Watanabe, Yutaka (Kyoto, JA)
Yamagishi, Fumiaki (Kyoto, JA)
Ueno, Hiroshi (Kyoto, JA)

05/287550

02/18/1975

09/08/1972

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Dai-Ichi Kogyo Seiyaku Co., Ltd. (Kyoto, JA)

510/327

510/353, 510/355, 510/354, 510/470

C11D3/22; C11D9/26; C11D9/04; C11D9/26; C11D1/04

252/89,108,132,135,DIG.1 260/234R

"Peformance Characteristics of Sucrose Ester Detergents," by A. M. Schwartz & C. A. Rader, J.A.O.C.S., Vol. 42, Sept. 1965, pages 800-804..

Willis Jr., P. E.

Armstrong, Nikaido & Wegner

1. A detergent composition consisting essentially of a mixture of 75 to 97% by weight of a soap with 25 to 3% by weight of a sucrose ester, said sucrose ester comprising at least one sucrose ester of a fatty acid having 12 to 14 carbonatoms and at least 70% by weight of said sucrose ester being mono-and di-esters, the degree of substitution of said sucrose ester given by the average value of the number of esterified fatty and molecules

2. A detergent composition according to claim 1, in which said sucrose ester comprises a sucrose ester of a mixed fatty acid, said mixed fatty acid comprising at least 50% by weight of saturated fatty acid having 12 to 14 carbon atoms and the remaining part of saturated fatty acid having 10 or less carbon atoms, saturated fatty acid having 16 or more carbon

3. A detergent composition according to claim 2, in which at least 65% by weight of said fatty acid consists of fatty acid having 12 to 14 carbon

4. A detergent composition according to claim 1, in which said soap is a member selected from the group consisting of K and Na salts of saturated

5. A detergent composition according to claim 4, in which said soap is a member selected from the group consisting of K and Na salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and mixtures

6. A detergent composition according to claim 5, in which said soap is a product obtained by saponifying a member selected from the group consisting of tallow, coconut oil, cotton seed oil, whale oil, palm oil,

7. A detergent composition according to claim 6, in which said soap is a product obtained by saponifying a mixture of at least 50% by weight of tallow with the remaining part of palm oil, palm kernel oil and soy bean

8. A detergent composition consisting essentially of 70 to 90% by weight of a mixture of a soap with a sucrose ester of fatty acid and 30 to 10% by weight of a saccharide, said mixture of a soap of sucrose ester of fatty acid consisting essentially of 75 to 97% by weight of a soap with 25 to 3% by weight of a sucrose ester of fatty acid having 12 to 14 carbon atoms, at least 70% by weight of said sucrose ester being mono-and di-esters, and the degree of substitution of said sucrose ester given by the average value of the number of esterfied fatty acid molecules per sucrose molecule

9. A detergent composition according to claim 8, in which said sucrose ester consists essentially of a sucrose ester of a mixed fatty acid, said mixed fatty acid comprising at least 50% by weight of saturated fatty acid having 12 to 14 carbon atoms and the remaining part of saturated fatty acid having 10 or less carbon atoms, saturated fatty acid having 16 or

10. A detergent composition according to claim 9, in which at least 65% by weight of said fatty acid consists of fatty acid having 12 to 14 carbon

11. A detergent composition according to claim 8, in which said soap is a member selected from the group consisting of K and Na salts of saturated

12. A detergent composition according to claim 11, in which said soap is a member selected from the group consisting of K and Na salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and mixtures

13. A detergent composition according to claim 12, in which said soap is a produce obtained by saponifying a member selected from the group consisting of tallow, coconut oil, cotton seed oil, whale oil, palm oil,

14. A detergent compositions according to claim 13, in which said soap is a product obtained by saponifying a mixture of at least 50% by weight of tallow with the remaining part of palm oil, palm kernel oil and soy bean

15. A detergent composition according to claim 8, in which said saccharide is a member selected from the group consisting of sucrose, sorbitol,

16. A detergent composition according to claim 15, in which said saccharide is non-reacted sucrose recovered in the production of said sucrose ester of fatty acid.

BACKGROUND OF THE INVENTION

The invention relates to new and improved detergent compositions, particularly to hazardless detergent compositions having improved detergency.

A typical detergent which has heretofore been used has an active component in the form of alkylbenzene sulfonate (hereinafter referred to as ABS) which is a petrochemical product. This detergent has a good detergency and is economical to manufacture and in this sense it may be said to be one of most desirable detergents. However, such detergent has caused various problems partly because it is used in increasing amounts. Thus, it causes a foam public hazard to sewage disposal facilities and rivers to which it is discharged. Further, the pollution of undergound water has recently become a problem, giving birth to various rumors about adverse effects on the human body. This is due to the fact that ABS is hardly decomposable in sewage water and retains its initial activity for a long time.

With these problems in mind, we have endeavored to develope a desirable detergent composition with main themes directed to;

A. Being no less better than any conventional detergents in point of detergency;

B. Being decidedly superior in biodegradivity; and

C. Being high in safety for the human body.

Soap, which, stated historically, has been used from of old, has very little toxicity or harmfulness to organisms and is highly satisfactory in biodegradivity, but on the other hand it is disadvantageous in that when it is present in water containing heavy metal ions such as calcium and magnesium, it cooperates with these heavy metals to form a metal soap, which then becomes a water-insoluble scum detracting from the detergency and sticking to the material to be washed to degrade the feeling. Such drawbacks of soap result in soap being driven out by synthetic detergents and unable to take over again synthetic detergent, which have caused public hazard problems.

The primarly object of the invention is to provide a detergent composition which has biodegradivity and causes no public hazard to the human body and which, moreover, is superior in detergency, foamability and foam stability.

On the other hand, soap has been used as a kind of detergent from old, but because of its very low detergency at low temperatures, its value as a detergent for home use is low. Among the oils and fats used as raw materials for soap, tallow is used most, accounting for 75-80% of the raw material oils and fats for soap, but the soap made of tallow is also poor in detergency at low temperatures, and in order to develop sufficient detergency it is necessary to heat to 40° - 50°C, this being unsuitable to domestic washing conditions.

Another object of the invention is to provide a detergent composition superior in detergency at low temperatures.

Detergents used in general homes to wash clothing consist mainly of ABS type surfactants discussed before with builder and other additives incorporated therein in accordance with various purposes. Also, in the case of preparing a detergent which imparts improved feeling and softening effect to the wash after washing, there may be thought of a method of providing the intended softening effect by adding a substance which is generally regarded as having a softening effect to a mixed product which has already been prepared as a detergent. Among these substances regarded as being capable of providing a softening effect there are the so-called textile softening agents. More particularly they are quaternary ammonium salts of higher alkyl amines, dialkyl trimethyl ammonium chloride, and polyamide type compounds of higher fatty acids. However, the method in which these substances capable of providing a softening effect are incorporated in detergent compositions is not practiced. What is actually practiced is to enhance the feeling and softening effect on the wash by treating the wash with a solution of a substance having such softening effect. This is because such softening agents as described above often greatly decrease the detergency so that it is difficult to obtain a good washing effect and a good softening effect at the same time. Moreover, the substances which are used as treating agents after washing are limited to such N-derivatives as described above, and since aninon type or non-ionic type softening agents do not provide sufficient effects, they are not much used as such sotening agents. In addition to the decrease of the detergency at low temperatures, soap reacts with metallic ions in water to form metallic soap during use, which builds up to deposit on a material being washed and cause the fibers to feel stiff.

A further object of the invention is thus to provide an improved detergent composition imparting improved feeling and softness to materials washed with it.

Other objects and advantages of the invention will be partly apparent and partly described in detail hereinafter.

SUMMARY OF THE INVENTION

The detergent composition according to the invention comprises essentially a mixture of a soap component with a sucrose ester component which comprises at least one sucrose ester of fatty acid. Preferably, the detergent composition may further include a saccharide component. In any cases, the sucrose ester component comprises at least one sucrose ester of fatty acid having 6 to 22 carbon atoms.

In a preferred embodiment of the invention, the detergent composition according to claim 1, in which said composition comprises a mixture of 75 to 95% by weight of a soap component with 25 to 5% by weight of sucrose ester component, said sucrose ester component comprising essentially at least one sucrose ester of fatty acid having 12 to 14 carbon atoms and 70% by weight of said sucrose ester being mono- and di-esters of fatty acid. This composition is particularly superior in detergency at relatively low temperatures.

The detergent composition comprising a sucrose ester component, a soap component and a saccharide component according to another embodiment of the invention has biodegradivity and causes no public hazard to the human body and which, moreover, is superior in detergency, foamability and foam stability. The saccharide component may preferably be a monosaccharide or disaccharide or decomposed products of them and may be selected from the group consisting of sucrose, sorbilol and decomposed product of sucrose.

The detergent composition which imparts softness to materials washed with it according to the invention may preferably comprise 75 to 97% by weight of a soap component and 25 to 3% by weight of a sucrose ester component, said sucrose ester component comprising essentially at least one sucrose ester of fatty acid having 16 or more carbon atoms and the degree of substitution of said sucrose ester given by the average value of the number of esterified fatty acid molecules per one sucrose molecule being within the range of 1.5 to 3.5.

In any of the preferred embodiments of the invention, the sucrose ester component may further include glyceride. The soap component may be a member selected from the group consisting of K and Na salts of saturated or unsaturated fatty acids having 8 to 22 carbon atoms. The sucrose ester component may preferably comprise at least 70% by weight of mono- and di-esters and the remaining part of tri- or higher polyesters.

DETAILED DESCRIPTION OF THE INVENTION

The detergent composition according to the invention comprises essentially a mixture of a soap component with a sucrose ester component. The sucrose ester component comprises at least one sucrose ester of fatty acid having 6 to 22 carbon atoms. Hereinafter, sucrose ester of fatty acid will be referred to merely as "SE".

It has particularly be found that the addition of a saccharide to the mixture of a soap with SE remarkably improves the detergency. The detergent composition comprising essentially soap, SE and saccharide has biodegradivity and causes no public hazard to the human body and which, moreover, is superior in detergency, foamability and foam stability. The merits obtained by the addition of a saccharide are superior to those obtainable by the use of any of sodium citrate, tartaric acid, etc. known as hazardless builders. It should be noted that this unexpected result can only be obtained in the case of a combination of a saccharide with a mixture of soap and SE. The addition of a saccharide to soap alone. SE alone, a combination of soap and ABS, a combination of soap and ethylene oxide adduct type non-ionic surfactant, or, a combination of soap and alkyl phosphate can never provide such a greatly improved detergency as obtained according to the invention.

The SE's useful in the present invention are sucrose esters of saturated or unsaturated fatty acids with 6-22, preferably, 12-18 carbon atoms, for example, such saturated fatty acids as laulic acid, myristic acid, palmitic acid and stearic acid, and such unsaturated fatty acids as oleic acid and linolic acid. The SE may be either sucrose ester of a sole fatty acid or sucrose ester of a mixed fatty acid comprising a mixture of the above mentioned fatty acids.

The sucrose ester component may further include a small amount of glyceride. Preferably, the sucrose ester component may be a product produced from fats and fatty oils with sucrose, said product including unreacted or by-product glyceride.

As for soaps, it is desirable to use, either independently or in combination, Na or K salts of saturated or unsaturated fatty acids with 8-22 carbon atoms, produced from tallow, coconut oil, cotton seed oil, whale oil, palm oil, palm kernel oil, soy bean oil or the like. Particularly desirable is a soap obtained by the saponification of oils and fatts consisting mainly of tallow (in an amount at least 50% by weight) with which is mixed about 50% or less of any other oil such as coconut oil, soy bean oil, etc.

As for saccharides used in the present invention, it is desirable to use those belonging to monosaccharides and disaccharides, particularly sucrose or sorbitol. De composed products of saccharides are also useful. For example, sucrose which in parts has been thermally decomposed by being heated, e.g. an unreacted sucrose contained in SE reaction crude product is useful. It is industrially advantageous and economical to suitably adjust and use such crude SE reaction product containing unreacted sucrose.

The detergent composition of the present invention consisting of soap, SE and saccharide may be used not only as it is but also as a basic component for various types of soaps including toilet soap, light duty detergents and liquid detergents. In addition it is also possible to finish it into heavy duty detergents by suitably incorporating therein sodium carbonate, sodium silicate, borax and other alkaline builders, sodium tripolyphosphate, NTA, EDTA, SODA (sodium diglycollate), sodium citrate, sodium polyacrylate and other additives which cooperate with metallic ions to form chelate compounds, fatty acid alkanol amide and other additives which have foam boosting effect, carboxymethyl cellulose, bleaching agents, fluoroescent dyes, etc.

According to the invention, a detergent composition superior in detergency at relatively low temperatures is provided by utilizing as a base material a mixture of a soap and a particular SE with or without a saccharide incorporated therein.

A detergent composition which has a good detergency at relatively low temperatures as well as at relatively high temperatures may comprise a mixture of 75 to 95% by weight of a soap component with 25 to 5% by weight of a sucrose ester component, said sucrose ester component comprising essentially at least one sucrose ester of fatty acid having 12 to 14 carbon atoms and 70% or more by weight of said sucrose ester being mono- and di-esters of fatty acid.

According to the invention the above mentioned particular SE is incorporated in the above mentioned particular proportions to soap, whereby it has become possible to improve the detergency at low temperatures such as 30°C or less, particularly 20°-10°C which have been insufficient for domestic detergents. In addition it has been found that the resulting detergency is superior to that of synthetic detergents. As a result, it is now possible to provide a detergent composition suitable for a domestic detergent which is superior in detergency at low temperatures and stands at advantage against public hazard problems.

For the above particular purpose, the sucrose ester component may preferably comprise a sucrose ester of a mixed fatty acid. The mixed fatty acid may comprise at least 50%, preferably at least 65% by weight of saturated fatty acid having 12 to 14 carbon atoms and the remaining part of saturated fatty acid having 10 or less carbon atoms, saturated fatty acid having 16 or more carbon atoms and various unsaturated fatty acids. Industrially and commercially, it is convenient to use as a raw material for SE a mixed fatty acid obtained from coconut oil, palm kernel oil, etc.

The total amount of mono- and di-esters in the SE component according to the invention must be 70% or more by weight. In other words, tri- or higher polyesters must be 30% or less by weight.

The soap component used in this embodiment may be a member selected from the group consisting of K and Na salts of saturated or unsaturated fatty acids having 8 to 22 carbon atoms. Preferably the soap component is a member selected from the group consisting of K and Na salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and mixtures thereof. More preferably, the soap may be a product obtained by saponifying a member selected from the group consisting tallow, coconut oil, cotton seed oil, whale oil, palm oil, palm kernel oil, soy bean oil and mixtures there of.

The composition ratio of the detergent composition having a good detergency at relatively low temperatures as described in the above is critical. The composition should comprise a mixture of 75 to 95%, preferably 80 to 90%, by weight of a soap with 25 to 5%, preferably 10 to 20%, by weight of a sucrose ester component. The good detergency at relatively low temperatures is only secured within this composition range. The optimum composition ratio depends on the nature of the SE to be used. Generally, the amount of SE to be used, within the above mentioned range, is comparatively small when the SE has a high degree of hydrophilicity, while when it has a low degree of hydrophilicity, a comparatively large amount of SE would be required to obtain the desired effect.

The detergent composition described having a good detergency at relatively low temperatures is ready to use as it is, either in the form of a solid or in the form of powder, but it may be finished into more effective and attractive detergent products by suitably incorporating thereto sodium carbonate, sodium silicate, borax and other alkaline builders, sodium tripolyphosphate, NTA, EDTA, SODA (sodium diglycollate), sodium citrate, sodium polyacrylate and other additives which cooperate with metallic ions to form chelate compounds, fatty acid alkanol amide and other additives which have foam boosting effect, carboxymethyl cellulose, bleaching agents, fluoroescent dyes, etc.

Some conventional methods of producing SE may result in providing crude reaction product with soap present mixed therein. In these case, it is possible to adjust such product along with soap included therein to the composition of the present invention and then to make industrial use thereof to advantage.

The sucrose ester component for the above detergent composition may also include a small amount of glyceride. Preferably, the sucrose ester component is a product produced from fats and fatty oils with sucrose, said product including unreacted or by-product glyceride.

The detergent composition having the above described good detergency at relatively low temperatures as well as at relatively high temperatures may further include a saccharide component. It has been found that the addition of saccharide further improves the detergency at relatively low temperatures and still maintains public hazardlessness. The effect of improving the detergency can only be achieved by adding a saccharide to the mixture of soap with SE. It has been found that the addition of a saccharide to any anionic surfactants (excluding soap) such as ABS or LAS, any non-ionic surfactants other than SE, any amphoionic surfactants, a mixture of any of those surfactants with either SE or soap can never result in improving the detergency at relatively low temperatures.

Among the useful saccharides there may be mentioned monosaccharides and disaccharides such as sucrose and solbitol. Decomposed products of those saccharides are also useful. For example, the unreacted sucrose component contained in the crude reaction mixture obtained in the production of SE is useful. This unreacted sucrose component includes decomposed products of sucrose.

The saccharide component is added so that the resultant composition may comprises 5 to 50% by weight of a saccharide component and 95 to 50% by weight of a mixture of soap with SE. In the production of SE, the crude reaction mixture may include an unreacted saccharide component including any decomposed product of sucrose. Such crude reaction mixture including SE and saccharide can be utilized for preparing the detergent composition according to the invention.

The present invention further provides a detergent composition making concurrent use of soap and a particular SE to greatly improve the feeling of the wash after washing and finish it soft, while acting on the skin very mildly. Such the detergent composition like this may comprise 75 to 97%, preferably, 80 to 95%, by weight of a soap and 25 to 3%, preferably 20 to 5%, by weight of a sucrose ester component. The sucrose ester component may comprise essentially at least one sucrose ester of fatty acid having 16 or more carbon atoms and the degree of substitution of said sucrose ester given by the average value of the number of esterified fatty acid molecules per one sucrose molecule is within the range of 1.5 to 3.5, preferably, within the range of 1.6 to 2.0. The fatty acid for the production of the SE may be either saturated one or unsaturated one. The sucrose ester component may comprise a sucrose ester of a mixed fatty acid. The mixed fatty acid should comprise at least 50% by weight of fatty acid having 16 or more carbon atoms and the remaining part of other fatty acid. The sucrose ester component may further include a small amount of glyceride. Preferably, the sucrose ester component is a product produced from fats and fatty oils with sucrose, said product including unreacted or by-product glyceride. The soap component may be a member selected from the group consisting of K and Na salts of saturated or unsaturated fatty acids having 8 to 22 carbon atoms. Among those fatty acids there may be included lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and mixtures thereof. The soap may be a product obtained by saponifying a member selected from the group consisting tallow, coconut oil, cotton seed oil, whale oil, palm oil, palm kernel oil, soy bean oil and mixtures thereof. Preferably, the soap can be prepared by saponifying a mixture of at least 50% by weight of tallow with the remaining part of palm oil, palm kernel oil and soy bean oil.

Considered from the standpoint of the impartation of softness to the wash, it is desirable to use SE consisting of a long-chained fatty acid and having a high degree of substitution, but such SE is little water-soluble or water-insoluble, causing inconvenience in the inherent detergency. According to the invention, however, the impartation of softness and the good detergency can be obtained comparatibly with each other. The present inventive detergent composition is the best from the standpoint of the balance between softness impartation to the wash and detergency.

The respective ranges for the degree of substitution and for the composition ratio are critical. Those values may, however, be varied, within the respective defined ranges, according to the circumstances under which the materials to be washed are placed. For example, for applications where importance is placed on softening effects on the wash such as babies' underwear and ladies' high-grade garments it would be recommendable to select such SE as having a higher degree of substitution and a relatively large content of SE, whereas where importance is placed on the removal of soil, a low degree of substitution and a lower content of SE would meet such requirement.

Phosphates such as polyphosphates, inorganic builders such as sodium carbonate and sodium silicate, salts such as of citric acid, malic acid and tartric acid, organic builders such as salts of amino acid, CMC, EDTA, fluorescing agents, and bleaching agents may be incorporated in the present inventive composition. The incorporation of sodium tripolyphosphate as a builder provides a detergency which stands comparison with known ABS type detergents which have high detergency but have become a problem because of their foam pollution and adverse effects on the human body.

The present inventive composition, unlike the conventional ABS type and AB type detergents, causes no foam pollution and has no adverse effects on the human body. Rather, it is capable of imparting a "mild" and "smooth" touch to the skin. In this connection, it has been ascertained that the detergent composition described also prevents metallic soap from being deposited on the washed materials, thereby ensuring that the washed materials may feel very soft. Thus, the present inventive composition alone can also fully play the role of the conventional softening agent.

The above detergent composition which can improve the feeling of wash and finish it soft may further include a saccharide component. It has been found that the addition of a saccharide further improves the detergency and still maintaining public hazardlessness. Among the useful saccharides there may be mentioned monosaccharides and disaccharides such as sucrose and solbitol. Decomposed products of those saccharides are also useful. For example, the unreacted sucrose component contained in the crude reaction mixture obtained in the production of SE is useful. This unreacted sucrose component include decomposed products of sucrose. The saccharide component is added so that the resultant composition may comprise 5 to 50% by weight of a saccharide component and 95 to 50% by weight of a mixture of soap with SE. In the production of SE, the crude reaction mixture usually includes an unreacted saccharide component including any decomposed product of sucrose. Such crude reaction mixture including SE and saccharide can be utilized for preparing the detergent composition according to the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

For the better and complete understanding of this invention, typical examples thereof together with some comparative examples are shown in the following, in which percentage and parts are indicated by weight:

EXAMPLE 1

Tallow soap and tallow SE (51.2% monoester, 36.4% diester and 13.4% tri- and higher esters were mixed together in various mixing ratios as noted in Table 1 and saccharides shown in Table 1 were added to 50g of said mixtures. The detergency thereof was measured under the following conditions and by the following method:

Washing Conditions:

Materials to be washed: Seven short sleeve shirts charged by wearing for three days. Bath Ratio: 1 : 3 Amount of detergent: 40g Amount of water: 30l Temperature of water: 30°C Washing time: 15 minutes Washing machine: electric washing machine on the marked (by Toshiba Ltd. in the trade name "Toshiba Ginga")

Method of Measuring Detergency:

The following standard soiled fabrics were sewn to the aforesaid materials to be washed one for each and were washed under the aforesaid washing conditions. The soiled fabrics were evaluated in terms of the following percentage detergency, using the average value of the seven fabrics:

Percentage Detergency ##SPC1##

Standard Soiled Fabric:

This is a fabric soiled in a bath of carbon tetrachloride having mixed therewith 4 parts of synthetic sebum and 1 part of solid pollutant, the reflectivity of the fabric being 30 ± 2%.

______________________________________ Synthetic sebum: 5 parts of oleic acid, 1 part of stearic acid, 1 part of cholesterol, 3 parts of whale oil, 9 parts of coconut oil, and 1 part of squalene Solid Pollutant: 9 parts of bentonite and 1 part of carbon black ______________________________________

The results are shown in Table 1.

Table 1 ____________________________________________________________ ______________ Percentage Detergency (%) Kind Tallow Se/ of tallow soap 100/0 75/25 50/50 25/75 0/100 sa- Amount of ccha- saccharide ride added(%) ____________________________________________________________ ______________ Sucrose 0 48 52 57 68 73 10 48 55 63 75 73 20 49 58 66 78 75 30 49 63 74 81 75 Sorbitol 20 48 56 63 73 73 Sucrose containing decomposed 20 49 67 75 83 77 products of sugar ____________________________________________________________ ______________

From Table 1 it will be observed that the addition of a saccharide to soap and SE, independently, does not contribute to the improvement of detergency but that the addition of a saccharide to a mixture of soap and SE surprisingly improves the detergency, such improvements being particularly remarkable in the case of sucrose containing the decomposed products of sugar.

EXAMPLE 2

Sucrose was added to soap plus other surfactants than SE in various mixing ratios noted in Table 2, and the detergency thereof was measured under the same conditions and by the same method as in Example 1.

The results were as shown in Table 2.

Table 2 ____________________________________________________________ ______________ Percentage Detergency (%) Kind Tallow soap of surfactant 100/0 75/25 50/50 25/75 0/100 sur- Amount of fac- Sucrose added tant (%) ____________________________________________________________ ______________ ABS 0 73 74 74 75 77 NA 20 75 75 75 78 81 Polyoxyethylene (P:10) lauryl ether 0 73 74 73 71 73 20 75 76 do. 73 75 Lauryl sulphate 0 73 70 68 66 65 20 75 72 69 68 68 ____________________________________________________________ ______________

From Table 2 it will be obserbed that the addition of sucrose to polyoxyethylene alone or to a mixed system thereof with soap does not make any contribution to the improvement of detergency. In the case of ABS-Na alone or lauryl sulphate-Na alone, the addition of sucrose slightly improves the detergency, but in the case of a mixed system thereof with soap, it has been found that there is no unique merit such as found in a mixed system of soap and SE.

EXAMPLE 3

Tallow soap and a mixed SE (tallow SE: coconut SE = 7 : 3; and 4% of monoester, 35% diester and 9% of triester and higher polyesters) were mixed in various ratios noted in Table 3 to prepare mixtures having the following mixture composition. To each of those mixtures was added 30% of a saccharide or various builders. The detergency thereof was measured in accordance with the same conditions and operations as in Example 1. The results were as shown in Table 3.

______________________________________ Mixture Composition: Tallow soap + mixed SE 75% Sodium metacilicate 5% Soda ash 20% ______________________________________

Table 3 ____________________________________________________________ ______________ Percentage Detergency (%) SE/tallow soap Additive 100/0 75/25 50/50 25/75 0/100 ____________________________________________________________ ______________ None 51 57 62 68 69 Sucrose containing the decomposed products 52 66 78 86 70 thereof of sugar Sodium citrate 53 58 63 69 71 Sodium gluconate 51 55 63 67 72 Sodium tartrate 53 59 63 70 70 Sodium sulfate 51 56 63 67 70 ____________________________________________________________ ______________

From Table 3 it will be observed that the addition of sucrose of soap and SE, independently, only provide the same merits as the addition of other builders but that said addition to a mixed system of soap and SE shows a remarkable improvement in detergency different from that attained by the addition of other builders.

Further, it has been found that the conventional ABS type detergents (containing sodium tripolyphosphate) have a percentage detergency of 83 and that the percent inventive article is by no means inferior to them in detergency.

EXAMPLE 4

Mixtures of tallow soap and tallow SE were prepared in various mixing ratios noted in Table 4. They were measured at a concentration of 0.2% and a temperature of 30°C for their foaming effect and foam retention by the Rossmiles method (JISK-3362). The results were as shown in Table 4. Further, sucrose and other builders were added to said mixtures as shown in Table 4 and then the mixtures were similarly measured. The results were as shown in Table 4.

Table 4 ______________________________________ Mixing ratio Kind of Mixing pro- Foaming height Tallow Tallow additive portion of Immedi- 5 minutes soap SE additive ately after after ______________________________________ 100 0 -- -- 101 73 50 50 -- -- 72 45 0 100 -- -- 53 23 50 50 Sucrose 10 84 63 do. do. do. 20 105 85 do. do. do. 30 117 97 do. do. Sodium 15 73 46 metasili- cate do. do. Sodium do. 75 44 citrate do. do. Sodium do. 74 47 gluconate do. do. Alkylol 10 107 89 amide (foaming agent) ______________________________________ ABS type detergent (containing sodium tri- 105 88 polyphosphate) available on the market as -"ALCO COLOR" produced by Nippon Sun- home Co. Ltd. ______________________________________

From Table 4 it will be observed that the addition of sucrose to a mixed system of soap and SE greatly improves foaming and preserves the stability thereof. Further inorganic and organic builders were incorporated in plate of sucrose, but almost no change was observed. Thus, it has been found that the present invention is by no means inferior to the conventional ABS type detergents on the market.

EXAMPLE 5

Mixtures consisting of 10% by weight of various SE's shown in Table 5 and 90% by weight of tallow soap were measured for their detergency under the following washing conditions and by the following method. The detergency was evaluated in terms of the following percentage detergency. The results were as shown in Table 5. In addition, such measurements were also taken of tallow soap alone and a mixture thereof with a conventional non-ionic surfactant and the results shown in Table 5 were obtained.

Washing conditions:

Materials to be washed: Five long sleeve shirts (weighing about 1 kg) which had been worn for three days Amount of detergent: 50g Amount of water: 30l Temperature of water: 10°C Washing time: 10 minutes Washing machine: Electric washing machine on the market (National Ultra High Speed "Uzushio" produced by Matsushita Electric Co., Ltd.)

Method of Measuring Detergency:

Standard cotton fabrics for detergency test use were soiled with a mixture of sebum from the human body and natural dust by using the Menken Type fabric soil testing machine.

The soiled fabrics were sewn to said shirts one for each and washed under said washing conditions. The soiled fabrics were evaluated in terms of the following percentage detergency, using the average value of the five fabrics.

Percentage Detergency ##SPC2##

Table 5 ______________________________________ Composition Ratios Percent- Kind of of respective age de- constituent esters in SE (%) tergency fatty acid in SE mono- di- tri- (%) and higher poly- ______________________________________ Lauric acid 100 0 0 74 do. 0 100 0 72 do. 0 0 100 43 Myristic acid 100 0 0 77 do. 0 100 0 70 Palmitic Acid 100 0 0 56 Stearic acid 100 0 0 41 Tallow fatty acid 100 0 0 45 Coconut fatty* acid 69.9 25.1 5.0 75 do. 60.6 29.8 9.6 72 do. 46.3 34.6 19.1 68 do. 32.6 38.0 29.4 63 do. 24.3 38.8 36.9 50 ______________________________________ Tallow soap alone 31 Mixture of 90% tallow soap and 10% polyoxyethylene lauryl ether** 55 ______________________________________ *Composition of coconut fatty acid: C ₆ - C ₁₀ saturated fatty acid 14% C ₁₂ - C ₁₄ do. 66% C ₁₆ - C ₁₈ do. 11% C ₁₈ unsaturated fatty acid 9% ______________________________________ **Addition product of 10 moles of ethylene oxide

From Table 5 it will be observed that amoung the SE's with 72 to 14 carbon atoms, monoesters and diesters are uniquely effective. Further, it has also been found that when coconut fatty acid, which is a typical industrial raw material, is used, if the amount of monoester and diester is 10% or more, superior effects are obtained and such superior effects can be maintained even if not more than 20% of fatty acid with 16 or more carbon atoms is undesirably contained. Still further, it has also been found that as compared with tallow soap and a mixture thereof with conventional typical non-ionic surfactants, the present inventive article has superior detergency at low temperatures.

EXAMPLE 6

With various mixing proportions selected as shown in Table 6, detergency was tested under the same conditions and by the same operation as in Example 5. The results were as shown in Table 6.

Table 6 ______________________________________ Kind of Composition Mixing Percentage constituent Ratios of proportion detergency fatty acid respective esters (%) (%) in SE in SE (%) mono- di- tri- & tal- SE higher low poly- soap ______________________________________ coconut 32.6 38.0 29.4 95 5 60 fatty acid do. do. do. do. 90 10 63 do. do. do. do. 85 15 67 do. do. do. do. 80 20 66 do. do. do. do. 75 25 61 do. do. do. do. 70 30 55 do. do. do. do. 50 50 45 do. 60.6 29.8 9.6 95 5 60 do. do. do. do. 90 10 72 do. do. do. do. 85 15 72 do. do. do. do. 80 20 67 do. do. do. do. 75 25 62 do. do. do. do. 70 30 54 do. do. do. do. 50 50 44 ______________________________________

From Table 6 it will be observed that superior detergency is obtained when the mixing ratio between SE and soap is within the range of 5:95-25:75. Further, it has been found that when the hydrophilicity of SE is comparatively low, a mixing proportion of about 15-20% of SE is most suitable while when it is comparatively high, about 10-15% is most suitable.

EXAMPLE 7

Saccharides and conventional builders were added to 50g of mixtures of SE and soap and the detergency was tested under the same conditions and by the same operations as in Example 5. The results were as shown in Table 7.

Table 7 ____________________________________________________________ ______________ Kind of Composition Mixing Kind Adding pro- Percentage constituent Ratios of proportion of portion (%) detergency fatty respective (%) saccharide (%) acid esters in or builder in SE SE (%) mono di tri & tall- SE SE+ saccharide poly ow soap or soap builder ____________________________________________________________ ______________ coconut 32.6 38.0 29.4 85 15 -- 100 0 67 fatty acid do. do. do. do. do. do. sucrose 90 10 73 do. do. do. do. do. do. do. 80 20 75 do. do. do. do. do. do. do. 70 30 76 do. unre- acted sucrose con'ng do. do. do. do. do. do. the de- 80 20 78 composed products do. do. do. do. do. do. thereof do. do. 70 sodium citrate do. do. do. do. do. do. sodium do. do. 69 tartrate do. 60.6 29.8 9.6 do. do. -- 100 0 72 do. do. do. do. do. do. sucrose 80 20 76 do. do. do. do. do. do. sorbitol do. do. 75 ____________________________________________________________ ______________

From Table 7 it will be observed that the addition of saccharide to a mixture of SE and soap further improves the detergency at low temperatures. Further, it has also been found that it exhibits superior effects as compared with conventional builders. Those which are adjusted by unreacted sucrose containing the decomposed products of sucrose exhibit outstanding effects.

EXAMPLE 8

Using the following detergents A, B, C, D, E and F, detergency was tested under the same conditions and by the same operation as in Example 5. The results were as shown in Table 8.

______________________________________ A. Preparation according to the present invention: Sucrose coconut fatty acid ester 8.4% (mono-: di-: tri- and higher poly- = 60.6: 29.8: 9.6) Tallow soap 36.3% Palm oil soap 16.3% sodium metacilicate 8.0% sodium carbonate 25.5% CMC 0.5% moisture 6.0% ______________________________________

B. Preparation according to the present invention: Sucrose coconut fatty acid ester 8.4% (mono-: di-: tri- and higher poly- = 60.6: 28.9: 9.6) Tallow soap 36.3% Coconut soap 16.3% Sucrose 20.0% Sodium carbonate 13.5% Moisture 6.0%

C. Preparation according to the present invention: Sucrose coconut fatty acid ester 10.8% (mono-: di-: tri- and higher poly- = 32.6: 38.0: 29.4) Tallow soap 36.1% Sperm whale oil fatty acid soap 13.1% NTA 6.0% Sodium metacilicate 3.0% Sodium carbonate 25.0% CMC 0.5% Moisture 5.5%

D. Preparation according to the present invention: Crude reaction sucrose coconut ester 25.0% (36% SE, 30% unreacted sucrose and 34% tallow soap) (SE mono-: di-: tri- and higher poly- = 51.5: 37.2: 11.3) Tallow soap 42.5% Sucrose 12.3% Sodium carbonate 13.5% CMC 0.5% Moisture 5.5%

E. Preparation of soap alone: Tallow soap 45.0% Coconut soap 15.0% Sodium metacilicate 8.0% Sodium carbonate 22.0% CMC 0.5% Moisture 9.5%

F. commercially available ABS type synthetic detergent:

(containing sodium tripolyphosphate)

(produced by Nippon Sunhome Co., Ltd.)

Table 8 ______________________________________ Percentage detergency (%) deter- washing gent temperature 10°C 20°C 30°C ______________________________________ A 75 78 80 B 78 81 83 C 72 77 79 D 80 82 85 E 35 42 69 F 59 72 78 ______________________________________

From Table 8 it will be observed that the present inventive articles A and C have greatly improved detergency at low temperatures as compared with the simple preparation of soap E, that the present inventive articles B and D having sugar incorporated therein have further improved detergency at low temperatures, and that each of the present inventive articles A-D has superior detergency at low temperatures as compared with the ABS type detergents on the market.

EXAMPLE 9

Using 5 parts of SE of various compositions shown in Table 9 and 45 parts of soap (sodium salt of a mixed fatty acid of 70% tallow fatty acid and 30% of palm fatty acid), the detergency and softening effects were tested under the following conditions by the following method, and the results were as shown Table 9.

______________________________________ Washing conditions: The wash: 5 long-sleeve cotton shirts which had been worn for three days, with the following soiled fabric (and which weighed about 1kg.) Amount of detergent: 50g Amount of water: 30l Temp. of water: 30°C Washing time: 10 minutes Washing machine: Commercially available electric washing machine (National Ultra High Speed "UZUSHIO") ______________________________________ Method of Measuring Detergency:

Using a Menken Type fabric soil testing machine, samples for detergency test were soiled with a mixture of human sebum and natural dust and dirt. These soiled fabrics were sewn each to one of said shirts and then washed under the above mentioned conditions. The soiled fabrics were evaluated in terms of the following percentage detergency, using the average value of the five. ##SPC3##

Method of Measurement of Softening Effect:

"Fuaimeter" (Feeling degree counter) produced by Uenoyama K. K. is used.

Three test pieces (regular square) were made of each washed long-sleeve shirt, or a total of 15 test pieces were made, and they were allowed to stand for 24 hours at RH65% 20°C, and then measurements were taken to find the average value.

Slit width, 10 mm.

As for detergents used, soap alone, SE alone, ABS type commercially available detergents and washing with water were the conditions adopted with the other conditions and the method being the same. The results are also shown.

Table 9 ____________________________________________________________ ______________ Kinds of SE Constituent Mono- Dies- Tri- & Degree of Percen- Fuai- fatty acid ester(%) ter(%) higher substitu- tage de- meter poly- tion tergency value* ester (%) ____________________________________________________________ ______________ Examples of the present invention Palmitic acid 42.2 35.8 22.0 1.62 70.2 62.0 Stearic acid 43.1 35.5 21.4 1.60 63.7 61.5 Behenic acid 45.2 34.9 19.9 1.57 55.0 57.0 Hydrogenated tallow fatty acid 10.5 21.7 67.8 3.20 57.0 55.0 do. 24.3 38.8 36.7 1.94 62.1 59.5 do. 32.6 38.8 29.4 1.78 64.5 62.0 do. 43.7 35.6 20.7 1.61 65.3 63.0 do. 49.5 33.7 16.8 1.50 71.3 65.0 Non-hydroge- nated fatty acid 42.6 35.7 21.7 1.61 68.5 63.0 Comparative examples Lauric acid 40.9 36.1 23.0 1.64 72.5 68.0 Myristic acid 44.2 35.2 20.6 1.59 75.8 68.5 Palm fatty acid 39.9 36.4 23.7 1.65 69.1 do. Hydroge- nated tallow fatty acid 60.6 29.8 9.6 1.36 74.2 67.5 do. 7.8 16.5 75.7 3.75 46.7 54.5 Soap alone 58.5 68.0 SE alone** 45.7 67.5 SE alone*** 31.3 62.0 ABS type commercially available detergent ("ALCO COLOR" by Nippon Sunhome Co., Ltd.) 73.3 69.0 Washing with water alone -- 69.5 ____________________________________________________________ ______________ *The Fuaimeter values indicate that the higher the value, the more stiff or that the lower the value, the softer. **Constituent fatty acid: Hydrogenated tallow fatty acid 49.5% monoester, 33.7% diester and 16.8% tri- and higher-polyester Degree of substitution: 1.50 ***Constituent fatty acid: Hydrogenated tallow fatty acid 32.6% monoester, 38.0% diester and 29.4% tri- or higher polyester Degree of substitution: 1.78 This SE alone example exhibited a dispersed state.

From Table 9 it will be observed that when soap and SE 50% or more by weight of whose constituent fatty acid consists of a fatty acid with 16 or more carbon atoms and whose degree of substitution is 1.5- 3.5 are concurrently used, the balanced result of the percentage detergency being 60 or more and of the Fuaimeter value being 65 or less can be obtained. It has also been found that when the degree of substitution is 1.6- 2.0, a better result can be obtained.

EXAMPLE 10

Using as detergents preparations of 30 parts of mixtures consisting of hardened tallow fatty acid ester with a degree of substitution of 1.61 and soap (sodium salt of a mixed fatty acid consisting of 70% non-hydrogenated tallow fatty acid and 30% palm fatty acid) in various proportions shown in Table 10, and 20 parts of sodium tripolyphosphate, measurements were taken with the other conditions and the method of measurement being the same as in Example 9, and the results shown in Table 10 were obtained.

Table 10 ____________________________________________________________ ______________ soap/SE 100/0 90/10 80/20 70/30 60/40 50/50 40/60 20/80 0/100 ____________________________________________________________ ______________ (%) percentage 81.3 80.7 78.5 75.4 69.3 65.2 64.0 62.8 57.3 detergency Fuaimeter 68.0 64.0 60.0 59.5 58.0 57.5 58.0 59.0 65.5 value ____________________________________________________________ ______________

From Table 10 it will be observed that concerning the mixing proportions of SE and soap, it is desirable in consideration of the relationship between detergency and softness impartation property that the amount of SE be 30% or less and the amount of soap be 70% or more.

EXAMPLE 11.

With the sodium tripolyphosphate in Example 10 being replaced in the same amount by various builders shown in Table 11 and with the other conditions and the method of measurement being the same as in Example 10, measurement were taken and the results shown in Table 11 were obtained.

Table 11 ______________________________________ Builder Percentage detergency (%) ______________________________________ sodium tripolyphosphate 78.5 sodium pyrophosphate 77.0 sodium carbonate 67.7 sodium metasilicate 65.3 sodium citrate 52.5 NTA 75.9 ______________________________________

From Table 11 it will be observed that the incorporation of phosphate type builders increases the detergency to the atlmost extent.

EXAMPLE 12.

Detergents consisting of the following compositions A-D were used under the following conditions and their detergency and softness impartation properties were tested in the manner similar to that in Example 9. The results were as shown in Table 12.

______________________________________ Detergent A: Sodium non-hydrogenated fatty acid 22% sodium tallow fatty acid 10% Hydrogenated tallow fatty acid SE 8% (degree of substitution: 1.61) Sodium tripolyphosphate 30% Sodium metasilicate 10% CMC 3% Moisture 17% ______________________________________

Detergent B: Sodium non-hydrogenated fatty acid 22% Sodium palm fatty acid 10% Hydrogenated fatty acid SE (degree 8% of substitution: 1.94) Sodium tripolyphosphate 30% Sodium metasilicate 10% CMC 3% Moisture 17%

Detergent C:

Higher alcohol type commercially available detergent ("Monogen" produced by Nippon Sunhome Co., Ltd.)

Detergent D:

ABS type commercially available detergent ("ALCO COLOR"by Nippon Sunhome Co., Ltd."

Preparation of active detergent component having 10% polyamide type softening agent

Washing Conditions: Soiled fabric: Three fabrics artificially soiled with natural dirt Method of washing: Terg-to-meter Washing concentration: 0.2% Washing temperature: 25°C Hardness of washing liquid: 30 ppm (as CaCO ₃ ) Washing time: 10 min. Number of revolutions: 100 rpm Bath ratio: 1 : 100

Table 12 ____________________________________________________________ ______________ Textile Acryl to be (Cashmilon washed Cotton Polyester/Cotton Nylon Taffeta Musline) test Deter- Fuai- Deter- Fuai- Deter- Fuai- Deter- Fuai- Item gent meter gent meter gent meter gent meter rate(%) value rate(%) value rate(%) value rate(%) value Detergent ____________________________________________________________ ______________ A 72.6 58.5 83.5 60.0 92.5 67.2 71.5 83.5 B 68.2 57.0 70.6 56.5 80.7 48.5 69.6 81.0 C 67.3 63.5 72.5 65.5 89.8 78.0 63.7 85.5 D 78.5 66.0 88.2 68.5 98.2 98.5 72.5 90.5 Non-washed textile -- 69.5 -- 75.0 -- 125.0 -- 92.5 Reflection factor of the solid 20.3 -- 35.7 -- 24.3 -- 25.5 -- original textile ____________________________________________________________ ______________

From Table 12 it will be observed that the present inventive articles A and B are superior in detergency to the detergent D having a softening agent incorporated therein.

Further, feeling evaluation of the wash tested in this example was carried out by 5 textile softening treatment evaluation technicians. The results were as shown in the following table. It has been found that the present inventive articles A and B exhibit superior softening effects also when subjected to feeling test.