CN1031286C - Improved soap bars - Google Patents
Improved soap bars Download PDFInfo
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- CN1031286C CN1031286C CN92101447.3A CN92101447A CN1031286C CN 1031286 C CN1031286 C CN 1031286C CN 92101447 A CN92101447 A CN 92101447A CN 1031286 C CN1031286 C CN 1031286C
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- Prior art keywords
- soap bar
- soap
- fatty acid
- reaction
- alkyl
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Classifications
-
- 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
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
-
- 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
- C11D9/22—Organic compounds, e.g. vitamins
- C11D9/30—Organic compounds, e.g. vitamins containing nitrogen
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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)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Bar soaps containing polyhydroxy fatty acid amides exhibit good 'smear' qualities, desirable hardness and good lather properties. The bars also have a decreased tendency to crack. Bars comprising soap and materials such as C12-C18 N-methyl glucamide are provided.
Description
The present invention relates to contain the soap bar of polyhydroxy fatty acid amide, especially Personal hygiene and/or cosmetic soap bar.
The prescription of personal washing bar (i.e. " washing soap bar ") has been continued to use for many years.Yet,, still have some problems relevant with soap bar no matter service condition is how in history.As everyone knows, prescription teacher and user do not wish that soap bar forms soap/water type glue, when the environment that can contact with water is stored down especially in use, for example in the soap dish, and the like situation under, be typically in the family expenses washroom and more do not wish to form this glue when using.Soap bar except that ugly, has in use also lost soap with deliquescing with make dirty in this case.It is a kind of method that reduces the soap bar stain that the water yield of soap bar is reduced.Yet, can follow again when storing cracking to occur along with the minimizing of the soap bar water yield.In addition, for the Personal hygiene soap bar, wish that again it has good lathering property.Otherwise, may disadvantageous effect be arranged to lathering property to reduce the loss as the water yield of adjustment criteria soap bar inadequately.The another kind of method that reduces the soap bar loss is to use senior saturated fatty acid (promptly low iodine number) to make the raw material of soap.Yet low iodine number soap lathering property is poor, and rimose soap has tedious sand feeling during storage.Therefore, people are just continuing to explore the method that is reduced to minimum degree with the loss of seeking soap bar, with the use that causes the human consumer can not produce soap bar is uneconomic impression, and to its lathering property, cleaning performance and other desirable performances do not have disadvantageous effect again.
The objective of the invention is, a kind of few stain that has is provided, with the relevant suitable soap bar hardness of reducing the loss, suitable lathering property (even improving to some extent) and when storing, be difficult for the rimose soap bar.
The present invention combines polyhydroxy fatty acid amide, to reach above-mentioned purpose with the method for introducing below with the sour soap of water-soluble fat.
Adding polyhydroxy fatty acid amide is to be inclined in order to reduce the soap bar agglomerative, thus the soap bar that obtains less stain and grow duration of service.In addition, polyhydroxy fatty acid amide helps bubbling and reduces the cracking of soap bar, will be seen that by the content of following announcement the present invention has reached these purposes and other purposes.
On April 4th, 1967 the disclosed U.S.P.3 that authorizes D.T.Hooker, 312,627 propose, soap bar when being soaked in water, wash one's hands and face with the loss of soap bar too much, solubleness is too big or problem such as too soft.Hooker provides and has wherein contained him and think that the invention of implementing him is soap bar (8 hurdles of fabulous some lipid acid lithium soap, 20 row), he has also introduced various types of nonionogenic tensides more widely and can comprise that its formula is RC (O) NR in the 4th hurdle 11-28 row
1(R
2) (wherein, RC (O) contains and has an appointment 10 to about 14 carbon atoms, and R
1And R
2Respectively be H or C
1-C
6Alkyl, the total number of carbon atoms that said alkyl contains is 2 to about 7, the substituting group hydroxyl add up to 2 to about 6) polyhydroxy amides.In its foaming composition, Hooker has introduced stearyl N-methyl glucose amide and lauroyl N-methyl glucose amide, referring to same in the disclosed U.S.P.3 that authorizes D.T.Hooker on April 4th, 1967,312,626.
The following reference used polyhydroxy fatty acid amide surfactant of Shi Hecheng the present invention: the U.S.P.2 that will help to fill a prescription, 016,962,1,985,424,2,703,798,2,993,887, EP-A285,768; Also can be referring to H.The Tenside surfactant detergent 25 (1988) 8-13 of Kelkenberg and Biochem J. (journal of biological chemistry) 1982.Vol.207, PP363-366.
In the art, various polyhydroxy fatty acid amides have been introduced.For example J.W.Goodby, M.A.Marcus; E.Chin and P.L.Finn are at liquid crystal (1988.Vol.3 No.11; PP1569-1581) is entitled as " the thermotropic liquid crystal property of some straight chain carbohydrate amphiphile " and A.Muller-Fahrnow on; V.Zabel; M.Steifa and R.Hilgenfeld are at J.Chem.Soc.Chem.Commun (chemical association chemical communication; 1986, PP1573-1574) is entitled as in " molecule of nonionic detergent nonanoyl-N-methyl glucose amide and crystalline structure " on and disclosed N-acyl group, N-methyl glucose amide.In recent years, on biological chemistry,, for example, be used to dissolve microbial film to using N-alkyl polyhydroxy acid amides surface words property agent interested especially." N-D-glucose-N-methyl-alkylamide compound is used for the new nonionic detergent of a class of membrane biochemistry " of on Biochem.J. (1982, Vol.207.PP363-366), delivering for example referring to J.E.K.Hildreth.
Also discussed N-alkyl glucose amide has been used for detergent composition.December 20 nineteen sixty the disclosed U.S.P.2 that authorizes E.R.Wilson, 965,576 and February 18 nineteen fifty-nine disclosed transfer give ThomasHedley; Co., the G.B.809060 of Ltd. has also related to the detergent composition that contains anion surfactant and can comprise some acidamide surfactant (as low temperature profoamer 1) of N-methyl glucose amide.These compounds comprise the N-acyl group of the senior straight chain fatty acid with 10-14 carbon atoms.These compositions also can contain auxiliary substance, as alkali metal phosphate, alkalimetal silicate, vitriol and carbonate.Usually also show, in said composition, also can contain other compositions that its composition given desired properties, for example fluorescence dye, SYNTHETIC OPTICAL WHITNER, spices etc.
March 8 nineteen fifty-five the disclosed U.S.P.2 that authorizes A.M.Schwartz, 703,798 relate to the aqueous detergent compositions of the condensation reaction products of the aliphatic ester that contains N-alkylated glucamine and lipid acid.Think that in the absence about being further purified, this reaction product can be used in the aqueous detergent compositions.As at the disclosed U.S.P.2 that authorizes A.M.Schwartz on September 13 nineteen fifty-five, disclose in 717,894 like that, the sulfuric ester of preparation acylations glycosamine also is known.
December 22 nineteen eighty-three is disclosed, the application people has related to the amphipathic compound that contains the poly-hydroxy aliphatic group of thinking to be suitable for multiple purpose for the PCT International Application No. WO 83/04412 of J.Hildreth, it is included in makeup, medicine, shampoo, lotion and the ophthalmic ointment and is used as tensio-active agent, as the emulsifying agent and the dispersion agent of medicine, be used for solubilising film, full cell or other tissue samples on the biological chemistry and be used to prepare liposome.Wherein the compound of Pi Luing comprises that having formula is R ' CON (R) CH
2The compound of R " and R " CON (R) R ' (wherein R is H or organic group, and R ' is the aliphatic hydrocarbyl that has 3 carbon atoms at least, and R " be the aldose base).
People's such as the disclosed H.Kelkenberg of authorizing on the 12nd EPO285768 related to and N-polyhydroxy alkyl fatty acid amide is used for the aqueous detergent system made thickening material October in 1988.Comprising formula is arranged is R
1C (O) N (X) R
2(R wherein
1Be C
1-C
17(preferred C
7-C
17) alkyl, R
2Be H, C
1-C
18(preferred C
1-C
6) alkyl or alkylene oxide, and X is the polyhydroxy alkyl that 4 to 7 carbon atoms are arranged, as N-methyl, coconut fatty acid glucamide) acid amides.Though the aqueous surfactant system can contain other anion surfactants.As alkylaryl sulphonate, alkene sulfonate, sulfo-succinic acid half ester salt and fatty alcohol ether sulfonate and such as poly alkyl alcohol glycol ethers, alkylphenol polyglycol ether, fatty acid polyglycol ester, poly(propylene oxide)-nonionogenic tensides such as polyethylene oxide mixed polymer, but show that also the thickening properties of acid amides is specially adapted to contain in the liquid surfactant system of alkane sulfonate.Alkane sulfonate/N-methyl coconut fatty acid glucamide/nonionogenic tenside shampoo prescription then is an example wherein.Except that the thickening attribute, think that this N-polyhydroxy alkyl fatty acid amide has excellent skin tolerance attribute.
On May 2nd, 1961 the disclosed U.S.P.2 that authorizes people such as Boettner, 982,737 relate to the nonionogenic tenside that contains urea, Sodium Lauryl Sulphate BP/USP anion surfactant and be selected from the N-alkyl glucose amide of N-methyl, N-sorb base laurylamide and N-methyl, N-sorb base myristic amide.
The DT2 that other glucamide tensio-active agents for example are disclosed in people such as the disclosed H.W.Eckert of authorizing on the 20th December in 1973,226, in 872, this patent has related to the detergent composition that contains one or more tensio-active agents and be selected from the builder salt of polymeric phosphate, sequestering agent and washing soda, and this detergent composition is to be R by the adding formula
1C (O) N (R
a) CH
2(CHOH)
nCH
2OH (wherein, R
1Be C
1-C
3Alkyl R
2Be C
10-C
22Alkyl, and n is 3 or 4) N-acyl group polyhydroxy alkylamines is improved.N-acyl group the polyhydroxy alkylamines that adds is intended for soil-suspending agent.
On April 4th, 1972 the disclosed U.S.P.3 that authorizes people such as H.W.Eckert, 654,166 have related to more such detergent composition, and it contains at least a tensio-active agent that is selected from negatively charged ion, zwitter-ion and nonionogenic tenside and the formula that contains as fabric softener is R
1N (Z) C (O) R
2(R wherein
1Be C
10-C
12Alkyl, R
2Be C
7-C
21Alkyl, R
1And R
2The total number of carbon atoms be 23 to 39, and Z can be that formula is-CH
2(CHOH)
mCH
2The polyhydroxy alkyl of OH (m is 3 or 4)) N-acyl group, N-alkyl polyhydroxy alkylate.
On May 3rd, 1977 is disclosed authorizes people's such as H.M_ller U.S.P.4, and 021,539 has related to the cosmetic composition of treatment skin, and said composition contains and comprises that formula is R
1N (R) CH (CHOH)
mR
2(R wherein
1Be H, low alkyl group, hydroxyl low-grade alkyl or aminoalkyl group and heterocyclic amino group alkyl, R and R
1Identical, but can not be H, R
2Be CH
2OH or COOH) N-polyhydroxy alkylamines of compound.
Disclosed French Patent 1,360,018 of authorizing Commercial Solvents company related to and was added with formula RC (O) N (R on April 26th, 1963
1) (wherein R is the carboxylic acid functional with at least 7 carbon atoms to G, R
1Be H or low alkyl group, and G is the sugar alcohol base with at least 5 carbon atoms) the stable formaldehyde solution of the anti-polymerization of acid amides.
February 29 nineteen sixty-eight the disclosed German Patent 1,261,861 of authorizing A.Heins to relate to the formula as wetting agent and dispersion agent be N (R) (R
1) (R
2) (wherein, R is the glycosyl of glycosamine, R
1Be C
10-C
20Alkyl, R
2Be C
1-C
5Acyl group) glycosamine derivative.
On February 15th, 1956 is disclosed authorizes Atlas Powder the G.B.745 of company, and 036 patent relates to heterocycleamide and its carboxylicesters that is considered to as chemical intermediate, emulsifying agent, wetting agent, dispersion agent, washing composition, fabric softener etc.This compound is with formula N (R) (R
1) C (O) R
2(wherein, R is dehydration hexane pentol or its carboxylicesters, R
1Be the monovalence alkyl, and-C (O) R
2Be acyl group with carboxylic acid of 2 to 25 carbon atoms) represent.
The present invention relates to the bar shaped soap composition, said composition comprises:
(a) about 75% water miscible substantially no lithium fatty acid soaps to about 85% (weight);
(b) polyhydroxy fatty acid amide surfactant of about 1% (weight); With
(c) remainder of this soap for example spices, sanitas etc. of water and optional submember normally.
Soap bar of the present invention generally contains the C of have an appointment 75% sodium to about 85% (weight), potassium, ammonium or alkanol ammonium salts form
12-C
18Soap; About 1% polyhydroxy fatty acid amide surfactant to about 10% (weight); About 8% water to about 12% (weight).Preferred polyhydroxy fatty acid amide surfactant is C
12-C
18Alkyl N-methyl glucose amide, and preferred fatty acid soaps contains blended C
12-C
18The sodium salt of lipid acid.It is about 3 that the preferred soap bar of the present invention is characterized in that hardness value is lower than, and more preferably is to be lower than approximately 2, and it is by " doing " (i.e. " former state ") penetrometer test determination.
The most preferred soap bar of the present invention comprises:
(a) having iodine number is about 25 to about 35 about 75% to about 85% soda soap;
(b) about 3%C
12-C
18N-methyl glucose amide tensio-active agent;
(c) about 0.3% to about 0.5%Nacl; With
(d) about 10% water, its remainder comprises soap bar submember commonly used.Said soap bar is characterized in that hardness value is about 2 to about 2.5.
The present invention also comprises the hardness method for quality that is used to improve the soap bar that contains water miscible substantially no lithium fatty acid soaps, wherein said soap bar contains 8% water to about 12% (weight) of having an appointment, but to the essentially no harmful effect of lathering property, or said soap bar does not have the rimose tendency when storing or use, prepare said soap bar, it comprised:
(a) about 8% to about 12% water;
(b) about 75% to the water miscible substantially no lithium fatty acid derived soap of about 85% (weight), and it is about 25 to about 35 that said soap preferably has the iodine number scope;
(c) about 1% to about 10% (weight) polyhydroxy fatty acid amide surfactant;
(d) about 0.2 to about 0.6% (weight) ionogen; With
(e) by processing technology commonly used said raw material is formed bar shaped.
Soap bar of the present invention also can comprise synthetic (" synthetic detergent ") non-soap, non-polyhydroxy fatty acid amide detergents arbitrarily, its content be generally this soap bar about 0% to about 30%, this will depend on the teacher's that fills a prescription requirement.
Except as otherwise noted, all in the present invention percentage ratio, ratio, ratio are all by weight.Patent that this paper quotes and described document are introduced into as a reference.
The preparation of soap bar of the present invention is to use technology and the equipment in industrial that know and standard, and the production operation that forms soap bar does not constitute part of the present invention.Yet, implement the present invention in order to help teacher of the prescription, following explanation is that by way of example method reaches, and is not limited to preparation soap bar method of operating used in the present invention.
In temperature is under about 120 °F (49 ℃), in " crutcher ", 189 pounds of (85.6kg) tallow fatty acids, 27 pounds of (12.2kg) stearic acid and 54 pounds of (24.4kg) coconut fatty acids are mixed, this crutcher is equipped with the steamer agitator and the circulating ring of standard, is further improved so that make to mix.Use then in the NaOH solution and the admixture of lipid acid.Need about 84 pounds of (38kg) 50% solution, so that fully with its neutralization.Before the hydro-oxidation thing, in this hydroxide solution, add 2.1 pounds of (0.95kg) salt (NaCl).During neutralizing, temperature rises to 180-190 °F (82 to 88 ℃).
After neutralization is finished, 9.78 pounds of (4.4kg) tallow alkyl N-methyl glucoside acid amides are joined in the neutral material with powder type, keep violent stirring simultaneously, so that produce the good mixing effect, temperature is maintained at about 180 °F (82 ℃).After adding tallow alkyl N-methyl glucose amide, stir about 15 minutes is to be enough to reach good mixing.
The mixture that makes contains about 30% moisture, then, under following operational condition, in the vacuum flash dryer, this mixture is dried to 10.5% moisture.
Temperature=180 (82 ℃) before the heat exchanger
Temperature=220 (104 ℃) after the heat exchanger
The temperature of drying products soap noodles=120 (49 ℃)
Vacuum chamber pressure=40mmHg
Then, use the processing units of standard: pre-grinding machine, amalgamator, shredder, plodder and printer, be processed into soap bar with exsiccant product soap noodles.The soap bar that makes in this way can have hardness level (" drying ") for about 2, and this is that the penetrometer of the test 1 by is hereinafter described measured.
Can use following method to measure the physical parameter of soap bar of the present invention.
The hardness test method: available following method is measured the hardness of the prepared soap bar of the present invention.Usually, have the hardness value scope and be lower than about 3 and preferably be lower than about 2 soap bar, in listed first test (test 1), provided good consumption figures, acceptable stain etc.Listed first test comprises and should " do " " aciculiform " penetration degree of soap bar, prints, and this soap bar is except with about 10% moisture in its soap bar contacts, and does not contact with other moisture.In another kind test (test 2 is below being also illustrated in), soap bar is at first wetted.In second test method, use " sphere " penetration degree, and in such test, it is about 1.25 that desirable penetration degree score value is lower than, and more preferably is lower than about 1.0.
Test 1
The test of bar shaped penetrometer
Equipment:
---1/10 millimeter scale tester (1 type-Meter of accurate penetrometer
538 Fisher Scientific)
---taper penetrometer (12.79g)
---230.6g is heavy
---the Kodak timing register
Method:
---with soap bar be placed on penetrometer awl below, this soap bar is placed on the plank simultaneously,
Cover soap bar with waxed tissue.
---metal needle in-degree taper meter is put down (will with surperficial contact of paraffin paper until the termination of awl
Paper is placed between soap bar and the awl, puts down awl and can not to removing paraffin paper until end points
Tear the position of paraffin paper).
---remove paraffin paper.
---the heavy 230.66g of awl of awl masthead portion.
---compress the release lever of awl, continued for 10 seconds; Loosen; Promote the awl arm; Move to
The lip-deep new position of soap bar; Repeat this working method.
---repetitive operation three times forms a trilateral with three penetration degree points on soap bar.
---downwards by the knob of top bar, so as to obtain for penetrometer length precision=
1/10 millimeter scale reading.
---reading will be the cumulative summation of three penetration degrees.
---obtain average penetrometer reading with 3 divided by accumulated total, remove with 10 then
To the reading of representing with millimeter, and write down this hardness value (representing) with millimeter.
Test 2
Spherical penetrometer test/100ML stain
Equipment:
---1/10 millimeter scale tester (1 type-Meter of accurate penetrometer
538 Fisher Scientific)。
---spherical penetrometer (11.40g).
---300.6g is heavy
---Petri dish, internal diameter 90mm, degree of depth 22mm.
---standard plastic frame (soap box type; Soap bar contacts with water hardly).
---scale cylinder or batching bottle.
Method:
---soap bar is placed on central authorities on the plastic processing frame in the Petri dish.
---get the chamber that soap bar is placed on 80/80 (80/80% relative humidity)
In, and add 100ml distilled water, be placed on 80/80 indoor spending the night.
---put back to testing laboratory to soap bar second day morning, gets from Petri dish at leisure
Go out soap bar, a wet side is placed under the penetrometer ball up.
---metal needle in-degree ball is put down, make it just touch the surface of soap bar.
---heavily heavy at the top of bar ball for 300.6g.
---for the soap bar of bending, when measuring, to guarantee to clamp soap bar.
---compress release lever, continued for 10 seconds; Loosen; Promote the ball arm, wipe mistake on the ball
Surplus gel moves to the lip-deep new position of soap bar to ball; Repeat this operation
Method.
---repetitive operation three times, for crooked soap bar, make it at 3 and pass this soap bar camber line,
For brick shape soap bar, then to form trilateral.
---downwards by the knob of top bar, so as to obtain for penetrometer length precision=
1/10 millimeter scale reading.
---reading will be the accumulated total of penetration degree.
---obtain average penetrometer reading with 3 divided by accumulated total, remove with 10 then
To the reading of representing with millimeter, and write down this hardness value (representing) with millimeter.
Implementing the used composition of the present invention is known substances, and its composition itself and their the whole bag of tricks of preparation do not constitute part of the present invention.On the contrary, these compositions are combined just obtains composition disclosed in this invention, thereby reaches required result, and its result has just constituted the present invention.Yet,, each composition is described below in order to help teacher of the prescription.
Soap: soap composition of the present invention is the commercial goods of knowing, and it comprises water miscible substantially soap, is generally C
12-C
18Soap.This class salt comprises alkali-metal salt, ammonium salt, alkanol ammonium salts etc.Sodium salt, sylvite, triethanol ammonium, ammonium salt etc. are mentioned as an example, but are not limited thereto.(water-insoluble soap, particularly lithium soap and insoluble calcium and magnesium soap all are not used as " soap " composition of soap bar of the present invention).Lipid acid can obtain by the synthetic method, or more typically is, for example lard, plam oil, tallow, coconut wet goods obtain by basic hydrolysis fat and oil.Coco-nut oil fatty acid, tallow fatty acids and palm oil fatty acid are mentioned as an example, but for general soap, its source is not limited to these lipid acid, can use the mixture by various sources derived fatty acid.In a preferred method, soap used in the present invention has lower degree of unsaturation, promptly has lower iodine number, and preferred iodine number scope is about 25 to about 35.Such just as well known in the art, the soap of the low iodine number of preparation can pass through hydrogenation fat soap raw material, or fatty soap raw material is mixed with saturated fatty acid, so that reduce total iodine number of this raw material.For example, obtain very ideal soap bar by the soap bar of blended tallow/tristearin of hereinafter mentioning/coconut fatty acid preparation, still, this can change according to the source of prescription teacher's requirement, purpose and raw material.
Water: for the finished product soap, the water-content of soap bar of the present invention is at least about 8%, and general range is about 8% to about 15%, preferred about 10% (weight).Prescription teacher employed water-content will depend on the chain length of pliability, the fatty acid soaps of prescription teacher and the acceptable soap bar of user, the quantity of the polyhydroxy fatty acid amide that uses etc. in soap bar.These all routinely situation regulate.
Ionogen: soap bar of the present invention will be chosen wantonly, but preferably contain ionogen, generally ionogen will be added in the soap bar, so that its soap becomes a kind of form that is referred to as " only " phase usually.The electrolytical selection of using in soap bar is the thing of prescription teacher decision.But, in general, cheap, water miscible on toxicity acceptable ionogen comprise various organic salts, or more typical be various inorganic salt, for example alkali metal halide, vitriol, phosphoric acid salt etc.In this class material, can illustrate by way of example fully, as sodium-chlor (preferably), Repone K, sodium sulfate, sodium phosphate etc., but be not limited thereto.In general, it is about 2% that electrolytical content is not greater than, and be more preferably about 0.2% to about 0.6% (in soap bar weight).
Optional material: for the type of using in washing one's hands and face with soap bar and cosmetic soap bar, soap bar of the present invention can randomly contain various supplementary components for common.Can comprise spices, opalizer, pearling agent, antiseptic-germicide, dyestuff, fatting agent such as glycerine, abrasive such as float stone by illustrational various compositions, or the like, but be not limited thereto.The common scope of this constituents can be for about 0.1% to about 15% (in soap bar weight), and this depends on the teacher's that fills a prescription purpose.
The optional member of a kind of addition type of using in soap bar of the present invention comprises synthetic detergent, as sulfation and sulfonated C
12-C
18Alcohol, alkylbenzene etc.Can use nonionic synthetic detergent such as C
12-C
18Polyethoxylated, C
12-C
18Alkylphosphonic, zwitter-ion, positively charged ion, synthetic detergents such as amine oxide.This class synthetic detergent is well-known, can be referring to Mccutcheon ' s index or other textbooks of standard meter.If you are using, the content that this class synthetic detergent is suitable is about 2% to about 15% (in soap bar weight).
Polyhydroxy fatty acid amide surfactant: these materials and synthetic their the whole bag of tricks all are known (for example referring to reference of introducing in the above-mentioned background technology) in its document.Yet,, be provided for the example that is fit to of the synthetic method of this class polyhydroxy fatty acid amide surfactant of the present invention below, but be not limited thereto in order further to help teacher of the prescription.
The reaction of the polyhydroxy amine that is used to prepare the polyhydroxy fatty acid amide surfactant of the present invention's use and prepares is called " R-1 " reaction, and illustrates R wherein with the formation of N-methylglucosamine
1It is methyl.
Reactant, solvent and the catalyzer of R-1 reaction usefulness is normally by the various markets available well-known material of originating.Be the example that can be used for unrestricted material of the present invention below.
The amine material: the amine that is used for R of the present invention-1 reaction is primary amine, and its formula is R
1NH
2, R wherein
1Can be for as alkyl, especially C
1-C
4Alkyl, or C
1-C
4Hydroxyalkyl.The example comprises as methyl, ethyl, propyl group, hydroxyethyl etc.The example that is used for unrestricted amine of the present invention comprises methylamine, ethamine, propylamine, butylamine, 2-isopropanolamine, 2-oxyethylamine, is preferably methylamine.All these class amine often are referred to as " N-alkylamine ".
Polyhydroxy substance: the preferred source that is used for the polyhydroxy substance of R-1 reaction comprises reducing sugar or reducing sugar derivative.Be used for more preferably reducing sugar of the present invention and comprise glucose (preferably), maltose, fructose, trisaccharide maltose, wood sugar, semi-lactosi, lactose or its mixture.Catalyzer: various hydrogenation catalysts all are applicable to R-1 reaction.In this class catalyzer, include nickel (preferably), platinum, palladium, iron, cobalt, tungsten and various hydrogenation alloys etc.Most preferred catalyzer of the present invention comprises " united catalyst G49B ", a kind ofly is stated from particulate state nickel catalyzator on the silicon-dioxide by what the Louisville.Kentucky of United Catalysts, Inc obtained.Solvent: forming adducts in R-1 step is to make solvent with excess amine, also excess amine can be used for the subsequent reactions with hydrogen.For H-H reaction, available alcohol such as methyl alcohol replace amine arbitrarily.Be used for the example that the present invention forms the typical solvent of amine-sugared adducts and comprise methylamine, ethamine and oxyethylamine, preferred methylamine also can use methylamine/water solvent.
The general condition of R-1 reaction: the reaction conditions of R-1 reaction is as follows:
(a) formation of adducts: the reaction times that is used to form adducts is generally about 0.5-20 hours, but depends on the temperature of reaction of selection to a certain extent.Generally speaking, react under 0 ℃～80 ℃ of lower temperature ranges, then need the long reaction times, vice versa.Usually, surpass 30 ℃-60 ℃ of preferred temperature of reaction, in 1-10 hours, can obtain gratifying adducts product.At amine: the mol ratio of sugar is about 4: 1 to 30: 1 times, reaches the formation of good adducts usually.General sugared reactant concn in amine solvent is 10%～60% (weight).The formation of adducts can be carried out under normal atmosphere or super-atmospheric pressure (preferably).
(b) and H-H reaction: in general, carry out under the following conditions with the reaction of hydrogen: for example, temperature is 40 ℃-120 ℃, and pressure is 50-1,000psi (pound/inch
2), perhaps as, temperature is 50 ℃-90 ℃, pressure is 100-500psi, the time is 0.1-35 hours, is generally 0.5-8 hours, is preferably 1-3 hours.Adducts/the solvent solution that uses in H-H reaction is generally the solute amount of 10%-60% (weight).(will recognize that being chosen in of hydroformylation reaction condition depended on the type of the available press device of prescription teacher in a way, therefore, in the case of without departing from the present invention, above-mentioned reaction conditions is changeable).For interrupter method, the H-H reaction catalyst consumption is generally 1% to 40%, is preferably about 2% to about 30% (solid weight), and this is by catalyst weight: reducing sugar substituting group weight is calculated for the basis.Certainly, continuous processing can be carried out under much higher catalyst consumption.The product of step (b) can carry out drying by solvent/water stripping or crystallization, development or by means of the effective dry agent.
Example I
With the dextrose anhydrous (36.00g that weighs; Aldrich chemical company) put into glass bushing, this glass bushing is put into the dry ice bath, and methylamine gas (68.00g; Matheson) be condensed and enter in this glass bushing.Then, sleeve pipe is put into swing autoclave (volume is 500ml), autoclave is heated to 50 ℃, and under 50 ℃, at 600psig (gauge pressure, pound/inch
2) nitrogen in, waved 5 hours, so that form adducts (N-methyl glucosyl amine).Then, this is reflected in the dry ice bath and cools off, and autoclave ventilation cooling.Add Raney nickel (the 7.2g50% suspension in water, W/2 type, Aldrich chemical company).In the hydrogen of 500-600psig, this reaction is heated to 50 ℃, and waves 16 hours.This is reflected in the dry ice bath and cools off, and with its ventilation with use purging with nitrogen gas.Reaction soln carries out pressure filtration, and its filtration is to finish by the Zeofluor strainer (tetrafluoroethylene, 47mm, 0.5 μ m strainer) of 4 inches beds using Celite 545 (FisherScientific company).This filtrate concentrates under nitrogen gas stream, so that obtain 8.9 gram white solids.The about 300ml water washing of this Celite plug, and water stripping on rotary evaporator are so that obtain the 18.77g white solid.Two kinds of solids are merged, and as analyzing, they have similar composition (90
+Purity is used gas chromatographic analysis).This product is N-methylglucosamine.
Example II
In the autoclave of the stirring that porous egress filtering device, trilobed wheel agitator, export and import pipe and plate washer are housed, repeat the method for embodiment 1.The reactant and the reaction conditions of preparation N-methylglucosamine are as follows: in 160ml methyl alcohol, with 15g20%G49B catalyzer (Ni/ silicon-dioxide; United Catalysts, Inc) and the 75g glucose powder (Aldrich Lot07605LW) is made into pulpous state, and uses H
2Pre-treatment 1 hour (50 ℃), cooling mixture and remove methyl alcohol then with pressure.
Reactor is chilled to below 5 ℃, and the 76ml liquid methylamine of packing into.
In the hydrogen of 250psi, through 46 minutes reaction mixture slowly is heated to 60 ℃ and sampling, under 60 ℃, continue heating 20 minutes, and take out sample 2, and continue 46 minutes (sample 3) of heating down at 60 ℃, continue 17 minutes (sample 4) of heating down at 60 ℃ then.Reaction mixture is heated 33 minutes (sample 5) in addition to 70 ℃.Total reaction times is 2.7 hours.Desciccate is 93.2%N-methylglucosamine (gas chromatographic analysis).
Need preferably to remove basically the polyhydroxy amine product of above-mentioned R-1 reaction of anhydrating, and it can be further used for form in the reaction of acid amides, this reaction is referred to herein as " R-2 " reaction.The reaction that typical R of the present invention-2 forms acid amides can illustrate by the formation of lauroyl N-methyl glucose amide, is described below.
R
2C (O) N (Me) CH
2(CHOH)
4CH
2OH+MeOH is R wherein
2Be C
11H
23Alkyl.
Therefore, make in the preparation polyhydroxy fatty acid amide surfactant all reactions comprise:
(a) in amine solvent (being preferably methylamine), reducing sugar (being preferably glucose) or reducing sugar derivative and amine reactant (being preferably methylamine) are reacted, so that obtain adducts;
(b) in the presence of metal catalyst, will be dissolved in said adducts and H-H reaction in the said amine solvent from step (a);
(c) remove from reaction mixture that said catalyzer and removing basically anhydrates and the solvent of excessive amine, so that the polyhydroxy amine reaction product is provided; And, after this be the R-2 reaction;
(d) in the presence of basic catalyst, in organic hydroxylic solvent (being preferably methyl alcohol or propylene glycol), from the said substantially anhydrous polyhydroxy amine product and the fatty acid ester reaction of step (c), to form polyhydroxy fatty acid amide surfactant (preferable reaction temperature is lower than about 100 ℃); With
(e), remove the said solvent that in step (d), uses arbitrarily when reactions steps (d) when finishing basically.
Say that more specifically with the step (R-1+R-2) that R of the present invention-1 and R-2 reaction bonded are got up and just provided all, it can be used for producing the polyhydroxy fatty acid amide surfactant of the present invention that is used for following formula:
Wherein: R
1Be H, C
1-C
4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture are preferably C
1-C
4Alkyl, more preferably C
1Or C
2Alkyl, most preferably be C
1Alkyl (being methyl); And R
2Be C
5-C
31Hydrocarbyl portion is preferably straight chain C
7-C
19Alkyl or alkenyl, more preferably straight chain C
9-C
17Alkyl or alkenyl most preferably are straight chain C
11-C
17Alkyl or alkenyl, or its mixture; And Z has to have the polyhydroxy alkyl part that at least 3 hydroxyls are directly linked the straight-chain alkyl chain on the chain, or its alkoxy derivative (being preferably ethoxylation or propoxylation), preferred Z is derived by reducing sugar in reductive amination process, and more preferably Z is the sugar alcohol base section.The reducing sugar that is fit to comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.Height contains the glucose maize treacle, height contains the fructose maize treacle and high each sugar that contains the maltose maize treacle and list above all can utilize as raw material.These maize treacle can provide the sugared mixture of ingredients for Z.Certainly never discharge other materials that are fit to as raw material.Z is selected from by-CH
2-(CHOH)
n-CH
2OH ,-CH (CH
2OH)-(CHOH)
N-1-CH
2OH ,-CH
2-(CHOH)
2(CHOR ') (CHOH)-CH
2The class group that OH forms, in above-mentioned group, n is 3 to 5 integer, and R ' is H or ring-type single or many saccharidess and its alkoxy derivative, is more preferably sugar alcohol base (wherein n is 4), particularly-CH
2-(CHOH)
4-CH
2OH.
In formula (I), R
1Can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-isobutyl-, N-2-hydroxyethyl or N-2-hydroxypropyl.
Can be for example coconut monoethanolamide (cocamide), stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, tallow acid amides etc.
Z is 1-deoxy-glucose alcohol radical, 2-deoxidation fructose alcohol radical, 1-deoxidation maltose alcohol radical, 1-deoxidation lactose alcohol radical, 1-deoxy-galactose alcohol radical, 1-deoxymannose alcohol radical, 1-deoxidation trisaccharide maltose alcohol radical etc.
Following reactant, catalyzer and solvent be all applicable in R of the present invention-2 reaction, and only by way of example method is listed it, but be not limited thereto.This class material all is well-known, and can obtain from various commercial source usually.
Reactant: various fatty acid esters all can be used in R one 2 reactions, and it comprises list, two and three esters (being triglyceride level).Methyl esters, ethyl ester etc. are all very suitable.The polyhydroxy amine reagent comprises the reactant that is obtained by above-mentioned R-1 reaction, for example has N-substituting group such as CH
3-, C
2H
5-, C
3H
7-, HOCH
2CH
2-N-the alkyl and the N-hydroxyalkyl polyhydroxy amine that wait.(polyhydroxy amine that is obtained by R-1 reaction is not preferably polluted by the metal hydrogenation catalyzer of remaining quantity, though can there be ppm (for example 1-20ppm)).Also can use the mixture of ester and the mixture of polyhydroxy amine reactant.
Catalyzer: the catalyzer that is used for R-2 reaction is an alkaline matter, for example alkoxide (preferably), oxyhydroxide (less selecting for use is because of hydrolysis reaction may take place), carbonate etc.Preferred alkoxide catalysis comprises basic metal C
1-C
4Alkoxide such as sodium methylate, potassium ethylate etc.Catalyzer can separate preparation with reaction mixture, maybe can use basic metal such as sodium to generate on the spot.For generating on the spot, the sodium metal in methanol solvate for example preferably, is finished just up to the generation of catalyzer and can be had other reactants.General catalyst consumption is about 5% (mole) of ester reactant.Also can use mixture of catalysts.
Solvent: the organic hydroxylic solvent that is used for R-2 reaction comprises, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, glycerol, 1,2-propylene glycol, 1,3-propylene glycol etc., methyl alcohol is preferred alcoholic solvent, and 1,2-propylene glycol is preferred diol solvent.Also can use the mixture of solvent.
General R-2 reaction conditions: preferably, prepare needed product, make the formation of cyclisation by product, esteramides and color bodies reach minimum degree again simultaneously.The temperature of reaction of using is lower than about 135 ℃, is generally about 40 ℃ to about 100 ℃, is preferably 50 ℃ to 80 ℃, so that reach this purpose, particularly in interrupter method, the reaction times was generally about 0.5-2 hours, even up to 6 hours.In continuous processing, higher slightly temperature is admissible, and residence time this moment can lack.
Following embodiment is to use by the N-polyhydroxy amine of above-mentioned disclosed R-1 prepared in reaction (remove basically and anhydrate) enforcement of R-2 reaction is described, but is not limited thereto.Should be noted that, the reactant in EXAMPLE III and the concentration range of solvent provide the reaction mixture that can be called as " 70% concentration " (for reactant), the mixture of this 70% concentration has reached good result, and this is because obtained the high yield of required polyhydroxy fatty acid amide product apace.Really, all situations show, in 1 hour or be less than 1 hour, this reaction is finished substantially.In the concentration of the reaction mixture of 70% concentration content for handling the condition created easily.Yet,,, even under these higher concentration, also can form less undesirable by product because chromatographic data shows even under 80% and 90% concentration content, also can obtain result preferably.Under higher concentration, the operation of reactive system is difficulty a little, and needs more effective stirring (because their initial thickness) etc., is like this in initial reaction stage at least.In case reaction proceeds to a certain degree, the viscosity of reactive system will reduce, and mixes and hand over easily gradually.
EXAMPLE III
In flask at the bottom of the garden that condenser, drying tube and logical argon gas covering protection are housed, product (9.00g with example I, 0.0461mol, N-methylglucosamine) mixes with the 8.22g anhydrous methanol, the methyl alcohol and the N-methylglucosamine of reaction are heated to reflux temperature, refluxed 15 minutes, add sodium methylate (0.1245g, 0.0023mol Aldrich chemical company) and methyl esters (10.18g, 0.0461mol, Procter ﹠amp; Gamble CE1270 comprises C
12～C
18Fatty acid ester), and reaction continue to reflux 3 hours.Then, under reduced pressure remove methyl alcohol, obtain colourless substantially white product.Because in drying preceding 30 minutes, sampling when 1 hour, 2 hours and 3 hours is not so write down productive rate.Dry sample washs with cold methanol, and it is filtered, and last drying is carried out under vacuum, obtains the 10.99g polyhydroxy fatty acid amide surfactant.
EXAMPLE IV
Under 80% reactant concn content, the institute that is used for synthesizing amide is as follows in steps.
Use is by 84.87g fatty acid methyl ester (source: Procter ﹠amp; Gamble methyl esters CE1270), 75g N-methylglucosamine (from the above embodiments I), 1.04g sodium methylate and total amount are the reaction mixture that 39.96g methyl alcohol (20% (weight) of about reaction mixture) is formed.Reactor comprises the standard circumfluence device is housed, and drying tube, condenser and mechanical stirring blade are housed on this device.In argon gas (backflow), heat N-methylglucosamine/methyl alcohol while stirring, when this solution reach temperature required after, add ester and sodium methoxide catalyst.Reaction mixture is kept and was refluxed 6 hours, finishes substantially at 1.5 hours internal reactions.After removing methyl alcohol, the heavy 105.57g of the product of recovery.Stratographic analysis shows to have only undesirable by product esteramides of trace to exist, and does not have the cyclisation by product that can measure.
EXAMPLE V
Under 90% reactant content, repeat the method for EXAMPLE IV, to carry out the synthesis step of polyhydroxy fatty acid amide, undesirable content of by-products is very low, and reaction in 30 minutes is finished substantially.In another approach, under 70% concentration of reactants, begin to react, but for example in reaction process stripped methanol and reaction proceeded to finish.
Example VI
Use ethanol (99%) and 1,2-propylene glycol (anhydrous basically) to repeat the method for EXAMPLE III respectively, products therefrom is satisfactory.In another approach, will be used for the step of R-2, stripped methanol in entire method as 1,2-propylene glycol solvent.Resulting tensio-active agent/ethylene glycol mixture can be directly used in the detergent composition.
When so disclosing reaction conditions (being included in the amine solvent in present method R-1 step), determine further that also amine/water solvent the mixture that is used for R-1 reaction can also provide additional advantage in R-1 reaction.Specifically, use the formed reaction product of amine/water solvent colourless basically, can at a good pace obtain the productive rate of high product.In reaction product, essentially no reducing sugar, and these reducing sugars can continue to form color in follow-up R-2 reaction.R-1 reaction in blended amine/water capacity agent is as follows.
Example VII A
Use the autoclave of stirring and the method for embodiment H, with the 15g649B catalyzer, 75g glucose powder (Aldrich) and 160ML methyl alcohol are made pulpous state and are used H
2Handle, to remove oxide compound from catalyst surface.Remove methyl alcohol, be lower than under 5 ℃, in glucose/catalyst mixture, add 80ML (52.8g) methylamine, under room temperature, add 22ML water.
In 34 minutes, this reaction mixture is heated to 70 ℃, under this temperature, kept 40 minutes during the hydrogenation.From said reactor, blow out water/methylamine solution (removing catalyzer) in the reaction product by frit, and dry N-methylglucosamine product.
When with blended amine/water solvent, generally using the amine (being preferably methylamine) and the weight ratio of water is about 10: 1 to about 1: 1.Then, as mentioned above, R-1 reaction product of anhydrous basically (preferably be lower than about 1%, more preferably less than about 0.3%, by water weight) can be used in R-2 reaction, so that the preparation polyhydroxy fatty acid amide.
Though front disclosed content has been usually directed to use fatty methyl esters to prepare the N-methyl polyhydroxy amine of N-methylglucosamine etc. and the flux method of fatty acid amide derivant thereof.Self-evident.Also can carry out various variations.Therefore as reducing sugar such as fructose, semi-lactosi, seminose, maltose and lactose and the high glucose maize treacle, height of containing contain the source that fructose maize treacle and height contain sugar such as maltose maize treacle and all can be used for preparing the polyhydroxy amine material (promptly replacing glycosamine) of said reaction.Equally, multiple fat and oil (triglyceride level) can be used for replacing the fatty ester enumerated previously in the present invention.For example fatty and oily, as the fat and the oily source that all can be used as the triglyceride level of present method use of soya-bean oil, oleum gossypii seminis, sunflower oil, butter, lard, Thistle oil, Semen Maydis oil, Canola oil, peanut oil, fish oil, vegetable seed wet goods or its sclerosis (hydrogenation) form.Because comparatively gentle temperature of reaction of the present invention and reaction conditions can obtain having the required product that forms minimum by product.So method of the present invention is particularly useful for making long-chain (as C
18) and the unsaturated fatty acids polyhydroxy amides.When using triglyceride level or long-chain methyl ester, can use the pre-polyhydroxy fatty acid amide surfactant that forms part, so that help to cause the reaction that R-2 forms acid amides as reactant.And, also help to cause R-2 reaction with propylene glycol or glycerol or its preformed monoesters.By storing solidified product (wherein containing a spot of solvent of carrying secretly and reactant) simply, just can improve the productive rate of the tensio-active agent in R-2 step.For example this operation is under 50 ℃, it is shifted out from reactor carried out in several hours.Store in this way obviously is to make back-page unreacted starting raw material continue to form required polyhydroxy fatty acid amide surfactant.So productive rate can be significantly improved, i.e. reaction reaches the degree of highly finishing, and this is significant in large-scale industrial production.
The for example clear above-mentioned all R-1 and the tensio-active agent product of R-2 step of using of following embodiment so that prepare bar composition with method of the present invention, but is not limited to these embodiment.This is because various tensio-active agents, spices and other optional ingredients that soap bar prescription teacher is known all can conventional usage quantity at random be used for this based composition.
Example VII A I
General soap bar is composed as follows:
Composition % (weight)
Fatty acid soaps
*83.75
Alkyl glucose amide
*3.00
NaCl 0.44
Submember (spices etc.) 2.5
Level is weighed
pH 10.25
*Sodium salt with 70/10/20 weight ratio blended ox ester/tristearin/coconut fatty acid.
*Press the blended tallow alkyl N-methyl glucose amide of the method preparation of EXAMPLE III, the carbonatoms of tallow alkyl group wherein is in 12～18 scopes.
Example I X
Said soap content is reduced to 76%, alkyl glucose amide (preparing by EXAMPLE IV) is increased to 10%, carry out modification, obtain softer soap bar thus with soap bar to example VII A I.
Embodiment X
Said soap content is increased to 85%, the content of said alkyl glucose amide tensio-active agent is reduced to 2%, carry out modification, obtain harder soap bar thus with soap bar to example VII A I.
Embodiment XI
Soap/synthetic detergent mixing soap bar is as follows:
Composition % (weight)
Fatty acid soaps
*78.0
Synthetic detergent
*6.0
Glucamide
* *8.0
NaCl/kcl (1: 1 weight) 0.38
Level is weighed
*1: 1 (weight) blended Na/K coconut soap.
*Blended C
14-18Alkyl-sulphate, sodium salt.
* *Blended C
12-C
18Alkyl N-methyl glucose amide (press the foregoing description V disclosed method preparation).
Claims (9)
1. bar composition, it comprises:
(a) the water miscible basically C of 75%-85% (weight)
12-C
18Fatty acid soaps;
(b) polyhydroxy fatty acid amide shown in the following formula of 1%-10% (weight)
R in the formula
1Be C
1-C
4Alkyl, R
2It is straight chain C
7-C
19Alkyl or alkenyl, and Z is by the reducing sugar deutero-in reductive amination process; And
(c) water of 8%-12% (weight).
2. according to the soap bar of claim 1, wherein said fatty acid soaps is sodium salt, sylvite, ammonium salt or alkanol ammonium salts form.
3. according to the soap bar of claim 1, the R in the general formula compound wherein
1It is methyl.
4. according to the soap bar of claim 3, wherein said fatty acid soaps comprises blended C
12-C
18The sodium salt of lipid acid.
5. according to the soap bar of claim 1, it is characterized in that hardness value is lower than 3.
6. according to the soap bar of claim 5, it is characterized in that hardness value is lower than 2.
7. according to the soap bar of claim 2, it comprise 75% to 85% (weight), to have the iodine number scope be 25 to 35 soda soap, said soap bar is characterized in that hardness value is 2 to 2.5.
8. according to the soap bar of claim 1, it also comprises the non-soap of synthetic of maximum 30% (weight), non-polyhydroxy fatty acid amide detergents in addition.
9. according to the soap bar of claim 7, it also comprises the ionogen of 0.2%-0.6% (weight).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64536191A | 1991-01-29 | 1991-01-29 | |
| US645,361 | 1991-01-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065678A CN1065678A (en) | 1992-10-28 |
| CN1031286C true CN1031286C (en) | 1996-03-13 |
Family
ID=24588696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92101447.3A Expired - Fee Related CN1031286C (en) | 1991-01-29 | 1992-01-29 | Improved soap bars |
Country Status (13)
| Country | Link |
|---|---|
| CN (1) | CN1031286C (en) |
| AR (1) | AR244794A1 (en) |
| AU (1) | AU1200692A (en) |
| IE (1) | IE920277A1 (en) |
| MA (1) | MA22404A1 (en) |
| MX (1) | MX9200341A (en) |
| MY (1) | MY108165A (en) |
| NZ (1) | NZ241423A (en) |
| PH (1) | PH30035A (en) |
| PT (1) | PT100070A (en) |
| TR (1) | TR26603A (en) |
| TW (1) | TW214567B (en) |
| WO (1) | WO1992013059A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08503732A (en) * | 1992-11-30 | 1996-04-23 | ザ、プロクター、エンド、ギャンブル、カンパニー | Highly foaming detergent composition containing special soap |
| FR2703993B1 (en) * | 1993-04-15 | 1995-06-09 | Oreal | Cosmetic use of lipophilic derivatives of amino deoxyalditols, cosmetic compositions containing them, and new alkyl carbamates. |
| US5616746A (en) * | 1993-04-15 | 1997-04-01 | L'oreal | Use in cosmetics of lipophilic derivatives of amino deoxyalditols, cosmetic compositions containing them, and novel alkyl carbamates |
| US5510049A (en) * | 1993-09-09 | 1996-04-23 | The Procter & Gamble Company | Bar composition with N-alkoxy or N-aryloxy polyhydroxy fatty acid amide surfactant |
| DE4331297A1 (en) * | 1993-09-15 | 1995-03-16 | Henkel Kgaa | Bar soaps |
| US5910476A (en) * | 1996-07-02 | 1999-06-08 | Henkel Corporation | Abrasive-containing soap bars |
| WO2007017619A1 (en) * | 2005-08-10 | 2007-02-15 | Appaya Raghunath Naik | Detergent formulations based on soap and fatty acid n-methyl glucamide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3312627A (en) * | 1965-09-03 | 1967-04-04 | Procter & Gamble | Toilet bar |
| US3576749A (en) * | 1969-02-06 | 1971-04-27 | Procter & Gamble | Soap toilet bars having improved smear characteristics |
| PT83523B (en) * | 1985-10-29 | 1988-11-30 | Procter & Gamble | PROCESS FOR THE PREPARATION OF A COSMETIC COMPOSITION USING SAUCE OF FATTY ACIDS C8-24 |
| DE3538451A1 (en) * | 1985-10-29 | 1987-05-07 | Sueddeutsche Zucker Ag | Fatty acid amides of amino polyols as non-ionic surfactants |
| DE3711776A1 (en) * | 1987-04-08 | 1988-10-27 | Huels Chemische Werke Ag | USE OF N-POLYHYDROXYALKYL Fatty Acid Amides As Thickeners For Liquid Aqueous Surfactant Systems |
-
1992
- 1992-01-21 AU AU12006/92A patent/AU1200692A/en not_active Abandoned
- 1992-01-21 TW TW081100416A patent/TW214567B/zh active
- 1992-01-21 WO PCT/US1992/000253 patent/WO1992013059A1/en active Application Filing
- 1992-01-24 PH PH43826A patent/PH30035A/en unknown
- 1992-01-27 AR AR92321693A patent/AR244794A1/en active
- 1992-01-28 IE IE027792A patent/IE920277A1/en not_active Application Discontinuation
- 1992-01-28 MX MX9200341A patent/MX9200341A/en unknown
- 1992-01-28 TR TR92/0054A patent/TR26603A/en unknown
- 1992-01-28 MA MA22690A patent/MA22404A1/en unknown
- 1992-01-28 NZ NZ241423A patent/NZ241423A/en unknown
- 1992-01-29 PT PT100070A patent/PT100070A/en not_active Application Discontinuation
- 1992-01-29 CN CN92101447.3A patent/CN1031286C/en not_active Expired - Fee Related
- 1992-01-29 MY MYPI92000137A patent/MY108165A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PT100070A (en) | 1993-06-30 |
| MA22404A1 (en) | 1992-10-01 |
| PH30035A (en) | 1996-11-08 |
| TW214567B (en) | 1993-10-11 |
| NZ241423A (en) | 1995-07-26 |
| TR26603A (en) | 1995-03-15 |
| MX9200341A (en) | 1994-03-31 |
| AU1200692A (en) | 1992-08-27 |
| AR244794A1 (en) | 1993-11-30 |
| CN1065678A (en) | 1992-10-28 |
| MY108165A (en) | 1996-08-30 |
| IE920277A1 (en) | 1992-07-29 |
| WO1992013059A1 (en) | 1992-08-06 |
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