CN106574216A

CN106574216A - Bar composition and methods for maintaining enhanced lather in presence of water with high electrolyte concentration

Info

Publication number: CN106574216A
Application number: CN201580040352.2A
Authority: CN
Inventors: R·阿斯托尔菲; E·A·d·R·加蒂; S·R·利奥波尔迪诺; L·F·C·维蒂加尔; V·维雅雅克里施南
Original assignee: Unilever NV
Current assignee: Unilever IP Holdings BV
Priority date: 2014-07-22
Filing date: 2015-06-17
Publication date: 2017-04-19
Also published as: BR112017001260A2; EP3172309B1; MX2017000839A; ES2833234T3; ZA201700174B; WO2016012163A1; EA201790006A1; EP3172309A1; BR112017001260B1; EA035754B1

Abstract

The invention relates to soap bar compositions comprising specific ratios of C10 to C12, maximum values of C14 and maximum values of unsaturated C18 other than oleic, which retain high foam compared to similar bars (made from the same oils in the same ratios) wherein noted criteria are not met. It further relates to a method of enhancing foam in water of water hardness greater than about 25 using said bar.

Description

For maintaining the soap of increased foam in the presence of the water with polyelectrolyte concentration Block composition and method

Background of invention

Soap for cleaning is generally prepared by the saponification (such as neutralizing) of triglyceride/fatty acid.In this saponification During, various fat (for example, fatty oil, Petiolus Trachycarpi oil and Oleum Cocois blend) are saponified in the presence of alkali (usually NaOH) To produce the basic salt (derivative so as to form triglyceride by fatty acid chain) and glycerol of fatty acid.Glycerol can optionally use saline (for example, with the water of high na concn) is extracted to produce the dilute fat comprising soap and water phase (such as 70% soap and 30% water phase) Fat acid soap solution.Then generally the soap solution is dried (for example, be dried to about 12% water), remaining material is ground, It is molded and strikes out soap blank.Or, soap solution can be poured in model, bubble-cap etc..

The chain length change of fatty acid soaps, depending on starting fat or oily raw material (be present specification purpose, " oil " and " fat " is used interchangeably, in the case of otherwise requiring in context).Fatty acid soaps (for example, the C of longer chain₁₆ Palmic acid or C₁₈Stearic acid) generally obtained by fatty oil and Petiolus Trachycarpi oil, compared with soap (for example, the C of short chain₁₂Lauric acid) can be generally by example As Oleum Cocois or palm-kernel oil are obtained.Prepared fatty acid soaps alternatively saturated or unsaturated (such as Oleic acid).

Generally, compared with fatty acid soaps (for example, the C of long molecule amount₁₄To C₂₂Soap) it is insoluble and does not produce foam, but It is that they can help to cause the foam by produced by other soluble soaps finer and smoother and more stable.Conversely, shorter molecular weight Soap (for example, C₈To C₁₂) fast foaming.However, what the soap of longer chain was intended to, because they maintain structure and do not allow It is soluble.Unsaturated soap (for example, Oleic acid) is soluble and fast foaming, as short chain soap, but formed it is denser, Finer and smoother foam, as long-chain soap.The specific blend of chain length is critical for quality, froth is established.

Typically, especially because producing and maintaining the structuring needed for bar soap (that is, to carry by the soap of longer chain length For structuring), the production with the pure mild soap for increasing foaming benefit (for example, fast foaming) is considered as extremely difficult.

When synthetic surfactant (for example, nonionic surfactant) is added to improve gentle degree (mildness), Generally soap still mainly of long-chain soap must be made up to guarantee soap blank by structuring well and can tie up in punching course Hold structure.

For example, WO 93/04161 (P＆G) is disclosed comprising soap, C₁₄–C₂₀Alkyl polyethoxylate nonionic and C₁₆–C₁₈ A kind of soap blank of the mixture of acyl isethinate (being also gentle surfactant).Soap used including at least fat (compared with Long chain, foams more slowly) and comprising cationic polymerization skin mildness auxiliary agent and the free fatty as wetting agent.

Foam and be even more stranded in the presence of the water comprising monovalence electrolyte and bivalent electrolyte (for example, sodium, calcium and magnesium) It is difficult.The polyelectrolyte water (also referred to as hard water or saline) is common in many regions in the world.As noted, currently Solid soap blank to show in saline be not fine (the usually short C because the larger soap of dissolubility₈、C₁₀、C₁₂Chain length Soap) precipitated by divalent salts such as calcium present in this saline and magnesium salt.Additionally, observing in laboratory test in saline The presence of the monovalent ion (such as sodium) of presence has negative effect.Particularly, monovalent ion appears the formation to micelle With affecting and therefore have impact on formation of foam.

In order to overcome the poor problem of foaming on the whole, disclosed use Jing is especially special for document of the prior art Soap (it is related to other, expensive process) and/or the conactivator (co-active) using other costliness.

For example, U.S. patents No.5 of Kefauver et al., 540,852 disclose gentle, foaming personal cleanliness's fertilizer Soap composition, it includes the tailored fatty acid soap of 30 to 85 weight %, the tailored fatty acid soap transfer and comprising 50% to 85% selected from following satisfied fatty acid soap：Myristic acid soap, palmitic acid soap and stearate soap.Kefauver and undisclosed spy Fixed capric acid and lauric fats acid soap proportional level, and maximum horizontal Semen Myristicae fatty acid or maximum horizontal except it is single not Unsaturated C beyond saturation Oleic acid₁₈Acid.

U.S. patents No.5 of Chambers et al., 656,579 disclose gentle fancy soap, and it includes soap with one kind or many Plant the blend of conactivator, lauric acid soap of the conactivator comprising at least 25 weight % for accounting for Active principals.Furthermore, Chambers and it is undisclosed have combined most with the ratio of capric acid required for protection in the present invention and the sour soap of lauric fats Substantial amounts of myristic acid soap or the maximum amount of unsaturated C in addition to Oleic acid₁₈Soap formula.

The gentle degree and/or performance for attempting raising before is carried by special special or using costliness conactivator For.

In the common pendent application 13/625,273 and 13/922 of applicant, in 764, applicant discloses fatty The specific blends of acid, therein defining C₈-C₁₀Soap and C₁₂The ratio of soap and disclose the maximum amount of C₁₄。

Applicant have now found that similar from those soap blanks in common pendent application (and facing with different restrictions Dividing value (criticality)) soap blank may be used in the water with polyelectrolyte concentration (for example, with the water of high restriction level The soap blank of hardness) in washing when increase foam.

Because fresh water only represent water in planet sub-fraction (1.75% frost and 0.75% from water-bearing layer, day So lake, cistern, rainwater) and remaining (97.5%) is saline, it is possible to find foam when using hard water it is good Soap blank is important.

Description of the drawings

Fig. 1 is a series of photographs for illustrating how to limit foam with visual score by using qualitative foam volume evaluation of programme Piece.The scoring is by numerical applications in qualitative determination.

The content of the invention

More specifically, applicant is it has been found surprisingly that the particular composition and method for increasing foam, wherein leading to Cross reequilibrate (rebalance) short-chain fatty acid (for example, C₁₀With C₁₂Ratio, use not more than the maximum amount of C₁₄, using spy The unsaturated C of quantitative and type₁₈), can produce abundant foam, or even in the water with polyelectrolyte concentration (for example, greater than about 25g salt/liter water, preferably greater than about 50g salt/liter water, the hydraulic angle value of preferably greater than about 75g salt/liter water are limited；Sea water The water hardness is for about 635g salt/liter water) in it is also such.

Specific embodiment

The present invention relates to make with the water (for example, with greater than about 25g salt/liter hardness of water) with polyelectrolyte concentration Used time increases the soap composition of foam.The soap blank compositionss are included：

A) the fatty acid soaps blend of the 30 to 90% of soap weight amount is accounted for, wherein：

i.C₁₀With C₁₂The ratio of fatty acid is of about 0.5:1.0 to about 1.5:1.0, preferably approximately 0.75:1 to 1.25: 1, more preferably from about 1:1；

ii.C₁₄Fatty acid is to account for 0 to about 3.5% maximum of soap blank composition weight, preferably approximately 0.1 to about 3.0% is present；

Iii. Oleic acid exists with account for soap blank composition weight about 25% to about 35%；

Iv. the unsaturated C in addition to Oleic acid₁₈The amount of fatty acid be 0 to about 10% maximum, preferably 0 to about 5%；

B) polyhydric alcohol of about 0.1 to about 15% of composition weight is accounted for；

C) account for composition weight about 0.1 to about 25%, preferably 0.1 to 15% mineral or organic granular；And

D) about 10% to 30%, preferably 13 to 20% water.

In this second embodiment, the present invention relates to be used for high-load dissolving salt, particularly divalent salts such as calcium Method with foam is increased in the water (that is, the water containing polyelectrolyte) of magnesium and monovalent salt such as sodium during washing.It is preferred that, have Greater than about 25g salt/liter water, more preferably greater than about increase foam in the water of 50g salt/liter hardness of water.Methods described includes apparatus The soap blank for having compositionss mentioned above foams to realize working as and use wherein C in the water with the hardness₁₀With C₁₂'s Ratio, C₁₄Maximum, the unsaturated C in addition to Oleic acid₁₈Maximum more than outside those scopes required for protection Increase foam (for example, the improvement of greater than about 30% foam) when the foam that soap blank is formed is compared.In particular, it is necessary to using being carried And standard.

Have 60 used in soap blank:During the ratio of 40 Petiolus Trachycarpi oil+palmitic stearin and palm-kernel oil (PKO), Jing is special System (" Jing designs ") is so that chain length distribution soap blank as above will be with than with identical 60:The same oil of 40 ratios but its Middle chain length ratio and some fatty acids (C₁₄；Unsaturated C in addition to Oleic acid₁₈) maximum not as the present invention in institute it is specific Claimed soap blank is high by greater than about 30%, be preferably greater than about 40% foam number (by usingFoam tester For exampleFoam tester R-2000 is with millimeter measurement amount；Or survey in the quantitative assessment test defined in scheme Amount).

Soap composition

The present invention relates to extrusion or melt casting personal cleansing soap blank, it includes the various fat of specified level and ratio Fat acid soap；The polyhydric alcohol of one or more optional addition, polymer, organic and inorganic assistant material, electrolyte, beneficial agent and Other submembers, and the water of surplus.It is as described below to these components for preparing and evaluating the soap blank compositionss of soap blank. The soap blank compositionss of the present invention can be by generally including the extrusion molding of soap blank or soap bar (billet) and by these soap Punching press is molded as the method for single piece, cake or soap blank and prepares, or the product can be obtained by melt casting method.

Fatty acid soaps blend

The all components of fatty acid soaps, other surfactants and actually soap blank shall be appropriate for and human skin Conventional contact, the preferred soap blank for producing height foaming.The soap blank produces preferable foam, or even when with high concentration two It is also such when washing in the water of valency salt and monovalent salt.By this foam with by being formed by identical oil-based material but wherein fatty acid The foam produced without soap blank special as defined is compared.(refer in embodiment with the soap blank for being unsatisfactory for limiting Contrast soap blank) compare, the improvement of foam is greater than about 30%, is preferably greater than about 40%.This quantitative survey defined in scheme In examination or also quantitative such as being obtained defined in schemeSet up in foam test machine data.

Offer improves the fatty acid blend soap of the amount of the soap composition comprising account for soap weight 30 to 85% of foam. It is further preferred that the fatty acid blend of amount of the fatty acid blend comprising account for soap weight 40 to 80%.Most preferably, fatty acid is common The fatty acid blend of amount of the mixed thing comprising account for soap weight 45 to 78%.

Fatty acid blend includes one or more surfactant.The surfactant of preferred type is fatty acid soaps. Herein term " soap ", i.e. aliphatic alkanes or the monocarboxylic alkali metal of alkene or alkanol ammonium salt are used with its general meaning.Sodium, Potassium, magnesium, an ethanol ammonium, diethanol ammonium and triethanolammonium cations or its combination are best suited for the object of the invention.Generally, at this No more than about 15% can be potassium, magnesium or triethanolamine soap in soda soap, but soap used in bright compositionss.Herein available soap is The known alkali metal salt of the naturally occurring or synthetic aliphatic acid (alkanoic acid or olefin(e) acid) with about 8 to about 24 carbon atoms.They can be retouched State is the saturation with about 8 to about 24 carbon atoms or the alkali metal carboxylate of unsaturated hydrocarbons.Alkali metal salt is preferred.

Fatty acid blend is by can be for different fatty acids, usually comprising having C₈To C₂₄The fat of the fatty acid part of chain length Fat processed with acid into.Fatty acid blend can also include one or more fatty acid of relative scale.Suitable fatty acid is included but not Be limited to butanoic acid, caproic acid, octanoic acid, capric acid, lauric acid, myristic acid, 14 carbon monoenoic acids (myristelaidic acid), 15 Alkanoic acid, Palmic acid, palmitoleic acid, heptadecanoic acid, heptadecenoic acid, stearic acid, Oleic acid, linoleic acid, linolenic acid, arachidic acid, 20 Carbon enoic acid, behenic acid and lignoceric acid and its isomer.It is preferable to minimize that or reduces the amount of butanoic acid and caproic acid.It is being preferable to carry out In scheme, fatty acid blend has a length of 10 (capric acid) and 12 used with the ratio being particularly limited to of wherein fatty acid part chain The fatty acid of (lauric acid) individual carbon atom.In preferred embodiments, fatty acid blend has low-level wherein saturated fat The fatty acid (myristic acid) of a length of 14 carbon atoms of fat acid moieties chain.

The fatty acid blend of the present invention comprising relatively high amount (for example, account for soap blank composition weight at least 3%, preferably At least capric acid 10%) and lauric acid, wherein C₁₀With C₁₂Ratio in the range of restriction.More particularly, C₈To C₁₄Fatty acid About 10% to about 32% (C of composition weight should be constituted₁₄Be separately formed composition weight no more than about 3.5%)；C₁₆ To C₁₈Long saturated chain should constitute about the 15% to 55% of composition weight；And long unsaturation C₁₈(for example, Oleic acid) should be constituted About 11% to 42% (the unsaturated C in addition to Oleic acid of composition weight₁₈10% or less of composition composition weight, it is excellent Select 8% or less, even more preferably 5% or less).These marginal values ensure that together with identical oil-based material but wherein not The soap blank for meeting marginal value (for example, special or design chain length) compares the preferable foam in polyelectrolyte water.

In preferred embodiments, it is 0.5 that fatty acid blend can have scope:1 to 1.5:1 capric acid with it is lauric Ratio.It is preferred that, the ratio is 0.75:1 to 1.25:1.

Fatty acid can finally for free fatty form, preferably be not higher than the 5% of fatty acid soaps blend amount.

Organic and inorganic assistant material

The aggregate level of the promoter material used in soap blank compositionss should be not higher than the amount of the 50% of soap composition weight.

The suitable starch material that can be used includes native starch (from Semen Maydiss, Semen Tritici aestivi, rice, Rhizoma Solani tuber osi, Maninot esculenta crantz. etc.), pre- Gelatinized starch, various physical modifications and chemical modification starch and its mixture.Term native starch mean without chemistry or The starch of physical modification --- also referred to as ative starch or former rice starch (native starch).

Preferred starch is from the natural of Semen Maydiss, corn, Maninot esculenta crantz., Semen Tritici aestivi, Rhizoma Solani tuber osi, rice and its other natural origins Starch or former rice starch.The ative starch of the amylose with different proportion and amylopectin：For example, (25% straight chain forms sediment Semen Maydiss Powder)；Waxy maize (0%)；Amylomaize (70%)；Rhizoma Solani tuber osi (23%)；Rice (16%)；Sago (27%)；Maninot esculenta crantz. (18%)；Semen Tritici aestivi (30%) etc..Ative starch can directly use during soap blank compositionss are prepared or be modified so as to So that starch becomes (either partial gelatinization or completely gelatinizing) of gelatinizing.

Another kind of suitable starch is pre-gelatinized, and it is before the composition in as soap blank compositionss of the present invention is added The starch of gelatinizing.Using the various forms of gelatinizing at different temperatures, for example can the scattered starch of cold water.It is a kind of suitable Commercially available pre-gelatinized starch by National Starch Co. (Brazil) with trade nameCS 3400 is carried For, but it is also suitable that other have the commercially available material of similar characteristics.

Polyhydric alcohol

Another kind of organic additive can be the mixture of polyhydric alcohol or polyhydric alcohol.Polyhydric alcohol is herein to represent height The term of water miscible, readily soluble preferably in the water compound with multiple (at least two, preferably at least three) hydroxyls.

Perhaps eurypalynous polyhydric alcohol be it is available, including：The short chain polyol of relatively low molecular weight, such as it is sweet Oil and Propylene Glycol；Sugar, such as Sorbitol, mannitol (manitol), sucrose and glucose；Modified carbohydrate is as hydrolyzed Starch, dextrin and maltodextrin, and polymerization synthesis polyhydric alcohol such as poly alkylene glycol, such as polyoxyethylene glycol (PEG) With polyoxypropylene diols (PPG).

Particularly preferred polyhydric alcohol is glycerol, Sorbitol and its mixture.

The content of polyhydric alcohol is suitable at a high speed manufacture (300-400 soap blanks are per minute) and is suitable for forming its material character It is crucial in thermoplastic as personal cleansing soap blank.It has been found that when polyol amount is too low, the material is being squeezed Go out at temperature (such as 40 DEG C to 45 DEG C) and there is no enough plasticity, and soap blank often shows higher soft gelatinizing And wear rate (mushing).Conversely, when polyol amount is too high, material becomes too soft, so that can not be in normal process temperature Degree is lower to form at a high speed soap blank.

In preferred embodiments, of the invention soap blank includes 0.1 to 20 weight %, preferably 0.5 to 15 weight % Polyhydric alcohol.As described above, it is preferred to polyhydric alcohol include glycerol, Sorbitol and its mixture.

Adjuvant system optionally includes the insoluble granule comprising a kind of material or combination of materials.Insoluble granule is referred to There is and is suitable for the material of personal cleansing with solid particulate.Preferably, there are mineral (such as inorganic) or organic Grain.

Insoluble granule should not be perceived as scraping the (scratchy) or granular of handss, therefore should have less than 300 Micron, more preferably less than 100 microns, more preferably less than 50 microns of granularity.

Preferred particulate inorganic material includes Talcum and Calcium Carbonate.Talcum is magnesium silicate minerals material, with flaky silicic acid Salt structure and Mg₃Si₄(OH)₂₂Composition, and can be obtained with hydrated form.It has lamellar morphology；And substantially Oleophylic/hydrophobic, i.e. it is by oil rather than is spontaneously wet out by water.

Calcium Carbonate or Chalk exist with three kinds of crystal forms：Calcite, aragonite and vaterite.The natural form of calcite is Rhombus or cube, the natural form of aragonite is needle-like or dendroid, and the natural form of vaterite is spherical.

It is commercial, it is referred to as the Calcium Carbonate or Chalk of winnofil and is prepared by carbonic acid gas full charge method, wherein by two The waterborne suspension that carbon oxide gas bubbling passes through calcium hydroxide.In the method, the crystal type of Calcium Carbonate be calcite or The mixture of calcite and aragonite.

The example of other optional insoluble particulate inorganic materials include aluminosilicate, aluminate, silicate, phosphate, Insoluble sulfur hydrochlorate, borate and clay (for example, Kaolin, china clay) and combinations thereof.

Organic particulate material includes：Insoluble polysaccharide, such as highly cross-linked or insoluble starch (for example, by with dredge The such as octenyl succinate reaction of water thing) and cellulose；Synthetic polymer, such as different polymer grid (lattice) and suspend Polymer；Insoluble soap and its mixture.

Soap blank compositionss preferably comprise 0.1 to 25 weight %, these ore deposits of preferred 5-15 weight % for accounting for soap blank compositionss Thing or organic granular.

Water

The soap blank of the present invention includes 10 to 30 weight %, the water of preferably 13 to 20 weight %.

Optional member

Synthetic surfactant：

Soap blank compositionss can optionally include surfactant (detergent) --- the so-called conjunction of the synthesis type of non-soap Into detergent.Synthetic detergent may include anion surfactant, nonionic surfactant, both sexes or amphion surface Activating agent and cationic surfactant.

The content of synthetic surfactant present in soap blank, based on the gross weight of soap blank compositionss, typically smaller than 25%, Preferably smaller than 15%, preferably up to 10%, most preferably 0 to 7%.

Anion surfactant can be such as aliphatic sulfonate, such as primary alkane (for example, C₈-C₂₂) sulfonate, primary alkane Hydrocarbon (for example, C₈-C₂₂) disulfonate, C₈-C₂₂Alkene sulfonate, C₈-C₂₂Hydroxyalkane sulfonates or alkyl glyceryl ether sulfonate (AGS)；Or aromatic sulphonate such as alkylbenzenesulfonate.Alhpa olefin sulfonate is another kind of suitable anion surfactant.

Anion surfactant can also be alkyl sulfate (for example, C₁₂-C₁₈Alkyl sulfate), particularly primary alconol Sulfate or alkyl ether sulfate (including alkyl glyceryl ether sulfates).

Anion surfactant can also be alpha-sulfonated fatty acid such as α-sulfonation tallow acid, sulfonated fatty acid ester such as α- Sulfonation tallow fatty acid methyl ester, or its mixture.

Anion surfactant can also be alkyl sulfo succinate (including monoalkyl and dialkyl group, such as C₆-C₂₂ Sulfosuccinate)；Alkyl and acyl taurine salt, alkyl and acyl sarcosinates, sulfosalicylic acetate, C₈-C₂₂Alkyl phosphonic acid Salt and phosphate, alkyl phosphate and alkoxyalkyl phosphate ester, acyl-lactate or dilactic acid salt (lactylate), C₈- C₂₂Mono-alkyl succinic acid salt and maleate, sulfosalicylic acetate and acyl-hydroxyethyl sulfonate.

Another analog anion surfactants are C₈To C₂₀Alkyl ethoxy (1-20EO) carboxylate.

Another kind of suitable anion surfactant is C₈-C₁₈Acyl isethionates.These esters pass through alkali metal Isethionate and with 6 to 18 carbon atoms and iodine number less than 20 mixed aliphatic series fatty acid between reaction prepare.Extremely Few 75% fatty acid mixed has 12 to 18 carbon atoms and most 25% fatty acid mixed has 6 to 10 carbon atoms. Acyl-hydroxyethyl sulfonate can also be the isethionate of alkoxylate.

When it is present, acyl-hydroxyethyl sulfonate generally accounts for about 0.5 weight % of total composition to about 25 weight %.

Generally, anionic group will constitute the most of synthetic surfactant used in soap blank compositionss.

The ampholytic detergent that can be used in the present invention includes at least one acid groups.This can be carboxylic acid or sulfonic acid group. They include quaternary nitrogen, therefore are season amic acids.They should generally include the alkyl or alkenyl of 7 to 18 carbon atoms.Suitable two Property surfactant include that both sexes acetate, alkyl and alkyl amido betaine and alkyl and alkyl amido sulfo group are sweet Dish alkali.

Possible amphion that both sexes acetate and two both sexes acetates (diamphoacetate) also can be used and/ Or amphoteric compound is covered.

Suitable nonionic surfactant includes compound (such as aliphatic alcohol with hydrophobic group and active hydrogen atom Or fatty acid) and epoxyalkane --- mixture of particularly single oxirane or oxirane and expoxy propane --- Product.Example includes aliphatic series (C₈-C₁₈) primary or secondary linear or branched alcohols with ethylene oxide condensation product, and by ring The product that oxidative ethane is prepared with the product condensation of expoxy propane and ethylenediamine.Other so-called nonionic detergent compounds Including long chain tertiary amine oxides, long-chain phosphine oxides and dialkyl sulphoxide.

Nonionic surfactant can also be sugared amide, such as alkyl polysaccharide and alkyl polysaccharide amide.

The example of cationic detegent is quaternary ammonium compound, for example alkyl dimethyl ammonium halide.

Other surfactants that can be used be described in Parran Jr. United States Patent (USP) No.3,723,325 and " the Surface Active Agents and Detergents " of Schwartz, Perry＆Berch (Vol.I＆II), Liang Zheye The application is included by way of quoting addition.

Finishing auxiliarieses material：

These materials are direct (spice) or indirectly (preservative) improves the aesthetic qualities of soap blank --- particularly vision, touch Feel and olfactory sensation (olefactory) characteristic --- composition.Various optional compositions can be included into the soap blank compositionss of the present invention In.The example of auxiliary agent is included but is not limited to：Spice；Opacifier, such as fatty alcohol, ethoxylated fatty acid, solid ester and TiO₂；Dye Material and pigment；Pearling agent, such as Jing TiO₂The Muscovitum of coating and other coated interference pigments；Lamellar minute surface granule (mirror Particle), such as organic flitter；Sensitizer (sensate), such as menthol and Rhizoma Zingiberis Recens；Preservative, such as dihydroxymethyl dimethyl Hydantoin (Glydant XL1000), p-Hydroxybenzoate, sorbic acid etc.；Antioxidant, such as Yoshinox BHT (BHT)；The salt and etidronic acid trisodium (trisodium etridronate) of chelating agen, such as ethylenediaminetetraacetic acid (EDTA)； Emulsion stabilizer；Supplementary thickener；Buffer agent；With their mixture.

The content of pearling agent should be about the 0.1% to about 3% of the gross weight for accounting for soap blank compositionss, preferably 0.1% to 0.5%th, most preferably from about 0.2 to about 0.4%.

Skin benefit agent：

The special optional member of a class that here is emphasized is comprising to promote skin and hair healthy and the skin of conditioning to have Beneficial agent.Potential beneficial agent is included but is not limited to：Lipid, such as cholesterol, ceramide and pseudoceramide；Antimicrobial Agent, such as triclosan (TRICLOSAN)；Sunscreen, such as cinnamate；Other types of exfoliation (exfoliant) granule, Such as polyethylene beads, Endocarpium Juglandiss, Fructus Pruni seed (apricot seed), petal and flower seed (flower seed), and it is inorganic Thing, such as silicon dioxide and Pumex；Other softening agent (skin soft agent), such as long-chain alcohol and wax such as lanoline；Other Wetting agent；Emollient；Skin-nourishing thing (skin nutrient), such as vitamin such as vitamin C, D and E and quintessence oil such as Buddhist Handss Citrus chachiensis Hort. oil, satsuma orange (citrus unshiu) oil, oil of Rhizoma Acori Graminei etc.；Avocado, Fructus Vitis viniferae, Semen Vitis viniferae, Myrrha, Fructus Cucumidis sativi, green water cress, Flos Inulae, Fols sambuci williamsii, Flos Pelargonii, Flos Tiliae, Amaranthus mangostanus L., Sargassum, Semen Ginkgo, Radix Ginseng, the water solublity of Radix Dauci Sativae or insoluble extraction Thing；Flos Impatientiss (impatiens balsamina), Camu Camu (camu camu), alpina leaves and other plant extracts such as gold Thread prunus mume (sieb.) sieb.et zucc., and its mixture.

The compositionss may also include the various other active component for providing additional skin (including scalp) benefit.Example bag Include anti-acne agents (anti-acne agent), such as salicylic acid and resorcinol；D the and L aminoacid of sulfur-bearing and its derivant and Salt, particularly their N- acetyl derivatives；Anti-wrinkle (anti-wrinkle), anti-skin atrophy and skin repair activity Material, such as vitamin (such as A, E and K), vitamin Arrcostab, mineral, magnesium, calcium, copper, zinc and other metal components；Tretinoin With ester and derivant such as retinal and retinol, vitamin b 3 compound, alpha-hydroxy acid, beta hydroxy acid, for example salicylic acid and its Derivant；Skin Soothing Agent (skin smoothing agent), such as Aloe, Jojoba oil, propanoic acid and acetogenin, goes out Sour (fenamic acid) derivant；Artificial self-tanning agent (tanning agent), such as dihydroxy acetone；L-Tyrosine；L-Tyrosine Ester, such as tyrosine ethyl ester and glucose tyrosine ester；Skin whitener (skin lightening agent), such as Aloe Extract and nicotiamide, Alpha-Glyceryl-L-AA, amino L-Tyrosine (tyroxine), DL-Lactic acid ammonium salt., glycolic, hydroquinone, 4- BHA；Sebum stimulators, such as bryonolic acid (bryonolic acid), dehydroepiandrosterone (DHEA) and orizano；Skin Fat inhibitor, such as polymeric aluminum chloride (aluminum hydroxy chloride), corticosteroid, dehydroactic acid and its salt, Dichlorobenzene base imidazoles dioxolanes (being available from Elubiol)；Antioxidant, albumen enzyme level；Firm agent (skin Tightening agent), such as vinyl pyrrolidone, (methyl) acrylic acid and by chain alkyl (methyl) acrylate group Into hydrophobic monomer terpolymer；Prurituss, such as hydrocortisone, methdilizine and the suppression of alimemazine hair growth System；5- alpha reductase inhibitors；Promote the reagent of desquamation；Anti-gfycation agent；Dandruff removing agent, such as vancide ZP；Hair growth promotees Enter agent, such as finasteride, minoxidil, novel vitamin D analogues and tretinoin and its mixture.

Electrolyte

Electrolyte of the soap comprising 0.5 weight % to 5 weight %.Preferred electrolyte includes alkali metal or alkaline-earth metal Chloride, sulfate and phosphate.It is not intended to be bound by theory, now thinks that electrolyte contributes to constructing cured soap blank simultaneously And also improved by common ion effect fusing block viscosity.It was found that the comparison soap without any electrolyte is softer.Chlorine It is most preferred electrolyte to change sodium and sodium sulfate, and its content is more preferably 0.6 to 3.6 weight %, most preferably 1.0 to 3.6 Weight %.

Polymer

Soap can include 0.1 to 5 weight % selected from acrylate or the polymer of cellulose ether.Preferred acrylate Acrylate, polyacrylic acid or sodium polyacrylate including crosslinking.Preferred cellulose ether includes carboxymethyl cellulose or hydroxyl alkane Base cellulose.Also the combination of these polymer can be used, premise soap blank part is that the total amount of polymer is less than 5 weight %.

Acrylate

Preferred soap blank is comprising 0.1 to 5% acrylate.Preferred soap blank is comprising 0.15 to 3% acrylate. The example of acrylate polymer is included such as the acrylic acid being crosslinked with polyallylsucrose described in United States Patent (USP) 2,798,053 Polymer and copolymer, the patent quoting addition by way of include herein.Other examples include polyacrylate, third The emulsion acrylic ester copolymer of olefin(e) acid ester copolymer or alkali swellable is (for example,33 Ex.Rohm and Haas；Aqua SF-1 Ex.Lubrizol Inc.), the copolymerization of hydrophobic modified alkali swellable Thing is (for example,22、28 Hes38ex.Rohm and Haas).It is commercially available can The acrylic acid cross-linked homopolymer for obtaining includes being available from Lubrizol Inc's934、940、941、956、 980 and 996 carbomers.Other commercially available crosslink propylene acid copolymers include being available from Lubrizol Inc'sUltrez kinds series (10th, 20 and 21) and ETD series (ETD 2020 and 2050).

Aqua SF-1 are a kind of particularly preferred acrylate.This compound is somewhat to be crosslinked , the acrylate copolymer of alkali swellable, it has three kinds of construction units：There are 3 to 10 carbon atoms one or more Carboxylic acid monomer, one or more acrylmonomers and one or more single or multiple unsaturated monomer.

Cellulose ether

Preferred soap blank is comprising 0.1 to 5% cellulose ether.Preferred soap blank is comprising 0.1 to 3% cellulose ether. Preferred cellulose ether is selected from alkylcellulose, hydroxy alkyl cellulose and carboxyl alkyl cellulose.Preferred soap blank includes hydroxyl alkane Base cellulose or carboxyl alkyl cellulose, particularly preferred soap blank includes carboxyl alkyl cellulose.

Preferred hydroxy alkyl cellulose includes hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and ethyl hydroxyl Ethyl cellulose.

Preferred carboxyl alkyl cellulose includes carboxymethyl cellulose.Particularly preferably carboxymethyl cellulose is carboxymethyl cellulose Sodium salt form.

Wax and poly alkylene glycol

Preferred wax includes paraffin and microwax.When using poly alkylene glycol, preferred soap blank can include 0.01 to 5 The poly alkylene glycol of weight %, more preferably 0.03 to 3 weight %, most preferably 0.5 to 1 weight %.Suitable example includes poly- Ethylene glycol and polypropylene glycol.Preferred commercially available prod is what Dow Chemical Company sold

The preferred composition of the present invention is comprising (by weight)：

1) soap of 30-85%, preferred soda soap；

2) 0.1 to 20% polyhydric alcohol, preferred glycerol, Sorbitol or mixture；

3) 0.1 to 25% granule；And

4) water of 10-30%.

In the preferred embodiment：

a)C₁₀With C₁₂The ratio of fatty acid is 0.5：1.0 to 1.5：1.0；

b)C₁₄Used with the amount less equal than 3.5 weight %；

C) Oleic acid accounts for 26-34 weight %；And

D) C in addition to Oleic acid₁₈Account for 0 to 8 weight %.

In preferred embodiments, soap blank is by using Petiolus Trachycarpi oil (PO), palmitic stearin (POS) and palm-kernel oil (PKO) prepared by mixture, wherein (PO+POS) is 75 with the ratio of PKO:25, preferably 60:40.

In a second embodiment of the present invention, the present invention includes increasing foam when washing in the water containing polyelectrolyte Method, methods described includes for soap blank compositionss as defined above being applied to skin or suitable base material, and wherein increases Plus foam is relative to the oil (for example, 60 by same type and ratio:40 (PO+POS)/PKO) it is obtained but wherein specific fat For sour blend is without the special soap blank to meet the specific criteria that the present invention is limited.

The soap blank of the present invention is not (for example, as special in what is limited by the present invention with the soap blank outside the scope of the invention ) increment (being surveyed in the water for limiting hardness) of the foam compared more than about 30%, be preferably above about 40%, it is Pass throughFoam tester is with measurement in mL measurement amounts or defined in scheme quantitative test.

In another embodiment, the present invention relates to be more than about 25 French hardness degrees (FH), be preferably greater than greatly in the water hardness Increase foam when washing in about 50 French hardness degrees, more preferably greater than about 75FH, the even more preferably greater than water of about 100FH Method, the method includes that the soap blank compositionss for being limited the compositionss of claim 1 are applied to skin or other base materials, wherein The foam of increase is relative to being made up of the oil of same type and ratio but wherein special fatty acid blend and not falling within is limited Fixed C₁₀:C₁₂Ratio, minimum C₁₄Amount and the minimum unsaturated C in addition to Oleic acid₁₈Amount soap blank product for.

Scheme and embodiment

Quantitative foam volume evaluation of programme：

1. introduction

The amount of the foam by produced by soap is an important parameter for affecting consumer preference to select.It is described herein Foam volume give one that foam at the standard conditions produces and measure, so as to objective ratio can be carried out to different soap formulations Compared with.

2. principle

Foam is produced by trained technical staff using standardized method.Collect foam and measure its volume.

3. equipment

Washing bowl (washing up bowl)-and per operator 1,10 liters of capacity

Soap water logging dish -1, each sample

Surgeon's rubber glovess-

High cylindric glass beaker -400mL, has (the Pyrex n ° 1000) of 25mL scales

Thermometer-

Glass rod-

Program

i.Piece pretreatment:

The surgeon's rubber glovess washed in common soap before putting on, before test program is started institute was rinsed There is test piece (such as soap blank) at least 10 minutes.They are turned into 180 ° (i.e. half preferably by under (about 30 DEG C) circulating water Circle) complete for about 20 times.

Ii. the water of the known hardness of about 5 liters under assigned temperature is placed in bowl.Generally, water temperature is of about 30 DEG C and keep constant in a series of given evaluations.Water is changed after each soap is tested.

Iii. piece is picked up, is dipped in water and is removed.The piece is turned 15 times between handss with 180 °.Described is placed on On soap disk.

Iv. foam is produced by the soap remained on glove.

1st stage：One hands in another, on hand rub with the hands 10 times in the same manner by (two handss are in the same direction).

2nd stage：The right hand is held with left hand, or left hand is held with the right hand, and foam is extruded into into the tip of finger.

The operation is repeated 5 times.

Repeated for the 1st and 2 stages.

Foam is placed in beaker.

v.The whole program that the foam started from the i-th ii sections is produced is repeated two more times, all foams are merged in beaker.

Vi., the foam of merging is lightly stirred the air bubble release so that big.Reading simultaneously records volume.

Then data analysiss carry out Turkey tests and carry out by two-way ANOVA.

UseThe measurement scheme (quantitative) of foam generator R2000 instruments：

1. it is by the parameter setting on equipment:

A) volume:250mL

B) bath temperature:37℃

C) measure:99

D) speed:800 turns per minute

E) time of vibration:20 seconds

2. 10 weight % solution of the soap in simulated seawater are prepared.(seawater compositions of simulation are defined in the table of embodiment 2 And the French hardness degrees with 635FH).

3. press start button and make machine operation.

Qualitative foam volume evaluation of programme：

1- moistenings handss and moistening soap blank；

2- makes soap blank rotate 15 times outside water；

Soap blank is placed in soap disk and is collected formed foam by 3-；

4- holds handss 3 times and collects formed foam；

The foam that 5- is with Qian Hou reciprocal movement friction handss 3 times and collection is formed；

6- holds handss 3 times and collects formed foam；

The foam that 7- is with Qian Hou reciprocal movement friction handss 3 times and collection is formed；

8- holds all foams that handss 3 times and collection are formed；

9- evaluates foam volume according to visual score, wherein (for example, no the view-based access control model for determining as shown in Figure 1 scores It is zero that frothy the tested compositionss of tool are judged as its level, and the compositionss with maximum foam are judged as it 10) level is.

Embodiment

The fatty acid radical of solid moisturizing personal cleansing soap blank different weight percentage is prepared according to formula hereinafter.

There is provided with following trade name by Cosmoquimica to the fatty acid for preparing pharmaceutical formulation：C8 98/100 (sad (Caprilic acid))；C10 98/100 (capric acid)；(the moons of C12 98/100 Cinnamic acid)；C14 98/100 (myristic acid)；C16 98/100 (Palmic acid)；C18 98/100 (stearic acid)；C18:1 98/100 (Oleic acid).

The possible supplier of other fatty acids be Qu í mico Anast á cio, Emery Oleochemicals and Aboissa óleos Vegetais。

Embodiment 1 and compare A and B

Various fatty acid soaps distributions are given in Table 1:

Table 1

* per the grams of 100g iodine.

Evaluation result * * when seawater is used	Relatively A	Relatively B	Embodiment 1

Foam number (ml) (quantitative test)	50	56	238
				Qualitative scoring (0-10)	0-2	0-2	8-10

* sea water has hardness pointed in following table in embodiment 2.

As a result illustrate, not by the amount (comparing B) for improving the natural oil wherein using more palm-kernel oils (PKO), But if reequilibrate short chain oils (C₈、C₁₀、C₁₂、C₁₄) amount, then produce abundant foam, or even using extreme water condition (for example, wherein the amount of every liter of water monovalence and divalent salts>3g/l, more than 6g/L or bigger) under it is also such.Particularly, increased C₁₀ And C₁₂Amount (and within the ratio for holding it according to claim hard constraints), while minimizing C₁₄With except Oleic acid with Outer unsaturated C₁₈Amount.As noted, in reequilibrate compositionss (embodiment 1), foam volume be 238ml (compared to 50 or trained group 56) and in qualitative scoring in Comparative examples A and B keep the score as 8-10.

Embodiment 2

Sea water and other hardnesss of water are given below：

The table 1 of water composition

* FH=French hardness degrees

As noted, the result of embodiment 1 is obtained using sea water.Embodiment is also shown for the brackish water of country variant High rigidity level (be more than 50, more than 100).

Applicant is also tested for and (uses in the seawaterScheme) indivedual C₈、C₁₀、C₁₂、C₁₄The most bulla of chain length Foam；The maximum foam of the compositionss of embodiment 1 and compare B compositionss maximum foam；And result is given below.

Table 2

Can clearly be seen that saline (for example, sodium ion) has strong negative effect, wherein C to foam₁₄Chain length is special It is not impacted.Can also be clear that, wherein the compositionss for optimizing shorter chain length relative to conventional soap blank have getting well Many foams.

Embodiment 3

Compositionss are diluted to different ratios by applicant also using the preparation (embodiment 1) containing optimization blend. " dilution " refers to the longer chain fatty acid that there is higher amount, it is believed that, it is contemplated that its foaming is less.Diluted compositionss are existed Test in laboratory and SITA testers, it is as a result as follows：

Table 2

As it can be noticed that " Jing designs " soap blank shows preferable performance, or even when being diluted to largely (80/20) when.Unforeseeable preferable foaming properties are obtained by using more large content of than conventional soap blank compared with short chain.

Claims

1. it is used to increase the soap blank compositionss of foam when washing during the water hardness is greater than about the water of 25g/ liter water, wherein the soap blank Comprising：

A) the alkali metal fatty acid soap or alkanol ammonium salt fatty acid soaps of the 30-90% of soap blank composition weight are accounted for, wherein：

(i)C₁₀Chain length fatty acids soap and C₁₂The ratio of chain length fatty acids soap is of about 0.5:1.0 to about 1.5:1.0；

(ii) wherein C₁₄The amount of chain length fatty acids is 0 to about 3.5% maximum of soap blank composition weight；

(iii) wherein unsaturation C₁₈Amount for soap blank composition weight about 25 to 35%；And

(iv) the unsaturated C wherein in addition to Oleic acid₁₈The amount of fatty acid is 0 to about 10% maximum for soap blank composition weight Value,

B) polyhydric alcohol of about 0.1 to about 15% of soap blank composition weight is accounted for；

C) mineral or organic granular of about 0.1 to 25 weight %；With

D) water of about 10 weight % to 30 weight %.

2. the compositionss of claim 1, wherein C₁₀With C₁₂Ratio be of about 1:1.

3. compositionss of claim 1 or 2, wherein C₁₄Amount be of about 0.1 to about 3.0 weight %.

4. compositionss of any one of aforementioned claim, wherein the unsaturated C in addition to Oleic acid₁₈The amount of fatty acid is 0 to big About 8%.

5. compositionss of any one of aforementioned claim, wherein the polyhydric alcohol is selected from glycol, Sorbitol and its mixture.

6. compositionss of any one of aforementioned claim, wherein the soap blank by Petiolus Trachycarpi oil (PO), palmitic stearin (POS) and The combination of palm-kernel oil (PKO) is made, wherein (PO and POS) is of about 60 with the ratio of PKO:40 to about 80:20.

7. compositionss of any one of aforementioned claim, the wherein water hardness are more than about 50.

8. compositionss of any one of aforementioned claim, the wherein water hardness are more than about 75.

9. during the water hardness is greater than about the water of 25 French hardness degrees (FH) wash when increase foam method, including by by Any one of aforementioned claimCompositionss limit soap blank compositionss application to skin or other bases Material, wherein increased foam is not fallen relative to the oil but wherein special fatty acid blend for coming from identical type and ratio Enter limited C₁₀:C₁₂Ratio, minimum C₁₄The unsaturated C in addition to Oleic acid of amount and minimum₁₈Soap blank product for.

10. the method for any one of aforementioned claim, the increment of wherein foam is the raising more than 30%, and the amount passes through SITA foams tester is with milliliter (mL) measurement amount.