DE2227602A1 - PROCESS FOR ACTIVATING PEROXY COMPOUNDS AND BLEACHING ORGANIC MATERIALS - Google Patents

Description

FARBWERKS HOECHST AKTIENGESELLSCHAFT '2227602 formerly Master Lucius & Brüning

File number: HOE 72 / F165

Date: June 6, 1972 Dr.Gr/cv

Process for activating peroxy compounds and bleaching organic materials

Well-known bleaches for lightening and bleaching organic Materials such as fibers and textile structures made from them, wood, oils and discolored organic materials Chemicals put hydrogen peroxide, alkali peroxides and general storage compounds of hydrogen peroxide on inorganic ones Compounds such as alkali perborates, furthermore hydroperoxides, peracids, peracid esters, persulfates and others «.

One of this range of peroxidic bleaches is hydrogen peroxide the most common bleaching agent for bleaching textiles for economic reasons. It unfolds its bleaching effect especially in the alkaline range as does naturally alkali peroxides and the addition compounds of hydrogen peroxide with salts of inorganic acids such as sodium borate or soda. (See also Melliand

^lu ^ "'' 30 98 8? / 123 0

Textile Reports 49 (1968), page 1195). Peracids such as Peracetic acid or possibly performic acid which may be formed in bleaching liquors, on the other hand, result good bleaching effects under acidic conditions (see also Deutsche Textiltechnik 10 (1960), page 191). Hydroperoxides again, the bleaching conditions customary in practice are not sufficiently effective in bleaching. Also mono and Dipersulfate could not prevail in practice because it is relatively difficult to use for textile bleaching processes are activated.

Under certain conditions, it is also possible to carry out bleaching with hydrogen peroxide in the acidic pH range (see Textil-Praxis 1971, pages 622-623). A bleaching process in the weakly acidic to neutral pH range is planned can be of great interest in practice because the peroxide bleaching takes place in the alkaline pH range Occurring impairment of the handle of the bleached goods due to the necessary use of the stabilizing effect Water glass is avoided. In addition, dizrch is acidic Treatment stages before those that follow later in the finishing process acid treatments of textiles, such as those commonly used in high-end finishing, there is no need to switch on a neutralization process. A bleach in the absence of Lye also helps the fact that the alkali lye is more difficult to wash out after alkaline bleaching, in particular circumvented with hydrogen peroxide and thus a more economical design of the bleaching process with lower Wastewater quantities is achieved.

The bleaching with hydrogen peroxide and hydrogen peroxide addition compounds In a weakly acidic to neutral pH range, however, it is not possible to use just the addition of acids or acidic salts, but only takes place in the presence of special activating compounds. Such compounds are, for example, formamide, alkyl-substituted formamides, formic acid esters (DTOS 1.469.608). / ^

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· "5 -

These compounds activate hydrogen peroxide or hydrogen peroxide addition products and enable a bleaching effect on textile substrates at pH values of 6-7. The degree of whiteness that can be achieved on textiles, however, falls in comparison to goods bleached with alkaline hydrogen peroxide liquors. That's why the acidic Bleaching with hydrogen peroxide in the presence of special activators is only used to a limited extent in textile practice could.

Based on this finding, the task was therefore to find more effective activators for peroxide bleaching also not only in a narrowly limited pH range, at pH values of 6-7, but also in the more acidic and possibly also have an activating effect in the alkaline range and thus bleach in acidic to alkaline pH ranges allow. A further aim is that the activators also have an activating effect on such peroxidic compounds that are normally considered to be more difficult to activate. The advantages of such activators would be one wider applicability and safe handling.

It has now been found that one can overcome the difficulties outlined when bleaching organic substances with peroxy compounds can deal with the activation of the peroxy compounds by esters of dicarbonic acid or their derivatives, how the monoester or dialkali salts of dicarbonic acid takes place.

The invention therefore relates to the activation of peroxy compounds and a method for continuously and discontinuously bleaching and purifying organic Materials with compounds which contain peroxy groups, characterized in that for activating the peroxy compounds Dicarbonate of the general formula

I) R ₁ - OC - 0 - CO - R ₀ ,

■ ti η ■ ^

0 0. A

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in which the radicals R ₁ and R _{2 can be} identical or different and alkyl groups each having 1 to 18 carbon atoms, which are phenyl or benzyl radicals, alkali metal or ammonium ions, are used.

The bleaching process according to the invention can be carried out by the material to be bleached in a or several treatment stages with the peroxy compounds as bleaching agent and the activating compound expedient ' treated in the form of aqueous or water-containing solutions, pastes or emulsions, i.e. as intimately as possible in contact brings.

The peroxy compounds to be activated according to the invention are the known inorganic and organic peroxy compounds. Examples of inorganic peroxy compounds are: peroxymono- and peroxydisulfuric acid, Peroxymono- and -diphosphoric acid and the Salts of these acids, also the peroxides of monovalent and divalent metals, e.g. sodium, zinc, magnesium, calcium, barium peroxide as well as ammonium peroxide and the addition products of hydrogen peroxide with inorganic compounds, e.g. Perborates, percarbonates and persilicates. Organic peroxy compounds to be activated are, for example, alkyl and Ary! Hydroperoxides and dialkyl and diaryl peroxides, such as tert. Butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide and dicumol peroxide, mono- and diacyl peroxides such as diacetyl, dibenzyl and dilauroyl peroxide, peresters such as tert-butyl perbenzoate, tert-butyl permaleate, tert-butyl perisononanate, also peroxy acids such as peracetic acid, performic acid, peroxybenzoic acid, mono- and diperadipic acid and Mono- and dipersebacic acid and also addition products of hydrogen peroxide with organic compounds v / ie e.g. Methyl ethyl ketone peroxide, cyclohexanone peroxide and carbamoyl peroxide.

/ 5 309882/1230

Diesters of dicarbonic acid (pyrocarbonic acid) corresponding to the formula I can be obtained, for example, from sodium alkyl carbonates and chlorocarbonic acid esters or phosgene are produced (see US Pat. No. 3,078,294). According to this mode of representation, it is possible dicarbonic acid diester with two of the same or else with different alkyl or phenyl radicals. Accordingly, for the activation according to the invention, Peroxy compounds dicarbonic acid diesters that contain two identical alkyl radicals or two phenyl radicals or those with different alkyl radicals or with one alkyl and one phenyl radical in the molecule. _

Finally !, mixtures of different dicarbonic acid diesters can also be used can be used. Suitable dicarbonates are, for example: benzyl ethyl dicarbonate, diethyl dicarbonate, Dimethyl dicarbonate, dibutyl dicarbonate, diisopropyl dicarbonate, dihexyl dicarbonate, dioctyl dicarbonate, diphenyl dicarbonate, Dibenzyl dicarbonate and bis (p-methyl benzyl) dicarbonate.

In the presence of aqueous alkali, the dicarbonic acid diesters are hydrolyzed, so that when an alkali is added to the Diesters in the order of half the equimolar amount can be assumed to be monoesters, or in other words Monoester salts of dicarbonic acid are formed. It can therefore depending on the application and bleaching conditions at different pH values in the bleaching medium either the diesters or the monoester salts of dicarbonic acid, finally the pure salts of dicarbonic acid are also present. The activation of the peroxy compounds taking place according to the invention, for example of hydrogen peroxide, by the diester of dicarbonic acid is therefore to be interpreted in such a way that both the Diesters and monoesters as well as the only limited stable salts of dicarbonic acid have an activating effect.

The activation of the peroxy compounds and thus the implementation the bleaching process using the dicarbonates

j ■ ■ - / 6

3098821/1230

according to the invention can take place in a very broad pH range. For textile bleaching, pH values above about pH 3 come into consideration. In general, the pH is from about 3 to about 10, preferably between pH 4 and 8.5. With only a short bleaching time of less than about 30 minutes, pH values in the strongly basic range of about pH 10 to 12 can also be used. The desired pH value of the bleaching medium can be set by adding inorganic or organic acids, salts or esters which split off these acids, or ammonia, metal hydroxides and alkaline salts. Preferably, a desired pH can only be set at a higher bleaching temperature through the use of compounds which disintegrate at a higher temperature. For example, metal salts of trichloroacetic acid decompose with elimination of metal hydroxides at temperatures from about 80 ^° C. When these compounds are used, without using the activators according to the invention, alkali bleaching, for example, only takes place at this temperature without other alkaline additives being required with hydrogen peroxide instead. Such a bleaching process can be optimized by adding a dicarbonate as an activator. The use of the dicarbonates according to the invention enables not only bleaching with peroxy compounds in the more acidic pH range, but also in the neutral range and in an alkaline medium. In order to avoid the difficulties, for example, from a practical point of view, with bleaching in the alkaline pH range, bleaching processes in the neutral range and at lower pH values with the activating additives according to the invention are of greater interest, because hand disadvantages are not observed, see above that light, sensitive textile materials, for example lace, tulle, textiles made of textured synthetic fibers, knitted fabrics, tricot days, can be gently bleached.

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It also shows. That, for example, an acidic hydrogen peroxide bleach in the presence of the activators according to the invention both "at low temperatures and" at high lead temperatures compared to bleaching in the presence of high amounts of alkali and in the absence of the activators according to the invention have clear advantages in terms of improved whiteness offers. A further advantage of the bleaching process according to the invention results from the fact that it is possible to carry out the bleaching in a wide temperature range. So come with longer bleaching times over several hours bleaching temperatures of 10 to 20 ^0C into consideration. The bleaching time is significantly shortened when higher temperatures come to 160 ° or up to 200 ⁰ C are used.

In the bleaching of textile material is allowed in general, the ¥ / are in the bleaching liquor or impregnated with the bleaching liquor product without drying at temperatures between about 10 ° to 200 ⁰ C, particularly at 20 ° - 16O ⁰ C until completion of the bleaching operation usually about 1 minute up to. Linger for 20 hours. The goods are then rinsed or washed with water. Thus, the addition of the activating bicarbonates enables optimal cold bleaching or high-temperature bleaching under extreme temperature conditions.

To support the bleaching process according to the invention can This can also take place under the influence of high-energy rays such as V "'or electron beams by adding water-soluble salts of divalent cations, such as magnesium, calcium or zinc salts, in particular Calcium salts, an increase in the degree of whiteness can be achieved.

The activating effect of the dicarbonates can also be used in their bleaching activity to increase. It should be emphasized for this application *

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area in turn the possibility under Heutralbedingungen or to wash and clean oxidatively bleaching in the acidic pH range. The combined application is particularly important here with so-called hygiene additives, such as Zinc silicofluoride and acid-stable peroxy compounds mentioned in the laundry in the household.

The dialkyl and diphenyl esters of dicarbonic acid are in Insufficiently soluble in water. They are therefore made using solubilizers such as aliphatic Alcohols, from the aqueous-alcoholic phase or from emulsions, which can also contain solubilizers, applied together with the bleach and other additives that may be required. But it is also possible the activator and the bleaching agent together with small proportions of water and optionally emulsifiers from organic Solvents, for example from alcohols, chlorinated hydrocarbons such as perchlorethylene, irichlorethylene, 1,1,1-trichloroethane, fluorocarbons or chlorofluorocarbons, To apply dimethylformamide, dimethyl sulfoxide or other to the materials to be bleached. The use of solvents also makes it possible to put bleach and activator in before the actual bleaching process to apply separate application stages on the grass to be bleached. The procedure here can be such that either the activator by means of a solvent on the first Bleaching material is brought and then in a second treatment by, for example, dipping, spraying or Brush the bleach and optionally other additives from water or that this The process is reversed. The actual bleaching process then takes place after the application.

An interesting variant of the process according to the invention is that the bleaching, for example, with hydrogen peroxide from hydrophilic solvents, such as, for example, compounds that contain at least one alkylene oxide radical

30 9882/1230 .. '/ 9

included, as they are besehrieben in the German patent application P 2148590.5, is possible. It has namely shown that alkaline peroxide bleach in the presence of high amounts of hydrophilic solvents., such as Polyalkylene glycols and / or alkylene oxide addition products is not optimally feasible. Step once during familiarization of the alkali in that there are often crystalline deposits in the concentrated solutions of the. hydrophilic organic solvents arise which interfere with the application, on the other hand there is a comparative effect less bleaching effect than when working from an aqueous alkaline solution. With the acidic hydrogen peroxide bleach these difficulties can be overcome in the presence of the dicarbonates and hydrophilic organic solvents bypass. Good bleaching effects are achieved.

The amount or the concentration of the bleaching agent to be used can vary within wide limits; it is directed especially according to the degree of discoloration of the goods to be bleached * When bleaching from solutions, emulsions or pastes, for example in textile bleaching liquors, the concentration of the peroxy compound is generally between about 0.1 and about 200 g / l, in particular between 1 and 50 g / l. the Concentration of the activating dicarbonates can also be between about 0.1. and about 200 g / l, in particular between 1 and 50 g / l. The weight ratio between the peroxy compounds and the dicarbonates vary considerably within the stated use concentrations ^ it is generally adjusted so that 1 part by weight of the activator to about 0.001 to 20 parts by weight, preferably 0.5 to 10 parts by weight of the peroxy compounds is used. It has also been shown that even with very small amounts used, below 0.1 g / l of the peroxy compounds a good bleaching effect is obtained when the amount of dicarbonate is relatively high, i.e. over 100 g / l is set.

309882 / 1230- '

The bleaching liquor can also contain other additives or auxiliaries, for example optical brighteners, dyes, wetting agents, complexing agents, softeners, thickeners, defoamers , ^; Contain protection agents, e.g. fiber protection agents, and possibly also other activators. Cleaning mixtures prepared with peroxy compounds and the activators according to the invention can contain builders, surfactants, dirt carriers, cleaning enhancers, etc.

The bleaching agent and the activators according to the invention and can be used on textiles. possibly other additions to any This is done, for example, by padding, exhausting, spraying, from spray cans, by doctoring, by patting and by applying it locally, if necessary together with a thickener · !! be applied. It is also possible, the more volatile activators according to the invention • heated together with steam, hot air or other inert ones Bring gases in the gaseous state into contact with the goods to be bleached, the bleaching agent before or afterwards are to be raised.

After the application process, the bleached material remains preferably discontinuous or continuous in the broad state. This can be done using bleaching machines, such as Wide bleaching units, J-Box, boilers, devices analogous to the so-called jet dyeing devices, docking systems are used,

Are peroxy compounds for the oxidative aftertreatment of If colorings are used, the activating effect of the diesters of dicarbonic acid can also be used for this purpose.

It is advisable to use suitable devices to ensure that only a small amount of water is produced during the bleaching process Loss of moisture takes place on the goods. This can be achieved that the goods are in a saturated or an overheated steam atmosphere or the bleached material is removed from the outside, for example by means of a film.

3098 ^ 2/1230 * ^{/ 11}

is covered.

The advantage of the process according to the invention is particularly evident in a possible continuous operation, particularly at temperatures above 100 ⁰ C., which, optionally after one or more rinsing cycles connect with or without drying once more Yeredlungsprozesse .Can.

The peroxy compounds can be used alone or in a mixture with one another, as well as together with. other bleaching agents, for example chlorites, especially sodium chlorite, which release chlorine organic substances, chlorine dioxide or hypochlorites and those necessary to activate the other bleaching agents Activators, stabilizers and anti-corrosion agents are used.

The fiber materials which are suitable for bleaching according to the process of the application include natural fibers, for example cotton, rayon, linen, also copper rayon, 2 1/2 acetate, triacetate, chemically modified CeITulosefibres, jute, sisal ,. Alginate fibers, animal fibers such as wool and hair, synthetic fibers made from polyesters, polyamides, polycarbonates, polyacrylonitrile, polyolefins, polyvinyl alcohol, polytetrafluoroethylene, polyacetals, polyurethanes and their copolymers, mixtures of natural and chemical fibers and furthermore feathers and human hair. As bleach goods also vorbestrahltes _t colored or equipped material may be used. -

The textile material can be flake, melt-spun or spun-moist Threads, yarn, twine, woven fabric, knitted fabric, fleece, stitch-bonded textile, felt, pile fabric (carpets), needled fleece or needled felt. The following laminates are possible: synthetic leather, paper-textile, foam-textile combinations, Wallpaper etc.

309882/1230 '

In the same way as textiles, solid substrates made of organic polymers, such as, for example, films, can be molded or natural materials such as leather, skins, wood, paper and cellulose, by applying mixtures of peroxy compounds, Bleach bicarbonates and possibly other additives to remove an adhering yellow tinge. Cosmetic too Preparations can be made by incorporating peroxy compounds, diesters of dicarbonic acid and, if necessary, other additives to be bleached.

The bleaching process according to the invention can also be carried out after a conventional bleaching process, as well also serve as a precursor to a conventional bleaching process.

The "Blrepho" photometer from C. Zeiss, Oberkochen, was used to evaluate the bleaching effects in the examples listed below. In the examples, unless otherwise stated, remissions were measured with the 461 m μ filter and given in percent. Barium sulfate served as the white standard. Unless expressly stated otherwise, the remaining percentages are percentages by weight and parts are parts by weight.

/ 13 30988 2/1230

example 1

De-bleached unbleached cotton fabrics were made with liquors impregnated, which in one liter of a water-ethanol mixture in a ratio of 1: 1 contained the following components

I. 20 g of a 30 follow v / ater toffperoxidlösung g of a wetting agent consisting of an order-reduction product of 1 mole Nony! Phenol and 10 moles Ithylenoxid

II «20 g of a 30 ^ igen hydrogen peroxide solution g of a wetting agent," consisting of a reaction product of 1 mole of nonylphenol and 10 moles of ethylene oxide
g sodium hydroxide

III. 20 g of a 30 ^ igen. V / water peroxide solution

g of a wetting agent, "consisting of. a reaction product from .1 mole of ekmylphenol and 10 moles of ethylene oxide

g sodium hydroxide

IV. 20 g of a 30% hydrogen peroxide solution

of a wetting agent, "consisting of an urn-.

Settlement product from 1 mole of nonylphenol

and 10 moles of ethylene oxide
Sodium hydroxide
Diethyldicar "bonat

V. 20 g of a 30% strength hydrogen peroxide solution

a wetting agent, "consisting of a reaction product of 1 EIoI of nonylphenol and 10 mol of ethylene oxide
0.5 g sodium hydroxide
g Dimethyldioar "bonate

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20th G 1 G 1 G 5 G 20th G 1 G

VI. 20 g of a 30% hydrogen peroxide solution

g of a wetting agent consisting of a conversion product from 1 mole of nonylphenol and 10 moles of ethylene oxide

0.5 g sodium hydroxide

VII. 20 g of a 30 follow hydrogen peroxide solution

g of a Netzraittels, "consisting of a reaction product of 1 mole of nonylphenol and 10 moles of ethylene oxide
g diethyl bicarbonate

VIII. 20 g of a 30% hydrogen peroxide solution

g of a wetting agent, "consisting of a reaction product from 1 mole of llonylpheriol and 10 moles of ethylene oxide

1.7 g soda

5 g of diethyl dicarbonate

IX. 20 g of a 30 follow hydrogen peroxide solution

g of a wetting agent consisting of a reaction product of 1 mole of nonylphenol and 10 moles of ethylene oxide

1.7 g soda

A fabric (X) that had only been impregnated with the water-ethanol mixture was used for comparison.

The squeezing effect was approx. 60-70 fi. The impregnated samples I. to X. were covered from the outside with foil and samples thereof were further treated as follows:

a.) 16 hours at 20 ° .- 22 ⁰ C,

b.) 4 hours at 20 ° - 22 ⁰ G,

c.) 3 hours at 35 ° and

d.) Stored at 60 ^° C. for 1 hour. ' /1

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After storage, it was rinsed twice in cold water, neutralized, air-dried and then the lead effect determined. The remission values obtained are compiled in Table I.

; / 16

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Table I.

treatment

pH of the bleaching flux

Remission <f »
linger
a.) 16 h 2O ⁰ C b.) 4 h 2O ⁰ C c.) 3 h 35 ⁰ C d.) 1 h 6O ⁰ C

to

ο
co

co

OO

NJ
CjO
O

I (according to the status of

Technology)

II (")

III (")

IV (according to the invention)

VI (according to the status of

Technology)

VII (according to the invention)

VIII (»)

IX (according to the status of

Technology)

X (comparison without

Bleach)

70.8

68.6

69.9

68.2

72.2

68.7

72.3

12.5 78.7 75.5 76.2 78.8 11.6 76.2 74.5 75.4 77.2 8.1 78.9 77.8 77.2 79.9 7.1 81.0 80.3 79.0 78.8 11.2 74.7 72.9 74.4 76.7 4.8 80.4 78.6 76.5 76.9 8.1 77.8 76, α 78.5 78.5 11.3 75.1 72.2 75.3 75.3

68.7

If one compares the remission values after the dwell. Processes a "to d were determined, it is found that after the bleaching process according to the invention in a" wide pH range can be bleached. Excellent bleaching effects result with both acidic and neutral, as well as with alkaline bleaching liquors. The bleaching process according to the invention without alkali additives (VII), at low bleaching temperatures (a, "b, c) the alkaline bleaching process (II) clearly superior to the state of the art. Another surprising advantage is that the large amounts of alkali metal hydroxide (II) can be reduced. The addition of the activator according to the invention does not result in any loss of temperature to be observed (comparison II, III on the one hand and IV, V on the other hand). In the case of methods Va, b, c even a significant increase in whiteness compared to bleaching with more alkaline liquors (II) achieved.

In addition, tests were carried out in which the pH-V / ert of the liquors according to the prior art and according to the invention have been set to the same value. To this end fleets were prepared that. per liter of a Y / water / ethanol mixture (1: 1)

A. 20 g of a 30% aqueous hydrogen peroxide solution

B. 20 g of a 30 $ aqueous hydrogen peroxide solution

5 g diethyl bicarbonate

contained and

a.) with sodium hydroxide to pH 10.0

b.) with sodium hydroxide to pH 9 »0

c.) with sodium hydroxide to pH 8.0

d.) with dilute sulfuric acid to pH 5.0

were discontinued. ,

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These liquors were used to impregnate BaTi3nwollrohgeweb, samples. The squeeze was about $ 80. After the impregnation, the treated fabric samples remained in a closed chamber for ¹ hour at 80 ° C. without loss of moisture. This was followed by rinsing, neutralization and drying. The reflectance values shown in Table II were determined:

Table II

pH liquor A liquor B

a.) 10.0 73.5 # 74.1 #

b.) 9.0 74.0 fo 79.5 #

c.) 8.0 73.3 f 80.6 $>

d.) 5.0 72.7 1o 75.4 #

It can be seen that the pH range according to the invention is found in a wide pH range Use of bicarbonates is very beneficial by increasing the bleaching effect.

Example 2i

This example shows the superiority of the invention acidic peroxide bleach using dialkyldicarbonic acid esters compared to the alkaline peroxide lead according to the prior art. There were samples of an unbleached cotton fabric impregnated with the following liquors.

Liquor I contained in 1 liter of an aqueous solution (according to the prior art)

30 g of a 30 follow hydrogen peroxide solution, 15 g water glass 38 ⁰ Be,

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8 g sodium hydroxide,

g of a complexing agent based on the sodium salt of ethylenediaminetetraacetic acid and

2 g of a wetting agent based on sodium

salt of an n-paraffin polysulfonate (served of η-paraffin with an average molecular weight of 216 and with a content of about 2.5 sulfonic acid groups in the molecule).

The aqueous-ethanolic (1: 1) hotten II to IV contained in liter

II. 30 g of a 30% hydrogen peroxide solution

2 g of a complexing agent based on the

The sodium salt of ethylenediaminetetraacetic acid g of a Metzmittel, as indicated under I, g of diethyl dicarbonate

III. 30 g of a 30% hydrogen peroxide solution

a complexing agent based on sodium salt of ethylenediaminetetraacetic acid of a wetting agent, as indicated under I, Sodium hydroxide

30th G 2 G 2 G 2 G 30th G 2 w G 2 G 2 G 15th G

IV. 30 g of a 30% hydrogen peroxide solution

a complexing agent based on the sodium salt of ethylenediaminetetraacetic acid of a Metzmittel, as indicated under I, sodium hydroxide,
Diethyl bicarbonate

Y / while the liquors II and IV the process according to the invention demonstrate, liquor III serves as a comparison to demonstrate the improved lead effect by the liquor IV according to the invention to show without the addition of the activating component,

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The gray fabric patterns were / o impregnated while maintaining a Abquetscheffektes of 80 ° with the liquors I to IV. The impregnated fabrics were rolled up at 20 ^° C. for 25 hours, covered on the outside with foil, stored, then rinsed, neutralized and dried. The measurement of the remission led to the following results:

Untreated goods $ 67.6

Fleet I (state of the art) 77.9 1 °

Fleet II (according to the invention) $ 80.8

Fleet III (comparison) 78.3 ^

Fleet IV (according to the invention) $ 79.4

Example 3?

Samples of a raw cotton fabric were impregnated with the following liquors, which per liter of water

I. 25 g of a 30% hydrogen peroxide solution

2 g of a wetting agent, as in Example 2 under I.

specified

5 g diethyl bicarbonate
300 g of ethanol

II. 25 g of a 30% hydrogen peroxide solution

2 g of a wetting agent based on a sodium salt of an n-paraffin polysulfonate (as under I)

2 g of a complexing agent based on the sodium salt of ethylenediaminetetraacetic acid

4 g sodium hydroxide

8 g water glass 38 ⁰ Be

contained.

The squeegee was $ 80. The damp fabric swatches

became

a.) 20 minutes at 100 ^° C.,. / 21 '

30 9 8 82/1230

b.) 10 minutes at 12O ⁰ G and

c.) for 5 minutes at 16O ⁰ C,

in screwed metal containers, stored, rinsed and dried. The remission measurements gave the following results

a.) b.) c.) Fleet I '78.1 # 77.3 % 75.0 fo

Fleet II 77.2 <fo 72.1 f 71.5 <? O

Example 4:

There are already various compounds for acidic peroxide bleach have been proposed as activators. It is the o-formic acid triethyl ester, formic acid methyl ester and formamide. (see_J) T0S 1 469 608) These connections were included in a series of experiments. For this purpose, samples of a raw cotton fabric with aqueous-ethanolic (1: 1) liquors were used impregnated, which contained the following components per liter;

I. 30 g of a 30 follow hydrogen peroxide solution

2 g of a wetting agent based on a sodium salt of an n-paraffin polysulfonate (cf. Example 2, I)

5 g diethyl bicarbonate

II. 30 g of a 30 follow hydrogen peroxide solution

2 g of a wetting agent, as indicated under I in Example 2,

III. 30 g eiiB r 3.0 follow hydrogen peroxide solution

2 g of a wetting agent as in Example 2 under I.

specified,.

• 30 9 8.82 / 123 0

5 g of triethyl o-formate

IV. 30 g of a 30% hydrogen peroxide solution

2 g of a wetting agent as in Example 2 under I.

stated, 5 g formamide

V. 30 g of a 30% hydrogen peroxide solution

2 g of a stimulant, as in Example 2 under I.

indicated, 5 g of methyl formate

The pH of the liquors was adjusted to 5.5 with dilute sulfuric acid. The squeezing effect was 80 io. The samples of the impregnated fabrics were stored for 10 minutes at 100.degree. C. in screwed metal containers, then rinsed and dried. The remission measurement resulted in the following values:

Untreated goods 68.2 Fleet I. 75.6 II 68.2 III 68.2 IV 67.5 V 67.6

Only after the method according to the invention is one clear visible lightening effect of the goods to be bleached.

Example 5:

Samples of a raw cotton yarn were used in aqueous-ethanolic (-1 si) liquors in the liter

I. 20 g of a 30% strength aqueous hydrogen peroxide solution

30 9 8-82 / 123 0 '/ ₂₃

II. 20 g of a 30% aqueous hydrogen peroxide solution

4 g of diisopropyl dicarbonate

four hours treated contained "at 4O ⁰ C". The liquor ratio was about 1:40. After this treatment, the
Yarns squeezed off, rinsed and dried. Compared to the
untreated goods (remission 55.4 %) showed those according to I and
II treated yarns reflectance values of $ 59.3 "and 72.6% .

To show that by adding the activating effect
Dicarbonate — the amount of oxidizing agent for the bleaching effect — can be reduced, more samples of the crude were made
Cotton yarn in Fleet I and, in parallel, in the following
aqueous-ethanolic (1: 1) fleets at 2O ⁰ C four hours
long treated that in the liter

III. 20 g of a 30 'follow aqueous hydrogen peroxide solution

Sodium hydroxide

20th G 2 G 15th G 1 G 4th G

IV. 15 g of a 30% aqueous hydrogen peroxide solution sodium hydroxide
Dimethyl dicarbonate

contained. The liquor ratio was 1:40. After this
Treatment, the yarns were squeezed off, rinsed and dried. For I, III and IV remission values of 55.8, 66.4
and 66.1 io determined.

Example 6:

A heavily yellowed wool fabric was impregnated with aqueous-ethanolic liquors in a mixing ratio of 1: 1, those per liter

I. 20 g of a 30 follow aqueous hydrogen peroxide solution 1 g of a wetting agent, consisting of an um-

settable product of 1 mole of nonylphenol and 10 moles of 3098-82 / 1230 '/ ₂₄

Ethylene oxide

II. 20 g of a 30% aqueous hydrogen peroxide solution

1 g of a wetting agent, as indicated under I, 1 g of ammonia

III. 20 g of a 30% aqueous hydrogen peroxide solution

1 g of a wetting agent as indicated under I, 1 g of diethyl dicarbonate

contained. The squeegee was $ 70. The impregnated fabrics were covered with foil, ^{stored for 2 hours at 50 °} C., then rinsed several times with cold water and dried in the air. Compared to I and II, the fabric treated according to the invention according to III shows the greater lightening.

Example 7:

An aqueous-ethanolic (1: 1) liquor containing 10 g / l of potassium persulfate and 2 g / l of a wetting agent based on a reaction product of 1 mol of nonylphenol and 10 mol of ethylene oxide and a liquor containing the same components, but also containing 4 g / l of diethyl dicarbonate are used to impregnate samples of an unbleached woolen fabric. If the impregnated fabric pieces are stored, for example, for one hour at 60 ^° C. without loss of moisture, the fabric impregnated with the liquor containing dicarbonate shows a clear improvement in whiteness, while the goods treated with potassium sulfate alone show no whiteness improvement.

/ 25 3 09 8-8 2/1230

OftlGlNAL INSPECTED '

Example 8;

Samples of a raw cotton fabric are impregnated with an aqueous-ethanolic (1: 1) solution containing 2227602

20 g of a 30% strength aqueous hydrogen peroxide solution and 10 g of sodium trichloroacetate
20 g diethyl bicarbonate

contained. The squeeze effect was 80 %. After staying for two hours at 75 ° C. in a closed chamber, a rinse cycle and subsequent drying, a reflectance value of 82.2% (initial reflectance: 68.3%) was measured. Without the addition of the alkyl dicarbonate according to the invention, a lower remission of 80.6 % results.

Under the same dwell conditions on were also with fabric samples treated with the following aqueous-ethanol mixtures comparatively examined those in the liter

I. a) 20 g tert. Butyl hydroperoxide
b) 20 g tert. Butyl hydroperoxide

20 g diethyl bicarbonate

II. A) 20 g of carbamoyl peroxide
b) 20 g of carbamoyl peroxide

5 g diethyl carbonate

III. a) 20 g of magnesium peroxide in suspended form b) 20 g of magnesium peroxide in suspended form

5 g diethyl bicarbonate

contained. The remission measurement led to the following results:

I. a.) 69.5 II.a) 82.6 III a.) 68.1. b.) 72.3 b) 83.8 b;) 72.5

_{/ 26}

309882/1230

Example 9:

Samples of a yellowed polyamide knitted fabric (remission 78.9 #) were after impregnation with the following aqueous-ethanolic (1: 1) liquors in the liter

I. 20 g of 40% aqueous peracetic acid

II. Peracetic acid 20 g 20 g 40 follow Diäthyldicarbonat

stored contain one hour "at 8O ⁰ C without Feuohtigkeitsverlust, then rinsed and dried.

The goods treated with liquor II were brightened significantly better than the sample impregnated with liquor I.

Example 10:

Samples of a raw cotton fabric were impregnated with liquors of the following composition:

I. 97.8 parts of polyethylene glycol (molecular weight 400)

2 parts of a 30 fig aqueous hydrogen peroxide

solution
0.2 parts sodium hydroxide

II. 96 parts of polyethylene glycol (molecular weight 400)

2 parts of a fig aqueous hydrogen peroxide solution
2 parts diethyl bicarbonate

III. 100 parts of polyethylene glycol (molecular weight 400)

The squeeze effect was 85 fe. The impregnated fabric samples were

3098-82 / 1230 '/ 27

a.) 20 hours at 20 ° C and b.) 3 hours at 60 ° C,

covered with foil on the outside, stored. After a During the rinsing process and drying, the following reflectance values and tear strengths (kg) according to DIN 53 858 were measured:

away

I 68.5 % 25.0 kg 71.3 % 25.4 kg

II 75.1% 25.3 kg 76.6% 24.8 kg

III 66.3% 24.5 kg 66.9% 24.8 kg

Apart from the fact that the incorporation of sodium hydroxide and Yüasserglas in concentrated solutions is more hydrophilic organic Solvents such as polyethylene glycols, oxethylated and oxpropylated organic compounds, difficult is achieved with the liquor containing little alkali hydroxide according to I no bleaching effect in contrast to the invention Procedure according to II.

Example 11:

A raw cotton fabric was impregnated with an aqueous-ethanolic (1: 1) liquor containing 20 g of a 30% aqueous hydrogen peroxide solution and 5 g of diethyl bicarbonate per liter (squeeze effect 80 %) and a Jf radiation dose of 1 Mrad ( Cobalt radiation source) without loss of moisture. After the irradiation, the fabric was rinsed and dried. The remission measurement gave a value of 77.3% (initial remission 69.1%).

received on

/ 28

309882 / t230

Gftt & NAL INSPECTED

Example 12;

ο, 6th G ο, 6th G 0, 3 G ο, 7th

A cotton fabric was boiled in red wine for 10 minutes and dried (remission value $ 53.5). Two sections of the discolored Each of the fabrics was treated with liquors in the Linitestgerät in the liter of water

I 2g of a surfactant based on a secondary

Alkanesulfonates

0.5 g. a reaction product of 1 mole of nonylphenol and 10 moles of ethylene oxide Na tri umpyr ο pho s pha t
Sodium tripolyphosphate dry water glass
Sodium perborate

II 2 'g of a surfactant based on a secondary

Alkanesulfonates

Ο, 5 g of a reaction product of 1 mole of nonylphenol and 10 moles of ethylene oxide sodium pyrophosphate
Sodium tripolyphosphate dry water glass
Sodium perborate
Diethyl bicarbonate

contained. To prepare the liquors, the procedure was such that a mixture of the single components was prepared and diluted accordingly. The liquor ratio was 1:40. The treatment was carried out twice for 20 minutes at 60 ⁰ C. Between the washing treatments, a wash cycle has been turned on with cold water. The remission values after the treatments were $ 79.8 > (I) and $ 84.4 (II). The inventive activator in liquor II is the cleaning. and the bleaching effect of AusgäiigsiaisCung I significantly increased.

3098-82 / 12 30 '/ 29

0.6 G 0.6 G 0.3 G 0.7 G 0.5 G

Example 13t

Natural human hair several times, contained a 9 provided by sodium hydroxide to pH 9 $ aqueous hydrogen peroxide solution and, parallel to show a 9 aqueous hydrogen peroxide solution, the additional 20 $ Diäthyldiearbonat, based on the amount of hydrogen peroxide, coated at 30 ⁰ C for 20 minutes, then rinsed and dried. The resulting lead effect was assessed visually; after the acidic bleaching treatment with the addition of the dicarbonic acid ester, a greater degree of lightening was achieved than the alkaline bleaching treatment. In addition, an additional ripple effect was observed.

Example 14t

An unbleached cotton fabric was impregnated with a solution of 2 parts of diethyl dicarbonate in 98 parts of perchlorethylene (squeeze effect $ 75) and air-dried. Thereafter, the fabric was treated with a 1 followed by aqueous hydrogen peroxide solution impregnated and stored for 1 hour at 90 ⁰ C without moisture loss. After rinsing and drying, a remission value of 78.5 was determined compared to the initial remission of $ 68.0.

Example 15t

An unbleached polyester-cotton mixed fabric (remission! 75.3 i ") was impregnated with a liquor containing one liter of a water-ethanol mixture

4 g sodium chlorite

15 g of a 30 follow aqueous hydrogen peroxide solution

5 g diethyl bicarbonate

0.5 g sodium hydroxide / 30

3098-82 / 1230

- t> 0 -

contained. The fleet uptake was about $ 75. After the rolled-up fabric covered with foil had remained for 1 hour at 90 ^° C., followed by rinsing and drying, a reflectance ^{value of 90.8 c} / o was measured.

Example 16;

Samples of unbleached, raw cotton yarns were stored in solutions I, II and III at 25 ^° C. for 18 hours.

I 50 parts of water 50 parts of ethanol

II 50 parts of water 48 parts of ethanol

2 parts of an aqueous hydrogen peroxide solution follow

III 48 parts of water 48.5 parts of ethanol

2 parts of a 30 follow aqueous hydrogen peroxide

solution 1.5 parts of diethyl dicarbonate

After storage, the yarns were squeezed off, rinsed and dried. The following reflectance values were measured for the treated yarns:

I 61.9 f>

II 68.9 1o

III 80.1 ° / o

/ 31 09 8-8 2/1230

Example 17:

These tests show how an additional increase in whiteness can be achieved by adding salts of divalent cations, in particular calcium chloride: Cotton raw fabric samples (remission: 62.8 fo) were impregnated with liquors that were contained in a liter of a water-ethanol mixture (1 :1)

I 20 g of a 30 ^ strength aqueous hydrogen peroxide solution

4 g diethyl bicarbonate

2 g calcium chloride '....

II 20 g of a 30 " aqueous peroxide solution

4 g diethyl bicarbonate

contained. The pH values of the liquors were 4.5. The squeeze effect was 80 fo. The fabrics were ^{stored in the rolled state at 80 °} C. for 1 hour without loss of moisture, then rinsed and dried. The measured reflectance * values are:: 76.7 1 ° (I) ,. and 76.2 fo (II).

Example 18:

Samples of unbleached, raw cotton yarns were put into solutions irradiated that

I 2 parts of a 30% strength aqueous hydrogen peroxide

solution

48 parts of water 50 parts of ethanol

II 2 parts of a 30 follow aqueous hydrogen peroxide

solution

48 parts of water 48 parts of ethanol

2 parts diethyl bicarbonate

'3098-82 / _1230/32

contained. The irradiation was performed with S rays of a Co-60 source at 25 ⁰ C. The radiation dose was 2 Mrad. After the irradiation, the yarns were removed from the glass irradiation vessels, squeezed off, rinsed and dried. The following reflectance values were measured: 72.5 9 »(I), 78.8 io (II). The initial remission of the yarn was 62.3 °.

This example shows the excellent activating effect of the dicarbonates, which can also be observed under radiation bleaching conditions.

Example 19:

A cotton raw fabric was impregnated with a liquor which in the liter of an aqueous-ethanolic solution (1: 2)

200 g diethyl bicarbonate

0.1 g of a 30% aqueous hydrogen peroxide solution

contained. The squeegee was $ 80. The tissue, rolled smoothly in the thin-walled glass vessel, was exposed to ^{γ radiation from a Co-60 radiation source at 25 ° C.} The radiation dose was 2 Mrad. After the irradiation, it was rinsed and dried. A remission value of 71.6 io was determined. Pure the starting material, impregnated with water / ethanol and irradiated with 2 Mrad, the reflectance value was 63.9%.

3098 * 82/1230 '/ 33

Claims (6)

Claims 1. Process for continuous or discontinuous Bleaching and cleaning of organic matter by treating with compounds containing peroxy groups, characterized in that the activation of the peroxy compounds by adding bicarbonates of the general formula R ₁ -OC-O-GO-R ₀ , ι "" £ 0 0 in which the radicals R. and R _{2 can be} identical or different and denote alkyl groups each having 1 to 18 carbon atoms, phenyl or benzyl radicals, alkali metal or ammonium ions. 2. The method according to claim 1, characterized in that as Activator diethyl bicarbonate is used. 3. The method according to claims 1 and 2, characterized in that that the bleaching process at pH values between pH 3 and. pH 10 takes place. 4. Process according to Claims 1 to 3, characterized in that the bleaching process takes place at pH values of 4 to 8.5. 5. Process according to Claims 1 to 4 _}, characterized in that alkali metal salts of triehloroacetic acid are used as alkali donors for bleaching with peroxy compounds. 6. The method according to claims 1 to 5, characterized in that in the bleaching process additional salts of divalent Cations are added. 3 (39882/1230