CN1225536C - Solid shaped detergent composition - Google Patents
Solid shaped detergent composition Download PDFInfo
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- CN1225536C CN1225536C CNB018204473A CN01820447A CN1225536C CN 1225536 C CN1225536 C CN 1225536C CN B018204473 A CNB018204473 A CN B018204473A CN 01820447 A CN01820447 A CN 01820447A CN 1225536 C CN1225536 C CN 1225536C
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0052—Cast detergent compositions
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
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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)
- Cosmetics (AREA)
Abstract
A melt-cast detergent composition which retains rigidity at least up to 40 DEG C comprising: (a) 2-50 (Xa) % by wt. saturated fatty acid soap comprising one or more salts of C6-C24 fatty acids; (b) 2-40 % by wt. of detergent active species; (c) 0.5-20 % by wt. of a salting-in electrolyte; and (d) 30-80 % by wt. water; wherein the fatty acid soap present forms an Xa % solution in water with a liquid phase having a viscosity less than 50 Pa.s at a shear rate of 1 sec<-1> in the temperature range 50-100 DEG C, shows phase separation and presence of a solid phase during cooling up to 20 DEG C and the solid phase is present at least up to 40 DEG C during heating.
Description
The present invention relates to provide the lipid acid and the combination thereof of the adequate types that forms soap, in order to obtain the solid shaped detergent composition of melt casting, said composition comprises very high-load water or the agent of liquid benefit skin.
Detergent bar and bar adopt the manufacturing of one of following two kinds of methods usually: (i) shearing processing/homogenizing of title complex, and extrude then and suppress, or (ii) cast.
When processing and extruding the manufacturing detergent bar by shearing, the water-content that can add in the title complex is usually less than～15%.These systems are multiphase mixtures, and this mixture shows the pattern type of " brick is suspended in the mortar ".Brick is a solid particulate, and for perfumed soap, these particles are crystalline salt, mineral filler of chain saturated fatty acids etc.Mortar is the mixture of various lyotropic liquid crystals or isotropic solution phase, comprises water, fluid additive and more water miscible soap or tensio-active agent.These compositions comprise the solid of 50-60% usually, and the 20-30% lyotropic liquid crystal mutually and about 10% isotropic liquid.
When utilizing cast to make detergent composition, the system of preparation becomes fluid state and injects mould by intensification, then cooling.This technology generally is used to make transparent personal cleansing piece, except that comprising other component (as soap and synthetic surfactant), also contains high price component such as the ethanol of 15-50% when cast, polyvalent alcohol, carbohydrate etc. in this detergent block.
United States Patent (USP) 4,165,293 (Amway, 1979) and WO 96/04361 (P﹠amp; G, 1996) a kind of solid transparent soap bar is disclosed, it comprises soap, synthetic surfactant and water miscible organic solvent such as propylene glycol.The content of water is generally about 10-32% in these compositions.
Opaque detergent bar is being that common composition does not form dumpable liquid during at elevated temperature with the problem in the casting production process.United States Patent (USP) 5,340,492 (P﹠amp; G, 1994) claimed a kind of elements for castable compositions with three-dimensional framework structure, it comprises relatively harder, interlock netted in crystal lipid acid (soap), synthetic surfactant and high-load water and other liquid.
United States Patent (USP) 5,340,492 claimed compositions are very soft, demonstrate the yielding stress less than 75kPa when measuring with cheese line cutting device (cheese wire cutter), therefore can not be held in the hand use easily as enough inflexible fritters are arranged.In order to improve the rigidity of bar, the embodiment in this patent has used polyol component (for example propylene glycol) with the name of so-called " bar shaped auxiliary agent " in composition.When synthetic surfactant also was present in the composition, this patent was not announced any composition that does not contain " bar shaped auxiliary agent ".These " bar shaped auxiliary agent " costlinesses, and reduce foam volume and expansion rate.
In our common pending application (717/Bom/99) open molten ionogen joins in the melt casting detergent composition that comprises fatty acid soaps, washing composition activator, very high-load water or the agent of liquid benefit skin with small amounts of salts, obtain hard solid molding goods, these goods demonstrate the yielding stress greater than 75kPa when measuring with cheese line cutting device.These compositions can be held in the hand, economy, and the foam number height also demonstrates good use character.Fatty acid soaps in the above-mentioned application is one or more neutral C
6-C
14Lipid acid.
Selected formation soap add in the detergent bar in and all of lipid acid be combined in the casting process from the high temperature cooling to 20-35 ℃ envrionment temperature the time will can not obtain solid-state product.Gu this must optimize the combination of fatty acid soaps so that obtain that enough inflexible detergent bars are arranged at ambient temperature, and it can be held in use easily.It also is very necessary keeping rigidity under the temperature that is higher than physical environment that detergent bar is often run in storing and transporting.
Therefore the object of the present invention is to provide required lipid acid combination, in order to forming the soap in the melt casting detergent bar composition, said composition comprises very high-content water or the agent of liquid benefit skin makes detergent composition form lump when temperature is higher than 20 ℃ and maintenance rigidity at least up to 40 ℃ the time.
Therefore, the present invention relates to a kind of melt casting solid shaped detergent composition, it forms hard goods and keep rigidity at least up to 40 ℃ the time when temperature is higher than 20 ℃, and it comprises:
A) the saturated fatty acid soap of 2-50 weight %, it comprises one or more C
6-C
14Soap,
B) detergent active material of 2-40 weight %,
C) the molten ionogen of a kind of salt of 0.5-20 weight % and
D) water of 30-80 weight % and other optional liquid benefit skin agent,
Wherein saturated soap comprises one or more C
6-C
24Soap, it is characterized in that liquid phase that its 2-50 weight % aqueous solution forms is 1/sec and temperature viscosity＜50Pa.s when being 50-100 ℃ in shearing rate, present in being cooled to the highest 20 ℃ process and be separated and have solid phase, this solid phase still exists at least up to 40 ℃ the time in the heat-processed.When cooling and heating detection solid phase, preferred speed is 0.1 ℃/minute to 10 ℃/minute, more preferably 1 ℃/minute.The low-field nuclear magnetic resonance technology for detection is preferably adopted in the existence of solid phase, and solid phase described in the detection shows relaxation time constant T
2Gauss's decay of＜15 μ sec.In the process that adopts low-field nuclear magnetic resonance technology for detection solid phase, preferably made the sample balance 30 minutes in detected temperatures.
Preferably the washing composition promoting agent mainly is an on-soap.
Another aspect of the present invention provides the method for making solid shaped detergent composition, and it may further comprise the steps:
A. select to comprise one or more C
6-C
24The fatty acid soaps of soap, making liquid phase that the aqueous solution of soap forms is 1/sec and temperature viscosity＜50Pa.s when being 50-100 ℃ in shearing rate, present in being cooled to the highest 20 ℃ process and be separated and solid phase occurs, this solid phase still exists at least up to 40 ℃ the time in the heat-processed;
B. the detergent active material of above-mentioned fatty acid soaps and 2-40%, the water of molten ionogen of the salt of 0.5-20% and 30-80% and other optional liquid benefit skin agent mix;
C. the composition of fusion step (b);
D. pour melts into mould and obtain desirable shape; And
E. cooling die causes solidification under the immobilized condition.
According to the preferred aspect of invention, the invention provides a kind of method of making cast solid shaped detergent composition in the packing, it may further comprise the steps:
A. select to comprise one or more C
6-C
24The fatty acid soaps of soap, making liquid phase that its aqueous solution forms is 1/sec and temperature viscosity＜50Pa.s when being 50-100 ℃ in shearing rate, present in being cooled to the highest 20 ℃ process and be separated and have solid phase, this solid phase still exists at least up to 40 ℃ the time in the heat-processed;
B. the detergent active material of above-mentioned fatty acid soaps and 2-40%, the water of molten ionogen of the salt of 0.5-20% and 30-80% and other optional liquid benefit skin agent mix;
C. the composition of fusion step (b), and pour melts into preformed polymeric molds, to obtain desirable shape;
D. sealed mold; And
E. cooling die causes solidification under the immobilized condition.
The present invention relates to the melt casting solid shaped detergent composition, it consists essentially of selects to contain one or more C
6-C
24The fatty acid soaps of soap, making liquid phase that the aqueous solution of soap forms is 1/sec and temperature viscosity＜50Pa.s when being 50-100 ℃ in shearing rate, presenting in being cooled to the highest 20 ℃ process is separated opens and has solid phase, and this solid phase still exists at least up to 40 ℃ the time in the heat-processed.When cooling that detects solid phase and heating, preferred speed is 0.1 ℃/minute to 10 ℃/minute, more preferably 1 ℃/minute.The low-field nuclear magnetic resonance technology for detection is preferably used in the existence of solid phase, and solid phase described in the detection shows relaxation time constant T
2Gauss's decay of＜15 μ sec.In the process that adopts low-field nuclear magnetic resonance technology for detection solid phase, preferably made the sample balance 30 minutes in detected temperatures.
The solid molding goods of the present composition are enough hard can be held in the hand easily, economy, and the foam number height also demonstrates good use character.When measuring with automatic penetrometer, composition exhibiting goes out the yielding stress greater than 75kPa.
Fatty acid soaps
The saturated fatty acid soap is preferably selected from one or more C
6-C
24The saturated fatty hydrochlorate.Used soap can be sodium, potassium, magnesium, aluminium, calcium or the lithium salts of saturated fatty acid.The preferred especially soap that obtains with the sodium or the potassium salt form of saturated fatty acid.
Saturated fatty acid soaps is preferably 5-50 weight %, more preferably 5-40 weight % in the composition.
The viscosity of 50-100 ℃ of following soap-aqueous systems is measured during for 1/sec in shearing rate with Carri-Med rheometer (model C SL500, TA instrument company).Viscosity measurement is carried out under the stable-state flow pattern, uses geometrical dimension to be diameter 2cm, the cone-plate and the solvent trap of angle 1 degree 58 minutes and 55 microns truncations.
The cooling of pyritous soap-aqueous systems melts the highest 20 ℃ to determine to occur to be separated and to form the temperature of solid phase.Heating systems is to guarantee that this solid phase still exists in the heat-processed at least up to 40 ℃ the time then.The existence of solid phase detects with the low-field nuclear magnetic resonance instrument that has the alternating temperature annex, and this solid phase described in the detection shows relaxation time constant T
2Gauss's decay of＜15 μ sec, detect the method for describing in the following reference that adopts: Suresh M.Nadakatti, " be used for the correction data processing that the quick low-field nuclear magnetic resonance of lyotropic liquid crystal mixture characterizes ", J.Surfactants and Detergents, 2 volumes, 4 phases, 515-521 page or leaf, 1999.
The washing composition promoting agent
Composition of the present invention comprises the washing composition activator, and they can be soap base or non-soap base.The preferred on-soap washing composition promoting agent that adopts, these promoting agents are selected from negatively charged ion, nonionic, positively charged ion, amphoteric or zwitterionic tensio-active agent or its mixture.
Suitable anionic detergent compound active agent is the water-soluble salt of organosulfur acidification reaction product, and it has the alkyl that contains 8 to 22 carbon atoms and is selected from sulfonic acid or the group of sulfate group and composition thereof on molecular structure.Some examples of synthetic anionic detergent compound active agent are linear alkylbenzene sulfonate, sodium lauryl sulphate, sodium lauryl tri(oxyethyl) sulfate, sulfonated, sulfated alkyl ether, fatty methyl ester sulfonate, the different thiosulphate of alkyl etc.
Only positively charged ion is sodium, potassium, ammonium and various amine for example monoethanolamine, diethanolamine and trolamine in above-mentioned detergent active material.
Suitable nonionic detergent active compound can be described as the compound by organic hydrophobic compound condensation generation of hydrophilic oxyalkylene group and aliphatics or alkyl aromatic widely.Common nonionogenic tenside is the condensation product of Fatty Alcohol(C12-C14 and C12-C18) and oxyethane, and these Fatty Alcohol(C12-C14 and C12-C18) contain 8 to 22 carbon atoms in the straight or branched structure, Oleum Cocois ethylene oxide condensate for example, and every mole of coconut alcohol contains 2 to 15 moles of ethylene oxide.Some examples of nonionogenic tenside are alkylphenol oxyethane (EO) condenses, tallow alcohol 10 ethylene oxide condensates, alkyl demethylation amine oxide, dodecyl single ethanol amide, glycolipid etc.
Some examples of ampholytic detergent promoting agent are coconut palm amido propyl betaine, coconut palm trimethyl-glycine etc.
According to the present invention, also can choose wantonly and in the present composition, comprise positively charged ion or zwitterionic detergent promoting agent.
Other example of suitable detergent active material provides in following well-known textbook: (i) " tensio-active agent ", volume I, author Schwartz and Perry, (ii) " tensio-active agent and washing composition ", volume II, author Schwartz, Perry and Berch, (iii) " tensio-active agent handbook ", M.R.Porter, Chapman and Hall, New York, 1991.
The washing composition promoting agent that is used in the detergent composition of the present invention is preferably anion active agent, and its consumption usually can be up to 50%, and more preferably 2 to 30%.
The molten ionogen of salt
Be used in the molten ionogen of salt in the composition and be selected from listed those in ' Hofmeister ' or ' Lyotrapic ' series.The molten ionogen of salt is the ionogen of the lyotropic number of those electrolytic anions＞10 normally.More anionic examples of lyotropic number＞10 are NO
2 -, ClO
3 -, Br
-, NO
3 -, ClO
4 -, I
-, CNS
-, C
6H
5SO
3 -, C
6H
4CH
3SO
3 -And Cr
2O
7 2-Being used for according to the molten electrolytical preferred embodiment of the salt of composition of the present invention is above-mentioned anionic an alkali metal salt.Being used for according to the molten electrolytical most preferably example of the salt of composition of the present invention is toluenesulfonic acid sodium salt, isopropyl benzene sodium sulfonate and sodium xylene sulfonate.
The molten electrolytical more examples of salt can be selected from those that describe in the following document: (i) Collins, K.D.; Washabaugh, M.W.Quart.Rev.Biophys., 1985,18,323; (ii) Schuster.P, Zundel.G and Sandorfy.C, 1976, ' hydrogen bond ', the latest developments of theoretical and experiment, volume III, northern Dutch publishing company, Amsterdam, New York, Oxford.
The agent of liquid benefit skin
According to the preferred aspect of invention, in composition, add liquid benefit skin material such as moistening agent, softener, sun-screening agent, anti-senescence compounds.Moistening agent, examples of humectants comprise polyvalent alcohol, glycerol, hexadecyl alcohol, Carbopol 934, ethoxylated castor oil, paraffin oil, lanolin and derivative thereof.Can also add silicone compounds, for example silicone surfactant such as DC3225C (Dow Corning) and/or silicone emollients, silicone oil (DC-20O Ex-DowCorning).Sun-screening agent comprises the 4-tertiary butyl-4 '-methoxy dibenzoyl methane (useful commercial name PARSOL 1789 obtain from Givaudan company) and/or 2-ethylhexyl Methoxycinnamate (useful commercial name PARSOL MCX obtains from Givaudan company) or other UV-A and UV-B sun-screening agent.
Optional ingredients
Can add other optional ingredients in the composition as wet agent, filler, pigment, spices, opalizer, sanitas, one or more non-water-soluble particulates such as talcum powder, kaolin, polysaccharide and other the conventional batching sent out.
Method
Manufacture method according to solid shaped detergent composition of the present invention may further comprise the steps:
A. select to comprise one or more C
6-C
24The fatty acid soaps of soap, making liquid phase that the aqueous solution of soap forms is 1/sec and temperature viscosity＜50Pa.s when being 50-100 ℃ in shearing rate, present when being cooled to the highest 20 ℃ and be separated and have solid phase, this solid phase still exists at least up to 40 ℃ the time in the heat-processed;
B. the detergent active material of above-mentioned fatty acid soaps and 2-40%, the molten ionogen of a kind of salt of 0.5-20% and the water of 30-80% and the agent of other optional liquid benefit skin mix;
C. the composition of fusion step (b);
D. pour melts into mould and obtain desirable shape; And
E. cooling die causes solidification under the immobilized condition.
Can select suitable mould to produce the fritter or the production bar/piece of nearly clean shape (near net shape).Bar/piece can further be configured as detergent body.
If adopt the solid-state detergent body of thermoforming polymer production of nearly clean shape, preferred sealed mold is to obtain packing the detergent composition of interior cast.In order to obtain packing the detergent composition of interior cast, preferably sealing immediately after being full of of mould.
Now the present invention is described according to following indefiniteness embodiment.
Embodiment
Embodiment 1
Screening is used for the fatty acid soaps mixture of preparing washing agent composition.
The mixture of several soaps and water is put into the round-bottomed flask of two liters of capacity, and wherein soap derives from lauric acid (C
12), tetradecanoic acid (C
14), palmitinic acid (C
16) and stearic acid (C
18) fatty acid mixt.The ratio variation of fatty acid soaps is listed in the table 1.
Make the charge temperature be elevated to and remain on 80 ℃ to obtain pourable liquid, the viscosity of this liquid when shearing rate is 1/sec is about 10Pa.s.
Low-field nuclear magnetic resonance
The low-field nuclear magnetic resonance technology is used for detecting the existence of solid phase in soap-aqueous systems.Solid phase shows relaxation time constant T
2Gauss's decay of＜15 μ sec.
The low-field nuclear magnetic resonance instrument that is used to study obtains (model MARAN 25) from Britain M/s ResonanceInstruments.This instrument has following feature: (i) projector of a 600W can produce～90 ° of pulses of 2 μ s, and (ii) the quanxtizer of a 5MHz allows every microsecond to collect 2 data points.The existence of solid phase adopts the process of describing in the following reference to detect in soap-aqueous systems: Suresh M.Nadakatti, " be used for the correction data processing that the quick low-field nuclear magnetic resonance of lyotropic liquid crystal mixture characterizes ", J.Surfactants and Detergents, 2 volumes, 4 phases, the 515-521 page or leaf, 1999.
Pack into the nmr tube of a 10mm diameter of fused soap-aqueous systems.Nmr tube is put into the sample chamber of low-field nuclear magnetic resonance instrument.Alternating temperature annex with instrument is elevated to 80 ℃ with temperature.Then system be cooled to 5 ℃ of intervals the highest 20 ℃, and under each temperature balance 30 minutes.Write down the temperature of be separated appearance and solid phase formation.Heating systems still exists at least up to 40 ℃ the time to guarantee solid phase described in the heat-processed then.
Table 1
| Composition (weight %) | Embodiment 1a | Embodiment 2a | Embodiment 3a | Embodiment 4a | Embodiment 5a | Embodiment 6a | Embodiment 7a | Embodiment 8a |
| Sodium stearate (c 18) sodium laurate (c 12) Sodium pentadecanecarboxylate (c 16) Sodium tetradecanoate (c 14) water | 16 4 - - 80 | 18 2 - - 80 | 28 2 - - 70 | 4 16 - - 80 | 2 18 - - 80 | 2.7 12 3.3 - 82 | 6.3 4 7.7 - 82 | - 5 - 25 70 |
| Whether 80 ℃ pourable? | Be | Be | Not | Be | Be | Be | Be | Be |
| The temperature of formation solid phase in the process of cooling (℃) | 55 | 60 | 60 | 0 | 5 | 20 | 50 | 50 |
| The top temperature that solid phase exists in the heat-processed (℃) | 60 | 60 | 60 | 30 | 35 | 35 | 55 | 60 |
The data that provide in the table 1 show to have only according to embodiments of the invention 1a, 2a, 7a, 8a to have pourability, and the top temperature that has provided its temperature that solid phase forms in process of cooling and existed in the heat-processed solid phase.
Embodiment 2
The method of preparing washing agent bar
Based on the screening method of describing among the embodiment 1, to join in the round-bottomed flask of two liters of capacity to the fatty acid mixt among the 8a corresponding to embodiment 1a, by following table 2 and on-soap washing composition promoting agent such as sulfonated (AOS) or sodium lauryl tri(oxyethyl) sulfate (SLES), molten ionogen of salt such as Sodium Toluene Sulphonate (STS) and water mix.Raise the temperature to 80 ℃.Aqueous sodium hydroxide solution join in the mixture with in and lipid acid.The charge temperature maintenance at 80 ℃ so that obtain limpid solution.The melts of detergent composition under 80 ℃ poured into the thermoformed polymeric mould and with the inlet seal of mould.Allow mold cools down to cause the curing of soap class, so the detergent bar of cast in obtaining packing.
Use following process to measure the rigidity of the bar of being processed by yielding stress.
Yielding stress is measured
Detergent bar is placed respectively in the baking oven of 25 ℃ of temperature and 40 ℃ and keep making it to reach in 4 hours balance.The yielding stress of detergent bar uses automatic penetrometer to measure with following method when 25 ℃ and 40 ℃.
The automatic penetrometer that is used for the yielding stress measurement is PNR 10 types of M/s Petrotest InstrumentsGmbH.Use standard hollow circular cone (part#18-0101 is according to ASTMD 217-IP 50) and plunger (part#18-0042) to measure.Circular cone is made up of the brass cone that has dismountable hardened steel point.The total mass of circular cone is 102.5g.The total mass of removable plunger is 47.5g.Therefore, dropping on the circular cone on the detergent bar and the total mass of plunger is 150g.Additional 50g and 100g weight (making the gross weight that drops on the sample be respectively 200g and 250g) have also been used.
Yield value of stress at 25 ℃ and 40 ℃ following samples adopts standard method to measure, and this method comprises the following steps:
1. detergent bar is placed on the worktable of penetrometer.
2. the measuring apparatus of reduction penetrometer makes penetrometer point contact detergent bar but does not thrust.
3. begin to measure operation by pressing " beginning " key.
4. penetration depth is that unit is read from indicating meter with mm.
5. the penetration value of measuring is used for calculating the yielding stress of detergent tablet, and the formula of employing is as follows:
Power/(shadow area of circular cone) of yielding stress=apply
=(m * g) * 10
3/ [π (tan θ+ tip diameter)
2]
Wherein
The unit of yielding stress is kPa
M: dropping on the total mass on the detergent bar plane surface, is unit with kg
G: universal gravity constant, with m/s
2Be unit
P: the penetration depth that obtains is a unit with mm
θ: cone angle (30 °)
Tip diameter=0.359mm
According to above-mentioned formula, if total mass 200g drops on the penetration depth＜10mm that records on the sample, the yielding stress＞75kPa of detergent tablet then.Calculate three yields value of stress for total mass 150g, the 200g and the 250g that drop on the detergent tablet, and the mean value of three values is used as the yielding stress of detergent tablet.
Table 2
| Composition (weight %) | Embodiment 1b | Implement 2b | Embodiment 3b | Embodiment 4b | Embodiment 5b | Embodiment 6b | Embodiment 7b | Embodiment 8b |
| Odium stearate (c18) sodium laurate (c12) sodium palmitate (C16) Sodium myristate (C14) SLES AOS coco betaine STS water | 16 4 - - 5 - - 2 73 | 18 2 - - 5 - - 2 73 | 28 2 - - 8 - - 3 59 | 4 16 - - 5 - - 2 73 | 2 18 - - 5 - - 2 73 | 2.7 12 3.3 - - 8 - 3 71 | 6.3 4 7.7 - - 8 - 3 71 | - 5 - 25 - - 8 2 60 |
| 25 ℃ of yielding stress (kPa) θ | 252 | 363 | ＜75 | Liquid | Liquid | Liquid | 132 | 481 |
| 40 ℃ of yielding stress (kPa) θ | 186 | 158 | ＜75 | Liquid | Liquid | Liquid | 80 | 343 |
The data that provide in the table 2 show when having only soap-aqueous systems according to the present invention could produce the solidified detergent bar, and obtains hard product when being cooled to more than 20 ℃ in casting process, and this product keeps rigidity at least up to 40 ℃ the time.Detergent bar (embodiment 1b, embodiment 2b, embodiment 7b, embodiment 8b) yielding stress digital proof this point, as (embodiment 1a, embodiment 2a according to the present invention, embodiment 7a, embodiment 8a) during screening soap-aqueous systems, yield value of stress＞75kPa that detergent bar shows.If soap-aqueous systems does not satisfy the screening requirement, will not form runner with the Betengent product of these soap class manufacturings.
Claims (9)
1. one kind keeps inflexible melt casting detergent composition at least up to 40 ℃ the time, and said composition comprises:
(a) the saturated fatty acid soap of 2-50 weight %, it comprises one or more C
6-C
24Soap;
(b) detergent active material of 2-40 weight %;
(c) the molten ionogen of the salt of 0.5-20 weight %; With
(d) water of 30-80 weight %;
Wherein the fatty acid soaps that exists forms the aqueous solution of 2-50 weight %, liquid phase is 1/sec and temperature viscosity＜50Pa.s when being 50-100 ℃ in shearing rate, and present in being cooled to the highest 20 ℃ process and be separated and have solid phase, this solid phase still exists at least up to 40 ℃ the time in the heat-processed.
2. wash the notes detergent composition according to the fusion of claim 1, wherein, detergent active material is the non-soap detergent actives that is selected from ion, nonionic, positively charged ion, amphoteric or zwitterionic tensio-active agent and composition thereof.
3. according to the melt casting detergent composition of claim 1 or claim 2, wherein, fatty acid soaps is C
6-C
24The sodium of saturated fatty acid, potassium, magnesium, aluminium, calcium or lithium salts.
4. according to the melt casting detergent composition of claim 3, wherein, the molten electrolytical anionic lyotropic number of salt＞10.
5. according to the melt casting detergent composition of claim 4, wherein, the molten ionogen of salt is to be selected from NO
2 -, ClO
3 -, Br
-, NO
3 -, ClO
4 -, I
-, CNS
-, C
6H
5SO
3 -, C
6H
4CH
3SO
3 -And Cr
2O
7 2-Anionic an alkali metal salt.
6. according to the melt casting detergent composition of claim 5, wherein, said composition also comprises the agent of liquid benefit skin.
7. according to the melt casting detergent composition of claim 6, wherein, the agent of liquid benefit skin is selected from moistening agent, softener, sun-screening agent, anti-senescence compounds.
8. method of making the melt casting solid shaped detergent composition, it may further comprise the steps:
(a) select to comprise one or more C
6-C
24The fatty acid soaps of soap, making liquid phase that the aqueous solution of soap forms is 1/sec and temperature viscosity＜50Pa.s when being 50-100 ℃ in shearing rate, present when being cooled to the highest 20 ℃ and be separated and have solid phase, this solid phase still exists at least up to 40 ℃ the time in the heat-processed;
(b) the detergent active material of above-mentioned fatty acid soaps and 2-40%, the molten ionogen of a kind of salt of 0.5-20% and the water of 30-80% mix;
(c) composition of fusion step (b);
(d) pour melts into mould and obtain desirable shape; And
(e) cooling die causes solidification under the immobilized condition.
9. the method in according to Claim 8, wherein, step (b) also comprises and adds the agent of liquid benefit skin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN926/MUM/00 | 2000-10-13 | ||
| IN926MU2000 | 2000-10-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1479785A CN1479785A (en) | 2004-03-03 |
| CN1225536C true CN1225536C (en) | 2005-11-02 |
Family
ID=11097297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018204473A Expired - Fee Related CN1225536C (en) | 2000-10-13 | 2001-10-09 | Solid shaped detergent composition |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1325104B1 (en) |
| JP (1) | JP2004511626A (en) |
| CN (1) | CN1225536C (en) |
| AR (1) | AR030881A1 (en) |
| AT (1) | ATE348143T1 (en) |
| AU (2) | AU9189201A (en) |
| BR (1) | BR0114810A (en) |
| CA (1) | CA2425294A1 (en) |
| DE (1) | DE60125206T2 (en) |
| MX (1) | MXPA03003257A (en) |
| WO (1) | WO2002031099A1 (en) |
| ZA (1) | ZA200302694B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1650290A3 (en) * | 2004-10-13 | 2006-05-17 | Unilever N.V. | Process for preparing a cleaning tablet |
| CN103013722B (en) * | 2012-12-12 | 2015-01-21 | 合肥豪豪日化有限公司 | High water content compound laundry bar soap and preparation method thereof |
| JP2019089927A (en) * | 2017-11-14 | 2019-06-13 | 花王株式会社 | Viscometric properties improver |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8928902D0 (en) * | 1989-12-21 | 1990-02-28 | Unilever Plc | Detergent bar |
| US5340492A (en) * | 1990-11-26 | 1994-08-23 | The Procter & Gamble Company | Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid |
| WO1998011864A2 (en) * | 1996-09-23 | 1998-03-26 | The Procter & Gamble Company | Lathering and cleansing personal cleansing bar compositions which contain elongated lipid particles |
| US5916856A (en) * | 1996-10-16 | 1999-06-29 | Lever Brothers Company | Pourable cast melt bar compositions comprising low levels of water and minimum ratios of polyol to water |
| US5929011A (en) * | 1996-10-30 | 1999-07-27 | Sunburst Chemicals, Inc. | Solid cast chlorinated cleaning composition |
| GB0003925D0 (en) * | 1999-10-25 | 2000-04-12 | Unilever Plc | Cast detergent composition |
-
2001
- 2001-10-09 JP JP2002534470A patent/JP2004511626A/en active Pending
- 2001-10-09 EP EP01972097A patent/EP1325104B1/en not_active Expired - Lifetime
- 2001-10-09 CA CA002425294A patent/CA2425294A1/en not_active Abandoned
- 2001-10-09 AT AT01972097T patent/ATE348143T1/en not_active IP Right Cessation
- 2001-10-09 DE DE60125206T patent/DE60125206T2/en not_active Expired - Fee Related
- 2001-10-09 CN CNB018204473A patent/CN1225536C/en not_active Expired - Fee Related
- 2001-10-09 MX MXPA03003257A patent/MXPA03003257A/en active IP Right Grant
- 2001-10-09 WO PCT/EP2001/011621 patent/WO2002031099A1/en active IP Right Grant
- 2001-10-09 AU AU9189201A patent/AU9189201A/en active Pending
- 2001-10-09 AU AU2001291892A patent/AU2001291892B2/en not_active Ceased
- 2001-10-09 BR BR0114810-9A patent/BR0114810A/en not_active IP Right Cessation
- 2001-10-12 AR ARP010104791A patent/AR030881A1/en active IP Right Grant
-
2003
- 2003-04-07 ZA ZA200302694A patent/ZA200302694B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA200302694B (en) | 2004-04-07 |
| CN1479785A (en) | 2004-03-03 |
| AU2001291892B2 (en) | 2006-03-16 |
| DE60125206T2 (en) | 2007-04-12 |
| AR030881A1 (en) | 2003-09-03 |
| CA2425294A1 (en) | 2002-04-18 |
| EP1325104B1 (en) | 2006-12-13 |
| JP2004511626A (en) | 2004-04-15 |
| AU9189201A (en) | 2002-04-22 |
| WO2002031099A1 (en) | 2002-04-18 |
| EP1325104A1 (en) | 2003-07-09 |
| DE60125206D1 (en) | 2007-01-25 |
| MXPA03003257A (en) | 2003-06-06 |
| BR0114810A (en) | 2003-09-30 |
| ATE348143T1 (en) | 2007-01-15 |
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