborate, 2) 0.5 - 20 % of the weight of the component a water-insoluble stabilizers for per compounds, 109 8 20 / 19U b) 95 - O wt -.% active oxygen not containing conventional, neutral or alkaline reacting constituents of such means, " 1) the type and amount of alkaline reactants Connections depending on "from Perborate: monopersulphate ratio should be chosen so that liquid aqueous solutions of the entire agent have a pH value in the range of 8-11 and 2) in the case of the presence of sodium perborate tetrahydrate (NaBCU. ^ H ₂ O) ₅ advantageously also in the presence of lower water perborate, the amount of water-insoluble stabilizer according to a2 · and 'the amount of any component b present together more than 1.3 times, preferably more than 3 times the amount of monopersulphate present « 8) Agent according to claim 7, characterized by an active oxygen content of Oi 5 - 7, preferably 1.5 - 3 * 5 wt .- ^. 9) Means according to claim 7 and 8, characterized in that the amount of active oxygen originating from the perborate 90-70 $ of the total active acid present; substance makes up ,, ■■ '- ■ -_ __ 1b9486A 10) means according to claim 7 - 9 * characterized in that that the pH value of a liquid aqueous solution of the agent is in the range of 8.5-10.5. A bleaching detergent component according to claim 7-10 containing 11), characterized in that it is composed in the following manner Items since - 40, preferably 12 - 50 wt _e - $ surfactants or combinations of surfactants consisting of 0 - 100, preferably 25 - 65 wt -.% surfactants of the sulfonate and / or sulfate type, 0 - 100, preferably 5 - 40 wt .- ^ nonionic surfactants, 0 - 100, preferably 10 - 50 wt .- ^ soap, 0 - 6, preferably 0.5 - 1 wt .- ^ foam stabilizer,
0 - 8, preferably 0.5-5 wt .- ^ foam inhibitor, - 82, preferably 35-75 wt .- ^ structural substance, where at least some of this structural substance reacts alkaline and the amount of the alkaline and neutrally reacting structural substances, preferably the 0.5 to 7faohe and especially 1 to 5 times the total What makes Qhaktivsutostanz, - 50, preferably 15 "55 wt -.% Of the inventive combination of perborate, monopersulphate .109820 / 1914 *. '. BAD ORJGiNAL and water-soluble inorganic stabilizers gates, but the amount of this combination is preferably so large that the active oxygen content of the total bleaching Detergent 1 - 4, preferably 1.5 - 3> * 5 Gew, - $ is, - 3.5 * preferably 2-12 wt -.% Of other detergent ingredients, such. B. dirt carriers, brighteners, perfume, dyes, water. . BATH ORIGINAL 109820/1914