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Publication numberUS3867301 A
Publication typeGrant
Publication dateFeb 18, 1975
Filing dateSep 8, 1972
Priority dateSep 11, 1971
Also published asDE2244310A1, DE2244310B2, DE2244310C3
Publication numberUS 3867301 A, US 3867301A, US-A-3867301, US3867301 A, US3867301A
InventorsUeno Hiroshi, Watanabe Yutaka, Yamagishi Fumiaki
Original AssigneeDai Ichi Kogyo Seiyaku Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent compositions
US 3867301 A
Abstract
The detergent composition comprises essentially a mixture of a soap component with a sucrose ester component which comprises at least one sucrose esster of fatty acid having 6 to 22 carbon atoms. The detergent composition may further include a saccharide component.
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Description  (OCR text may contain errors)

United States Patent Watanabe et al.

[451 Feb. 18,1975

[" 1 DETERGENT COMPOSITIONS [75] Inventors: Yutaka Watanabe; Fumiaki Y'amagishi; Hiroshi Ueno, all of Kyoto, Japan [73] Assignee: Dai-Ichi Kogyo Seiyaku Co., Ltd.,

Kyoto, Japan [22] Filed: Sept. 8, 1972 [21] Appl. No.: 287,550

[30] Foreign Application Priority Data Sept. 11, 1971 Japan 46-70554 Sept. 13, 1971 Japan 46-71484 Oct. 6, 1971 Japan 46-78872 [52] ms. Cl 252/108, 252/132 [51] Int. Cl. Clld 1/04, C1 1d 9/26 [58] Field of Search 252/89, 108, 132, 135, 252/DIG. 1; 260/234 R [56] References Cited UNITED STATES .PATENTS 2,114,491) 4/1938 Harris 252/119 2,893,990 7/1959 Nass ct a1 260/234 R OTHER PUBLICATIONS 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.

Primary Examiner-P. E. Willis, Jr. Attorney, Agent, or Firm-Armstrong, Nikaido & Wegner '57 ABSTRACT The detergent composition comprises essentially a mixture of a soap component with a sucrose ester component which comprises at least one sucrose esster of fatty acid having 6 to 22 carbon atoms. The detergent composition may further include a saccharide component.

16 Claims, N0 Drawings 1 DETERGENT COMPOSITIONS 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 4050C, this being unsuitable to domestic washing conditions.

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

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 socalled 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.

Otherobjects 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 by weight of said sucrose ester being monoand 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 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 monoand diesters and the remaining part of trior higher polyesters.

I 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 ob tainable 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 SEs useful in the present invention are sucrose esters of saturated or unsaturated fatty acids with 622, preferably, l2-l 8 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 saccharidesused 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 advantageousand 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 monoand 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 30C or less, particularly 20l0C 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 by weight of saturated fatty acid having l.2 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 monoand di-esters in the SE component according to the invention must be or more by weight. In other words, trior 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 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 to 97%, preferably, to 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 7 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 ofsoil, 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 ofwash and finish it soft may further include a saccharide component. It has been found that the addition of a saccharide further improves the detergency 3 and still maintaining public hazardlessness. Among the useful saccharides there may be mentioned monosaca 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 ineluding SE and saccharide can be utilized for preparing the detergent composition according to the invention.

LII

Solid Pollutant:

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

EXAMPLE 1 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: 30! Temperature of water: 30C Washing time: I 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 Reflectivity of soiled Reflectivity of fabric after washing soiled fabric Refiectivity of Reflectivity of original fabric soiled fabric Standard Soiled Fabric:

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

5 parts ololeic acid, 1 part of stearic acid. l part of cholesterol, 3 parts of whale oil, 9 parts of coconut oil, and 1 part of squalenc 9 parts of hentonite and l part of carbon black Synthetic sebum:

The results are shown in Table 1.

Table 1 Percentage Detcrgency ("/r) Kind Tallow Se/ of tallow soap 100/0 75/25 /50 25/75 0/100 sa- Amount of cchasaccharidc ride addedWr) Sucrose 0 48 52 57 68 73 I0 48 63 73 20 49 58 66 78 75 30 49 63 74 BI 75 Sorbitol 20 4s 5s 63 73 73 Sucrose containing decom- 20 49 67 75 83 77 posed products of sugar From Table 1 it will be observed that the addition of a saecharide to soap and SE, independently, does not Mixture Composition: Tallow p SE 75% contribute to the improvement of detergeney but that gggg 'g 3'; the addition of a saccharide to a mixture of soap and Table 3 Percentage Detergency SE/tallow soap Additive 100/0 75/25 50/50 25/75 /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 S9 (13 70 70 Sodium sulfate 56 63 70 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 Detergeney Kind Tallow soap of surfactant 100/0 75/25 /50 25/75 0/100 sur- Amount of fac- Sucrose added tan! ABS 1 0 73 74 74 75 77 NA Polyoxyethylene (P210) lauryl ether 0 73 74 73 71 73 20 .75 76 do. 73 75 Lauryl sulphate 0 73 68 66 65 20 72 69 68 68 From Table 2 it will be obserbed that the addition of EXAMPLE 4 sucrose to polyoxyethylene alone or to a mixed system thereof w1th soap does not make any contributlon to 50 Mixtures oftauow soap and tanow SE were prepared 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 60 in various mixing ratios noted in Table 4. They were measured at a concentration of 0.2% and a temperature of 30C for their foaming effect and foam retention by the Rossmilcs method (SK-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 Continued Mixing ratio Foaming height 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 by weight of various SEs 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 washedz Five long sleeve shirts (weighing about 1 kg) which had been worn for three days Amount of detergent: 50g Amount of water: 30]

Temperature of water: 10C

Washing time: l0 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.

lorcontvugo detergency lt.t .lloot.ivit. of soiled Reflectivity of fabric nfixu' washing soiled fabric 7 Reflectivity of lfolloc taivitrvof original f:|.l)rio soiled fabric Table 5 Composition Ratios Pcrccnt- Kind of of respective age deconstituent esters in SE tcrgcncy fatty acid in SE monodi triand higher Lauric acid 100 0 0 74 do. 0 I00 0 72 do. 0 0 ,iOO 43 Myristic acid 100 0 0 77 do. 0 I00 0 Palmitic Acid I00 0 0 56 Stearic acid I00 0 0 4| Tallow fatty acid 100 0 0 45 Coconut fatty* acid 699 25.1 5.0 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 3] Mixture of tallow soap and l0% polyoxyethylene lauryl ether 55 Composition of coconut fatty acid:

C a saturated fatty acid 14% C C do. 66% C C do. 1 1% unsaturated fatty acid 9% "Addition product of 10 moles of ethylene oxide From Table 5 it will be observed that amoung the SEs with 72 to 14 carbon atoms, monoesters and dies- 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.

I Table 6 Kind of Composition Mixing Percentage constituent Ratios of proportion detergency fatty acid respective esters in SE in SE monoditri- & tal- SE higher low polysoap coconut 32.6 38.0 29.4 5 60 fatty acid do. do. do. do. 90 IO 63 do. do. do. do. 85 I5 67 do. do. do. .do. 80 2O 66 do. do. do. do. 75 25 6i 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. )0 I0 72 do. do. do. dov X5 l5 72 do. do. do. do. X0 20 67 do. do. do. do. 75 25 62 do. do. do. do. 70 3f) 54 do. do. do. do. 50 50 44 From Table 6 it will be observed that superior deter- C. Preparation according to the present invention:

Sucrose coconut fatty acid ester Hi8; geney lh obta ned when the mixing ratio between SE (mom. dig "Land higherpolyj and soap is within the range of :95-25:75. Further, it 32.6: 38.0: 29.4)-

Tallowsoap 30.1% has been lound that when the hydrophrltcrty of SE ts 5 Sperm whae on {any acid soap Hm comparatively low, a m|xmg proportion of about NTA om 15-20% of SE is most suitable while when it is compar- I I h. h b t 15,7 t bl Sodium carbonate 25.0% ativc y tg a ou 0 ts mos surta e. CMC

Moisture 5.5% EXAMPLE 7 m D. Preparation according to the present invention:

Sacchartdes and conventional builders were added to C de reaction sucrose conut ester 2 .0% 50g of mixtures of SE and soap and the detergency was gfigf gggw sums and 34% tested under the same conditions and by the same oper- (SE mono-: di-: triand higher polyations as in Example 5. The results were as shown in 513721 Tallow soap 42.5% Table 7. Sucrose 12.3%

Table 7 Kind of Composition Mixing Kind Adding pro- Percentage constituent Ratios of proportion of portion (72) 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 I00 0 67 fatty acid do. do. do. do. do. do. sucrose 90 I0 73 do. do. do. do. do. do. do. 80 75 do. do. do. do. do. do. do. 70 76 do. unreacted SLICI'OSE conng 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. r00 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 Sodium carbonate 13.5% saccharide to a mixture of SE and soap further imfiss 2-23: proves the detergency at low temperatures. Further, it has also been found that it exh bits superior effects as B Preparation of soap akme: compared with conventlonal builders. Those which are low soap 45.0% adjusted by unreacted sucrose containing the decom- 150% Sodium metacilicate 8.0%

posed products of sucrose exhibit outstanding effects. sodium carbonate 220% CMC 0.5%

EXAMPLE 8 Moisture 9.5%

Using the following detergents A, B, C, D, E and F,

a F. Commercial] available AB 11 ti detergency was tested under the same conditions and y S type sy the c deter al g g ggag g gga g m Example The results (containing sodium tripolyphosphate) (produced by Nippon Sunhome Co., Ltd.)

A. Preparation according to the present invention: Table 8 Sucrose coconut fatty acid ester 8.4%

and P Percentage detergency Tallow sa 3o 3% washing Palm oil map 3 gent temperature [0C 20C 30C sodium metacilicate 8.0% sodium carbonate 25.5% A 78 30 CMC 15% B 78 8] 83 moisture 6.0% C 72 77 79 D so x2 35 r. .15 42 o) ll. Preparation according to the present invention: l" 5) 72 7X Sucrose coconut fatty acid ester 3.4% (mono: di-: tri and higher poly- 5 60.6: 28.9: 9.6) Tallow mp 363% From Table 8 it Wlll be observed that the present tn- Coconut soap g-gg ventive articles A and C have greatly improved detercarbonam I 1 gency atlow temperatures as compared with the simple Moisture 6.0% preparation of soap E, that the present inventive artiperior detergency at low temperatures as compared 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 with the ABS type detergents on the market. 5 percentage detergency, using the average value of the five. EXAMPLE 9 a P r Ustng 5 parts of SE of various compostttons shown 1n ercentage detergenc Table 9 and 45 parts of soap (sodium salt of a mtxed Reflectivity of soiled Reflectivity of fatty actd of 70% tallow fatty actd and of palm 1O fabri c after washing soiled fabnc fatty actd), the detergency and softening effects were R X100 eflecttvtty of Reflectivity of tested under the followtng condtttons by the following Original fabricsoiled fab'ric method, and the results were as shown Table 9.

Method of Measurement of Softening Effect: w n 15 Fuaimeter (Feeling degree counter) produced by mg CO I NJl'lSI I The wash: 5 long-sleeve cotton shirts which had been Uenoyama ls used I worn for three days, with the following soiled Three test pieces (regular square) were made of each fabric (and which weighed about lkg.) Amoumof detergent: g washed long sleeve shtrt, or a total of 15 test pieces Amoum f water; 301 were made, and they were allowed to stand for 24 p; of w 20 hours at Rl-l% 20C, and then measurements were Washtng time: 10 mtnutes k d h I Washing machine: Commercially available electric washing ta m t 6 average Va machine (National Ultra High Speed Sltt width, 10 mm.

UZUSHlO As for detergents used, soap alone, SE alone, ABS type commercially available detergents and washing Method of Measuring Detergency: 25 with water were the conditions adopted with the other Using a Menken Type fabric soil testing machine, conditions and the method being the same. The results samples for detergency test were soiled with a mixture are also shown.

Table 9 Kinds of SE Constituent Mono- Dies- Tri- & Degree of Percen- Fuaifatty acid ester(%) ter(%) higher substitutage dc meter polytion tergency value* ester 7!) 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 G0. 24.3 38.8 36.7 1.94 62.1 59.5 d0. 32.6 38.8 29.4 1.78 64.5 62.0 ClO. 43.7 35.6 20.7 1.61 65.3 63.0 do. 49.5 33.7 l6.8 1.50 71.3 65.0 Non-hydrogenated 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 75.1; 68.5 Palm fatty acid 39.9 36.4 23.7 1.65 69.1 (10. Hydrogenated tallow fatty acid 60.6 29.8 9.6 1.36 74.2 67.5 G0. 7.1; 16.5 75.7 3.75 46.7 54.5

Soap alone 58.5 68.0 SE alone" 45.7 67.5 SE alone"" 3L3 62.0 ABS type commercially available detergent ("ALCO COLOR by Nippon Sunhome Co.. Ltd.) 73.3 69.0 Washing with water alone 69.5 3

The Fuainteter values indicate that the higher the value. the more still. or that the lower the value. the softer.

"Constituent fatty acid: Hydrogenated tallow fatty acid 49.51 mnnoester. 33.7'1 diester and 16.8; tri' and lllgllLFPtllyesleI Degree of substitution: 1.50

'Cnnstitucnt fatty acid: Hydrogenated tallow fatty acid 32.6% monocster. 18.0; dicster and 29.4% trior higher polyester Degree of substitution: L78

This SE alone example exhibited a dispersed stale.

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 1.62.0, a better result can be obtained.

EXAMPLE 10- Using as detergents preparations of 30 parts of mix- From Table 1 1 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

10 results were as shown in Table 12.

. Detergent A:

tures cons1st1ng of hardened tallow fatty acid ester with Sodium non-hydrogenated fatty acid 22% a degree of substitution of 1.61 and soap (sodium salt SDdlum 10% f d f u .d S.st.n o 707 o 5 Hydrogenated tallow fatty acid SE 8% O a mlxe a y COP l l g 0 (degree of subst1tut1on: 1.61) hydrogenated tallow fatty ac1d and 30% palm fatty Sodium tripolyphosphate 30% acid) in various proportions shown in Table 10, and 20 fi' me'asmca'e parts of sodium tripolyphosphate, measurements were Moisture 17% taken with the other conditions and the method of measurement being the same as in Example 9, and the 20 Dcicigc'" T bl l0 bt d Sod um non-hydrogenated fatty acid 22% results shown In a e were 0 mm Sodlum palm fatty aCld Table 10 soap/SE 100/0 90/10 80/20 70/30 60/40 50/50 40/60 /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 y gg fatty acid SE (degree 8% e o su stitution:1.94)

the mix ng proportions of SE and soap, 1t 1s deslrable sodium tripolyphosphate 1n cons1derat1on of the relationshlp between deter- Sodium metasilieate 10% gency and softness impartation property that the f g g amount of SE be 30% or less and the amount of soap be or more.

EXAMPLE 11.

With the sodium tripolyphosphate in Example 10 being replaced in the same amount by various builders shown in Table 1 1 and with the other conditions and the method of measurement being the same as in Example l0. measurement were taken and the results shown in Table 11 were obtained.

Table 1 l Builder Percentage detergency Detergent C:

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

Detergent D:

5 10% polyamide type softening agent Washing Conditions:

Soiled fabric: Three fabrics artificially soiled with natural dirt Method of washing: Terg-to-meter sodium tripolyphosphate 78.5 50 Wash ng concentration: 0.2% sodium pyrophosphate 77.0 Washmg temperature: 25C sodium carbonate 67.7 l'lardness of washing sodium metasilicate 65.3 liquid: 30 ppm (as CaCO sodium citrate 52.5 Washing time: 10 min. NTA 75.9 Number of revolutions: rpm

Bath ratio: 1 100 Table 12 Textile Acryl to be (Cashmilon washed Cotton Polyester/Cotton Nylon Taffeta Musline) test Deter Fuai Deter- Fuai- Dcter- Fuai- Deter- Fuailtem gent meter gent meter gent meter gent meter rate(7r) value rate('7i) value rute('7() value rate('7l) 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 I) 78.5 66.0 38.2 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 55.7 24.3 5.5 original textile effects also when subjected to feeling test.

TABLE 13 Evnluutonnu. l 3 3 4 5 Detergent:

H. o o n o o t A O A X O I) A X 0 A X No'rEs.-@=Judgvd to have fairly high softness; O=Judgcd to have good softness; A=Judged to have some softness; X=Judgcd not to be so different from the original fabric.

Which is claimed is:

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 per one sucrose molecule being within the range of 1.5 to 3.5.

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 l2 to 14 carbon atoms and the remaining part of saturated fatty acid having or less carbon atoms, saturated fatty acid having 16 or more carbon atoms and various unsaturated fatty acids.

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 atoms.

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 or unsaturated fatty acids having 8 to 22 carbon atoms. p

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 thereof.

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, palm kernel oil, soy bean oil and mixtures thereof.

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

8. A detergent composition consisting essentially of 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 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 diesters, 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 being within the range of 1.5 to 3.5.

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 more carbon atoms and various unsaturated fatty acids.

10. A detergent composition according to claim 9, in

which at least 65% by weight of said fatty acid consist of fatty acid having 12 to 14 carbon atoms. 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 or unsaturated fatty acids having 8 to 22 carbon atoms.

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 oil.

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

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.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4211675 *Jan 17, 1979Jul 8, 1980Lever Brothers CompanyAcyl isethionate, sucrose ester
US4231904 *Feb 26, 1979Nov 4, 1980Lever Brothers CompanyDetergent bars with improved properties
US4298730 *Jul 31, 1980Nov 3, 1981Talres Development (N.A.) N.V.Process for the production of a surfactant containing sucrose esters
US5415801 *Aug 27, 1993May 16, 1995The Procter & Gamble CompanyConcentrated light duty liquid or gel dishwashing detergent compositions containing sugar
US5447648 *Apr 5, 1994Sep 5, 1995Ecolab Inc.For dishwashers, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerol fatty acid ester
US5474710 *Aug 27, 1993Dec 12, 1995Ofosu-Asanta; KofiProcess for preparing concentrated surfactant mixtures containing magnesium
US5507970 *Dec 14, 1993Apr 16, 1996Lion CorporationDetergent composition
US5968566 *May 14, 1997Oct 19, 1999Mlp Operating CompanyFlour and water with yeast for dough, also containing polyvalent fatty acid ester and nonionic surfactant sensory, rheological or other functional characteristics. a method of making a pizza dough product
US6384089 *May 1, 1998May 7, 2002Mitsubishi-Kagaku Foods CorpAqueous liquid for forming soap bubbles
US6497898 *May 31, 1994Dec 24, 2002Kanebo LtdStability, drug and cosmetic delivery
EP0075994A2 *Sep 22, 1982Apr 6, 1983THE PROCTER & GAMBLE COMPANYDetergent compositions containing mixture of alkylpolysaccharide and amine oxide surfactants and fatty acid soap
EP0380406A2 *Jan 23, 1990Aug 1, 1990Colgate-Palmolive CompanyFine fabric laundry detergent with sugar esters as softening and whitening agents
WO1980000452A1 *Aug 30, 1979Mar 20, 1980Milen CNon-polluting detergent composition containing soap and sucrose esters
WO2013144603A1 *Mar 26, 2013Oct 3, 2013Reckitt & Colman (Overseas) LimitedBar soaps
Classifications
U.S. Classification510/327, 510/355, 510/353, 510/354, 510/470
International ClassificationC11D3/22, C11D9/04, C11D9/26, C11D10/04, C11D10/00, C11D1/66
Cooperative ClassificationC11D10/045, C11D1/667, C11D1/662, C11D9/262
European ClassificationC11D1/66E, C11D1/66B, C11D10/04D, C11D9/26B