DE1122658B - Liquid detergent - Google Patents

Description

The invention relates to an improved liquid cleaning agent containing detergent substances, the is characterized by improved clarity, durability and good retention of the degree of whiteness, and a method for its production using a degraded water-soluble carboxyalkyl cellulose ether.

Although the invention is generally applicable to water-soluble carboxyalkyl cellulose ethers, For the sake of simplicity, it is mostly referred to as carboxymethyl cellulose (CMC) preferred cellulose ethers described.

As is well known, the technical term »maintaining the degree of whiteness« denotes the ability of one Detergent to suspend the dirt removed during the washing process and thus a to prevent renewed deposition of this dirt on the laundry. The technical term »detergent value« means the difference between the reflectance of the washed and the dirty laundry.

Detergents contain a number of ingredients and many of these are identified in the industry by their trademarks alone. The trademarks used in the following are »Naccanol 60S« - a triethanolamine alkylarylsulphonate (60% solids), »Naxonate 4L« - sodium xylene sulphonate (40% solids), »Kasil 6« - potassium silicate hydrate, K ₂ O · 1 SiO ₂ ( 40% solids). Alizarine Sapphire AR is an acidic tar dye and is abbreviated as alizarin dye in the following.

The number of products used in liquid cleaning agents so far is quite considerable and varied, these include CMC and various phosphates. Although CMC is quite a valuable one Constituent, the main problem so far has been to keep the C M C from falling out and settling or To prevent ascending. Any good liquid detergent must have good whiteness retention and the CMC used for this must be kept evenly incorporated into the agent. This property is due to previously known cleaning agents not achieved as the CMC either settled down or rose up.

This disadvantage is overcome by the invention.

The carboxyalkyl cellulose ether and the ingredients necessary for liquid detergent compositions containing detergents is characterized in that it is a clear transparent solution contains a degraded water-soluble carboxyalkyl cellulose ether, the 2O% aqueous solution of which contains a

Applicant:
Hercules Powder, Wilmington, Del. (V. St. A.)

Representative: Dr.-Ing. A. van der Werth, patent attorney, Hamburg-Harburg 1, Wilstorfer Str. 32

Claimed priority:
V. St. ν. America dated August 13, 1959 (no.833 377)

Jack Barry Batdorf, Wilmington, Del.,

and Robert Wright Ellis, Plainfield, N.J. (V. St. Α.), have been named as inventors

Not preferably not having viscosity greater than 5000 centipoise, greater than 1000 cP at a temperature of 25 ⁰ C.

The carboxyalkyl cellulose ether is in an amount of at least 0.5, preferably 0.5 to 1.5 percent by weight based on the total amount of detergent mass present.

According to the invention, preference is given to carboxymethyl cellulose, carboxymethylbydroxyethyl cellulose or carboxymethylethyl cellulose is used.

The method used primarily for the production of the detergent according to the invention process is that an aqueous solution of a detergent base material and a degraded water-soluble Carboxyalkylcelluloseäthers whose 2O ° / oig ^e aqueous solution has a viscosity of not more than 5000 cP, preferably not more than 1000 cP, at a temperature of 25 ^° C., and further constituents required for liquid cleaning agent compositions are incorporated into the resulting mixture.

According to the invention is therefore to achieve a liquid cleaning agent that is under unfavorable Shipping and storage conditions are clear and remain clear and a good degree of whiteness is maintained has, it is necessary that the water-soluble carboxyalkyl cellulose ether used is a degraded one Material represents. The ether must be degraded to the extent indicated. Cellulose ethers that less than broken down to this value naturally had higher viscosities and were found to be as unsatisfactory according to the invention. They lead to cloudy or dull liquid cleaning agents, and a significant proportion of the cellulose ether

109 787/384

either settled on the floor or rose to the surface after standing for 24 hours under room conditions, the amount of cellulose ether separating from the detergent solution and the rate of separation increasing with increasing temperature, which also occurred when the temperature reached about Freezing point has been reduced. The cleaning agents containing these insufficiently degraded cellulose ethers remained cloudy when they were then brought back to room temperature. In contrast to this, the cleaning agents produced ^{according to the invention were somewhat cloudy at a temperature of 50 °} C. and during freezing, but became clear again when they were returned to room temperature and remained that way.

In degraded to a small extent ether yielded from the outset no clear transparent detergent, and these funds clouded on standing at room temperature more, and also solids from the solution failed when the cleaners were heated to about 5O ⁰ C. The same process occurred with freezing. These compositions also remained cloudy after being returned to room temperature. The cellulose ether is preferably degraded at least to the extent that the viscosity of a 20% strength aqueous solution thereof at a temperature of 25 ° C. does not exceed about 1000 cP.

The cellulose can be degraded by oxidation, hydrolysis, etc. either before or after etherification. The degraded CMC used according to the invention was z. B. obtained from a commercially available CMC, which had been produced by the process of US Pat. No. 2,715,124. To each 100 g of completely dry CMC was added 600 ml of 99% isopropyl alcohol and 125 ml of 12 ^o / oiges hydrogen peroxide added thereto with stirring, whereby a slurry. The pn value of the slurry was adjusted to more than 11 with sodium hydroxide and the same was then heated ^{to a temperature of 60 to 70 ° C. for about 15 minutes.}

According to the invention, water-soluble cellulose ethers can be used which have a carboxyalkyl group and have been dismantled in the specified manner. Such ethers include z. B. Carboxyalkyl cellulose derivatives such as CMC (carboxymethyl cellulose), carboxyethyl cellulose, carboxypropyl cellulose and the like, carboxyalkylalkyl cellulose derivatives such as carboxymethylpropyl cellulose, carboxymethylmethyl cellulose, Carboxymethylethyl cellulose and the like, carboxyalkylhydroxyalkyl cellulose derivatives, such as carboxymethylhydroxyethyl cellulose, carboxymethylhydroxypropyl cellulose, carboxyethylhydroxyethyl cellulose and the like. Mixtures of these ethers can also be used. These ethers can be used in the form of their free acid or the alkali or ammonium salts thereof.

The ratio between the amount of carboxyalkyl cellulose ether used in the detergent and maintaining the whiteness of this detergent is known. Although one any amount of the carboxyalkyl cellulose ether leads to a certain retention of the degree of whiteness, an amount is generally used which will maintain the whiteness of at least gives about 95% and preferably 98 to 100%. It is well known that too large a quantity of nothing gained by such an addition. In order to maintain the degree of whiteness of around 95%, is the application of about 0.75 percent by weight of cellulose ether to the total amount of Detergent compound necessary. In most cases it will be at least about 0.50 weight percent apply on the same basis. Although larger amounts of cellulose ether are used seems to have no practical justification for using more than about 1.5 percent by weight Cellulose ether to be present on the total amount of detergent. In most cases, the Use of about 1 percent by weight of cellulose ether on the total amount of detergent is preferred. This means that the degree of whiteness is maintained at around 98 to 100%.

The following examples illustrate the invention without limiting it. All viscosities were measured at a temperature of 25 ^{° C.}

example 1

Starting from a commercially available CMC variety (CMC 70 low), different ones became Samples produced by degradation of the CMC by means of oxidation to different viscosity values. It 20% aqueous solutions of these degraded CMC were prepared from a portion of each sample and their viscosities are determined. A 2% aqueous solution of the usual undegraded CMC 70 low was prepared and its viscosity was determined. Then, from a further portion of each sample, the degraded CMC prepared 10% aqueous solutions, starting in the same way from a common non-degraded CMC proceeded. For each of the 10% aqueous solutions of the degraded and non-degraded CMC were Naxonate 4L, Nacconol 60S and a 63% aqueous solution of Tetrapotassium pyrophosphate (TKPP) added, resulting in a pH of 7 to 8. The pH was adjusted to about 12 by adding a 60% aqueous potassium hydroxide solution so as to achieve the Allow addition of Kasil No. 6. Together with Kasil No. 6, more potassium hydroxide was added, to maintain the pH. Stirring was continued for an additional 30 minutes. Appropriate Numbers relating to the proportions of the detergent compositions are given below Table I given.

Table I.
Detergent composition

Cleaning Weight percent Cleaning medium No. 1, Cleaning medium No. 8, Components degraded middle
Vf- 0 u; _c 7 usual CMC 7OL 1 ^) 1. Δ Dia /,
degraded CMC 70L 1.00 CMC 70L 1.01 CMC. 18.4 1.82 19.2 water 15.9 16.38 15.7 CPM 65% .. 30.0 22.7 29.5 Nacconol 60S 22.9 27.3 23.2 Naxonate 4L .. 5.4 20.8 5.05 Case No. 6 ... 6.4 4.9 6.34 KOH 60% .. 6.1 Alizarine 0.006 no Dye .. 100.0 no 100.0 100.0

Each cleaning agent was then examined and observed with regard to its compatibility. Although these detergents varied in the degree of their suitability with regard to the compatibility (the compatibility varies inversely proportional to the viscosity, ie the lower the viscosity, the higher the compatibility), all detergents 1 to 4 of Table II were overall satisfactory when the same 8 days of storage under room conditions were warmed to a temperature of 50 ° C, and were also satisfactorily tolerated when they were frozen and then brought back to room temperature. In contrast, the cleaning agents were clouded 5 in the manufacture to 8 in the following Table II, and a significant amount of solids precipitated out under ambient conditions with heating to a temperature of 5O ⁰ C and also at the freezing after 8 days of storage. Both temperature changes resulted in the separation of solids from the detergents 5 to 8. Furthermore, these compositions were cloudy and remained in this state even after they were brought back to room temperature.

Table II

Properties and performance of the detergent

30th

35

40

¹ The viscosity of cleaning agent 8 (customary, undegraded CMC) was determined on a 2% strength aqueous solution of the same. The viscosities of cleaning agents 1 to 7 (degraded CMC) were determined on a 20% strength aqueous solution of the same.

CMC
Viscose
rate cP ¹ Compatible
speed Clean
gearing
middle-
value at 100.6 Reini
gungs
medium no. retention
of white
unity
degree 98.28 312 excellent 14.72 7o 2 870 excellent 12.71 102.0 3 2100 Well 10.43 102.2 1 4780 mediocre 12.39 100.0 4th 5640 bad 102.0 5 5900 bad Not checked 6th 8080 bad Not checked 7th 25 to 50 bad 14.62 8th 10.70

Detergents 1 to 4, 7 and 8 of Table II were used in a Baker-Terg-O-Tometer using standardized soiled laundry items from the United States Testing Company identical cleaning agent tests carried out. The viscosities of the CMC and the cleaning performance achieved is given in Table II.

Claims (4)

PATENT CLAIMS: 1. Liquid, carboxyalkyl cellulose ether and detergent containing detergent, characterized in that it contains a clear transparent solution of a degraded water-soluble carboxyalkyl cellulose ether, whose 2O% aqueous solution has a viscosity of not more than 5000 cP, preferably not more than 1000 cP, at one Has a temperature of 25 ⁰ C. 2. Liquid cleaning agent according to claim 1, characterized in that the carboxyalkyl cellulose ether in an amount of at least 0.5, preferably from 0.5 to 1.5 percent by weight with respect to the total amount of detergent mass is present. 3. Liquid cleaning agent according to one of the preceding claims, characterized by a content of carboxymethyl cellulose, carboxymethylhydroxyethyl cellulose or carboxymethylethyl cellulose. 4. A process for preparing a liquid cleaning agent according to any one of the preceding claims, characterized in that an aqueous solution of a detergent base material and a degraded water-soluble Carboxyalkylcelluloseäthers, the 20 ° / ₀ aqueous solution of not more than 5000 cP, preferably has a viscosity not more than 1000 cP, at a temperature of 25 ⁰ C, mixed and incorporated into the resulting mixture further components required for liquid cleaning agent compositions. Considered publications: Stupel, »Synthetic detergents and cleaning agents«, 2nd edition, 1957, p. 393. © 109 787/384 1.62