(12) INTERNATIONAL APPLICATION PUBLISHED UNDEI ‘THE PATENT COOPERATION TREATY (PCT) Orman Tnmatoal Bureau i 008 0 (43) Imvermatonal Publication Date (40) International Publication Number 31 December 2003 (31.12.2003) PcT WO 2004/000981 A2 (61) International Patent Classification CLID (74) Agent: CHOW WENG WENG: No. 151, Chin Swee Road, #09-11/13, Manhattan House, 169876 Singapore (80). (21) International Application Numb PCTISG20051000150 (51) Designated States (national): AP, AG, AL, AM, A, AU, AZ, BA, BB, BG, BR, BY, BZ, CA, CH,CN, CO, CR, CU, ate: 16 June 2003 (16.06.2003) CZ, DE, DK, DM, DZ, EC, EE, ES, F, GB, GD, GE, GI (GM, HR, HU, 1D, TL, IN, IS, JP KE, KG, KP, KR, KZ,LC, English LK, LR, LS, LT, LU, LY, MA, MD, MG, MK, MIN, MW, MX, MZ, NO, NZ, OM, PH, PL, PT, RO, RU, SD, SE, SG, SK, SL, TI, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, 7M, ZW. (22) International Filing (25) Filing Language English 0) Priority Data: (84 Designated States (regional): ARIPO patent (GH, GM, 20022355 24 June 2002 (24.06.2002) MY KE, LS, MW, MZ, SD, SL, 87, 12, UG, 7M, 2), urasian patent (AM, AZ, BY, KG, KZ, MD, RU, 3, TM), Baropean patent (AI, BE, BG, CH, CY, CZ, DE, DK, EE, (71) Applicants (for all designated States except US}: DE Ear ‘ RICHEM (M) SDN BHD [MY/MYE 2411 Lorong ES: Fl, FR, GB, GR, HU, TE, TT, LU, MC, NL, PT, RO, Perusahaan Satu, Prai Industrial Complex, 13600 Pri ‘SE, SI, SK, TR), OAPI patent (BF, BY, CF, CG, Cl, CM, Penang (MY). ACIDCHEM (SINGAPORE) PTE LID GA; GN, GQ, GW, ML, MR, NE, SN, TD, 16). [SG/SG}; 101 Plaza, 210 Middle Road, #06-09, 188994 Singapore (S Published: — without intemational search report and 10 be republished upon receipt ofthat report (72) Inventor; and (75) Inventor/Applicant (for US only): CHOONG, Wal, For nvo-leter codes and other abbreviations, refer tothe "Guid ‘Tuck [MYMY}; 26, Lebuhraya Batu Maung, 11960 ance Notes on Codes and Abbreviations” appearing athe begin- Bayan Lepas, Penang (MY). hing of each regular issue ofthe PCT Gace ($4) Title: IMPROVED SATURATED SOAP NOODLES THAT MAY OR MAY NOT CONTAIN PRESERVATIV TIVES. ‘OR ADDI 000981 A2 lll SF 657) Abstract: This invention elaes to an improved saturated soap composition for use in cosmetics, woiletry, omamental, and SF pharmaceutical without the additions of preservatives or alitives to enlsance its performance. This improved composition of sai S taied soap noodle virtually eliminates the need for preservatives, possess whiteness superior than conventional soaps and show less ‘mush and swelling tendencies. Conventional soap manufacturers add preservatives, antioxidants or chelating agents to preserve the ‘quality of the soap against oxidation; also adding appearance enhancing additives such as uoreseent whitening agents or optical brighteners to improve the soap whiteness, The problem of swelling and mush tendencies of soaps with high liquid aitives has yet BB be soled asain. The rina dsadvanaes of reserva and uperane enhancing aves aon cos and ‘environmental and health rstitions.10 15 20 25 30 WO 2004/000981 PCT/SG2003/000150 Improved Saturated Soap Noodles That May or May Not Contain Preservatives Or Field Of The Invention The present invention relates to saturated soap noodles, which may be used in cosmetics, toiletry, ornamental, and pharmaceutical applications to replace conventional toiletry soap noodle. Soap noodles produced by this inventive method are extremely mild, foam well and provide consumer-desired sensory properties. Background Of Invention Soaps are constantly moving towards better formulations that ultimately will provide some enhanced skin care, for example, minimizing levels of skin invitation and enhancing moisturization as well as providing desirable properties such as voluminous creamy lather and not become slimy when left in a soap dish after used. Conventional toilet soap noodles are made from oil and fats or their fatty acids from animal or vegetable based sources by saponification or neutralization with an alkali, Some common problems faced by these compositions include poor stability towards oxidation, high tendency of soap mush and swelling when formulated with liquids and in the case of oil saponification, low soap whiteness, Soap noodles manufacturers add preservatives, antioxidants or chelating agents, to preserve the quality of the soap noodle against oxidation; whereas the soap whiteness can be increased with appearance enhancing additives such es fluorescent whitening agents or optical brighteners. However, the problem of swelling and mush tendencies of soaps with high liquid additives has yet to be solved satisfactorily. But the principal disadvantages of preservatives and appearance enhancing additives are additional cost and environmental and health restrictions. Saturated soap noodle virtually eliminates the need for preservatives, possess whiteness superior than conventional soap noodles and show less mush and swelling tendencies. Conventional toilet soaps are made from blends of oil and fats or their equivalent distilled fatty acids from animal or vegetable based sources, Fatty acids are produced by the hydrolysis of the oil under high pressure and temperature in the presence of water to yield a10 15 20 30 Wo 20047000981 PCT/SG2005/000150 crude mixture of fatty acids and glycerol. This process is commonly referred to as splitting The crude fatty acids are then purified to the required purity through the process of distillation, and the valuable by-product of glycerol is processed separately to yield pharmaceutical grades of glycerine with purity of 99.5 99.7%. The desired blend of distilled fatty acids, obtained either by blending different oil and fats before the splitting process or after the splitting process in which the individual fatty acid components are blended to form the desired fatty acid composition, shall then be reacted with an alkali to form soap and water. Such reactions are termed according to their raw material used, in the case of oil and fats is saponification and in terms of fatty acid is neutralization. Another method of manufacturing involves ester interchange in which methanolysis of the oil and fats to yield methyl esters, which is then reacted with sodium hydroxide to form soap. GB Patent No. 1059089 to D Megson teaches a toilet soap compositions which comprises of substantially saturated fatty acid radicals containing from 10 ~ 18 carbon atoms, the weight ratio of Cio to Cy fatty acid radicals to Cig ~ Cis fatty acid radicals being from 0.4:1 to 1.1:1, in which the fatty acid radicals being partially saponified as mixed sodium and potassium soaps. In contrast to the subject invention, the Cio fatty acid radicals are not included because Cio fatty acid is known to cause slight skin imitation, The referred patent also used significantly high proportion of free fatty acids ie. 12% to 18% by weigh of the soap composition in which such level of composition can lead to high oxidation. Consequently, preservatives, antioxidants or chelating agents have to be added in order to preserve the quality of the soap; in addition, appearance-enhancing additives also have to be added in order to improve the whiteness of the soap. Further, the applicants of the subject invention saturated soap noodles uses only saturated fatty acids therefore it has superior heat and light stability, as well as having less tendency to oxidized or discoloration and less tendency to swell. Summary Of The Invention In one embodiment of the invention, the invention relates to bar soap noodles compositions comprising substantially saturated fatty acid metal salts at least 96% by weight of these substantially saturated fatty acid radicals containing from 12 to 18 carbon atoms, the %10 15 20 25 30 WO 2004/000981 PCT/SG2003/000150 weight of Cig ~ Cig fatty acid radicals is 40% to 80% and % weight of Cig ~ Cis fatty acid radicals is 20% to 60%, Preferably the weight ratio of Cjz — Cys fatty acid radicals to Cig — Cig fatty acid radicals is about 1.5:1. In one embodiment of the invention, the fatty acid radicals being partially neutralized as mixed sodium and potassium soaps, the ratio of sodium to potassium expressed as @ weight ratio of sodium hydroxide (NaOH) to potassium hydroxide (KOH) being from 9:1 to 2:1, preferably the weight ratio is from 7:1 to 3:1, Another embodiment of the invention, the amount of neutralized fatty acid radicals being such that the toilet soap composition contains from zero to 7% of free fatty acids by weight of the soap s composition; preferably the proportion is from 3% to 6%. A further embodiment of the invention, the soap noodles composition contains more than 12% of water by weight of the soap composition at the time of manufacturing A farther embodiment of the invention, the soap noodles composition contains less than 1% of sodium chloride by weight of the soap composition. A further embodiment of the invention, the total fatty acid composition has iodine value of less 0.5%, A further embodiment of the invention, the soap noodles does not need addition of preservatives in order to improve the quality of the soap noodles Detailed Description Of The Invention ‘This invention relates to saturated soap noodles, which may be used in cosmetics, toiletry, ormamental, and pharmaceutical applications to replace conventional toiletry soap. This new invention involves the manufacturing of soap noodles without unsaturated fatty acids by fractionating the split oil and fats to remove unsaturated fatty acid from the fat, As such the fatty acid composition of the fractionated fatty acid will differ from the naturally occurring oil and fats. ‘The fractionation process can be done on the blended oil and fats or on its individual component prior splitting. The removed unsaturated fatty acids are10 15 20 25 30 WO 2004/000981 PCT/SG2003/000150 compensated with the increase of the other fatty acids. The fractionation process and its effects on the fatty acid composition of final soap noodle is explained below: CH2OCORI | CHOCOR2 Splitting 3R1/2/3COOH | CH20COR3 Triglyceride Fatty Acids Where R1, R2 and R3 are alkyl groups of different linear carbon chain length. Each triglyceride molecule may differ from the types and combinations of the alkyl group. ‘inctive distribution of carbon chain However, naturally occurring oil and fats will have a length distribution that is dependent on the organism, After the splitting process, the total fatty acids obtained will have the distribution similar to the original oil or fat. In the conventional soap making neutralization process, the fatty acid will be distilled to remove impurities. In the distillation process, the whole portfolio of the fatty acid (including unsaturated fatty acids) with different carbon chain lengths composition, prior and after the distillation process will not be changed as the fatty acid blend is merely being purified. In the preparation of the fatty acid blend without unsaturated fatty acids, the split fatty acid will undergo a fractionation process in which the portfolio of the fatty acid will be changed and will differ from that of the original oil or fat prior splitting. Majority of the unsaturated fatty acids will be removed fiom the fatty acid blend. The subsequent process of converting the fractionated fatty acid blend to soap via neutralization is similar to conventional methods in which distilled fatty acid blends are converted to soap. Another alternative in which the fatty acid blend without unsaturated fatty acids can be obtained is by the process of blending high purity fractionated fatty acids of different chain lengths, however this alternative involves more handling thus uneconomical,10 15 20 25 30 Wo 2004/000981 PCT/SG2005/000150 This new invention is chemically a blend of potassium and sodium salt of fatty acid to form saturated soap noodles. It has high contents of salt of saturated fatty acids such as lauric, myristic, palmitic and stearic and very low contents of unsaturated fatty acids (oleic, linoleic and linolenic acid) as measured by gas chromatography. Soap noodles produced according to this invention will have superior heat and light stability without the need for preservatives such chelating agents or antioxidants. The soap noodles is thus more natural as it does not contain preservatives. Unsaturated fatty materials will be prone to auto-oxidation than its saturated counterpart, as the free radical intermediates generated in such fatty materials are resonance stabilized by unsaturation. For polyunsaturated materials, far more resonance-stabilized structures are possible; thus, the higher the number of unsaturation, the greater the tendency to auto-oxidized. In a system where both saturated and unsaturated acids are present, the saturated fatty acid merely behaves as inert diluents. In the kinetics of auto-oxidation, the propagation step involving hydrogen abstraction from unsaturated fats is slow: ROO+ RH > ROOH+ R The abstraction becomes selective for the weakest bound hydrogen, The ease of hydroperoxidation thus depends on the number of double bonds present. The relative rate of auto-oxidation of oleate linoleate : linolenate was reported to be in the order of 1: 40-50 : 100 on the basis of oxygen uptake, and in the order of 1 : 12 : 25 on the basis of peroxide development. More recently the initial rate of oxidation of linolenate in solution compared to linoleate was reported to be in the order of 2.0 ~ 2.5, based on oxygen uptake. The presence of doubly allylic methylene in linoleate explains its much higher reactivity than oleate. The single allylic methylene in oleate has a bond strength estimated at 77kcal/mole compared to 52kcal/mole for the doubly allylic methylene in linoleate, Linolenate has two doubly allylic methylenes but the other does not activate each, and the rate is therefore only about two times that of linoleate. The ease of breakdown of hydroperoxides also depends on the number of double bonds present. Linolenate peroxides are particularly unstable and the decomposition pathways become much more important with linolenate than with either oleate or linoleate. Activation of the methylene group adjacent to the double bonds will ease the initiation of free radicals on the methylene group. Resonance effect of the free radical with adjacent double bonds will stabilize the free radicals and accelerate the free radical formation. These two factors accounts for the big difference in oxidation rates. If the double bonds of10 15 20 25 30 Wo 2004/000981 PCT/SG2005/000150 polyunsaturated fatty acids are conjugated form, the activation of methylene group provided by the conjugated double bonds is greater than that by unconjugated double bonds. It is, therefore, easier to initiate free radical formation and cause faster oxidation. The double bond in naturally occurring fatty acids are normally in cis-configuration. When the double bond position is shifted during the free radical formation, the newly formed double bond will be in the more stable trans-configuration. The double bond in polyunsaturated fatty acids will be conjugated. Due to the absence of unsaturated fatty acids, saturated soap noodle is inherently stable and does not require supplement of additives such as antioxidants or chelating agents. This soap noodles also addresses the problem of EDTA usage in Japan and other EU countries. Whiteness appearance of the soap noodles is measured in the Hunter Lab Whiteness scale using the Hunter Lab Color Quest 45/0 with DP9000 (related to ASTM E313-73). This instrument is based on the representation of color components in a three dimensional color cube having an L-axis, a b-axis and an a-axis. The L is a lightness/darkness measurement or “whiteness level”. The a-axis is a red to green range, and the b-axis is a yellow to blue range. Both a and b axis can have either positive or negative values, In base soap the predominate color impression has been found to relate principally to the “L” and “b” readings, A “whiteness index” for soap that is very useful for comparison can be represented by the equation: L-3b= Hunter Whiteness Index (HW1) Conventional white toilet soap bases (without appearance enhancing additives) have HWI range from 50 — 75, however, saturated soaps has found to have whiteness indexes above 75. This superior whiteness permits the production of visually attractive white soap without the need of optical brighteners and/or opacifiers to “whiten” the color of the finished soap and the use of color pigments to beautify the soap. Good soap whiteness is of paramount importance for additive-free soap (due to its tendency to discoloration) and syndets/combars especially when it needs to be formulated with dark color additives such as LABS. In another embodiment of the present invention, saturated fatty acid feedstock show less tendency to oxidize (and discoloration) during storage and during the neutralization process allowing consistent and small batch-to-batch whiteness of soap to be produced from different10 15 20 25 30 Wo 2004/000981 PCT/SG2005/000150 production runs. Due to unsaturated fatty acids, conventional soap feedstock will deteriorate with storage (even in nitrogen-blanketed tanks) and this results in a gradual increase in the feedstock color (eventually reducing the whiteness of the soap produced from it), With this reason, it is not advisable to keep feedstock for more than one week for making white soap. Moreover, it is also not advisable to keep feedstock in large quantities as this may result in gradual decrease in whiteness of the soap produced when the tank is full to emptying of the tank, Chemically, saturated fatty acids do not show the tendency to oxidize as compared to conventional soap feedstock containing unsaturated and saturated fatty acids. This enables longer storage of fatty acid feedstock for soap production and reduce batch-to-batch whiteness variation of the feedstock. The stability of saturated fatty acids allow for consistent soap whiteness within and beyond a production batch. In another embodiment of the present invention, the formulation for this new invention imparts smoother bar feel and reduce grittiness feels in soaps. The use of KOH on the soap has profound effect on the soap bar. The KOH content in the soap has an inverse affect on soap hardness i.e, the higher the KOH content, the softer the soap, As saturated soap lacks dissociation capability due to the absence of unsaturated fatty acid, both KOH and glycerine imparts the necessary solubility to the soap and also gives some plasticizing effect. The elevated contents of glycerine and the presence of KOH imparts slippery soap feel to the bar and thus minimizes the grittiness of the soap. In another embodiment of the present invention, the soap noodles produced according to this formulation shows lower tendency to mush and smear. The soap mush and swelling tests measures the consumer-perceived bar economy. It gives an indication on the tendency of the soap to form unsightly mushy soap paste in dish. In the case of saturated soap, the absence of unsaturated soap as well as the higher contents of lauric acid (which forms part of the crystals) is the most probable cause for the reduction in mush and swelling tendency. Compared to other solid soap crystals i.e, a, B and 8, w crystals show the least tendency to swelling and disintegrating, A further embodiment of the invention, the soap noodles does not need addition of preservatives in order to preserve the quality of the soaps. The absence of bleaching agents and the non-requirement of optical brighteners, fluorescent whitening agents and chelating10 15 20 25 30 WO 2004/000981 PCT/SG2003/000150 agents (EDTA), contribute towards environmental protection as well as reduction in processing cost and resources. According to the present invention, there is provided a toilet soap composition in which substantially all the fatty acid radicals are substantially saturated fatty acid radicals at least 96% by weight of these substantially saturated fatty acid radicals containing from 12 to 18 carbon atoms, the % weight of Cr2 — C4 fatty acid radicals is 40% to 80% and % weight of Cig — Cig fatty acid radicals is 20% to 60%. The fatty acid composition of fatty acid metal salt is Cyz 45%-70%, C14 0%-50%, Cis 15%-30% and Cig 10%-25%. The fatty acid radicals being partially neutralized as mixed sodium and potassium soaps, the ratio of sodium to potassium expressed as a weight ratio of sodium hydroxide (NaOH) to potassium hydroxide (KOH) being from 9:1 to 2:1, the amount of neutralized fatty acid radicals being such that the toilet soap noodles composition contains from zero to 7% of free fatty acids; the toilet soap composition contains more than 12% of water by weight of a soap noodle composition at the time of manufacturing and less than 1% by weight of a soap noodle composition of sodium chloride, The fatty acid composition is derived from vegetable or animal based fatty acid. The C2 — Cig fatty acids may be derived from coconut and/or palm kernel oil where the C5, Cg and Cio fatty acids are preferably removed with fractionation as both is known to cause slight skin invitation. The Cis— Cis acids may be obtained from hydrogenation or fractionation of tallow, palm oil or simply in the form of commercial stearic and/or palm triple pressed acid. The iodine value of the total fatty acid content is less than 0.5%, If the weight ratio of C12 — Ci fatty acid radicals to Cis — Cre fatty acid radicals is more than 2:1, the soap lacks surface activity (“cleaning power”) even though its foams very well. Contrary to consumer perception, foaming does not equate detergency of soap. However if the ratio drops below 0.2:1, the soap base becomes too hard and brittle and does not have satisfactory dissolution especially in cool water. The recommended weight ratio of Ciy ~ Cis fatty acid radicals to Cig— Cis fatty acid radicals is 2:1 to 0.2:1 with the optimum at 1.5:1. The ratio of sodium to potassium soap in the composition is also expressed as a weight ratio of sodium hydroxide to potassium hydroxide. If this ratio is above 7:1, the soap base lack solubility but below the ratio of 3:1, the soap becomes too soft, sticky and has high mush10 15 20 25 WO 2004/000981 PCT/SG2003/000150 tendency. The recommended working ratio of sodium to potassium soap in the composition is Tl to 3:1. The neutralization is done such that the final soap composition contains from 3% to 6% of free fatty acids. Below 3% superfatting, the soap does not lather well but above 6% superfatting the soap’s stability towards oxidation is reduced. The soap products containing free fatty acids have a greater tendency to undergo auto-oxidation. The presence of fatty acids in fats and oils also tends to show a similar effect; the presence of a free carboxylic group is necessary for this catalytic effect. Itis believed that the free fatty acid catalyzes the decomposition of hydroperoxides, resulting in the formation of fiee radicals. The mechanism proposed for this action of free fatty acids involves a complex formation between the fatty acid and the hydroperoxide; this results in accelerated splitting of hydroperoxides to produce free radicals: RCOOH + RIOOH~>[RCOOH.RIOOH] > R10++R++CO2+H20 It is very likely that peroxy esters are first produced as intermediates in the above fatty acid catalyzed decomposition of hydroperoxides; the peroxy esters then readily decompose to produce the free radicals. Therefore, the recommended working range of superfatting is 3% to 6%. The moisture content of the soap can be more than 12%. At moisture contents below 8%, the soap tends to be hard and difficult to process on conventional plodders whereas moisture above 18% causes the soap to be too soft to be plodded. ‘The sodium chloride content of the soap is less than 1%, With dosages below 0.3%, the soap tends to be soft whereas dosages above 1.5% will cause plodding difficulties. With all the advantages, such saturated soap noodles is well suited to serve as a base formulation for syndets and combars, and additive-free soap. Mush and swelling problems are specific in Combat/Syndets due to enhanced solubility delivered through the use of surfactants a higher tendency to mush, as they are unable to loose sufficient water from the mush layer to return to a solid state under normal use.10 10 WO 2004/000981 PCT/SG2003/000150 Conventional methods to resolve the current issues including: 1) Control solubility by the addition of organic or inorganic salts but the drawback of such measure is negative lather performance, 2) To select constituents of high solubility but the drawback of such measure is high wear rate, With the introduction of present invention of saturated soap, the absence of ‘unsaturated soap as well as the higher contents of laurie acid is the most probable cause for the reduction in mush and swelling tendency. This base will solve the problems with formulation of syndets and combars without sacrificing on other quality parameters. In addition, the need for a soap base that does not contain preservative and appearance enhancing additives for the Japanese additive-free soap is fully met by the saturated soap base10 15 20 25 30 it WO 2004/000981 PCT/SG2003/000150 Claims What is claimed is: 1. An improved saturated soap composition comprising: (@) saturated fatty acid radicals with at least 96% by weight of these saturated fatty acid radicals comprises predominantly a mixture of saturated C12 - Cis; (©) % weight of C12 — Cis fatty acid radicals is 40% to 80% and % weight of Cig — Cis fatty acid radicals is 20% to 60%; (©) fatty acid composition of fatty acid metal salt is C12 45%-70%, Cry 0%-50%, Cis 15%-30% and Cig 10%-25%; @ fatty acid radicals are partially neutralized as mixed sodium and potassium soap noodles, with a weight ratio of sodium hydroxide (NaOH) to potassium hydroxide (KOH) being from 9:1 to 2:1; (©) zero to 7% of free fatty acids by weight of a soap noodle composition; (© water content can be more than 12% by weight of a soap noodle composition at the time of manufacturing; and (g) _less than 1% of sodium chloride by weight of a soap noodle composition. 2, An improved saturated soap composition as claimed in claim 1 wherein weight ratio of Cy - Cig fatty acids to Cig ~ Crs fatty acids is about 1.5:1 3. An improved saturated soap composition as claimed in claims 1 and 2 wherein a weight ratio of sodium hydroxide to potassium hydroxide is from 7:1 to 3:1. 4, An improved saturated soap composition as claimed in any of the claims 1 to 3 wherein the proportion of free fatty acids is from 3% to 6%, by weight of a soap noodle composition. 5, An improved saturated soap composition as claimed in any of the claims 1 to 4 wherein at least a major proportion of the acid radicals of the free fatty acids contain from 16 to 18 carbon atoms, 6, An improved saturated soap composition as claimed in claim 1 wherein the composition of sodium chloride content is less than 1%, by weight of a soap noodle composition.12 WO 2004/000981 PCT/SG2003/000150 7. An improved saturated soap composition as claimed in any of the claims 1 to 6 wherein said fatty acid composition is derived from vegetable or animal based fatty acid. 8. An improved saturated soap composition as claimed in any of the claims 1 to 7 wherein said total fatty acid content has iodine value less than 0.5%. 9. An improved saturated soap composition as claimed in any of the claims 1 to 8 wherein preservatives (antioxidants or chelating agents) may not be added.