JPH04145200A - Particle containing polymer - Google Patents

Abstract

A granulate useful in detergent formulations is disclosed, which comprises at least 10% by weight of polymer useful in such formulations and at least 20% by weight of at least one inorganic component which is also useful in such formulations. The granulate has a bulk density of at least 700 g/l, and possesses low hygroscopicity. A process formaking such a granulate is also disclosed.

Description

DETAILED DESCRIPTION OF THE INVENTION Liao 1 and Tateno The present invention relates to polymer-containing granules useful as bulk ingredients in detergent formulations. In the following, "detergent formulations" is intended to include cleaning agents for both fabrics and hard surfaces.

W'' Environmental reasons have made it desirable to reduce or eliminate the phosphate content of detergent formulations.

As a result, alternative ingredients must be added that provide similar properties, such as inhibition of redeposition of salts and dirt to washed fabrics and hard surfaces, and improved brightness. Polymeric additives, especially polycarboxylated polymers, are suitable for this purpose.

The polymer is generally added to detergent formulations in the form of a dry polymer produced by spray drying a solution, dispersion, slurry or emulsion of the polymer in a liquid (a "wet polymer"); or added directly as a wet polymer to detergent formulations in the form of a slurry before drying. In either case, the final product has a number of undesirable properties.

The dry polymer produced by spray drying the wet polymer alone is a material that tends to become "sticky" on storage or in the final formulation itself because it is hygroscopic.

Darning dry polymers also have low bulk densities, typically 30
It has a weight of 0 to 500 g//. This is 700g/
In typical detergent formulations having densities in the f range, the polymer tends to separate, meaning that it also reduces the bulk density of the formulation. moreover,
Dry polymer powders usually have a high proportion of fines, which leads to undesirable dust problems in the final formulation and also contributes to segregation problems.

One method of adding the wet polymer is to add the wet 1YHII polymer to the other ingredients of the final formulation before drying;
Spray drying the polymer with other ingredients. An example of a granular composition produced by such a method is DE-
A-3316513, in which granules containing 30-75% zeolite with at least 5x polycarboxylate for use as a phosphate substitute are spray-dried from a slurry of the components. It is manufactured by. Such spray drying methods always produce granular products of undesirable low density; in fact, the highest density achieved with this composition is 610 g/l, and the incidental water introduced with the polymer is removed. There must be.

Another method for adding the wet polymer is to add the wet polymer directly to the final formulation and mix and dry it in a rotating drum mixer.

However, since wet polymers contain liquid (usually water) and polymer in a ratio of about 1.1, adding more than a few percent of polymer also requires the addition of a significant amount of liquid. ,
Also, liquid solubilization of other ingredients in the formulation tends to cause paste formation in the dryer. This problem cannot be avoided by reducing the liquid content of the polymer before addition. This is because the viscosity of the wet polymer is too high for satisfactory flow properties, even when the polymer is distributed among the other components.

The ``force'' method for adding wet polymer may not be used if the polymer is used as a flocculant for the salt; in such cases, the polymer is added at a concentration of about 0.5%. Since the liquid is only added at a certain temperature, the trouble caused by excess liquid becomes negligible.

- Packing problems can also be avoided by adding the polymer to a solution of other salts to be used in the final formulation, such as phosphates or carbonates, and then evaporating to dryness. is impossible. This is because the polymers used are effective crystallization inhibitors for these salts.

Thus, in summary, conventionally produced dry polymer forms have proven unsatisfactory for detergent formulations. (i) polymers dried alone have problems with particle size, hygroscopicity, and density, and (ii)
Polymer dried in the presence of the remaining components of the formulation will induce baset formation if it is dried in a spray mixer and will also induce low baset formation if dried in a spray tower. It becomes too dense. There is no indication that the polymer and the constituents of the other ingredients for the detergent formulation have been successfully combined into a particulate form with the desired particle size and bulk density for addition to the detergent formulation. However, actually (i
Experience in i) denies this.

High-density polymer-containing granules are E P-A-36813
Known since 7. It contains 60-80% zeolite, 2-15% polycarboxylate, and 14-2
Contains 5% water by weight and 750-1000
g/l! It has a density of However, the presence of such a large proportion of water-insoluble zeolites has disadvantages. Water-insoluble salts have a tendency to stick to fabrics, which is a challenge that the addition of polymers is at least partially intended to offset by containing such high proportions of water-insoluble salts per polymer. In such granules, the dispersant action that the polymer was intended to have would be substantially negated by the large amount of zeolite introduced with the polymer.

A granular detergent additive is known from U 5-A-4698174. It is 20-80% polymer, 20-80%
of ditrilotoriacetic acid (NTA) and optionally up to 20% of other additives such as sodium sulfate.

Densities up to 690 g/l are disclosed and the product is claimed to have low hygroscopicity.

However, the usefulness of this additive is limited by the need to include a significant proportion of NTA to obtain satisfactory performance. A large proportion of NTA is environment.”
This is considered undesirable from two standpoints. Furthermore, the densities disclosed therein are generally less than the average density of typical detergents.

One aspect of the invention is to provide a composition in the form of granules useful as a component of detergent formulations, each granule containing at least 10% by weight of the polymer useful in such formulations. and the bulk density of said composition is at least 700 g/l. Preferred inorganic components are sulfates and carbonates. Salts such as salts and silicates. Perborates (both I- and tetrahydrates), percarbonates, and persulfates are also useful. Formulations where phosphates are still present In products, they may also be used as carriers.For the above-mentioned materials, the l.lium form is preferred.

The invention is also applicable when the inorganic component is a zeolite or a clay, both of which are water-insoluble. In such a case, the water-insoluble component 4] as described in 1-
A larger proportion of polymer is required to offset the tendency to stick. Another aspect of the present invention provides a composition in the form of granules useful as an ingredient in detergent formulations, each granule containing a weight effective as an ingredient in such formulations. At least 20% by weight during coalescence and at least 20% (zeolite)
% by weight, and the bulk density of said composition is at least 70
It is 0g/p.

In either case, the granules may contain minor amounts of other ingredients suitable for use in detergent compositions.

The density of grain autumn products is 300 g/I! It can be as low as 700-1200 g/l, or as high as 1400 g/l.
Densities in the range / are preferred. Particularly good is 900g/7G or higher. The density depends on the type of inorganic component ([carrier]) or the type of polymer, and also on the manufacturing process conditions and equipment (
(as explained below) and also on the polymer(s) and carrier(s).

Therefore, granules containing up to 80% by weight of polymer can also be produced. In this case, the density of such granules will be at the lower end of the desired range. Typically, between 10 and 50% of the zeolite will be present in the granules; however, if zeolite is present, it will be at least 20%, preferably 25%), and more typically It is 20-40%. The most preferred amount of polymer is 30%.

Suitable polymers include dicarboxylic acids such as maleic acid,
Itaconic acid, mesaconic acid, fumaric acid, citraconic acid, and anhydrides of cisdicarboxylic acids such as maleic anhydride, monocarboxylic acids such as acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, and acryloxoprobionic acid 1 and Unsaturated noncarboxylic acids, e.g.
Argyl esters of acrylic or methacrylic acid, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and isobutyl methacrylate, hydroxyalkyl esters of acrylic or methacrylic acid, such as hydroxyethyl Acrylates, Hydroxypropyl acrylate, Hydroxylethyl methacryl/-)-1 and Hydroxyethyl acrylate (including polyethoxylated esters), Acrylamide, Methacrylamide, Nte
rt-butylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide acrylonitrile, methacrylaterile, allyl alcohol, allylsulfonic acid, allylbosponic acid, vinylphosponic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, phosphoethyl methacrylate, N -vinylpyrrolidone, N-vinylpormamide, N-vinylimidazole, ethylene glycol diacrylate,)
- Homopolymers or copolymers of lyncholpropane triacrylate, diallylphthale-1, vinyl acetate, styrene, vinyl sulfonic acid and its salts, and 2-acrylamido-2-methylbrobanesulfonic acid (8MPS) and its salts. includes. Diisobutylene and I-
Monomers of 1-olefins such as octene are also suitable, as is the polymer rPOcJ (the reaction product of acrylic acid and berogysodisulfate).

The polymer may be in an acid state, ] or Na
, NH, or other counterions (COυnt
erion) may be neutralized or partially neutralized. The molecular weight of the polymer may be between 500 and 5.000.000. Generally, the higher the molecular weight, the greater the degree of agglomeration obtained during the manufacture of the granules, and therefore the larger the granules.

Therefore, the selection of molecular weight will depend, at least in part, on the desired product particle size.

An example of a polymer used in the present invention has a weight average molecular weight of 450
0, and an acrylic/maleic copolymer with a weight average molecular weight of about 70,000.

The granules of the present invention can have a wide size distribution from 1 micron to 2 mm or more in diameter. 14 US mesh (mesh size 1.80 particles in 18 mm LI-
% or up to 80% of the particles passing through a 100 US mesh (mesh size 0.15 mm). Preferably less than 50% by weight passes through the 100 US mesh. In a preferred option, the size of the granules produced is equal to the average size of particles in standard detergent compositions (typically 0.2 to 0.4 m
m).

The granular compositions of the present invention provide polymers suitable for use in detergent compositions in a form that is considerably advantageous over the prior art. Dry granules may be added directly to the final formulation;
All the disadvantages associated with wet polymers are thereby eliminated. The composition can be tailored to have a particle size and density that closely resembles that of other components in the final formulation, thereby avoiding segregation and dusting problems associated with spray-dried polymers. . Additionally, the granular compositions of the present invention do not affect the spray-dried polymer and do not suffer from hygroscopic problems. The larger particle size provides less surface area per unit weight for absorbing moisture and the proportion of hygroscopic polymer in each granule is significantly smaller than in one dry polymer powder. For the purposes of the present invention, the granules absorb less than 20% of their own weight of water when exposed to moisture, preferably less than 10% in particular. The method used to determine this % water absorption was as follows: A pre-weighed container was placed in an air-conditioned room at a temperature of 20°C and a humidity of 50%, and a thin layer (5 to 2
0 mm) and immediately weighed, at which point the test started. The container and polymer were then weighed at 10 minute intervals for the first hour, at 30 minute intervals for the next hour, at 1 hour intervals for the next 5 hours, and every 24 hours thereafter. The % increase in weight indicates the amount of water absorbed and the figures quoted are the values reached when steady state was reached.

The present invention therefore addresses the problem of obtaining a polymer in a form acceptable for direct addition to detergent formulations, whether associated with a liquid carrier in combination with the polymer or as a result of the initial removal of that liquid carrier. It was successfully solved without any problems.

Furthermore, the present invention provides a much more flexible solution to the above problem than the previously described known compositions. That is, there is a wide variety of inorganic compounds that can be incorporated into the polymer, although they are not essentially required upfront. Also, the density of the compositions of the invention can be significantly higher than is possible with known compositions.

Furthermore, the present invention provides detergent formulations containing polymers in the form of compositions as defined above. Furthermore, the invention consists in using the composition as defined above as a component in detergent formulations.

The proportion of the granular composition of the present invention required in a typical detergent formulation is generally such that the active polymer content in the formulation is between 0.1 and 2.
0% by weight, more usually 1 to 5% by weight.

Typical detergents for which the granular compositions of the present invention are suitable are usually based on a builder of surfactants and optionally either precipitants or sequestrants. Suitable surfactants are, for example, anionic surfactants such as (C, ~c
1. ) Argylbenzene sulfonate, (CI2-C4
) alkanolhone-1, (C11-C1,) alkylsulfony, (C,th-C8,) alkylsulposuccinate and (C1!-C1,) sulfated ethysylated alkatol. The nonionic surfactant is (C,
~c1. ) alkylphenol ethoxylate, (C+
z~.C1°) alkanolalcogyl-1. and a block copolymer of ethylene oxide and propylene oxide. Optionally, the end groups of the polyalkylene oxide may be blocked. This means that the free fiOH groups of the polyalkylene oxide can be etherified, esterified, acetalized and/or aminated. Another modification consists of reacting the free OH groups of the polyalkylene oxide with isocyanates.

Nonionic surfactants also include (04-C, ,) alkyl glucosides as well as alkoxylated products obtainable by alkoxylating them, especially those obtainable by reaction of alkyl glucosides with ethylene oxide. Surfactants useful in detergents can also have amphoteric properties, and they can be soaps. Generally, surfactants constitute 2-50% by weight of the detergent.

The sequestrant builders contained in detergents have generally been phosphates, orthophosphates, pyrophosphates, or especially sodium tripolyphosphates. However, because of the serious environmental pollution caused by the use of phosphates, the phosphate content of detergents and cleaning agents has been increasingly reduced, and current detergents have a phosphate content of less than 25% or preferably Contains no phosphates. As discussed above, the compositions of the present invention are primarily of value as a means of introducing partial or complete replacements for phosphates into detergents, and are useful for the use of heavy-duty agents such as those listed above. Including coalescence. Other builders include zeolites, sodium carbonate, nitrilotriacetic acid, citric acid, tartaric acid, salts of the aforementioned acids, and monomeric or oligomeric or polymeric phosponates. Various amounts of each substance are used in the manufacture of detergent formulations. For example, sodium carbonate may be used in amounts up to 80% by weight based on the entire detergent formulation, and phosphates may be used in amounts up to 80% by weight based on the total detergent formulation.
Amounts of up to 0%, zeolites up to 40%, nitrilotriacetic acid and phosphonates up to 10%, and polycarboxylic acids up to 30% may be used.

Typical detergent formulations optionally contain corrosion inhibitors such as silicates as additional additives. Suitable silicates are, for example, sodium silicate, sodium disilicate, and sulfur-lium metasilicate. Corrosion inhibitors are part of detergent formulations.
It can constitute up to 0% by weight. Other customary additives to detergent and cleaning agent formulations are bleaching agents, used in amounts up to 30% by weight. 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 anti-graying agents. Known substances of this type are carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, and graft copolymers of vinyl acetate and polyalkylene oxide with molecular weights from 1000 to 5.000. Antigraying agents are used in detergent formulations in amounts up to 5%. Other conventional detergent additives that can optionally be used are optical brighteners, enzymes and fragrances.

Powder detergent formulations can also contain up to 50% by weight of diluents such as sodium sulfate.

Detergent formulations may be anhydrous or may contain small amounts of water, for example up to 10% by weight.

The compositions of the invention can be manufactured by the methods of the invention. The method involves mixing a polymer useful in a detergent composition with a liquid suitable to support or solubilize the polymer and at least one solid inorganic component, the ratio of polymer:inorganic component being from 1:9 to 5. =1 and subjecting said mixture to conditions of agitation and heating such that granules are produced. Generally, the polymer and liquid are introduced together, eg, as a slurry, solution, emulsion or dispersion of the polymer in the liquid. Preferably, the granules produced are as defined above.

The specific heat and agitation conditions required to produce the desired granules are complex and depend on many interrelated variables. Subjecting the polymer, liquid, and inorganic components to a degree of turbulence such that rapid and homogeneous mixing and -like heating is achieved.

In addition, especially when the inorganic components are soluble in the liquid, it is very important to evaporate the liquid very quickly after forming the mixture, which requires a rapid and efficient heat transfer rate. is important.

In a preferred embodiment of the method for accomplishing the above requirements, the components are mixed in a horizontal cylindrical chamber having an axial shaft with a series of radial blades extending almost to the walls of the chamber, and the mixture is forced to the walls of the chamber. into a thin, highly disordered layer around the . The pressure differential moves the mixture along the chamber where it is further heated by either or both hot air blown into the chamber and heating of the chamber walls in contact with the mixture layer. The mixture may be heated as soon as it enters the chamber, or alternatively, the mixture may be heated after a short passage along the chamber so that the initial mixing occurs before the start of evaporation.

This alternative procedure may be embodied by using two chambers in series, the first chamber subjecting the mixture only to a high degree of agitation, and the second chamber subjecting it to both agitation and heating. let Although this method allows for greater control over the degree of turbulence at each stage, for the reasons outlined above, the residence time in the initial mixing chamber should be determined to ensure a not too late onset of evaporation. You will need to be careful.

The chamber(s) is preferably horizontal, but this is not essential; it may be inclined or vertical.

The unique combination of turbulence and heat transfer rate provided by the method of the present invention results in products previously unattainable.

The granules produced are generally agglomerates of many particles, each particle containing an inorganic component (“carrier J”) coated with a layer of polymer.
), but under certain conditions a homogeneous mixture may be produced.

The method of the invention is particularly advantageous when the inorganic component is soluble in the polymer-bearing liquid (usually water). A specific example is when the inorganic component is a sulfate, which is soluble in water. In such cases, evaporation of the liquid in the present process is so rapid that solubilization of the inorganic carrier occurs to an insufficient extent to detrimentally affect the density or particle size of the final granular product. This would not be possible with conventional technology.

As mentioned above, the parameters that influence the properties of the final product are numerous and complex. The relative proportions of polymer and carrier are significant; increasing the proportion of polymer reduces the density of the final granules and produces larger granules by causing greater agglomeration. The characteristics of the ingredients are also significant. As discussed above, the molecular weight of the polymer can affect the particle size of the final product. It may be advantageous for the inorganic component to be an anhydrous salt. This is because the anhydrous salt absorbs the water that carries the polymer during mixing, leaving less to evaporate and speeding up the process. The two main process conditions that need to be influenced are the rate of heat transfer to the components as they are mixed and the degree of turbulence of the mixing. Generally speaking, any increase in the rate of heat transfer or degree of turbulence will reduce the degree of agglomeration and therefore the size of the particles.

The heat transfer rate may be increased by increasing either the temperature or the flow rate of hot air passing through the chamber, or by increasing the temperature of the heating jacket around the walls of the chamber. As discussed above, the hot air introduction [] and the position of the heating jacket may be adjusted to affect the timing and rate of heat transfer. The initial temperature of the liquid carrying the heavy tetramers may be varied; increasing this not only improves the evaporation capacity of the device, but also reduces the initial viscosity of the liquid/polymer system, thereby increasing the final granule temperature. It also improves homogeneity. Heat transfer rate is also increased by greater turbulence.

Turbulence of the mixture in the chamber may be increased by increasing the rotational speed of the shaft and blades. It is influenced by blade characteristics, number of blades, shape, orientation, etc. It will be appreciated that the exact effectiveness of the blade is a matter of evaluation in each case.

Another factor of significance is the residence time of the mixture in the chamber, ie the length of time it is exposed to heating and/or turbulent mixing, which must be adjusted to give the optimum balance. The mixture is pulled through the chamber primarily by the pressure differential. Of course, variations in pressure differential will change the residence time. The length of the chamber or its division into a mixing chamber and a mixing/heating chamber is another influencing factor.

Preferred embodiments of both the method and composition of the invention will now be described with reference to the drawings, in which FIG. 1 is a drawing depicting an aggregation apparatus suitable for carrying out the preferred method of the invention; The figure is a graph representing the particle size of the composition of the invention.

With reference to FIG. 1, the preferred apparatus for the agglomeration process of the present invention has an inlet 4.6 for the liquid/polymer system and the dry inorganic carrier reservoir, respectively, at one end and the granular product at the other end. It consists of a horizontal cylindrical chamber 2 with an outlet 8 for. Air compressor 22 pushes air (and thus material) along the chamber, and fan 10 contributes to the pressure drop and also helps move material through.

Heating is achieved partially by hot air injected into the chamber through inlet I2 and partially by a coaxial heating jacket 14 around the chamber. Since the hot air mass 12 and jacket 14 are spaced along the chamber from the raw material mass 4, 6, the material in the initial part of the chamber is not heated, but is subjected to mixing. As discussed above, in another embodiment, this initial mixing without (which is not always essential) heating the phases may be performed in a separate chamber.

Turbulent mixing may be effected by means of a rapidly rotating shaft 16 carrying a series of blades 18 each extending radially towards the walls of the chamber.

In this embodiment, each blade is substantially rectangular and its outer end is spaced from the inner wall of the chamber by a few mm (this spacing is adjustable). Shirt H6
is driven by a motor 20. In certain embodiments, movement of material along the chamber may be effected solely by rotation of the blade without the need for a pressure differential.

The operation of the apparatus of FIG. 1 will now be described below with reference to a preferred composition comprising a polymer/water system.

The dry carrier and the aqueous solution of the polymer enter the chamber through respective inlets 4.6. The polymer solution may be prepared at an elevated temperature to reduce its viscosity and improve mixing.

Inside the chamber, the shaft I6 and its blade 1
8 rotates at high speed, typically between 500 and 3000 rpm. The speed used will of course depend on factors such as the diameter of the drum.

However, the most important parameter is the tangential velocity imparted to the mixture at the surface of the chamber wall (
In this embodiment, the tangential velocity is generally 10
~30rns).

A mixture of polymer, water, and carrier is drawn through the chamber by the combined action of compressor 22 and fan 10;
Meanwhile, the centrifugal force generated by the rapidly rotating blades 18 forces the dispersion into a highly dynamic dispersion in the form of a laminar layer around the inner surface of the chamber wall. The exact thickness of the layer depends on a number of factors, in particular the degree of centrifugal force exerted on the layer, but the layer is approximately 1-2 mm.

Preferably, the blade is close enough to the chamber such that the outer end of the blade contacts and breaks up the agglomerating mixture, thereby creating further turbulence and suppressing the appearance of excessively large particles. They are arranged in an extended manner.

The residence time of the mixture I'j in the first unheated part of the chamber is very short, on the order of a few seconds.

If the carrier is water-soluble, it is particularly important that the carrier does not begin to dissolve before water evaporation begins.

Of course, if desired, the device may be arranged to subject the mixture to heating as soon as it enters the mixing chamber.

After this initial mixing layer, the mixture is heated through the inlet 12 by hot air introduced at ] and saturated sutee passed around the jacket 14. Goichi 1! As such, they provide a highly efficient combination of both convective and conductive heat transfer, resulting in rapid evaporation of water from the mixture. Continuous rotation of the mixture layer and the individual particles therein provides ideal conditions for turbulence and particle separation, allowing uniform heating and excellent agglomeration.

The mixture is heated with water being removed as steam.
The outlet 8 is reached during a period of time ranging from about 10 seconds to several minutes, which is the time for the mixture to coagulate into dense dry particles of polymer and carrier.

Specific examples of the granular composition of the present invention produced by the method exemplified above are as follows. Granules containing 30% dry polymer were obtained as follows: Sulfuric acid 100kg/h of sodium and 95k of a 45% aqueous solution of acrylic acid homopolymer with a weight average molecular weight of 4500
g/h was continuously fed into the mixer chamber.

The shaft rotation speed is 900 rpm, and the hot air is 225 rpm.
°C and 280rr? /h into the mixing chamber (
(simultaneously with the flow of granules). Saturated steam at 160°C was supplied to the jacket.

The final product (granules) was produced at 143 m
kg,/h, 0.5% residual moisture and +00°C,
Continuous release started. The density of the product is 1000 g
/lt, and the particle size spectrum compared to the main fabric laundry detergents is shown in FIG.

Zoo 1! ! L7 - Using the same process conditions as in Example 1, but with 100 kg/h of sodium sulfate and a weight average molecular weight of 70,00
By using 28 kg/h of 0.0 acrylic/maleic copolymer, a product containing 10% dry polymer was obtained.

The density of the granules was 1200 g/lt and the particle size distribution was shown in FIG.

Example 1: A product containing 30! The shaft rotation speed was 1800 rpm,
And hot air was simultaneously supplied at 200°C. Saturated steam at 180°C was fed into the Jaquera J. The final product was obtained at 70°C with 1% residual moisture. The density of the product was 860 g/lt and the particle size spectrum is shown in FIG.

[Brief explanation of drawings]

FIG. 1 is a diagram representing an agglomeration apparatus suitable for carrying out the preferred method of the invention, and FIGS. 2-4 are graphs showing the particle size of the compositions of the invention.

Claims (16)

[Claims] (1) Granules effective as ingredients in detergent formulations,
each comprising at least 10% by weight of a polymer useful in such formulations and at least 20% by weight of at least one water-soluble inorganic component also useful in such formulations, wherein said composition has a bulk density of at least 700 g/l. The said granule which is. (2) A claim in which the inorganic component is one or more of sulfates, carbonates, phosphates, silicates, percarbonates or perborates, preferably sulfates or carbonates. The grain in the first term of the range. (3) Granules effective as ingredients in detergent formulations,
each containing at least 20% by weight of polymer useful in such formulations and at least 20% by weight of zeolite and, alternatively, clay, such that the bulk density of said composition is at least 7.
00 g/l of the granules. (4) Granules according to any one of claims 1 to 3, having a bulk density of at least 900 g/l. (5) The polymer is a polycarboxylated polymer, preferably acrylic acid, methacrylic acid, maleic acid, acrylamide, itaconic acid, (C_1-C_4) alkyl (
Any one of claims 1 to 4, which is a homopolymer or copolymer of one or more of meth)acrylate or amide, α-chloroacrylic acid, alkyl vinyl ether or vinyl ester. or one granule. (6) The proportion of polymer is 20-40%, preferably 30%
The granules according to any one of claims 1 to 5. (7) The granule according to any one of claims 1 to 6, wherein the granule size is such that less than 50% by weight passes through a 100 US mesh (mesh size 0.15 mm). . (8) has a water absorption of less than 20% of its weight, preferably less than 10% by weight, when exposed to moisture and tested according to the method described below.
Granules according to any one of paragraph 7. (9) A method of using the granules according to any one of claims 1 to 8 as a component in a detergent formulation. (10) A detergent formulation containing a polymer in the form of granules according to any one of claims 1 to 8. (11) mixing a polymer useful in detergent formulations with a liquid suitable for supporting or dissolving said polymer and at least one solid inorganic component that is itself useful in detergent formulations; The ratio of combined to inorganic components is from 1:9 to 5:1, and the mixture is subjected to conditions of agitation and heat such that granules are formed. Manufacturing method of contained ingredients. (12) The mixture is placed in a cylindrical chamber (2) containing a rapidly rotating shaft (16) carrying a series of blades (18).
12. The granules of claim 11, wherein the granules are introduced into the chamber and heat is applied to the mixture along at least a portion of the length of the chamber. 13. The granules of claim 12, wherein the mixture is first introduced into a first cylindrical chamber containing a rapidly rotating shaft also carrying a series of blades, in which no heating occurs. 14. The method of claim 12 or 13, wherein said heating is applied by either or both of hot air injected into said chamber (2) and heating of the inner surface of said chamber. (15) The inorganic component is zeolite, clay, or one defined in claim 2, and the polymer is defined in claim 5. A method according to any one of claims 11 to 14. (16) The method according to any one of claims 11 to 15, wherein the liquid is water.