CN1062759A

CN1062759A - The formation solid that makes with the rigid staggered network of carboxylic acid after the neutralization

Info

Publication number: CN1062759A
Application number: CN91111928.0A
Authority: CN
Inventors: M·L·卡彻; J·E·坦纳利; J·B·卡姆登; P·E·维斯特; S·J·包尔斯
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1990-11-26
Filing date: 1991-11-26
Publication date: 1992-07-15
Anticipated expiration: 2006-11-26
Also published as: JPH06503122A; NO931848L; WO1992009679A1; CZ283495B6; EP0559837B1; HK1006179A1; FI932366A0; CZ98793A3; HU9301532D0; IE72087B1; ATE129522T1; DK0559837T3; KR100226393B1; NZ240709A; PT99606A; BR9107125A; CA2095351A1; AR247426A1; HUT76489A; EP0559837A1

Abstract

The invention provides a kind of three-dimensional framework structure of formation solid, it comprises: in and the quite firm staggered-mesh of post crystallization carboxylic acid.On the other hand, the invention provides a kind of by neutralization back carboxylic acid, be more preferably that rigid staggered network by sodium soap fiber constitutes through improved cleansing bars.The preferred cleansing bars of this class can be formulated into and be substantially free of the soap bar goo.Some cleansing bars contains big unexpected water and other liquid of getting of its amount, even and it soaked overnight in water still can be kept its rigidity and superior goo characteristic.

Description

The formation solid that makes with the rigid staggered network of carboxylic acid after the neutralization

The application is the partial continuous application of the U.S. Patent application (sequence number No.07/617827) of submission on November 26 nineteen ninety.

Things such as the shaping solids composition, particularly cleansing bars of carboxylic acid, soap blank, soap bar, synthesis clean soap bar after the present invention relates to neutralize.

The product made from the form of shaping solid, piece and bar is a large amount of.Cleansing bars is known in the prior art.

In the prior art, reported and had the cleansing bars that can reduce the soap bar goo,, authorized the U.S. Patent No. 2,988 of Mills as 1961,6,13,511(be incorporated herein with reference to) a kind of low soap bar that is clamminess disclosed.

The goo of soap bar is also referred to as inert material, is when the surface forms when under water with cleansing bars soft solid or mashed prod, and that this is thought by the human consumer is dirty, do not have magnetism and uneconomic.

It is a large amount of forming the product that makes with shaping solid, piece and bar.For example, 1986,8,19 U.S. Patent No.s 4,606,839 of authorizing Harding disclose the human body cleansing bars of some high-moisture and low goo.Harding has used coconut/and palm-kernel oil.

As long as people check the human body cleansing bars that uses and just will appreciate that the improvement cleansing bars that still need have only seldom or not have goo in the bathroom.

At 1940Journal of American Chemical Society(Vol63, pp1990-1993) in, people such as L.Marton have reported the formation of the rigidity soap coagulum fiber of sodium laurate.This report does not relate to the coagulative purposes of soap.By shaping solid defined herein is not the disclosed mistakes of people such as Marton.

Japanese Patent J5 7030-798(1980,7,30) disclose transparent solid soap bar that form or that be molded as, the lipid acid that wherein constitutes this soap component is Semen Myristicae, palm and stearic acid.90%(weight at least in the described transparent soap), the lipid acid that constitutes this soap component is tetradecanoic acid, palmitinic acid and stearic acid.The product of being reported is a kind of have good foaming and curing performance, and the transparent solid soap low to people's skin irritation.Do not show at the method for Japanese Patent J5 7030-798 illustrated and clear bar soap composition and to contain synthetic surfactant.

Contain higher amount (15-40%) moisture (when particularly having multiple synthetic surfactant to exist), non-solid and the soft solid of hygroscopic surface promoting agent and/or higher amount, greasy solid as water-soluble polyol and hydrocarbon system, non-thickness soap bar also is difficult to prepare.

The invention provides a kind of shaping solid three-dimensional framework structure, during it comprises and the post crystallization carboxylic acid, quite firm staggered-mesh, on the other hand, the invention provides a kind of by described skeleton structure, the i.e. rigid staggered network of neutralization back carboxylic acid, be preferably improvement that sodium soap fiber forms cleansing bars.Some cleansing bars contains big the beat all water of its amount and other liquid, and even when with its soaked overnight in water, still keep the performance of its rigidity and good goo aspect.

Fig. 1-8 shows the enlarged view of soap bar sample of the present invention.Fig. 9 and 10 shows the enlarged view of two kinds of different conventional soap bars.

The preparation of SEM (SEM) sample comprises that simply pressurization makes the shaped solid fragmentation and obtains fresh surface for inspection purpose. The size (using slasher) of the sample after the fragmentation is reduced to the rectangle that thickness is about 10mm * 15mm of about 5mm. With the silver coating adhesive this sample is placed in the SEM short column of aluminium. In Pelco sputter coating machine with the gold/palladium of 300 dusts on the sample plating of placing. Sample being stood a period of time before plating is enough to remove for guaranteeing the application of vacuum of the necessary soap bar moisture content of coating quality. Behind the plating, sample is moved on to the SEM chamber and detect to observe skeleton (arbor) structure with Hitachi Model S570 ESEM under the SEM of standard condition.

Fig. 1 and 2 is the copy of the skeleton arbor structure photo of high power amplification, and this structure comprises in the extended and the rigid staggered network of back carboxylic acid crystalline fibers.Or rather, be to amplify 5000X and 2500X extended C doubly respectively among Fig. 1 and 2 ₁₂Sodium soap fiber.The structure of Fig. 1 and 2 is the soap with 5%, and 94% water and 1% sodium-chlor make.Referring to the embodiment in this paper table 7 10.Notice that bigger fiber can be by less fibrous in the staggered-mesh.Be also noted that " space " space.Referring to Fig. 2.

Fig. 3,4 and 5 is the sodium C with 25% ₁₂The copy of the skeleton structure photo that soap, 74% water and 1% sodium-chlor make, the magnification with 3000X, 5000X and 1000X illustrates crystalline fibers shape structure respectively.

Fig. 6 be with 20% 1, the copy of the skeleton structure photo that the disodium salt of 12-dodecandioic acid makes.With the 2000X magnification this crystalline fibers shape structure is shown.Referring to embodiment 26.

Fig. 7 illustrates with the magnification of 1500X and contains in the crystalline lithium and C ₁₄The copy of the skeleton of carboxylic acid network (arbor) structure photo.Referring to embodiment 27.

Fig. 8 is the copy of cleansing bars (embodiment 1 hereinafter) photo, and it comprises the C through applying _14-16Sodium soap fiber.These fibers are to apply and/or miscellaneous with it with other component.Magnification is 1500X.

Fig. 9 illustrates a kind of commercially available IVORY that makes with sodium/potassium coconut/tallow soap with the magnification of 1000X

The sample of refrigerator soap bar.Air in the IVORY soap bar makes its energy floating.

Figure 10 shows a kind of commercially available NEUTROGENA with the magnification of 1500X

The sample of transparent soap bar.

In Fig. 1 and 2, earlier these samples are melted cooling again on glass slide then on the thermometal plate.Other sample, Fig. 3-10, be primary shaping solid structure sample or by this paper the sample of conventional soap bar of old method preparation.

The invention provides a kind of have two-phase or heterogenetic shaping solid.One is the crystallization skeleton structure mutually, and this structure comprises the staggered open three-dimensional network of elongation crystalline rigidity of neutralization back carboxylic acid.In addition be substantially mutually a kind of in 25 ℃ for the soft or flowable water that contains.

Or rather, this skeleton structure is the list that neutralized and/or the quite firm staggered open three-dimensional network of elongation crystalline of dicarboxylic acid.

Term: skeleton structure (skeleton structure), skeleton shape structure (skeletal structure), arbor (core) and skeleton frame (skeleton frame) often are used alternatingly in this article.

Term used herein " shaping solid " comprises such as forms such as bar, pieces.Term used herein " bar " except that other has special explanation, comprises above-mentioned identical implication.

Term used herein " network " is meant the staggered crystallization back bone network of being seen when observing that has space or opening under scanning electron microscope is amplified.

On the other hand, the invention provides a kind of improved cleansing bars of forming by described skeleton structure.Some shaping solid is the solid of cleansing bars form, and these cleansing bars contain and exceed people to give material ground high, comprise water, the described water of other liquid and soft material.Although a large amount of waters that contains is arranged, preferred soap bar of the present invention even when its soaked overnight in water is still kept its rigidity and the good performance relevant with goo.When being not limited to any theory, the shaping solid kind that comprises these phases is similar to firmer wet sponge.

Crystallization phases comprises staggered platelet and/or fibrous crystal, and with fibrous be good.Preferably, described fiber is made of soda soap.When even the staggered-mesh of described fiber and/or platelet has the soft material of high-content water or other, even when making it in water, still can give this three-dimensional structure with intensity during soaked overnight.The intensity of the skeleton structure solid hardness that can be shaped is done indirect measurement, and promptly the pin of weighing with standard is worn hardness tester probe (standard weighted pentrometer probe) and determined that this solid penetration resistance makes this mensuration.(Bar Hardness Test) then knows its details referring to following soap bar hardness test.Skeleton structure is a kind of structure that enough rigidity is arranged, and it can make the value of penetrating of the thick or thicker cleansing bars sample of 20mm reach the about 12mm of about 0mm-, is preferably the about 10mm of about 1mm-, is more preferred from the about 8mm of about 3mm-.Because crystalline size and other characteristic, soap bar of the present invention are different from conventional transparent soap bar.Form the crystal of staggered-mesh structure of the present invention or the size of brilliant bundle and be advisable, thereby be that diameter or length all should be greater than 400nm can make optical diffraction.On the contrary, conventional transparent soap bar has transparency owing to crystal diameter or length less than white light wavelength (the white light wavelength is approximately greater than 400nm).Thereby can not diffracted ray.

The soap bar (shaping solid) that contains cross structure of the present invention is in case after forming, when it has born as the U.S. Patent No. 4 people such as Small, 812,253 or people's such as Medcalf U.S. Patent No. 4,820, in the disclosed conventional mold pressing soap bar manufacturing process during used those fracture mechanical forces, then lose its rigidity immediately in 447.This is because less sheet is sheared and be broken into to crushing mechanism power with rigid skeleton structure.Thereby, when soap bar of the present invention is sheared, just form much soft soap bar.

Otherwise when mold pressing or again during the conventional soap bar of mold pressing finished product, this conventional soap bar through mold pressing again is still stone.Desire to know the details of this respect, referring to embodiment 28 and table 12.

This skeleton structure has many " space " zone, and the soft and/or liquid water that contains is being filled in these zones.The present invention is surprising, and part is, the physicals of soap bar depends on crystallization staggered-mesh structure as the hardness of soap bar and goo seldom, basically even also be like this when other accounts for the main part of this existing material mutually.In conventional soap bar, many components can influence the comprehensive physicals of this soap bar, because these components or changed the phase and the structure of soap, or changed the component of synthetic surfactant, and the physicals of soap bar is mainly determined by them.Two-phase or heterogenetic have changed colloidal structure sharp in conjunction with (as the soap and the aqueous solution), thereby have changed the physicals of conventional soap bar.

Therefore, compare with the present invention, conventional soap bar is in the type that can mix the soft phase material in the soap bar, and content and composition aspect are subjected to more restriction.These comprise fluent material most or that can flow mutually, or the material softer than the lowest hardness of qualified soap bar.These comprise the aqueous solution mutually, the mesomorphic phase of being made up of water and tensio-active agent, polymkeric substance; The crystallization phases that particularly contains tensio-active agent; Especially the crystallization phases that contains the hygroscopic surface promoting agent, these promoting agents are tending towards deliquescing or become sticky thick when mixing with water or other liquid phase (comprising water-soluble organic compounds, as propylene glycol and glycerol), hydrophobic material (as mineral oil, liquid triglyceride) or soft hydrophobic material (as vaseline, low melt point paraffin and low melting point tri-glyceride).

Say that on physics all these mutually all can be characterized by flowable liquid, or soft to described standard above weigh pin wear the hardness tester probe can everywhere it be penetrated through the thick sample of 12mm.Comprise selectively that in structure of the present invention these are mutually and without detriment to this staggered-mesh structure and performance that some is desired.

The present invention is a kind of shaping solid that comprises skeleton structure, and this structure is that neutralization back list and/or dicarboxylic acid elongate firmer the interlocking of crystalline, open three-dimensional network.

Preferable embodiment is a cleansing soap, and it comprises at least 2 phases: (1) is about the water that contains of 12mm to the dark sample value of penetrating of 12mm; The described water that contains is soft or flowable; (2) comprise the rigidity crystallization phases of rigidity crystallization phases skeleton structure, this skeleton structure comprises neutralization back list and/or dicarboxylic acid elongates staggered, the open three-dimensional network of crystalline; The described cleansing bars that wherein comprises described rigidity crystallization phases skeleton structure and described water is the about 12mm of 0-to the value of penetrating of the dark sample of 25mm, the wherein said value of penetrating is in 25 ℃, wear with the standards of the 247 grams pin of weighing that the hardness tester probe records, this probe has a taper pin that links to each other with the bar of 9 inches (22.9cm), weigh 47 grams, said masthead add 200g heavy and make gross weight be described 247 the gram, described taper pin top is 19/32 inch (1.51cm), and needle point is 1/32 inch (0.08cm).

The carboxylic acid system of above-mentioned cleansing bars after described neutralization is preferable when being selected from the thing group of being made up of following material: lithium and/or sodium neutral monocarboxylic acid (soap) and/or dicarboxylic acid; And composition thereof; Wherein said monocarboxylic acid contains fatty alkyl (alkylidene group) chain of about 24 carbon atoms of the 12-that has an appointment; Wherein said dicarboxylic acid contains fatty alkyl (alkylidene group) chain of about 18 carbon atoms of the 12-that has an appointment; Wherein contain saturated alkyl (alkylidene group) chain at least about 80% described carboxylic acid; Wherein said rigidity crystallization phases skeleton structure accounts for described cleansing bars volume about more than 3% to about 75%; Wherein said neutralization back carboxylic acid accounts for about more than 5%-Yue 75%; Wherein cleansing bars contain described cleansing bars weight about 15%-approximately less than 94% water.

Above-mentioned cleansing bars at least 80%, is preferably when being preferably 90% carboxylic acid and having following general formula:

Wherein:

a+b＝8-20

A, b each=0-20

X=H, OR,

, R, or these groups exist simultaneously

R=C ₁-C ₃Alkyl, H, or these groups exist simultaneously

M=Na, Li or its exist simultaneously.

Above-mentioned cleansing bars is at described a+b=10-16; Described a, b each=0-16; Described X=H, OR; R=H; And it is then better during M=Na.

Above-mentioned cleansing bars is that the fibrous sodium fatty acid soaps of single segmental is formed at described extended crystal system by the described saturated fatty alkyl chain at least about 25%; Wherein said soap bar contains: the described soda soap of about 15%-about 75%; The wherein said ratio of carboxylic acid and the soap of neutralization (free) is about 1, and: 2-is about 0, and promptly to be not more than soap in this prescription be particularly preferred in heavy 50% o'clock to free fatty acids.

Contain described soda soap and water at described soap bar; About 2%-about 60% be selected from synthetic surfactant in the thing group of forming by following material the time above-mentioned cleansing bars be preferable: alkyl-sulphate; alkane sulfonate; alkyl glycerol ether sulfonate; acyl sarcosinate; methyl-acyl taurine salt; linear alkylbenzene sulfonate; the N-acyl glutamate; alkyl glucoside; the α sulfo fatty acid ester; acyl isethinate; alkyl sulfo succinate; the alkyl ether carboxy acid salt; the alkylphosphonic ester; the ethoxylated alkyl phosphate ester; methyl glucose ester; the protein condenses; alkyl amine oxide; alkyl betaine; alkyl Sultaines; the sulfated alkyl ether that contains 1-12 ethoxy group; and their mixture, wherein said tensio-active agent contains C ₈-C ₂₂Alkyl chain.

When described synthetic surfactant was water absorbability, above-mentioned cleansing bars was preferable; Described hygroscopic surface promoting agent is defined as: under 26 ℃ and 80% relative humidity, be absorbed as the tensio-active agent of 20% water of its dry weight at least in three days in water, wherein said soap bar is non-swelling.

At described hygroscopic surface promoting agent is that above-mentioned cleansing bars is preferable when being selected from the thing group of being made up of with their mixture α sulfo-fatty acid fat, alkyl-sulphate, alkyl ether carboxylate, alkyl betaine, alkyl Sultaines, alkyl amine oxide, sulfated alkyl ether.

Ratio at described water and described soap is about 1: about 5: 1 of 1-; Described water amount is about 60% for about 25%-, and wherein said aliphatic alkyl chain is C ₁₄-C ₂₂And the content at soap described in the described soap bar is about 15%-about 35%; Be saturated wherein at least about 85% described alkyl chain; The wherein said not carboxylic acid of neutralization (dissociating) and the weight ratio of described soap are about 1: 4-0; The content of wherein said synthetic surfactant is about 4%-about 25% of this soap bar weight; and described tensio-active agent is that above-mentioned cleansing bars is preferable: hydroxyethyl acyl sodium sulfonate, acyl group sodium sarcosinate, α sulfo-fatty acid sodium ester, paraffinic hydrocarbons sodium sulfonate, sodium alkylether sulphate, sodium alkyl sulfate, linear alkylbenzene sulphonic acid, alkyl betaine, alkyl Sultaines, trialkylamine oxides when being selected from the thing group of being made up of following compounds.

When the ratio of described water and soap is about 1.5: about 2: 1 of 1-; Described not in and the ratio of carboxylic acid (dissociating) and described soap be about 1: 6-0; The content of described water is about 30%-about 45%; Described aliphatic alkyl chain is about C ₁₄-C ₁₈; Be saturated wherein at least about 95% described alkyl chain; Described soap content is about 15%-about 30%; Described synthetic surfactant is about 16% o'clock of about 8%-, and above-mentioned cleansing bars is preferable.

When described soap bar contained hydrophobic material in the thing group that being selected from of about 0.1%-about 40% be made up of following material, above-mentioned cleansing bars was preferable: the triglyceride level of Microcrystalline Wax, vaseline, carnauba wax, palm wax, gama wax, sugar-cane wax, plant derivation, beeswax, spermaceti, lanolin, haze tallow, lac are cured, above-mentioned cleansing bars is preferably during triglyceride level, montar, ozocerite, ceresin and fischer-tropsch (Fischer-Tropsh) synthetic wax of animal derived.

Above-mentioned cleansing bars contains about 2%-about 35% at described soap bar, and is better when being selected from the described hydrophobic material of the thing group that is made of following material: vaseline and wax, and described vaseline and wax, and composition thereof melt at about 49 ℃ (120 °F)-Yue 85 ℃ (185 °F).

Above-mentioned cleansing bars is preferable when described soap bar contains the paraffin of the heavy about 5%-of soap bar about 25%.

The solubleness that contains about 1%-about 50% when described soap bar be in 10 parts water molten at least 5 parts non-volatile, can water-soluble, nonionic organic substance, and wherein said water-soluble nonionic organic substance system is selected from by the polyvalent alcohol of array structure down:

R wherein ₁=H, C ₁-C ₄; R ₂=H, CH ₃; And n=1-200;

C ₂-C ₁₀Alkane diol; Sorbyl alcohol; Glycerol, carbohydrate, sugar derivatives; Urea; And formula is (HOCH ₂CH ₂) _xNH _yThanomin (x=1-3 wherein; Y=0-2; During the thing group x+y=3) and composition thereof formed, above-mentioned cleansing soap is preferable.

Above-mentioned cleansing bars is preferable when described soap bar contains described non-volatile, water-soluble, the nonionic organism of about 2%-about 40%.

Above-mentioned cleansing bars is at described non-volatile, water-soluble, about 5%-about 20% that the nonionic organism is this soap bar weight; And wherein said organic substance system is preferable when being selected from the thing group of being formed by propylene glycol, glycerol, sucrose, urea, with its mixture.

Above-mentioned cleansing bars contains described soda soap at described soap, and following other composition of described water and described synthetic surfactant and about 0.1%-about 70% is for better, and these compositions are selected from the thing group of being made up of following material:

The described potash soap of about 1%-about 10%;

The described magnesium soap of about 1%-about 35%;

The described calcium soap of about 1%-about 35%;

The triethanol ammonium soap of about 1%-about 15%;

About 1%-about 60% is selected from trickle water-insoluble material in the thing group of being made up of lime carbonate and talcum;

The about 20% polymerization skin feel auxiliary agent of about 0.1%-, wherein said polymerization skin feel auxiliary agent are to be selected from by cationic polysaccharides, are preferably the cationic guar gum of molecular weight 1000-3000000; Positively charged ion polyalkyleneimine, oxyethyl group polyalkyleneimine and poly-[N-[-3-(Dimethyl Ammonium) propyl group]-N '-[3-vinyloxy group ethylene ammonium methyl) propyl group] urea dichloride], silica alkanamine and silicone liquid, JR polymkeric substance, Celquat

The thing group of being formed.

The alumino-silicate clays of about 0.5%-about 25% and/or other clay, wherein said silico-aluminate and clay system be selected from by zeolite, kaolin, kaolinite, montmorillonite, attapulgite, illite, wilkinite, halloysite, and the thing group formed of ripe clay in;

About 50% salt of about 1%-and salt hydrate, and composition thereof, wherein said salt and salt hydrate contain and are selected from sodium, potassium, magnesium, calcium, aluminium, lithium, ammonium, the monoethanolamine ammonium, the positively charged ion of the material in the thing group that di-alcohol ammonium and triethanol ammonium are formed, and wherein said salt and salt hydrate are selected from muriate, bromide, vitriol, metasilicate, orthophosphoric acid salt, pyrophosphate salt, polyphosphate, metaborate, tetraborate, carbonate, supercarbonate, hydrophosphate, sulfuric acid-methyl esters and 6 or be lower than the list of 6 carbon atoms and thing group that polycarboxylate is formed in the negatively charged ion of material.

Above-mentioned cleansing bars comprises platelet in described extended crystal, and wherein said soap system by in the lithium and monocarboxylic acid then preferable when forming.

Above-mentioned cleansing bars is fibrous at described extended crystal, and the dicarboxylic acid that wherein is neutralized is 1, and the equal 20%-about 70% that the disodium salt of 12-dodecandioic acid, the wherein said dicarboxylate that is neutralized account for described soap bar weight is for better.

The preferred approach for preparing this soap bar

The method for preparing above-mentioned cleansing bars of the present invention may further comprise the steps:

I, a kind of weight percent that accounts for of formation are the water of about 15%-about 94% and the described moisture melt liquid of carboxylic acid afterwards that neutralizes of about 6%-about 75%;

II, described melt liquid is injected the soap bar shaping die;

III, through the cooling described melt liquid crystallization result through molding is obtained described cleansing bars.

Aforesaid method is preferably: with the neutralization and make this moisture melt liquid under the temperature of about 50 ℃ (120)-95 ℃ (205) under stirring of the aqueous mixture of described carboxylic acid and sodium hydroxide or lithium hydroxide.

Aforesaid method is the about 15%(weight of about 2%-of described soap bar preferably) be a kind of " crystallization reinforcement salt ", this salt system is selected from the thing group that is made of the sodium of sulfuric acid, muriate, acetate and citric acid or lithium salts and composition thereof.

Aforesaid method preferably, described moisture melt liquid water contains the soluble additive that adds of about 2%-about 40%, this auxiliary agent system is selected from the thing group that following material forms:

(a) non-volatile, water-soluble nonionic organic solvent, this solvent system is selected from the thing group of being made up of following material:

Structural formula is

Polyvalent alcohol, R wherein ₁=H, C ₁-C ₄; R ₂=H, CH ₃; And n=1-200; C ₂-C ₁₀Alkane diol; Sorbyl alcohol; Glycerol; Carbohydrate; Sugar derivatives; Urea; And general formula is (HOCH ₂CH ₂) _xNH _yThanomin, x=1-3 wherein; Y=0-2; X+y=3;

(b) alcohols of 1-5 carbon atom;

(c) be selected from by the synthetic surfactant in the following material constituent group: alkyl-sulphate, alkane sulfonate, alkyl glycerol ether sulfonate, anionic acyl sarcosinates, methyl-acyl taurine salt, linear alkylbenzene sulfonate, the N-acyl glutamate, alkyl glucoside, the α sulfo fatty acid ester, acyl isethinate, alkyl sulfo succinate, the alkyl ether carboxy acid salt, the alkylphosphonic ester, the ethoxylated alkyl phosphate ester, methyl glucose ester, the protein condenses, alkyl amine oxide, alkyl betaine, alkyl Sultaines, the sulfated alkyl ether that contains 1-12 oxyethyl group with and composition thereof; Wherein said tensio-active agent contains C ₈-C ₂₂Alkylidene chain;

And their mixture;

The wherein said soluble additive that adds is to add for amount that raising is dissolved in the carboxylic acid after the described neutralization of the described continuous fusion aqueous phase in the step I.

Aforesaid method is better when described water contains the water of the about 20%-of described water weight about 100%.

During carboxylic acid after described rigidity crystallization phases contains the described neutralization of about 75%-about 100% of described crystallization phases weight, aforesaid method is better.

When the penetrating value to described 25mm soap bar sample of described soap bar was the about 9mm of about 3mm-, aforesaid method was better.

Described soap bar contains droplet or the non-carboxylic acid phase times of crystalline miscellaneous such as being selected from wax, vaseline, clay, and aforesaid method is better.

Highly preferred embodiment of the present invention is: a kind of human body cleansing bars composition that comprises extended soda soap crystalline rigidity crystallization staggered-mesh; Described soap bar contains: about 15%-'s about 50%, the fatty acid sodium soap of being made up of the satisfied fatty alkylidene chain with 12-24 carbon atom (the described saturated fatty alkylidene chain at least about 25% is the strand section) that is about 50% at least; The water of about 15%-about 60%; The synthetic surfactant of moisture absorption and the about 60%(weight of about 2%-) when wherein said moisture absorption synthetic surfactant system is selected from 26 ℃, adsorbed the tensio-active agent of about 20% water of its dry weight in three days in water under 80% the relative humidity.

When the tensio-active agent of described moisture absorption system was selected from the thing group that following material constitutes, above-mentioned highly preferred human body cleansing bars was then better: α sulfo fatty acid ester, alkyl-sulphate, alkyl ether carboxy acid salt, alkyl betaine, alkyl Sultaines, alkyl amine oxide, sulfated alkyl ether and their mixture.

When described soap bar contains the salt of about 0.5%-about 40% and/or the hydrate of salt, and they are when being selected from the thing group of being made up of following material, and this highly preferred human body cleansing bars is then better: the mixable salt of sodium-chlor, sodium sulfate, Sodium phosphate dibasic, trisodium phosphate, sodium tetraborate, sodium acetate, Trisodium Citrate and other mineral acid and short chain organic acid.

A kind of highly preferred soap bar contains: the arbor structure of sodium soap fiber, water, soft synthetic surfactant, the various combination of the agent of soap bar appearance stablity, skin soft additive and other cleansing bars assistant agent.The preferred soap bar of this class can be made into and the result is substantially free of the soap bar goo.

Some preferred soap bar of the present invention comprises: the staggered-mesh of the fibrous arbor of carboxylic acid after a kind of inflexible, the neutralization, this arbor is made of fatty acid sodium soap basically, and this soda soap is made up of the aliphatic alkyl chain of the satisfied 12-24 of having carbon atom of 50% at least.Be preferably, the said saturated alkyl chain at least about 25% is single segmental chain.

Some composition of the present invention comprises above-mentioned moisture or water-free rigidity network.These compositions must water or with another proper solvent system formation.These goods can be made with big water gaging, and the water content in this end article can reduce to about 1% or 2%.

Yet the special advantage of some structure described herein is the integrity that they can not lose network through dehydration.Some solid that preferably is shaped can be through dehydration and its outside dimension does not have noticeable change.Although other soap bar is keeping its three-dimensional configuration but to shrink.Some soap bar of this paper has not because of dehydration destructive excellent specific property.

Complicated soap bar of the present invention comprises the skeleton structure that contains other fatty acid salt, and these salt systems are selected from potassium, magnesium, triethanol ammonium and/or the calcium soap that is used for the sodium of selecting content and/or lithium soap combination.Complicated cleansing bars can contain the big synthetic surfactant that gets beat all water, gentleness of its amount, the agent of soap bar appearance stablity, skin soft additive and other cleansing bars assistant agent, but and they are soft and have fabulous low goo characteristic.

Table 1-3 shows the preferable soap bar that some makes with the sodium salt of aliphatic carboxylic acid (FA) soap.

Removing other has special explanation, and the per-cent of this paper, ratio and part are all in composition total weight.Removing other has special explanation, and these all content and scope are approximation.

Table 1

Preferable soap bar, chain length and content

Preferable better the best

Water-content 15-94% 25-60% 30-45%

Water: the ratio of soap 0.7: 11: 1-5: 1 1.5: 1-2: 1

FA chain length C _12-24C _14-22C _14-18

FA soap amount 6-50% 15-35% 15-30% in total prescription

Whole high value and low values need not be shown in table 1.For example some soda soap through selecting can use by its content up to about 75%.Therefore, this scope is about 5%-about 75%.Between positively charged ion and the positively charged ion etc., and this preferable content is different with ratio between monocarboxylic acid and the poly carboxylic acid.

Soap bar shown in the table 1 is to make with specified water-content, but can reduce in the final soap bar water-content with obtain containing reduced water-content or even seldom or anhydrous soap bar.The preferable content of water is about 20%-about 80% of soap bar weight.

Following table 2 shows some preferable content of single FA segmental soap.Table 3 shows some the preferable content of the unsaturation FA among the FA used in each composition of the present invention.Some preferred compositional only contains seldom or does not contain the short chain FA of 10 or carbon atom still less.Term used herein " soap ", " lipid acid (FA) salt " and " monocarboxylate " can be used alternatingly sometimes.Because more easily explanation, so and be that preferable embodiment is used " soap ".

Table 2

(total fiber shape soap content) strand section soap %

Preferable better the best

C _12-2425-100% 50-100% 25-100%

Table 3

Unsaturated or low (C ₁₀Or littler) total % of chain length soap

General preferable better

C ₁₂0-15% 0-5% 0-1%

C _14-240-50% 0-10% 0-1%

Listed high value and the low value of preferable optional member of some key of the complicated bar composition of the present invention in the table 4.Arbor structure for basic preferable soap bar does not have these compositions basically.The Schwellenwert of each optional member is 0.Some preferable soap bar can contain total amount and mostly be these compositions of about 70% most for about 0.1%-.The meaning is that most soap bar can contain other a large amount of compositions except that soda soap and water.The value of listing in the table 4 is exclusively used in explanation and contains greater than the soda soap through selecting of about 5%-about 75% and the soap bar of other composition.

Should be understood that, can be only with lithium soap or only make solid shape with the poly carboxylic acid after neutralizing, but what can give material is with different by soda soap fixed content and scope.

Table 4

The height of other compositions and low %(weight in the more complicated soda soap bar)

Preferable better the best

Neutralization back dicarboxylic acid 1-40% 2-30% 5-25%

Lithium " soap " 1-40% 2-30% 5-25%

Potash soap 1-10% 2-10% 5-8%

Magnesium or calcium soap 1-35% 1-12% 3-8%

Triethanol ammonium soap 1-15% 2-15% 5-10%

Synthetic surfactant 1-60% 4-25% 8-16%

The hydrate 0.5-50% 1-25% 2-15% of other salts and salt

Non-volatile water-soluble nonionic organism 1.0-50% 2-40% 5-20%

The gentle toughener 0.1-20% of polymerization 0.25-10% 1-5%

Wax 0.1-40% 2-35% 3-10%

The water-insoluble matter 1-60% 4-25% 8-16% that other are fine

Silico-aluminate/clay 0.5-25% 1-10% 3-8%

The soap of practicality of the present invention can be identical alkyl chain length, promptly is selected from those of 12 to 24 carbon atoms listing in the table 2.Identical chain length is applicable to other non-soda soaps that use in the soap bar of the present invention.

Soda soap content better is to be at least about 50% of soap in the soap bar.

The content of potash soap and/or triethanol ammonium soap should not surpass 1/2nd of soda soap content, be preferably 1/3rd, and preferably less than 1/4th, and the content of magnesium soap should not surpass the about 1/3rd of soda soap content, better less than 1/4th of about soda soap content.

The total amount of other soaps except lithium soap, better should not surpass 1/2nd of soda soap, better is no more than 1/3rd.

The synthetic detergent composition of bar composition of the present invention can be appointed as from negatively charged ion, nonionic, both sexes and zwitterionic synthetic detergent.Can use low and high the foaming and high and low water solubility tensio-active agent in the bar composition of the present invention.

Be suitable for synthetic detergent example that the present invention uses and be being disclosed in United States Patent (USP) NO.3351558(1967 and November 7 authorized Zimmerer) 6 hurdles 70 walk to those in 7 hurdles, 74 row, this patent in conjunction with people this paper for participate-reform.

Example comprises the water-soluble salt of organic acid, sulfonic acid and aliphatic sulfate, and the water-soluble salt of organosulfur acid-respons product just, this product have molecular structure to be the alkyl of 10-22 carbon atom and to be selected from the group of being made up of sulfonic acid and sulfate group.

Significant especially synthetic sulfate detergent normally has the solid alkali metal salt of the positive structure uncle aliphatic alcohol sulfate of 10-22 carbon atom.Therefore, the present invention can use the sodium and the sylvite of the alkylsurfuric acid that is obtained by the blended higher alcohols, and above-mentioned higher alcohols is by reduction Tallow, beef or spendable other coconut class oil deutero-of reduction Oleum Cocois, plam oil, stearine oil, palm-kernel oil, babassu oil or this paper.

Other aliphatic sulfates applicatory comprise the water-soluble salt with the polyvalent alcohol sulfuric ester of the incomplete esterification of carboxylic acid of high molecular formation soap.These synthetic detergents comprise the water-soluble alkali metal salts of high molecular weight fatty acid direactive glyceride sulfuric ester, as 1, the sodium of 2-hydroxy propane-3-sulfuric ester coco-nut oil fatty acid monoesters and sylvite, single myristyl ethylidene glycol sodium sulfate and potassium and single lauroyl Glycerol dimer sodium sulfate and potassium.

The present invention also uses synthetic surfactant and other optional materials of using in conventional cleaning product.In fact, some composition, as some moisture absorption synthetic surfactant of using and be difficult to mix in the common cleaning soap slab with liquid state be very compatible in soap bar of the present invention.Like this, basically, all known synthetic surfactants that are used in the cleaning product all are useful in the present composition.The patent documentation full disclosure of cleaning product synthetic surfactant.Some preferred surfactant and other cleaning product compositions are disclosed in the following document:

Patent No. NO. date of grant contriver

People such as 4,061,602 12/1977 Oberstar

4234464??11/1980??Morshauser

People such as 4,472,297 9/1984 Bolich

People such as 4,491,539 1/1985 Hoskins

4540507??9/1985??Grollier

4565647??1/1986??Llenado

People such as 4,673,525 6/1987 Small

4704224??11/1987??Saud

4,788,006 11/1988 Bolich, Jr. waits the people

People such as 4,812,253 3/1989 Small

People such as 4,820,447 4/1989 Medcalf

People such as 4,906,459 3/1990 Cobb

People such as 4,923,635 5/1990 Simion

People such as 4,954,282 9/1990 Rys

Above-mentioned all these patents all supply participate-reform in conjunction with people this paper.Some preferred synthetic surfactant is shown in this paper embodiment.Soap bar appearance stability, whipability, detergency and the mildness of preferable synthetic surfactant system have been indicated selectively.

It should be noted that the tensio-active agent mildness can measure by the skin barrier rupture test, this test is used for the pungency of test surfaces promoting agent.In this test, tensio-active agent is gentleer, and skin barrier destroys fewer.The destruction of skin barrier by radiolabeled water ( ³H-H ₂O) relative quantity is measured, and this radio-labeling water is entered by skin appearance by testing liquid and oozes out in the physiological buffer contained in the sap cavity.This test is disclosed in J.Invest.Dermatol.(T.J.Franz, 1975,64, PP190-195) and people such as United States Patent (USP) NO.4673525(Small, on June 16th, 1987 authorized) in, be incorporated herein for referencely, they disclose the surfactant based soap-synthetic bar of mild alkyl glyceryl ether sulfonate (AGS) that contains " standard " alkyl glyceryl ether sulfonate mixture.The skin barrier rupture test is used for selecting gentle tensio-active agent.Some mild synthetic surfactants are disclosed in people's patents such as people's patents such as above-mentioned Small and Rvs.In embodiments of the present invention, some particular instances of preferred surfactant have been used.

The example that detergent surfactant, mild tensio-active agent are strengthened in good foaming has, for example sodium lauroyl sareosine, alkyl glyceryl ether sulfonate, sulfonated fatty ester, paraffin sulfonate and alpha-sulfonated fatty acid.

The example of many other tensio-active agents is disclosed in and is incorporated herein in the patent of participate-reform.They comprise the mixture of other alkyl-sulphates, anionic acyl sarcosinates, methyl-acyl taurine salt, N-acyl glutamate, acyl isethinate, alkyl sulfo succinate, alkylphosphonic ester, ethoxylated alkyl phosphate ester, trideceth vitriol, protein condenses, ethoxylated alkyl sulfates and alkyl amine oxide, trimethyl-glycine, Sultaines and the mixture of above-claimed cpd.This tensio-active agent also comprises the lauryl ether sulfate of the sulfated alkyl ether that contains 1-12 oxyethyl group, particularly ammonium and sodium.

The alkyl chain of these other tensio-active agents is C ₈-C ₂₂, be preferably C ₁₀-C ₁₈Alkyl glycoside and methyl glucose ester are preferred gentle nonionogenic tensides, and it can mix with other gentle negatively charged ion or amphoterics in the present composition.The alkyl poly glucoside washing composition is useful suds booster.Alkyl can change to about 22 from 8, and the glycoside units of each molecule can change to about 5 from about 1.1, with suitable balance between the hydrophilic and hydrophobic part that molecule is provided.Be preferably, the about 1.1-2.7 of combination average glycosidation degree, preferable about 1.2-2.5, C ₈-C ₁₈, be preferably C ₁₂-C ₁₆Alkylpolyglycosides.

The sulfonated ester of aliphatic ester preferably,, wherein the carboxylic acid chain length is C ₈-C ₂₂, be preferably C ₁₂-C ₁₈; Ester alcohol chain length is C ₁-C ₆They comprise alpha-sulfo methyl sodium laurate, alpha-sulfo methyl coconut acid sodium and alpha-sulfo methyl animal resin acid sodium.

The amine oxide washing composition is good suds booster.Some amine oxides are C preferably ₈-C ₁₈, be more preferably C ₁₀-C ₁₆Alkyl dimethyl amine oxide and C ₈-C ₁₈, be more preferably C ₁₂-C ₁₆Fatty acyl amido propyl-dimethyl amine oxide and composition thereof.

Marlamid is good suds booster.Some preferably alkanolamide be C ₈-C ₁₆, be more preferably C ₁₂-C ₁₆Single ethanol amide, diglycollic amide, single isopropanol amide and composition thereof.

Other detergent surfactants are the alkyl ethoxy carboxylates with following general formula:

Wherein R is C _8-22Alkyl, K are the integers of 0-10, and M is a positively charged ion; The polyhydroxy fatty acid amide that has following general formula in addition:

R wherein ¹Be H, C _1-4There are R simultaneously in alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups ²Be C _5-31Alkyl, and Z has to be with the straight-chain alkyl polyhydroxy alkyl of directly linking 3 hydroxyls on the chain or its alkoxy derivative at least.

Trimethyl-glycine is good suds booster.Trimethyl-glycine, for example C ₈-C ₁₆, be more preferably C ₁₂-C ₁₆Alkyl betaine is as coconut trimethyl-glycine or C ₈-C ₁₆, be more preferably C ₁₂-C ₁₆Amido betaine, as the coconut monoethanolamide CAB, and composition thereof, these all are preferred.

Some preferred surfactants are synthetic surfactants of moisture absorption, and they absorbed about 20% of its dry weight in three days at least under 26 ℃ and 80% relative humidity.The hygroscopic surface promoting agent helps to improve the foaming of soap bar.Some preferred moisture absorption synthetic surfactants are listed as follows.Note this not every moisture absorption synthetic surfactant.

The water absorbability of some tensio-active agents

The specified hygroscopic surface promoting agent of the present invention under 26 ℃ and 80% relative humidity after three days total humidity to increase minimum be 20%.

Nonionic type

Sulfonate absorbs total humidity % ^*

C ₈Glyceryl ether sodium sulfonate 39.8

C _12-14Glyceryl ether sulphonyl sodium 22.9

C ₁₆Glyceryl ether sodium sulfonate 71.4

Coconut coconut monoglyceride 3.5

C ₈-C ₁₆The alkyl glycerylether sulfonate sodium

Alpha-sulfo ester and acid absorb total humidity % ^*

Alpha-sulfo methyl sodium laurate/Sodium tetradecanoate 39.3

Alpha-sulfo methyl Sodium tetradecanoate 44.5

Alpha-sulfo hexyl sodium laurate 23.2

Alpha-sulfo methyl/hexyl sodium laurate and Sodium tetradecanoate 26.3

Alpha-sulfo methyl palmitic acid sodium 3.7

Alpha-sulfo methyl sodium stearate 4.2

2-sulfolauric acid sodium 0.2

2-sulfo group Sodium pentadecanecarboxylate 3.8

2-sulfosalicylic stearate sodium 0.0

Na ⁺R ₁-C(SO - ₃)-CO ₂R ₂R ₁=C ₈-C ₁₄Alkyl R ₂=C ₁-C ₆Alkyl

The alkyl hydroxyethyl sulfonate absorbs total humidity % ^*

Lauryl hydroxyethyl sulfonate 31.7

Coco group hydroxyethyl sulfonate 11.0

Sarcosinate absorbs total humidity % ^*

Sodium lauryl sarcosinate 8.8

Stearyl sodium sarcosinate 13.3

Coco group sodium sarcosinate 18.7

Alkyl-sulphate absorbs total humidity % ^*

Sodium Lauryl Sulphate BP/USP 28.2

The sodium sulfate 37.6 of lauryl polyoxyethylene-1(Laureth-1)

Oil base sodium sulfate 20.3

Mix spermaceti-stearyl (Cetearyl) sodium sulfate 4.7

Hexadecyl sodium sulfate 2.25

Na ⁺R ₁(OCH ₂CH ₂) _nOSO ^- ₃R ₁=C ₈-C ₁₄Alkyl is at least with two keys

C _16-20(Asia) alkyl, n=0-18

Acyl glutamate absorbs total humidity % ^*

Coconut sodium glutamate acyl 26.7

Sodium lauroyl glutamate 17.8

Myristoyl Sodium Glutamate 18.1

Stearoyl-glutamic acid sodium 12.0

The alkyl ether carboxy acid salt absorbs total humidity % ^*

The carboxylic acid sodium 32.2 of lauryl polyoxyethylene-5(Laureth-5)

Palm-20 carboxylic acid sodium 50.2

Na ⁺R ₁-(O-CH ₂CH ₂) _nCO ^- ₂R ₁=C _8-18Alkyl, n=1-30

Sulfosuccinate absorbs total humidity % ^*

Lauryl polyoxyethylene (Laureth) 33.6

Disodium sulfosuccinate

The total humidity % of phosphate absorption ^*

Monoalkyl (70%C ₁₂/ 30%C ₁₄) sodium phosphate 21.1

Trimethyl-glycine absorbs total humidity % ^*

Coconut trimethyl-glycine 70.0

Coconut monoethanolamide CAB 48.2

Palmitic amide CAB 46.5

Isostearoyl amine CAB 44.3

Sultaines absorbs total humidity % ^*

The coconut monoethanolamide third hydroxyl Sultaine 59.5

Amine oxide absorbs total humidity % ^*

Palmityl dimethyl amine oxide 34.0

Myristyl dimethyl amine oxide 46.0

Coconut monoethanolamide propyl group amine oxide 43.3

The total humidity % of the absorption of protein derived ^*

Na/TEAC ₁₂Hydrolysis of keratin 34.7

* 3 days, 26 ℃/80% relative humidity

The gentle skin auxiliary agent of polymeric is disclosed in people's such as people such as Small and Medcalf the patent.Cationic polysaccharide and cation synthesising copolymer are disclosed.The synthetic polymers of the useful positively charged ion of the present invention is positively charged ion polyalkyleneimine, oxyethyl group polyalkyleneimine and poly-[N-[-3-(Dimethyl Ammonium)-propyl group]-N '-[3-(ethylidene oxygen ethylene ammonium methyl) propyl group] urea dichloride, the latter can be by Miranol Chemical Company, Inc., buy, trade mark is MiranolA-15, CAS Reg.No.68555-36-2.

Preferred cation polymerization skin conditioning agent of the present invention is the cationic polysaccharide of cationic guar gum class, and its molecular weight is 1000-3000000.Preferred molecular weight is 2500-350000.These polymkeric substance all have the glycan main chain of being made up of the polygalactomannan unit, and have the positively charged ion substitution value of every anhydroglucose unit about 0.04 to every anhydroglucose unit about 0.80, its cationic substituent is 2, the adducts of 3-epoxypropyl trimethyl ammonium muriate on natural glycan main chain.Example has JAGUAR C-14-S, and C-15 and C-17 are sold by Celanese Corporation.In order to reach advantage of the present invention, this polymkeric substance must have following feature: structure and physicals all are suitable for and abundant hydration is also mixed in the soap base matter subsequently well.

The clean skin soap bar of mild of the present invention can contain the mixture of about 0.5%-20% siloxanes colloid and siloxane fluid, wherein colloid: the ratio of fluid is about 10: about 1: 10 of 1-, more preferably about 4: about 1: 4 of 1-is preferably about 3: about 2: 3 of 2-.

Siloxanes colloid and fluid mixture have been disclosed in people such as U.S. Patent No. 4906459(Cobb as shampoo and/or amendment, authorize March 16 nineteen ninety), 4788006(Bolich, Jr. wait the people, on November 29th, 1988 authorized), people such as 4741855(Grote, on May 3rd, 1988 authorized), people such as 4728457(Fieler), on March 1st, 1988 authorized), people such as 4704272(Oh, on November 3rd, 1987 authorized) and 2826551(Geen, on March 11st, 1958 authorized), it is for reference that above-mentioned all patents all are incorporated into this paper.

Silicone components can exist with the content of the skin benefit that effectively softens in soap bar, for example is about 0.5%-20% of composition, more preferably about 1.5%-16%, and be preferably about 3%-12%.The siloxane fluid that the present invention uses refers at 25 ℃ of about 5-600000 centistokes of siloxanes viscosity, is preferably about 350-100000 centistoke.The siloxanes colloid that the present invention uses refers to molecular weight and is about 200000-1000000, and viscosity is greater than the siloxanes of about 600000 centistokes.The molecular weight and the viscosity of the special siloxanes of selecting will determine that it is colloid or fluid.This siloxanes colloid and fluid mixed be incorporated in the present composition.

Other components of the present invention are selected by various uses.For example, use spices in the clean skin product of preparation, its consumption is about 0.1%-2.0% of composition usually.Also can use alcohol, hydrotropic agent, tinting material and filler such as talcum, clay, water-fast trickle lime carbonate and dextrin.Spermaceti-stearyl (Cetearyl) alcohol is the mixture of hexadecanol and stearyl alcohol.Preservatives, sodium ethylene diamine tetracetate (EDTA) for example, general content can join in the clean skin product less than 1% of composition, to prevent the degraded of color and smell.Antiseptic-germicide also can add, and general content is no more than 1.5%.Above-mentioned patent disclosure or relate to these operable composition and prescriptions in soap bar of the present invention is incorporated herein for reference.

Some soap bars of the present invention contain has an appointment greater than 5%-about 75% above-mentioned fatty acid sodium soap fiber; About 10%-is approximately less than 94% water; With at least about 1% another kind of soap bar composition, these compositions are selected from: other soaps, moistening agent, tinting material, solvent, filler, synthetic detergent tensio-active agent, polymerization skin feel and gentle skin auxiliary agent, spices, preservatives and composition thereof.

Some soap bar of the present invention contains: greater than the fibrous fatty acid sodium soap of 5%-50%, it contains the about 50% radical of saturated aliphatic alkyl chain with 12-24 carbon atom at least, this radical of saturated aliphatic alkyl chain be the strand section at least about 25%.

Some soap bar of the present invention contains above-mentioned fiber, and this fiber accounts for the about 3%-75% of soap bar structural volume, better accounts for about 15%-40%.

Some soap bar contain the low structure that is clamminess of inflexible greater than the 5%-75% fatty acid sodium soap, this soap contains the radical of saturated aliphatic alkyl chain that has a 12-24 carbon atom at least about 50%, above-mentioned radical of saturated aliphatic alkyl chain is the strand section at least about 25%; Above-mentioned soap bar also contains the 10%-94% water of having an appointment; With the about 0% soap bar composition to other selections of total amount about 70%, this selection component is selected from above-mentioned table 4 a thing group of more listing.

Some human body cleansing bars composition contains the rigid staggered network of sodium soap fiber; Wherein fatty acid sodium soap contains the radical of saturated aliphatic alkyl chain that has a 12-24 carbon atom at least about 50%, and above-mentioned radical of saturated aliphatic alkyl chain is the strand section at least about 25%; Above-mentioned soap bar also contains the 2%-40%(weight of having an appointment) the moisture absorption synthetic surfactant, wherein said moisture absorption synthetic surfactant is selected under 26 ℃ and 80% relative humidity about 20% the tensio-active agent that absorbed its dry weight in three days at least.

Soap bar outward appearance auxiliary agent

Preferred soap bar outward appearance (keeping moisture and/or prevent shrinking) auxiliary agent is selected from the thing group of being made up of the listed material of above-mentioned table 4:

The compatible salt and the hydrate of salt;

Water soluble organic substance, polyvalent alcohol for example, urea;

Silico-aluminate and clay; And their mixture.

Water soluble organic substance also is used for stablizing the outward appearance of soap slab of the present invention.Some preferred water soluble organic substance is propylene glycol, glycerol, ethylene glycol, sucrose and urea, and other compatible polyvalent alcohols.

The water soluble organic substance of particularly suitable is a propylene glycol.Other compatible organism comprise polyvalent alcohol, as ethylene glycol or 1, the 7-heptanediol, are that list and molecular weight are not more than about 8000 polyoxyethylene glycol and polypropylene glycol, their single arbitrarily C respectively _1-4Alkyl oxide, Sorbitol Powder, glycerol, monose (glycose), Glycerol dimer, sucrose, lactose, dextrose, 2-amylalcohol, 1-butanols, list-, two-and triethanol ammonium, 2-amino-1-butanols or the like, particularly polyvalent alcohol.

Term " polyol " used herein comprises non-reducing sugar, for example sucrose.Sucrose does not reduce fehling's solution, thereby is categorized as " non-reduced " disaccharide.Unless otherwise indicated, term used herein " sucrose " comprises sucrose, its derivative and similar non-reducing sugar and be no more than stable basically similar polyvalent alcohol under about 210 (98 ℃) in the soap processing temperature, for example contract sugar (trialose), raffinose and stachyose of three aldehyde; And Sorbitol Powder, Saccharum lactis and maltose alcohol.

Use compatible salt and salt hydrate to stablize the soap slab outward appearance by keeping moisture.Some preferred salt are sodium-chlor, sodium sulfate, Sodium phosphate dibasic, trisodium phosphate and sodium tetraborate.

Usually, compatible salt and salt hydrate comprise mineral acid and small molecules chain (6 carbon atoms or littler) carboxylic acid or other organic acid sodium, potassium, magnesium, calcium, aluminium, lithium and ammonium salt, corresponding hydrate and composition thereof, and these all are suitable for.Inorganic salt comprise muriate, bromide, vitriol, silicate, orthophosphoric acid salt, pyrophosphate salt, polyphosphate, metaborate, tetraborate and carbonate.Organic salt comprises acetate, formate, Methylsulfate and Citrate trianion.

Also can use water soluble salt of ammonia.Monoethanolamine, diethanolamine and triethanol ammonium (TEA) villaumite preferably.

Silico-aluminate and other clays also are useful in the present invention.Some preferred clays are disclosed among U.S. Patent No. 4605509 and the No.4274975, and this paper quotes for reference.

The clay of other types comprises zeolite, kaolinite, montmorillonite, attapulgite, illite, wilkinite and halloysite.Preferred another kind of clay is a kaolin.

Wax comprises paraffinic base wax class (paraffin, Microcrystalline Wax and vaseline), plant base wax class (triglyceride level that obtains in babassu, palm wax, little candelilla wax, sugar-cane wax and the plant), animal base wax class (triglyceride level that obtains in beeswax, spermaceti, wool wax, shellac wax and the animal), mineral wax class (montar, ceresine and ceresin) and synthetic wax class (Fischer-Tropsch process wax).

Preferred wax is used for the embodiment of the invention.Practical wax fusing point (M.P.) is about 120-185 (49-85 ℃), better is about 125-175 (52-79 ℃).Preferred paraffin is the abundant purified paraffin of fusing point about 130-140 (49-60 ℃).This wax is not have to smell tastelessly, and satisfies FDA needs as food and food Package coating.These paraffin are easy to buy.Very suitable paraffin for example can be buied from The Standard Oil Company of Ohio, and its commodity are called Factowax R-133.

Other suitable wax classes are sold by the National Wax Co., and trade(brand)name is respectively 9182 and 6971, and its fusing point is 131 and 130 (～55 ℃).

The content of paraffin better is about 5%-20%(weight in soap bar).In product, use the paraffin composition to give its gentle skin, plastic, firm and processability.Also provide gloss and smooth feeling to soap bar.

Randomly replenish the paraffin composition with Microcrystalline Wax.Suitable Microcrystalline Wax fusing point for example is about 140 °F (60 ℃)-185 °F (85 ℃), is about 145 °F (62 ℃)-175 °F (79 ℃) preferably.This wax should satisfy food grade Microcrystalline Wax FDA needs preferably.Can buy the most suitable Microcrystalline Wax of commodity Multiwax X-145A by name by Witco Chemical Company.Microcrystalline Wax content is preferably about 0.5%-5%(weight in the soap bar).The Microcrystalline Wax composition is given the soap bar snappiness in room temperature.

Embodiment

Below described embodiment do not limit the scope of the invention.Unneutralized or " dissociating " lipid acid that uses in an embodiment is to make employed those the identical chain lengths of soap bar except as otherwise noted.Except as otherwise noted, all content used herein and scope, temperature, result etc. are approximations.

Make the framework processing method of soap bar of the present invention

Except as otherwise noted, the cleansing bars among the embodiment is pressed following processing method manufacturing:

1, lipid acid precursor, propylene glycol, sodium-chlor and water (not considering the water that other raw materials are brought into) are mixed and be heated to 71 ℃.

2, add caustic solution (50% sodium hydroxide), and stir the mixture, form the moisture fusing fluid that contains 15%-94% water and 5.5%-75% soap (neutralization back carboxylic acid) up to stably.In melt and the time temperature be elevated to～95 ℃.

3, preferably add in the following order other compositions and temperature remain on～88 ℃: coconut trimethyl-glycine, sodium lauroyl sareosine or alpha-sulfo methyl coconut acid sodium, kaolinton or hydrated zeolite (synthetic sodium silicoaluminate) and paraffin; Add spices at last.

4, the fusing fluid mixture is injected in the pattern.

5, fusing fluid crystallization when being cooled to room temperature (curing), and from mould, take out the soap bar that generates.

Except as otherwise noted, the soap bar of these embodiment is all used above-mentioned general step manufacturing.

Be noted that importantly the prescription that uses in the embodiment of the invention carries out conventional mold pressing or refrigerator when handling, and forms very soft soap bar or does not have soap bar formation.The embodiment II is very highly preferred general soap bar.

Table 5

Preferred soap bar

Composition embodiment I embodiment II embodiment III embodiment IV

(weight %) (weight %) (weight %) (weight %)

C ₁₄Na soap 20 20--

C ₁₆Na soap--20 16

C ₁₆K soap---4

Free fatty acids 1111

Sodium lauroyl sareosine 77 12-

Alpha-sulfo methyl coconut acid sodium---7

Coconut trimethyl-glycine 5575

Sodium-chlor 3.0 3.0 3.0 3.0

Propylene glycol 14.5 14.5 14.5 15.0

Hydrated zeolite A(silico-aluminate) 4.0-4.0-

Kaolinton-4.0-4.0

Paraffin (M.P.=55 ℃) 6.5 6.5 4.5-

Spices 1111

Water 37.25 37.25 31.95 36.25

Hardness (mm) 5.5 6.4 4.2 5.1

Goo 9.5 9.0 8.5 8.5

Embodiment tests explanation

The soap bar hardness test

1, enter the hardness that soap bar penetration depth (in millimeter) is measured soap bar by measuring down 247 gram indicated weight penetrometer probes at 25 ℃, this syringe needle is conical pin, and it is contained in the 22.9cm(9 inch) bar on, weigh 47 grams, on masthead, add 200 grams.5mm or littler measurement hardness represent that soap bar is very hard; 5-10mm represents that soap bar is medium hard; 10-12mm represents that soap bar is softer a little but also can accept; And represent that greater than 12mm soap bar is very soft, most of purposes can not be accepted.Except as otherwise noted, define " hardness " used herein like this.

The test of soap bar goo

2, measuring the goo degree is soap bar to be placed on the axle of diameter 1400mm garden dish by (1); (2) water of 200ml room temperature is added to soap bar bottom 3mm is immersed in the water; (3) make soap bar soaked overnight (15 hours); (4) the upset soap bar is to the binding capacity of goo, and the characteristic of goo carries out qualitative classification, and the goo degree of depth equaled inviscid thing at 10 o'clock on scale, and 8.0-9.5 equals low goo, 5.0-7.5 equal the moderate tack thing, this is similar to the most commercial soap bar; And 4.5 or equal very poor goo more for a short time.

The commercial soap bar of selling, for example SAFEGUARD

, ZEST , IVORY

And LAVA The goo value be respectively about 5,6.6 and 6.More data is referring to table 12.

The soap bar contraction test

3, measure shrinking is to remain on 26 ℃ by the fresh unpackaged soap bar that makes is placed on temperature, relative humidity 15% indoor through a week.Determine the shrinkage of original soap type on scale qualitatively, 0 expression does not have and shrinks ,+expression slight shrinkage, ++ the expression intermediate collapsed, and ++ the very big contraction of+expression.

List soap bar 1-10 in table 6 and the table 7 with C shown in the expression ₁₀, C ₁₂, C ₁₄, C ₁₆And C ₁₈Soap hardness, goo and the contraction of alkyl chain soap.The preferred alkyl chain soap of the present invention is listed in above-mentioned table 1 and 2.

It is comparative example that term " X " means this embodiment.

Table 6

Composition embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5

(weight %) (weight %) (weight %) (weight %) (weight %)

Soda soap

C ₁₀33 - - - -

C ₁₂- 33 - - -

C ₁₄- - 33 - -

C ₁₆- - - 33 -

C ₁₈- - - - 33

Free fatty acids 1.0 1.0 1.0 1.0 2.0

Excessive sodium hydrate

Sodium-chlor 2.0 1.0 1.0 1.0 1.0

Water 64 65 65 65 64

Hardness (mm) 8.9 2.3 2.2 5.4 4.2

Goo 3 10 10 9.5 10.0

Shrink +++++++ 0

Attention: embodiment 1 has very bad goo, though hardness is 8.9, this is because the goo methodology dissolves soluble C ₁₀Soap.

Table 7

Component X 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10

(weight %) (weight %) (weight %) (weight %) (weight %)

Soda soap

C ₁₂- - - 15 5

C ₁₆- 10 - - -

C ₁₈- - 10 - -

C _18∶133 - - - -

Free fatty acids 1.0-2.0 1.0-

Excessive sodium hydrate-0.07---

Sodium-chlor 1.0 1.0 1.0 1.0 1.0

Water 65 87 82.8 83 94

Hardness (mm) * * 11.8 11.9 14.0

Goo 10.0 10.0 9.0

Shrink 0 +++++ ++ ++ ++

* because unsaturated soap is too many, do not form the solid soap bar.

Embodiment 10 has rigid structure, but is not best as cleansing bars, because its hardness is 14.

Table 8

Soda soap/the water analysis of double-stranded section

Component X 11 embodiment 12 embodiment 13

Soda soap (weight %) (weight %) (weight %)

C ₁₀- - 16.5

C ₁₂16.5 - -

C ₁₄- 16.5 16.5

C _16∶116.5 16.5 -

Free fatty acids 1.0 1.0 1.0

Excessive sodium hydrate

Sodium-chlor 1.0 1.0 1.0

Water 65 65 65

Hardness (mm) * * 9.0 9.0

Goo 9.0 8.0

* is because and C ₁₂Soap bonded degree of unsaturation is too big, does not form the solid soap bar.

Table 9

The analysis of two saturated chain length soda soap/water

Composition embodiment 14 embodiment 15 embodiment 16

Weight % weight % weight %

Soda soap

C ₁₂16.5 - -

C ₁₄16.5 - -

C ₁₆- 16.5 10

C ₁₈- 16.5 10

Free fatty acids 1.0 1.0 1.0

Sodium-chlor 1.0 1.0 1.0

Water 65 65 78

Hardness (mm) 2.8 4.5 7.3

Goo 9.5 10.0 10.0

Shrink 0 ++

Embodiment 12-16 is a fabulous soap bar of the present invention.

Table 10

The analysis of complicated chain length soda soap/water

Composition embodiment 17 embodiment 18 embodiment 19

Weight % weight % weight %

Soda soap *

Emersol132??-??（33）??（15）

C ₈0.56 - -

C ₁₀0.64 - -

C ₁₂10.14 0.12 8.1（8.0）

C ₁₄4.54 0.79 10.4（10.0）

C ₁₆8.51 15.6 7.10

C ₁₇0.76 0.76 0.35

C ₁₈19.85 15.3 7.0

C ₂₀- 0.26 0.12

Free fatty acids-1.0-

Sodium-chlor 1.1 1.0 1.0

Water 53.9 65 66

Hardness (mm) 7.6 4.7 5.8

Goo 9.5 10 9.5

Shrink+++

* by the component of chain length branch, () represents the actual content of material.

Embodiment 17-19 uses than more complicated the preceding embodiment soap mixture to make.They form the good soap bar of the present invention.They have only a bit or do not have goo.Its hardness and goo and the soap bar made with general tallow and coconut soap relatively be shown in table 11.

Table 11

The analysis of complicated chain length soda soap/water

Composition comparative example 20 comparative examples 21 comparative examples 22

Weight % weight % weight %

Soda soap *

Tallow (33)-(26.4)

Coconut soap-(33) (6.6)

C ₈- 2.31 0.46

C ₁₀- 2.0 0.40

C ₁₂- 16.5 3.3

C ₁₄1.0 5.94 4.95

C ₁₆7.92 2.81 6.90

C ₁₈0.5 - 0.40

C ₂₀6.6 1.0 5.48

C _14∶10.33 - 0.26

C _16∶10.83 - 0.66

C _18∶114.2 2.0 11.76

C _18∶20.75 0.5 0.7

Free fatty acids 1.0 1.0 1.0

Sodium-chlor 1.0 1.0 1.0

Water 65 65 65

Hardness (mm) soft 15.8 12.5

Goo bad 3.0 5.0

Comparative example 20,21 and 22 does not form rigid structure of the present invention.It is also noted that they make with typical commercially available soap.With by 65% water and C ₁₆And C ₁₈Saturated soap is made and is formed the embodiment of the invention 15 of the hard soap bar of not being with goo and compares, and they are the soft soaps that have the over-drastic goo.

Embodiment 23 is a kind of soap bars of the present invention, and it contains the synthetic surfactant of Duoing than soap.It has the foaming that low amount goo is become reconciled.Embodiment 24 is a kind of soap bars of the present invention, and it contains polymkeric substance and other soap bar composition.

Embodiment 23

The Syndet soaps regulations

Composition weight %

Sodium pentadecanecarboxylate 20

Sodium lauroyl sareosine 9 ^*

The sodium sulfate 7 of lauryl polyoxyethylene-3(laureth-3) ^*

Mix spermaceti-stearyl (Cetearyl) sodium sulfate 5 ^*

Free fatty acids (palmitinic acid) 1

Sodium-chlor 3

Propylene glycol 14

Hydrated zeolite A 3

Spices 1

Water 37

* the synthetic surfactant total amount is 21%

Embodiment 24

Contain the polymkeric substance example

Composition weight %

Sodium pentadecanecarboxylate 20

Alpha-sulfo methyl coconut acid sodium 8.7

Coconut trimethyl-glycine 4.65

JaguarC376??1.5

Propylene glycol 15

Kaolinton 5

Paraffin (M.P.=55 ℃) 4.5

Sodium-chlor 3

Spices 1

Water 35.5

Embodiment 23 and 24 is similar to the embodiment IV of table 5.

Embodiment 24 is the mild perfumed soap prescriptions that contain the gentle auxiliary agent of polymerization skin.

Embodiment 25-27

Composition embodiment 25 embodiment 26 embodiment 27

Weight % weight % weight %

Lithium myristate 33--

Lithium chloride 5--

The disodium salt of dodecandioic acid-20 20

Sodium lauroyl sareosine--5

Water 62 80 75

Penetrating value N/A N/A N/A

N/A=can not obtain

For embodiment 25, this prescription is by the lipid acid precursor is heated to 71 ℃, separately lithium hydroxide is added in the water, then lipid acid is added with lithium hydroxide solution and be in the same place, remain at least 71 ℃ of heating, they were mixed 30 minutes, interpolation chlorination lithium salts also stirred 5 minutes, in the impouring mould, make its cooling and solidify to prepare then.Form solid-state perfumed soap like this with superior goo performance.

For embodiment 26 and 27,, add (90 ℃) caustic solution (2 normal NaOH) of heat with bisgallic acid fusing (150-180 ℃).Mixture was stirred～5 minutes.For embodiment 27, sodium lauroyl sareosine given being dissolved in earlier in the caustic/water solution.Cooling makes perfumed soap become solid, during degraded, for example arrive about 35～40% water of perfumed soap weight, further hardens.

Embodiment 25 proofs do not need soda soap to form the ability of high moisture content, firm and inviscid thing perfumed soap.Embodiment 26 and 27 proofs form the ability of not having the soap product fully and still obtaining suitable rigid staggered network fibrous texture.

Freezing soap bar embodiment 28

Following embodiment 28 prepares by the freezing soap bar technology in the U.S. Patent application that is disclosed in common transfer (sequence number No.07/731163, people such as Taneri, 1991,7,15 applications).This technology provides a kind of human body to clean freezing soap bar, this soap bar have suitable inflexible, staggered, semi-continuous, open, three-dimensional in and the skeleton structure of the crystalline network of carboxylic soap, this soap bar follows these steps to preparation:

(1) molten mixture that will contain the water of the soap that accounts for soap bar weight about 15% to about 85% and about 15% to about 40% mixes:

(2) said mixture is cooled to semi-solid state in scraping wall type heat exchange water cooler;

(3) the semi-solid state mixture is squeezed into soft pillars; With

(4) make soft pillars further cooling and crystallization, until firm and obtain human body and clean freezing soap bar.

Step 1-mixes

Soap by the prescription regulation is on-the-spot by with desired fats acid, particularly contains C ₁₂-C ₂₄The lipid acid of chain length and the alkali or the mixture of alkali, particularly sodium hydroxide, lithium, magnesium, calcium and potassium and the trolamine that are fit to are mixed with mutually.Lipid acid, alkali and water are mixed and the formation soap at about 170 °F to about 200 °F (76～93 ℃).In embodiment 28, use 180 °F.Use enough water can stir to cause mixture.Keeping temperature is about 180 to about 200 (82～93 ℃), adds other composition.180 of embodiment 28 usefulness.Best mixing temperature can change according to specific prescription.

Step 2(is optional) inflation, accessory additive and sharply dry (choosing wantonly)

Mixture is inflated (choosing wantonly) and add spices (having only when dry) and other less important additive with positive-displacement pump or other line mixer.Embodiment 28 does not inflate or is dry.Randomly, be reduced to required degree, preferably the water of 20-40% with the amount that causes water with the mixture drying of step (1).About 30 to 100Psi(115-517mmHg) sharply dry under the pressure, temperature is about 225 to about 315 (135-157 ℃).

Step 3-is freezing

If it is dry, with scraping wall type heat exchanger (refrigerator) cooling mixture, make it to be chilled to outlet temperature and to make the component partial crystallization from beginning temperature about 180 to about 200 (82-93 ℃) or about 200 to about 200 (93 °-104 ℃), above-mentioned outlet temperature is advisable with about 135 °F to about 180 °F (57-82 ℃), be more preferably about 145 to about 180 (63-82 ℃), preferably about 155 to about 175 (68-79 ℃).In this article, this outlet temperature (also referring to refrigerator temperature out (FOT)) generally is such top temperature, forms smooth column form object under this temperature, and is being extruded into (its shape of maintenance after the step 4) on the travelling belt.The FOT of embodiment 28 is 175 °F.

Step 4-extruding

The cooling mixture of step 3 is extruded on the travelling belt with soft column form object, makes column form object cooling and all crystallizations then, so print and pack.This column form object is preferably made with the extrusion process described in the above-mentioned U.S. Patent No. 3835059.(crystallization in the step 3) for obtaining standing the semisolid with enough viscosity on tape, is pushed further crystallization of back to some components, and the result causes the soap bar hardening at refrigerator.The final crystallization of soda soap makes and forms staggered, semi-continuous, open network structure in the freezing soap bar of the present invention.

Embodiment 28

Composition weight %

Sodium C ₁₄Soap 27.99

Magnesium C ₁₄Soap 5.00

Sodium lauroyl sareosine 3.00

Coconut trimethyl-glycine 10.00

Propylene glycol 3.50

Vaseline 22.49

Sodium-chlor 2.58

Free fatty acids (C ₁₄) 0.50

Spices 0.50

Water 24.44

The hardness test of mold pressing impression soap bar

Use mold pressing impression soap bar hardness test so that difference soap bar of the present invention and other soap bar.Four kinds of commercially available soap bar: SAFEGUARD of the various soapmaking methods of choosing representative

, a kind of development soap bar; ZEST

, a kind of soap of development/synthetics soap bar; IVORY

, a kind of freezing soap bar and LAVA

A kind of framed soap kui bar.With the sample of the soap bar that forms in these commercially available soap bars and embodiment 28 and the II by following process stempressing.

Generally speaking, compare, want how firmly and have a goo preferably after the commercially available soap bar mold pressing with the embodiment 28 after the mold pressing or the sample of embodiment II.Detailed data is listed in table 12.Clearly this test is to distinguish to have the superior method of rigid-skeleton soap bar and other soap bar.In brief, compare with conventional soap bar, soap bar of the present invention becomes much soft after the mold pressing again.

Mould pressing process is as follows:

1,, the soap bar (about 2.5Kg or more) that forms is put in the single-station die press (4 inches/10.16cm cap shape single-station die press), and made it by the soap bar plate without vacuum.This soap bar plate has the hole of 19 0.37 inch (0.93cm) on the plate face of 3.1 inches (8cm).Barrel temperature is 120 °F (49 ℃), and end region temperature is 110 °F (43.5 ℃).

2, with soap bar repeating step 1.

3, the soap bar of step 2 is put in the single-station die press (4 inches/10.16cm cap shape single-station die press) that vacuumizes, and made it aperture by the checkers type.Squeeze out size and be roughly the checkers type column form object of 1.88 inches (4.6cm) (height) * 1.16 inch (3cm) (wide) * 3 inch (7.6cm) (length).These column form object internal temperatures are that 90 °F (32 ℃) are to 105 °F (41 ℃).

4, these column form objects are pressed in the checkers pattern cool to room temperature before mensuration (at least 12 hours).

Table 12

Soap bar mold pressing data

Soap bar hardness (mm) ^*

1SAFEGUARD

Commercially available soap bar 3.18

2SAFEGUARD

(mold pressing/impression) 3.13

δ (value of soap bar 1-soap bar 2) 0.05

1ZEST

Commercially available soap bar 2.25

2ZEST

(mold pressing/impression) 2.33

δ??（0.08）

1IVORY

Commercially available soap bar 1.93

2IVORY

(mold pressing/impression) 3.03

δ??（1.10）

1LAVA

Commercially available soap bar 1.90

2LAVA

(mold pressing/impression) 2.47

δ??（0.57）

The soap bar that 1 embodiment 28(forms) 3.35

2 embodiment 28(mold pressing/impressions) 10.67

δ??（7.32）

1 embodiment II (soap bar of formation) 6.43

2 embodiment II (mold pressing/do not impress) 18.07

δ??（11.64）

* for the soap bar of every kind of test, " hardness " of " mold pressing/impression " soap bar is to quote by the soap bar in the table 12 2.This hardness test also appears at other place of this paper.

Though bound by theory not, δ value are 4 or bigger strong the showing of mold pressing soap bar, in former soap bar skeleton structure are arranged, this structure is crushed or destroy when mold pressing.Hard soap bar of the present invention forms soft sticking soap bar when soap preparing process mold pressing routinely.

The soap bar of embodiment 28 is at first made with above-mentioned cold method, and the soap bar of embodiment II is at first made with above-mentioned framed soap kui method.

Every kind of soap bar has 5-10kg to be molded approximately and impresses.

Commercially available soap bar is made by tallow and cupraol natural soap.The SAFEGUARD of mold pressing And ZEST The hardness of soap bar and former soap bar hardness are roughly the same.IVORY

And LAVA

Mold pressing soap bar (2) is softer slightly than former soap bar.

On the other hand, the mold pressing soap bar 2 of embodiment 28 is much softer than the former soap bar of embodiment 28 1.More surprising is, disintegrate during mold pressing soap bar 2 mold pressings of embodiment II, and too soft can not the impression.Its hardness is the soft water hardness that contains after the mold pressing, and rigidity of this table courage skeleton structure disappears basically.

Claims

1, a kind of solid of shaping is characterized in that it contains neutral list-and/or quite firm, staggered, the skeleton structure open, three-dimensional network of two-carboxylic acid extended crystals.

2, a kind of cleansing bars is characterized in that it contains at least two kinds of phases:

The penetrating value of the dark sample of 12mm is the water that contains of 12mm, and this contains water and is that 25 ℃ is soft or flowable;

Contain that the neutral list-and/or two-carboxylic acid extended crystals is staggered, rigidity crystallization phases skeleton structure open, three-dimensional network;

Wherein, containing above-mentioned rigidity crystallization phases skeleton structure and the above-mentioned penetrating value that contains this cleansing bars of water, is 0 to about 12mm for this dark cleansing bars sample of 25mm;

Wherein, above-mentioned penetrating value is to wear the hardness tester probe measurement at 25 ℃ of pins with 247 gram standard weights, this probe has and is connected in 9 inches taper pins on (22.9cm) bar, weigh 47 grams, add 200 grams on the above-mentioned masthead end, gross weight 247 grams, above-mentioned taper pin top is 19/32 inch (1.51cm), and the tip is 1/32 inch (0.08cm).

3, the cleansing bars of claim 2, wherein, said neutral carboxylic acid is selected from lithium and/or sodium neutral monocarboxylic acid (soap) and/or two carboxylic acids and composition thereof;

Wherein, said monocarboxylic acid has about 12 aliphatics to about 24 carbon atoms (Asia) alkyl chain;

Wherein, the said pair of carboxylic acid have about 12 aliphatics (Asia) alkyl chain to about 18 carbon atoms and

Wherein, has the saturated alkyl chain at least about 80% said carboxylic acid;

Wherein, said rigidity crystallization phases skeleton structure accounts for about 3% to about 75% of said cleansing bars volume.

Wherein, in said and carboxylic acid account for 5% or more extremely about 75% of said cleansing bars weight; With

Wherein, said cleansing bars contains about 15% to about 94% water.

4, the cleansing bars of claim 2, wherein, at least 80% said carboxylic acid has following general formula:

Wherein:

a+b＝8-20

Each a, b=0-20

X=H, OR,

, R or these groups exist simultaneously,

R=C ₁-C ₃Alkyl, H or these groups exist simultaneously,

M=Na, Li or its exist simultaneously.

5, the cleansing bars of claim 4, wherein said a+b=10-16, each a, b=0-16; Described X=H, OR; R=H; And M=Na.

6, the cleansing bars of claim 3, wherein said extended crystals is made of the fibrous sodium fatty acid soaps that at least about 25% described representative examples of saturated aliphatic alkyl chain is strand length; And wherein said soap bar contains about 15% to about 75% described soda soap; Wherein said soap bar contains unneutralized (free) carboxylic acid that is not more than described soap weight 50%.

7, the cleansing bars of claim 6, wherein said soap bar contains described soda soap and water; With about 2% to about 60% synthetic surfactant; this tensio-active agent is selected from alkyl-sulphate; alkane sulfonate; alkyl glycerol ether sulfonate; acyl sarcosinate; methyl-acyl taurine salt (taurates); linear alkylbenzene sulfonate; the N-acyl glutamate; alkyl glucoside; alpha-sulfo fatty acid ester; acyl isethinate; alkyl sulfo succinate; the alkyl ether carboxy acid salt; the alkylphosphonic ester; the ethoxylated alkyl phosphate ester; methyl glucose ester; the protein condenses; alkyl amine oxide; alkyl betaine; alkyl Sultaines; with sulfated alkyl ether or its mixture of 1 to 12 oxyethyl group, wherein above-mentioned tensio-active agent contains C ₆-C ₂₂Alkyl chain.

8, the cleansing bars of claim 7, wherein said synthetic surfactant is moisture absorption; The definition of this hygroscopic surface promoting agent is the tensio-active agent that absorbed the water of its dry weight 20% under 20 ℃ and 80% relative humidity in three days at least, and wherein soap bar is non-swelling relatively.

9, the cleansing bars of claim 8, wherein said hygroscopic surface promoting agent is selected from alpha-sulfo fatty acid ester, alkyl-sulphate, alkyl ether carboxy acid salt, alkyl betaine, alkyl Sultaines, alkyl amine oxide, sulfated alkyl ether or its mixture.

10, the cleansing bars of claim 7, wherein said water is about 1: 1 to about 5: 1 with the ratio of described soap; The content of described water is about 25% to about 60%; Wherein said soap has C ₁₄-C ₂₂The aliphatic alkyl chain, the content of described soap in described soap bar is about 15% to about 35%, is saturated at least about 85% described soap alkyl chain wherein; Wherein said the neutralization (free) carboxylic acid be described soap heavy 0 to about 25%; wherein said synthetic surfactant content is about 4% to about 25% of this soap bar weight; described tensio-active agent is selected from hydroxyethyl acyl sodium sulfonate; the acyl group sodium sarcosinate, alpha-sulfo fatty acid ester sodium, paraffinic hydrocarbons sodium sulfonate, sodium alkylether sulphate, sodium alkyl sulfate, linear alkylbenzene sulphonic acid, alkyl betaine, alkyl Sultaines or trialkylamine oxides.

11, the cleansing bars of claim 10, wherein said water is about 1.5: 1 to about 2: 1 with the ratio of described soap, described unneutralized (free) carboxylic acid be described soap heavy 0 to about 17%, described water-content is about 30% to about 45%; The aliphatic alkyl chain of described soap is about C ₁₄To about C ₁₈; Wherein at least 95% described alkyl chain is saturated, and described soap content is about 15% to about 30%, and described synthetic surfactant content is about 8% to about 16%.

12, the cleansing bars of claim 7, wherein said soap bar contains about 0.1% to about 40% hygroscopic material, and this hygroscopic material is selected from Witepsol W-S 55, montar, ceresine, ceresin or the f-t synthetic wax that Witepsol W-S 55, beeswax, spermaceti, lanolin, haze tallow, shellac wax, animal that Microcrystalline Wax, vaseline, carnauba wax, palm wax, gama wax, sugar-cane wax, plant obtain obtain.

13, the cleansing bars of claim 12, wherein said soap bar contain about 2% to about 35% hygroscopic material, and this hygroscopic material is selected from vaseline and wax, and the fusing point of this vaseline and wax and composition thereof is about 49 ℃ (120 °F) to about 85 ℃ (185 °F).

14, the cleansing bars of claim 13, wherein said soap bar contain the paraffin of this soap bar weight about 5% to about 25%.

15, the cleansing bars of claim 7, wherein said soap bar contain about 1% to about 50% nonvolatile, water-soluble, nonionic organic substance, and this solubility of substances is in 10 parts of water molten at least 5 parts, and wherein this water-soluble nonionic organic substance is selected from structural formula and is:

(R in the formula ₁=H, C ₁-C ₄Alkyl; R ₂=H, CH ₃; N=1-200) polyvalent alcohol, C ₂-C ₁₀Derivative, urea and the general formula of paraffinic hydrocarbons glycol, Sorbitol Powder, glycerine, carbohydrate, sugar are (HOCH ₂CH ₂) _xNH _y(X=1-3 in the formula; Y=0-2; X+Y=3) thanomin or its mixture.

16, the cleansing bars of claim 15, wherein said soap bar contain about 2% to about 40% described nonvolatile, water-soluble, non-ionic organic substance.

17, the cleansing bars of claim 16, wherein said nonvolatile, water-soluble, non-ionic organic substance account for this soap bar weight about 5% to about 20%, wherein this organic substance is selected from propylene glycol, glycerine, sucrose, urea or its mixture.

18, the cleansing bars of claim 7, wherein said soap bar contain other composition of described soda soap, described water and described synthetic surfactant and about 1% to about 70%, and this other composition is selected from:

About 1% to about 10% described potash soap,

About 1% to about 35% described magnesium soap,

About 1% to about 35% described calcium soap,

About 1% to about 15% triethanol ammonium soap,

About 1% to about 60% be selected from the trickle water-fast material of lime carbonate and steatitic,

About 1% to about 20% polymerization skin feel auxiliary agent,

About 0.5% to about 25% alumino-silicate clays and/or other clay; Wherein said silico-aluminate and clay are selected from zeolite, kaolin, kaolinite soil, polynite, carclazyte (attapul-gite), illite clay, wilkinite, halloysite or ripe clay.

About 1% to about 50% salt and hydrate of salt and composition thereof; The hydrate of wherein said salt and salt has the positively charged ion that is selected from sodium, potassium, magnesium, calcium, aluminium, lithium, ammonium, monoethanolamine ammonium, di-alcohol ammonium or triethanol ammonium; The hydrate of wherein said salt and salt has and is selected from muriate, bromide, vitriol, silicate, orthophosphoric acid salt, pyrophosphate salt, polyphosphate, metaborate, tetraborate, carbonate, supercarbonate, hydrophosphate, Methylsulfate or 6 carbon atoms or list still less-and negatively charged ion of multi-carboxylate.

19, the cleansing bars of claim 2, the crystal of wherein said elongation contains platelets, and wherein said soap is made of lithium neutral monocarboxylic acid.

20, the cleansing bars of claim 2, the crystal of wherein said elongation is fibrous, the two carboxylic acids of wherein said neutral are disodium salts 1, the 12-dodecandioic acid, wherein the two carboxylic acids of neutralization account for about 20% to about 70% of soap bar weight.

21, make the method for cleansing bars, this soap bar is characterised in that and contains two-phase at least:

For 12mm dark contain the water that contains that the water sample has about 12mm penetrating value; This contains water is soft or flowable at 25 ℃;

Contain neutral list-and/or the rigidity crystallization phases quite firm, staggered, skeleton structure open, three-dimensional network of two-carboxylic acid extended crystals;

The wherein said penetrating value of the dark sample of 25mm that contains rigidity crystallization phases skeleton structure and contain the cleansing bars of water is 0 to about 12mm.

Wherein above-mentioned penetrating value is to wear the hardness tester probe measurement at 25 ℃ of pins with a 247g standard weight, this probe has one to be connected in 9 inches taper pins on (22.9cm) bar, 47g weighs, add the 200g on the above-mentioned masthead, gross weight is 247g, and above-mentioned taper needle set has 19/32 inch (1.51cm) top and 1/32 inch (0.08cm) tip;

Aforesaid method is characterised in that and may further comprise the steps:

I, form a kind of water peace treaty that contains soap bar weight about 20% to about 94% greater than 5% to about 75% described in and the moisture melt of carboxylic acid;

II, described melt is poured in the soap bar shaping mould; With

III, cooling make described melt crystallization and obtain described cleansing bars.

22, the method for claim 21, wherein this aqueous melt is to use in the oxyhydroxide and the aqueous mixture of described carboxylic acid, and stir to the temperature of about 95 ℃ (205) at about 50 ℃ (120 °F) and to make, above-mentioned oxyhydroxide is selected from sodium hydroxide or lithium hydroxide and composition thereof.

23, the method for claim 21, about 2% to about 15% of wherein said soap bar weight is " crystallization enhancing salt ", this salt is selected from vitriol, muriate, acetate and Citrate trianion or its mixture of sodium or lithium.

24, the method for claim 21 wherein contains described moisture melt and contains water and contain about 2% to about 40% the soluble additive that adds, and this adds soluble additive and is selected from:

(a) nonvolatile, water-soluble, nonionic organic solvent, this solvent is selected from structural formula and is

(R in the formula ₁=H, C ₁-C ₄Alkyl; R ₂=H, CH ₃; N=1-200) polyvalent alcohol, C ₂-C ₁₀Derivative, urea and the general formula of paraffinic hydrocarbons glycol, Sorbitol Powder, glycerine, carbohydrate, sugar are (HOCH ₂CH ₂) _xNH _y(X=1-3 in the formula; Y=0-2; And X+Y=3) thanomin;

(b) alcohols of 1-5 carbon atom;

(c) tensio-active agent; be selected from alkyl-sulphate; alkane sulfonate; alkyl glycerol ether sulfonate; anionic acyl sarcosinates; methyl-acyl taurine salt (taurates); linear alkylbenzene sulfonate; the N-acyl glutamate; alkyl glucoside; alpha-sulfo fatty acid ester; acyl isethinate; alkyl sulfo succinate; the alkyl ether carboxy acid salt; the alkylphosphonic ester; the ethoxylated alkyl phosphate ester; methyl glucose ester; the protein condenses; alkyl amine oxide; alkyl betaine; alkyl Sultaines; sulfated alkyl ether or its mixture of 1-12 oxyethyl group of band, wherein above-mentioned tensio-active agent contains C ₈-C ₂₂Alkyl chain and composition thereof; With

Wherein add the above-mentioned soluble additive that adds and be dissolved in the amount that the continuous melting described in the step 1 contains aqueous phase to increase described neutral carboxylic acid.

25, the method for claim 21, the wherein said water that contains contains and accounts for the described water that contains water weight about 20% to about 100%.

26, the method for claim 21, wherein said inflexible crystallization phases contain and account in the described crystallization phases weight about 75% to about 100% and carboxylic acid.

27, the method for claim 21, the penetrating value of the 25mm soap bar sample of wherein said soap bar are that about 3mm is to about 9mm.

28, the method for claim 21, wherein said soap bar contain the non-carboxylic acid phase of miscellaneous, and this contains droplet or the crystal that is selected from wax, vaseline and clay mutually.

29, a kind of human body cleansing bars composition that contains the soda soap crystalline rigidity crystallization staggered-mesh of elongation, this soap bar contains 15% to about 50% the described fatty acid sodium soap of having an appointment, this soda soap is made of at least 50% representative examples of saturated aliphatic alkyl chain, this chain has 12-24 carbon atom, and is that strand is long at least about 25% representative examples of saturated aliphatic alkyl chain; This cleansing bars also contains 15% to about 60% the water of having an appointment; Contain about 2% to about 60%(weight) the moisture absorption synthetic surfactant, wherein the tensio-active agent of this moisture absorption is selected under 26 ℃ and 80% relative humidity the tensio-active agent of about 20% the water that absorbed its dry weight in three days at least.

30, the human body cleansing bars of claim 29, wherein said water absorbability synthetic surfactant is selected from alpha-sulfo fatty acid ester, alkyl-sulphate, alkyl ether carboxy acid salt, alkyl betaine, alkyl sultaines, alkyl amine oxide, sulfated alkyl ether or its mixture.

31, the soap bar of claim 29, wherein said soap bar contains about 0.5% to about 40% the salt and/or the hydrate of salt, and they are selected from the compatible salt of sodium-chlor, sodium sulfate, Sodium phosphate dibasic, trisodium phosphate, sodium tetraborate, sodium acetate, Trisodium Citrate or other mineral acid and short chain organic acid.