DE1802576A1 - Bleach and detergent - Google Patents

Description

(US 679 611 - prio 1 Ά & 7 - 5W ^:)

Colgate-Palmolive Company _r> .

New York, N, Y. / V.St »A»

τ- ο U 2 5 7 6 Hamburg, October 9th, 1968

Bleach · »and detergent

The invention relates to agents for bleaching and washing Textiles and in particular compounds and mixtures which can be used for these purposes, with which particularly high Bleaching effects can be achieved.

The use of bleach as an aid in washing fabrics is common practice and is being used in Many of today's commercial detergents contain certain detergents Amounts of Bleach as Essential Ingredients Such bleaches are known and in the technical and patent literature described in detail, In particular, these are the Chlorine bleach like the alkali hypochlorites and the active ones Oxygen-releasing peroxide compounds such as the inorganic persalts, ZoB. the perborates, percarbonates, perphosphates, Persilicates, persulfates, hydrogen peroxide, sodium peroxide and the same.

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The peroxide type bleaching agents are generally preferred because they are more beneficial to the fabric, i.e. the fabrics treated with it are softer to the touch "suck" able to stay white longer and the like. On the other hand, with other types of bleach, which are also in relative be used on a large scale, without exception fabrics with a pronounced tendency to discolour, e.g. to yellow, obtain. In addition, the fabrics treated with these bleaching agents show a loss of strength in many cases, so that repeated treatment with them Means the life span of the tissue is shortened considerably.

Despite the many advantages which the peroxide-type bleaching agents have, they have the considerable disadvantage that their advantageous properties normally only come into effect when higher temperatures are used, ie temperatures above about 85.degree. Experience has shown that when using peroxide bleaching agents, temperatures of 90 ° C. and above are required in order to achieve the desired bleaching effect. This critical temperature dependency of Peroxydbleichmittel and in particular the PersalzbleiehmitteltWie for example sodium perborate is a considerable disadvantage in view of the widespread use of washing machines at temperatures ranging from about 50 to about 6O ⁰ C, ie at tempera doors

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BATH ORIGINAL

which are substantially below the temperatures required for • Sufficient bleaching effect in · normal household requirements. As a result, it is in PSIlen where washing one Obtained relatively high lead effect at low temperatures should be, so far inevitable, other bleaching agents than that use of the peroxide type m and the disadvantages associated therewith, x.B. the impairment of the Paserfestlgkelt, the Acceptance of oewebee su discoloration and the like su take.

In order to make greater economic use of the advantageous properties of the peroxide type bleaching agents, considerable amounts are required Research and development work has been carried out, welohe the effectiveness of these bleaching agents at lower temperatures and especially in the temperature range of to improve about 50 to 60 ° C and thus expand their range of action su.

It has proven to be particularly advantageous in this regard Use peroxide lubricants together with one or more compounds that activate the lead effect of the peroxide, in order to prepare the optimal lead effect in the deeper To achieve temperature range.

• 09832/139

BATH ORIGINAL

The exact mechanism of action of this type of activator is given 1st «was not yet clearly clarified» but it is assumed that instead of « Finding reactions lead to the formation of intermediate products, which in turn act as bleaching agents. Xn The activator plus peroxide thus act as a substance in this context Vorlaufereystem, which in situ for the formation of'Verbin. fertilize with an effective lead effect.

This theory can be explained by the fact that activator » form compounds with acylated molecules of various types duroh reaction with the bleaching agent peracids, which in turn act as a bleaching agent «From this it can again be concluded that the effectiveness of the activator depends on the strength of the acid formed in situ» i.e. is determined by the pKa value of such an acid. Regardless of the correctness of this theory, experience has has shown that the bleaching effect of peroxide compounds is significantly increased by the use of auxiliaries of this type.

Due to the need for detergents and bleaches for use in cold water, the use of such activator compounds has acquired particular importance. It 1st

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BATH ORIGINAL

^{r; i} > ■ "'' ■■ " ■ "''"'■ ■

It is known that washing and bleaching of fabrics in cold water of about tap water temperature in many In terms of advantageous 1st. For example, the dyes contained in many textiles are extremely tempera « temperature sensitive, i. e. their solubility increases with increasing Temperature to and their affinity to the Paser, their resistance, etc. decrease at the same time. As a result, you have to When washing such fabrics, comply with certain conditions i to prevent the colors from leaching or blending together and the like. In such cases there has to be a sufficient washing and bleaching effect even at relatively low temperatures »e.g. in the range from about 20 to 40 ° C.

The activator compounds known hitherto for such purposes already lead to satisfactory results in some respects, but they still have one Number of disadvantages on * One of the main disadvantage · is that these compounds are within the economical conditional limits do not lead to the desired bleaching effect. Especially not at the temperatures used for "cold" washing. So it is necessary with many of the known agents to use the activator and / or the bleaching agent in very high concentrations when one wants to get satisfactory results. In other cases

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BATH ORIGINAL

are the proposed activators not general » but only in connection with very specific types of Peroxide bleach applicable »

It has now been found that when used together of peroxides with compounds of a very specific class in bleaches and / or detergents a very high bleaching effect at significantly lower temperatures, dolu in the case of the "Cold" wash Usual temperatures, can achieve »

The present invention is therefore based on the object of activators for use together with peroxide compounds to propose in bleaches and detergents with which the disadvantages of the previously known for this purpose Connections are completely or at least largely eliminated; such activators should in particular to promote the bleaching effect of peroxide compounds when used in cold or lukewarm water are suggested ο Furthermore, it is the object of the invention Activators to synergistically increase the bleaching effect of peroxy compounds when used relatively lower Propose activator concentrations. In the end the invention is intended to propose activator compounds and detergents and bleaches containing them, which give the textiles treated with it good absorbency

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BATH ORIGINAL

• 7 -

ability> which gives a grip and resistance to discoloration during «washing and storage *

According to the invention, these tasks are performed by activators common use «never perojcyd type bleaches solved «which from compounds of the general formula

consist «where X is a halogen atom * e.g. chlorine« bromine or like "and Z is the one to complete a heterocyclic nucleus of the hydantoin or Suoclnlmidtyp represents required atoms.

Particularly advantageous results in relation to an increased bleaching effect with low peroxide concentrates are achieved with compounds of the above formula "in which X represents a chlorine atom" e.g. N-m-chlorobenzoyl- <o euocinimide and N-n-chlorobenzoyl-5 »5 ~ diiaethylhydantoin <. With ^ these compounds will, in spite of their application in very much k> small amounts, i.e. only fractions of the concentrations required for the previously - "proposed activators"

° a bleaching effect that is several times higher is achieved.

Effect can be achieved when using amounts of peroxide · which only supply S - k parts of available oxygen per 1 million parts of wash liquor. In general, for most washing processes, amounts of peroxide are sufficient, which provide 2 to 20 ppm of available oxygen in the washing solution. These concentrations of available oxygen can be easily obtained with the use of products with a based on the total product Peroxydgehalt of about 2 to 20 wt.%.

The ratio in which the activator compound and the Bleaching agents are used * is of essential importance for the system according to the invention, since it has a critical effect on the bleaching effect. This is how the activator works in such amounts are used »that a molar ratio of perborate to activator in the range from about 0.5: 1 to about 6: 1 is obtained «Within this range, the ratio can be chosen depending on the bleaching problem at hand will; in general, the bleaching effects will be optimal however, achieved at a molar ratio of perborate to activator of about 1: 1. In special and unusual However, in cases, as described in more detail below, it may be necessary to deviate from this optimal ratio in order, for example, to have harmful effects to turn off certain types of dyed fabrics.

Θ09832 / 1309

The superior bleaching effect of the bleaching system according to the invention is shown in the following on the basis of examples Unless otherwise stated, relate in the examples all quantities on the weight

Example, 1 “to J

There were placed in a Tergotometer at 49 ⁰ C using sodium molecular weight of from 154 to # 1O available oxygen and Nm-Chlorbenzoylsuccinimid activator compound in 1000 ml conducted tests of a 0.15 # solution of a commercially available detergent; the detergent used had the following composition:

water

Straight chain tridecylbenzosulfonate sodium sulfate

Pentasodium tripolyphosphate sodium silicate

Borax (as Na ₂ BJjO ^ ₀ IOH ₂ O)

Sodium carboxymethyl cellulose Polyvinyl alcohol

Antioxidants, brighteners, etc. "

In all tests, 7.5 χ 15 cm cotton rags stained with coffee and tea were used as test fabrics * The tergotometer beaker with the test cloth and the activated perborate detergent solution were 10 minutes

io, 5 Parts 21.0 ! ( 25 * 8 !! 33.5 H 7 * 0 tr 1.0 Tt 0.4 dd 0.2 Il difference to 100

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th was stirred at 75 rpm for a long time »after rinsing the test cloths dried and evaluated. Before and after washing, reflection measurements were made on the sample cloths and the differences between these measurements are noted as Δ Rd «The results are shown in the following Table 1 reproduced:

Table 1
At-,
game
No. Wa schmittelzusammensetzung Δ Rd

Commercial Na-Per-Aktiva- ppm ver ppm Molverwaschborat tor *; Available share holdings mean O ₅₅ vat or Perporat

* : Assets

gate

1 93.2 # 2, 5% 4, ■% 4 70 1: 1 4

2 88.3 # 4.1Jg 7.6 ^ 7 130 1: 1 7> 8

8.455 7.35 ^ 15 130 2; 1 6.2

'N-m-chlorobenzoylsuecinimide

As can be seen from the values above, one Available oxygen content of only 4 ppm is a good one Bleaching effect achieved · The reflection values given under Δ Rd are significantly higher than the corresponding values, which obtained using known activators under the same test conditions with the same detergent compositions * The ΔRd value of 4 obtained in Example 1 is

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In view of the low concentration of available oxygen and the relatively low temperature of 49 ⁰ C, at which the test was carried out, »astonishingly high. Such a value means a considerable bleaching effect, especially in view of the short washing time (10 minutes).

As can also be seen from the table above, optimal 4 Rd values were achieved using a molar ratio of perborate to activator of 1: 1. Mole ratios substantially above the equimolar range seem to affect the effectiveness of the system somewhat. However, the reflection values are always less still exceptionally good and significantly better than many of the previously proposed activator compounds.

For most household purposes, a molar ratio of 1: 1 is suggested; for purely economic reasons For reasons, an excessively high amount of Ferborat should be avoided »because of a given increase in concentration none corresponding increase in the bleaching effect is achieved.

If a perborate: activator-molar ratio is observed From about 1 t 1 the bleaching effect is increased by using larger amounts of activator / anti-fouling agent system. this

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is also evident from the table above, according to which an increase in the Rd value to about double was achieved by increasing the activator and perborate amounts while maintaining a perborate: activator molar ratio of 1: 1 «

Example 4 to 6

The same tests as in Example 1 to 2 were carried out with N-m-chlorobenzoyl-J ^ S-dimethylhydantoin as an activator repeated The results are given in Table 2 below:

Table 2 With washer fluid composition Δ Rd

play trade Na acti- ppm ver ppm molar

^{nr #} wash- per-movator ^ available activity

medium rat O ₀ vator perborate

^d : activator

99.2 * 2, # *,; #. 4 70 1: 1 K ₉ ? 88.3Ji k, Vfi IM 7 150 1: 1 8.1 84.3 ^ 8.4 * l, yf> 15 150 2: 1 4.9

V N-m-chlorobenzoyl-5,5-dimethylhydantoin

As can be seen from the table, reflectance values similar to those in Examples 1 to 3 were obtained. Compare with known activators showed a clear superiority

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the activators according to the invention, the difference being / at an available oxygen concentration of 7 ppm was particularly evident. The improvements in terms of on the ARd values also took part in these experiments Approaching a perborate: activator molar ratio of 2t1 from; likewise, the 4Rd values increased with increasing activator and perborate concentration if the concentration was maintained a molar ratio of 1: 1 *

Example ? until 17

As has already been explained, the improvements achieved with the system according to the invention are strongly dependent on the ratio of the perborate and activator concentration. However, the optimum proportions may vary depending on the particular use of the bleaching system * e.g. Type of fiber to be bleached, the chemical and physical properties of the colors fixed on the fiber and the like "vary in the stated range from 0.5: 1 to 6 ': 1". This is illustrated by the following examples, in which the effects of various molar ratios of perborate to activator on the Reflectance value ΔRd are shown, with the results also apply to tissue types other than those previously tested «

909832/1309

The same procedure as in Examples 1 to 5 was followed. As an activator was used in all experiments N-m-Chlorobenzoyl-sucoinimide uses «The perborate: activator molar ratios were given in the tables specified ranges vary «In order to determine the influence of various molar ratios as comprehensively as possible, the tests with detergent solutions with different

Content of sodium perborate tetrahydrate carried out so that

* „J · the specified molar ratios with 1.0 χ 10 - *, 5.2 χ 10

H
and 2.6 10 mol of activator per liter were obtained «The Reflectance measurements were again taken before and after washing. The results are in the following Table 5 given again:

Molar ratio
nis perborate
: Activator Table "p 5.2x10 " ⁴ moles
Activator 2.6XlO ^-1 W
Activator 0.5: 1 6.7 j
*
5.7 at
game
No. ₀ 1: 1 7.8 5.0 7th 2: 1 Color differences in ARd units 4.8 5.6 8th 2: 1 1, OxIO " ⁵ moles
Activator 4.5 2.5 9 4: 1 7.0 5.2 1.6 10 9.0 11th 7.4 7.0 6.5

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- lp -

The influences of different molar ratios of sodium perborate to N-m-chlorobenzoylsuocinolnide with constant content of available oxygen from the perborate of 16 ppn are shown in the following table 4:

Molar ratio
Perborate:
Activator Table 4 Color difference
in ARd-
units at
game
Ρ * · 0.5 * 1 Mole perborate 9.2 12th 0.8: 1 1.0 χ 10 " ³ 10.2 13th 1: 1 1.0 χ ΙΟ ** ⁵ 9.0 1* 2: 1 1.0 χ ΙΟ " ³ 6.8 15th 3: 1 1.0 χ 10 " ³ 4.1 16 4: 1 1.0 χ OK ** ⁵ 17th 1.0 χ 10 " ⁵

As can be seen from the tables above, optimum improvements in the reflectance values are achieved with a perborate: activator molar ratio of 1: 1. This value apparently represents a kink in the activity curve, in that molar ratios above this gave somewhat lower Δ Rd values. Similar results were obtained when Nm-chlorobenzoyl-5,5 * dimethylhydantoln was used as the activator

The results shown in the above tables confirm the observation that the activator according to the invention

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Connections the required rate of concentration er » reduce heblloh and improve the brightening dm iewttote eyntrgistlsoh »

Example 18 to 21

The degree of bleaching as a function of the concentration of verfugbarem oxygen is, as already mentioned "by the erflndungsgemäfie system significantly improved" from the following examples show »DAFL the syner m gletlsohe bleaching effect at very low Aktivatorkonsentrationen and very low temperatures occur. The general procedure described in Examples 1 to 3 was repeated, with Nm-chlorobenzoylsuecinimide being used as the activator in all cases. In all cases a molar ratio of perborate to activator of 1: 1 was used in conjunction with a detergent of the following composition suitable for 2 µm washing in cold or hot water:

Water 8.5 parts

*. Straight-chain trldecylbene sulfonate 12 * 0 ⁿ

Sodium sulfate 34.9 "

Na ₅ P ₅ O ₁₀ 32

Sodium silicate 5.0 " Carboxymethyl cellulose 0.5 " Fluorine color 0.4 ⁿ

Soap 3 * 1 "

Polyvinyl alcohol 0.2 " Antioxidants, perfume, etc. difference

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The results of these experiments are as follows Table 5 reproduced:

tempera
tur <> c Tabel 5 ppm ^of Δ Rd units
available O ₂ 16 ppm at
game
No. 27 Color differences in
at a content of 3.5 8 ppm 5.2 18th 38 2 yyypm 4 6.7 4.7 6.9 19th 49 2.0 5.8 6.3 8.4 20th 60 2.8 4.6 7.8 9.4 21 2.0 9 * 0 2.6

The above values show the extremely advantageous property of Nm-halobenzoyl amide activators to strongly promote the bleaching effect with a low perborate content even at temperatures of only 27 ° C. The particularly good usability of these activators for washing and bleaching at low temperatures is therefore clear. In addition, what is equally important, the improved bleaching effect is easily achieved with extremely small amounts of perborate, i. E. For example, Table 5 shows a Δ Rd value of 6.7, ie a very high bleeding effect at an available oxygen concentration of only

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4 ppm and a relatively low temperature of only 38 ⁰ C from «

The effectiveness of the bleaching agent / activator systems according to the invention at low temperatures and low concentrations of available oxygen has thus been proven. It is also pointed out once again that the N-yn-halobenzoylimide activators are also advantageous for bleaching at higher temperatures Temperature range from about 50 to 60 ° C and above, can be used by simply increasing the concentration of available oxygen. Here too, optimal results are achieved with mol ratios of perborate to activator of about 1: 1. It is therefore possible, by simply changing the perborate content, to produce agents for use in hot or cold water, depending on the requirements of the consumer ppm, although it is a little lower than the otherwise specified values, still represents a very high bleaching effect if one takes into account ^{the low temperature of 27 0 C «}

Example 2 2 to 27

When washing and bleaching textiles it is of course of the utmost importance that the fabrics are

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lung nloht sum yellowing tend to have optimal bleaching effects show, therefore, usually in a bluish white

Appearance of the laundry. The appearance of the washed fabric

Critical in this regard is »Many the commercial activators give the washed

However, fabrics show an undesirable color shift from white

according to OeIb. In many cases this is a direct consequence the need to use the activator as well as the perborate bleach mlttel To be used in very high concentrations »Similar

Results are obtained when the activator and / or I. Perborate concentrations are insufficient to achieve the required Orad to bring about the bleaching effect.

The superior ability of the activators according to the invention to achieve a significant relief effect is shown in the following examples. The same procedure was carried out as in Examples 1 to 3, ie with regard to the detergent used, the washing time, the stirring treatment, the soiled test cloths, and so on. In all experiments, the available oxygen from the sodium perborate was kept at 16 ppm. The amount of activator was varied in order to obtain the desired molar ratio. An increase in the Δ b values on the negative side corresponds to a higher blue content and thus the absence of oily tones, the numerical values being relative

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Assessment of this property · N-m-chlorobenzoylsucciniraid was used as the activator. The results are summarized in the following table:

Table 6 -

Example molar ratio No. perborate: activator

Rd

22nd 0, 5 23 0, 75 ' 24 * 25th 2 - 26th 3 27 4: : 1 : 1 . ι . j : 1 ί 1

9.2 -3.8 10.2 -6.7 9.0 -7.8 6.8 -5.5 4.1 -4.5 3.5 -4.6

As can be seen from the above values, optimal values for Δ Rd and Ab are obtained when using perborate: activator molar ratios around 1: 1. The values mentioned decrease somewhat with an increase in the perborate: activator molar ratio, but they still show a superior bleaching effect and a very advantageous bluish-white appearance of the tissue * The optimal results are also achieved with perborate: activator molar ratios scored by 1: 1 »

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- el -

As already mentioned, difficulties can arise in certain cases with regard to achieving the desired values for Δ Rd and Ab »This is particularly the case when bleaching and washing dyed textiles such as blue cotton percale. Such difficulties can arise with the system according to the invention can be easily eliminated if the perborate and activator are employed in molar ratios of about 2: 1 and above. Furthermore, the blueing effect is promoted by using the system at higher temperatures. However, considerable bleaching effects on dyed fabrics of the type mentioned can also be achieved at low temperatures of, for example, about 27 ^° C.

In any case, the optimal conditions can be found within the mentioned limits for the molar ratio of perborate Activator, treatment temperature, etc «, for each special one Purpose of use can easily be determined by simple laboratory tests »Guarantee the values recommended above however, generally optimal results ^

Example A and B

The activators used in the above examples were produced in the following ways:

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Α · Production of Nm ~ ChlorbengOffl8UcciniEiid

To 20.0 g of succinimide and 40 ml of pyridine, which initially had room temperature, 35 "0 g ra" chlorobenzoyl chloride "were added dropwise over 50 minutes with stirring. The mixture was then stirred for another JO minutes and the mixture was then left to stand at room temperature for several hours »The solidified mass was with 100 wil Xthanol

* added and the undissolved crude product filtered off * through Recrystallization from hot ethanol gave about 19.5 g N-m-chlorobenzoyl succinimide with a melting point of 127.5 to 128 ° C obtained.

B. Preparation of N ^ m ^ Chlorbenzoyldi methylhydantoin 140.0 g of m-Chlorbenzoyldi methylhydantoin were added to 102.4 g of dimethylhydanioin and 160.0 g of pyridine over the course of about 2.5 hours with stirring. The reaction temperature was 25 to 62 ° C «Then the reaction

* Mixture mixed with 2 liters of water, which concentrated 400 ml Hydrochloric acid contained o Then the mixture was stirred for about 10 minutes and then the white precipitate filtered off and dried to constant weight. The crude product was recrystallized from ethanol, whereby N-m-chlorobenzoyldimethylhydantoin with a melting point from 144.5 to l45.5 ° C was obtained »

809832/1309

results similar to the above examples were obtained achieved if, instead of sodium perborate, one or more other peroxides such as sodium percarbonate, potassium perphosphate » Sodium pereillkat and the like were used in equivalent amounts. The water-soluble peroxide detergents used according to the invention can be characterized as compounds which form hydrogen peroxide when dissolved in water. It is therefore assumed that these compounds contain hydrogen peroxide bound in crystalline form.

The peroxide / activator systems described can be used both as pure bleach can be used as well as in full laundry detergents. In the latter case, the detergents can use the contain a wide variety of organic washing active substances of the anion-active, non-ionic * cation-active or amphoteric type

- 24 -

809832/1309

-At-

Anlon-active surface-active substances which can be used in these detergents are compounds with an organic hydrophobic group and an anionic solubilizing group. Typical anionic solubilizing groups are, for example, sulfonate, sulfate, caftoxylate, phosphonate and Phosphate groups. Xn tracks the invention usable anionic "ψ laundry actives therefore include the soaps, ie dl" water-soluble salts of higher FottsKuren or HarssSuren, which are derived from animal or vegetable fats, oils or waxes, such as the sodium soaps of tallow, narrow "- coconut oil - or tall oil whores or mixtures thereof, and the

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ORIGINAL INSPECTED

sulphated and sulphonated synthetic detergent active ingredients, especially those with about 8 to 26 and preferably about up to 22 carbon atoms in the molecule.

Suitable synthetic anionic detergent actives are also the higher mononuclear alkylarylsulfonates with 10 to 16 carbon atoms in the straight-chain or branched alkyl group, e.g. the sodium salts of deeyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl or hexadecylbenzoisulfonate or the higher alkyl toluene, -xylene- and phenol sulfonates, alkyl naphthalene sulfonates, e.g., ammonium diamyl naphthalene sulfonate and sodium dinonyl naphthalene sulfonate, and like that.

Other suitable anionic detergent active ingredients are the olefin sulfonates such as the long-chain alkene sulfonates, the long-chain hydroxyalkane sulfonates or mixtures of alkene and hydroxyalkane sulfonates: These olefin sulfonates can be converted into known catfish by reacting SO with long-chain olefins with 8-25 and preferably 12-21 carbon atoms of the general formula RCHeCHR ₁ , where R is an alkyl group and R _{1 is} an alleyl group or a hydrogen atom, to a mixture of sultones and alkene sulfonic acids and subsequent treatment of the mixture to convert the sultones into sulfonates. Further

Θ09832 / 13Q9

are suitable sulfated or sulfonated detergent actives the paraffin sulfonates as well as the reaction products of C-C olefins with bisulfites, e.g. sodium bisulfite, e.g. primary Paraffin sulfonates about 10-20, and preferably about 15-20 Carbon atoms, the higher alcohol sulfates and the salts of oC sulfo fatty acid esters with, for example, about 10 »20 carbon atoms such as methyl ac-sulfomyristate or - oo-sulfotalg fatty acid ester.

Suitable sulfates of higher alcohols are sodium lauryl sulfate, sodium tallow alcohol sulfate, Turkish red oil or other sulfated oils and sulfates of fatty acid monoglycerides or diglycerides such as stearic acid monoglyceride monosulfate, alkyl polyethylenoxy ether sulfates such as the sulfates of the condensation ethyl alcohol products usually of lauryl alcohol products to Kthylenoxydgruppen is molecule, lauryl or other higher Alkylglyceryläthersulfonate, aromatic Polyäthenoxyäthersulfate as the sulfates of the condensation products of nonyl phenol with Kthyienoxyd * and usually 1-20, and preferably 2-12 "tnylenoxydgruppen in the molecule,

Suitable anionic detergent actives are also the acyl sarcosinates, e.g. sodium lusyl sarcosinate, the acyl esters, e.g. oleic acid esters, of isfithionates and the acyl-N-methyltaurides, e.g. potassium-N-methyl-lauroyl or oleyl tauride.

9 09832/1309

The water-soluble anionic detergent actives preferred for the purposes of the invention are the alkali, e.g. sodium and potassium, alkaline earth, e.g. calcium and magnesium and ammonium salts as well as substituted ammonium salts, e.g. the mono-, di- and triethanolamine salts of higher alkylbenzenesulfonates, olefin sulfonates, higher alkyl sulfates and higher fatty acid monoglyceride sulfates. The type and amount of these salts may vary depending on the person desired composition of the detergent can be selected.

Niohtionogenic surface-active substances which can be used for the purposes according to the invention are compounds with an organic hydrophobic group and

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ORIGINAL INSPECTED

a hydrophilic group, which by reacting a solubilizing group such as a carboxylate, hydroxyl, Amido or amino group with ethylene oxide or polyethylene glycol is formed.

Nonionic detergent active substances which can be used for the products according to the invention are the condensation products of alkylphenols with ethylene oxide, for example the reaction product of isooctylphenol with about 6 to 3,000 ethylene oxide groups, the condensation products of alkylthiophenols with 10 to 15 -'thylenoxyderuppen, the condensation products of higher fatty alcohols such as tridecyl alcohol , the ethylene oxide adducts of monoesters of hexavalent alcohols and internal ethers of the same such as sorbitan monolaurate, sorbitan monooleate and mannitan monopalmotate and the condensation products of polypropylene glycol with ethylene oxide.

Cation-active detergent ingredients can also be used for the inventive Products are used, which are made up of compounds with an organic and hydrophobic group consist of a cationic solubilizing group. Typical cationic solubilizing groups are the amine groups and quaternary groups.

909832/1309

Examples of suitable synthetic, cationic detergent actives are: diamines of the general formula RNHCgH ^ NHg, where R is an alkyl group with about 12 to 22 carbon atoms, eg N-2-aminoethylstearylamine and N-2-aminoethylmyristylamine, aminoamides of the general formula R CONHC ₂ H ^ NH ₂ , where R is an alkyl group of about 9 to 20 carbon atoms. e.g. N-2-Aminoäthylstearylamid and N-Arainoäthylmyristylamid, quaternary ammonium compounds in which one of the alkyl groups bonded to the nitrogen atom contain about 12 to 18 carbon atoms and three of the alkyl groups bonded to the nitrogen atom each contain 1 to 2 carbon atoms, the latter three groups also being inert Substituents such as phenyl groups, and an anion such as a halogen, acetate or methosulfate anion or the like is present. Quaternary ammonium compounds of this type are, for example, ethyl-dlmethylstearyl-ammonium chloride, benzyl-dimethyl-stearyl-ammonium chloride, benzyl-dimethyl-stearyl-ammonium bromide, trimethyl-stearyl-ammonium chloride, trimethyl-cetyl-ammonium bromide, dimethyl-ethyl-dilauryl-ammonium-ammonium chloride, dimethyl-dilauryl-ammonium-stearyl-ammonium chloride, dimethylethyl-dilauryl-ammonium-ammonium chloride, dimethylethyl-dilauryl-ammonium-ammonium chloride, dimethylethyl-dilauryl-ammonium-ammonium chloride, benzyl-dimethyl-stearyl-ammonium chloride and the corresponding methosulfates and acetates.

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Amphoteric detergent active substances, which in the invention Products that can be used are compounds with an ahionic and a cationic Group and a hydrophobic organic group, which preferably consists of a higher aliphatic radical with for example 10 to 20 carbon atoms. These include the N-alkylaminocarboxylic acids, e.g. those the general formula

R ₂

RN "-R ⁹ -COOM,

the N-alkylinodicarboxylic acids, for example those of the general formula RN (R ^B C00M) _{? s} and the N-alkylbetaines, for example those of the general formula

R- N -H ^P -COO

in which R is a long-chain alkyl group with, for example, about 10 to 20 carbon atoms, R ^{5 is} a divalent radical connecting the amino part and the carboxy part of an amino acid, for example an alkylene radical with 1 to 4 carbon atoms, M is hydrogen or a salt-forming radical

2
Metal, R is hydrogen or some other monovalent substituent, e.g. a methyl or other lower alk> 4-

3 and R ^
group, and R / in each case a monovalent substituent bonded to the nitrogen atom via a carbon atom, e.g.

909832/1309

Is methyl or other lower alkyl substituent. Such amphoteric washing active substances are for example H-alkyl-ß-aminopropionic acid, N-alkyl-ß-iminodipropionic acid and N-alkyl- ^ N-dimethylglyoin, in which the Alkyl group, for example from coeos fatty alcohol, lauryl alcohol, Myristyl alcohol or a mixture of lauryl and myristyl alcohol, hydrogenated tallow alcohol, cetyl alcohol, stearyl alcohol or mixtures of such alcohols,

can guide. The substituted aminopropion and imino ™

Dlpropionic acids are often in the sodium form or other salt form traded, which is also in the

inventive products can be used. Further suitable amphoteric detergent active substances are, for example, the fatty acid imidazolines such as those obtained by reacting long-chain fatty acids with, for example, 10 to 20 carbons. Substance atoms with diethylenetriamine and monohalocarboxylic acids with 2 to 6 carbon atoms obtained products, for example l-coconut-S-hydroxyethyl-S-carboxymethylimidazoline, i

Betaines with a sulfonic acid group instead of the carboxylic acid group, Betaines, in which the long-chain substance j

tuent directly, i.e. not via a nitrogen atom, to \

the carboxyl group is bound, e.g. the inner salts' of 2-trimethylamino fatty acids such as 2-trimethylaminolauric acid, and compounds of the types described above in which, however, the nitrogen atom has been replaced by phosphorus.

Θ09832 / 1309

The detergents can also contain one or more water-soluble builders of an organic or inorganic nature, for example trisodium phosphate, tetranatriurapyrophosphate, acid sodium pyrophosphate, sodium tripolyphosphate, monobasic sodium phosphate, dibasic sodium phosphate, sodium sodium metasilicate,
hexaraetaphosphate / sodium silicates with Na ₂ 0: Si0g-> ratios

from 1: 1.6 to 1: 3> 2, sodium carbonate, sodium sulfate, borax, fe the tetrasodium salt of ethylenediaminetetraacetic acid and like that. Mixtures of two or more inorganic salts and / or organic salts can also be used.

Builders particularly preferred for the present purpose are the water-soluble alkali metal polyphosphates, which are mixed with the in hard Calcium and magnesium ions contained in water form water-soluble complexes and thereby the emergence of insoluble ones Prevent salts that can build up on the textiles during washing. In addition, these phosphates increase the purification effect of anion-active detergent ingredients and support foam regulation and the suspension of the dirty textiles remove dirt particles in the detergent solution.

Various other substances can furthermore add to the inventive Laundry detergents, which are in solid or liquid form may be present, can be added in a known manner. For this

909832/130 9

include, for example, the higher fatty acid amides such as coconut or LaurinsKuremonoäthanolamld, -isopropanolamld and the like, hydrotropic solubilizers such as xylene or toluene sulfonates, organic solubilizers such as ethanol, ^ ethylene glycol and hexylene glycol »sodium carboxymethylcel.luiose and polyvinyl alcohol to prevent the redeposition of dirt, optical and fluorescent brighteners, dyes, Corrosion inhibitors, germicides, fragrances, blue stains and the same.

The preferred detergents contain a hydrophobic colloidal cellulosic soil dispersant which is soluble or dispersible in water. A particularly good dirt dioping effect when washing various textiles such as cotton and synthetic fibers, for example nylon and Dacron, and resin-impregnated cotton is achieved by using such a cellulose-like compound together with polyvinyl alcohol. This mixture is preferably used in an on ßesamtfest- (substance-related amount of O, ßew 1 to 2. #. Preferred cellulosic compounds are the alkali metal salts of carboxyalkyl "celluloses having at most 3 carbon atoms in the alkyl group such as the sodium or potassium salt of Carboxymethyl cellulose or sodium carboxyethyl cellulose; furthermore suitable

909832/1 309

the cellulose sulfate © and lower alkyl and hydroxyalkyl cellulose ethers such as methyl, ethyl and hydroxyethyl cellulose.

The quantitative composition of the detergents according to the invention is not critical and can vary within the generally customary limits. Thus, the organic washing-active substance may, for example, based on the total product amounts of about 2 wt.% To about 50GeVf be included ₄ ^. The organic and / or inorganic builders are used in amounts of about 10% by weight to about 95% by weight, based on the product as a whole.

The desired pH can easily be achieved by adding more suitable Buffer substances can be adjusted to the bleaching agent, whereby the bleaching agent is in the form of solutions * powders, granules, Flakes, etc. may be present. The bleaching agents according to the invention can have a good effect at relatively high pH so they can be used in conjunction with common household soaps and detergents can be used for gentle bleaching of textiles. Is particularly advantageous, especially in high mineral content dee water, the use of

909832/1309

BAD ORiQfNAL

""'!"" ¹¹ I ¹¹¹ IIi " ¹ :""» I *! If HjniJIillil! »! Γ p: §§ \\\ i« I i ι! 11 i; κ' ■ ■ ι;; III « ™!] !!: '· »ίμμ; ■ ■, ■

- 35 -

Chelating agents such as sodium salts of diethylenetriarainpentaeBSetic acid, of ethylenediaminetetraacetic acid etc. and / or magnesium silicate For the most bleach and / or wasoh treatments will use one Recommended pH value in the range of around 6-10 »

hb / mü / raa

909832/1309

Claims (1)

(US 679 βΐΐ τ prio 1.11.67 - 5774) Colgate-Palmolive Company New York, NY . / V.St.A. Hamburg, October 9, 1968 Claims 1. Bleaching agent »characterized by a content of solid, stable peroxygen and water-soluble Imide of the general formula O ^c -u where X is a halogen atom and Z is the one to complete a heterocyclic nucleus of the hydantoin or succinimide type represents required atoms. 2 bleaching agent according to claim I, characterized in that that it contains N-m ~ chlorobenzoyisuocinimide as an imide. 5. Bleaching agent according to claim 1, characterized in that that it is as an imide H-m-chlorobenzoyl ~ 5,5-dimethylhydantoin contains. 4. Bleaching agent according to Claims 1 to J>, characterized in that it contains sodium perborate as the peroxygen compound. 909832/1309 IIIPII II! »! II! ■ ι >: «'■ illiiisilf« - ι- ·.;.! ; ■ .-. ■ st 5. bleaching agent according to claims 1 to 4, characterized characterized in that there is perborate and imide in a molar ratio Perborate: Contains imide from about 0.5 to about 6 * 0. 6. bleaching agent according to claims 1 to 5 »characterized in that it also contains an active detergent in I an amount based on the total product of about 2 to 50 wt.g, 7 * bleaching process, characterized in that the material to be bleached with an aqueous solution of a System according to claim 1 to 6 treated. 8. Imide of the general formula where X is a halogen atom and 2 is those to complete of a heterocyclic nucleus of the hydantoin or succinimide type represents the atoms required. ^hbiraU 809832/1309