CN1094088A - The soap composition that contains trisodium phosphate - Google Patents
The soap composition that contains trisodium phosphate Download PDFInfo
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- CN1094088A CN1094088A CN94101070A CN94101070A CN1094088A CN 1094088 A CN1094088 A CN 1094088A CN 94101070 A CN94101070 A CN 94101070A CN 94101070 A CN94101070 A CN 94101070A CN 1094088 A CN1094088 A CN 1094088A
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- soap
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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
- C11D9/02—Compositions of detergents based essentially on soap on alkali or ammonium soaps
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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
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Bar shaped washing soap composition, it comprises: (1) saturated or unsaturated fatty acids alkali metal soap or ammonium soaps or their mixture, (2) account for the moisture of gross weight about 6-14%, the structure activator that is selected from tetrasodium pyrophosphate, tetrasodium pyrophosphate hydrate (TSPP) and composition thereof of (3) about 0.5-about 15% (weight).This structure activator can improve mashed performance of the structural integrity, hardness, paste of soap bar and abrasion performance and resistance to cracking.The method for preparing this washing soap composition is also disclosed, it comprises: in stirrer, in the temperature that is higher than 80 ℃ soap, water and TSPP are mixed, remove unnecessary water under about 80 ℃ temperature and reach time enough being higher than then, make this mixture total water content reduce to 6-14% (weight), cool off then and be shaped to strip.
Description
Structural integrity, hardness, the anti-soap bar composition of sticking with paste mashed property, wear resistant and anti-cracking performance have been the present invention relates to improve.
The solubleness of soap in water generally is very high, and is particularly all the more so when they contain more unsaturated fatty acid salt (as oleate and linoleate).The soap that is made by senior Oleum Cocois has wear hardness preferably, but the mashed property of their anti-paste is relatively poor.This class soap produces good soap foam, and anti-cracking; Yet the mashed performance of wear rate and paste is the important attribute of soap bar.In soap bar, generally all used structure activator or filler to improve its performance.Provide structural integrity with them, and the physicals of improving the soap bar that adds these fillers.For example, in soap bar, add ionogen (sodium oxide) and various polymkeric substance, improve its abrasion resistance by the liquid phase in the soap bar of saltouing.Yet the foam of the soap that obtains like this is relatively poor and tearing tendency increases.
Tetrasodium pyrophosphate (TSPP) originally just was used as filler in the prescription of soap bar.Its solubleness (at room temperature being 7-8%) in water is low, transition temperature (80 ℃) and water-absorbent (be himself weight 60%) height.TSPP forms long needle-like and sexangle sheet thing when recrystallization.
For example, United States Patent (USP) 2,686,761 is open, adds TSPP in the water content bar composition of higher (promptly being higher than 20% weight).Yet, when TSPP mixes with the soap of high-moisture in stirrer, its mixture must be subjected to that play splits kneads, shearing and compacting, saltouts with the soap and the water that cause molten state, thereby obtains having porphyrize soap performance and be wax shape, translucent and mainly be in the soap bar of β phase.
Yet the soap bar that obtains like this has higher total water-content, and its cost is to have reduced soap content.In addition, having too much moisture to exist in the soap bar causes tearing tendency to increase.Those skilled in the art will recognize, at United States Patent (USP) 2,686, in the disclosed soap bar, the effect of TSPP is an inert filler in 761, and it makes and provide a kind of moisture morely, contains less and the composition that structure properties is poor of soap.
United States Patent (USP) 4,308,158 relate to a kind of synthetic surfactant composition that contains ortho-phosphoric acid an alkali metal salt, alkali metal pyrophosphate salts and tripolyphosphate alkali metal salt mixture component.
United States Patent (USP) 3,639,286 is open, adds three metaphosphoric acid an alkali metal salts and absorb wherein contained water in synthesis of detergent bar or cake, makes the only suitable content of tri-polyphosphate crystal water of final water-content.
United States Patent (USP) 3,494,869 disclose a kind of superfatted soap bar that contains the souring agent of being made up of phosphorous acid or its strong acid salt.It is to react with the soap of forming that this souring agent exists, and forms free fatty acid on the spot.
United States Patent (USP) 2,868,731 is open, contains TSPP as a kind of filler in non-soap detergent bar.
United States Patent (USP) 2,970,116 and 3,274,119 have related to and a kind ofly have high water content and contain the ionogen that the comprises tripoly phosphate sodium STPP transparent soap bar with the water outlet of saltouing.
United States Patent (USP) 3,370,015 discloses high dense, the instant washing sheet that contains hydratable condensed phosphate (as TSPP).
United States Patent (USP) 4,297,230 have narrated the noncrystalline transparent soap bar of a kind of 4-20% of containing potash soap and ionogen (can comprise tetrasodium pyrophosphate).
United States Patent (USP) 3,344,076 relate to contain 20%(weight at least) the washing sheet or the detergent block of phosphate component (tetrapotassium pyrophosphate or pentasodium triphosphate or five potassium).These washing sheets design to such an extent that have in the higher washing machine and disperse and dissolution rate.
United States Patent (USP) 3,798,181 disclose a kind of tetrapotassium pyrophosphate that contains as the structure activator, the enzyme-containing detergent bar that is used to do washing.
The purpose of this invention is to provide a kind of soap detergent bar that has low water content and improved performances such as structural integrity, hardness, the mashed property of anti-paste, wear resistant, cracking resistance.
Above-mentioned target and other target have been realized by the present invention, one embodiment of the invention are a kind of bar shaped laundry soap compositions, it comprises the alkali metal soap or the ammonium soaps of (1) saturated or unsaturated fatty acids, or their mixture, (2) total water content is lower than 14%(weight), and the about 15%(weight of (3) about 0.5-) the structure activator that is selected from tetrasodium pyrophosphate, tetrasodium pyrophosphate hydrate or their mixtures; This structure activator can improve structural integrity, hardness, the anti-mashed property and abrasion performance and resistance to cracking of sticking with paste.
Another embodiment of the invention is the method for the above-mentioned laundry soap based composition of preparation, this method is included in temperature and is higher than under about 80 ℃, alkali metal soap or ammonium soaps or their mixture, water and at least a portion tetrasodium pyrophosphate of or unsaturated fatty acids saturated in stirrer for mixing, keep this soap temperature then and be higher than 80 ℃ and carry out vacuum-drying, making final water-content is 6-14%.
Fig. 1 and Fig. 2 have compared the present invention with graphic interpretation and have contained the soap bar of TSPP and the control group soap bar percentage of water loss and the time relation that do not contain TSPP.
Fig. 3 illustrates the distribution plan of contained humidity in containing the TSPP soap bar.
The present invention is based on following discovery, namely tetrasodium pyrophosphate (TSPP) has improved structural intergrity and the physical property of the soap detergent bar of water content 6-14% uniquely. In addition, TSPP has also improved the processing characteristics that adds it and be configured as the soap based composition of detergent bar or washing cake.
Indicated as the prior art of discussing in front, in soap class detergent bar, once added TSPP. But its use is limited in the special fatty acid composition soap class of high-moisture, and its function is as filler. Such as, above-mentioned United States Patent (USP) 2,686,761 has been narrated a kind of method, by adding TSPP under certain processing conditions in the soap based composition, can consume the soap of less component and produces the soap bar that contains high water content. In addition, the soap bar that obtains mainly is to be in the β phase. As everyone knows, for the soap bar of water content higher (20-40%), along with the mutually percentile increase of β, abrasion speed also increases. In addition, at United States Patent (USP) 2,686, the aliphatic acid soap that the method for narrating in 761 can only be used for some type (is that iodine number is higher than 25 fatty basis soap class, and having no more than 40% carbon number to be less than 16 saturated fatty acid in the aliphatic acid that wherein comprises, 20% is the saturated fatty acid that contains 16-22 carbon atom and have at least in the aliphatic acid that wherein comprises). And the said composition that contains soap, water and TSPP must be subjected to the shearing of extreme condition after the mixer relaying is mixed, so that must To the performance of " the porphyrize soap " of expecting, and it mainly is the β phase. Can find out that also for form β phase this point in the soap bar that obtains, the aliphatic acid soap that uses above-mentioned restriction class is a key.
To those skilled in the art fully aware of be that at United States Patent (USP) 2,686, in 761 the soap bar composition, it is filler and " saltouing " agent that the function of TSPP strictly is limited to, so that can obtain containing the soap bar that large quantity of moisture and a small amount of are in β soap mutually.
In soap bar of the present invention, the effect of TSPP is then different fully.At first, the present invention is applicable to and makes all used fatty acid soaps of washing composition soap bar.
In addition, the effect of TSPP is not only as the filler that can obtain containing than the soap bar of juicy, and a kind of especially functionality reactant, and it can obtain the detergent bar of moisture content less and improve many physicalies of soap bar effectively.
In addition, the effect of TSPP also is a kind of processing aid in the detergent bar prescription.
At last, do not need picture at United States Patent (USP) 2,686, method is such described in 761, allows soap/water/TSPP be subjected to powerful the shearing to obtain required product in stirrer.
Though will not be to put forward to come the present invention of this place narration is limited in order to the reliability and the accuracy of any theory of explaining essence of the present invention or effect, but we still think, the great excellent properties of cleansing bar of the present invention results from stirrer each component of composition is mixed, and the mixture that obtains is carried out dry this unique method.Such as, successfully it is essential for of the present invention, to major general's part, preferably whole TSPP is added in the soap mixture in the stirrer.Then the transition temperature of this mixture heating up to the TSPP hydrate is higher than more than 80 ℃, carrying out vacuum-drying under this temperature, to make final water content be 6-14%.To the present invention's success key is to remove excessive moisture at the drying step that the transition temperature that is higher than TSPP promptly is higher than under 80 ℃.
In addition, it is believed that TSPP in final soap bar and residual TSPP hydrate have formed minute hand shape and hexagonal plate crystallization in the middle of whole soap bar structure, they have constituted the fibrous matrix network of some amount in the soap bar.The enhancing network that it is believed that this TSPP and TSPP hydrate crystal provides structural integrity, hardness, anti-mashed property and abrasion performance and the anti-cracking performance stuck with paste that has improved for cleansing bar of the present invention.
No matter be used to make any lipid acid of cleansing bar or their mixture traditionally, be saturated fatty acid or unsaturated fatty acids, all can be used to implement the present invention.Because the every principle of the described the present invention of this specification sheets, one skilled in the art will appreciate that the essence of the special fatty acid that is used for preparing soap/TSPP/ water mixture is not too crucial.The suitable example that is used for making this lipid acid of described soap (preferably sodium salt) is that alkyl chain length is C
8-C
22, C preferably
12-C
18Lipid acid.
Preferred lipid acid is the lipid acid that obtains from butter/coconut oil blend, and wherein the ratio of neat soap/Oleum Cocois soap is 1: 1 to 9: 1.The Oleum Cocois soap can change the palm-kernel oil soap into.Neat soap can change palm oil soap into or other is any by C
16The hard soap of above lipid acid preparation.
TSPP can be added in the soap pot, also can add when soap is put into stirrer, can also add stirrer at soap and add later on again.In an embodiment preferred, most of TSPP adds in the stirrer together in company with soap, and all the other then join in the mixer.
As what notice in front, for successfully implementing the present invention, crucially being to heat soap/TSPP/ water mixture under the invert point that is higher than the TSPP hydrate, is 6-14%(weight at this soap mixture of the temperature drying more than 80 ℃ to final total water content then).
Certainly, in the present composition, can add preparing washing soap bar auxiliary agent commonly used.The example of these auxiliary agents has sequestrant such as EDTA, DTPA, opacifying agent such as TiO
2, whitening agent such as Tinopol
Whitening agent, and filler such as talcum, kaolin etc.
Following non-limiting example is used for illustrating the present invention.
Embodiment
The batch of material that will contain following each component is by stirrer and mixer.
Material formula in the stirrer (soap flakes)
Composition weight (%)
Clean soap (85% neat soap/15% Oleum Cocois soap) 96.95-100
TSPP 0-3
EDTA（Na）
40.03
The BHT(Yoshinox BHT) 0.02
Material formula in the mixer
Soap flakes 98.5
Spices 1.5
The clean soap of water content 30% is 80 ℃ of fusions in pot.In this soap, adding anhydrous tetrasodium pyrophosphate (TSPP) under 80 ℃, this mixture was mixed 30 minutes.By 90-110 ℃ of following vacuum-drying, make water content to 6-14%, mixture is made soap flakes thus.
These soap flakes are mixed with spices and tinting material, and on roller refining machine, grind 3 times and pressing mold.Then soap bar is pressed into bulk.
Use neat soap/Oleum Cocois soap (85/15) preparation totally 7 batch of materials (seeing Table 1).The 1st batch and second batch does not add and adds 3% TSPP respectively.Final water content maintains approximately 8% in the soap bar, and TSPP adds in stirrer.It is 9-10% that 3-5 criticizes the soap bar water-content, does not add and add 3% TSPP respectively, and TSPP adds in stirrer.At the 5th batch, also in mixer, add 1.5% TSPP again.The 6th batch and the 7th batch of difference do not add and add 3% TSPP, and TSPP adds at mixer.
Under similar control condition, tested different soap bar attribute (water content, hardness, cracking performance, dry spot defective, the mashed performance of paste, wear rate and rate-of-loss of coolant) (seeing Table 1) for each prescription.Measure rate-of-loss of coolant (seeing Fig. 1 and Fig. 2) by determining timed interval weighing soap bar weight.
Used following term and definition in this manual:
Volatile component-quote volatile component by percentage weightlessness.This loss amount equals the loss of moisture, fragrant substance and other volatile component in vacuum drying oven (180,25 " mercury column) heat-processed.
Hardness-measure soap bar hardness with pin degree of penetrating meter.This instrument has used the needle point of a loading, measures the degree of depth that pin penetrates the soap interior surface every 10 seconds.Minimumly get 10 data points, average result is represented with millimeter.This result provides relative evaluation to soap bar hardness.
Wet cracking-with soap bar was suspended in the tap water that is in room temperature (about 75) 4 hours, made it dry 24 hours before estimating.Weigh any crackle that on soap bar surface produce to 5 degree (expression serious cracking) from numeral with 0 degree (expression does not have cracking), summation then.Such as a soap bar 51 degree rimose crackles are arranged, add 24 degree rimose crackles, so total measuring is 13.If always measure and be considered to unacceptable greater than 25.
Dry spot defective-use temperature is 55-85 a water washing soap bar, measures the granule number of this soap bar.15 at every interval is to soap bar evaluation and counting.0-25 is acceptable, and the unacceptable dry spot value of increase is 50,75 and 100.
Stick with paste the initial weight of mashed property (low humidity, room temperature)-record soap bar.This soap bar is put in the plastics soap box (120 millimeters * 75 millimeters * 16 millimeters) of at room temperature filling tap water.In this water, kept soap 17 hours.Take away soft soap with hand then, at room temperature dry this soap bar 24 hours is also weighed.Weight with per 100 gram losses provides test result.
Stick with paste mashed property testing (high humidity)-record soap bar weight in grams number.Under 100 °F, washed this soap bar 2 times at interval, each 10 seconds, test then with 30 minutes.This soap bar is placed in the soap box (120 millimeters * 75 millimeters * 16 millimeters).In soap box, fill tap water, under 35-40 ℃ and 100% relative humidity, this soap bar was kept in water 17 hours.Remove the soft material (mashed) of formation at the 17th hour end with the finger extruding.Under 21-25 ℃,, write down the weight of soap bar then with this soap bar dry air 24 hours.Determine weightless by the amount of per 100 gram losses.
Hand washing abrasion repeatedly-in this second method, repetitive scrubbing soap bar allow its drying then.Carry out this test to imitate daily use 4 days times.Write down the initial weight of soap bar earlier.Several different human temperature are washed this soap bar (90-100), each 10 seconds from the beginning.Then soap bar is placed in the apertured soap box, water is flowed out.Allow this soap bar drying, between each washing 30 minutes at least at interval.This soap bar is subjected to sum 20 times altogether, and each 10 seconds washing dry 24 hours then, is weighed again.The result is by per 100 gram weightlessness, also by each use weightlessness.
Have only when in clean soap, adding TSPP, maintain then when vacuum is removed excessive moisture under the temperature that is higher than 80 ℃ and just can observe the improvement that TSPP brings to performance.In other words, in mixer, add TSPP and can reduce total soap content, but not necessarily can improve as soap bar performances such as hardness, the mashed performance of paste and wear hardnesss to pre-dry soap flakes.In the superincumbent table 1, the 7th batch is equivalent to add the soap bar that TSPP makes in mixer.Relatively can find out obviously that the TSPP that adds is to all round properties and moment-less influence in mixer with its control group (the 6th batch).The main benefit that adds TSPP in stirrer is summarised in the following table 2.
Table 2 contains TSPP soap bar improved performance
Add the TSPP place
Add at the blender machine, add at stirrer,
Relatively compare with control group with control group
Hardness=+
Cracking++
The dry spot defective-=
Stick with paste mashed (low humidity)=++
Stick with paste mashed (high humidity)=++
Abrasion=++
Rate-of-loss of coolant+++
The no considerable change of=expression
± expression has considerable change
The soap bar that contains TSPP, it is stuck with paste mashed performance and is better than not containing TSPP person's (all like this in high humidity and low humidity test condition).Add TSPP and improved soap bar hardness, its anti-cracking performance of soap bar that contains TSPP is also better.The wear rate that contains the TSPP soap bar descends, and the dehydrating speed that contains the TSPP soap bar is slower than the control group soap bar.
The distribution of water in the TSPP soap bar
As everyone knows, TSPP and water have formed hydrate, and the water that its absorbs can reach 60% of himself weight.(DSC) studied the aqueous distribution of soap bar with differential scanning calorimeter.Sample 180 dryings in vacuum drying oven were obtained total water content in 24 hours, calculate free-water with the endothermic transition of the water of DSC from the soap sample when the fusion.The difference of the total water content and the free water yield is exactly to sum up the amount of Heshui in the soap bar.Calculate soap combined water (seeing Table 3) by the TSPP water-content in the total binding water yield and the soap then.
Table 3 contains the distribution of the middle moisture of soap (70% neat soap/30% Oleum Cocois soap) of TSPP
TSPP free-water Total Water is summed up Heshui TSPP soft soap combination water
(%) (%) (%) (%) (%) (%)
0 17.6 28.6 11.0 0 11.0
4.8 12.6 26.1 13.5 2.9 10.6
9.1 11.5 23.0 11.5 5.5 6.0
13.0 3.7 19.3 15.9 7.8 8.1
15.7 3.9 20.9 17.0 9.4 7.6
23.0 -- 20.4 20.4 13.8 6.6
28.6 -- 19.4 19.4 17.2 --
33.3 -- 17.8 17.8 20.2 --
Can be observed the total binding water yield, TSPP hydration level and free water content and the linear variation of TSPP concentration in the soap bar, constantly absorb 10 mole of water (see figure 3)s for every mole of anhydrous TSPP.
The distribution of phosphorus in the soap bar
With the X-ray analysis (EDX) that can loose the district is opened in the truncation of soap bar and carry out the element detection, the one, the quantitative assay element is to measure element distribution (first vegetarian refreshments distribution plan) in addition.With butter/Oleum Cocois soap is that basic soap adds that the synthetic surfactant that is selected from anion surfactant (the single glycerine vitriol of coconut alcohol, coconut acyl group sodium isethionate, alkyl glycerol sulfonate) of 0-25% makes following cellular (Combar) sample, and analyzes with EDX:
Sample 1#-adds 4%TSPP in mixer
Sample 4#-adds 4%TSPP in stirrer
In sample 2#, do not detect the phosphorus of significant amounts.At the detection zone of sample 1#, first vegetarian refreshments distribution plan points out that phosphorus is concentrated unevenly, and at sample 3# and sample 4#, phosphorus shows in little stirrer and distributed equably.
Also use four neat soaps/Oleum Cocois soap (85%/15%) sample before abrasion and abrasion backs (wash 20 times) with the distribution of EDX test soap bar surface phosphorus, observe the influence of abrasion to adding TSPP mode.
1. sample 1#-adds 3% TSPP in stirrer
2. sample 1#-is through after wearing away
3. sample 2#-adds 3%TSPP in mixer
4. sample 2#-is through after wearing away
In stirrer, add TSPP and at high temperature dry and soap bar (sample 2#) that distribution detected phosphorus in the soap bar (sample 1#) that makes makes than add TSPP in mixer is even.These two kinds of samples all pass through after the abrasion, and the concentration of phosphorus will be significantly less than sample 1# among the sample 2#.This result shows, when adding TSPP in stirrer is also at high temperature dry, has formed network in soap bar inside.
The TSPP that adds the soap bar that TSPP at high temperature obtains the soap flakes drying then in stirrer distributes in whole soap bar equably.The mashed performance of the paste of this soap bar and wear resistant be improved with add TSPP after to have changed the surface property of these soap bars relevant.
Improved with the soap bar of the TSPP of 2-4% processing and to have stuck with paste mashed performance, also alleviated abrasion than the soap bar that does not add TSPP, and little cracking easily.These results and TSPP exist as the structure activator in soap bar and also meet.
Solid phase in the soap bar
With the X diffractogram the not homophase of the soap bar that contains and do not contain TSPP is analyzed.Do not add the dominant Ω of the being phase of soap bar of TSPP, it is the β phase that 9-14% is arranged simultaneously.Yet the diffractogram owing to TSPP in containing the soap bar of TSPP has shielded the zone that generally can be observed the β phase, thereby can not detect the β phase.Therefore, can't the β that contain in the TSPP soap bar be carried out quantitatively mutually.
Therefore, according to the invention provides the cleansing bar that contains TSPP, owing to add the method for TSPP in soap bar TSPP is not only as a kind of filler, especially as a kind of function reagent and structure activator, the result can produce water content height, soap bar that saponified matter content is low.
Claims (5)
1, bar shaped laundry soap composition, it comprises:
(a) saturated or unsaturated fatty acids alkali metal soap or ammonium soaps or their mixture;
(b) content is at about 6% moisture to the scope of about 14% (weight); And
(c) about 0.5% the structure activator that is selected from tetrasodium pyrophosphate, tetrasodium pyrophosphate hydrate and their mixtures to about 15% (weight);
Described structure activator can improve structural integrity, hardness, the mashed performance of paste and abrasion performance and resistance to cracking.
2, the composition of claim 1, wherein said soap comprise having C
8-C
20The saturated fatty acid soap of carbochain or its mixture.
3, the composition of claim 1, wherein said soap comprise that by the soap that butter/the coconut oil fat acid mixture obtains the ratio of neat soap/Oleum Cocois soap is about 1: 1 to about 9: 1 here.
4, the laundry soap method for compositions of preparation claim 1, it is included in the stirrer saturated or unsaturated fatty acids alkali metal soap or ammonium soaps, or the described tetrasodium pyrophosphate of their mixture, water and at least a portion is mixed being higher than under about 80 ℃ temperature, remain on then to be higher than under about 80 ℃ temperature and remove redundant moisture from the mixture that forms under vacuum, extremely final water content is about 6% to about 14%.
5, the method for claim 4 wherein is that whole described tetrasodium pyrophosphate are added in the stirrer basically.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US315293A | 1993-01-11 | 1993-01-11 | |
| US003,152 | 1993-01-11 | ||
| US5604993A | 1993-04-30 | 1993-04-30 | |
| US056,049 | 1993-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1094088A true CN1094088A (en) | 1994-10-26 |
Family
ID=26671394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94101070A Pending CN1094088A (en) | 1993-01-11 | 1994-01-10 | The soap composition that contains trisodium phosphate |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0607004A3 (en) |
| KR (1) | KR940018461A (en) |
| CN (1) | CN1094088A (en) |
| BR (1) | BR9400061A (en) |
| CZ (1) | CZ6894A3 (en) |
| HU (1) | HUT67658A (en) |
| MX (1) | MXPA94000372A (en) |
| RO (1) | RO114345B1 (en) |
| SK (1) | SK3294A3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2738255B1 (en) * | 1995-09-05 | 1997-10-17 | Talc De Luzenac | SOAP-BASED CLEANING COMPOSITION HAVING LOW DRYING PROPERTIES, AND METHOD OF PREPARATION |
| US5888952A (en) * | 1997-06-13 | 1999-03-30 | Colgate-Palmolive Co. | Solid cleansing composition comprising tetrasodium pyrophosphate |
Family Cites Families (7)
| 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 (en) * | 1938-11-22 | |||
| US2686761A (en) * | 1950-06-02 | 1954-08-17 | Procter & Gamble | Detergent product having milled soap properties |
| BE515112A (en) * | 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 |
-
1994
- 1994-01-10 BR BR9400061A patent/BR9400061A/en not_active Application Discontinuation
- 1994-01-10 CN CN94101070A patent/CN1094088A/en active Pending
- 1994-01-10 EP EP94300155A patent/EP0607004A3/en not_active Withdrawn
- 1994-01-10 RO RO94-00026A patent/RO114345B1/en unknown
- 1994-01-10 KR KR1019940000317A patent/KR940018461A/en not_active Application Discontinuation
- 1994-01-11 CZ CZ9468A patent/CZ6894A3/en unknown
- 1994-01-11 MX MXPA94000372A patent/MXPA94000372A/en unknown
- 1994-01-11 HU HU9400072A patent/HUT67658A/en unknown
- 1994-01-11 SK SK32-94A patent/SK3294A3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0607004A3 (en) | 1995-03-08 |
| RO114345B1 (en) | 1999-03-30 |
| CZ6894A3 (en) | 1995-02-15 |
| KR940018461A (en) | 1994-08-18 |
| HU9400072D0 (en) | 1994-05-30 |
| BR9400061A (en) | 1994-08-16 |
| MXPA94000372A (en) | 2004-08-20 |
| HUT67658A (en) | 1995-04-28 |
| SK3294A3 (en) | 1994-08-10 |
| EP0607004A2 (en) | 1994-07-20 |
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