DE1072348B - laundry detergent - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

PATENT LETTER 1 072

INTERNAT. KL. CLId REGISTRATION DATE: SEPTEMBER 28, 1957

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: DECEMBER 31, 1959

ISSUE OF

PATENT DOCUMENT: June 3, 1960

AGREES WITH EXIT 1 072 348 (P 19396 IVa / 23 e)

It is a known fact that white tissues often have a yellowish or whitish-gray tinge accept, especially after repeated washing. To avoid such discoloration and in order to restore a white appearance to such dyed fabrics, two main methods have been used developed. The first is to use bluing agents on the fabrics to be washed pull on directly and the tissues become white due to a blue color that compensates for the yellow color Give color and thereby make it more pleasing to the eye. The second of these methods includes the use of so-called fluorescent optical brighteners, which also apply directly to the tissue pull up and this by emitting light of a certain wavelength a visible whiteness to lend.

Typical foaming agents in use are, for example: Iron-based foaming agents such as Turnbulls Blue and Prussian blue, as well as pigments such as ultramarine. These foaming agents are usually after Wash the fabric applied with a water rinse. It would of course be useful to have this blueing to be achieved by incorporating the bleaching agent directly into the detergent, which is why in this direction various attempts have already been made. Attempts at this were for various reasons Adding bleaching agent to a detergent, but not completely satisfactory.

A bleaching agent should be used as a component of detergents, if it is present in effective concentrations, no permanent stains on the fabrics when the dry detergent comes into contact with damp Fabrics or when a pulp or a concentrated solution of the detergent comes into contact with the fabrics cause when removing local contamination. The blowing agent should also with the Usual detergent ingredients compatible and, since detergents are usually alkaline, in the presence be stable from alkali. If the detergent is to be liquid, the blowing agent must be in the liquid Medium soluble or easily dispersible. The blowing agent should also be relatively heat-resistant so that it can be introduced during the manufacture and processing of the detergent. Furthermore, in the effective concentrations it should not discolour the detergent itself.

None of the commonly used blowing agents has all of the beneficial properties mentioned above.

Using fluorescent brighteners is the second most important method of preserving the skin original whiteness of fabrics and to freshen up the white color of repeatedly washed detergent

Patented for:

The Procter & Gamble Company,
Cincinnati, Ohio (V. St. A.)

Claimed © Priority:
V. St. v. America, October 1, 1956

Edmund Frederick Gebhardt, Glendale, Ohio

(V. St. A.),
has been named as the inventor

tissues. However, many of these brighteners give the fabrics a weak residual color for usually pink or green. Although this residual color is seen much better than a yellowish or whitish-gray one Shimmer, it is undesirable for many consumers. This disadvantage becomes special Obvious when consumer lists are drawn up, which on the one hand favor a blue and white sheen on the fabrics and on the other hand to express such a residual color.

The detergents according to the invention give an effective and beneficial blueing effect without Permanent stains occur when these detergents come into direct contact with damp fabrics or when a slurry or concentrated solution of the detergent is applied directly to the fabric. In addition to this very unusual affinity for fabrics, this is also found in the detergents according to the invention The foaming agent contained is compatible with the usual detergent ingredients, stable to alkali, see above far heat resistant that it is in effective concentrations during the manufacture of the detergent in this can be introduced, soluble in water and washing solutions and confers in the effective concentrations the detergent itself no undesirable coloring. The blending agent also improves the appearance of tissues that have already taken on a pink or green tinge, which often occurs when washing fabrics in the presence of the brightener.

009 543/213

In the detergents according to the invention, a water-soluble alkali metal salt is used as the foaming agent Condensation product of 2 moles of 1-amino-4-bromo-2-anthraquinone sulfonic acid and 1 mole of ρ, ρ'-diaminodiphenyldimethylmethane is used. The sodium salt has the following structural formula:

O NH, H, NO

The invention is based on the discovery that this particular dye is the most unique and unexpected Has the property of interacting with alkaline cleaning agents in such a way that that the intensity of the blueing effect in the respective washing process and the respective fabric depends on the ratio of dye to detergent substance, but on the concentration of the The dye in the wash solution is essentially independent over a wide range of concentrations is. As far as is known, this property has never been achieved, nor is it known to be achieved with any other dye can be obtained. Because of this property, the invention, the Detergents containing foaming agents do not stain at all, as will be explained in more detail below.

The above blowing agent is known in the art, and the commercial product is under sold under the trade name "Polar Brilliant Blue GAW 180%". It contains according to the information of the manufacturer 10% ineffective diluent and 90% effective dye, which is made from the sodium salt of the The reaction product obtained above condensation exists. Below is when specifying the concentration of the effective dye constituent, reference is made to this reaction product. Simplicity The term "bluing agent" is used to identify the active dye component.

The detergent substance in the detergents according to the invention can be a water-soluble alkali soap or one of the known anionic or nonionic detergent substances or a mixture the same alone or in combination with water-soluble alkali metal polyphosphates, e.g. B. tripolyphosphate, Pyrophosphate, etc. The detergents can have the usual physical properties, z. B. in the form of granules, liquids or flakes. Since the affinity of the foaming agent for Cotton is the strongest, the detergents according to the invention are particularly suitable for washing of cotton fabrics. Other fabrics such as polyamide fabrics and other fine fabrics also show one increased whiteness after washing with detergents containing the whitening agent, namely with or without the addition of brighteners.

The amount of the expanding agent which, after incorporation into the detergent according to the invention, is the amount washed with it Gives the desired bluish whiteness to fabrics, fluctuates largely and depends primarily Line depends on the amount and type of active washing substance and the type of fabric to be washed. However, it is both through the effect of other components on the affinity, the tone and the Degree of discoloration of the fabrics to be washed, the presence or absence of brighteners as well affects the degree of blue color considered acceptable.

For detergents in which alkali soaps are about 95 percent by weight of the total composition make up, a minimum concentration of 0.0014 percent by weight is sufficient when washing cotton fabrics of the bleaching agent, based on the active washing substance, to a favorable bluish whiteness to achieve. On the other hand, in the case of liquid detergents, they gave water, pyrophosphate and various Ingredients in an amount of 87 percent by weight of the total composition and in which the anion-active detergent substance from 9.0 percent by weight, based on the total detergent, Sodium alkylbenzenesulfonate (the alkyl group was derived from polypropylene and contained an average of 12 carbon atoms per molecule) and 4 percent by weight,

ao based on the total detergent, made from potassium alkyl glycerol ether sulfonate (which is sulfonated and neutralized by the reaction of epichlorohydrin with coconut fatty alcohols having 10 to 14 carbon atoms Product) consisted of about 0.005 to 0.03 percent by weight of the foaming agent, based on the detergent Substance, when washing cotton fabrics a favorable bluish whiteness, without any too strong blue tone appeared. Other detergents that contain significant amounts of tripolyphosphate, sodium sulfate etc., d. H. 82.5 percent by weight and 17.5 percent by weight as the detergent substance, based on the total product, sodium alkylbenzenesulfonate (the alkyl group was derived from polypropylene and contained an average of 12 carbon atoms per molecule), was achieved at a minimum concentration of the foaming agent of 0.004 percent by weight, based on the detergent substance, when washing Cotton towels have a cheap bluish whiteness. Of course, when washing fabrics, for which the affinity of the blowing agent is lower "than for cotton, larger amounts of the blowing agent for Achieving an equivalent blueing effect is required.

As stated above, a minimum concentration of the foaming agent of 0.0014 percent by weight results in based on the detergent substance, a desired one in certain detergents according to the invention bluish whiteness, but this minimum concentration depends on that in the detergent contained active cleaning agent changes. Of course, the maximum concentration fluctuates in the same way of the bleaching agent, but avoiding amounts that give a definite blue color. In no case has a higher concentration of the foaming agent than 0.04%, based on the weight of the active detergent substance, proven to be beneficial.

Generally speaking, the detergents according to the invention impart aqueous solutions with conventional solutions Detergent concentrations of e.g. B. about 0.1 to about 0.3 percent by weight, based on the water, an alkaline reaction. They contain at least one detergent substance and at least about 0.0014 percent by weight of the expanding agent, based on the detergent substance, as an effective expanding agent concentration. In addition to soaps and nonionic detergent substances, the detergents according to the invention contain preferably an anionic synthetic detergent substance of the alkali sulfate or alkali sulfonate type, which contain an alkyl radical with about 8 to 22 carbon atoms in the molecule. In addition,

20th

hold the detergents according to the invention preferably alkali pyrophosphates and alkali polyphosphates, in particular Alkali tripolyphosphate. Alkali salts include both potassium and sodium salts Roger that. The ratio of alkali polyphosphate to the anionic detergent substance is expedient between 1: 1 and 5: 1. Products with a ratio between about 1: 1 and 3: 1 have a particularly good performance. The preferred expanded concentration range in these detergents ίο is about 0.004 to 0.03 percent by weight, based on the anion-active substance.

The following examples explain the invention in more detail. For all given in these examples In testing, the washing conditions were comparable to those for normal household laundry.

example 1

Detergent granules dried by spraying. The quantities given are parts by weight:
Sodium alkylbenzenesulfonate (the alkyl group is derived from polypropylene and
contains an average of 12 carbon atoms

per molecule) 17.5

Sodium tripolyphosphate 47.0 _a g

Water soluble sodium silicate solids 6.0

Sodium sulfate 16.3

The monoethanolamide of coconut oil

fatty acids with 10 to 14 carbon atoms 2.7
Water, carboxymethyl cellulose, the 3 ,,

Discoloration of metal surfaces
preventive substances and fragrances 8.5
Polar Brilliant Blue GAW 180% (90%

active expanding agent) 0.0015

The _pH value of this composition was in a conventional washing concentration of 2.32 g / l in 54.5 ° C water 10.1. The blowing agent made up 0.0078 percent by weight based on the sodium alkylbenzenesulfonate. As such, the spray-dried product was light blue in color.

Cotton terry towels, specimens made of cotton muslin, polyamide, viscose rayon, acetate rayon, Polyacrylonitrile, polyethylene terephthalate, silk and wool were put together in a perpendicular standing miniature washing machine washed in the following way: 3.8 1 water, the 8.8 g of the detergent Contained, an amount of substance corresponding to 6 percent by weight of the water was added. the Fabric was then washed for 10 minutes at 54.5 ° C, rinsed, dried, a second time under the same Conditions washed, rinsed again and dried.

As a control and as a basis for comparisons, the same cloths were washed under the same conditions, however, the control detergent did not contain any blowing agent. When comparing the in the absence Towels washed with the bleaching agent showed the corresponding cotton terry towels, the cotton muslin fabric and the polyamide fabric, which was washed in the essence of the blowing agent, was a definite one and desirable bluish whites. The blue color of the cotton fabrics was, as expected, more pronounced, since the expansion capacity of the expanding agent in the detergents according to the invention on cotton is stronger than on polyamide fabric. With viscose rayon, acetate rayon, the Polyacrylonitrile cloth, polyethylene terephthalate cloth, silk and wool were the desirable ones bluish whiteness visually imperceptible.

Example 2

Liquid detergent made from the following parts by weight:

Sodium alkylbenzenesulfonate (the alkyl group is derived from polypropylene
and contains an average of 12 C-

Atoms per molecule) 9.0

Potassium alkyl glycerol ether sulfonate (the
by reaction of erpichlorohydrin
Coconut fatty alcohols with 10 to
14 carbon atoms obtained sulfonated

and neutralized product) 4.0

Potassium pyrophosphate 18.0

The monoethanolamide of coconut oil fatty acids with 10 to 14 carbon atoms 3.0

Potassium Toluenesulfonate 8.5

Ethyl alcohol 4.0

Water soluble sodium silicate solids 4.25
Sodium - 4,4'-bis- (4,6 - dianilino - s - triazo - 2 - y lamino) -2,2'-stilbene - disulfonate (fluorescent optical brightener 0.110

Sodium 2-sulfo-4- (2-naphtho- [1,2] -triazolyl) -stilbene (fluorescent

optical brightener) 0.040

Polar Brilliant Blue GAW 180% (90%

active expanding agent) 0.003

Water 49.15

The _pH value of this detergent was in aqueous solution at 54.5 ° C and at typical detergent concentrations of 3.27 g / l 11.3, and the color of the liquid detergent were used both in terms of gloss and color tone to extremely satisfactory. The concentration of the foaming agent was 0.021 percent by weight, based on the sum of the detergent substance, ie sodium alkylbenzenesulfonate plus potassium alkylglycerol ether sulfonate.

Cotton terry towels, swatches of cotton muslin, Polyamide fabric, acetate rayon, viscose rayon, polyacrylonitrile fabric, polyethylene terephthalate fabric, Silk and wool were put together in a vertical miniature washing machine washed in the following way: 3.81 Water containing 12.4 g of the above detergent was added to a 6 percent by weight of the water corresponding amount of substance. The fabric was washed for 10 minutes at a temperature of 54.5 ° C, rinsed, dried and then washed a second time under identical conditions, rinsed and dried.

As a control and as a basis for comparisons, the same fabric samples were washed under the same conditions, however, the detergent used as a control did not contain any blowing agent. It should be noted that the control detergent, however, contained fluorescent brighteners, which were applied to cotton, polyamide, Peel viscose rayon and acetate rayon fabrics directly on.

The cotton, polyamide, viscose rayon and acetate rayon fabrics washed with the control detergent had an appearance typical of fabrics washed in the presence of this brightener, d. H. a pale pink sheen.

When compared, the cotton terry towels, the cotton muslin, the polyamide fabric and the rayon that was washed in the presence of the bleaching agent was a definite one and desirable bluish whiteness which the respective controls did not exhibit. As in the case of

Game 1, the bluish whiteness of the cotton fabrics was more pronounced, showing the blue color a blue intensity that is extremely desirable for the average consumer. The polyamide fabric had also assumed a pronounced, desirable bluish whiteness, but was somewhat less bluish than the cotton fabric. The foaming agent concentration of the detergent used in this example was also sufficient to make the viscose rayon to impart a pronounced bluish whiteness, a result which was not observed in Example 1. The acetate silk, the polyacrylonitrile, polyalkylene terephthalate, As in Example 1, silks and wool showed no visually perceptible desirable ones bluish whiteness.

To determine the staining of the foaming agents contained in the detergents according to the invention, the undiluted, liquid detergent according to this example was applied directly to a small area of each of the following fabrics: cotton, polyamide fabric, viscose rayon, acetate rayon, polyacrylonitrile, polyethylene terephthalate, silk and wool. After a contact time of 15 hours, the fabrics were rinsed in water, dried and visually checked for staining. The color imparted to the fabric during 15 hours of contact with the detergent had been rinsed out to such an extent that no stain could be seen. Probably the detergent resulted in the combination of the properties of the nouns Bläumittels and the solubilizing effect of the high local concentration of the detergent active substance in the alkaline _pH value _is a uniform distribution of the Bläumittels throughout the tissue. A practical consequence of this fact is that the liquid detergent according to this example can be applied directly to very soiled parts of a garment made of one of the above fabrics. Examples of this are the collars and cuffs of white cotton shirts, in which case no permanent staining is to be feared.

As far as is known, no other blowing agent is effective when present in a detergent Concentrations of these advantageous or even comparable properties.

Example 3

Laundry detergent in flake form. The amounts given are parts by weight.

A mixture of sodium and
Potassium soaps of the higher sebum fatty acids (20 percent by weight K salt
and 80% by weight sodium salt). .. 94.5

Water :. 4.3

Polar Brilliant Blue GAW 180% (90%

active expanding agent) 0.0015

Sodium chloride and glycerin 1,2

60

The Pj ₁ value of this detergent was 10.4 at a usual washing concentration of 2.32 g / l in 54.5 ° C. warm water, and the cam-shaped product was light blue. The foaming agent made up 0.0014 percent by weight based on the sebum soap. Cotton terry towels, cotton muslin, polyamide fabric, acetate rayon, viscose rayon, polyacrylonitrile, polyethylene terephthalate, silk and wool were washed together as in Example 1 in a vertical miniature washing machine.

As in Examples 1 and 2, the same fabric samples were used under the same conditions for comparison purposes washed with a detergent, which is only distinguished by the lack of the bleaching agent from the the first difference.

The cotton terry towels washed in the presence of the bleaching agent and the cotton muslin fabric exhibited a desirable bluish whiteness when compared to the cotton control fabrics. at Polyamide fabric, viscose synthetic silk, acetate synthetic silk, polyaeryl nitrile fabric, polyethylene terephthalate fabric, no noticeably favorable bluish whiteness was visually perceptible in the silk and wool fabrics.

In the detergent used in this example, 10 parts of the sebum soap can be divided by 10 parts of the alkylbenzenesulfonate used in Example 2 with essentially the same results be replaced.

Example 4

The washing procedure of Example 3 was repeated using the detergent from Example 3, this, however, additionally used as a brightener 0.02 parts by weight of sodium - 4,4 '- to - (4,6 - dianilino-s-triazo-2-ylamino) -2,2'-stilbene-disulfonate contained. An increase in the bluish whiteness of the cotton terry towels and the cotton muslin fabric was observed due to the bleaching agent and a slightly greater perceptible intensity of the blue color than in the Example 3.

Example 5

In accordance with the invention, the following detergent was used to achieve an effective and desirable blue stain, all amounts being given as parts by weight. The _pH value of this composition was in a conventional washing concentration of 2.32 g / l in water at 54.5 ° C 10.1. The foaming agent was 0.0085 percent by weight, based on the sum of the detergent substances, ie based on the condensation product of tall oil and ethylene oxide.

The condensation product of tall oil
and ethylene oxide containing 1.6 parts

Ethylene oxide per part tall oil 16.0

Sodium tripolyphosphate 21.0

Sodium pyrophosphate 21.0

Water soluble sodium silicate solids 10.0

Sodium carbonate 20.0

Carboxymethyl cellulose 1.0

Sodium 4,4 '- bis - (4,6-dianilino - s - triazo-2-ylamino) - 2.2 '- stilbene - disulfonate (fluorescent optical brightener) 0.09

Sodium-2-sulfo-4- (2-naphtho- [1,2] -triazolyl) -stilbene (fluorescent

optical brightener) 0.03

Polar Brilliant Blue GAW 180% (90%

active expanding agent) 0.0015

Water 11.0

Cotton terry towels, cotton muslin, polyamide, acetate artificial silk, viscose artificial silk, Polyacrylonitrile, polyethylene terephthalate, silk and wool samples were placed together in a vertical standing miniature washing machine washed in the following way: 3.8 1 8.8 g of the detergent containing Water was added to an amount of substance amounting to 6 percent by weight of the water. The fabric was

Washed for 10 minutes at 54.5 ° C, rinsed, dried and then a second time under identical conditions washed, felt and dried. The basis for comparison and control were the same Swatches were washed under the same conditions, except that the control detergent did not contain a whitening agent contained.

When the fabrics were washed in the detergent according to the above example, the following were obtained Results. When compared with corresponding ones washed in the absence of foaming agent The cotton terry towels washed in the presence of the bleaching agent, the cotton muslin cloth, showed fabrics and the polyamide fabric has a distinct and desirable bluish whiteness, where the intensity of the blue color was more pronounced in the cottons. A desirable bluish one Whiteness was in the viscose rayon, the acetate rayon, the polyacrylonitrile fabric, the polyethylene terephthalate fabric, the silk and wool are not visually perceptible.

The condensate from tall oil and ethylene oxide, in the detergent composition of this example, other nonionic s) ^r nthetische washing-active substances to be replaced, without thereby th the substantive natural sheep, ie the direct substantivity of Bläumittels.ungünstig is affected. As a replacement z. B. a nonylphenoläthylenoxydkondensat with an average of 15 moles of ethylene oxide per mole of nonylphenol and a coconut alcohol ethylene oxide condensate with 15 moles of ethylene oxide per mole of coconut alcohol in question, the coconut alcohol fraction used contains 10 to 14 carbon atoms.

Claims (3)

PATENT APPLICATIONS: 1. Detergent made from soap and / or at least one which gives alkaline washing liquors anionic or nonionic detergent organic agents, characterized by the content a water-soluble alkali salt of O NH, as a blowing agent in an amount of at least about 0.0014 percent by weight, based on the water-soluble, washing-active, organic agents. 2. Detergent according to claim 1, characterized by a. Content of the foaming agent between about 0.004 and about 0.03 weight percent. 3. detergent according to claim 1, characterized in that that it also contains a fluorescent optical brightener. β 909 707/326 12.59 (009 543/213 6.60)