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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3915—Sulfur-containing 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents

Definitions

• This invention relates to non-phosphorus detergent bleach compositions.
• it relates to aluminosilicate built laundry detergent bleach compositions having improved cleaning and stain-removal performances.
• zeolites Water-insoluble aluminosilicates, commonly known as zeolites, have been used in detergent compositions as important alternative builders to phosphates (see, for example, GB-A-­1429143; GB-A-1470250; GB-A-1504211; GB-A-1529454 and US-A-­4064062). Bleaching experiments have indicated, however, that the bleach performances of aluminosilicate built formulations are well below those of phosphate built products.
• aluminosilicate built detergent compositions which contain 0.01-4% by weight of a polyphosphonate sequestering agent and 5-25% by weight of citric acid or citrates as pH-regulating agent. These compositions are unsatisfactory when used for washing at the low wash temperature region of 40°C and below.
• non-­phosphorus detergent bleach composition comprising at least one detergent-active material and :
• the detergent composition of the invention necessarily contains a peroxybenzoic acid bleach precursor as the bleach activator, which on perhydrolysis generates a peroxybenzoic acid.
• a peroxybenzoic acid bleach precursor as the bleach activator, which on perhydrolysis generates a peroxybenzoic acid.
• Other bleach precursors such as the most commonly used tetraacetylene diamine (TAED), which generates peracetic acid, are much less effective and hence unsuitable for use in the present invention.
• TAED tetraacetylene diamine
• Peroxybenzoic acid precursors are known in the art, e.g. from GB-A-836988. Examples thereof are phenylbenzoate; phenyl p-­nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenyl benzoate; sodium or potassium benzoyloxybenzenesulphonate; and benzoic anhydride.
• the compounds have the general formula : wherein R is H or a substituent selected from -NO2 and halogens, and L is a leaving group, the conjugate acid of which has a pKa in the range of from about 6 to about 13.
• L can be essentially any suitable leaving group that is displaced from the bleach precursor as a consequence of the nucleophilic attack on the bleach precursor by the perhydroxide anion, HOO ⁇ .
• This perhydrolysis reaction results in the formation of the peroxybenzoic acid.
• a group to be a suitable leaving group it must exert an electron-attracting effect, which facilitates the nucleophilic attack by the perhydroxide anion.
• Leaving groups that exhibit such behaviour are those in which their conjugate acid has a pKa in the range of from 6 to 13, preferably from about 7 to about 11, and most preferably from 8 to 11.
• L examples of suitable L are : wherein R1 is an alkylene chain containing from 1 to 8 carbon atoms; R2 is H or an alkyl chain containing from 1 to 8 carbon atoms; R3 is phenyl or an alkyl chain containing from 5 to 18 carbon atoms; and Y is a solubilizing group, preferably selected from -SO3 ⁇ M+, -COO ⁇ M+ or -SO4 ⁇ M+.
• a preferred peroxybenzoic acid bleach precursor is sodium p-­benzoyloxybenzene sulphonate of the formula :
• the inorganic peroxide compounds usable in the present invention can be true persalts or perhydrates, which liberate hydrogen peroxide in aqueous solution.
• examples or inorganic peroxide compounds are the alkali metal perborates, percarbonates, and persilicates, the perborates, particularly sodium perborate tetra- and monohydrate being preferred because of their commercial availability.
• the inorganic peroxide compound and the peroxybenzoic acid bleach precursor in the composition of the invention may be present in a molar ratio of between 0.5:1 and about 20:1, preferably from 1:1 to 10:1. Under certain wash conditions a molar ratio of about 2:1 may be of advantage.
• composition of the invention contains at least one detergent-active material which can be an organic soap or synthetic detergent surfactant material.
• an organic, anionic, nonionic, amphoteric or zwitterionic detergent compound, soap, or mixtures thereof is included.
• Many suitable detergent-active compounds are commercially available and are fully described in literature, for example in US-A-4222905 and US-A-4239659 and in "Surface Active Agents and Detergents", Vol. I and II, by Schwartz, Perry and Berch.
• the preferred detergent-active compounds which can be used are synthetic anionic, soap and nonionic compounds.
• the first-mentioned are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
• suitable synthetic, anionic detergent compounds are sodium and potassium alkyl sulphates, especia­lly those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of
• Suitable soaps are the alkali metal salts of long chain C8-C22 fatty acids such as the sodium soaps of tallow, coconut oil, palmkernel oil, palm oil or hardened rapeseed oil fatty acids or mixtures thereof.
• the preferred anionic detergent compounds are sodium (C11-C15) alkyl benzene sulphonates and sodium (C16-C18) alkyl sulphates.
• nonionic detergent compounds examples include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, genera­lly 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
• nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
• detergent-active compounds for example mixed anionic or mixed anionic and nonionic compounds
• Amounts of amphoteric or zwitterionic detergent-active compounds can also be used in the compositions of the invention, but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic, detergent-active compounds are used, it is generally in small amounts in the compositions based on the much more commonly used synthetic anionic and/or nonionic detergent-active compounds.
• the detergent composition of the invention also contains a water-insoluble aluminosilicate cation-exchange material in an amount of from 15% to about 40% by weight, preferably from 20% to 35% by weight.
• the aluminosilicate can be crystalline or amorphous in character, preferred materials having the unit cell formula I M z [(AlO2) z (SiO2) y ] xH2O I wherein M is a calcium-exchange cation, z and y are at least 6; the molar ratio of z to y is from about 1.0 to about 0.5 and x is at least 5, preferably from about 7.5 to about 276, more preferably from about 10 to about 264.
• the aluminosilic­ate materials are in hydrated form and are preferably crystalline containing from about 10% to about 28%, more preferably from about 18% to about 22% water.
• the aluminosilicate ion-exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns, preferably from about 0.2 micron to about 4 microns.
• particle size diameter herein represents the average particle size diameter of a given ion-­exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
• the aluminosilicate ion-exchange materials herein are usually further characteri­zed by their calcium ion-exchange capacity, which is at least about 200 mg.
• aluminosilicate ion- exchange materials herein are still further characterized by their calcium ion-­exchange rate which is at least about 2 grains Ca++/gallon/­minute/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/­gallon/minute/gram/gallon to about 6 grains/gallon/minute/­gram/gallon, based on calcium ion hardness.
• Optimum aluminosilicates for builder purposes exhibit a calcium ion-­exchange rate of at least about 4 grains/gallon/minute/gram/­gallon.
• Aluminosilicate ion-exchange materials useful in the practice of this invention are commercially available and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion-exchange materials is discussed in US-A-3985669.
• Preferred synthetic crystalline aluminosilicate ion-exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
• the crystalline aluminosilicate ion-exchange material is Zeolite A and has the formula Na12[AlO2)12 (SiO2)12] xH2O wherein x is from about 20 to about 30, especially about 27.
• Zeolite X of formula Na86 [(AlO2)86)(SiO2)106] .276 H2O is also suitable, as well as Zeolite HS of formula Na6 [(AlO2)6 (SiO2)6] 7.5 H2O).
• the detergent composition of the invention further contains an alkali metal citrate or citric acid in an amount of from about 1% to about 15%, preferably from 2 to 10%, by weight of the composition.
• a preferred alkali metal citrate is sodium citrate, particularly trisodium citrate, i.e. C6H5O7.Na3.2H2O.
• the detergent composition herein can contain any of the conventional additives and adjuncts in the amounts in which such materials are normally employed in fabric washing compositions.
• additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel and coconut fatty acids; lather depressants such as alkyl phosphates, silicones and waxes; anti-­redeposition agents such as sodium carboxymethyl cellulose (SCMC), polyvinyl pyrrolidone (PVP) and the cellulose ethers, such as methylcellulose and ethyl hydroxyethyl cellulose; stabilizers such as ethylene diamine tetraacetate; fabric softening agents; inorganic salts such as sodium sulphate and sodium carbonate; and - usually present in very minor amounts - fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases; germicides and colourants.
• lather boosters such as alkanolamides, particularly the monoethanol
• Polycarboxylate polymers though not essential, may also be included as desired in amounts of e.g. from about 0.5% to 6% by weight of the total composition.
• the polycarboxylate polymers herein are preferably selected from co-polymeric polycarboxylic acids and their salts derived from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid or mesaconic acid as a first monomer and ethylene, methyl vinyl ether, acrylic acid or metacrylic acid as a second monomer, the co-polymer comprising at least about 10 mole%, preferably at least about 20 mole% of polycarboxylic acid units and having weight average molecular weights of at least about 10,000, preferably at least about 30,000; homopolyacrylates and homopolymethacrylates having a weight average molecular weight of from about 1000 to about 10,000, preferably from about 5000 to about 50,000; and mixtures thereof.
• the detergent bleach compositions of the invention are alkaline and will advantageously have a solution pH (2-10 g/l) of from 8-11, with an optimal pH of between 8 and 9.
• a wash pH of, say, 8.5 appears to give the best compromise for achieving good bleaching, detergency and enzymatic soil removal.
• buffering agents such as borax, may be necessary.
• the detergent compositions of the invention are preferably presented in free-flowing particulate, e.g. powdered or granular form, and can be produced by any of the known techniques commonly employed in the manufacture of such washing compositions, but preferably by spray-drying an aqueous slurry comprising the surfactant(s), the alumino­silicate and the alkali metal citrate to form a detergent base powder, to which the heat-sensitive ingredients, including the peroxybenzoic acid bleach precursor, the inorganic percompound, enzymes and optionally some other ingredients as conveniently desirable are added.
• the alkali metal citrate can be separately dry-mixed with the spray-dried base powder.
• the bleach precursor and enzymes are preferably added as granulated particles. It is preferred that the process used to form the compositions should result in a product having a moisture content of up to about 15%, more preferably from about 7% to about 14% by weight.
• composition A Parts by weight Sodium linear alkylbenzene sulphonate 9.0 Fatty alcohol-7 ethoxylate 1.5
• Maleic acid/acrylic acid copolymer Sokalan ® CP5 ex BASF
• 4.0 Sodium aluminosilicate Zeolite A 24.0
• Sodium sulphate anhydrous
• EDTA ethylenediamine tetraacetate
• Na2CO3 Sodium carbonate
• Composition B Sodium perborate monohydrate 13.0 Anti-foaming agent 2.5
• Proteolytic enzyme Savinase ® ex NOVO
• trisodium citrate boosts the bleach performances on tea and wine stains without a negative effect on detergency and enzyme action, i.e. protein soil removal.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)

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• 1987
  • 1987-10-23 GB GB878724900A patent/GB8724900D0/en active Pending
• 1988
  • 1988-10-07 EP EP88202244A patent/EP0313144A3/de not_active Ceased
  • 1988-10-19 CA CA000580630A patent/CA1316790C/en not_active Expired - Fee Related
  • 1988-10-19 AU AU24007/88A patent/AU612711B2/en not_active Ceased
  • 1988-10-21 NO NO88884700A patent/NO884700L/no unknown
  • 1988-10-21 JP JP63265912A patent/JPH01146997A/ja active Pending
  • 1988-10-21 BR BR8805450A patent/BR8805450A/pt not_active Application Discontinuation
  • 1988-10-22 KR KR1019880013799A patent/KR920002085B1/ko not_active IP Right Cessation

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