WO2000040691A1 - Laundry detergent bar composition - Google Patents
Laundry detergent bar composition Download PDFInfo
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- WO2000040691A1 WO2000040691A1 PCT/US1999/000193 US9900193W WO0040691A1 WO 2000040691 A1 WO2000040691 A1 WO 2000040691A1 US 9900193 W US9900193 W US 9900193W WO 0040691 A1 WO0040691 A1 WO 0040691A1
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- laundry detergent
- detergent bar
- las
- benzene sulfonate
- surfactants
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
Definitions
- the present invention relates to laundry detergent compositions. Specifically, the present invention relates to a laundry detergent bar composition containing an anionic surfactant.
- laundry detergent bars are used for cleaning clothes.
- Technical developments in the field of laundry detergent bars have concerned formulating laundry detergent bars which are effective in cleaning clothes; which have acceptable sudsing characteristics in warm and cool water, and in hard and soft water; which have acceptable in-use wear rates, hardness, durability, and feel; which have low smear and rapid drying; and which have a pleasing odor and appearance.
- Laundry detergent bar processes are also well known in the art. Prior art disclosing laundry detergent bars and laundry detergent bar processes include: U.S. Patent 3,178,370, Okenfuss, issued April 13, 1965; and Philippine Patent 13778 to Anderson, issued September 23, 1980.
- Surfactants especially anionic surfactants, are well-known to provide detersive benefits in laundry detergent bars.
- Certain surfactants, such as anionic surfactants are especially useful in laundry detergent bar compositions, as they contain a hydrophobic portion which may attach to soils, and a hydrophilic portion which hydrogen bonds to water.
- anionic surfactants can provide detersive benefits as they bind to soils, and remove them from, for example, fabrics and clothing.
- Typical anionic surfactants include soaps and non-soap surfactants.
- Linear alkyl benzene sulfonate is a common non-soap anionic surfactant in cleaning compositions, and especially laundry detergent bars, as it provides excellent soil removal benefits, and is widely available. Recently, greater attention has been paid to the environment by society, corporations, and governments. Thus, it has become highly desirable to increase the biodegradability of products, such as detergent compositions. LAS is a highly preferred, easily biodegradable surfactant.
- paraffin and benzene from, for example, crude oil are typically combined in a catalytic process to produce linear alkyl benzene (LAB).
- Catalytic processes for producing LAB utilize catalysts containing aluminum chloride, hydrofluoric acid, and fluorine-containing mordenite.
- the LAB is sulfonated with sulfuric and/or sulfonic acid, and subsequently neutralized with an alkaline material to produce the corresponding alkaline salt of LAS, such as the sodium salt of LAS.
- DBB dialkyl bi-cyclic benzene
- the need remains for a laundry detergent bar having improved surfactancy, and increased biodegradability.
- a laundry detergent bar which also possesses acceptable in-use wear rates, hardness, durability, rapid drying, and low smear.
- a laundry detergent bar may possess improved surfactancy and increased biodegradability. It has also been found that a laundry detergent bar may also possess acceptable in-use wear rates, hardness, durability, rapid drying, and/or low smear.
- the present invention relates to a laundry detergent bar containing a linear alkyl benzene sulfonate surfactant and the balance adjunct materials.
- the linear alkyl benzene sulfonate surfactant has at least 30 molar % 2-phenyl isomer and less than about 5 weight % dialkyl bi-cyclic benzene sulfonate impurities.
- alkyl means a hydrocarbyl moiety which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl moieties are preferably saturated or unsaturated with double bonds, preferably with less than two double bonds. Included in the term “alkyl” is the alkyl portion of acyl groups.
- linear indicates that the alkyl portions thereof contain less than about 30%, preferably less than bout 20%, more preferably less than about 10% branched alkyl chains.
- substantially free indicates that the impurities contained in the laundry detergent bar of the present invention contains are insufficient to contribute positively or negatively to the cleaning effectiveness of the composition.
- the laundry detergent bar of the present invention preferably contains, by weight, less than about 5%, more preferably less than about 2%, and even more preferably less than about 0.5% of the indicated material. It is desirable to increase the surfactancy of, for example, LAS.
- LAB and the corresponding LAS contains a distribution of isomers in which the benzene moiety is attached in various positions on the hydrophobic alkyl chain. It is the hydrophobic portion of LAS which attaches to soils on. For a given alkyl chain length, the most hydrophobic alkyl chain is achieved when the benzene ring is attached to the alkyl chain at the 2-position, because this provides the longest hydrophobic "tail.”
- Such an LAS is described as the "2-phenyl LAS" isomer and possesses improved surfactancy as compared to corresponding isomers where the benzene moiety is attached to the alkyl chain at, for example, the 3-position.
- the typical LAB used to form LAS contains a distribution of various LAB isomers, such as 2-phenyl LAB, 3-phenyl LAB, 4-phenyl LAB, etc.
- R 1 represents a linear alkyl group; typically R ⁇ is between about 6 and about 19 carbon atoms in length (i.e., the alkyl chain, excluding the benzene group, is thus typically from about 8 to about 22 carbon atoms in length).
- LAB isomers are then sulfonated to produce LAS. Accordingly, for a given alkyl chain, it is desirable to attach the benzene moiety as close to a terminal end as possible, so as to achieve the most hydrophobic isomer. A more hydrophobic isomer in turn, leads to increased surfactancy.
- the present invention also recognizes that in addition to the increased crystallinity caused by a higher proportion of 2-phenyl LAS, the reduction of DBBS impurities also increases the crystallinity and decreases the dissolution rate of solid compositions containing this LAS. Without intending to be limited by theory, it is believed that the reduction of DBBS also increases the crystallinity and reduces the dissolution rate via two mechanisms. First, it has been recognized herein that when present, DBBS impurities interfere with the regularity of the LAS crystalline lattice structure. Thus, it is believed that a reduction of the DBBS content results in an increase in the crystallinity of the LAS.
- DBBS is an excellent hydrotrope for the corresponding linear alkyl benzene sulfonate.
- the dissolution rate of the LAS is also reduced.
- high crystallinity may lead to increased gel layer formation upon contact with water, which further reduces the dissolution rate of a solid composition.
- the increase in crystallinity and reduction in dissolution rate are undesirable.
- high crystallinity and a reduced dissolution rate are highly desirable in a laundry detergent bar composition.
- the present invention may instead provide significantly enhanced cleaning. Without intending to be limited by theory, it is believed that as a detergent bar is typically rubbed directly onto clothing, and subsequently rinsed by hand, the overall performance of detergent composition is not impaired by the slower dissolution rate of the LAS.
- An additional benefit of the present invention is that fewer, or lowered levels of, structurants, fillers, and/or co-surfactants may be required herein. This may lower the formulation cost of the laundry detergent bar, and thus provide additional value for customers. Alternatively, it allows greater flexibility in formulating laundry detergent bars with acceptable physical properties and cleaning abilities.
- a bleach i.e., sodium perborate monohydrate or sodium percarbonate, is easier to incorporate into the laundry detergent bar of the present invention.
- the LAS useful herein typically contains at least about 30 molar % 2-phenyl isomer, preferably at least 40 molar % 2-phenyl isomer, more preferably at least 50 molar % 2-phenyl isomer, and even more preferably at least 60 molar % 2-phenyl isomer.
- Such molar percentages of 2-phenyl isomers in the LAB provide the improved surfactancy and increased crystallinity desired in the present invention.
- compositional parameters of conventional LAB and LAS See, for example Surfactant Science Series, Volume 40, Chapter 7 and Surfactant Science Series, Volume 73, Chapter 7. Typically this is done by GC and/or GC-mass spectroscopy for the alkyl benzenes and HPLC for the alkyl benzene sulfonates or sulfonic acids; 13 C NMR is also commonly used. Another common practice is desulfonation. This permits GC and/or GC-mass spectroscopy to be used, since desulfonation converts the sulfonates or sulfonic acids to the alkyl benzenes which are tractable by such methods.
- a preferred method is to prepare LAB sample solution at 100 mg/ml concentration by dissolving 0.5 g of LAB sample in 5 ml of n-hexane. 1 ⁇ L of this solution is then injected into a GC/MS equipped with an ionization detector. The resulting chromatogram is analyzed based on the MS results. The minor peaks in-between all linear alkyl benzene species are summarized and calculated as the sum of the DBB impurities, including dialkyl tetralins and dialkyl indans.
- the GC/MS instrument suitable for such analysis can be HP 5890 II GC/HP 5971 MSD (ANI-59).
- the GC/FID system can be HP 5890 II GC (ANI- 61).
- the column is kept at 100 °C for 1 minute then increased to 180 °C at 2 °C/min.
- the FIC is operated at 70 eV.
- the mass scan was done in between 50 to 500 m/z at 3 scans/sec.
- the sample injection was done with a splitter at a ratio of 100 to 1.
- the system can be operated at 120 kPa helium carrier gas with all other parameters staying the same.
- the DBB impurities are formed in the LAB production process when a single alkyl chain interacts with the same benzene ring twice.
- Typical dialkyl bi- cyclic benzene impurities have the following structures:
- the LAS useful herein contains, by weight of the LAS, less than about 5 weight % DBBS impurities, preferably less than about 3 weight % DBBS impurities, more preferably less than about 2 weight % DBBS impurities, and even more preferably less than about 1 weight % DBBS impurities.
- the LAS herein is substantially free of DBBS impurities.
- the LAS herein contains, by weight of the LAS, less than about 2.5 weight % dialkyl tetralin sulfonate impurities, preferably less than about 1.3 weight % dialkyl tetralin sulfonate impurities, and more preferably less than about 0.5 weight % dialkyl tetralin sulfonate impurities.
- the weight % of DBBS impurities such as dialkyl tetralin sulfonates and dialkyl indan sulfonates may be determined by methods such as those described above (e.g., GC or HPLC) for characterizing LAB and/or LAS.
- the laundry detergent bars herein typically comprise from about 1% to about 99%, preferably from about 5% to about 50%, and more preferably from about 5% to about 25% LAS as described herein, by weight of the laundry detergent bar. It is also desirable that the LAS useful herein has from about 8 to about 22, preferably from about 8 to about 18, and more preferably from about 10 to about 16 carbon atoms in the alkyl group, for example, the C 10 . 16 linear alkyl benzene sulfonates.
- the LAS suitable for use herein includes the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms, as described above, and a sulfonic acid group.
- the alkali metal salts, particularly the sodium salts, the potassium salts, or mixtures thereof are preferred.
- an effective amount of an added hydrotrope may be provided and added to the LAS described herein, or a laundry detergent bar containing the LAS described herein.
- the "added hydrotrope” herein is a hydrotrope which is deliberately added to the LAB, linear alkyl benzene acid active, LAS, and/or a composition containing the LAS, and is not intended to include those hydrotropes which are present solely as by- products of the LAB production process.
- any added hydrotrope be biodegradable, preferably at least as biodegradable as the LAS parent compound.
- an effective amount of an added hydrotrope may, for example, ease processing.
- the "effective amount" of added hydrotrope useful herein is preferably at least about 0.1%, more preferably from about 1% to about 25%, and even more preferably from about 1 % to about 10%, by weight of the LAS.
- the hydrotrope may reduce the effects of the LAS described herein.
- the laundry detergent bar is substantially free of added hydrotrope.
- the added hydrotrope useful herein may be either branched, linear, aromatic, or a mixture thereof. Linear added hydrotropes having an attached aromatic moiety are preferred herein.
- the added hydrotrope precursor includes non-sulfonatable added hydrotropes and sulfonatable added hydrotropes having sulfonatable functional groups, such as an alkyl benzene, an olefin (e.g., an alpha olefin or an internal olefin) with at least one carbon-carbon double bond, a methyl or ethyl ester of a carboxylic acid, an alkyl alcohol, and mixtures thereof.
- sulfonatable added hydrotropes having sulfonatable functional groups, such as an alkyl benzene, an olefin (e.g., an alpha olefin or an internal olefin) with at least one carbon-carbon double bond, a methyl or ethyl ester of a carboxylic acid, an alkyl alcohol, and mixtures thereof.
- alkyls and alkyl benzenes useful herein as added hydrotrope precursors typically contain from about 1 to about 8 carbon atoms in their alkyl chains, while the olefins, methyl esters, and alkyl alcohols typically contain less than or equal to about 10 carbon atoms therein.
- Nonlimiting examples of the preferred added hydrotrope include the alkali metal and ammonium salts, preferably the sodium, potassium, ammonium, and magnesium salts of the above compounds.
- the added hydrotrope useful herein includes a paraffin sulfonate, an alkyl benzene sulfonate, an olefin sulfonate, a methyl or ethyl ester sulfonate, an alkyl sulphate, non-sulfonated added hydrotropes, and mixtures thereof.
- Non- sulfonated added hydrotropes useful herein include octanol ethoxylates, hexanol ethoxylates, ethylhexanol ethoxylates, secondary alcohol ethoxylates, octanol monoglyceride, hexanol monoglyceride, ethylhexanol glyceride, octyl glycoside or di-glycosides, octanoic mono-amine glucose amide, hexanoic mono-amine glycose amide, and mixtures thereof.
- Nonlimiting examples of preferred sulfonatable added hydrotropes useful herein include toluene sulfonate, xylene sulfonate, cumene sulfonate, olefin sulfonates, methyl ester sulfonates, alcohol sulfates, and mixtures thereof.
- the added hydrotrope or its precursor may be added at any stage of the laundry detergent bar process, for example, prior to an LAB sulfonation step, or after addition of the LAS.
- the added hydrotrope or its precursor is added to the LAB and homogenized therewith. The homogenized mixture is then sulfonated, and neutralized to form an LAS surfactant paste, which is further processed into a laundry detergent bar.
- Such added hydrotropes are commonly available from, for example,
- Their precursors, i.e. toluene, xylene, cumene, etc. are widely available from companies such as Basis Petroleum; Exxon; Texaco of Houston, Texas, U. S. A.; Petroquimica Uniao Sa of San Paulo, Brazil; Fina Oil of Dallas, Texas, U. S. A.; etc.
- the laundry detergent bar of the present invention contains a linear alkyl benzene sulfonate surfactant as described herein, and the balance adjunct materials.
- Typical adjunct materials useful herein include a bleach, a builder, a chelating agent, an enzyme, a filler, other surfactants, a soil suspension agent, a structurant, and mixtures thereof.
- the bleach useful herein is typically a bleach precursor product, but may include an actual bleach, such as, for example, a hypochlorite bleach.
- a bleach precursor product containing an active oxygen source is provided herein.
- the active oxygen source useful herein includes compounds which form available peroxyacid oxygen when exposed to a bleach activator, an alkalinity source, and moisture.
- An active oxygen source can be hydrophilic, hydrophobic, or both.
- the active oxygen source useful in the present invention can be any of the oxidizing agents known for laundry, hard surface cleaning, automatic dishwashing, or denture cleaning purposes, including oxygen.
- a preferred active oxygen source of the peroxygen type includes hydrogen peroxide, inorganic per- compounds, inorganic peroxohydrates, organic peroxohydrates, and mixtures thereof; a more preferred active oxygen source includes hydrogen peroxide, perborate, percarbonate, and mixtures thereof. If present, an active oxygen source will typically be at a level of from about 1% to about 30%, more typically from about 5% to about 20%, of the laundry detergent bar.
- a bleach activator may comprise an alkalinity source, either alone, or in conjunction with amides, imides, esters, anhydrides, and mixtures thereof.
- at least one substituted or unsubstituted acyl moiety is present, covalently connected to a leaving group as in the structure R-C(O)-L.
- the atom in the leaving group connecting to the peracid-forming acyl moiety R(C)O- is most typically O or N.
- a bleach activator can have non-charged, positively or negatively charged peracid- forming moieties and/or noncharged, positively or negatively charged leaving groups.
- One or more peracid-forming moieties or leaving-groups can be present.
- a preferred class of bleach activator includes the esters, including acyl phenol sulfonates, acyl alkyl phenol sulfonates or acyl oxybenzenesulfonates
- a preferred hydrophobic bleach activator includes sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), sodium decanoyloxybenzene sulfonate (DOBS), sodium dodecanoiyloxybenzene sulfonate (LOBS), sodium nonanoyloxybenzene carboxylate (NOBA), sodium nonanoyloxybenzene carboxylate (DOBA), sodium dodecanoyloxybenzene carboxylate (LOBA), substituted amide types described in detail hereinafter, and the bleach activators related to certain imidoperacid bleaches.
- NOBS or SNOBS sodium decanoyloxybenzene sulfonate
- DOBS sodium dodecanoiyloxybenzene sulfonate
- NOBA sodium nonanoyloxybenzene carboxylate
- DOBA sodium nonanoyloxybenzene carboxylate
- LOBA sodium dodecanoyloxybenzene carboxylate
- Another suitable bleach activator includes sodium-4-benzoyloxy benzene sulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4- sulphonate; sodium-4-methyl-3-benzoyloxy benzoate; trimethyl ammonium toluyloxy-benzene sulfonate; sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS), and mixtures thereof.
- a preferred bleach activator includes N,N,N'N'-tetraacetyl ethylene diamine (TAED) or any of its close relatives including the triacetyl or other unsymmetrical derivatives, and mixtures thereof.
- TAED and the acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose are preferred.
- Builders may optionally be included in the laundry detergent bars herein to assist in controlling mineral hardness. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. Laundry detergent bars typically contain from about 3% to about 60%, preferably from about 5% to about 50%, more preferably from about 10% to about 30% builder, by weight of the final composition.
- Useful inorganic or phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates such as zeolites.
- non-phosphate builders are required in some locales.
- compositions herein function surprisingly well even in the presence of the so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
- a non- phosphate builder such as inorganic detergency builders, include the water soluble inorganic carbonate and bicarbonate salts.
- the alkali metal (e.g., sodium and potassium) carbonates and bicarbonates are particularly useful herein.
- Other specifically preferred examples of a builder useful herein include polycarboxylates.
- Especially preferred as builders herein are co-polymers of acrylic acid and maleic acid. Accordingly, in a preferred embodiment, the laundry detergent bar of the present invention is substantially free of phosphate.
- the optional chelating agent may be one or more iron and/or manganese chelating agents.
- Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
- Amino carboxylates useful as optional chelating agents include ethylenediaminetetrace- tates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylene- triaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
- Amino phosphonates are also suitable for use as chelating agents when at least low levels of total phosphorus are permitted in the laundry detergent bar, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
- these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
- Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
- Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.
- a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
- these chelating agents will generally comprise from about 0.1% to about 15% by weight of the laundry detergent bar. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of the laundry detergent bar.
- An enzyme may also be useful herein for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
- a suitable enzyme herein includes an amylase, a cellulase, a cutinase, a lipase, a peroxidase, a protease, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
- Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
- bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
- typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the laundry detergent bar.
- the laundry detergent bars herein will typically comprise, by weight of the final bar, from about 0.001 % to about 5%, preferably from about 0.01% to about 1% of a commercial enzyme preparation.
- Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of the laundry detergent bar.
- amylase useful herein includes, for example, -amylases described in GB 1 ,296,839 to Outtrup H, et al., published November 22, 1972 to Novo Industries A S of Denmark (hereinafter, "Novo”); RAPIDASE® from International Bio-Synthetics, Inc.; TERMAMYL® from Novo; and FUNGAMYL® from Novo.
- Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
- U.S. 4,435,307 to Barbesgoard, et al., March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
- Suitable cellulases are also disclosed in GB-B-2,075,028 to Barbesgaar, et al., issued March 28, 1984; GB-B-2,095,275 to Murata, et al., issued August 7, 1985 and DE-OS-2,247,832 to Horikoshi and Ikeda, issued June 27 1974. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 91/17243 to Hagen, et al., published November 14, 1991.
- Cutinase enzymes suitable for use herein are described in WO 88/09367A to Kolattukudy, et al., published December 1 , 1988.
- Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1 ,372,034 to Dijk and Berg, published October 30, 1974. See also lipases in Japanese Patent Application 53-20487 to Inugai, published February 24, 1978.
- This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P.”
- Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., the Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE®, from Novo, is a preferred lipase for use herein.
- LIPOLASE® is derived from Humicola lanuginosa, see also EP 341 ,947 to Cornelissen, et al., issued August 31 , 1994. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 94/14951 to Halkier, et al., published July 7, 1994 A to Novo. See also WO 92/05249 to Clausen, et al., published April 2, 1992.
- Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
- peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
- Peroxidase-containing detergent compositions are disclosed in WO 89/09813 A to Damhus, et al., published October 19, 1989.
- a suitable example of a protease is a subtilisin, which is obtained from particular strains of B. subtilis and ⁇ . licheniformis.
- One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo.
- Other examples of a suitable protease includes ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., the Netherlands; as well as Protease A and Protease B as disclosed in EP 130,756 A to Bott, published January 9, 1985.
- An especially preferred protease referred to as "Protease D," as described in U.S. Patent 5,679,630 to A.
- a preferred embodiment comprises an enzyme prill which contains an enzyme.
- Preferred examples of commercially- available enzymes useful herein include SAVINASE®, sold by Novo Corporation, Maxacal sold by Gist-brocades, Opticlean sold by Solvay-lnterox, Co, and Enzoguard sold by Genencor.
- Fillers useful herein include water-soluble and water-insoluble fillers known in the art, such as the alkali and alkali earth metals salts of carbonate, sulphate, and mixtures thereof. Fillers also include minerals, such as talc, bentonite, and hydrated magnesium silicate-containing minerals, where the silicate is mixed with other minerals, e.g., old mother rocks such as dolomite. Sodium sulfate is a well-known filler useful herein. It may be a by-product of the surfactant sulfation and sulfonation processes, or it can be added separately. As noted above, the laundry detergent bars of the present invention may require lower amounts of filler, or may not require a filler at all. Filler materials are typically used, if included, at levels up to 40%, preferably from about 5% to about 25%.
- the laundry detergent bar comprises at least about 0.01% of an other surfactant; more preferably at least about 0.1%; more preferably at least about 1 %; more preferably still, from about
- Preferred other surfactants are cationic surfactants, nonionic surfactants, ampholytic surfactants, zwitterionic surfactants, other anionic surfactants, and mixtures thereof, further described herein below.
- Nonlimiting examples of other surfactants useful in the laundry detergent bar include, the primary, branched-chain and random C-10-C20 alkyl sulfates, the C10-C18 secondary
- M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C-
- unsaturated sulfates such as oleyl sulfate, the C-
- the conventional nonionic and amphoteric surfactants such as the C-12-C18 alkyl ethoxylates including the so-called narrow peaked alkyl ethoxylates and C ⁇ -C ⁇ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines, C-10-C18 amine oxides, and the like, can also be included in the overall compositions.
- the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C-I8 N- methylglucamides. See WO 92/06154 to Cook, et al., published April 16,1992.
- sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C ⁇
- the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
- C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched- chain C-10-C16 soaps may be used.
- Mixtures of anionic and nonionic surfactants are especially useful.
- Coconut fatty alcohol sulfate is an anionic surfactant which is especially useful in combination with the LAS described herein.
- Other conventional useful surfactants are listed in standard texts, and are useful herein as well.
- a soil suspending agent may also be used herein.
- One such soil suspending agent is an acrylic/maleic copolymer, commercially available as Sokolan®, from BASF Corp.
- Other soil suspending agents include polyethylene glycols having a molecular weight of about 400 to 10,000, and ethoxylated mono- and polyamines, and quaternary salts thereof.
- a highly preferred soil suspending agent is a water-soluble salt of carboxymethylcellulose and carboxyhydroxymethylcellulose.
- the soil suspending agent may be used at a level up to about 5%, preferably about 0.1 % to about 1%, by weight of the laundry detergent bar
- the laundry detergent bars of the present invention may also contain structurants to increase the hardness of the bar, reduce smear, etc.
- structurants include, for example, water-insoluble matrices, silicates, calcium oxides, sodium swelling clays, polyvinyl alcohol- borate complexes, gelling agents such as cross linked polyacrylates, and mixtures thereof.
- adjunct materials useful in cleaning compositions and detergent compositions may also be useful herein, including other active ingredients such as carriers, processing aids, suds supressors, suds boosters, dyes, pigments, perfumes, perfume derivatives, dye transfer inhibitors, optical brighteners, clay soil removal agents, dispersants, alkalinity sources, soil suspension polymers, anti-redeposition polymers, etc.
- the laundry detergent bars of the present invention may be processed in conventional soap or detergent bar making equipment with some of all of the following key equipment: blender/mixer, mill or refining plodder, two-stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper.
- the preferred mixer type to be used is a high shear mixer.
- Suitable equipment can include: Sigma (single arm or double arms) blender, manufactured by Mazzoni; Winkworth RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, U.K.; Eirich, series RV, manufactured by Gustau Eirich Hardheim, Germany; Lodige, series FM for batch mixing; series Baud KM for continuous mixing, manufactured by Lodige Machinenbau GmbH.
- Other types of suitable mixers for this application are Twin Screw Extruders, supplied by APV Bakes (CP series), Werner and Pfleiderer (continua series).
- more than one mixer is used herein.
- the raw materials are mixed in the blender.
- An acid active such as a linear alkyl benzene sulfonic acid corresponding to the LAS described herein, is preferably premixed with an added hydrotrope, if present, and then reacted with alkaline inorganic salts such as a builder, to complete neutralization.
- the amount of alkaline inorganic salt is at least sufficient to completely neutralize the acid active.
- a pre- neutralized LAS surfactant as described herein is added in the blender.
- Other adjunct materials are then added to the mixture, such as coconut fatty alkyl sulfate. If present, the added hydrotrope may also be added at this point.
- adjunct materials may be present in the mixer when the LAS is added thereto. Alternatively, the adjunct materials may be added thereafter.
- the composition is then mixed to homogeneity. The mixing can take from one minute to one hour, with the usual mixing time being from about two to twenty minutes.
- the blender mix is charged to a surge tank. The product is conveyed from the surge tank to the mill, or refining plodder via a multi-worm conveyor, and further processed to form a laundry detergent bar.
- a preferred mixed LAS/alkyl sulfate laundry detergent bar composition is made by the following method: The raw materials are first mixed in a blender. Sodium carbonate and pre-neutralized coconut fatty alkyl sulfate is mixed for about 1-2 minutes.
- the blender mix is charged to a surge tank.
- the product is conveyed from the surge tank to the mill or refining plodder via a multi-worm conveyor. After milling or preliminary plodding, the product is then conveyed to a two-stage vacuum plodder, operating at high vacuum, e.g. 600 to 740 mm of mercury vacuum, so that entrapped air is removed.
- the product is extruded and cut to the desired bar length, and printed with the product brand name.
- the printed bar can be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage. This laundry detergent bar is substantially free of an added hydrotrope.
- Laundry detergent bars of the present invention possess acceptable physical properties such as hardness, a smooth feel, rapid drying, and acceptable in-use properties.
- a preferred method to measure the hardness of the solid composition is to measure the penetration of a needle through the surface under a standard weight, for 5 seconds using a cone penetrometer.
- a cone penetrometer is made by Associated Instrument Manufacturers India Pvt. Ltd. (Model number AIM 512).
- the weight of the rod and the cone is 149 grams and an additional 50 gram weight is placed on the cone.
- the penetration reading of a fresh, acceptable laundry bar will typically be about 35-50 (1/10 mm) immediately after plodding.
- Acceptable laundry bars aged about 3 days at ambient conditions will typically have a bar penetration reading of about 5-25 (1/10 mm).
- Yet another physical property of consumer relevance is the rate of drying of the bar after usage and storage under high humidity conditions.
- a preferred method to measure this property is to place a bar with dimensions of 75mm x 55mm with one of its large flat surface in contact with about 20 ml of water in a petri dish for 2 hours and then scraping the gel formed. This procedure is repeated for a second cycle except that the gel is not scraped off from the bar surface after the second contact with water.
- the bar is then stored under 30 degrees C and 88% Relative Humidity for 24 hours and then the bar surface which was exposed to the water is graded for dryness on a 1-5 grading scale by experienced operators as illustrated below:
- the desired dryness grade is typically between 3.5-5.0.
- Preferred bars of the present invention have a dryness grade within this range.
- C X . Y LAS LAS as described herein, containing an average of from x to y carbon atoms in the alkyl chain.
- NaCFAS Sodium coconut fatty alcohol sulfate
- STPP Sodium tripolyphosphate
- laundry detergent bars are prepared according to the present invention.
- t indicates linear alkyl benzene sulfonate surfactant having about 80 molar % 2-phenyl LAS and about 1 weight % dialkyl tetralin sulfonate impurities, and less than about 0.5 weight % dialkyl tetralin sulfonate impurities.
- compositions possess excellent surfactancy and a high level of biodegradability. Furthermore, all the above examples possess acceptable in-use wear rates, hardness, durability, rapid drying, and/or low smear.
- Synthetic detergent bars are prepared as described below. Process scale up is obvious to those skilled in the art.
- a chelant diethylene triamine pentaphophonate sodium salt, and 1 g coconut fatty alcohol are then added, and mixed for 1 minute.
- Fillers (18.2 g calcium carbonate and 5 g sodium sulfate fine particles) are added, and mixed for 1 minute.
- minor additives i.e., about 0.7 g titanium dioxide, 1 g polyacrylate/ maleic copolymer (50% active), 0.2 g soil release polymer, and 2 g coconut fatty acid monoethanol amide, are then added, and mixed for 30 seconds.
- Unstable ingredients include: 4.5 g sodium perborate monohydrate, 0.1 g SAVINASE® 4T, 0.05 g zinc phthalocyanine sulfonate are added, and briefly mixed. The final mix is then pressed in a mold to form the bar.
- the above synthetic detergent bar composition possesses excellent surfactancy and a high level of biodegradability. Furthermore, the above example possesses acceptable in-use wear rates, hardness, durability, rapid drying, and/or low smear.
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- Engineering & Computer Science (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU23111/99A AU2311199A (en) | 1999-01-06 | 1999-01-06 | Laundry detergent bar composition |
PCT/US1999/000193 WO2000040691A1 (en) | 1999-01-06 | 1999-01-06 | Laundry detergent bar composition |
EP99902987A EP1141219A1 (en) | 1999-01-06 | 1999-01-06 | Laundry detergent bar composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/000193 WO2000040691A1 (en) | 1999-01-06 | 1999-01-06 | Laundry detergent bar composition |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000040691A1 true WO2000040691A1 (en) | 2000-07-13 |
Family
ID=22271940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/000193 WO2000040691A1 (en) | 1999-01-06 | 1999-01-06 | Laundry detergent bar composition |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1141219A1 (en) |
AU (1) | AU2311199A (en) |
WO (1) | WO2000040691A1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001055287A1 (en) * | 2000-01-28 | 2001-08-02 | Huntsman Petrochemical Corporation | Solid alkylbenzene sulfonates and cleaning compositions having enhanced water hardness tolerance |
WO2002024845A2 (en) * | 2000-09-19 | 2002-03-28 | Huntsman Petrochemical Corporation | Alkyl toluene sulfonate detergents |
EP2360233A1 (en) | 2010-01-25 | 2011-08-24 | Rohm and Haas Company | Laundry detergent bar composition |
EP3339417A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339414A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339418A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339416A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339420A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339415A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339419A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
JP2019529678A (en) * | 2016-09-07 | 2019-10-17 | エコラボ ユーエスエー インコーポレイティド | Method for adjusting the dispensing rate of a solid detergent using a solid detergent composition and a solid anionic surfactant |
WO2022040488A1 (en) | 2020-08-21 | 2022-02-24 | Dow Global Technologies Llc | Non-soap detergent bar composition |
Citations (6)
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EP0112048A1 (en) * | 1982-11-16 | 1984-06-27 | Unilever N.V. | Detergent compositions |
DE3640541A1 (en) * | 1986-11-27 | 1988-06-01 | Henkel Kgaa | Granular detergent |
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WO1997036985A1 (en) * | 1996-03-29 | 1997-10-09 | The Procter & Gamble Company | Low moisture laundry detergent bar with improved enzyme stability |
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-
1999
- 1999-01-06 AU AU23111/99A patent/AU2311199A/en not_active Abandoned
- 1999-01-06 WO PCT/US1999/000193 patent/WO2000040691A1/en not_active Application Discontinuation
- 1999-01-06 EP EP99902987A patent/EP1141219A1/en not_active Ceased
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EP0112048A1 (en) * | 1982-11-16 | 1984-06-27 | Unilever N.V. | Detergent compositions |
DE3640541A1 (en) * | 1986-11-27 | 1988-06-01 | Henkel Kgaa | Granular detergent |
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Title |
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COHEN L. ET AL.: "INFLUENCE OF 2-PHENYL ALKANE AND TETRALIN CONTENT ON SOLUBILITY AND VISCOSITY OF LINEAR ALKYLBENZENE SULFONATE", JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY, vol. 72, no. 1, 1 January 1995 (1995-01-01), pages 115 - 122, XP000490482, ISSN: 0003-021X * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001055287A1 (en) * | 2000-01-28 | 2001-08-02 | Huntsman Petrochemical Corporation | Solid alkylbenzene sulfonates and cleaning compositions having enhanced water hardness tolerance |
WO2002024845A2 (en) * | 2000-09-19 | 2002-03-28 | Huntsman Petrochemical Corporation | Alkyl toluene sulfonate detergents |
WO2002024845A3 (en) * | 2000-09-19 | 2002-07-11 | Huntsman Spec Chem Corp | Alkyl toluene sulfonate detergents |
EP2360233A1 (en) | 2010-01-25 | 2011-08-24 | Rohm and Haas Company | Laundry detergent bar composition |
JP2019529678A (en) * | 2016-09-07 | 2019-10-17 | エコラボ ユーエスエー インコーポレイティド | Method for adjusting the dispensing rate of a solid detergent using a solid detergent composition and a solid anionic surfactant |
US11820962B2 (en) | 2016-09-07 | 2023-11-21 | Ecolab Usa Inc. | Solid detergent compositions and methods of adjusting the dispense rate of solid detergents using solid anionic surfactants |
US11136529B2 (en) | 2016-09-07 | 2021-10-05 | Ecolab Usa Inc. | Solid detergent compositions and methods of adjusting the dispense rate of solid detergents using solid anionic surfactants |
EP3339418A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339420A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339415A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339419A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339416A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339414A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
EP3339417A1 (en) * | 2016-12-22 | 2018-06-27 | The Procter & Gamble Company | Laundry detergent composition |
WO2022040488A1 (en) | 2020-08-21 | 2022-02-24 | Dow Global Technologies Llc | Non-soap detergent bar composition |
Also Published As
Publication number | Publication date |
---|---|
AU2311199A (en) | 2000-07-24 |
EP1141219A1 (en) | 2001-10-10 |
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