A NATURAL CLEANING PRODUCT

Field of the Invention

The present invention relates to a natural cleaning product which is developed by enhancing the solubility of the structures having natural and vegetable -based washing and cleaning functions with the purpose of eliminating all negative effects of the products; which are used in cleaning sector, are in the form of granules, flakes or powder, and fulfill the function of washing laundry; against human and environmental health.

Background of the Invention

The soap, which is produced by neutralization of oils and fatty acids with any one of NaOH, KOH and TEA or a combination of 2 or 3 of them, is the oldest surfactant known to be used in laundry washing and personal cleaning. The first laundry soap bar was produced in the 1800s. Laundry soaps have two different formula structures, and are divided into two as follows:

V Pure, filler free and scented soaps and

V Scented soaps with fillers containing synthetic raw materials.

The soap can be obtained by means of

V saponification achieved by reacting vegetable oils or animal fats with the above mentioned alkalis (See Figure 1) or

V mixing the fatty acids obtained as a result of the hydrolysis and distillation of vegetable oils and animal fats at desired proportions and reacting them with the above-mentioned alkalis (distillation saponification) (See Figure 2).

Vegetable palm oil is present in the semi-solid phase under room conditions and the liquid part (palm olein) and the solid part (palm stearin) are separated to obtain palm stearin and palm olein. Glycerin and fatty acids are obtained as a result of mixing palm stearin and palm kernel oil obtained from the palm fruit seed at a desired proportion followed by hydrolysis thereof at high pressure and high temperature in the splitter. Separation of the oils/fats into fatty acids and glycerin via hydrolysis and saponification of the fatty acids with caustic are as follows:

The mixture of fatty acids from the splitter is separated into fatty acids in the range of C8 to C20 using distillation and fractionation method. The proportions of use of the fatty acids in the saponification reaction are determined by taking into account the targeted specifications of the end product.

Glycerin and salt are added during the saponification reaction taking place between the fatty acids and alkalis taken into the reactor. Then, the drying process is started and the drying process continues until the moisture content targeted in the end product is reached. The resulting product is called“Soap Noodle”. The resulting soap noodles are treated in the mixer, extruder and soap cutting machinery to obtain granular soap having targeted particle size.

The fatty acid distributions in the contents of commercially available cleaning products in the form of natural granules, powders and flakes produced by known techniques and formulas are shown in Table 1. Table 1: Carbon chain distribution of granule soaps

According to the results of the study conducted by Stanford University Department of Chemistry published in the Journal of the American Oil Chemists Society in 1948, it was found that the temperatures required for the dissolution of the sodium salts of fatty acids in water were different. While the dissolution temperatures of sodium stearate and sodium palmitate are in the range of 70 to 80°C, the dissolution temperatures of sodium laurate and sodium myristate having shorter chain structure are between 40 and 50°C. In the same study, the dissolution temperature of unsaturated sodium oleate having long chain structure was found to be 28 °C.

In one study, the solubility of fatty acids in water also affects solubility of the end product in water [1] In another study, the temperature at which the water solubility of the product increases is defined as the“Kraft temperature” and at this temperature the solubility becomes equal to the critical micelle concentration. When micelles are formed in the solution, the soap can dissolve in the micelles more easily than in the water and the solubility increases rapidly [2] .

Although soap-based cleaning products in granule, powder and flake form have high solubility in warm and hot water in washing machines, due to their capacity of reduced water solubility in short wash programs (15 min - 30 min), especially at a temperature of 20°C to 40°C, the main problem thereof is that they cause the following problems:

Ö Decrease in stain removal performance,

Ö Agglomeration in the detergent drawers of the washing machines,

Ö Clogging in the drain pipes of the washing machines,

Ö Pauses in the machine as a result of clogging and leaving residues on the laundry due to insolubility.

Summary of the Invention

The objective of the present invention is to improve the solubility of laundry washing products in granule, flake and powder form in order to eliminate all potential negative effects thereof on human and environmental health.

Another objective of the invention is to enhance the stain removing potentials of laundry washing products on the laundry.

A further objective of the present invention is to eliminate the problems of agglomeration, clogging and leaving residues in the automatic washing machines due to insolubility of the laundry washing products.

Detailed Description of the Invention

“A Natural Cleaning Product” developed to fulfill the objective of the present invention is illustrated in the accompanying figures wherein,

Figure 1. shows the flow chart of Neutral Saponification.

Figure 2. shows the flow chart of Distillation Saponification.

Figure 3. shows the diagram of the resolution performance increase according to the changes in ((C16+C18)/C18:l)) ratio ((a) ((C16+C18)/C18:l))=2.17, (b) ((C16+C18)/C18:l))=1.81, (c)

((C16+C18)/C18:l))=1.37, (d) ((C 16+C 18)/C 18 : 1 ))= 1.0) In the scope of the invention, the solubility of laundry washing products in granule, flake and powder form is enabled to be enhanced in order to eliminate the potential negative effects thereof on human and environmental health.

Figure 1 shows the conventional technique. The oils are neutralized directly, without hydrolysis of the oils and separation thereof into fatty acids, with one of NaOH, KOH and TEA or a combination of 2 or 3 of these, and the fatty acid content of the end product is determined by the fatty acid content in the oils that react. In the process of Figure 1, the oils are neutralized with one of NaOH, KOH and TEA, or a combination of 2 or 3 of these, and the resulting product is soap and glycerin. The glycerin is removed from the process by being washed off with brine and the soap is obtained in a crude form. Since, in the production method illustrated in Figure 1, the fatty acids cannot be separated from the oils used and the desired fatty acids cannot be used in desired combinations, studies that will improve the dissolution performance cannot be provided with this process.

In Figure 2, oils are separated into fatty acids and glycerin via hydrolysis reaction under high pressure and temperature. The separated fatty acid mixture is further separated one by one according to the boiling point difference via fractionation and distillation processes. Fractionation process is applied for fatty acids which have close boiling points and are not separated from each other. Each of the fatty acids has a different dissolution temperature. While the dissolution temperatures of the long carbon chain fatty acids are in the range of 70-80°C, the dissolution temperatures of the shorter chain fatty acids are between 40-50°C. The dissolution temperature of sodium oleate, which is an unsaturated long chain fatty acid, is lower than that of the saturated long chain and short chain fatty acids, and the dissolution temperature of sodium oleate is 28°C. It has been observed that, when long-chain saturated fatty acids, short-chain saturated fatty acids and unsaturated fatty acids are mixed at different percentages by weight, the solubility varies depending on the percentages of the fatty acids contained in the fatty acid mixture. Since sodium oleate has a low dissolution temperature, it decreases the dissolution temperature of soap when used in high amounts. In addition, use of sodium oleate in high proportions causes softening of the soap. In the studies conducted, the fatty acids were mixed in different combinations, and the range, in which the optimum dissolution temperature was achieved and the soap exhibited good performance, was found to be 2-20% for C12, and 0.50-1.25% for ((C16+C18)/C18:l)) ratio. The dissolution performance is enhanced by obtaining mixtures from different structures of C12, C14, C16, C18 and 08:1 fatty acids having different carbon chain lengths obtained by subjecting the fatty acid mixture obtained as a result of hydrolysis of the oils illustrated in Figure 2 to fractionation and distillation processes according to the boiling point differences, and adjusting ((06 + 08) / 08: 1)) ratio in the range of 0.50-1.25% and 02 in the range of 2-20%. Although the ratio of ((06+08)/08:l)) depends on the fatty acid distributions of the oils that are used, this depends on mixing the fatty acids obtained from the oils at the desired ratio. In conventional saponification, these fatty acid ratios cannot be adjusted and they vary. With the increase in the dissolution performance, the stain removal potential of the products on the laundry increases and the problems of clogging, agglomeration and residues on the laundry are solved, especially in automatic washing machines.

The present invention is a natural cleaning product in the form of granule, powder or flake which is obtained from vegetable oil or animal fats via neutralization or distillation, and includes all natural cleaning products comprising

- 50% to 90% total fatty acid by weight,

- 10% to 40% moisture by weight,

- 0.4% to 1.20% inorganic salt by weight,

- 0% to 5% perfume and dye by weight,

- 0.1% to 2% antifoaming silicone derivatives by weight.

In the scope of the invention, particularly in these natural cleaning products; C12 ratio is 2% to 20% by weight and (C16+C18)/(C18:1) ratio is 0.5 to 1.25. Experimental Studies

In the scope of the invention, it was observed that the percentage distributions of the fatty acids having carbon distribution ranging from C8 to C20 of the cleaning products in the form of granule, powder and flakes have effects on the dissolution of the product in water. As a result of the studies conducted, it was proved that the major fatty acids having impact on solubility are palmitic acid (C16), stearic acid (Cl 8) and oleic acid (Cl 8:1). The increase in the total amount of palmitic and stearic acids, which are the long-chain and saturated fatty acids, in the product, caused a negative impact on the water solubility of the end product, whereas the increase in the proportion of the oleic acid, which is an unsaturated fatty acid, positively increased the solubility of the end product.

It has been measured via spectrophotometer measurements that having a (C16+C18)/(C18:1) ratio from 0.5 to 1.25% by weight in tallow, palm or tallow/palm containing cleaning products having a total fatty acid content of 50% to 90% by weight, a titer temperature varying from 35°C to 45°C and C12 content ranging from 2% to 20% by weight; provides high dissolution capacity and accordingly high stain removal performance in washing machines and hand washes despite temperature and short- washing cycles.

Below are given some examples of undissolved particle distribution, observed at the bottom of the beaker, of the results of the studies designed to simulate washing machine and hand wash situations and conducted at

Ö 30°C fixed temperature,

Ö fixed stirring of 30 minutes.

As shown in Figure 3 (a-d), it has been proved that the solubility increases when the (C16+ C18) / 08:1 ratio drops below a certain ratio. In addition, color measurements of the standard stained fabrics were conducted by Konica-Minolta Spectrophotometer CM-700d before and after washing. The difference (DE) between the values measured before and after washing was calculated. The cleaning performance of the cleaning products having different (C16+C18)/C18:l ratios on various stains is given in Table 2.

Table 2. DE values measured on stains washed by cleaning products having different (C 16+C 18)/C 18:1 ratios by weight.

With the experimental studies carried out within the scope of the present invention; after transforming the natural origin soaps, which are obtained as a result of reaction of directly the natural oil sources or the fatty acids derived from these sources with NaOH, KOH and TEA alone or in combinations of two or three of these alkalis, into cleaning products in the form of granules, powders and flakes; the optimum fatty acid ratios for enhancing solubility of the product that is used in the washing machines and in hand washes were determined. As a result of this study, the product having a (C16+C18)/C18:l ratio of 1 by weight was observed to be more effective on stains. As a result of all the studies and measurements conducted, it was proved that the parameter which is important for enhancing solubility is the requirement of having (C16+C18)/C18:l ratio in the range of 0.5 to 1.25 by weight which is not found in any source. Titer process is carried out at a temperature in the range of 37°C to 45°C. The titer temperature is defined as the temperature at which the fatty acids solidify. It is measured with a standard model set by the American Oil Chemists’ Society. Saturated fatty acids solidify at a higher temperature than unsaturated fatty acids. With the titer test, the mixture containing saturated and unsaturated fatty acids is cooled and the temperature at which solidification occurs is recorded. Mixtures containing higher amount of saturated fatty acids by weight will have a higher titer, solidification temperature, than the mixtures having lower amount of saturated fatty acids by weight.

In the test procedure; the mixture is heated to 130°C to remove the moisture contained in the fatty acid mixture. The mixture is then taken into the test tube and filled to a height of 57 mm. The water bath is filled to the specified level. The water bath temperature is set 15 to 20°C below the expected titer temperature. While stirring, decrease in the temperature is observed. After the temperature has stabilized, stirring is stopped. After some time, the temperature will rise by 0.1 to 0.2°C and then it will start to decline. The point, where the temperature rises by 0.1 to 0.2°C after the stabilization point, is recorded as the titer temperature.

In the studies conducted, the ratio of the saturated fatty acids to the unsaturated fatty acids was reduced and titer temperature measurements were performed and as a result, it was observed that the increase in the unsaturated fatty acid ratio reduced the titer temperature and increased the solubility of the natural cleaning product which is the end product.

The effect of different ratios of fatty acids having a carbon chain length of C16, C18 and Cl 8:1 on solubility was investigated and the contribution of the combinations of various ratios on the water- solubility and stain removal performance of the end product was measured. As a result of these measurements, the problem of insolubility in washing machines and hand washes especially in cold water and in the short wash cycles was solved. In addition, upon measurements by means of objective methods it was determined that there is an increase in the performance of removing stains on the laundry upon washing with the natural cleaning product having the (C16+C18)/C18:l ratio specified within the scope of the invention.

REFERENCES

[1]. McBain, J.W. et al.:“The solubility of sodium and potassium soaps and the phase diagrams of aqueous potassium soaps”, Journal of the American Oil Chemists’ Society; 25: 221; 1948.

[2]. Hall, N.:“Implications of a soap structure for formulations and user properties”, Spitz, L., Soap Manufacturing Technology. AOCS Press, 2016.