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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions

Definitions

• the present invention relates to liquid detergents and in particular liquid detergents with whitening action, stable in storage.
• Liquid household detergents are increasingly used in place of powdered household detergents for washing clothes, by hand or in a washing machine.
• liquid bleaching detergents constituted by a detergent base and containing a peroxidized compound such as sodium perborate tetrahydrate or hydrogen peroxide and a stabilizer, and whose pH is between 8 and 10.
• the patent application FR 2,552,124 relates to detergent fluid formulations with whitening action for textiles stable in storage containing, in anhydrous state, hydrogen peroxide and usual ingredients of washing baths other than persalts and peroxyhydrates.
• This technique of using hydrogen peroxide in an anhydrous medium does not yet seem to have resulted industrially.
• the only compositions currently on the market are produced in aqueous media without bleaching agent.
• aqueous and alkaline liquid detergent composition containing a bleaching agent has been sought.
• the particularity of these perborated detergents lies in the fact that the bleaching agent, the source of active oxygen, specially chosen, is added with stabilizers which make it possible to obtain, despite the alkalinity of the medium in aqueous phase, very good stability of said bleaching agent.
• the composition contains an agent maintaining the homogeneity of the detergent mixture.
• the preferred bleaching agent is sodium perborate monohydrate.
• Perborate tetrahydrate can hardly be used because its use requires increasing the viscosity of the detergent mixture to avoid settling and phase shifting.
• the detergent mixture is in this case too viscous to flow easily from its container.
• Sodium percarbonate which is a commonly manufactured perhydrate is not suitable in the field of the invention because of its unstable character in aqueous medium. Certain stabilizers can greatly improve its stability, but the results obtained are insufficient to be used industrially in the case of aqueous alkaline liquid detergents.
• Compositions have been produced with different particle sizes of perborate monohydrate from standard quality where the particle size distribution is between 800 ⁇ and 100 ⁇ to ground products of which 75% of the grains of perborate monohydrate are less than 50 ⁇ .
• the weight percentages of sodium perborate monohydrate, in the liquid detergents of the invention can reach 20%, and are between 4 and 15%, and preferably 6 and 12%.
• the stabilizing effect is obtained by adding a synthetic magnesium silicate Mg 3.5 SiO2 to the detergent mixture.
• This magnesium silicate is prepared by adding stable organic complexing agents introduced during the manufacturing process.
• This magnesium silicate thus synthesized is a defined product where the exchangeable magnesium of the magnesium silicate is in the form of a magnesium salt of the complexing agent or agents.
• This preparation method makes the magnesium silicate Mg 3.5 SiO2 very resistant to use, and gives it excellent properties as regards its stabilization of peroxides or perhydrates, this product is marketed under the brand Sydex R.
• This stabilizer is used at particularly favorable concentrations at doses of between 0.1 and 2.5%. These weight percentages are calculated relative to the detergent composition.
• the stabilizing effect is reinforced by the addition to the detergent composition of sodium acid pyrophosphate, which acts as a pH buffer in addition to its stabilizing properties.
• the sodium acid pyrophosphate is preferably used in weight doses of between 0.5 and 10% relative to the detergent composition.
• a viscosity regulator is an integral part of the new detergent compositions, with a view to maintaining the initial homogeneous appearance for several months and in order to avoid any sedimentation or the appearance of distinct phases.
• copolymers suitable as a viscosity regulator are in particular the polyethylene glycol-dialkyl ether copolymers, the alkyl residue of which may be a straight or branched chain of 8 to 18 carbon atoms.
• the copolymer is used in doses of between 0.5 and 7.5% by weight, preferably 2 and 5% relative to the detergent composition.
• the stabilizing composition consisting of the magnesium silicate couple Mg 3.5 SiO2 + sodium acid pyrophosphate participates with the viscosity regulator, the polyethylene glycol dialkyl ether, in obtaining the permanent homogeneity of the detergent.
• compositions produced as a control without the viscosity regulator do not retain their homogeneous appearance.
• compositions containing neither magnesium silicate Mg 3.5 SiO2, nor sodium acid pyrophosphate with only the viscosity regulator lose their homogeneous appearance after a few days, a transparent liquid phase forming above a thick phase and opaque.
• the aqueous detergent composition contains the usual elements: - nonionic and anionic detergents neutralized with triethanolamine or sodium hydroxide for example to obtain an adequate pH of the order of 7 to 10; - detergency builders mainly to capture calcium and magnesium ions, they are considered as anti-scaling agents like phosphates, acrylic derivatives, citrates, etc ...
• - fluidizing agents to regulate the viscosity of the detergent, such as for example isopropyl alcohol for fluidizing nonionic surfactants; - anti-redepositing agents to keep dirt in suspension in the washing bath, such as, for example, carboxymethyl cellulose or polyvinylpyrrolidone; - optical brighteners with affinity for textile fibers to increase the visual sensation of whiteness; - enzymes, such as amylases, proteases and lipases, associated with enzyme stabilizers to degrade protein and starch spots; - perfumes and possibly dyes.
• liquid bleaching detergents of the invention make it possible to obtain very satisfactory washing and bleaching results at conventional treatment temperatures preferably between 40 and 90 ° C.
• the durations of the washing treatments are conventional, preferably between 10 and 60 minutes.
• This composition has very good behavior both from the point of view of fluidity and permanence of the appearance of the mixture as well as the stability of the perborate monohydrate used.
• the perborate monohydrate used in this composition is a fine ground quality, the particle size of which comprises 75% of product less than 50 ⁇ .
• a composition analogous to that of Example 1 without the copolymers of polyethylene glycols - dialkyl ether quickly presented a non-homogeneous appearance characterized by the appearance of a transparent liquid phase above a thick and opaque phase.
• Composition # 2 Alcohol 16 - 18 tallow condensed with 11 mol OE .... 10% Sodium dodecylbenzene sulfonate .... 9% Carboxymethylcellulose .... 1% Caustic soda .... 1.2% Sodium acid pyrophosphate .... 4% Sydex R .... 1% Optical brightener (TINOPAL CBS - X R Ciba-Geigy) .... 0.2% Polyethylene - glycol dialkyl ether copolymer .... 2.25% Sodium perborate monohydrate (crushed fines) .... 10% Q.S. water for 100% either .... 61.35%
• This composition reinforced with non-ionic surfactant, has very good storage behavior both in terms of appearance and active oxygen content.
• the rate of perborate has practically not changed in 3 months, it went from 10.1% to 9.85%, that is to say a loss of 0.25%.
• Technicians know in the case of powdered product variations of this order without inconvenience.
• composition analogous to composition no. 2 was produced using fine quality sodium perborate tetrahydrate to replace fine quality sodium perborate monohydrate.
• Composition # 3 Alcohol 16 - 18 tallow condensed with 11 mol OE .... 10% Sodium dodecylbenzene sulfonate .... 9% Carboxymethylcellulose .... 1% Caustic soda .... 1.2% Sodium acid pyrophosphate .... 4% Sydex R .... 1%
• Optical brightener (TINOPAL CBS - X R Ciba - Geigy) .... 0.2% Polyethylene glycol dialkyl ether .... 2.25% Sodium perborate tetrahydrate (fine quality) .... 15% QS water for 100% or .... 56.35%
• this composition whose active oxygen content is identical to that of Example 2, had a non-homogeneous appearance characterized by a transparent liquid phase above a thick and opaque phase.
• Composition # 4 Alcohol 16 - 18 tallow condensed with 11 mol OE .... 10% Sodium dodecylbenzene sulfonate .... 9% Carboxymethylcellulose .... 1% Caustic soda .... 1.2% Sodium acid pyrophosphate (Na2H2P207) .... 4% Sydex R .... 1% Tinopal CBS - X R (Ciba Geigy) ... 0.2% Polyethylene glycol - dialkyl ether .... 2.25% Sodium perborate monohydrate .... 10% Q.S. water for 100% either .... 61.35%
• composition No. 4 the sodium perborate monohydrate was of standard quality, that is to say of a particle size between 100 and 800 ⁇ without disadvantage for the conservation of the homogeneous appearance of the product for several months.
• the particle size of the perborate has no influence on its stability in the field of aqueous alkaline liquid detergents within the scope of the invention.
• Composition # 5 Ethoxylated fatty alcohol, lauric type with 9 mol of EO ... 5% Ethoxylated fatty alcohol with 7 mol of EO (Synperonic A7 from HERE) .... 5% Sodium dodecylbenzene sulfonate .... 9% Carboxymethylcellulose .... 1% Caustic soda .... 0.9% Sodium acid pyrophosphate .... 4% Sydex R .... 1% Polyethylene glycol didodecyl ether .... 3.15% Optical brightener - Tinapal CBS - X R - Ciba Geigy) .... 0.2% Enzyme - Esperase 8.0 L R 0.8% Enzyme stabilizer (Calcium salt) .... 0.2% Antifoam (Rhodorsil 412 R de Rhône - Poulenc) .... 0.05% Sodium perborate monohydrate .... 10% Q.S. water for 100% either .... 59.7%
• composition was produced with fine quality sodium perborate monohydrate, the grain size of which is 75% between 125 ⁇ m and 40 ⁇ m.
• Esperase R 8.0 L in liquid form from NOVO INDUSTRI A / S.
• an enzyme protector such as a calcium salt, for example calcium chloride or lime.
• composition like the previous ones, has a stable and homogeneous appearance which does not change as a function of the duration of storage.
• WB Effect of brightening evaluated according to the formula of Ms. BERGER: RY + 3 (RZ-RX) after determination of the reflectors RX, RY and RZ under UV illuminant (XENON lamp without filter).
• Example 1 The composition of Example 1 was not tested due to the absence of an optical brightener to avoid an unfair comparison.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (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)

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• 1988
  • 1988-04-22 FR FR8805335A patent/FR2630454B1/fr not_active Expired - Fee Related
• 1989
  • 1989-04-19 DE DE8989401084T patent/DE68901888T2/de not_active Expired - Fee Related
  • 1989-04-19 EP EP89401084A patent/EP0338921B1/de not_active Expired - Lifetime
  • 1989-04-19 ES ES198989401084T patent/ES2032663T3/es not_active Expired - Lifetime
  • 1989-04-19 AT AT89401084T patent/ATE77651T1/de not_active IP Right Cessation
  • 1989-04-21 JP JP1100334A patent/JPH0268359A/ja active Pending
  • 1989-04-21 CA CA000597356A patent/CA1334735C/fr not_active Expired - Fee Related
• 1990
  • 1990-11-13 US US07/614,050 patent/US5160656A/en not_active Expired - Fee Related

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