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
  • C11D3/12—Water-insoluble 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
  • C11D3/02—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
  • C11D3/37—Polymers
• • 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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the invention relates to a phosphate-free detergent builder.
• the invention relates to a phosphate-free detergent builder consisting of a water-insoluble silicate capable of binding calcium ions and a mixture of two different acrylic acid polymers which have a different viscosity number.
• the mixture of the two different acrylic acid polymers can preferably consist of two homopolymers.
• the mixture of the two acrylic acid polymers can consist of a homopolymer and a copolymer.
• the mixture of the two acrylic acid polymers can consist of two different copolymers.
• the acrylic acid polymers can have a viscosity number of 15 to 60, in particular between 20 and 35, and from 80 to 200, in particular between 90 and 120.
• the water-insoluble silicate capable of binding calcium ions a finely divided, bound water-containing, synthetically produced, water-insoluble compound of the general formula (Cat 2 / n O) x . Me2O3. (SiO2) y (I), in the cat use a cation exchangeable with calcium of the valence n, x denotes a number from 0.7 to 1.5, Me boron or aluminum and y denotes a number from 0.8 to 6.
• Aluminum silicates are particularly preferably used.
• the aluminum silicates to be used can be amorphous or crystalline products, although it is of course also possible to use mixtures of amorphous and crystalline products and also partially crystalline products.
• the aluminum silicates can be naturally occurring or else synthetically produced products, with the synthetically produced products being preferred.
• the production can e.g. B. by reaction of water-soluble silicates with water-soluble aluminates in the presence of water.
• aqueous solutions of the starting materials can be mixed with one another or a component present in the solid state can be reacted with the other component present as an aqueous solution.
• the desired aluminum silicates are also obtained by mixing both components in the solid state in the presence of water.
• Aluminum silicates can also be prepared from Al (OH) 3, Al2O3 or SiO2 by reaction with alkali silicate or aluminate solutions. The production can also be carried out by other known processes. In particular, the invention relates to aluminum silicates which have a three-dimensional space lattice structure.
• the preferred calcium binding capacity which is approximately in the range from 100 to 200 mg CaO / g AS, usually around 100 to 180 mg CaO / g AS, is found above all in compounds of the composition: 0.7 - 1.1, Na2O. Al2O3. 1.3-3.3 SiO2
• This molecular formula comprises two types of different crystal structures (or their non-crystalline precursors), which also differ in their molecular formulas. They are: a) 0.7 - 1.1 Na2O. Al2O3. 1.3 - 2.4 SiO2 b) 0.7 - 1.1 Na2O. Al2O3. 2.4-3.3 SiO2
• the different crystal structures are shown in the X-ray diffraction diagram.
• the amorphous or crystalline aluminum silicate present in aqueous suspension can be separated from the remaining aqueous solution by filtration and at temperatures of e.g. B. dry 50 to 400 ° C. Depending on the drying conditions, the product contains more or less bound water.
• Such high drying temperatures are generally not recommended; Expediently, the temperature does not exceed 200 ° C. if the aluminum silicate is intended for use in detergents and cleaning agents.
• the aluminum silicates do not need to be dried at all after their preparation in order to prepare a suspension according to the invention; rather - and this is particularly advantageous - an aluminum silicate that is still moist from manufacture can be used.
• dried aluminum silicates can also be used to prepare suspensions according to the invention at medium temperatures, for example at 80 to 200 ° C., until the adhering liquid water has been removed.
• the particle size of the individual aluminum silicate particles can be different and z. B. are in the range between 0.1 ⁇ and 0.1 mm. This information relates to the primary particle size, i.e. the size of the particles obtained during the precipitation and, if appropriate, the subsequent crystallization. It is particularly advantageous to use aluminum silicates which consist of at least 80% by weight of particles with a size of 10 to 0.01 ⁇ , in particular 8 to 0.1 ⁇ .
• These aluminum silicates preferably no longer contain primary or secondary particles with diameters above 45 ⁇ .
• Secondary particles are particles that are formed by agglomeration of the primary particles into larger structures.
• the use of the aluminum silicates which are still moist from their production for the production of the suspensions according to the invention has proven particularly useful, since it has been found that the formation of secondary particles is practically completely prevented when these still moist products are used.
• powdered zeolite of type A with a particularly defined particle spectrum is used as component A.
• Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE-OS 26 51 445, DE-OS 26 51 485 can be produced. They then have the partial distribution curves given there.
• a powdery zeolite of type A can be used, which has the particle size distribution described in DE-OS 26 51 485.
• the resulting polymers can be used both as an acid and as a salt or as a partially neutralized substance; metal ions and nitrogen-containing cations are suitable as counterions.
• the acrylic acid polymers used in the detergent builder according to the invention are homopolymers of acrylic acid or copolymers of acrylic acid with a content of at least 50 mol% of acrylic acid.
• the copolymers may contain other ethylenically unsaturated mono- or dicarboxylic acids with 3 to 8 carbon atoms as further monomers, such as, for. B. methacrylic acid, itaconic acid or maleic acid or their anhydride.
• the proportion of these monomers containing carboxyl groups in the copolymer can be up to 50%.
• the copolymers can contain up to 20 mol% of ethylenically unsaturated monomers which are free of carboxyl groups.
• carboxyl group-free monomers for example called acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, vinyl acetate, vinyl propionate, esters of acrylic acid or the Methacrylic acid with 1 to 8 carbon atoms in the alcohol residue, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, hydroxyethyl (meth) acrylate, hydrocypropyl (meth) acrylate, dialkylaminoethyl (meth) acrylate, vinyl alcohol, ethylene, allyl Propylene, isobutylene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether,
• the acrylic acid polymers are prepared by known processes.
• the homopolymers or copolymers can be prepared by all customary free-radical polymerization processes. For example, the following are mentioned as production methods: solution polymerization, the monomers being dissolved in water or in another solvent or solvent mixture with any additions of low molecular weight organic and / or inorganic compounds. Precipitation polymerization in solvents in which the monomers are at least partially soluble and the polymers are not soluble. Emulsion polymerization and suspension polymerization in solvents in which the monomers are not soluble and the emulsions or suspensions are stabilized by adding low and / or high molecular weight substances.
• the monomer concentration is between 5% and 70%, with 25% to 50% being preferred, depending on the viscosity of the polymer solution formed.
• Suitable initiators are both thermally decomposable radical donors which have sufficient solubility in the desired solvent or in the monomer, and also multi-component redox initiators.
• Radiation-induced polymerization can also be used to prepare the acrylic acid polymers.
• the polymerization temperature is used together with the amount of initiator to control the molecular weight of the desired polymer. It is between 30 ° C and 180 ° C, and it is advantageous to keep it between 60 ° C and 120 ° C. Low temperatures usually lead to high molecular weight polymers, too high temperatures can cause polymer degradation and coloring.
• the molecular weight can also be controlled by suitable regulators such as thio derivatives and low molecular weight alcohols.
• suitable regulators such as thio derivatives and low molecular weight alcohols.
• a relative measure of the average molecular weight is the viscosity number (ml / g).
• the polymer mixture according to the invention contains at least one homo- or copolymer (a) with a viscosity number (VZ) between 15 and 60, preferably between 20 and 35, and a homo- or copolymer (b) with VZ between 80 and 200, preferably between 90 and 120.
• VZ viscosity number
• the ratio a / b varies between 1/99 and 99/1, preferably between 25/75 and 75/25.
• the preparation according to the invention can be both Mixing of the separately prepared polymers can also be produced in a single synthetic step, the polymers with different molecular weight or viscosity being formed one after the other by controlling the metering time of the various components, the reaction temperature and the reaction time.
• the polymer mixture or the polymers produced in one step have the same physicochemical and application properties.
• the viscosity number is a known quantity. Their determination is described in the test specification DIN 53727.
• the viscosity number of the various acrylic acid polymers used according to the invention is carried out as follows:
• Viscotimer (Schott) Measuring stand (Schott) Viscotimer frame made of V4A steel Ubbelohde viscometer capillary Oa Lauda see-through thermostat D40-SN Evaluation can be carried out with the HP 97 S calculator
• the viscosity number (ml / g) is a relative measure of the average molecular weight and the average degree of polymerization.
• the viscosity number VZ is the relative change in viscosity divided by the concentration c the solution.
• the concentration c is specified at 2.0 g / 100 cm3, so it is a single-point measurement.
• the VZ is therefore only defined if the capillary, capillary constant, concentration, solvent and measuring temperature are specified.
• This dimensionless number represents the ratio of the outflow time of the polymer solution (t corr) and the solvent (t o corr), and is the basis for the calculation of VZ.
• the result depends on the measurement conditions.
• eta-rel should not exceed 2, otherwise a different polymer concentration or a different capillary must be selected.
• the intrinsic viscosity and the average molecular weight M can be calculated from the VZ.
• the throughput time t of the measuring (polymer) solution is determined in the same viscometer.
• the solids content of the POC-HS or PAS * is to be determined according to AV 318.1.
• the acid number of the POC-HS or PAS * is to be determined according to AV 319.1.
• * P 0.393 correction factor, since polycarboxylic acid is weighed in, but the measuring solution must be 2% of polycarboxylic acid Na salt.
• SZ-F solid acid number in mgKOH / g determined according to AV 319.1
• the average weight average molecular weight can be calculated as follows:
• the detergent builder according to the invention has the following advantages: Very good calcium binding capacity Very good anti-disposition effect Very good inhibition of heating rod incrustations Very good inhibition of tissue incrustation While the phosphate-free detergent builder according to the invention shows excellent advantages, balanced in all four points, the known detergent builders are only unbalanced in some points.
• the VZ is measured using an Ubbelohde capillary viscometer with capillary Oa at 25 °.
• the throughput time of a 2% (weight) polymer solution in 0.1 molar NaBr at pH 10 is measured.
• the pH is adjusted by adding NAOH.
• VZ is the difference between the throughput time, the sample and that of the pure solvent, divided by the polymer concentration of the measured sample.
• the parts given below are parts by weight.
• the reactor can be thermostatted, designed for a pressure up to 10 bar, equipped with a stirrer and with supply lines for the various components.
• the detergents are produced on a Telschig spray mixer.
• the surfactants are combined with the opt. Brightener sprayed hot. Then powder with Sikalon D, enzyme, beef soap, tallow soap and tallow alcohol.
• the washing tests are carried out on 3 Miele washing machines, W 763, alternating cyclically with a water hardness of approx. 20 ° dH and a washing temperature of 60 ° C in the boiling / colored program for 25 washes.
• the balast fabric consists of 3 kg of terry and brown wool fabric.
• 150 g of washing powder are dosed per wash for pre-wash and main wash.
• the degree of graying was measured on cotton with green stripes (WFK) after the 10th and 25th wash.
• the colorimetric sampling is carried out on the RFC 3 filter color measuring device (Zeiss).
• the degree of whiteness according to Berger is used for the evaluation.
• the evaluation takes place under statistical history points. In order to keep the measuring effort within reasonable limits (measuring area: 3 cm ⁇ , measuring time: approx. 2 ′ per measuring point) the following measuring points are taken.
• Primary wash 3 points per soiling, with 3 repetitions, for a total of 9 points.
• Graying 3 measuring points each (1) Lothar Sachs, Applied Statistics, 4th edition, Springer-Verlag, 1973, pp. 219-221 (2) ibid, pp. 57, 58 (3) ibid, p. 394; Tables on p. 116-124 (4) ibid., Pp. 63, 386-389
• s 2nd in is called "variance within the group” (mean value of the squared deviations of the individual values around the group mean values) and is calculated using the following formula from the individual standard deviations s i of the group (4).
• the averages x i are ordered in descending order of magnitude and the mean differences are checked for significance using the LSD criterion. Insignificant differences are identified by underlining the mean values with a common line. (5) ibid., Pp. 426-429
• the Wilcoxon-Wilcox test (multiple mean value comparisons based on rank numbers) (5) is used to assess the primary wash capacity as a whole. For each soiling, a ranking of 1-8 is established with regard to the 8 recipes (the same mean values receive an "average" rank number) and the individual ranks added for each recipe. The differences between these ranks are examined for significance by comparison with tabulated values (5% level).
• the graying (Table 4) shows a clear gradation in the range of effects of the PAS. Surprisingly, it is found that significantly better whiteness levels can be achieved with polymer mixtures than with the individual PAS, especially compared to the two commercially available products (recipes 1 and 8). This behavior clearly indicates synergistic effects that are only effective with the mixtures.

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• 1987
  • 1987-05-06 DE DE19873715051 patent/DE3715051A1/de not_active Withdrawn
• 1988
  • 1988-03-23 EP EP88104629A patent/EP0289768A3/fr not_active Withdrawn
  • 1988-05-03 IN IN358/CAL/88A patent/IN170841B/en unknown
  • 1988-05-04 FI FI882074A patent/FI882074A/fi not_active IP Right Cessation
  • 1988-05-04 KR KR1019880005180A patent/KR900004495B1/ko not_active IP Right Cessation
  • 1988-05-05 PT PT87411A patent/PT87411B/pt not_active IP Right Cessation
  • 1988-05-05 DK DK244788A patent/DK244788A/da not_active Application Discontinuation
  • 1988-05-06 JP JP63109246A patent/JPS63286494A/ja active Pending
• 1990
  • 1990-02-06 US US07/474,658 patent/US5076957A/en not_active Expired - Fee Related

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