EP0421664A2 - Polymer enthaltende Granulate - Google Patents

Polymer enthaltende Granulate Download PDF

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Publication number
EP0421664A2
EP0421664A2 EP90310547A EP90310547A EP0421664A2 EP 0421664 A2 EP0421664 A2 EP 0421664A2 EP 90310547 A EP90310547 A EP 90310547A EP 90310547 A EP90310547 A EP 90310547A EP 0421664 A2 EP0421664 A2 EP 0421664A2
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EP
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Prior art keywords
polymer
granules
useful
chamber
weight
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EP90310547A
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English (en)
French (fr)
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EP0421664A3 (en
EP0421664B1 (de
Inventor
Maurizio Pastori
Paolo Zini
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Rohm and Haas Co
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Rohm and Haas Co
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    • 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
    • C11D3/046—Salts
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • 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
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • detergent formulations is intended to encompass cleaning agents for both fabrics and hard surfaces.
  • Polymers are generally added to detergent formulations either in the form of a dry powder, formed by spray-drying a solution, dispersion, slurry or emulsion of polymer in a liquid ('wet polymer'), or directly as wet polymer to a detergent formulation in slurry form before drying. In both cases, the final product has a number of undesirable features.
  • the dry powder formed by spray-drying wet polymer alone is a material which is hygroscopic and therefore tends to become 'sticky' upon storage or in the final formulation itself.
  • Such dry polymer also has a low bulk density, typically 300-500 g/l, which means that in a typical detergent formulation having density in the region of 700 g/l the polymer has a tendency to separate out; it also reduces the bulk density of the formulation.
  • the dry polymer powder usually has a high proportion of fine material, leading to undesirable dusting problems in the final formulation, and further contributing to the problem of separation.
  • One method of adding wet polymer is to add it to other components of the final formulation before drying, and then to spray-dry the polymer and other components together.
  • An example of a granulate composition made by such a method is disclosed in DE-A-3316513, in which a granule for use as a phosphate substitute, containing 30-75% zeolite together with at least 5% polycarboxylate, is made by spray-drying a slurry of the components.
  • Such a spray-drying process invariably yields a granulated product of undesirably low density, and indeed the highest density achieved by this composition is 610 g/l; also, additional water - that introduced with the polymer - has to be removed.
  • wet polymer contains liquid (usually water) and polymer in a ratio of about 1:1, so that adding more than just a few percent of polymer requires the addition of a significant amount of liquid also: solubilization by the liquid of other components in the formulation tends to result in the formulation of a paste in the dryer. This problem cannot be avoided by reducing the liquid content of the polymer prior to addition, because the viscosity of the wet polymer becomes too high for satisfactory flowability and even distribution of the polymer amongst the other components.
  • the above method of adding wet polymer may be used when polymers are to be employed as agglomerating agents for salts; in such a case they are added at concentrations of only about 0.5%, so that the difficulties with excess liquid become insignificant.
  • a high density polymer-containing granulate is known, from EP-A-368137; it contains 60-80% zeolite, 2-15% polycarboxylate, and 14-25% by weight of water, and has a density of 750-1000 g/l.
  • water-insoluble salts have a tendency to deposit on fabrics, a problem which the addition of polymers is at least partly intended to counteract; in a granule containing such a high ratio of water-insoluble salt to polymer, any effect as a suspending agent which the polymer might have been intended to have would be virtually nullified by the large amount of zeolite introduced with the polymer.
  • a granular detergent additive is known from US-A-46981 74 which comprises 20-80% polymer, 20-80% nitrilotriacetic acid (NTA) and optionally up to 20% of another additive such as sodium sulphate. Densities of up to 690 g/l are disclosed, and the product is also said to have low hygroscopicity. However, the usefulness of this additive is limited by the necessity for it to comprise a significant proportion of NTA to obtain satisfactory performance; large proportions of NTA may be considered undesirable on environmental grounds. Furthermore the densities disclosed are still generally less than the average density of a typical detergent.
  • the present invention provides a composition, useful as a component of a detergent formulation, in the form of granules each comprising at least 10% by weight of polymer useful in such formulations and at least 20% by weight of at least one water-soluble inorganic component also useful in such formulations, the bulk density of said composition being at least 700 g/l.
  • Preferred inorganic components are salts, such as sulphates, carbonates and silicates. Perborates (both mono- and tetrahydrate), percarbonates and persulphates may also be useful. In formulations where phosphates are still present, they may also be used as carriers. For all the above salts, the sodium form is preferred.
  • the present invention is also applicable to the case where the inorganic component is zeolite or clay, which are both water-insoluble.
  • the present invention provides a composition, useful as a component in detergent formulations, in the form of granules each comprising at least 20% by weight of polymer useful in such formulations and at least 20% by weight of zeolite, the bulk of density of said composition being at least 700 g/l.
  • the granules may contain minor amounts of other components which are suitable for use in detergent compositions.
  • the density of the granulate may be as low as 300 g/l or as high as 1400 g/l, although a density in the range from 700 to 1200 g/l is preferred, particularly over 900 g/l.
  • the density depends on the type of inorganic component ("carrier"), on polymer type, and on manufacturing process conditions and equipment (discussed hereinafter), and also on the relative proportions of polymer(s) and carrier(s).
  • carrier inorganic component
  • polymer type polymer type
  • manufacturing process conditions and equipment discussed hereinafter
  • the density of such granules will be at the bottom end of the desired range.
  • 10% to 50% by weight polymer is present in the granule (but at least 20%, preferably at least 25% where zeolite is present) , and more typically from 20% to 40%.
  • the most preferred amount of polymer is 30%.
  • Suitable polymers include homopolymers or copolymers of dicarboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, citraconic acid and the anhydrides of ds dicarboxylic acids, such as maleic anhydride; monocarboxylic acids such as acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid and acryloxypropionic acid; and unsaturated non-carboxylic aceds such as alkyl esters of acrylic or methacrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isobutyl methacrylate; hydroxyalkyl esters of acrylic or methacrylic acids such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacryl
  • Polymers can be in acid or neutralized or partially neutralized form with Na, K, NH4 or other counterions.
  • Molecular weights of the polymers may be from 500 to 5,000,000. Generally the higher molecular weight, the greater the degree of agglomeration obtained during manufacture of the granules and hence the larger the granules. Thus the choice of molecular weight will be at least partly dependent on the granulometry of the product required.
  • polymers employed in the present invention are an acrylic acid homo-polymer having a weight-average molecular weight of 4500 and an acrylic/maleic copolymer having a weight-average molecular weight of about 70,000.
  • the granules of the present invention can have a wide range of size distributions, from 1 micron to 2mm or more in diameter. Granulates with up to 80-% particles on 14 U.S. mesh (mesh size 1.18 mm) or with up to 80% particles through 100 U.S. mesh (mesh size 0.15 mm) can be produced. It is preferred that less than 50% by weight pass through 100 U.S. mesh. In a preferred option, the size of the granules formed is such that it approximates to the average size of particles in a standard detergent composition (0.2-­0.4mm typically).
  • the granular composition of the invention provides polymer suitable for use in detergent formulations in a form which has considerable advantages over the prior art.
  • the dry granule may be added direct to the final formulation, thereby circumventing all the disadvantages associated with wet polymer.
  • the composition can be adjusted to have a granulometry and density very similar to that of the other components in the final formulation, thereby avoiding the problems of separation and dusting associated with spray-dried polymer.
  • the granular composition of the present invention does not suffer from the problems of hygroscopicity which affects spray-dried polymer.
  • the larger particulate size means that there is less surface area per unit weight to absorb moisture, and also the proportion of hygroscopic polymer in each granule is obviously less than in 'dry polymer' powder.
  • a granulate which absorbs less than 20% of its own weight in water when exposed to moisture is preferred, particularly less than 10%. The method employed to determine this percentage of water absorption is as follows:
  • a previously weighed container is placed in an air-conditioned room at a temperature of 20°C and humidity of 50%, filled with a thin layer (5-20mm) of polymer and immediately reweighed, at which point the test starts.
  • the container and polymer are then reweighed at ten minute intervals during the first hour, 30 minute intervals during the second hour, hourly during the next five hours and then every 24 hours.
  • the percentage increase in weight gives the amount of water absorbed, and the figure quoted is that attained when a steady state has been reached.
  • the present invention has successfully solved the problem of obtaining polymer in a form which is acceptable for direct addition to detergent formulations, without the attendant problems either of the liquid carrier associated with the polymer, or of the consequences of having removed that liquid carrier first. Furthermore, the present invention provides a much more flexible solution to the previous problems than known compositions such as those described hereinabove, in that there is a wide variety of inorganic components which can be incorporated with the polymer, with no individual compound being an essential prerequisite. Additionally, the density of the composition of the invention can be significantly higher than that possible with known compositions.
  • the present invention also provides, in further aspect, a detergent formulation containing polymer in the form of a composition as defined above; and in a still further aspect it comprises the use of a composition as defined above as a component in a detergent formulation.
  • the proportion of the granulate composition of this invention required in a typical detergent formulation will generally be such as to give an active polymer content in the formulation of from 0.1 to 20% by weight, more usually between 1 and 5%.
  • Typical detergents for which the granular composition of the present invention may be suitable are usually based on surfactants and, optionally, on either precipitant or sequestrant builders.
  • Suitable surfactants are, for example, anionic surfactants, such as (C8 to C12) alkylbenzenesulfonates, (C12 to C16) alkane sulfonates, (C12 to C16) alkylsulfates, (C12 to C16) alkylsulfosuccinates and (C12 to C16) sulfated ethoxylated alkanols.
  • Nonionic surfactants may be (C6 to C12) alkylphenol ethoxylates, (C12 to C20) alkanol alkoxylates, and block copolymers of ethylene oxide and propylene oxide.
  • the end groups of polyalkylene oxides can be blocked. This means the free OH groups of the polyalkylene oxides can be etherified, esterified, acetalised and/or aminated. Another modification consists of reacting the free -OH groups of the polyalkylene oxides with isocyanates.
  • Nonionic surfactants may also include (C4 to C18) alkyl glucosides as well as the alkoxylated products obtainable therefrom by alkoxylation, particularly those obtainable by reaction of alkyl glucosides with ethylene oxide.
  • Surfactants useful in detergents can also have an amphoteric character and they can be soaps. In general, the surfactants constitute from 2 to 50 wt % of a detergent.
  • Sequestrant builders contained in detergents have generally been phosphates, orthophosphates, pyrophosphates or especially sodium tripolyphosphate.
  • the phosphate content of detergents and cleaning agents is increasingly being reduced so that detergents currently contain up to 25% of phosphates or preferably are phosphate-free.
  • the composition of the present invention is primarily of value as a means for introducing into the detergent a partial or complete replacement for phosphates, comprising polymers as previously listed.
  • zeolites sodium carbonate, nitrilotriacetic acid, citric acid, tartaric acid, the salts of the aforesaid acids and the monomeric, oligomeric or polymeric phosphonates. Varying amounts of the individual substances are used in the preparation of detergent formulations. For example, sodium carbonate may be used in an amount of up to 80%, phosphates up to 80%, zeolites up to 40%, nitrilotriacetic acid and phosphonates up to 10% and polycarboxylic acids in an amount of up to 30% by weight based on the total detergent formulation.
  • Typical detergent formulations optionally also contain corrosion inhibitors, such as silicates as additional additives.
  • Suitable silicates are, for example, sodium silicate, sodium disilicate and sodium metasilicate.
  • the corrosion inhibitors can constitute up to 50 wt % of the detergent formulation.
  • Other common additives to detergent and cleaning agent formulations are bleaching agents used in an amount of up to 30 wt %. Suitable bleaching agents are for example, perborates, percarbonates, or chlorine-generating substances, such as chloroisocyanurates.
  • Another group of additives that can be used in detergents are greying inhibitors.
  • Known substances of this type are carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose and graft copolymers of vinyl acetate and polyalkylene oxides having a molecular weight of 1000 to 15,000. Greying inhibitors are used in the detergent formulations in an amount of up to 5%.
  • Other common detergent additives that can optionally be used are optical brighteners, enzymes and perfume.
  • Powdered detergent formulations can also contain up to 50 wt % of a diluent, such as sodium sulfate.
  • the detergent formulations can be anhydrous or they can obtain small amounts, for example up to 10 wt %, of water.
  • composition of the present invention may be made by a process according to a further aspect of the invention, which comprises mixing polymer useful in detergent compositions with a liquid suitable for carrying or solubilizing said polymer and at least one solid inorganic component, the ratio of polymer to inorganic component being from 1:9 to 5:1, and subjecting the mixture to conditions of agitation and heat such that granules are formed.
  • the polymer and liquid are introduced together - as a slurry, solution, emulsion, suspension or dispersion of polymer in liquid.
  • the granules formed are as defined hereinabove.
  • the components are mixed in a horizontal cylindrical chamber having an axial shaft which carries a series of radial blades extending almost to the wall of the chamber, which forces the mixture into a highly turbulent thin layer around the wall of the chamber.
  • a pressure differential moves the mixture along the chamber, where it is additionally subjected to heating by one or both of hot air blown through the chamber and heating of the chamber wall in contact with the mixture layer.
  • the mixture may be subjected to heating as soon as it enters the chamber; alternatively, heat may be applied after the mixture has passed a little way along the chamber, so that initial mixing occurs before the commencement of evaporation.
  • This alternative procedure may also be embodied by employing two chambers, in series, the first of which subjects the mixture solely to high agitation and the second of which subjects it both to agitation and to heating.
  • This method allows greater control of the degree of turbulence at each stage, although, for reasons outlined above, care may be needed in determining the residence time in the initial mixing chamber to ensure that evaporation does not commence too late.
  • the chamber(s) is preferably horizontal, this is not essential and it may be inclined or even vertical.
  • the unique combination of turbulence and rate of heat transfer provided by the process of this invention results in a product which was not previously achievable.
  • the granules produced are generally an agglomeration of many particles, each particle comprising a core of inorganic component ('carrier') coated with a layer of polymer, although under certain conditions a homogeneous mixture may be formed.
  • the process of the invention is particularly advantageous in the case where the inorganic component is soluble in the liquid (usually water) carrying the polymer.
  • the inorganic component is a sulphate, which is soluble in water.
  • the parameters influencing the nature of the final product are many and complex.
  • the relative proportions of polymer and carrier are significant; increasing the proportion of polymer reduces the density of the final granules, and also results in larger granules by causing more agglomeration.
  • the nature of the components is also significant.
  • the molecular weight of the polymer can influence the granulometry of the final product.
  • the inorganic component can be an anhydrous salt, since this will absorb water carrying the polymer during mixing, thereby leaving less to be evaporated and speeding the process.
  • the two main process conditions which need to be influenced are the rate of heat transfer to the components as they are being mixed, and the degree of turbulence of that mixing. As a generalisation, increasing either the rate of heat transfer or the turbulence reduces the degree of agglomeration, and hence the size of the particles.
  • the rate of heat transfer may be enhanced by increasing either the temperature or the flowrate of the hot air which is passed through the chamber, or by increasing the temperature of the heating jacket around the wall of the chamber. As discussed previously, the positions of the hot air inlet and the heating jacket may also be adjusted to influence the timing and rate of heat transfer.
  • the initial temperature of the liquid carrying the polymer may also be varied; increasing this not only improves the evaporation capacity of the apparatus, but also the homogeneity of the final granule by reducing the initial viscosity of the liquid/polymer system.
  • the rate of heat transfer is also increased by greater turbulence.
  • the turbulence of the mixture in the chamber may be increased by increasing the speed of rotation of the shaft and blades. It is also influenced by the nature of the blades - their number, shape, orientation, etc; it will be appreciated that the precise effect of the blades is a matter for assessment in each case.
  • Another factor of significance is the residence time of the mixture in the chamber - i.e. the length of time of its exposure to heating and/or turbulent mixing, which has to be adjusted to provide the optimum balance.
  • the mixture is drawn through the chamber largely by a pressure differential, variation of which will of course alter the residence time.
  • the length of the chamber - or separation into a mixing and a mixing/heating chamber - is another influencing factor.
  • preferred apparatus for the agglomeration process of the invention comprises a horizontal cylindrical chamber 2 having at one end inlets 4,6 for the liquid/polymer system and dry inorganic carrier respectively, and at its other end an outlet 8 for the granulated product.
  • An air compressor 22 pushes the air (and hence the material) along the chamber, and a fan 10 contributes to a pressure drop which also helps to draw the material through.
  • Heating is accomplished partly by hot air injected into the chamber through inlet 12, and partly by a coaxial heating jacket 14 around the chamber.
  • Hot air inlet 12 and jacket 14 are spaced along the chamber from the raw material inlets 4,6 so that material in the initial portion of the chamber is not subjected to heating, but only to mixing.
  • this initial mixing without heating phase (which is not always essential) may be performed in a separate chamber.
  • Turbulent mixing is accomplished by means of a rapidly rotating axial shaft 16 which carries a series of blades 18 each extending radially towards the wall of the chamber.
  • each blade is substantially rectangular, and its outer edge is spaced from the internal wall of the chamber 2 by a few millimetres (this spacing being adjustable).
  • Shaft 16 is driven by a motor 20.
  • movement of the material along the chamber may be accomplished solely by the rotating blades, without the need for a pressure differential.
  • the polymer solution may already be at elevated temperature in order to reduce its viscosity and improve mixing.
  • the mixture of polymer, water and carrier is drawn through the chamber by the combined action of compressor 22 and fan 10, whilst the centrifugal force created by the rapdily rotating blades 18 forces the mixture into a highly dynamic suspension in the form of a thin layer around the internal surface of the chamber wall.
  • the precise thickness of the layer depends on a number of factors, particularly the degree of centrifugal force exerted on it, but it is approximately 1-2 mm.
  • the blades are preferably arranged to extend close enough to the chamber wall that their outer edges contact and disrupt the layer of agglomerating mixture, thereby generating further turbulence and inhibiting the development of excessively large granules.
  • the residence time of the mixture in the initial unheated portion of the chamber is very short - of the order of a few seconds. It is especially important if the carrier is soluble in water that the carrier does not begin to dissolve before evaporation of the water begins. Of course, if necessary the apparatus may be arranged so that the mixture is subjected to heating as soon as it enters the mixing chamber.
  • the mixture is subjected to heating by hot air injected through inlet 12 and saturated steam passing around jacket 14.
  • hot air injected through inlet 12 and saturated steam passing around jacket 14.
  • the mixture reaches outlet 8 after a time period of from around 10 seconds to a few minutes, by which time it has agglomerated into dense, dry granules of polymer and carrier, with the water being removed as vapour.
  • compositions of the present invention produced by the above exemplified process are as follows:
  • a granulate containing 30% dry polymer is obtained as follows: 100 kg/h of sodium sulphate and 95 kg/h of a 45% water solution of an acrylic acid homopolymer having a weight average molecular weight of 4500 are fed continuously into the mixer chamber.
  • the shaft speed rotation is 900 rpm
  • the hot air is fed (co-currently with the granule flow) into the mixing chamber at 225°C and 280 m3/h.
  • Saturated steam at 160°C is fed into the jacket.
  • Finished product (granulates) is discharged continuously starting about one minute after the operation start-up, at 143 kg/h, 0,5% residual moisture and 100°C.
  • the density of the product is 1000 g/lt and the granulometry spectrum, compared with leading fabric wash detergents, is shown in Figure 2.
  • a product containing 10% dry polymer is obtained by employing the same process conditions as Example 1, but with 100 kg/h of sodium sulphate and 28 kg/h of an acrylic/maleic copolymer having a weight average molecular weight of 70,000.
  • Density of the granulates is 1200 g/lt, and the granulometry distribution is shown in Figure 3.
  • a product containing 30% dry polymer is obtained as follows: 120 kg/h of sodium carbonate and 115 kg/h of the polymer of Example 1 are fed continuously into the mixing chamber. The shaft speed rotation is 1800 rpm, the hot air is fed co-currently at 200°C. Saturated steam at 180°C is fed into the jacket. Finished product is obtained at 1% residual moisture at 70°C. The density of the product is 860 g/lt and the granulometry spectrum is shown in Figure 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)
EP90310547A 1989-10-02 1990-09-26 Polymer enthaltende Granulate Revoked EP0421664B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898922179A GB8922179D0 (en) 1989-10-02 1989-10-02 Polymer-containing granulates
GB8922179 1989-10-02

Publications (3)

Publication Number Publication Date
EP0421664A2 true EP0421664A2 (de) 1991-04-10
EP0421664A3 EP0421664A3 (en) 1991-12-18
EP0421664B1 EP0421664B1 (de) 1999-02-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP90310547A Revoked EP0421664B1 (de) 1989-10-02 1990-09-26 Polymer enthaltende Granulate

Country Status (12)

Country Link
EP (1) EP0421664B1 (de)
JP (1) JP2851149B2 (de)
AT (1) ATE176496T1 (de)
AU (1) AU645501B2 (de)
BR (1) BR9004904A (de)
CA (1) CA2025832A1 (de)
DE (1) DE69032929T2 (de)
GB (1) GB8922179D0 (de)
IN (1) IN180189B (de)
PH (1) PH30938A (de)
PT (1) PT95484A (de)
ZA (1) ZA907826B (de)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992013937A1 (de) * 1991-02-11 1992-08-20 Henkel Kommanditgesellschaft Auf Aktien Granulares additiv für wasch- und reinigungsmittel
WO1992017565A1 (de) * 1991-03-30 1992-10-15 Henkel Kommanditgesellschaft Auf Aktien Niederalkalische, chlor- und phosphatfreie maschinengeschirrspülmittel in form von schwerpulvern und -granulaten
EP0523950A1 (de) * 1991-07-19 1993-01-20 Rohm And Haas Company Verwendung von Acrylsäure/Äthylacrylat Copolymeren als Zusatz zu Flüssigwaschmitteln zwecks verbesserter Fleckenentfernung
WO1993010210A1 (de) * 1991-11-14 1993-05-27 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung niederalkalischer, aktivchlor- und phosphatfreier maschinengeschirrspülmittel in form von schwergranulaten
EP0572724A1 (de) * 1992-06-02 1993-12-08 The Procter & Gamble Company Bleichmittelzusammensetzung für Wäsche
WO1994003567A2 (en) * 1992-08-03 1994-02-17 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrrolidone
DE4229660A1 (de) * 1992-09-04 1994-03-10 Henkel Kgaa Wasch- und Reinigungsmittel mit Buildersubstanzen
WO1994013775A1 (de) * 1992-12-16 1994-06-23 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von pulverförmigen waschmitteln
US5518646A (en) * 1993-04-01 1996-05-21 Lever Industrial Company, Division Of Indopco, Inc. Solid detergent briquettes
WO1999011749A1 (en) * 1997-08-28 1999-03-11 The Procter & Gamble Company Agglomeration process for producing a particulate modifier polyamine detergent admix
US5998357A (en) * 1995-09-04 1999-12-07 Lever Brothers Company Non-sray-drying process for preparing detergent compositions
WO2000077148A1 (fr) * 1999-06-14 2000-12-21 Kao Corporation Granules destines a porter un tensioactif et leur procede de production
WO2001012770A2 (de) * 1999-08-14 2001-02-22 Henkel Kommanditgesellschaft Auf Aktien Verhinderung von ablagerungen
EP1529834A1 (de) * 2003-11-10 2005-05-11 The Procter & Gamble Company Waschmittelteilchen
EP1529833A1 (de) * 2003-11-10 2005-05-11 The Procter & Gamble Company Waschmittelteilchen
CN100425684C (zh) * 1999-06-14 2008-10-15 花王株式会社 表面活性剂载带用颗粒群及其制法

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US5962389A (en) * 1995-11-17 1999-10-05 The Dial Corporation Detergent having improved color retention properties
US5726142A (en) * 1995-11-17 1998-03-10 The Dial Corp Detergent having improved properties and method of preparing the detergent
US9279097B1 (en) 2014-08-14 2016-03-08 Ecolab USA, Inc. Polymers for industrial laundry detergents

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US4414130A (en) * 1976-08-17 1983-11-08 Colgate Palmolive Company Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them
EP0200163A2 (de) * 1985-05-02 1986-11-05 Henkel Kommanditgesellschaft auf Aktien Bleichwirkstoff, seine Herstellung und seine Verwendung
EP0256443A2 (de) * 1986-08-15 1988-02-24 Unilever N.V. Peroxisäurebleichmittel und dessen Anwendung in Reinigungsmitteln
EP0289768A2 (de) * 1987-05-06 1988-11-09 Degussa Aktiengesellschaft Phosphatfreier Waschmittelbuilder
WO1990005175A1 (de) * 1988-11-10 1990-05-17 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung zeolithhaltiger granulate hoher dichte

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CH654121A5 (de) * 1983-03-25 1986-01-31 Ciba Geigy Ag Verfahren zur herstellung von festen photoaktivatorpraeparaten.
CA1334389C (en) * 1986-03-26 1995-02-14 Ernest H. Brumbaugh Machine dishwasher water spot control composition

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US4414130A (en) * 1976-08-17 1983-11-08 Colgate Palmolive Company Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them
FR2401987A1 (fr) * 1977-08-31 1979-03-30 Colgate Palmolive Co Agglomerats d'auxiliaire de detergence aisement desintegrables et compositions en contenant
EP0200163A2 (de) * 1985-05-02 1986-11-05 Henkel Kommanditgesellschaft auf Aktien Bleichwirkstoff, seine Herstellung und seine Verwendung
EP0256443A2 (de) * 1986-08-15 1988-02-24 Unilever N.V. Peroxisäurebleichmittel und dessen Anwendung in Reinigungsmitteln
EP0289768A2 (de) * 1987-05-06 1988-11-09 Degussa Aktiengesellschaft Phosphatfreier Waschmittelbuilder
WO1990005175A1 (de) * 1988-11-10 1990-05-17 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung zeolithhaltiger granulate hoher dichte

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992013937A1 (de) * 1991-02-11 1992-08-20 Henkel Kommanditgesellschaft Auf Aktien Granulares additiv für wasch- und reinigungsmittel
WO1992017565A1 (de) * 1991-03-30 1992-10-15 Henkel Kommanditgesellschaft Auf Aktien Niederalkalische, chlor- und phosphatfreie maschinengeschirrspülmittel in form von schwerpulvern und -granulaten
EP0523950A1 (de) * 1991-07-19 1993-01-20 Rohm And Haas Company Verwendung von Acrylsäure/Äthylacrylat Copolymeren als Zusatz zu Flüssigwaschmitteln zwecks verbesserter Fleckenentfernung
US5409629A (en) * 1991-07-19 1995-04-25 Rohm And Haas Company Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents
WO1993010210A1 (de) * 1991-11-14 1993-05-27 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung niederalkalischer, aktivchlor- und phosphatfreier maschinengeschirrspülmittel in form von schwergranulaten
EP0572724A1 (de) * 1992-06-02 1993-12-08 The Procter & Gamble Company Bleichmittelzusammensetzung für Wäsche
WO1994003567A3 (en) * 1992-08-03 1994-06-23 Procter & Gamble Particulate laundry detergent compositions with polyvinyl pyrrolidone
WO1994003567A2 (en) * 1992-08-03 1994-02-17 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrrolidone
CN1039028C (zh) * 1992-08-03 1998-07-08 普罗格特-甘布尔公司 含有聚乙烯吡咯烷酮的粒状洗衣洗涤剂组合物
DE4229660A1 (de) * 1992-09-04 1994-03-10 Henkel Kgaa Wasch- und Reinigungsmittel mit Buildersubstanzen
WO1994005764A1 (de) * 1992-09-04 1994-03-17 Henkel Kommanditgesellschaft Auf Aktien Wasch- und reinigungsmittel mit buildersubstanzen
WO1994013775A1 (de) * 1992-12-16 1994-06-23 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von pulverförmigen waschmitteln
US5518646A (en) * 1993-04-01 1996-05-21 Lever Industrial Company, Division Of Indopco, Inc. Solid detergent briquettes
EP0861318B1 (de) * 1995-09-04 2001-11-14 Unilever Plc Waschmittelzusammensetzungen und verfahren zu ihrer herstellung
US5998357A (en) * 1995-09-04 1999-12-07 Lever Brothers Company Non-sray-drying process for preparing detergent compositions
US6025320A (en) * 1995-09-04 2000-02-15 Lever Brothers Company Detergent compositions and process for preparing them
WO1999011749A1 (en) * 1997-08-28 1999-03-11 The Procter & Gamble Company Agglomeration process for producing a particulate modifier polyamine detergent admix
WO2000077148A1 (fr) * 1999-06-14 2000-12-21 Kao Corporation Granules destines a porter un tensioactif et leur procede de production
US6864221B1 (en) 1999-06-14 2005-03-08 Kao Corporation Granules for carrying surfactant and method for producing the same
CN100425684C (zh) * 1999-06-14 2008-10-15 花王株式会社 表面活性剂载带用颗粒群及其制法
WO2001012770A2 (de) * 1999-08-14 2001-02-22 Henkel Kommanditgesellschaft Auf Aktien Verhinderung von ablagerungen
WO2001012770A3 (de) * 1999-08-14 2001-07-05 Henkel Kgaa Verhinderung von ablagerungen
EP1529834A1 (de) * 2003-11-10 2005-05-11 The Procter & Gamble Company Waschmittelteilchen
EP1529833A1 (de) * 2003-11-10 2005-05-11 The Procter & Gamble Company Waschmittelteilchen
WO2005047442A1 (en) * 2003-11-10 2005-05-26 The Procter & Gamble Company Detergent particles

Also Published As

Publication number Publication date
BR9004904A (pt) 1991-09-10
EP0421664A3 (en) 1991-12-18
ZA907826B (en) 1991-07-31
IN180189B (de) 1998-01-17
ATE176496T1 (de) 1999-02-15
PT95484A (pt) 1991-06-25
JPH04145200A (ja) 1992-05-19
DE69032929D1 (de) 1999-03-18
JP2851149B2 (ja) 1999-01-27
PH30938A (en) 1997-12-23
CA2025832A1 (en) 1991-04-03
EP0421664B1 (de) 1999-02-03
AU645501B2 (en) 1994-01-20
AU6326490A (en) 1991-04-11
GB8922179D0 (en) 1989-11-15
DE69032929T2 (de) 1999-09-30

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