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 copolymers based on polyoxyethylene and polyoxyalkylene used as anti-deposition agents in the washing of textiles.
• ccpolymers are used more particularly as an antiredepositing agent for washing aqueous, polymeric, organic and synthetic materials.
• the present invention which has overcome all of these technical problems, relates to detergent compositions characterized in that they contain at least one antiredepositing copolymer useful in particular for washing synthetic organic polymeric materials which comprises at least one unit chosen from the oxide group. ethylene, alkylene oxide and which reduces 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; the compositions being used under conditions such that the amount of copolymer adsorbed per gram of tissue is at least 0.02 mg.
• zeta potential is understood to mean the absolute value of this parameter.
• copolymers which meet the definition of the invention fall into four main groups which do not limit the concept of the invention.
• a molecular mass less than or equal to 150,000 and even more preferably between 2,000 and 150,000 and even more particularly between 4,000 and 100,000.
• the copolymers according to the invention preferably contain 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.
• the first group of copolymers which can be used according to the invention consists of copolymers composed of linear or branched polyoxyethylene and polyoxyalkylene blocks containing in particular from 3 to 6 carbon atones per alkylene group.
• the alkylene groups are preferably propylene or butylene groups.
• copolymers sold under the trademark "PLURONICS” ® are prepared in a known manner, for example according to the process described in US Pat. No. 2,674,619. They are used for the most part and essentially for polyoxyethylene-polyoxyalkylene copolymers as a removal agent dirt, we had never used, as an anti-depositing agent, some of them which reduce the zeta potential of the fiber to a value less than or equal to 0.5 times the zeta potential of the bare fiber.
• 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.
• the polyoxyalkylenes can be chosen in particular from polycxypropylenes.
• copolymers of formula (III) mention may be made of those for which A represents a hexamethylene, toluylene, isophorne, diphenylalkane radical.
• the group 4 copolymers those which have: a molecular mass of between 4,000 and 40,000 and very particularly between 4,000 and 25,000, a weight amount of ethylene oxide of between 40 and 50%, polyoxyethylene blocks with molecular masses less than 3,500 and even more preferably between 550 and 1,600 and polyoxyalkylene blocks with molecular masses less than 4,000 and preferably between 500 and 2,000.
• copolymers of formula (III) are obtained for example by condensation of polyoxyethylene and polyoxyalkylene or of polyoxyethylene - polyoxyalkylene copolymers as defined in the first group of copolymers according to the invention with diisocyanates chosen from hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, di (isocyanatophenyl) alkanes, in an anhydrous medium in the presence of tin salt.
• diisocyanates chosen from hexamethylene diisocyanate, toluene 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 metallic support, with 100 ml of a NaCl solution. (3 g / 1) containing the polymer, in a cell thermostatically controlled at 25 ° C. The environment is agitated. 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 (C.R. 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 (J.S. 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 medium 3 g / 1, so as to adsorb the copolymer on the fibers. After this adsorption phase, the washers of tissue 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 0.1 and 5 mg / g of tissue.
• the preferred amount of adsorbed copolymer is between 0.02 and 5 mg / g of tissue.
• the preferential amount of adsorbed copolymer is greater than approximately 0.3 mg / g and even more preferably between 0.4 and 5 mg / g of tissue.
• the preferred amount of adsorbed copolymer is between 0.05 and 5 mg / g of tissue.
• the support carrying the tissue sample is removed and immersed in 100 ml of distilled water stirred by a magnetic bar. This rinsing operation lasts three ninutes.
• the deposition on the textile fibers is evaluated by the difference ⁇ R (measured by a "ELREPHO" photometer from ZEISS®, filter No. 10) between the reflectance of the initially clean fabric and that of the fabric after contact with the suspension of carbon black.
• ⁇ R the higher the deposition. In the absence of a copolymer, the value of ⁇ R is 40. It can be considered that an anti-depositing additive has good efficacy during this test if it reduces AR to a value between 10 and 18, below 10 , the performance of the additive is excellent.
• 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 / l for each washing cycle.
• the concentration of detergent used is 6 g / l, its hanging composition is as follows:
• 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.
• Each pot of the "Terg-0-Tometer” contains 6 rectangles of fabric (10 x 12 cm).
• the concentration of anti-depositing additive used is 50 mg / 1.
• the redeposition is quantified by the difference A R (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 A R is reduced by at least 3 points in the presence of the polymer compared to the value of A R measured in the absence of additive.
• Table 1 gives the results of the anti-depositing effect (AR) measured according to test 1 of products marketed under the brand PLURONICS®.
• the products for which ⁇ / ⁇ o is less than 0.50 (examples 1, 2, 3, 5) have an anti-depositing effect markedly improved compared to those which do not meet the criteria of the invention.
• Example 6 shows in particular that Pluronic L 64 known to have a good soil removal effect does not meet the criteria of the invention.
• Examples 20 to 33 were carried out using copolymers obtained by condensation of products of group 1 PLURONICS® by means of hexanethylene diisocyanate (HDI) at a temperature between 80 and 105 ° C in the optional presence of a catalyst such as dibutyltin dilaurate. Tests 20 to 33 are reported in Table 4a.
• Examples 34 to 58 were carried out using copolymers obtained by condensation of polyoxyethylene and polyoxyalkylene in the presence of hexanethylene diisocyanate. Tests 34 to 58 are reported in Table 4b, 4c and 4d.
• 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 preparing 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.
• the amount of copolymer added is such that it represents 0.2 to 5% approximately 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 can be used 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.
• copolymer on a support.
• a suitable silica for example a silica of the TIXOSIL 38A type.
• copolymer and of sulfonic acids such as, for example, arylsulfonic, alkylsulfonic or alkylarylsulfonic acids, in particular linear alkylbenzene sulfonic acids.
• sulfonic acids such as, for example, arylsulfonic, alkylsulfonic or alkylarylsulfonic acids, in particular linear alkylbenzene sulfonic acids.
• a slurry is prepared comprising LABS and sodium sulphate, stearate, silicate and tripolyphosphate by 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 39 (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 antirepleting agent used represents 1 X 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 equi- technical alents of the means described as well as their combinations if these are used in the context of protection as claimed.

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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)
• Detergent Compositions (AREA)

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Cited By (7)

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• 1985
  • 1985-05-15 DE DE8585400956T patent/DE3568455D1/de not_active Expired
  • 1985-05-15 EP EP85400956A patent/EP0165136B1/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 PT PT80513A patent/PT80513B/pt not_active IP Right Cessation
  • 1985-05-22 ES ES543378A patent/ES8702485A1/es not_active Expired
  • 1985-05-22 DK DK227385A patent/DK227385A/da not_active Application Discontinuation
  • 1985-05-22 FI FI852050A patent/FI80472C/fi not_active IP Right Cessation
  • 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

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