EP0607004A2 - Composition de savon contenant du pyrophosphate sodique - Google Patents

Composition de savon contenant du pyrophosphate sodique Download PDF

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Publication number
EP0607004A2
EP0607004A2 EP94300155A EP94300155A EP0607004A2 EP 0607004 A2 EP0607004 A2 EP 0607004A2 EP 94300155 A EP94300155 A EP 94300155A EP 94300155 A EP94300155 A EP 94300155A EP 0607004 A2 EP0607004 A2 EP 0607004A2
Authority
EP
European Patent Office
Prior art keywords
soap
tspp
bars
bar
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94300155A
Other languages
German (de)
English (en)
Other versions
EP0607004A3 (fr
Inventor
Syed Husain Abbas
Ravi Subramanyam
Suman Kumar Chopra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0607004A2 publication Critical patent/EP0607004A2/fr
Publication of EP0607004A3 publication Critical patent/EP0607004A3/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/08—Water-soluble compounds
    • C11D9/10—Salts
    • C11D9/14—Phosphates; Polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/02—Compositions of detergents based essentially on soap on alkali or ammonium soaps

Definitions

  • the present invention relates to soap bar compositions having enhanced structural integrity, hardness, slough and wear- and crack-resistant properties.
  • soaps in water are generally very high, especially when they contain high levels of salts of unsaturated fatty acids (oleate and linoleate).
  • Soaps derived from high levels of coconut oil have high wear properties, and they possess poor slough characteristics. These soaps produce good lather and are resistant to crack; however, rate of wear and slough properties are important attributes in a soap bar.
  • Structurants or fillers have been commonly used in detergent bars to improve the properties of the bar. They are used to provide structural integrity, as well as to improve the physical properties of the soap bars in which they are incorporated. For example, electrolytes (sodium chloride) and various polymers have been added to soap bars to improve the wear characteristics by salting out the liquid phase in the bar. However, the resulting soaps have poor lather and increased tendency to crack.
  • Tetrasodium pyrophosphate has been previously used in detergent bar formulations as a filler. It has low solubility in water (7-8% at room temperature), high transition temperature (80°C) and absorbs water (60% of its weight). On recrystallization, TSPP forms long needle and hexagonal platelets.
  • U.S. Patent No. 2,686,761 discloses the addition of TSPP to soap bar compositions containing high moisture levels, i.e., greater than 20% by weight.
  • the TSPP is combined with the high moisture content soap in the crutcher: however, the mixture must be subjected to rigorous kneading, shearing and compacting to result in a "salting-out" of the molten soap and water so as to produce a bar having milled soap properties and which is waxy, translucent and predominantly in the beta phase.
  • the resulting bar has a high total water content, however, at a cost of reduced soap content.
  • the presence of excess moisture in the bar leads to an increased tendency to crack.
  • the TSPP functions as an inert filler in the soap bar disclosed in U.S. Patent No. 2,686,761, thereby enabling the provision of a composition containing more water and less soap with inferior structural properties.
  • U.S. Patent No. 4,308,158 relates to a synthetic surfactant composition containing a builder which comprises a mixture of alkali metal orthophosphate, alkali metal pyrophosphate and alkali metal tripolyphosphate.
  • U.S. Patent No. 3,639,286 discloses the addition of an alkali metal trimetaphosphate to a synthetic detergent bar or cake to absorb the water content thereof such that the final water content is as water of crystallization of the tripolyphosphate salt.
  • U.S. Patent No. 3,494,869 describes a superfatted soap bar containing an acidulating agent which may comprise a phosphorous acid or a strong acid salt thereof.
  • the acidulating agent is present to react with the constituent soaps to form free fatty acids in situ.
  • U.S. Patent No. 2,868,731 discloses the inclusion of TSPP in non-soap detergent bars to function as a "filler.”
  • U.S. Patent Nos. 2,970,116 and 3,274,119 relate to a transparent soap bar having a high moisture content and containing an electrolyte including sodium tripolyphosphate to salt out the water.
  • U.S. Patent No. 3,370,015 discloses strong, fast-dissolving detergent tablets containing a hydratable condensed phosphate such as TSPP.
  • U.S. Patent No. 4,297,230 describes a non-crystallizing transparent soap bar containing 4 to 20% potassium soap and an electrolyte which may comprise tetrasodium pyrophosphate.
  • U.S. Patent No. 3,344,076 relates to detergent tablets or briquettes containing at least 20% by weight of a phosphate component (tetrapotassium pyrophosphate or pentasodium or pentapotassium tripolyphosphate).
  • a phosphate component tetrapotassium pyrophosphate or pentasodium or pentapotassium tripolyphosphate.
  • the tablets are designed to have a high rate of disintegration and solubilization in washing machines.
  • U.S. Patent No. 3,798,181 discloses an enzymatic detergent bar useful for washing laundry and containing, as a builder, tetrapotassium pyrophosphate.
  • a detergent soap composition in bar form comprising (1) an alkali metal or ammonium soap of a saturated or unsaturated fatty acid or mixture thereof, (2) no more than about 14% by weight, preferably 6 to 14 % by weight of total water, and (3) from about 0.5 to about 15% by weight of a structurant selected from the group consisting of tetrasodium pyrophosphate, a hydrate of tetrasodium pyrophosphate and mixtures thereof; the structurant providing enhanced structural integrity, hardness, slough and wear- and crack-resistant characteristics thereto.
  • An additional embodiment of the invention is a method of preparing the above-described detergent soap composition comprising mixing in a crutcher the alkali metal or ammonium soap of a saturated or unsaturated fatty acid or mixture thereof, water and at least a portion of the tetrasodium pyrophosphate at a temperature above about 80°C and then vacuum drying to a final moisture level of 6-14% while maintaining the soap temperature above 80°C.
  • Figs. 1 and 2 graphically compare rates of moisture loss over time of soap bars of the invention containing TSPP compound with a control bar containing no TSPP.
  • Fig. 3 graphically depicts mapping of water content in soap bars containing TSPP.
  • TSPP tetrasodium pyrophosphate
  • TSPP has been incorporated in soap detergent bars.
  • its use has been limited to soaps of specific fatty acid compositions having high moisture content, wherein it functions as a filler.
  • U.S. Patent No. 2,686,761 describes a process which, by adding TSPP to the soap composition under certain processing conditions, enables the production of a soap bar containing a high proportion of water at the expense of a lower proportion of soap.
  • the resulting soap bar is Predominantly in the beta phase. It is well known that, in high moisture (20-40%) soap bars, the rate of wear increases as the percentage of beta phase increases.
  • 2,686,761 is applicable only to a certain class of fatty acid soaps (i.e., soap of a fat stock of iodine value above 25 and wherein not more than 40% of the combined fatty acids of which are saturated and of less than 16 carbon atoms and at least 20% of the combined fatty acids of which are saturated and of from 16 to 22 carbon atoms).
  • the composition containing soap, water and TSPP must be subjected to extreme conditions of shear following mixing in the crutcher to achieve the desired "milled soap properties" and predominantly beta phase. It also appears that the use of the above-described limited class of fatty acid soaps is critical for the formation of the beta phase in the resulting soap bars.
  • TSPP functions in the soap bar compositions of U.S. Patent No. 2,686,761 strictly as a filler and as a "salting-out" agent to enable the production of bars containing large amounts of water and low proportions of soap which are in the beta phase.
  • TSPP functions in an entirely different manner.
  • the invention is applicable to all fatty soaps used in manufacturing soap detergent bars.
  • the TSPP functions not merely as a filler enabling the production of soap bars containing a high amount of water, but rather as a functional reagent which enables the production of a low water content soap detergent bar and which effectively enhances many of the physical properties of the bar.
  • the TSPP acts as a processing aid in the formation of the detergent bars.
  • the highly advantageous properties of the soap detergent bars of the invention are produced by the unique method of mixing the components of the composition in the crutcher and drying the resulting mixture.
  • at least a portion, and preferably all, of the TSPP be added to the soap mixture in the crutcher.
  • the mixture is then heated to a temperature above about 80°C, the transition temperature of the hydrate of TSPP, and dried under vacuum at that temperature to a final moisture level of 6-14%.
  • the excess moisture be removed during the drying step at a temperature above the transition temperature of TSPP, i.e., 80°C.
  • TSPP and remaining TSPP hydrate in the finished bars are believed to form long needle and hexagonal platelet crystals throughout the soap bar structure, thereby forming what amounts to a fibrous-type matrix network therein.
  • This reinforcing network of TSPP and TSPP hydrate crystals is believed to provide the enhanced structural integrity, hardness, slough and wear- and crack-resistant properties associated with the soap detergent bars of the invention.
  • any fatty acid or mixture thereof, whether saturated or unsaturated, conventionally employed to prepare soap detergent bars may be employed in the practice of the invention.
  • fatty acids employed to prepare the soap/TSPP/H2O mixture is not overly critical.
  • suitable such fatty acids from which the soaps (preferably sodium salts) are derived are fatty acids with alkyl chain lengths of C8 to C22, and preferably C12 to C18.
  • Preferred fatty acids are those derived from tallow/coconut blends wherein the ratio of tallow/coco soap ranges from 1:1 to 9:1. Coco soap is interchangeable with palm kernel oil soap. Tallow soap is interchangeable with palm derived soap, or any other hardened soap derived from C16 and above fatty acids.
  • the TSPP may be added to the kettle soap or therewith when the latter is fed to the crutcher, or it may be added to the crutcher following addition of the soap. In a preferred embodiment, most of the TSPP is added to the crutcher with the soap and the remainder is added in the amalgamator.
  • Adjuvants typically employed in the preparation of detergent soap bars may, of course, be added to the compositions of the invention.
  • exemplary of such adjuvants are: chelating agents such as EDTA, DTPA; opacifiers, e.g., TiO2; brighteners such as Tinopal; and fillers, e.g., talc, kaolin, etc.
  • the invention is illustrated by the following non-limiting example.
  • Crutcher Formula (Soap Chips) Ingredients Weight % Neat Soap (85% tallow/15% coco) 96.95 - 100 TSPP 0 - 3 EDTA (Na)4 0.03 BHT (butylated hydroxytoluene) 0.02 Amalgamator Formula Soap chips 98.5 Perfume 1.5
  • TSPP tetrasodium pyrophosphate
  • the soap chips were mixed with perfume and colorants, milled on a roll mill three times and plodded. The bars were then pressed into brick shape.
  • Examples 1 to 7 were prepared using 85/15 tallow/coco soap (see Table 1).
  • Examples 1, 3 and 6 are comparison examples.
  • Batches 1 and 2 were made with and without 3% TSPP. The final moisture in the bars was maintained at approximately 8% and TSPP was added in the crutcher.
  • Batches 3-5 were made with 9-10% moisture content in the soap bar with and without 3% TSPP, and TSPP was added in the crutcher.
  • an additional 1.5% TSPP was added in the amalgamator.
  • Batches 6 and 7 were made with and without 3% TSPP, and TSPP was added in the amalgamator.
  • Volatiles The volatiles are reported as percent weight loss. This loss equals water plus fragrance and other volatiles lost during heating overnight (12 hours) using a vacuum oven (180°F, 25'' Hg). (82°C, 63.5 mm Hg) (see col 3 in Table 1).
  • Hardness The bar hardness was determined using a needle penetrometer (Prevision Scientific Co. Model 11-12). This apparatus uses a weighted needle point, and the depth of penetration into the soap surface was measured for a 10-second interval. A minimum of ten data points were taken, and average results are given in millimeters. The results provide a relative assessment of bar hardness (see col 4 in Table 1).
  • a rating of 0-25 is acceptable, and values of increasing and unacceptable specks are 50, 75 and 100 (see col 6 in Table 1).
  • Slough (low humidity, room temperature) The initial weights of the soap bars were recorded. The bars were placed in plastic soap dishes (120 mm x 75 mm x 16 mm) filled with tap water at room temperature. The soap remained in the water for 17 hours. The soft soap was then removed by hand, and the bars were dried at room temperature for 24 hours and weighed. The test results are given as the weight loss per 100 grams (see col 7 in Table 1). Slough Test (high humidity) - The weight of the bar was recorded in grams. The bars were washed twice at 30 minute intervals for 10 seconds at 100°F (38°C) before testing.
  • the bar was placed in a soap dish (120 mm x 75 mm x 16 mm). The dish was filled with tap water, and the bar remained in the water for 17 hours at 35-40°C at 100% relative humidity. At the end of 17 hours, the resulting soft material (slough) was removed using finger pressure. The bar was air-dried for 24 hours at 21-25°C, after which the bar weight was recorded. The weight loss was determined as the loss per 100 grams. (see col 8 in Table 1). Wear By Repeated Hand Wash - In this second method, the soap bars were repeatedly washed and then allowed to dry. The test was carried out over a 4-day period in order to simulate at-home usage. The initial weights of the bars were recorded.
  • the slough properties of bars containing TSPP were superior to the bars without TSPP (both in high and low humidity testing conditions).
  • the hardness of bars improved with the addition of TSPP and bars with TSPP were better in crack resistance.
  • TSPP forms a hydrate with water and absorbs water up to 60% of its weight.
  • the mapping of the water content of soap bars was studied by Differential Scanning Calorimeter (DSC).
  • the total water content was obtained by drying the samples in a vacuum oven at 180°F (82°C) for 24 hours, whereas the free water was calculated from the endothermic transition of melting of ice in the soap samples by DSC.
  • the difference between the total moisture and the free water is the total bound water in the soap bars. Soap water was then calculated from the total bound and TSPP water content in the soap (see Table 3).
  • the flat (cleaved) regions of the soap bars were elementally characterized both in a qualitative fashion and by elemental distribution (dot map or elemental) surveys by energy dispersive X-ray analysis (EDX).
  • EDX energy dispersive X-ray analysis
  • the following combar samples were prepared with tallow coco soap base with 0-25% synthetic surfactants selected from anionic surfactants (coco-monoglyceridesulfate, sodium cocoyl isethionate, alkylglycerylsulfonate) and analyzed by EDX: Sample #1 - TSPP (4%) added in the amalgamator Sample #2 - TSPP (0%) Sample #3 - TSPP (3%) added in the crutcher Sample #4 - TSPP (4%) added in the crutcher.
  • sample #2 phosphorus was not detected in significant amounts.
  • elemental dot mapping indicated that phosphorus was concentrated unevenly, whereas in sample #3 and sample #4, phosphorus appeared to be evenly distributed in small clusters.
  • Soap bars prepared with and without TSPP were analyzed for different phases by X-ray diffraction pattern. Soap bars without TSPP have predominantly omega phase with 9-14% beta phase. However, the beta phase in TSPP-containing soap bars could not be determined as the diffraction pattern of TSPP blocks the region where beta phase is generally observed. Therefore, it is not possible to quantify the beta phase in TSPP-containing soap bars.
  • detergent soap bars containing TSPP which, due to the manner in which it is incorporated into the bars, acts as a functional reagent and structurant rather than merely as a filler, enabling the production of bars having high water and low soap contents.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP94300155A 1993-01-11 1994-01-10 Composition de savon contenant du pyrophosphate sodique. Withdrawn EP0607004A3 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US315293A 1993-01-11 1993-01-11
US3152 1993-01-11
US5604993A 1993-04-30 1993-04-30
US56049 1993-04-30

Publications (2)

Publication Number Publication Date
EP0607004A2 true EP0607004A2 (fr) 1994-07-20
EP0607004A3 EP0607004A3 (fr) 1995-03-08

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ID=26671394

Family Applications (1)

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EP94300155A Withdrawn EP0607004A3 (fr) 1993-01-11 1994-01-10 Composition de savon contenant du pyrophosphate sodique.

Country Status (9)

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EP (1) EP0607004A3 (fr)
KR (1) KR940018461A (fr)
CN (1) CN1094088A (fr)
BR (1) BR9400061A (fr)
CZ (1) CZ6894A3 (fr)
HU (1) HUT67658A (fr)
MX (1) MXPA94000372A (fr)
RO (1) RO114345B1 (fr)
SK (1) SK3294A3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2738255A1 (fr) * 1995-09-05 1997-03-07 Talc De Luzenac Composition de nettoyage a base de savon presentant de faibles proprietes dessechantes, et procede de preparation
WO1998056891A1 (fr) * 1997-06-13 1998-12-17 Colgate-Palmolive Company Composition demaquillante solide contenant du savon

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2093927A (en) * 1935-05-08 1937-09-21 Procter & Gamble Soap builder of reduced alkalinity
US2277730A (en) * 1938-03-22 1942-03-31 Lever Brothers Ltd Soap
BE437050A (fr) * 1938-11-22
US2686761A (en) * 1950-06-02 1954-08-17 Procter & Gamble Detergent product having milled soap properties
BE515112A (fr) * 1951-10-25
GB8823656D0 (en) * 1988-10-07 1988-11-16 Unilever Plc Soap composition
GB8911006D0 (en) * 1989-05-12 1989-06-28 Unilever Plc Soap composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2738255A1 (fr) * 1995-09-05 1997-03-07 Talc De Luzenac Composition de nettoyage a base de savon presentant de faibles proprietes dessechantes, et procede de preparation
WO1997009413A1 (fr) * 1995-09-05 1997-03-13 Talc De Luzenac Composition de nettoyage a base de savon
WO1998056891A1 (fr) * 1997-06-13 1998-12-17 Colgate-Palmolive Company Composition demaquillante solide contenant du savon
US5888952A (en) * 1997-06-13 1999-03-30 Colgate-Palmolive Co. Solid cleansing composition comprising tetrasodium pyrophosphate

Also Published As

Publication number Publication date
BR9400061A (pt) 1994-08-16
RO114345B1 (ro) 1999-03-30
EP0607004A3 (fr) 1995-03-08
KR940018461A (ko) 1994-08-18
SK3294A3 (en) 1994-08-10
HU9400072D0 (en) 1994-05-30
HUT67658A (en) 1995-04-28
CZ6894A3 (en) 1995-02-15
MXPA94000372A (es) 2004-08-20
CN1094088A (zh) 1994-10-26

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