DE2265710C1 - Detergent and cleaning agent mixture - Google Patents

Description

The present invention relates to a washing and cleaning agent mixture which is combined in one Washing and bleaching processes can be used for household linen.

In common household washing processes for white goods, such as bed linen, table linen and white cotton goods, the objects to be treated are subjected to a combined washing and bleaching process in which the objects are treated in an aqueous bath containing an organic detergent and a bleaching agent (i.e. a stain removing agent ) contains. Other common detergent adjuncts such as alkaline builders, e.g. The stain remover is usually a »Pero compound, which releases oxygen at the washing temperature. Sodium perborate is the most commonly used material for this purpose. In some cases, stain removal can be carried out as a separate step using a compound that releases available chlorine, such as sodium hypochlorite, or N-chloro-organic compounds, such as dichlorocyanuric acid or its salts, or trichlorocyanuric acid.
The usual chemical processes for removing stains therefore lead to varying degrees of degradation of the textile fibers.

Oxidation reactions photosensitized by dyes are known in organic chemistry, however So far no attempt has been made to apply this type of oxidation to textiles. It has now been found that very effective stain removal can be obtained from textiles when textiles are in an aqueous bath in the presence of atmospheric oxygen and certain photosensitizing agents Connections are treated when simultaneously the textiles with visible light are irradiated, and this stain removal process expediently with a conventional washing process can be combined.

The laundry detergent and cleaning agent mixtures according to the invention, which contain an organic detergent and an alkaline detergent Contain builder salt, are characterized by a photosensitizer from eosin, rose bengal, Fluorescein, chlorophyll, metal-free porphyrin, sulfonated phthalocyanine and sulfonated zinc phthalocyanine comprehensive group.

When these mixtures are used for washing and removing stains from textiles, they become too treating stained textiles in an aqueous bath containing at least one alkaline detergent builder salt, an organic detergent and an effective amount of a photosensitizer selected from the group of eosin, rose bengal, fluorescein, chlorophyll, metal-free porphyrin, sulfonated phthalocyanine and sulfonated Zinc phthalocyanine is selected, In the presence of oxygen, during the process the Textiles are irradiated with visible light, treated.

The aqueous bath contains, and can, an organic detergent such as soap or synthetic detergent other detergent additives such as soil suspending agents, e.g. sodium carboxymethyl cellulose, and

so contain optical brighteners. The effective photosensitizers are eosin, rose bengal, fluorescein, chlorophyll, metal-free porphyrin, sulfonated phthalocyanine, and sulfonated zinc phthalocyanine. The proportion of the photosensitizer is preferably 1 to 50 mg / l of the treatment bath. The preferred photosensitizer is sulfonated zinc phthalocyanine.
The stain removal process can be carried out at a temperature of 10 to 82 ° C and is conveniently carried out at temperatures in the range of about 26 to 71 "C for a period of 15 minutes or longer, for example for a period of 15 minutes to 5 hours, preferably 15 Minutes to 60 minutes, for example at a temperature in the range from about 15.6 to 7PC.
Although no binding theory can be given, it is believed that the stain removal process takes the course given below; first the photosensitizer absorbs light to go into the triplet state.

'Sensitiser-4-h γ - · ' Sensitizer.

This reacts with Trilplel-Saucrstol'f to form singlet oxygen
¹ O ₂ + 'sensitizer - ¹ O ₂ +' sensitizer.

The singlet oxygen oxidizes the tail with the formation of colorless or water-soluble oxidation products
¹ O, + stern -. Stern O ₂ .

One such theory of the photosensitive oxidation of organic compounds is by Foote and Wcxlcr in J.A.C.S., vol. 86, p. 38X0 (1964).

The photosensitizer is preferably present in an amount of from 0.025% to 1.25% by weight of the total mixture before. The preferred photosensitive agent is sulfonated zinc phthalocyanine.

Production of the sulfonated zinc phthalocyanine:

2 g zinc phthalocyanine and 2 ml oleum (30% free sulfur trioxide) are heated to 100 ° C. for 3 hours. After cooling, the mixture is made using 5 η-sodium hydroxide solution (which is added dropwise with stirring is added) neutralized (pll 7). The solid residue is filtered and dried in vacuo. the Yield of sulfonated! Zinc phthalocyanine (contaminated with sodium sulfate) is 1.8 g.

The unpurified product is used in Example 1 as described below.

A very effective photosensitizer for use in the mixtures according to the invention is sulfonated Zinc phthalocyanine which is free from unsulfonated zinc phthalocyanine. The product can be made according to a procedure similar to that described above, but with a larger size Excess of oleum is used in the sulfonation step. A typical production method is the following:

10 g of zinc phthalocyanine and 30 ml of oleum (30% free SO ₁ ) are stirred together vigorously at 100-120 ° C. for 3 hours (effective stirring is essential and ensures that the end product does not contain any unsulphonated material). The mixture is cooled to 0 ° C. and adjusted to a pH of 7 to 8 with the addition of 40% sodium hydroxide solution. The resulting paste is subjected to suction filtration and the solid is washed with 120 ml of cold water. The solid (19 g) A mixture of the sodium salt of unsulfonated zinc phthalocyanine and sodium sulfate Fr is a very effective photosensitizer for the bleaching process. Especially when it is used in an amount of 6 mg / l.

The filtrate obtained during the production of catfish gives a solid residue after evaporation to dryness (32 g). which is also a mixture of the salt of zinc phthalocyanine and sodium sulfate, but one higher content of sodium sulphate reveals this product is an effective photosensitizer for the Bleaching method. Particularly when it is used in an amount of 50 mg / l.

Thin layer chromatography on Sillcagel using the lower phase of a mixture of 2 parts by volume of pyridine, 1 part by volume of chloroform and 1 part by volume of water as the eluent and running unsulfonated zinc phthalocyanine in the same chromatogram as the standard shows that both samples of the sulfonated material are free from unsulfonated zinc phthalocyanine. The absence of unsulfonated zinc phthalocyanine can also be demonstrated by electrophoresis on a Polyacrylamldgel using a gepuf- to pH 8 tt ferten solution.

It is believed that the active material is a mixture of di-, tri- and trasulfonates of zinc phthalocyanine is, with only traces of the monosulfonate being present. Small variations in the proportions of these components do not seem to affect the product's efficacy as a photosensor.

It has been found that if the photosensitive generator is contaminated with unsulfonated phthalocyanine, Tissues that come into contact with such material in the absence of light develop greenish spots can.

Sulphonated zinc phthalocyanine contaminated with unsulphonated material can be purified as a result Be sure to put the material on a sintered glass filter with copious amounts of water until nothing is left dissolves, washes. The unsulfonicrtc material remains undissolved on the filter and the filtrate is evaporated to dryness, whereby a photosensitive image is obtained which is free of unsulfonated material.

It is essential, as the following experiments show, that the bleaching liquid is water-soluble, alkaline Detergent Builder Sal / Revealed.

In the following tests, 2 standard cotton rags (6.3x6.3 cm) soiled with tea were, stirred with a magnetic stirrer in I I water in a beaker with 11.4 cm diameter, the Bulb of an electric tungsten shop lamp of 100 W placed 7.6 cm above the surface of the liquid was. The temperature and tent were as shown below and the water contained those below specified additives. The photosensitive agent used was sulfated zinc phthalocyanine, that of unsulfonated Was phthalocyanine free and prepared according to the procedure described above. Other additives were used as indicated. At the end of the experiment, the rags were rinsed and dried and the percentage of stain removal was determined by reflection measurement on the non-stained Cloths, the stained cloths and the treated cloths. The results are given in Table I.

Table I.

Content of 11 bleach bath, 0 0 Builder PH value Tempe time in % Stain Photosensitive surfactant 900 mg sodium linear alkyl (ing) rature Min. at least bilizer: (Ci2) -benzenesulfonate 500 mg tridecanoimide ( ⁰ C) tion (in mg) 700 mg sodium decyl sulfonate (a) (b) 700 mg potassium dodecyl sulfonate (C) (d) (e) ω (G) 25th 0 500 mg C ₁₂ E ₆ **) 0 6th 50 30th 0 25th 900 mg sodium linear alkyl 500 mg of dodecyl betaine (Ci2-benzenesulfonate 200 mg dimethyloctadecyl 0 6th 50 30th 0 25th 900 mg sodium linear alkyl amine oxide (Ci ₂ ) benzene sulfonate 500 mg of dodecyl betaine 0 10 50 30th 0 25th 700 mg sodium decyl sulfonate 0 6th 50 30th 0 25th 700 mg sodium decyl sulfonate 500 mg tridecanoimide 0 10 50 30th 0 25th 500 mg of dodecyl betaine 0 6th 50 30th 0 25th 200 mg dimethyloctadecyl 500 mg CuE ₆ **) amine oxide 0 6th 50 30th 0 25th 500 mg dimethyldodecylamine oxide 1.6STP *) - 50 30th 45 25th 0 1.6STP *) - 50 30th 46 25th 0 1.29 sodium 0 citrate - 50 30th 33 25th 1.6STP *) - 50 30th 33 25th 1.6STP *) - 50 30th 40 25th 1.6STP *) - 50 30th 47 25th 1.6STP *) - 50 30th 33 25th 1.6STP *) - 50 30th 40 25th 1.6STP *) - 50 30th 30th 25th 1.2 sodium citrate - 50 30th 11th 25th 1.2 sodium citrate - 50 30th 11th 25th 1.2 sodium citrate 50 30th 33 25th 1.2 sodium citrate - 50 30th 33 5 1 Na ₂ CO ₃ - 50 25th 32 5 1.2 Na ₂ SiO ₃ - 50 25th 27 5 0 - 50 25th 0

*) STP = pentasodium tripolyphosphate.

**) C12E6 = primary C ^ alcohol, which is condensed with an average of 6 ethylene oxide groups.

Table I shows that a builder salt is necessary. Neither mere alkalinity nor a surfactant is effective in Absence of scaffolding stolT. Suitable frameworks are sodium tripolyphosphate, sodium citral, sodium carbonate and sodium silicate.

The bleaching process requires the passage of visible light and the visible light must have light with it a wavelength of 640 nm or more.

Experiments similar to those described above in connection with Table I were carried out in 1 liter of water using standard cotton swabs soiled with tea, which contained 0.4 g of a commercially available washing powder "A" with the following composition:

Sodium dodecyl (linear) benzene sulfonate 17.6Hi

Sodium toluenesulfonate 1.8%

Sodium tripolyphosphate 462.0%

Sodium silicate 7.3%

Coconut fatty acid monoethanol amide 1 $%

Sodium carboxymethyl cellulose 1.0%

Sodium salt of ethylenediaminetetraacetic acid 0.3%

Purl by 0.1 ",,

! • tightness] (), () ""

Sodium sulfate remainder

The photosensor was a sulphurous zinc phthalocyanine, which was present in an amount of 5 mg / l. The reading was carried out in a canopy, the wound and base of which were covered on the outside with an aluminum foil and the top of which could be completely covered with an Ilford glass filter. The light source was a 100 W incandescent bulb mounted 15.2 cm above the liquid surface. The test cloths were stirred for 30 minutes at 5O ⁰ C.

The light filters used were "Tricolor Red" filters, which were in the wavelength range from 640 nm to ins Infrared were transparent, and "cyan", which allows light in the range from 360 to 580 nm, was not transparent in the range from 590 to 690 nm and shows a very low transmittance above 690 nm.

The results obtained were as follows:

Stern reduction:

Unfiltered light 67%

"Tricolor Red" filter 62%

"Cyan" filter 32 ¹ V

Under the same conditions but in the absence of the photosensitizer, treatment with gave unfiltered light a spot reduction of 30v

It is therefore clear that a wavelength in the range from 640 nm to the upper limit of the wavelength which is a Incandescent lamp emits (approx. 720 nm), required lsi. The photosensor itself absorbs strongly in the area from 640 to 690 nm, so this is most likely the effective length band.

A suitable source is sunlight or one or more incandescent lamps. Certain electrical ones Fluorescent lamps, which emit white light, are not suitable, apparently because they im 640 Do not emit strongly up to 690 Nonomctcrband.

The intensity of the visible light with which the textiles are irradiated is, for example, at least 1000 lumens Suitable light intensity is created by a lamp of 100 W, the 1000 to 1200 -TO Lumen emitted and placed 3 to 6 inches above the liquid surface. The one for stain removal required time can be shortened. By using stronger lamps, like a "photo lamp" of 500 W, which emits 16,000 lumens.

B e i s ρ I e I 1

4 g of the synthetic detergent powder "A", as mentioned above, become 1 l of water (for 50 "C) Place in a 11.4 cm diameter beaker and use the solution for 30 seconds stirred a Magnel stirrer. The required amount of the sulfonated zinc phthalocyanine is added and the solution is stirred for an additional 1 minute. Two standard cotton cloth cloths (/ u each 6.3 χ 6.3 cm) that come with Tea stained are placed in the liquid and a photolamp of 500 W is placed 7.6 cm above the Liquid surface mounted. The liquid is stirred for 30 minutes at 50 "C with the light switched on, whereupon the cloths are removed, rinsed, / wipe filter paper, dried and ironed. The stain removal is determined by measuring the reflection of the tissue before and after treatment.

The results are given in the following table:

Knn / .cnlrutlon; in suHonlcrlem ■ · "I leak / Inkphlhalotyanln, mg / 1: unlearning 2 47 5 65 IO 66 15th 61 30th 62

Using 10 mg / 1 sulfonated! Zinc phthalocyanine and increase the application time to 60 Minutes you get 81% stain removal.

If the same conditions are used, but different photosensitizers in amounts of 10 mg / 1 and with a washing time of 30 minutes, the following results are obtained:

60

l'hotüscnslblllsator: ",, I leak-

Resolution:

Pink bengal 39

53

A similar experiment was carried out for 30 minutes in the absence of the phosphorescent substance and without exposure to light, but carried out using 1 g / l Nalrlumperborat In tier washing liquid; there was a stain

removal of 38%.

Effective stain removal can be obtained when the above-described procedure is followed by usual Outside temperatures and textiles in the treatment bath daylight, preferably sunlight, get abandoned.

The method is therefore extremely suitable for household washing purposes in such areas, in soft the household washing methods outdoors, usually in strong sunlight with the use of water be carried out at ambient temperature. Under such conditions is a stirring of the bath uncommon, and longer periods of posture than if the process were agitated is carried out in a bathroom with artificial light.

B c i s ρ i e 1 2

This example illustrates the implementation of the method under normal external conditions. That The detergent and cleaning agent mixture was the same as that used in Example 1.

2 standard cotton cloth flaps (dimensions 6.3x6.3 cm each) that have been stained with tea are, in 1 1 of water at 15 "C, the 4 g of the detergent and cleaning agent mixture and 30 mg of sulfonated Contains zinc phthalocyanine and is in a plastic bowl.

The bowl is taken outside; the sky was overcast, but the sun was shining from time to time. The contents of the key have not been moved.
After 2 hours, the percentage of stain removal 50 ', ¹ O, and after 5 hours was 70'a ₁ stain removal.

Similar attempts were made using the photosensitizer, but in the absence of washing and washing Detergent mixture carried out with a 16% stain removal in 2 hours; one try water alone did not remove the stain after 2 hours. The lighting intensity during the trial varied from 20,000 to 40,000 lumens.

Claims (3)

Patent claims: 1. detergent and cleaning agent mixture containing an organic detergent and an alkaline Gerüslstofl'salz, characterized by a photosensitizer made from eosin, rose bengal, fluorescein, Chlorophyll, metallic porphyrin, sulfonated phthalocyanine and sulfonated zinc phthalocyanine Group. 2. detergent and cleaning agent mixture according to claim 1, characterized in that the proportion of the Photosensitizers 0.025% by weight to 1.25% by weight of the total weight. 3. detergent and cleaning agent mixture according to claim 1 or 2, characterized in that the photosensitizer is sulfonated zinc phthalocyanine, which is essentially unsulfonated zinc phthalocyanine free 1st.