EP0559837B1 - Solide faconne compose d'une maille rigide a emboitements d'acide carboxylique neutralise - Google Patents

Solide faconne compose d'une maille rigide a emboitements d'acide carboxylique neutralise Download PDF

Info

Publication number
EP0559837B1
EP0559837B1 EP92904074A EP92904074A EP0559837B1 EP 0559837 B1 EP0559837 B1 EP 0559837B1 EP 92904074 A EP92904074 A EP 92904074A EP 92904074 A EP92904074 A EP 92904074A EP 0559837 B1 EP0559837 B1 EP 0559837B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
bar
weight
sodium
soap
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92904074A
Other languages
German (de)
English (en)
Other versions
EP0559837A1 (fr
Inventor
Mark Leslie Kacher
James Eden Taneri
James Berger Camden
Paul Edward Vest
Sylvia Jean Bowles
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/782,956 external-priority patent/US5340492A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0559837A1 publication Critical patent/EP0559837A1/fr
Application granted granted Critical
Publication of EP0559837B1 publication Critical patent/EP0559837B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0069—Laundry bars
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/32—Protein hydrolysates; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines

Definitions

  • This invention relates to neutralized carboxylic acid shaped solid compositions, particularly cleansing bars, cakes, soap bars, synbars and the like.
  • Products made in the form of shaped solids, cakes and bars are numerous. Cleansing bars are well known in the art.
  • Bar smear also referred to as bar sloth
  • bar sloth is the soft solid or mush that forms at the surface of a bar when submerged in water and is regarded by consumers as messy, unattractive, and uneconomical.
  • Products made in the form of shaped solids, cakes and bars are numerous.
  • E.g., certain high moisture and low smear personal cleansing bars are disclosed in US-A-4,606,839 Harding, issued Aug. 19, 1986. Harding uses coconut and/or palm kernel oil soap.
  • JP-A-7030-798 discloses transparent solid framed or molded soap bar in which fatty acids constituting the soap component are myristic, palmitic, and stearic acids.
  • a transparent soap is described in which at least 90 wt.% of the fatty acids which constitute the soap component are myristic acid, palmitic acid, and stearic acid.
  • the product is reported as a transparent, solid soap having good frothing and solidifying properties, good storage stability, and a low irritant effect on human skin.
  • the process and transparent bar soap composition exemplified in JP-A-7030-798 do not appear to contain synthetic surfactant.
  • the invention provides a cleansing bar comprising a shaped, solid three-dimensional skeleton structure comprising: a relatively rigid, interlocking mesh of neutralized crystalline carboxylic acid, wherein the rigid, interlocking mesh of neutralized carboxylic acid, preferably comprises sodium soap fibers.
  • Some cleansing bars which comprise surprisingly large amounts of water and other liquids while maintaining their rigidity and excellent smear properties; even when allowed to soak overnight in water.
  • Figures 1-8 show magnified views of bar samples of the present invention.
  • Figures 9 and 10 show magnified views of two different conventional soap bars.
  • the Scanning Electron Microscopy (SEM) sample preparation involves fracturing a shaped solid with simple pressure to obtain a fresh surface for examination.
  • the fractured sample is reduced in size (razor blade) to approximately a 10 mm x 15 mm rectangle with a thickness of about 5 mm.
  • the sample is mounted on an aluminum SEM stub using silver paint adhesive.
  • the mounted sample is coated with approximately 300 angstroms of gold/palladium in a Pelco sputter coater. Prior to coating, the sample is subjected to vacuum for a period of time which is sufficient to allow sufficient loss of bar moisture assuring acceptable coating quality. After coating, the sample is transferred to the SEM chamber and examined under standard SEM operating conditions with an Hitachi Model S570 Scanning Electron Microscope in order to see the skeletal (core) frame.
  • FIGS. 1 and 2 are copies of photographs of a highly enlarged skeleton core structure comprising a rigid, interlocking mesh of elongated neutralized carboxylic acid crystalline fibers. More specifically FIGS. 1 and 2 are elongated C12 sodium soap fibers, enlarged respectively at 5000X and 2500X magnifications. The structure of FIGS. 1 and 2 are made with 5% soap; 94% water; and 1% sodium chloride. See Example 10 in Table 7 herein. Note that larger fibers in the interlocking mesh can be composed of smaller fibers. Also, note the "void" spaces. See FIG. 2.
  • FIGS. 3, 4 and 5 are copies of photographs of a skeleton structure made with 25% sodium C12 soap; 74% water; and 1% sodium chloride.
  • the crystalline fiber-like structure is shown respectively at 3000X, 5000X and 1000X magnifications.
  • FIG. 6 is a copy of a photograph of a skeleton structure made with 20% disodium salt of 1,12-dodecanedioic acid.
  • the crystalline fiber-like structure is shown at 2000X magnification. See Example 26.
  • FIG. 7 is a copy of a photograph of a skeleton (core) structure comprising crystalline lithium neutralized C14 carboxylic acid mesh, shown at 1500X magnification. See Example 27.
  • FIG. 8 is a copy of a photograph of a cleansing bar (Example I hereinbelow) comprising: coated C14 ⁇ 16 sodium soap fibers. The fibers are coated and/or commingled with the other bar components. The magnification is 1500X.
  • FIG. 9 shows a sample of a market IVORY (RTM) freezer bar made with sodium/potassium coconut/tallow soap at 1000X on the scale.
  • the air in the IVORY (RTM) bar soap makes it float.
  • FIG. 10 shows a sample of a market NEUTROGENA (RTM) transparent bar at 1500X.
  • FIGS. 1 and 2 the samples are first melted on a hot plate and recooled on a glass slide.
  • the other samples, FIGS. 3-10, are samples of original shaped solid structures or the conventional bar prepared as set out herein.
  • the invention provides a cleansing bar comprising a shaped solid comprising two or more phases.
  • One phase is a crystalline skeleton structure comprising a rigid interlocking, open, three-dimensional mesh of neutralized carboxylic acid elongated crystals.
  • the other essential phase is an aqueous phase which is soft or flowable at 25°C.
  • the skeleton structure is a relatively rigid, interlocking, open, three-dimensional mesh of neutralized mono- and/or di-carboxylic acid elongated crystals.
  • skeleton structure skeletal structure, core, and skeleton frame are often used interchangeably herein.
  • shaped solids as used herein includes forms such as bars, cakes and the like.
  • bar as used herein includes the same unless otherwise specified.
  • mesh as used herein means an interlocking crystalline skeleton network with voids or openings when viewed under magnification by scanning electron microscopy.
  • the present invention provides an improved cleansing bar which is comprised of said skeleton structure.
  • Some shaped solids are in the form of cleansing bars which contain surprisingly high levels of said aqueous phase comprising water, other liquids and soft materials. Notwithstanding the presence of relatively large levels of an aqueous phase, the preferred bars of the present invention maintain their rigidity and excellent smear properties, even when allowed to soak overnight in water. While not being bound to any theory, the shaped solid comprising these phases is similar to a relatively rigid wet sponge.
  • the crystalline phase comprises crystals in the form of either interlocking platelets and/or fibers, preferably fibers.
  • said fibers are composed of sodium soap.
  • the interlocking mesh of said fibers and/or platelets imparts strength to the three-dimensional structure, even in the presence of relatively high levels of water or other soft materials; even when allowed to soak overnight in water.
  • the strength of the skeleton structure can be measured indirectly by the hardness of the shaped solid, as determined by the resistance to penetration of the solid using a Standard Weighted Penetrometer Probe. See Bar Hardness Test below for more details.
  • the skeleton structure is of sufficient rigidity that a 25 mm thick or greater cleansing bar sample has a penetration of from zero mm to 12 mm, preferably from 1 mm to 10 mm, more preferably from 3 mm to 8 mm.
  • the present bars are distinguished from conventional transparent bars based on crystal size, as well as other characteristics.
  • the crystals or crystal bundles that make-up the interlocking mesh structure of the present invention are of a size that diffracts light and consequently are greater than 400 nm in either diameter or length.
  • conventional transparent bars gain their transparency by having crystal diameters or length less than the wavelength of white light, which is greater than about 400 nm and consequently do not diffract light.
  • a bar (shaped solid) comprising the rigid skeletal structure of the present invention loses its rigidity when subjected to fracturing mechanical forces, e.g., those used in a conventional plodded bar making process as disclosed in US-A-4,812,253, Small et al., or US-A-4,820,447, Medcalf et al. This is because the fracturing mechanical forces, shear and break up the rigid, skeletal structure into smaller pieces. Thus, when a bar of the present invention is sheared in a plodder, a much softer bar results.
  • fracturing mechanical forces e.g., those used in a conventional plodded bar making process as disclosed in US-A-4,812,253, Small et al., or US-A-4,820,447, Medcalf et al.
  • the skeletal structure contains substantial "void" areas which are filled by soft and/or liquid aqueous phases. It is a surprising aspect of this invention that the physical properties of the bar, such as bar hardness and little smear, are mostly dependent on the crystalline interlocking mesh structure, even when the other phases make up a majority of the materials present. In conventional bars, many components can impact the overall bar physical properties because the components either modify the phase and structure of the soap or synthetic surfactant components that primarily determine the bar's physical properties. The combination of two or more phases (e.g., soap and aqueous solution) drastically changes the colloidal structure, and consequently, the physical properties of a conventional bar.
  • two or more phases e.g., soap and aqueous solution
  • phase materials that can be incorporated into the bar than the present invention.
  • Such phases include most materials that are either flowable liquids or materials that are softer than the minimum hardness of an acceptable bar.
  • These phases include aqueous solutions, liquid crystalline phases composed of water and surfactant, polymers; particularly surfactant-containing crystalline phases, and especially hygroscopic surfactants, which tend to become soft and sticky when mixed with water or other liquid phases including water-soluble organics (e.g., propylene glycol and glycerine), hydrophobic materials (e.g., mineral oil, liquid triglycerides), or soft hydrophobic materials, e.g., petrolatum, low melting paraffin, and low melting triglycerides.
  • water-soluble organics e.g., propylene glycol and glycerine
  • hydrophobic materials e.g., mineral oil, liquid triglycerides
  • soft hydrophobic materials e.g., petrolatum, low melting paraffin, and
  • phase can be characterized as being flowable liquids or so soft that a Standard Weighted Penetrometer Probe, as defined herein, will penetrate all the way through a 12 mm thick sample.
  • phase can be selectively included in the structure of the present invention without loss of the interlocking mesh structure and certain desirable physical properties.
  • the invention is a non-transparent cleansing bar comprising at least two phases: (1) an aqueous phase having a penetration value of 12 mm for a 12 mm deep sample; said aqueous phase being soft or flowable at 25°C; (2) a rigid crystalline phase comprising a rigid crystalline phase skeleton structure comprising an interlocking, open three-dimensional mesh of neutralized mono- and/or di-carboxylic acid elongated crystals light diffracting having a diameter or length greater than 400 nm; wherein said cleansing bar comprising said rigid crystalline phase skeleton structure and said aqueous phase has a penetration value of of from zero to 12 mm for a 25 mm deep sample; and wherein said penetration values are measured as 25°C using a 247 gram Standard Weighted Penetrometer Probe having a conical needle attach to a 9 inch (22.9 cm) shaft weighing 47 grams, with 200 grams on top of said shaft for a total of said 247 grams, said conical needle having a 19/32 inch (1.51
  • said neutralized carboxylic acid is selected from the group consisting of: lithium and/or sodium neutralized: monocarboxylic acid (soap) and/or dicarboxylic acid; and mixtures thereof; wherein said monocarboxylic acid has a fatty alkyl(ene) chain of from about 12 to about 24 carbon atoms; wherein said dicarboxylic acid has a fatty alkyl(ene) chain of from about 12 to about 18 carbon atoms; and wherein at least about 80% of said carboxylic acid has saturated alkyl(ene) chains; and wherein said rigid crystalline phase skeleton structure occupies from above 3% to 75% of said cleansing bar by volume; and wherein said neutralized carboxylic acid comprises from above 5% to 75%; and wherein said cleansing bar contains from 15% to less than 94% water by weight of said cleansing bar.
  • the above cleansing bar is highly preferred when said elongated crystals are composed of fiber-like sodium fatty acid soap of which at least 25% of said saturated fatty alkyl chains is of a single chain length; and wherein said bar contains: from 15% to 75% by weight of said sodium soap; wherein the ratio of said unneutralized (free) carboxylic acid to soap is from 1:2 to 0. In other words, the free fatty acid is no more than 50% by weight of the soap in the formulation.
  • the above cleansing bar is preferred when said bar contains said sodium soap and water; and from 2% to 60% by weight of a synthetic surfactant selected from the group consisting of: alkyl sulfates, paraffin sulfonates, alkylglycerylether sulfonates, acyl sarcosinates, methylacyl taurates, linear alkyl benzene sulfonates, N-acyl glutamates, alkyl glucosides, alpha sulfo fatty acid esters, acyl isethionates, alkyl sulfosuccinates, alkyl ether carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, methyl glucose esters, protein condensates, alkyl amine oxides, alkyl betaines, alkyl sultaines, the alkyl ether sulfates with 1 to 12 ethoxy groups, and mixtures thereof
  • the above cleansing bar is preferred when said synthetic surfactant is hygroscopic; said hygroscopic surfactant being defined as a surfactant which absorbs at least 20% of its dry weight in water at 26°C and 80% Relative Humidity in three days and wherein said bar is relatively non-swelling.
  • the above cleansing bar is preferred when said hygroscopic surfactant is selected from the group consisting of alpha sulfo fatty acid esters; alkyl sulfates; alkyl ether carboxylates; alkyl betaines; alkyl sultaines; alkyl amine oxides; alkyl ether sulfates; and mixtures thereof.
  • the above cleansing bar is preferred when the ratio of said water to said soap is from 1:1 to 5:1; said water is present at a level of from 25% to 60% by weight; wherein said fatty alkyl chains are C14 to C22 and said soap level in said bar is from 15% to 35% by weight; wherein at least 85% of said alkyl chains are saturated; wherein the weight ratio of said unneutralized (free) carboxylic acid to said soap is from 1:4 to 0; and wherein said synthetic surfactant level is from 4% to 25% by weight of the bar and said surfactant is selected from the group consisting of: sodium acyl isethionates, sodium acyl sarcosinates, sodium alpha sulfo fatty acid esters, sodium paraffin sulfonates, sodium alkyl ether sulfates, sodium alkyl sulfates, sodium linear alkyl benzene sulfonates, alkyl betaines, alkyl sultaines, and trialkyl
  • the above cleansing bar is preferred when the ratio of said water to soap ratio is from 1.5:1 to 2:1; the ratio of said unneutralized (free) carboxylic acid to said soap is from 1:6 to 0; said water level is from about 30% to about 45% by weight; said fatty alkyl chain is from C14 to C18; wherein at least 95% of said alkyl chains are saturated; said soap level is from 15% to 30% by weight; and said synthetic surfactant level is from 8% to 16% by weight.
  • the above cleansing bar is preferred when said bar contains from 0.1% to 40% by weight of a hydrophobic material selected from the group consisting of: microcrystalline wax, petrolatum, carnauba wax, palm wax, candelilla wax, sugarcane wax, vegetable derived triglycerides, beeswax, spemaceti, lanolin, wood wax, shellac wax, animal derived triglycerides, montar, ozokerite, ceresin, and Fischer-Tropsch wax.
  • a hydrophobic material selected from the group consisting of: microcrystalline wax, petrolatum, carnauba wax, palm wax, candelilla wax, sugarcane wax, vegetable derived triglycerides, beeswax, spemaceti, lanolin, wood wax, shellac wax, animal derived triglycerides, montar, ozokerite, ceresin, and Fischer-Tropsch wax.
  • the above cleansing bar is preferred when said bar contains from 2% to 35% by weight of said hydrophobic material selected from the group consisting of petrolatum and wax, said petrolatum and wax, and mixtures thereof melting melting 49°C (120°F) to 85°C (185°F).
  • said hydrophobic material selected from the group consisting of petrolatum and wax, said petrolatum and wax, and mixtures thereof melting melting 49°C (120°F) to 85°C (185°F).
  • the above cleansing bar is preferred when said bar comprises from 5% to 25% by weight of the bar of paraffin wax.
  • the above cleansing bar is preferred when said bar contains from 2% to 40% by weight of said non-volatile, water-soluble, nonionic organic material.
  • non-volatile, water-soluble, nonionic organic material comprises from 5% to 20% by weight of the bar; and wherein said organic material is selected from the group consisting of: propylene glycol, glycerine, sucrose, and urea, and mixtures thereof.
  • the above cleansing bar is preferred when said bar contains said sodium soap, said water, and said synthetic surfactant, and from 0.1% to 70% by weight of other ingredients selected from the group consisting of: from 1% to 10% by weight said potassium soap; from 1% to 35% by weight said magnesium soap; from 1% to 35% by weight said calcium soap; from 1% to 15% by weight triethanolammonium soap; from 1% to 60% by weight of impalpable water-insoluble materials selected from the group consisting of calcium carbonate and talc; from 0.1% to 20% by weight of a polymeric skin feel aid; wherein said polymeric skin feel aid is selected from the group consisting of cationic polysaccharides, preferably cationic guar gum with molecular weights of 1,000 to 3,000,000; cationic polyalkylene imines, ethoxypolyalkylene imines, and poly[N-[-3-(dimethylammonio)propyl]-N'-[3-ethyleneoxyethylene dimethylammonio)propyl]urea dichloride]
  • the above cleansing bar is preferred when said elongated crystals contain platelets and wherein said soap consists of lithium neutralized monocarboxylic acid.
  • the above cleansing bar is preferred when said elongated crystals are fiber-like and wherein said neutralized dicarboxylic acid is the disodium salt 1,12-dodecanedioic acid and wherein said neutralized dicarboxylic acid comprises from 20% to 70% by weight of said bar.
  • a process of making the above cleansing bar of the present invention comprises the steps of:
  • aqueous phase contains from 20% to 100% water by weight of said aqueous phase.
  • said rigid crystalline phase contains from 75% to 100% of said neutralized carboxylic acid by weight of said crystalline phase.
  • miscellaneous non-carboxylic acid phases comprising droplets or crystals selected from waxes, petrolatum, clays, and the like.
  • a preferred embodiment of the present invention is: a personal cleansing bar composition comprising a rigid, crystalline interlocking mesh of elongated sodium soap crystals; said soap bar comprising: from 15% to 50% by weight sodium fatty acid soap composed of at least 50% saturated fatty alkylene chains having 12-24 carbon atoms of which at least 25% of said saturated fatty alkyl chains is of a single chain length; from 15% to 60% water by weight; and from 2% to 60% by weight of a hygroscopic synthetic surfactant wherein said hygroscopic synthetic surfactant is selected from surfactants which absorb at least 20% of their dry weight in water at 26°C and 80% Relative Humidity in three days.
  • the above preferred personal cleansing bar is more preferred when said hygroscopic synthetic surfactant is selected from the group consisting of alpha sulfo fatty acid esters; alkyl sulfates; alkyl ether carboxylates; alkyl betaines; alkyl sultaines; alkyl amine oxides; alkyl ether sulfates; and mixtures thereof.
  • This preferred personal cleansing bar is more preferred when said bar contains from 0.5% to 40% by weight of salts and/or salt hydrates selected from the group consisting of: sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium citrate, and other compatible salts of inorganic acids and short chain organic acids.
  • salts and/or salt hydrates selected from the group consisting of: sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate, sodium acetate, sodium citrate, and other compatible salts of inorganic acids and short chain organic acids.
  • a highly preferred cleansing bar comprises: various combinations of the core structure of sodium soap fibers, water, mild synthetic surfactants, bar appearance stabilizers, skin mildness aides and other cleansing bar adjuvants.
  • Such preferred bar can be formulated to have essentially no bar smear.
  • Some preferred bars of the present invention comprise: a rigid, interlocking mesh of neutralized carboxylic acid fiber-like core consisting essentially of sodium fatty acid soap composed of at least 50% saturated fatty alkyl chains having 12 to 24 carbon atoms. Preferably at least about 25% of said saturated alkyl chains are of a single chain length.
  • compositions of this invention comprise the above-defined rigid mesh with water and without water. These compositions must be formed with water or another suitable solvent system.
  • the compositions can be made with large amounts of water and the water level in the final composition can be reduced to as low as 1% or 2% by weight.
  • More complex bars of the present invention comprise a skeletal structure comprising other salts of fatty acids selected from potassium, magnesium, triethanolammonium and/or calcium soaps used in combination with the selected levels of sodium and/or lithium soaps.
  • More complex cleansing bars can contain surprisingly large amounts of water, mild synthetic surfactants, bar appearance stabilizers, skin mildness aids and other cleansing bar adjuvants; yet are mild and have very good low smear.
  • Tables 1-3 set out some preferred bars which are made with the sodium salts of the fatty carboxylic acid (FA) soap.
  • the bars shown in Table 1 are made with the level of water indicated, but the water level of the final bars can be reduced to provide bars which contain reduced levels of water or even little or no water.
  • a preferred level of water is from 20% to 80% by weight of the bar.
  • Table 2 below shows some preferred levels of soaps of a single FA chain length.
  • Table 3 shows some preferred levels of unsaturation in the FA's used in the compositions of the present invention.
  • Some preferred compositions contain little or no short chain FA's of ten carbon atoms or less.
  • the terms “soap”, “fatty acid (FA) salts” and “monocarboxylic acid salts” as used herein are sometimes interchangeable. "Soap” is used since it is easier to relate to and is the preferred embodiment.
  • the highs and lows of some key preferred optional ingredients for complex soap bar compositions of this invention are set out in Table 4. None of these ingredients is essential for the basic, preferred bar core structure. Zero is the lowest level for each optional ingredient. Some preferred bars can contain a total of from 0.1% up to 70% by weight of such ingredients. The idea here is that the core bars can contain large amounts of other ingredients besides soap and water.
  • the levels set out in Table 4 are particularly illustrative for bars containing from more than 5% to 75% by weight selected sodium soap and other ingredients.
  • the soaps useful in the present invention can be of the same alkyl chain lengths, i.e., which are selected from the 12 to 24 carbon atoms as set out in Table 2.
  • the same chain lengths apply for the other non-sodium soaps used in the bars of the present invention.
  • the sodium soap is preferably at least 50% by weight of the soap present in the bar.
  • the levels of potassium soap and/or triethanolammonium soap should not exceed one-half, preferably one-third, more preferably less than one-fourth, that of the sodium soap and the level of magnesium soap should not exceed about one-third of the level of sodium soap, and is preferably less than about one-fourth that of the sodium soap.
  • the total of other soaps, save lithium soap, should preferably not exceed one-half, preferably one-third, of the sodium soap.
  • the synthetic detergent constituent of the bar compositions of the invention can be designated as being a detergent from the class consisting of anionic, nonionic, amphoteric and zwitterionic synthetic detergents. Both low and high lathering and high and low water-soluble surfactants can be used in the bar compositions of the present invention.
  • Examples include the water-soluble salts of organic, sulfonic acids and of aliphatic sulfuric acid esters, that is, water-soluble salts of organic sulfuric reaction products having in the molecular structure an alkyl radical of from 10 to 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • Synthetic sulfate detergents of special interest are the normally solid alkali metal salts of sulfuric acid esters of normal primary aliphatic alcohols having from 10 to 22 carbon atoms.
  • the sodium and potassium salts of alkyl sulfuric acids obtained from the mixed higher alcohols derived by the reduction of tallow or by the reduction of coconut oil, palm oil, stearine, palm kernel oil, babassu kernel oil or other oils of the coconut group can be used herein.
  • aliphatic sulfuric acid esters which can be suitably employed include the water-soluble salts of sulfuric acid esters of polyhydric alcohols incompletely esterified with high molecular weight soap-forming carboxylic acids.
  • Such synthetic detergents include the water-soluble alkali metal salts of sulfuric acid esters of higher molecular weight fatty acid monoglycerides such as the sodium and potassium salts of the coconut oil fatty acid monoester of 1,2-hydroxypropane-3-sulfuric acid ester, sodium and potassium monomyristoyl ethylene glycol sulfate, and sodium and potassium monolauroyl diglycerol sulfate.
  • the synthetic surfactants and other optional materials useful in conventional cleaning products are also useful in the present invention.
  • some ingredients such as certain hygroscopic synthetic surfactants which are normally used in liquids and which are very difficult to incorporate into normal cleansing bars are very compatible in the bars of the present invention.
  • synthetic surfactants which are useful in cleansing products are useful in the compositions of the present invention.
  • the cleansing product patent literature is full of synthetic surfactant disclosures. Some preferred surfactants as well as other cleansing product ingredients are disclosed in the following references: Pat. No. Issue Date Inventor(s) US-A-4,061,602 12/1977 Oberstar et al.
  • Preferred synthetic surfactant systems are selectively designed for bar appearance stability, lather, cleansing and mildness.
  • surfactant mildness can be measured by a skin barrier destruction test which is used to assess the irritancy potential of surfactants. In this, test the milder the surfactant, the lesser the skin barrier is destroyed. Skin barrier destruction is measured by the relative amount of radio-labeled water (3H-H2O) which passes from the test solution through the skin epidermis into the physiological buffer contained in the diffusate chamber. This test is described by T.J. Franz in the J. Invest. Dermatol. , 1975, 64, pp.
  • Some examples of good lather enhancing detergent surfactants mild ones, are e.g., sodium lauroyl sarcosinate, alkyl glyceryl ether sulfonate, sulfonated fatty esters, paraffin sulfonates, and sulfonated fatty acids.
  • surfactants include other alkyl sulfates, anionic acyl sarcosinates, methyl acyl taurates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, trideceth sulfates, protein condensates, mixtures of ethoxylated alkyl sulfates and alkyl amine oxides, betaines, sultaines, and mixtures thereof. Included in the surfactants are the alkyl ether sulfates with 1 to 12 ethoxy groups, especially ammonium and sodium lauryl ether sulfates.
  • Alkyl chains for these other surfactants are C8-C22, preferably C10-C18.
  • Alkyl glycosides and methyl glucose esters are preferred mild nonionics which may be mixed with other mild anionic or amphoteric surfactants in the compositions of this invention.
  • Alkyl polyglycoside detergents are useful lather enhancers.
  • the alkyl group can vary from 8 to 22 and the glycoside units per molecule can vary from 1.1 to 5 to provide an appropriate balance between the hydrophilic and hydrophobic portions of the molecule.
  • Combinations of C8-C18, preferably C12-C16, alkyl polyglycosides with average degrees of glycosidation ranging from 1.1 to 2.7, preferably from 1.2 to 2.5, are preferred.
  • Sulfonated esters of fatty esters are preferred wherein the chain length of the carboxylic acid is C8-C22, preferably C12-C18; the chain length of the ester alcohol is C1-C6.
  • These include sodium alpha sulfomethyl laurate, sodium alpha sulfomethyl cocoate, and sodium alpha sulfomethyl tallowate.
  • Amine oxide detergents are good lather enhancers.
  • Some preferred amine oxides are C8-C18, preferably C10-C16, alkyl dimethyl amine oxides and C8-C18, preferably C12-C16, fatty acyl amidopropyl dimethyl amine oxides and mixtures thereof.
  • Fatty acid alkanolamides are good lather enhancers.
  • Some preferred alkanolamides are C8-C18, preferably C12-C16, monoethanolamides, diethanolamides, and monoisopropanolamides and mixtures thereof.
  • alkyl ethoxy carboxylates having the general formula RO(CH2CH2O) k CH2COO ⁇ M+ wherein R is a C8 ⁇ 22 alkyl group, k is an integer ranging from 0 to 10, and M is a cation; and polyhydroxy fatty acid amides having the general formula wherein R1 is H, a C1 ⁇ 4 alkyl group, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a C5 ⁇ 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof.
  • Betaines are good lather enhancers. Betaines such as C8-C18, preferably C12-C16, alkyl betaines, e.g., coco betaines or C8-C18, preferably C12-C16, acyl amido betaines, e.g., cocoamidopropyl betaine, and mixtures thereof, are preferred.
  • Some of the preferred surfactants are hygroscopic synthetic surfactants which absorb at least 20% of their dry weight at 26°C and 80% relative humidity in three days. Hygroscopic surfactants help to improve bar lather. Some preferred hygroscopic synthetic surfactants are listed below. Note that all are not hygroscopic.
  • the hygroscopic surfactants are defined herein as having a minimum of 20% total moisture gain after 3 days at 26°C and 80% Relative Humidity.
  • Betaines Total % Moisture Pick-Up* Coco Betaine 70.0 Cocoamidopropyl Betaine 48.2 Palmitylamidopropyl Betaine 46.5 Isostearamidopropyl Betaine 44.3 *3 days, 26°C/80% Relative Humidity
  • the cationic synthetic polymers useful in the present invention are cationic polyalkylene imines, ethoxypolyalklene imines, and poly[N-[-3-(dimethylammonio)-propyl]-N'-[3-(ethyleneoxyethylene dimethylammonio)propyl]urea dichloride] the latter of which is available from Miranol Chemical Company, Inc. under the trademark of Miranol (RTM) A-15, CAS Reg. No. 68555-36-2.
  • Preferred cationic polymeric skin conditioning agents of the present invention are those cationic polysaccharides of the cationic guar gum class with molecular weights of 1,000 to 3,000,000. More preferred molecular weights are from 2,500 to 350,000. These polymers have a polysaccharide backbone comprised of galactomannan units and a degree of cationic substitution ranging from about 0.04 per anhydroglucose unit to about 0.80 per anhydroglucose unit with the substituent cationic group being the adduct of 2,3-epoxypropyltrimethyl ammonium chloride to the natural polysaccharide backbone.
  • the polymer must have characteristics, either structural or physical which allow it to be suitably and fully hydrated and subsequently well incorporated into the soap matrix.
  • a mild skin cleansing bar of the present invention can contain from 0.5% to 20% by weight of a mixture of a silicone gum and a silicone fluid wherein the gum:fluid ratio is from 10:1 to 1:10, preferably from 4:1 to 1:4, most preferably from 3:2 to 2:3.
  • Silicone gum and fluid blends have been disclosed for use in shampoos and/or conditioners in US-A-4,906,459, Cobb et al., issued March 6, 1990; US-A-4,788,006, Bolich, Jr. et al., issued Nov. 29, 1988; US-A-4,741,855, Grote et al., issued May 3, 1988; US-A-4,728,457, Fieler et al., issued March 1, 1988; US-A-4,704,272, Oh et al., issued Nov. 3, 1987; and US-A-2,826,551, Geen, issued March 11, 1958.
  • the silicone component can be present in the bar at a level which is effective to deliver a skin mildness benefit, for example, from 0.5% to 20% by weight, preferably from 1.5% to 16% by weight, and most preferably from 3% to 12% by weight of the composition.
  • Silicone fluid denotes a silicone with viscosities ranging from 5 to 600,000 mm2s ⁇ 1 (centistokes), most preferably from 350 to 100,000 mm2s ⁇ 1 (centistokes), at 25°C.
  • Silicone gum denotes a silicone with a mass molecular weight of from 200,000 to 1,000,000 and with a viscosity of greater than 600,000 mm2s ⁇ 1 (centistokes). The molecular weight and viscosity of the particular selected siloxanes will determine whether it is a gum or a fluid.
  • the silicone gum and fluid are mixed together and incorporated into the compositions of the present invention.
  • perfumes can be used in formulating the skin cleansing products, generally at a level of from 0.1% to 2.0% by weight of the composition.
  • Alcohols, hydrotropes, colorants, and fillers such as talc, clay, water-insoluble, impalpable calcium carbonate and dextrin can also be used.
  • Cetearyl alcohol is a mixture of cetyl and stearyl alcohols.
  • Preservatives e.g., sodium ethylenediaminetetraacetate (EDTA), generally at a level of less than 1% by weight of the composition, can be incorporated in the cleansing products to prevent color and odor degradation.
  • Antibacterials can also be incorporated, usually at levels up to 1.5% by weight.
  • the above patents disclose or refer to such ingredients and formulations which can be used in the bars of this invention.
  • Some bars of this invention contain from about more than 5% to 75% by weight said sodium fatty acid soap fibers; from 10% to less than 94% by weight water; and at least 1% by weight of another bar ingredient selected from: other soaps, moisturizers, colorants, solvents, fillers, synthetic detergent surfactants, polymeric skin feel and mildness aids, perfumes, preservatives, and mixtures thereof.
  • Some bars of this invention comprise: more 5% to 50% by weight fibrous sodium fatty acid soap composed of at least 50% saturated fatty alkyl chains having 12-24 carbon atoms of which at least 25% of said saturated fatty alkyl chains is of a single chain length.
  • Some bars of this invention comprise said fibers which occupy from 3% to 75% by weight, preferably from 15% to 40% by weight, of the volume of the bar structure.
  • Some bars comprise a rigid, low smearing structure of: more than 5% to 75% by weight sodium fatty acid soap composed of at least 50% saturated fatty alkyl chains having 12-24 carbon atoms of which at least 25% of said saturated fatty alkyl chains is of a single chain length; from 10% to 94% by weight water; and 0% to a total of 70% by weight of other selected soap bar ingredients selected from the group set out above in Table 4.
  • Some personal cleansing soap bar compositions comprise a rigid interlocked mesh of sodium soap fibers; wherein the sodium fatty acid soap is composed of at least 50% by weight saturated fatty alkyl chains having 12-24 carbon atoms of which at least about 25% of said saturated fatty alkyl chains is of a single chain length; and from 2% to 40% by weight of a hygroscopic synthetic surfactant wherein said hygroscopic synthetic surfactant is selected from surfactants which absorb at least 20% of its dry weight in water at 26°C and 80% Relative Humidity in three days.
  • Bar appearance (water-retaining and/or shrinkage prevention) aids are preferably selected from the group consisting of: compatible salt and salt hydrates; water-soluble organics such as polyols, urea; aluminumosilicates and clays; and mixtures thereof, as set out above in Table 4.
  • Water-soluble organics are also used to stabilize the appearance of the bar soaps of the present invention.
  • Some preferred water-soluble organics are propylene glycol, glycerine, ethylene glycol, sucrose, and urea, and other compatible polyols.
  • a particularly suitable water-soluble organic is propylene glycol.
  • Other compatible organics include polyols, such as ethylene glycol or 1,7-heptane-diol, respectively the mono- and polyethylene and propylene glycols of up to about 8,000 molecular weight, any mono-C1 ⁇ 4 alkyl ethers thereof, sorbitol, glycerol, glycose, diglycerol, sucrose, lactose, dextrose, 2-pentanol, 1-butanol, mono- di- and triethanolammonium, 2-amino-1-butanol, and the like, especially the polyhydric alcohols.
  • polyol as used herein includes non-reducing sugar, e.g., sucrose. Sucrose will not reduce Fehling's solution and therefore is classified as a "non-reducing" disaccharide. Unless otherwise specified, the term “sucrose” as used herein includes sucrose, its derivatives, and similar non-reducing sugars and similar polyols which are substantially stable at a soap processing temperature of up to about 210°F (98°C), e.g., trialose, raffinose, and stachyose; and sorbitol, lactitol and maltitol.
  • Compatible salt and salt hydrates are used to stabilize the bar soap appearance via the retention of water.
  • Some preferred salts are sodium chloride, sodium sulfate, disodium hydrogen phosphate, sodium pyrophosphate, sodium tetraborate.
  • compatible salts and salt hydrates include the sodium, potassium, magnesium, calcium, aluminum, lithium, and ammonium salts of inorganic acids and small (6 carbons or less) carboxylic or other organic acids, corresponding hydrates, and mixtures thereof, are applicable.
  • the inorganic salts include chloride, bromide, sulfate, metasilicate, orthophosphate, pyrophosphate, polyphosphate, metaborate, tetraborate, and carbonate.
  • the organic salts include acetate, formate, methyl sulfate, and citrate.
  • Water-soluble amine salts can also be used. Monoethanolamine, diethanolamine, and triethanolammonium (TEA) chloride salts are preferred.
  • Aluminosilicates and other clays are useful in the present invention. Some preferred clays are disclosed in US-A-4,605,509 and US-A-4,274,975.
  • clays include zeolite, kaolinite, montmorillonite, attapulgite, illite, bentonite, and halloysite.
  • Another preferred clay is kaolin.
  • Waxes include petroleum based waxes (paraffin, microcrystalline, and petrolatum), vegetable based waxes (carnauba, palm wax, candelilla, sugarcane wax, and vegetable derived triglycerides) animal waxes (beeswax, spemaceti, wool wax, shellac wax, and animal derived triglycerides), mineral waxes (montar, ozokerite, and ceresin) and synthetic waxes (Fischer-Tropsch).
  • paraffin, microcrystalline, and petrolatum vegetable based waxes
  • vegetable based waxes carnauba, palm wax, candelilla, sugarcane wax, and vegetable derived triglycerides
  • animal waxes beeswax, spemaceti, wool wax, shellac wax, and animal derived triglycerides
  • mineral waxes montar, ozokerite, and ceresin
  • synthetic waxes Fischer-Tropsch
  • a preferred wax is used in the Examples herein.
  • a useful wax has a melting point (M.P.) of from about 120°F to about 185°F (49°-85°C), preferably from about 125°F to about 175°F (52°-79°C).
  • a preferred paraffin wax is a fully refined petroleum wax having a melting point ranging from about 130°F to about 140°F (49°-60°C). This wax is odorless and tasteless and meets FDA requirements for use as coatings for food and food packages.
  • paraffins are readily available commercially.
  • a very suitable paraffin can be obtained, for example from The Standard Oil Company of Ohio under the trade name Factowax R-133 (RTM).
  • the paraffin preferably is present in the bar in an amount ranging from 5% to 20% by weight.
  • the paraffin ingredient is used in the product to impart skin mildness, plasticity, firmness, and processability. It also provides a glossy look and smooth feel to the bar.
  • the paraffin ingredient is optionally supplemented by a microcrystalline wax.
  • a suitable microcrystalline wax has a melting point ranging, for example, from about 140°F (60°C) to about 185°F (85°C), preferably from about 145°F (62°C) to about 175°F (79°C).
  • the wax preferably should meet the FDA requirements for food grade microcrystalline waxes.
  • a very suitable microcrystalline wax is obtained from Witco Chemical Company under the trade name Multiwax X-145A (RTM).
  • the microcrystalline wax preferably is present in the bar in an amount ranging from 0.5% to 5% by weight.
  • the microcrystalline wax ingredient imparts pliability to the bar at room temperatures.
  • Example 10 has the rigid structure, but is not preferred as a cleaning bar because its hardness is 14.
  • TABLE 8 Binary Chain Length Sodium Soap/Water Study Ingredient X.11 Wt.% Ex.12 Wt.% Ex.13 Wt.% Sodium Soap C10 - - 16.5 C12 16.5 - - C14 - 16.5 16.5 C18:1 16.5 16.5 - Free Fatty Acid 1.0 1.0 1.0 Excess Sodium Hydroxide Sodium Chloride 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Water 65 65 65 65 Hardness (mm) ** 9.0 9.0 Smear 9.0 8.0 **Solid Bar not formed due to too much unsaturation combined with C12 soap.
  • Examples 12-16 are excellent bars of the present invention.
  • Examples 17-19 are made with more complex mixtures of soaps than the prior examples. They form very good bars of the present invention. They have little or no smear. Compare their hardness and smears with those made with conventional tallow and coconut soap shown in Table 11.
  • coconut - (33) (6.6) C8 - 2.31 0.46 C10 - 2.0 0.40 C12 - 16.5 3.3 C14 1.0 5.94 4.95 C16 7.92 2.81 6.90 C18 0.5 - 0.40 C20 6.6 1.0 5.48 C14:1 0.33 - 0.26 C16:1 0.83 - 0.66 C18:1 14.2 2.0 11.76 C18:2 0.75 0.5 0.7 Free Fatty Acid 1.0 1.0 1.0 1.0 Sodium Chloride 1.0 1.0 Water 65 65 65 Hardness (mm)
  • Example 23 is a bar of the present invention which contains more synthetic surfactant than soap. It has low smear and good lather.
  • Example 24 is a bar of the present invention which contains polymer and other bar soap ingredients.
  • Examples 23 and 24 are similar to Example IV of Table 5.
  • Example 24 is a mild bar formulation with polymeric skin mildness aid.
  • Example 25 the formulation is prepared by heating the fatty acid precursor to 71°C, separately adding lithium hydroxide to water, and then adding the fatty acid and lithium hydroxide solution together, mixing together for 30 minutes maintaining the heat at least at 71°C, adding lithium chloride salt and stirring for an additional 5 minutes, then pouring into a mold and letting cool and solidify. A solid bar with excellent smear properties is formed.
  • Example 26 the diacid is melted (150-180°C) and a hot (90°C) caustic solution (two equivalents of NaOH) is added. The mixture is stirred for ⁇ 5 minutes.
  • Example 27 the sodium lauroyl sarcosinate is predissolved in the caustic/water solution. The bar becomes solid on cooling, with further hardening occurring upon degradation, e.g., to 35-40% water by weight of the bar.
  • Example 25 demonstrates the ability to form high moisture, firm and non-smearing bars without the need for sodium soap.
  • Examples 26 and 27 demonstrate the ability to form a totally soap-free product and still obtain the relatively rigid intermeshed fiber structure.
  • Example 28 below is made by a freezer bar process disclosed in commonly assigned, U.S. Pat. Application Ser. No. 07/731,163, Taneri et al., filed July 15, 1991.
  • This process provides a personal cleansing freezer bar comprising a skeleton structure having a relatively rigid, interlocking, semi-continuous, open, three-dimensional, crystalline mesh of neutralized carboxylic acid soap made by the following steps:
  • the soap specified in the formulation is made in situ by mixing the desired fatty acids, consisting essentially of C12-C24 chain lengths, with the appropriate base or mixture of bases, consisting essentially of sodium, lithium, magnesium, calcium, and potassium hydroxide and triethanolamine.
  • the fatty acid, base, and water are mixed at from about 170°F to about 200°F (76°-93°C) to form the soap.
  • 180°F is used.
  • Sufficient water is used such that the mixture is stirrable.
  • the other ingredients are added, maintaining the temperature of from about 180°F to about 200°F (82°-93°C).
  • Example 28 - 180°F The optimal mixing temperatures can vary depending on the particular formulation.
  • Example 28 is not aerated or dried.
  • the mixture of Step (1) is optionally dried to reduce the amount of said water to the desired level, preferably 20-40% by weight water.
  • the flash drying temperature is from about 225°F to about 315°F (135°-157°C) at pressure of from about 30 to abut 100 psi (115-517 mm Hg).
  • This final temperature also referred to herein as the Freezer Outlet Temperature (FOT) is typically the maximum temperature that will form a smooth plug that holds its shape once extruded onto a moving belt (Step 4).
  • the FOT for Example 28 is 175°F.
  • the cooled mix of Step 3 is extruded out onto a moving belt as a soft plug which is then cooled and fully crystallized and then stamped and packaged.
  • the plugs are preferably formed via an extrusion operation, as shown in US-A-3,835,059, supra.
  • Some of the composition crystallizes in the freezer (Step 3) in order to provide a semi-solid having a sufficient viscosity to stand up on the belt, while further crystallization occurs after extrusion, resulting in hardening of the bar.
  • the final crystallization of the sodium soap forms the interlocking, semi-continuous, open mesh structure in the freezer bar of the present invention.
  • the Plodding Stamped Bar Hardness Test can be used to differentiate the bars of this invention from other bars.
  • Four trade bars are selected that represent various soap processes: SAFEGUARD (RTM), a soap milled bar; ZEST (RTM), a soap synthetic milled bar; IVORY (RTM), a freezer bar; and LAVA (RTM), a framed bar. Samples of these market bars and formed bars of Example 28 and Example II are plodded using the procedure set out below.
  • plodded bars with Delta's of 4 or greater is a strong indication that there is a skeletal structure in the original which is fractured or destroyed when plodded.
  • the hard bars of the present invention will form soft, messy bars when plodded in a conventional bar process.
  • Example 28 bars are first formed using the above freezer process.
  • the bars of Example II are first formed using the above-described frame bar process.
  • the market bars are made of tallow and coconut natural soaps.
  • the hardness of plodded SAFEGUARD (RTM) and ZEST (RTM) bars are about the same as the original bars.
  • the IVORY (RTM) and LAVA (RTM) plodded bars (2) are slightly softer than the original bars.
  • the plodded Bar 2 of Example 28 is much softer than the original Bar 1 of Example 28. More dramatically, the plodded Bar 2 of Example II falls apart upon plodding and is too soft to stamp. Its hardness after plodding is that of a soft aqueous phase, indicating that the rigidity of the skeletal structure is essentially destroyed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Solide façonné présentant une structure de squelette tridimensionnelle comprenant une maille relativement rigide à emboîtements d'acide carboxylique cristallin neutralisé. La présente invention se rapporte également à une barre détergente comprenant la maille rigide à emboîtements d'acide carboxylique neutralisé, de préférence en fibres de savon de sodium. On peut formuler ces barres détergentes afin qu'elles ne présentent pratiquement pas de manque de consistance superficielle. Certaines barres détergentes contiennent des quantités étonnamment élevées d'eau et d'autres liquides, et conservent leur rigidité et d'excellentes propriétés de consistance superficielle même après avoir trempé dans l'eau pendant toute une nuit.

Claims (12)

  1. Pain nettoyant non transparent, comprenant au moins deux phases:
       une phase aqueuse ayant un indice de pénétration de 12 mm pour un échantillon de profondeur 12 mm; ladite phase aqueuse étant molle ou fluide à 25°C;
       une structure principale de phase cristalline rigide comprenant un réseau maillé tridimensionnel ouvert, enchevêtré, de cristaux allongés, diffractant la lumière, d'acide mono- et/ou di-carboxylique neutralisé ayant un diamètre ou une longueur supérieur à 400 nm;
       dans lequel ledit pain nettoyant comprenant ladite structure principale de phase cristalline rigide et ladite phase aqueuse possède un indice de pénétration de zéro à environ 12 mm pour un échantillon de profondeur 25 mm de ce pain nettoyant;
       dans lequel lesdits indices de pénétration sont mesurés à 25°C à l'aide d'une sonde de pénétromètre pondérée standard de 247 grammes munie d'une aiguille conique fixée sur un axe de 9 pouces (22,9 cm), pesant 47 grammes, avec 200 grammes au sommet de cet axe pour faire un total de 247 grammes, ladite aiguille conique ayant un sommet de 19/32 pouce (1,51 cm) et une pointe de 1/32 pouce (0,08 cm);
       dans lequel ledit acide carboxylique neutralisé est choisi dans le groupe constitué par un acide monocarboxylique (savon) et/ou un acide dicarboxylique, neutralisé au lithium et/ou au sodium, et leurs mélanges;
       dans lequel ledit acide monocarboxylique possède une chaîne alkyle ou alkylène grasse d'environ 12 à environ 24 atomes de carbone;
       dans lequel ledit acide dicarboxylique possède une chaîne alkyle ou alkylène grasse d'environ 12 à environ 18 atomes de carbone; et
       dans lequel au moins 80% dudit acide carboxylique possède des chaînes alkyle saturées;
       dans lequel ladite structure principale de phase cristalline rigide occupe de 3% à 75% en volume de ce pain nettoyant; et
       dans lequel ledit acide carboxylique neutralisé constitue de plus de 5% à 75% en poids de ce pain nettoyant; et
       dans lequel ledit pain nettoyant contient de 15% à 94% en poids d'eau.
  2. Pain nettoyant selon la revendication 1, dans lequel au moins 80% dudit acide carboxylique répond à la formule générale:
    Figure imgb0019
     dans laquelle: a + b = 8 à 20
    Figure imgb0020
        chaque a, b = 0 à 20
       X = H, OR,
    Figure imgb0021
     R, ou leurs mélanges
       R = alkyle en C₁-C₃, H, ou leurs mélanges
       M = Na, Li, ou leurs mélanges.
  3. Pain nettoyant selon la revendication 2, dans lequel a + b = 10-16
    Figure imgb0022
     ; chacun desdits a, b = 0-16; X = H, OR; R = H; et M = Na.
  4. Pain nettoyant selon la revendication 3, dans lequel lesdits cristaux allongés se composent de savon d'acide gras sodique d'aspect fribreux dont au moins 25% desdites chaînes alkyle grasses saturées sont une seule longueur de chaîne; et dans lequel ledit pain contient: de 15% à 75% en poids dudit savon sodique; dans lequel ledit pain contient un acide carboxylique non neutralisé (libre) à raison de pas plus de 50% en poids dudit savon; et, de préférence, dans lequel ledit pain contient ledit savon sodique et de l'eau; et de 2% à 60% en poids d'un tensioactif synthétique choisi dans le groupe constitué par les alkylsulfates, les paraffinesulfonates, les alkylglycéryléthersulfonates, les acylsarcosinates, les méthylacyltaurates, les alkyl(linéaires)benzènesulfonates, les N-acylglutamates, les alkylglucosides, les esters d'α-sulfo-acides gras, les acyliséthionates, les alkylsulfosuccinates, les alkyléthercarboxylates, les esters alkylphosphates, les esters alkylphosphates éthoxylés, les esters de méthylglucose, les produits de condensation de protéines, les oxydes d'alkylamines, les alkylbétaïnes, les alkylsultaïnes, les alkyléthersulfates comportant 1 à 12 groupes éthoxy, et leurs mélanges, dans lequel lesdits tensioactifs contiennent des chaînes alkyle en C₈-C₂₂.
  5. Pain nettoyant selon la revendication 4, dans lequel ledit tensioactif synthétique est hygroscopique; ledit tensioactif hygroscopique étant défini comme étant un tensioactif qui absorbe au moins 20% de son poids sec en eau à 26°C et à 80% d'humidité relative en trois jours, et dans lequel ledit pain est relativement non gonflant; et, de préférence, dans lequel ledit tensioactif hygroscopique est choisi dans le groupe constitué par les esters d'α-sulfo-acides gras; les alkylsulfates; les alkyléthercarboxylates; les alkylbétaïnes; les alkylsultaïnes; les oxydes d'alkylamines; les alkyléthersulfates; et leurs mélanges.
  6. Pain nettoyant selon la revendication 4 ou 5, dans lequel le rapport de ladite eau audit savon est d'environ 1:1 à environ 5:1; ladite eau est présente à raison de 25% à 60% en poids; dans lequel ledit savon possède des chaînes alkyle grasses en C₁₄ à C₂₂ et ladite proportion de savon dans ledit pain est de 15% à 35% en poids; dans lequel au moins 85% desdites chaînes alkyle de savon sont saturées; dans lequel ledit acide carboxylique non neutralisé (libre) représente de zéro à environ 25% en poids de ce savon; et dans lequel la proportion de ce tensioactif synthétique est de 4% à 25% en poids du pain et ledit tensioactif est choisi dans le groupe constitué par les acyliséthionates de sodium, les acylsarcosinates de sodium, les esters d'α-sulfo-acides gras de sodium, les paraffinesulfonates de sodium, les alkyléthersulfates de sodium, les alkylsulfates de sodium, les alkyl(linéaires)benzènesulfonates de sodium, les alkylbétaïnes, les alkylsultaïnes et les oxydes de trialkylamines; et de préférence dans lequel ledit rapport de l'eau au savon est d'environ 1,5:1 à environ 2:1; ledit acide carboxylique non neutralisé (libre) représente de zéro à 17% en poids dudit savon; la proportion de ladite eau est de 30% à 45% en poids; ladite chaîne alkyle grasse de savon comporte d'environ 14 à environ 18 atomes de carbone; dans lequel au moins 95% desdites chaînes alkyle sont saturées; la proportion dudit savon est de 15% à 30% en poids; et la proportion dudit tensioactif synthétique est de 8% à 16% en poids.
  7. Pain nettoyant selon la revendication 5 ou 6, dans lequel ledit pain contient de 0,1% à 40% en poids d'une matière hydrophobe choisie dans le groupe constitué par: la cire microcristalline, la vaseline, la cire de carnauba, la cire de palme, la cire de candelilla, la cire de canne à sucre, les triglycérides végétaux, la cire d'abeille, le blanc de baleine, la lanoline, la cire de bois, la cire de shellac, les triglycérides animaux, la cire minérale, l'ozocérite, la cérésine et la cire de Fischer-Tropsch; et de préférence dans lequel ledit pain contient de 2% à 35% en poids de ladite matière hydrophobe, choisie dans le groupe constitué par la vaseline et la cire, ladite vaseline et ladite cire, et leurs mélanges, ayant un point de fusion d'environ 49°C (120°F) à environ 85°C (185°F); et mieux encore dans lequel ledit pain comprend de 5% à 25%, en poids du pain, de cire de paraffine; et dans lequel ledit pain contient de 1% à 50% en poids d'une matière organique non ionique, non volatile, soluble dans l'eau, ayant une solubilité d'au moins 5 parties dans 10 parties d'eau; et dans lequel ladite matière organique soluble dans l'eau est choisie dans le groupe constitué par un polyol de structure:
    Figure imgb0023
     dans laquelle R₁ = H, alkyle en C₁-C₄; R₂ = H CH₃; et n = 1-200;
    les alcane-diols en C₂-C₁₀; le sorbitol; la glycérine; les sucres; les dérivés de sucres; l'urée; et
    les éthanolamines de structure générale (HOCH₂CH₂)xNHy, dans laquelle x = 1-3; y = 0-2; et x + y = 3
    Figure imgb0024
    Figure imgb0025
     , et leurs mélanges; et de préférence dans lequel la matière organique non ionique, non volatile, soluble dans l'eau, constitue de 5% à 20% en poids du pain; ladite matière organique est choisie dans le groupe constitué par le propylèneglycol, la glycérine, le saccharose et l'urée, et leurs mélanges.
  8. Pain nettoyant selon la revendication 5, 6 ou 7, dans lequel ledit pain contient ledit savon de sodium, ladite eau et ledit tensioactif synthétique et de 0,1% à 70% en poids d'autres ingrédients choisis dans le groupe constitué par:
       de 1% à 10% en poids de savon de potassium;
       de 1% à 35% en poids de savon de magnésium;
       de 1% à 35% en poids de savon de calcium;
       de 1% à 15% en poids de savon de triéthanolammonium;
       de 1% à 60% en poids de matières impalpables insolubles dans l'eau, choisies dans le groupe constitué par le carbonate de calcium et le talc;
       de 0,1% à 20% en poids d'un émollient polymère;
       de 0,5% à 25% en poids d'une argile aluminosilicate et/ou d'autres argiles; dans lequel lesdits aluminosilicates et lesdites argiles sont choisis dans le groupe constitué par les zéolithes; le kaolin, la kaolinite, la montmorillonite, l'attapulgite, l'illite, la bentonite, l'halloysite, et les argiles calcinées;
       de 1% à 50% en poids de sel et d'hydrates de sels; et leurs mélanges; et dans lequel ledit sel et hydrate de sel possède un cation choisi dans le groupe constitué par: le sodium, le potassium, le magnésium, le calcium, l'aluminium, le lithium, l'ammonium, le monoéthanolammonium, le diéthanolammonium et le triéthanolammonium; et dans lequel ledit sel et hydrate de sel possèdent un anion choisi dans le groupe constitué par: le chlorure, le bromure, le sulfate, le métasilicate, l'orthophosphate, le pyrophosphate, le polyphosphate, le métaborate, le tétraborate, le carbonate, le bicarbonate, l'hydrogénophosphate, le méthylsulfate et les mono- et poly-carboxylates de 6 atomes de carbone ou moins.
  9. Procédé de fabrication d'un pain nettoyant selon les revendications 1 à 8, ledit procédé comprenant les étapes qui consistent à:
    I. former un liquide fondu aqueux comprenant de 20% à 94% en poids d'eau et d'environ plus de 5% à 75%, en poids du pain, dudit acide carboxylique neutralisé;
    II. verser ledit liquide fondu dans un moule à savon en forme de pain; et
    III. cristalliser ledit liquide fondu moulé en refroidissant pour obtenir ledit pain nettoyant; de préférence
    dans lequel le liquide fondu aqueux est préparé par neutralisation d'un mélange aqueux dudit acide carboxylique avec un hydroxyde choisi dans le groupe constitué par l'hydroxyde de sodium ou l'hydroxyde de lithium, et leurs mélanges, sous agitation à une température d'environ 50°C (120°F) à environ 95°C (205°F); et ledit liquide fondu contient de 2% à 15%, en poids dudit pain, d'un "sel favorisant la cristallisation" choisi dans le groupe constitué par un sel de sodium ou de lithium sulfate, chlorure acétate et citrate, et leurs mélanges; et de préférence, lorsque ladite phase aqueuse de liquide fondu aqueux contient de 2% à 40% d'un auxiliaire de solubilisation, ledit auxiliaire de solubilisation est choisi dans le groupe constitué par:
    (a) les solvants organiques non ioniques, non volatils, solubles dans l'eau, choisis dans le groupe constitué par un polyol de structure:
    Figure imgb0026
     dans laquelle R₁ = H, alkyle en C₁-C₄; R₂ = H, CH₃; et n = 1-200;
    les alcane-diols en C₂-C₁₀; le sorbitol; la glycérine; les sucres; les dérivés de sucres; l'urée; et les éthanolamines de structure générale (HOCH₂CH₂)xNHy, dans laquelle x = 1-3; y = 0-2; et x + y = 3
    Figure imgb0027
    Figure imgb0028
     ;
    (b) les alcools de 1 à 5 atomes de carbone;
    (c) un tensioactif synthétique choisi dans le groupe constitué par les alkylsulfates, les paraffinesulfonates, les alkylglycéryléthersulfonates, les acylsarcosinates anioniques, les méthylacyltaurates, les alkyl(linéaires)benzènesulfonates, les N-acylglutamates, les alkylglucosides, les esters d'α-sulfo-acides gras, les acyliséthionates, les alkylsulfosuccinates, les alkyléthercarboxylates, les esters alkylphosphates, les esters alkylphosphates éthoxylés, les esters de méthylglucose, les produits de condensation de protéines, les oxydes d'alkylamines, les alkylbétaïnes, les alkylsultaïnes, les alkyléthersulfates comportant 1 à 12 groupes éthoxy, et leurs mélanges, dans lequel lesdits tensioactifs contiennent des chaînes alkyle en C₈-C₂₂; et
    leurs mélanges; et
    dans lequel ledit auxiliaire de solubilisation est ajouté pour augmenter la proportion dudit acide carboxylique neutralisé dissous dans ladite phase aqueuse fondue continue dans l'étape I.
  10. Procédé selon la revendication 9, dans lequel ladite phase aqueuse contient de 20% à 100% d'eau, en poids de ladite phase aqueuse; et dans lequel ladite phase cristalline rigide contient de 75% à 100% dudit acide carboxylique neutralisé, en poids de ladite phase cristalline; et dans lequel ledit pain possède un indice de pénétration de 3 mm à 9 mm pour ledit échantillon de savon de 25 mm.
  11. Composition de pain nettoyant pour la toilette selon la revendication 1, comprenant un réseau maillé cristallin tridimensionnel ouvert, enchevêtré, rigide, de cristaux de savon de sodium allongés ayant un diamètre ou une longueur supérieure à 400 nm; ledit pain de savon comprenant: de 15% à 50% en poids de savon d'acide gras de sodium composé d'au moins 50% de chaînes alkylène grasses saturées comportant 12-24 atomes de carbone, dont au moins 25% desdites chaînes alkyle grasses saturées ont une seule longueur de chaîne; de 15% à 60% en poids d'eau; et de 2% à 60% en poids d'un tensioactif synthétique hygroscopique, dans lequel ledit tensioactif synthétique hygroscopique est choisi parmi les tensioactifs qui absorbent au moins 20% de leur poids sec en eau 26°C et à 80% d'humidité relative en trois jours.
  12. Pain nettoyant pour la toilette selon la revendication 11, dans lequel ledit tensioactif synthétique hygroscopique est choisi dans le groupe constitué par les esters d'α-sulfo-acides gras; les alkylsulfates; les alkyléthercarboxylates; les alkylbétaïnes; les alkylsultaïnes; les oxydes d'alkylamines; les alkyléthersulfates; et leurs mélanges; et dans lequel ledit pain contient de 0,5% à 40% en poids de sels et/ou d'hydrates de sels choisis dans le groupe constitué par le chlorure de sodium, le sulfate de sodium, l'hydrogénophosphate disodique, le pyrophosphate de sodium, le tétraborate de sodium, l'acétate de sodium, le citrate de sodium, et d'autres sels compatibles d'acides minéraux et d'acides organiques à chaîne courte.
EP92904074A 1990-11-26 1991-11-20 Solide faconne compose d'une maille rigide a emboitements d'acide carboxylique neutralise Expired - Lifetime EP0559837B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US61782790A 1990-11-26 1990-11-26
US617827 1990-11-26
US07/782,956 US5340492A (en) 1990-11-26 1991-11-01 Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid
US782956 1991-11-01
PCT/US1991/008733 WO1992009679A1 (fr) 1990-11-26 1991-11-20 Solide façonne compose d'une maille rigide a emboitements d'acide carboxylique neutralise

Publications (2)

Publication Number Publication Date
EP0559837A1 EP0559837A1 (fr) 1993-09-15
EP0559837B1 true EP0559837B1 (fr) 1995-10-25

Family

ID=27088104

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92904074A Expired - Lifetime EP0559837B1 (fr) 1990-11-26 1991-11-20 Solide faconne compose d'une maille rigide a emboitements d'acide carboxylique neutralise

Country Status (28)

Country Link
EP (1) EP0559837B1 (fr)
JP (1) JPH06503122A (fr)
KR (1) KR100226393B1 (fr)
CN (1) CN1036529C (fr)
AR (1) AR247426A1 (fr)
AT (1) ATE129522T1 (fr)
AU (1) AU657295B2 (fr)
BR (1) BR9107125A (fr)
CA (1) CA2095351C (fr)
CZ (1) CZ283495B6 (fr)
DE (1) DE69114143T2 (fr)
DK (1) DK0559837T3 (fr)
EG (1) EG19580A (fr)
ES (1) ES2079180T3 (fr)
FI (1) FI932366A (fr)
GR (1) GR3017892T3 (fr)
HK (1) HK1006179A1 (fr)
HU (1) HU215484B (fr)
IE (1) IE72087B1 (fr)
MA (1) MA22349A1 (fr)
MX (1) MX9102229A (fr)
NO (1) NO931848L (fr)
NZ (1) NZ240709A (fr)
PT (1) PT99606A (fr)
RU (1) RU2080365C1 (fr)
SG (1) SG59939A1 (fr)
SK (1) SK52693A3 (fr)
WO (1) WO1992009679A1 (fr)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2647741B1 (fr) * 1989-05-31 1991-08-23 Bendix France Procede de reglage de la valeur du saut d'un servomoteur d'assistance au freinage
DE4017463A1 (de) * 1990-05-30 1991-12-05 Henkel Kgaa Verfahren zur herstellung hochkonzentrierter pasten von alpha-sulfofettsaeure- alkylester-alkalimetallsalzen
AU2294792A (en) * 1991-07-15 1993-02-23 Procter & Gamble Company, The A personal cleansing freezer bar made with a rigid, interlocking mesh of neutralized carboxylic acid
US5262079A (en) * 1992-03-20 1993-11-16 The Procter & Gamble Company Framed neutral pH cleansing bar
US5227086A (en) * 1992-03-20 1993-07-13 The Procter & Gamble Company Framed skin pH cleansing bar
EP0670885B1 (fr) * 1992-11-30 1997-08-20 The Procter & Gamble Company Compositions detergentes au pouvoir moussant eleve contenant des savons specialement selectionnes
CA2147674C (fr) * 1994-05-16 1999-03-30 David Robert Zint Detergent semi-solide ou solide pour lave-vaisselle
WO1997022684A1 (fr) * 1995-12-20 1997-06-26 The Procter & Gamble Company Barre nettoyante a usage personnel moulee par coulee
WO1998011864A2 (fr) * 1996-09-23 1998-03-26 The Procter & Gamble Company Compositions de pains de savon moussants pour hygiene corporelle, contenant des particules lipidiques allongees
WO1998016611A1 (fr) * 1996-10-11 1998-04-23 The Procter & Gamble Company Compositions de pains de lessive comprenant de l'alcool dihydrique
JP3227694B2 (ja) * 1996-12-11 2001-11-12 花王株式会社 枠練り石鹸組成物
WO1998027193A1 (fr) * 1996-12-16 1998-06-25 The Procter & Gamble Company Composition d'hygiene personnelle, sous forme de pain, contenant du lauroyl-lactylate de sodium
BR0308352A (pt) * 2002-04-02 2005-01-25 Unilever Nv Composição em barra de detergente listrada, e, processo para preparar a mesma
AU2003266622A1 (en) * 2002-09-25 2004-04-19 Sankyo Company, Limited Medicinal composition for inhibiting increase in blood gastrin concentration
DE10346954A1 (de) * 2003-10-09 2005-06-09 Beiersdorf Ag Temperaturstabile kosmetische Reinigungszubereitung mit Dicarbonsäuren
JP5367494B2 (ja) * 2009-08-06 2013-12-11 花王株式会社 枠練り石鹸の製造方法
EP2875114B1 (fr) 2012-07-23 2016-03-02 Unilever N.V. Procédé de préparation de composition de savon dans un mélangeur de soc
CN106544157A (zh) * 2016-11-02 2017-03-29 广州精点高分子材料制品有限公司 一种美容洁面皂及其制备方法
CN107245391A (zh) * 2016-12-25 2017-10-13 池州市建东生物科技有限公司 一种皮肤病专用肥皂
US11377628B2 (en) 2018-01-26 2022-07-05 Ecolab Usa Inc. Solidifying liquid anionic surfactants
EP3743494A1 (fr) 2018-01-26 2020-12-02 Ecolab Usa Inc. Solidification de tensioactifs d'oxyde d'amine, de bétaïne et/ou de sultaïne liquide à l'aide d'un liant et d'un éventuel un vecteur
CA3089629A1 (fr) 2018-01-26 2019-08-01 Ecolab Usa Inc. Solidification de tensioactifs liquides d'oxyde d'amine, de betaine et/ou de sultaine ayant un vehicule
WO2021207442A1 (fr) * 2020-04-10 2021-10-14 The Procter & Gamble Company Composition orale solide rhéologique
EP4133048A1 (fr) 2020-04-10 2023-02-15 The Procter & Gamble Company Outil de nettoyage avec une composition solide rhéologique
US20210322287A1 (en) * 2020-04-10 2021-10-21 The Procter & Gamble Company Oral care product comprising an oral care rheological solid composition
US11833237B2 (en) 2021-03-09 2023-12-05 The Procter & Gamble Company Method for enhancing scalp active deposition
EP4098243A1 (fr) * 2021-05-31 2022-12-07 BIC Violex Single Member S.A. Composition solide d'aide au rasage
CN118043442A (zh) * 2022-08-12 2024-05-14 宝洁公司 固体可溶性组合物
CN117940547A (zh) * 2022-08-12 2024-04-26 宝洁公司 固体可溶性组合物
WO2024036124A1 (fr) * 2022-08-12 2024-02-15 The Procter & Gamble Company Compositions solides solubles
WO2024036122A1 (fr) * 2022-08-12 2024-02-15 The Procter & Gamble Company Compositions solubles solides

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226329A (en) * 1961-09-14 1965-12-28 Procter & Gamble Germicidal cleansing composition
DE2132035C3 (de) * 1971-06-28 1979-08-30 Henkel Kgaa, 4000 Duesseldorf Geformte Waschmittelkomposition
US3793214A (en) * 1971-10-22 1974-02-19 Avon Prod Inc Transparent soap composition
US4396521A (en) * 1976-04-22 1983-08-02 Giuseppe Borrello Solid detergent spotter
US4165293A (en) * 1977-05-16 1979-08-21 Amway Corporation Solid transparent cleanser
DE3246796A1 (de) * 1981-12-23 1983-07-21 Colgate-Palmolive Co., 10022 New York, N.Y. Rissfreies seifenstueck
US4851147A (en) * 1987-02-26 1989-07-25 Finetex, Inc. Transparent combination soap-synthetic detergent bar
US4758370A (en) * 1987-04-30 1988-07-19 Neutrogena Corp. Compositions and processes for the continuous production of transparent soap
ATE103801T1 (de) * 1987-09-17 1994-04-15 Procter & Gamble Ultramildes hautreinigungsstueck mit einer mischung ausgewaehlter polymere.

Also Published As

Publication number Publication date
IE72087B1 (en) 1997-03-12
DK0559837T3 (da) 1996-03-04
AU657295B2 (en) 1995-03-09
CA2095351C (fr) 1998-12-15
RU2080365C1 (ru) 1997-05-27
CN1062759A (zh) 1992-07-15
HK1006179A1 (en) 1999-02-12
EP0559837A1 (fr) 1993-09-15
NO931848D0 (no) 1993-05-21
PT99606A (pt) 1992-10-30
NZ240709A (en) 1995-04-27
CN1036529C (zh) 1997-11-26
CZ98793A3 (en) 1994-07-13
MA22349A1 (fr) 1992-07-01
CA2095351A1 (fr) 1992-05-27
AU9176391A (en) 1992-06-25
AR247426A1 (es) 1994-12-29
SG59939A1 (en) 1999-02-22
ES2079180T3 (es) 1996-01-01
DE69114143D1 (de) 1995-11-30
EG19580A (en) 1995-08-30
BR9107125A (pt) 1993-11-09
KR100226393B1 (ko) 1999-10-15
JPH06503122A (ja) 1994-04-07
WO1992009679A1 (fr) 1992-06-11
GR3017892T3 (en) 1996-01-31
HU9301532D0 (en) 1993-09-28
IE914094A1 (en) 1992-06-03
FI932366A0 (fi) 1993-05-25
NO931848L (no) 1993-07-23
DE69114143T2 (de) 1996-04-25
HUT76489A (en) 1997-09-29
FI932366A (fi) 1993-05-25
SK52693A3 (en) 1994-01-12
HU215484B (hu) 1999-01-28
ATE129522T1 (de) 1995-11-15
CZ283495B6 (cs) 1998-04-15
MX9102229A (es) 1992-07-08

Similar Documents

Publication Publication Date Title
EP0559837B1 (fr) Solide faconne compose d'une maille rigide a emboitements d'acide carboxylique neutralise
US5340492A (en) Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid
EP0631614B1 (fr) SAVONNETTE A pH EGAL A CELUI DE LA PEAU
EP0631611B1 (fr) SAVON EN BARRE AU pH NEUTRE
EP0594703B1 (fr) Savonnette detergente a usage personnel fabriquee a partir d'un maillage a entrecroisement rigide a base d'acide carboxylique neutralise
US5225097A (en) Skin pH freezer bar and process
US5264144A (en) Freezer personal cleansing bar with selected fatty acid soaps for improved mildness and good lather
US5264145A (en) Personal cleansing freezer bar with selected fatty acid soaps and synthetic surfactant for reduced bathtub ring, improved mildness, and good lather
US5225098A (en) Neutral pH freezer bar and process
NZ248471A (en) A "freezer" soap bar comprising mostly na and k soaps of: myristic, palmitic and stearic acids plus oleic and/or lauric acid and/or minor fatty acid soap; water; and optionally a lathering synthetic surfactant and a sugar

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930514

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19931206

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 129522

Country of ref document: AT

Date of ref document: 19951115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69114143

Country of ref document: DE

Date of ref document: 19951130

ET Fr: translation filed
ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3017892

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19960101

Year of fee payment: 5

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2079180

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & SEIFERT PATENTANWAELTE VSP

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19961107

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19961120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971231

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20001003

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20001027

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20001103

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20001214

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20010103

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011130

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011130

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011130

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 20011130

EUG Se: european patent has lapsed

Ref document number: 92904074.9

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20021002

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20021011

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021105

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20021118

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20021127

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040602

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20031120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040730

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20040601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20031121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051120