NO142127B - DETERGENT MIXTURE THAT INCREASES THE CLEAR WHITE IN WHICH WASHED MATERIAL - Google Patents

Description

The invention relates to the problem of making textile materials "bluer" or of improving the apparent whiteness of textile materials

hot by treating these with aqueous solutions of mixtures of water-soluble, organic, blue-tinting dyes. The invention has its greatest utility in supplying to the textile materials, especially cotton, highly diluted solutions of the mixed dyes selected so that together they give a desired blue tone or apparent whiteness, these results being at least partially attributable to the dyes' adhesion and stability in the solutions from which they are applied to the dry, treated textile materials.

The average person seems to prefer white objects, such as washed textiles, which have a slight blue tint. In other words, for most housewives, truly white, i.e. achromatically white textile materials will not appear as white or have as appealing an appearance as corresponding textile materials that have been made bluer. It has therefore been known to treat material

alers with bluing agents to improve the appearance of the materials. Water-soluble dyes and pigments have been added to detergents and other products for the treatment of textile materials to give the treated materials a bluish appearance. Some of these water-soluble dyes have been shown to have undesirable properties in that they change color shade and are converted into different and undesirable colors due to chemical action, such as e.g. of bleaching agents. In some laundry products, especially those containing blue pigments, the coloring material tends to deposit on the textile material to a similar extent with each treatment, and repeated treatments can cause an unwanted build-up to such an extent that a bluing effect is no longer preferred, but considered as contributing to an undesirable color which is

damaging the whiteness of the treated materials.

Fluorescent dyes, sometimes referred to as optical brighteners or optical brighteners, convert ultraviolet light into visible light. They have been used in mixtures, e.g. detergents, to make the materials shinier or whiter. A relatively large proportion of the most widely accepted fluorescent whitening agents give the treated materials a corresponding red-blue or violet hue, which is not as preferred as a neutral blue or less reddish hue on washed materials.

Although the products for cleaning and whitening clothes, textiles and other materials, such as e.g. made from cotton, wool, linen, synthetic textile materials (including nylon grades, acetates, polyesters, rayon grades and synthetic blends) and blends of natural and synthetic materials, e.g. cotton-polyester blends, have been greatly improved in recent years, prior to the present invention there were still problems in connection with the production of the second desired "white" blue tones for washed materials while avoiding an accumulation of the bluing dye to such an extent that the was undesirable, and so that, if desired, the blue tone could be completely removed, and it was likewise desired with such a flexible production that products of other colors than those used for the production of the bluing agents could be used for the production of the products by means of the desired manufacturing methods without this affecting the coloring effect due to chemical or other forms of degradation. With the help of the present detergent mixtures, textile materials can be given the desired degree of whiteness using very small relative amounts of water-soluble dyes, and the products used for this can contain small colored spots, they can be made of other colors or they can have a white appearance , and it can be used according to commercially competitive production methods. All these purposes are achieved with very low expenses.

Thus, according to the invention, a detergent mixture is provided which increases the apparent whiteness of the washed material, containing 5-85% by weight of a synthetic, organic, detergent-active material or a mixture of such materials consisting of anionic, non-ionic and amphoteric, detergent-active materials and 15-95% by weight of one or more builders, fluorescent whitening agent, fillers, solvents, dyes and other additives, and the detergent mixture is characterized by the fact that 0.2-2.0% by weight of a whitening agent is used as fluorescent whitening agent, which means that treated material acquires a red-blue or violet hue, and that 0.0005-0.01% by weight of a mixture of the per se known dyes is used as dye:

the green-blue dye with the formula

in which the radicals R are hydrogen or lower alkyl with 1-3 carbon atoms, and the red-blue dye with the formula in the form of the corresponding bis-copper complex and in which the radicals R' are hydrogen or lower alkyl with 1-3 carbon atoms, preferably the green-blue dye with the formula and the red-blue dye with the formula

in the form of the corresponding bis-copper complex, in an amount of 0.0001-0.004 wt.% green-blue, synthetic dye and 0.0001-0.004 wt.% red-blue, synthetic, organic dye, the ratio of green-blue, synthetic dye to red-blue, synthetic dye is 2:1 - 4:1 and the ratio of the mixture of the substantive, synthetic, organic dyes and fluorescent dye is 5:10000 ~ 5:1000, all percentages based on the weight of the detergent mixture.

According to the invention, it is preferred that the dyes are incorporated into the detergent mixture together with a mixture of synthetic anionic and non-ionic detergent-active compounds.

The important features of the invention are the choice of the two dyes. The dyes balanced in relation to each other give a desired white or almost imperceptible neutral blue tint to the washing water or the materials being treated, and their tint will not be significantly changed by the usual chemical treatments, e.g. hypochlorite bleaching or per-compound bleaching, and the desired blue tint will be retained on dried textile materials between treatments. When using the two dyes to achieve a desired shade, the relative amounts of these can be adjusted to satisfy the user's wishes. This change in the relative amounts of the dyes is also useful for achieving the desired color when other materials in the mixture, e.g. fluorescent whiteners, colored detergent compounds or splashes of builders or fluorescent pigments, also contribute to the color of the treated textile material.

It is another important feature of the invention that the dyes can be removed simply by hypochlorite bleaching. Thereby, too strong an accumulation of the bluing agents is prevented. If it were desired to obtain a certain degree of such accumulation and if bleaching is important for removing stains or for other purposes, bleaching with per compounds, e.g. perborate, is carried out without destroying the dye heritage. The dyes used according to the invention can be introduced into alkaline solutions or slurries which are used for most washing, soaking and twisting operations. With the help of the present invention, a desired controllable bluing effect can be achieved in a reasonable way, the blue tone can be removed, and the product will be so weakly colored by the bluing agents that other dyes or whitening agents that may be present will exert a significant coloring effect on the appearance of the product. Dye shades will not be changed by bleaching chemicals or other treatments of the textile materials.

US patent documents no. 2893818 and no. 2930760 describe laundry detergents in which a single blue-toned dye is used, possibly together with a fluorescent whitening agent. Nowhere in these patent documents is it proposed that two blue-toning dyes should be used together, and far from together with a fluorescent whitening agent, let alone a combination according to the invention of a green-blue-toning dye and a red-blue-toning dye together with a fluorescent whitening agent. The highly advantageous possibility of regulating the blue tone of the thus washed laundry, which can be achieved by using this combination according to the invention, is clearly substantiated in the present description.

An essential feature of the invention is shown in the drawing of which

Fig. 1 graphically shows the color tones for different dyes that have been applied to cotton from aqueous solutions, such as solutions of detergents, and Fig. 2, in the same way as Fig. 1, is a graphic representation where the color tones of green-blue and red-blue dyes on textile materials are shown separately, the color tone of a mixture of these in the presence of fluorescent whiteners is shown, and the bleaching of the dyes using a hypochlorite solution is shown. It appears that the +a-axis on the drawing indicates the degree of redness and the -a-axis the degree of greenness. Similarly, the +b axis indicates yellow and the -b axis blue. By choosing a combination of dyes designated as J and K, a color can be formed on treated textile materials that lies between the colors of the selected dyes, and in such cases as shown in Fig. 2 where a fluorescent white-medium reddish hue occurs, a suitable choice of ratio between the dyes can give the treated textile material a neutral blue colour. The arrows along the lines in Fig. 2 represent the bluing effect obtained after a single typical laundry and hypochlorite bleaching carried out after washing with the dye in the detergent product. When using perborate or other per compounds or when bleaching with peroxides, a considerably smaller removal of dye is obtained, as a rule 1/10 - 1/3 at normal washing temperatures, e.g. 48-60°C, of the bleaching effect with hypo-

chlorite. The dyes designated as J and K are discussed in more detail below.

It appears from Fig. 1 that the dye J is blue-green and that the usual fluorescent whiteners and the dye K are red-blue.

It also appears that when choosing a suitable combination of dyes, e.g. a 1:3 ratio of red-blue and green-blue dyes (K and J), the color of a laundry detergent containing fluorescent whiteners with the shade F can be brought back to neutral blue. It should be noted that washed laundry will reflect a lot of white light and that the bleach will still emit white light, but the violet shade will change to a neutral blue. 3 an overall effect will be a shiny white cloth with a faint tint of neutral blue, instead of yellow as may be the case in connection with ordinary washings, without dyes or bleaching agents, or violet as when bleaching agents are present without bluing dyes. By choosing the best of a number of ratios of the two adherent bluing dyes, the best bluing effects can be obtained with any mixture of the large number of whiteners available, all commercially available types of which seem to produce a red-blue or violet tint.

As shown in Fig. 2, the dyes J and K were on cotton, which

was subjected to ordinary hypochlorite bleaching in accordance with the manufacturer's instructions for sodium hypochlorite aqueous bleaches, completely bleached, and the cotton fabrics returned to an almost achromatic white color. Such results are also obtained when the bleaching is carried out during washing. Also, substantially all of the color was removed from other textile materials, such as synthetic polymers or blends, which had been "blued" with the dyes. The effect of the fluorescent whitening agent is also lost

occasionally after bleaching, although some whitening agents are resistant to bleaching. The shown neutral blue color obtained can thus be completely removed. When bleaching is carried out with sodium perborate at a temperature of approx. 49°C, which is a realistic water temperature for washing machines in the USA, only approx. 1/3 of the dye.

A housewife can thus choose the bleaching agent she wishes to use, and by choosing the right one, regulate whether the bluing effect caused by the dye mixture present is to be kept on the laundry or removed. Fig. 2 also shows colors obtained by using different ratios between the dyes J and K.

It appears that none of the perborates, other percompounds or hypochlorite bleaches change the color tone of the present dye mixtures.

The mixture used preferably has such a concentration that a suitable "blueing" of the most adherent material in the laundry is obtained. In most cases, the fabric that most strongly attracts dyes is cotton, and the concentrations of dyes will therefore be chosen so that the cotton does not become too blue. The degree of bluing for less absorbent materials may indeed be lower, but they will usually also absorb less fluorescent dye and will therefore usually have the desired colour.

Although the invention is primarily advantageous for synthetic detergent mixtures in the form of spray-dried balls or granular products, it is also useful for other washing products which may be solid, chunky, cake-like, particulate solid materials, paste-like, gel-like, in the form of solutions, dispersions and emulsions or in other forms. The invention is thus useful for synthetic coarse detergent mixtures, synthetic fine detergent mixtures, detergent mixtures which are primarily used because of their bluing effect or fabric softeners and soaking products. The rest of the description will mainly concern the most preferred embodiments of the invention, i.e. spray-dried detergent mixtures, but the teaching presented will also apply to other of the indicated products.

The dyes in the detergent mixtures according to the invention have the following structural formulas:

Dye J (green-blue) :

, where R is a hydrogen atom or a lower alkyl group with 1-3 carbon atoms.

Dye K (red-blue):

which is used as the corresponding bis-copper complex, in which R' is a hydrogen atom or a lower alkyl group with 1-3 carbon atoms.

The various dyes can of course be used in the suitable acid form or salt form, and equivalent modifications of the described structural formulas are also useful.

Preferred dyes are those in which the lower alkyl groups

R and R<1> are methyl groups. The dyes marked J and K are commercially available under the designation "Direct Brilliant Sky Blue 6 B Extra Conc." and "Solophenyl Violet 4 BL" . The reference numbers for these dyes are 24410 ("CI. Direct Blue 1") and 29120 ("CI. Direct Violet 66").

In detergent mixtures (hereafter for simplicity referred to as "detergents") in which the aforementioned dye mixtures are used, the active cleaning component is preferably an anionic detergent-active material, and the more preferred detergents of this type also contain a non-ionic detergent-active material. Mixtures of such materials and amphoteric materials can also be used. The anionic detergent-active materials usually contain 8-26, preferably 10-20 carbon atoms in a higher organic, hydrophobic group and comprise at least one water-solubilizing radical consisting of sulfonates, sulfates, carboxylates, phosphates and phosphonates to obtain a water-soluble detergent-active material. Examples of suitable anionic detergent-active materials are water-soluble, sulphated and sulphonated synthetic detergent-active compounds containing an alkyl group with 8-20, preferably 12-18 carbon atoms. Such a group can form part of a higher acyl group. Of the linear alkylbenzene sulfonates, those having 12-15 carbon atoms in the chain and in which the salt-forming cation is sodium are strongly preferred. The most important condition for obtaining a good washing-active compound of this type is that it must have a linear chain so that the product becomes biochemically degradable.

The non-ionic, synthetic, organic, detergent-active compounds are usually made up of condensation products of organic, aliphatic or alkylaromatic hydrophobic compounds and hydrophilic lower alkylene oxide groups. A number of different hydrophobic compounds containing carboxyl, hydroxyl, amide or amino groups with a free hydrogen atom on the nitrogen atom can be condensed with a lower alkylene oxide or an equivalent compound, such as ethylene oxide, polyethylene oxide, or polyethylene glycol, forming nelisation of the non-ionic detergent-active compounds.

Although not generally used in detergents, amphoteric detergent-active materials are useful. These are usually water-soluble salts of derivatives of aliphatic amines containing at least one cationically active group, e.g. a quaternary ammonium, non-quaternary nitrogen or quaternary phosphonium group, one or two alkyl groups of 8-18 carbon atoms and an anionically active, water-solubilizing carboxyl, sulfo, sulfate, phosphate or phosphonium group. The groups can be straight or branched, and the cationically active nitrogen atom or phosphorus atom can be present in a heterocyclic ring.

Cationic surfactants are generally avoided in the present detergents, but they can be used if no anionic agents are present or when a laundry detergent is primarily used because of its antibacterial effect.

Detergents in which the above dyes have been introduced may also contain building salts, fillers, solvents and other additives. Typical examples of building salts that can be used are the inorganic building salts, such as alkali metal polyphosphate salts, e.g. pentasodium tripolyphosphate, tetrasodium pyrophosphate and the corresponding potassium compounds. Other builders that are particularly popular in mixtures with a low phosphate content are alkali metal silicates and carbonates and also the corresponding borates and bicarbonates. The organic builders used are the sodium salt of the citrates, diglycolates, gluconates and ethylenediaminetetraacetic acid and trisodium nitrile triacetate. Mixtures of builders can of course be used, and they can be supplemented with fillers which generally have no significant function in terms of increasing the product's washing power. Suitable fillers include the sulphates, chlorides, nitrates and acetates, usually in the form of the alkali metal salts thereof, e.g. sodium sulfate. Usable solvents are primarily aqueous solvents, and any supplementary solvent will generally be a lower alcohol, e.g. ethanol and isopropanol, or a polyol, e.g. polyethylene glycol and glycerol. Other organic solvents can of course also be present, e.g. in the form of emulsions.

The various other additives used besides

the fluorescent dyes, include germicides, fungicides, perborate bleaches, enzymes, soil suspending agents, fabric softeners, thickeners, corrosion inhibitors, sequestering agents, stain inhibitors, perfumes and various other materials which are intended to increase the functional and aesthetic properties of the detergent, such materials are well known in the art and therefore do not need to be described in more detail here.

Of the additives that can be used for detergents, there are materials that can be used alone in other laundry detergents together with mixtures of the above-mentioned dyes. Enzymes can e.g. added to detergents or they can be introduced into a soaking product. Dirt suspending agents, e.g. sodium carboxymethyl cellulose, methyl cellulose and hydroxypropyl methyl cellulose, may also be present in the detergents or the soaking agents. A useful antibacterial effect can be obtained by adding germicides to the detergent or by using these for separate treatments after washing is finished. Fabric softeners can be used in a similar way.

The concentration of dye mixture used is such that

an effective amount of the mixture is obtained, usually up to approx. 3 parts per million parts of the laundry to be whitened. The dyes used, which have substantially the same adhesion to the fabric to be treated, will improve the whiteness of the fabric regardless of whether they are added in diluted or concentrated solutions or for a longer or shorter time. The dye mixture is usually dissolved in an aqueous medium with generally more than 99% water so that the concentration of the dye mixture will be 0.01-0.2

parts per million, as the relative amounts between the

different dyes are 1 : 5 - 5 : 1. In the detergent, the dye mixture will usually make up 0.005 - 0.01% of the detergent, which in turn will make up 0.05 - 1% of the washing water.

The application temperature for the different clothing products and the contact time can vary relatively strongly. The general temperature range for application is 10-90°C, and a preferred range is 40-60°C. Such a range is considered "preferred" because it is the most common temperature range for most washing operations. The contact time between the dye mixture solutions and the fabric can also be varied greatly from 1 minute to 1 hour, usually from 10 to 45 minutes. In order to achieve uniform dyeing, it is generally preferred that the solution of dye mixture is kept in motion in relation to the clothes or the laundry being treated.

The optical whitening agents used, which cause the thus treated material to acquire a red-blue or violet hue, will generally be known whitening agents for use in connection with cotton qualities and synthetic textile materials, and they are present in a concentration of 0.2 - 2%, preferably 0 .5 - 1.5%, of the detergents. Almost all fluorescent whiteners give the treated fabric a red-blue tint, and the concentration of the dye mixture used is such that a bluer whiteness is obtained. Selected mixtures of the above-described green-blue synthetic dye and the above-described red-blue synthetic dye in which the concentrations of both dyes in the detergents are within the described ranges have been effective in counteracting the fluorescent dyes' red-blue hues and "whitening" the laundry, and especially if the concentrations of the detergent in the wash water are 0.1 - 0.5%.

In the detergents, the content of the dye mixture is 0.0005-0.01%, and the concentrations of each of the green-blue and red-blue dyes are 0.0001-0.004%, preferably respectively. 0.001 - 0.003% and 0.0003 - 0.001%. The detergents contain 5-85%, preferably 10-50%, synthetic, organic, detergent-active material (including soap) or a mixture of such detergent-active materials, and 15-95%, preferably 25-75%, builders, fillers, solvents and other additives. When the detergents are liquid, the quantities of the detergent-active materials can of course be relatively high and often 50-85%, and when the products are particulate solids the quantities of builders and fillers can be high, usually a total of 30-95%, and preferably 15- 45% building and 15-50% filler salt. The amounts of the other additives are usually small and often total below 10% and occasionally as small as below 5%.

Water, which is the most commonly used solvent, can make up 50-95% of the liquid detergents and often 1-20% of the content of particulate, solid detergents. The non-ionic detergent material which can be used together with 5-30% synthetic anionic detergent material usually makes up 1-10% of the product, but it can be present in as much as 50% of the liquid content. The ratio between non-ionic detergent-active material and anionic detergent-active material is usually below 1:2. The ratio of green-blue dye to red-blue dye is 2:1-4:1, and the ratio in a mixture of the adhesive synthetic dye to the fluorescent dye is 5:10,000 - 5:1000.

In highly preferred detergents, such as those described in the examples below, the anionic detergent material consisting of a sodium salt of a higher linear tridecylbenzenesulfonic acid constitutes 7-15% of the product and the nonionic detergent material consisting of a higher fatty alcohol condensation product with ethylene oxide constitutes 1-<*>+ %. In such products, the molar ratio between higher fatty alcohol and ethylene oxide is approx. 1 : 8 - 1 : 1<>>+. The building salt present in this detergent is made up of 20 or 25 - 35% pentasodium tripolyphosphate and 5 - 10% sodium silicate with a ratio Na20:SiC>2 of 1:2 - 1:3. Of the amount of genetic material used, the green-blue dye contributes 0.001 - 0.003% and the red-blue dye 0.0003 - 0.001%. The best of the products described below contain 25-50% sodium sulfate as a filler which has such a particle size that no particles pass through the opening in a No. 8 U.S. standard sieve and not more than 10% pass through a No. 100 sieve. However, particles within the range 6 - 160 mesh can also be used. Such products are preferably produced by spray-toking an aqueous mixture from a soap mixing apparatus and in which the preferred building salt is pentasodium tripolyphosphate.

The spray drying itself is carried out with a watery mixture containing 30 - 70% of solid materials under normal conditions, with the rest usually being made up of water or another suitable aqueous medium. Less than 0.01% of the mixture is made up of compatible blue dyes with different color shades. The mixture can be carried out at a suitable temperature from room temperature (20°C) to 90°C, and the spray drying is carried out by spraying the mixture through spray nozzles under high pressure, e.g. 21 -70 kp/cm 2 , into a dry gas with a temperature of 110 - ^-00 C. Cocurrent or countercurrent spray towers can be used. Due to the content of alkaline building materials, the mixture in the soap mixer will usually have a pH in the range of 9-11, and despite such a high pH and the high drying temperature, the color of the dyes present does not change during the treatment.

Whenever clothing is treated by applying thereto an aqueous solution or solvent solution or suspension of treatment materials, the presence of the mixed dyes described above will contribute a bluing effect so that the whiteness of the treated toys is enhanced. The detergent

can of course be available for use in the form of a liquid, a solid material, a paste, an emulsion or in another suitable form.

Instead of spray drying, the dyes can be subsequently sprayed in the form of a solution on detergent particles or on part of such particles. If desired, the dyes can be used to color only a part of particulate, solid materials, e.g. 0.2-10%, preferably 0.5-5%, of these. The colors can be shiny if high concentrations are used in connection with only a small part of the particles, or they can be very bright, as when the dyes are distributed evenly over all particles. If desired, other covering dyes can be used, preferably "volatile dyes" which do not have a permanent effect on the color of the treated textile materials. Such dyes include "Polar Brilliant Blue RAW", "Levalon Blue FFR" and "Acilon Sapphirol BNA".

In the examples below, all parts are based on weight and all temperatures in °C unless otherwise stated.

Example 1

A synthetic, organic coarse detergent intended for use in cold or hot water was produced by spraying a mixture from a soap mixing device ("crutcher") with the following composition in a countercurrent tower:

The above aqueous slurry was stirred in a heated mixer at a temperature of approx. 60°C for 5 minutes after the addition of all components. It was then pumped through spray nozzles and spray-dried in a counter-current spray exchange tower, with the spray exchange pressure being approx. h2 kp/cm and the temperature of the cooling air in the sprbyte tower approx. 350°C. The spray nozzles had such an opening that they produced particles within the particle size range of 6 - 160 mesh (U.S. standard sieves). After processing, particles outside this area were sieved or separated in some other way. The moisture loss was approx. 33% in and the final product had a moisture content of approx. 11%. After that, approx. 0.2$ perfume sprinkled on the surface of the particles.

The product produced was essentially white with a slight

blue hue. It was used for washing cotton wool with a detergent concentration of 0.15% in water with a temperature of <1>+9°C and a hardness of 150 parts per million. The washing was carried out in

standard washing machines in different washing times of 10 - 30 minutes. After rinsing and drying, the washed items were compared visually by ten experts with washed items washed with the same described product, but without the green and red dyes. In daylight, lamplight and fluorescent light, the experts clearly preferred the color of the toy items that had been washed with the detergent containing the dye mixture. Clothes and other toy items that have been washed with this detergent are easy to clean and have an appealing white color that is preferred by most people.

In a similar experiment, the concentrations of the greenish blue

and the reddish blue dye baked approx. 3 times. After five washes of mixed textile items including cotton items and items made of synthetic materials, e.g. mixtures of cotton goods and polyester goods, nylon goods and acetate goods, the treated materials were judged, and the materials that had been treated with the detergent containing the dye mixture were preferred in a ratio of 2:1 over textiles washed with a control detergent. However, some of the experts stated that the color of the cotton goods was "almost too blue", and to avoid this, the content of the dyes in the product can be reduced. In both of the above-mentioned trials, the pH of the mixtures affects so that it was approx. 10.5, and that of the washing water, which was approx. 2, not detrimental to the stability of the dyes. When the washed goods were again washed with the same detergent, but containing 0.2 1 of a 3% sodium hypochlorite solution per 57 1 washing water, the dyes in the mixture were bleached so that the textiles had a more achromatic white appearance. Such bleaching of a J:K=3 dye mixture is shown by the line

for J:K=3 in fig.2 which goes back to near the origin a little over on the "brownish" side of the a-axis. When sodium perborate is used as a bleaching agent in a concentration of 2-20$ in the detergent, the dye's color is not so strongly bleached, and approx. 2/3 of the color power remains. Nevertheless, stains on the washed goods are removed by this bleaching.

In preferred products, the spray drying properties are regulated so that a product is obtained in which the particles have a size greater than 8 mesh and less than 10% of the particles pass through a 100 mesh sieve.

The same results are obtained when the washing is carried out in soft water

and in very hard with a hardness of respectively 50 parts per million and 200-300 parts per million. The product's color change from the violet area to the more neutral blue area is noted by the experts and can also be confirmed using suitable equipment.

The experiments described above were repeated, but by application

of a non-ionic fine detergent containing 40% nonylphenol polyoxyethylene ether with approx. 15 oxyethylene groups per molecule, together with 2% of the amphoteric detergent active material "Miranol", 10% sodium sulphate and the rest water and smaller amounts of other additives.

Such a product also dyes cotton washed with this blue, and the blue color can be bleached with a sodium or calcium hypochlorite solution. Such essentially non-ionic detergents can be prepared with

a content of up to 50$ of the non-ionic detergent active material and 10$ of the amphoteric detergent active material while still achieving the results described above. The non-ionic detergents can be prepared in the form of solutions, emulsions, pastes or creams.

In other variations of the above-mentioned main recipe, the relative amounts of synthetic, organic, detergent-active material and of the builder-filler combination were varied so that the content of synthetic, detergent-active material was increased by 50$ and the content of builders was decreased by 50$. The reverse change was also made,

and in both cases the more neutral blue color obtained with the dye mixture was preferred by the observers.

When the pentasodium tripolyphosphate is replaced by half the amount

of trisodium nitrile triacetate and the sodium sulfate content is increased accordingly, a slightly neutral blue tint is still obtained. This is also achieved when the slurry of the linear tridecylbenzene sulfonate is replaced with an equivalent amount of sodium lauryl sulfate, sulfated polyoxyethylene lauryl alcohol or the sodium salt of branched dodecylbenzene sulfonato. In a similar way, such results are obtained when the soap content increased to 2$ and when the amount of fluorescent whitening agent is doubled or halved. When the content of fluorescent whitening agent forandroc,, it is preferred to change the content of dye mixture in a corresponding way„

Example 2

A spray-dried, granular laundry detergent with the following composition was produced:

The spray drying was carried out under the conditions described in example 1, and the product had a particle size in the range of 8-100mesh. The green-blue and red-blue dyes J and K described in example 1 were applied in the form of an aqueous solution at 2% by weight

of the particles, and the particles acquired a dark blue colour. The product was a speckled or multi-coloured detergent powder and gave the same results in tests as the product according to example 1 in terms of improving the color of textiles that were washed with the product. In some cases, when the losses of non-ionic detergent-active materials are very high during the spray-drying, part of the non-ionic, detergent-active materials can be subsequently sprayed onto the detergent particles. The dyes must then be applied together with the non-ionic detergent-active materials. In another embodiment for the production of products with the above-mentioned composition, the mixed dyes were added to the mixing apparatus, and after production of the detergent particles which were light-coloured, part of them or the whole product was colored with a volatile dye, such as Polar Brilliant Blue RAW or any of the other dyes described in the above l<r>.S. Patent Document No. 15^692.

When a product with the composition according to example 2 is changed by replacing 20 parts sodium sulfate with sodium perborate, a bleaching detergent is obtained which leads to an improved neutral blue dyeing of washed cotton clothes, such as terry towels, and synthetic fabrics. After repeated use of a sodium hypochlorite bleach, either alone or in a detergent, the blue color is bleached out and the tissues acquire an almost achromatic white colour.

Example 3

A laundry soap powder was prepared by mixing together the following granular materials in the amounts indicated:

The dyes were applied by spraying a diluted solution (1% in water) on the surface of the granular materials in the mixture while this was stirred.

The product obtained had a very light color and gave a more neutral blue color to the tdy washed with the mixture than when the dyes were sloyed.

Example h -

A fabric softener with the following composition was produced:

In a five-time trial wash, this mixture proved to give better whiteness than a control mixture under three types of light, i.e. lamp light, daylight from the north and fluorescent light, when it was used with the same final dilution as the detergent according to example 1. The treated products were soft and had a dark neutral blue colour.

Example 5

A blood-laying agent with the following composition was produced:

After an immersion test with pure tdy for approx. one hour each, cotton terry towels and diapers dipped in the mixture had a preferred color compared to the result using knn-troll blotting agents. Similar results were also obtained in connection with cloths made of synthetic textile materials. The treated clothes had a more neutral blue color and could still be bleached with hypochlorite if this was desired. The final concentrations of the dyes used were similar to those described in Example 1.

Claims (1)

Detergent mixture which increases the apparent whiteness of the washed material, containing 5-85% by weight of a synthetic, organic detergent-active material or a mixture of such materials consisting of anionic, non-ionic and amphoteric detergent-active materials and 15-95% by weight of one or more builders, fluorescent whitening agent, fillers, solvents, dyes and other additives, characterized by the fact that 0.2-2.0% by weight of a whitening agent is used as fluorescent whitening agent which causes material treated in this way to acquire a red-blue or violet hue, and that 0.0005-0.01% by weight of a mixture of dyes known per se is used as dye: the green-blue dye with the formula in which the radicals R are hydrogen or lower alkyl with 1-3 carbon atoms, and the red-blue dye with the formula in the form of the corresponding bis-copper complex and in which the radicals R' are hydrogen or lower alkyl with 1-3 carbon atoms, preferably the green-blue dye with the formula and the red-blue dye with the formula in the form of the corresponding bis-copper complex, in an amount of 0.0001-0.004 wt% green-blue, synthetic dye and 0.0001-0.004 wt% red-blue, synthetic, organic dye, the ratio between green blue synthetic dye and red blue synthetic dye is 2:1 - 4:1 and the ratio of the mixture of the substitute synthetic organic dyes and fluorescent dye is 5:10000 - 5:1000, all percentages based on the weight of the detergent mixture.