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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3726—Polyurethanes
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
  • C11D3/3738—Alkoxylated silicones

Definitions

• the present invention relates to polyoxyalkylene-based copolymers used as anti-deposition agents in the washing of textiles.
• copolymers are used more particularly as an antiredepositing agent for washing in aqueous medium of polymeric, organic and synthetic materials.
• the present invention which has overcome all these technical problems relates to detergent compositions according to claim 1 below.
• zeta potential is understood to mean the absolute value of this parameter.
• copolymers which meet the definition of the invention all preferably have a molecular weight less than or equal to 150,000 and even more preferably between 2000 and 150,000 and even more particularly between 4000 and 100,000.
• the copolymers according to the invention preferably comprise an amount by weight of ethylene oxide relative to the polymer of between 10% and 90% and even more preferably an amount between 30 and 90% and very particularly an amount between 40 and 70%.
• the ethylene oxide groups constitute the hydrophilic part of the copolymer and therefore allow the solubilization of the copolymer in water which is essential for a detergency application in an aqueous medium.
• the alkylene oxide groups constitute the hydrophobic part of the copolymers and allow the adsorption of the copolymer on the fiber made up of synthetic organic polymers. This adsorption of the copolymer on the fiber will allow the desired effect, that is to say the anti-deposition.
• composition for dry cleaning is known, based in particular on an ethylene-propylene polyglycol in solution in a solvent of the hydrocarbon type.
• compositions for dry cleaning in a solvent medium and not for washing in an aqueous medium relate to compositions for dry cleaning in a solvent medium and not for washing in an aqueous medium.
• a first group of anti-depositing copolymers used in the prior art consists of copolymers composed of linear or branched polyoxyethylene and polyoxyalkylene blocks of alkylene oxide containing in particular from 3 to 6 carbon atoms per alkylene group.
• the alkylene groups are preferably propylene or butylene groups.
• copolymers marketed under the brand name "PLURONICS”" are prepared in a known manner, for example according to the process described in US Patent No. 2,674,619. They are used for the most part and essentially for polyoxyethylene-polyoxyalkylene copolymers as removal agent dirt, according to US Patent No. 4,276,205, for example, which relates to compositions based on an amine oxide, an ethoxylated alcohol or an ethoxylated alkylphenol and a condensation product d alkylene oxides - C 2- C 4 .
• compositions are presented as having a significant soil removal effect, in particular for greases, the amine oxide promoting the liquefaction of these.
• the polyoxyalkylene groups are preferably chosen from polyoxypropylene and polyoxybutylene.
• the copolymers of formula (I) can optionally be made ionizable by quaternizing the nitrogen atom (s). This quaternization can be carried out for example by a hydrogen atom or by an alkyl group.
• copolymers of formula (II) sold are prepared in a manner known per se, for example described in US Patent No. 2,970,150, Example 16.
• polyoxyalkylenes can be chosen in particular from polyoxypropylenes.
• French Patent No. 2,308,646 describes polyurethanes having an anti-redeposition action for polyester-cotton fibers.
• copolymers of formula (III) mention may be made of those for which A represents a hexamethylene, toluylene, isophorone, diphenylalkane radical.
• copolymers of formula (III) those which have: a molecular mass of between 4000 and 40,000 and very particularly between 4000 and 25,000, a weight amount of ethylene oxide of between 40 and 50%, polyoxyethylene blocks with molecular weights less than 3500 and even more preferably between 550 and 1600 and polyoxyalkylene blocks with molecular masses less than 4000 and preferably between 500 and 2000.
• copolymers of formula (III) are obtained for example by condensation of polyoxyethylene, of polyoxyalkylene of alkylene oxide of 3 to 6 carbon atoms or of block copolymers of polyoxyethylene-polyoxyalkylene with diisocyanates chosen from hexamethylene diisocyanate, toluylene diisocyanate, isophorone diisocyanate, di (isocyanatophenyl) alkanes, in an anhydrous medium in the presence of tin salt.
• diisocyanates chosen from hexamethylene diisocyanate, toluylene diisocyanate, isophorone diisocyanate, di (isocyanatophenyl) alkanes
• copolymers obtained by condensation of the homopolymers with diisocyanates have markedly improved anti-depositing properties.
• copolymers described above can be used according to the invention as anti-depositing agents when they lower the zeta potential of the textile fiber to a value less than or equal to 0.5 times the zeta potential of the bare fiber.
• This decrease in zeta potential is a function of the amount of copolymer adsorbed. This amount must be greater than 0.02 mg / g.
• the quantity adsorbed is measured by bringing a sample of fabric made of polymeric, organic, synthetic material (TERGAL "type) of a mass close to 3.5 g fixed on a metal support, with 100 ml of a NaCl solution. (3 g / l) containing the polymer, in a cell thermostatically controlled at 25 ° C. The medium is stirred When the adsorption equilibrium is reached, the quantity adsorbed is determined by an assay of the concentration of polymer remaining in solution according to the method described by BALEUX (CR Acad. Sc., 274 series C, (1972), 1617).
• the zeta potential of the fiber is measured before contact with the copolymer and after contact.
• zeta potential or electrokinetic potential
• the variation of the potential difference at the ends of the buffer as a function of the pressure applied to the solution makes it possible to determine the zeta potential of the fibers (JS STANLEY J. Phys. Chem. 58, (1954), 533).
• the tissue washers Before measuring the electrokinetic potential, the tissue washers are brought into contact for 24 hours with a polymer solution in NaCl 3 g / l medium, so as to adsorb the copolymer on the fibers. After this adsorption phase, the tissue washers are placed in the filter of the apparatus and the copolymer solution used during the adsorption period circulates under the effect of a pressure through the tissue pad.
• the anti-depositing effect of the copolymer can be measured by a series of different tests in the presence of dirt.
• the anti-depositing effect is achieved when the zeta potential of the fiber on which the copolymer is adsorbed is equal to or less than 0.5 times that of the bare fiber.
• This reduction in zeta potential is achieved for amounts of adsorbed copolymer equal to or greater than 0.02 mg / g of tissue.
• the preferred amount of adsorbed copolymer varies with the type of adsorbed copolymer.
• the preferred amount of adsorbed copolymer is between 0.05 and 5 mg / g of tissue.
• the anti-depositing efficacy of an additive is evaluated by carrying out five cumulative “Terg-O-Tometer” washing cycles (United States Testing Company Inc. Hobokin, NJ) in the presence of “complete” soiling.
• the total soil concentration used is 50 g / I for each wash cycle.
• the fabric samples used during our washing tests are polyester samples ("DACRON" 54 "from TESTFABRIC) washed beforehand at 60 ° C in a machine supplied with fresh water and in the absence of detergent.
• the concentration of anti-depositing additive used is 50 mg / 1.
• the redeposition is quantified by the difference AR (measured by a GARDNER photometer "", filter Y) between the reflectance of the initially clean fabric and that of the fabric after five washing cycles.
• the anti-depositing agent is all the more effective when ⁇ R is low.
• an additive has a significant anti-depositing effect if the value of AR is reduced by at least 3 points in the presence of the polymer compared to the value of AR measured in the absence of additive.
• Examples 1 to 14 were carried out using copolymers obtained by condensation of PLURONICS "by means of hexamethylene diisocyanate (HDI) at a temperature between 80 and 105 ° C. in the optional presence of a catalyst such as dilaurate dibutyltin Tests 1 to 14 are reported in Table 1a.
• a catalyst such as dilaurate dibutyltin Tests 1 to 14 are reported in Table 1a.
• Examples 15 to 39 were carried out using copolymers obtained by condensation of polyoxyethylene and another polyoxyalkylene in the presence of hexamethylene diisocyanate. Tests 15 to 39 are reported in Table 1b, 1c and 1d.
• the invention also relates to the preparation of detergent compositions comprising the copolymers of the type described above, a simple and effective preparation process has been developed.
• the process for the preparation of detergent compositions of the type of the invention is characterized in that the anti-depositing copolymer is added to a slurry comprising other constituents of the compositions, the mixture thus obtained is then dried.
• copolymer thus introduced retains all of these properties in the composition obtained. This is an advantageous advantage because the copolymers of the invention can be used without appreciably modifying the conventional methods of preparation of detergent compositions.
• the preparation of the slurry is done in a manner known per se.
• the copolymer is added thereto with stirring.
• the mixture obtained is then dried by any suitable means.
• Any dry additive used in detergent compositions can be mixed with the dry product thus obtained: bleaching agents, anti-foaming agent, perfumes, dyes, enzymes for example.
• the amount of copolymer added is such that it represents in particular approximately 0.2 to 5% and preferably between 1 and 2% by weight of the final composition.
• the copolymer When added to the slurry, the copolymer can be presented in different forms.
• a first possibility consists in presenting the copolymer in the form of a solution in water.
• the concentration of copolymer in the solution is between 5 and 20% and preferably 10 to 15%.
• Another possibility is to prepare a solution of the copolymer in a water-alcohol mixture.
• an aliphatic alcohol such as for example ethanol or a compound which can be used in detergency as a nonionic surfactant such as for example polyoxyethylenated alkylphenols, polyoxyethylenated aliphatic alcohols, glycols and polyglycols.
• a nonionic surfactant such as for example polyoxyethylenated alkylphenols, polyoxyethylenated aliphatic alcohols, glycols and polyglycols.
• a suitable silica can be used as support, for example a silica of the TIXOSIL "38A type.
• copolymer and of sulfonic acids such as for example arylsulfonic, alkylsulfonic, alkylarylsulfonic acids, in particular linear alkylbenzene sulfonic acids.
• sulfonic acids such as for example arylsulfonic, alkylsulfonic, alkylarylsulfonic acids, in particular linear alkylbenzene sulfonic acids.
• a slurry is prepared comprising LABS and sodium sulfate, stearate, silicate and tripolyphosphate, with stirring for 20 minutes at 85-90 ° C.
• the antiredepositing agent according to the invention is not added to the formulation.
• the slurry is then dried at 4 hours at 150 ° C. and then mixed with the other constituents of the composition.
• an antiredeposition agent is added with stirring for 15 minutes at 80 ° C. in the form of a 10% solution in water according to the invention.
• This agent is that corresponding to Example 20 (copolymer obtained by condensation of polyoxyethylene and polyoxyalkylene in the presence of hexamethylene diisocyanate).
• the slurry thus prepared is mixed after drying (4 hours at 150 ° C) with the other components of the composition.
• the amount of anti-depositing agent used represents 1% of the total weight of the composition.
• the concentration of the washing composition is 6 g / l.
• the reflectance Ry of the textile is evaluated after washing. The higher the reflectance Ry, the lower the redeposition. The results are given below:
• the invention is in no way limited to the embodiments described which have been given only by way of examples.
• it includes all the means constituting technical equivalents of the means described as well as their combinations if these are used in the context of protection as claimed.

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)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (2)

Family

ID=26223980

Family Applications (1)

Country Status (9)

Families Citing this family (19)

Family Cites Families (12)

• 1985
  • 1985-05-15 EP EP85400956A patent/EP0165136B1/fr not_active Expired
  • 1985-05-15 DE DE8585400956T patent/DE3568455D1/de not_active Expired
  • 1985-05-21 GR GR851258A patent/GR851258B/el unknown
  • 1985-05-21 NO NO852017A patent/NO163866C/no unknown
  • 1985-05-22 ES ES543378A patent/ES8702485A1/es not_active Expired
  • 1985-05-22 PT PT80513A patent/PT80513B/pt not_active IP Right Cessation
  • 1985-05-22 FI FI852050A patent/FI80472C/fi not_active IP Right Cessation
  • 1985-05-22 DK DK227385A patent/DK227385A/da not_active Application Discontinuation
  • 1985-05-23 US US06/737,044 patent/US4724095A/en not_active Expired - Fee Related
• 1986
  • 1986-07-16 ES ES556897A patent/ES8801365A1/es not_active Expired
  • 1986-07-16 ES ES556898A patent/ES8801366A1/es not_active Expired

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events