JPH06500141A - detergent composition - Google Patents

Abstract

Particulate laundry detergent compositions are disclosed incorporating 5 % to 50 % of a surfactant, from 10 % to 95 % of a three-component non-phosphorus builder system comprising a mixture of a sodium aluminosilicate zeolite, a water-soluble monomeric or oligomeric carboxylate chelating agent and a crystalline layered sodium silicate, and from 0 % to 40 % of non-surfactant, non-builder detergent ingredients. The crystalline layered silicate is of composition NaMSixO2x+1.yH2O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Preferably M is sodium, x is 2 and y is O.

Description

[Detailed description of the invention] detergent composition Technical field The present invention relates to laundry detergent compositions, and more particularly, to laundry detergent compositions containing almost no phosphorus-containing materials. relates to a laundry detergent composition containing nothing. This type of laundry detergent composition Environmental impacts of aqueous effluents from untreated or partially treated domestic sewage containing sphate Widely used as a result of public concern and/or management legislation regarding sound effects. The commercial introduction of phosphorus-free detergent products has increased the environmental impact of detergent products. Fulfills the primary objective of reducing phosphate loading, but increases formulation complexity and The burden of organic substances on the environment has also increased. Phosphate-free compositions are phosphate builder The main ingredients are usually water-soluble inorganic salts and Water-insoluble sodium aluminosilicate supplemented by a mixture with polymeric organic salts It is zeolite.

Much effort has been made by those skilled in the art in developing such multi-component bilgoo systems. , whose needs exceed all of the functions previously fulfilled by phosphate builders. arises from the difficulty of finding a single substance that will do the same thing. not fully characterized However, their function is to reduce the amount of dirt removed from the fabric during the cleaning process. Ca++ ion hardness and Mg++ ion together with veptization and suspension Both chelation and hardness are mentioned.

Demonstration of invention Crystalline or so-called layered silicas with specific combinations of detergency builder ingredients The use of carbonate (known per se) provides enhanced performance and reduces the amount of other materials comprising It has now been discovered that it is possible to reduce or omit the resulting granular detergent from products. It was done. In a preferred embodiment of the present invention, the cleaning performance of existing products is improved. Superior cleaning performance can be obtained with significantly lower amounts of detersive builder ingredients. , thereby reducing the burden on the environment. Other advantages include high granular product at the beginning of the wash cycle in automatic domestic washing machines. dispersion and/or dissolution of insoluble precipitates (ash) on fabrics and fabric damage. There is a decrease.

According to the invention, (a) one or more anionic surfactants, nonionic surfactants, amphoteric surfactants, Zwitterionic surfactants or cationic surfactants or mixtures of any of them5~ 50% by weight; (b) (i) 20-60% by weight of the mixture of sodium aluminosilicate zeolite; and, (10 to 30% by weight of the In mixture water-soluble monomer or oligomeric organic carboxylic acid) a sylate chelating agent; and (iii) 10 to 65% by weight of the mixture of composition NaM. Sixo2x+biyH2o (wherein M is sodium or hydrogen, and X is 1. a number from 9 to 4, and y is a number from 0 to 20) Um and a detersive builder system consisting of a mixture of 10% to 95%; and (c) a granular form characterized by containing 0 to 40% of a non-surfactant, non-builder detergent component; A detergent composition is provided.

Preferably, builder component (b) (111) is α, β, γ or δ-N 112Si205 and components (b) and (i) are unit cell formula %formula% (where 2 and y are at least 6 and the ratio of 2 to y is between 1.0 and 0.5. and X is at least 5, preferably from 7.5 to 276) is a synthetic hydrated zeolite.

Preferably, also a monomeric or oligomeric organic carboxylate chelating agent is the first carboxyl log acidity constant (pKl) less than 9, preferably 2 to 8. 5.

The present invention utilizes one or more surfactants and three main components: sodium aluminosilicate. Thorium zeolite and water-soluble monomeric or oligomeric organic carboxylate Contains a detergent builder system consisting of a drying agent and crystalline layered sodium silicate. The present invention relates to a granular detergent composition. Preferred compositions according to the invention contain other non-surfactant Also contains builder detergent ingredients.

BEST MODE FOR CARRYING OUT THE INVENTION A wide variety of surfactants can be used in detergent compositions. Anionic surfactant, non-ionic surfactants, amphoteric surfactants and zwitterionic surfactants and these surfactants A typical list of species is provided in U.S. Pat. ．． No. 664,961.

Mixtures of anionic surfactants, especially in a weight ratio of 5:1 to 1:2, preferably 3:1 to 2=3, more preferably 3:1 to 1:1 sulfonate surfactant and monkey Mixtures with phatic surfactants are particularly suitable here.

Preferred sulfonates have 9 to 15, especially 11 to 13, atoms in the alkyl group. Alkylbenzene sulfonates having carbon atoms and fatty acids 012-C1 α-sulfonated methyl fats derived from 8 fat sources, preferably from 016 to C18 fat sources. Examples include fatty acid esters. In each case the cation is an alkali metal, preferably It is sodium.

Preferred sulfate surfactants have 12 to 22 alkyl groups, preferably Alkyl sulfates with 14 to 18 carbon atoms (optionally alkyl having 10 to 20, preferably 10 to 16 carbon atoms in the group and an average ethyl (a mixture with ethoxy sulfate having a degree of sulfurization of 1 to 6). in each case The cation is again an alkali metal cation, preferably sodium.

One type of nonionic surfactant useful in the present invention has an average hydrophilic-lipophilic balance of (HLB) 8-17, preferably 9.5-13.5, more preferably 10-12 ．． Condensation of ethylene oxide with a hydrophobic moiety to give a surfactant with 5 It is a thing. Hydrophobic (lipophilic) moieties may be aliphatic or aromatic in nature. In addition, the length of the polyoxyethylene group that condenses with a specific hydrophobic group is determined by the hydrophilic element. to produce a water-soluble compound with the desired degree of balance between can be easily adjusted.

Particularly preferred nonionic surfactants of this type are from 3 to 8 moles per mole of alcohol. C9-C15 primary alcohol ethoxylate containing ethylene oxide , especially CI4 containing 6 to 8 moles of ethylene oxide per mole of alcohol ~C15 quaternary alcohol and 3 to 5 moles of ethylene per mole of alcohol It is a 012-C14 primary alcohol containing an oxide.

Another type of nonionic surfactant has the general formula %) (In the formula, Z is a moiety derived from glucose; R is a saturated hydrophobic moiety having 12 to 18 carbon atoms. is an aqueous alkyl group; t is 0 to 10; n is 2 or 3; X is 1. 3-4) of alkyl polyglucoside compounds (compounds contain less than 10% unreacted fatty alcohol and and short chain alkyl polyglucosides). This type of compound and use in detergent compositions, EP-B 0070074, No. 00 Specification No. 70077, Specification No. 0075996, and Specification No. 0094118 It is disclosed in the book.

Still other types of surfactants are semipolar surfactants such as amine oxides.

Suitable amine oxides are monoC-C, preferably 01o-014N-alkyl or alkenylamine oxide and propylene-1,3-diaminedioxy (remaining N positions substituted with methyl, hydroxyethyl or hydroxypropyl groups) selected from).

Cationic surfactants may also be used in the detergent compositions of the present invention, including preferred quaternary ammonium surfactants. The surfactant may be monoc-c, preferably C1o-Cl4N-alkyl or Or 8 18ゝ Alkenylammonium surfactant (remaining N position is methyl, hydroxyethyl or or substituted with a hydroxypropyl group).

The detergent composition can contain 5 to 50% by weight of surfactant, but usually 5 to 30% by weight. % by weight, more preferably 5-15% by weight. A combination of surfactant types is preferred. particularly, anionic surfactant-nonionic surfactant blends and also Anionic surfactant-nonionic surfactant-cationic surfactant blends are preferred. Yes. A particularly preferred combination is GB 2040987 and E It is described in P-A No. 0087914. Surfactant mixed into the composition can be formulated as a product, optimizing the physical properties of the composition and avoiding processing problems. Therefore, it is preferable to control the addition point of each surfactant. Preference for adding surfactant The new mode and order are described below.

The second essential component of the composition according to the invention is a defined amount of sodium aluminosilicate zeolite. Light and water-soluble monomeric or oligomeric carboxylate chelators and crystalline Detergent builder system consisting of a mixture with layered sodium silicate.

Although a wide range of aluminosilicate ion exchange materials can be used, the preferred aluminosilicate Sodium silicate zeolite unit cell type %formula% (wherein 2 and y are at least 6 and the molar ratio of 2 to y is between 1.0 and 0.5) and X is at least 5, preferably 7.5 to 276, more preferably 10 to 2 64) has. The aluminosilicate material is in hydrated form and preferably crystalline. It contains 10% to 28% water, more preferably 18% to 22% water.

The aluminosilicate ion exchange material preferably has a particle size of 0.1 to 10 μm. Further characterized by 0.2-4 μm. The term “particle size” here usually refers to measured by analytical techniques, e.g. microscopy using scanning electron microscopy. means the average particle size of a given ion exchange material when aluminosilicate ion The exchange material has a CaCOs water hardness of at least 200 I1g calculated on an anhydrous basis. Equivalent / 1 g of aluminosilicate, generally 300 mgeq / g ~ 35 Further characterized by a calcium ion exchange capacity that is within the range of 2 mgeq/g can be attached. The aluminosilicate ion exchange material of the present invention is an aluminosilicate ion exchange material. (anhydrous basis) Ca CO3 at least 130a+g equivalent/II/min/(g/ f [: 2 grains Ca / gallon / minute / (g / gallon)], and is generally CaCO3130 ■ equivalent / II / min / (g / l) [2 g Ren/gal/min/(g/gal)]~Ca　C03390mg equivalent/II/min / (g/j2) [6 grains/gal/min/(g/gal)] It is still further characterized by its rate of ion exchange. Ideal for builder purposes The luminosilicate contains at least 260 g equivalent of CaCO3/f1/min/(g/ Calcium ion exchange rate of (4 grains/gal/min/(g/gal)) show.

Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and Although they can be naturally occurring substances, they are preferably synthetically derived. aluminosi Processes for making silicate ion exchange materials are discussed in U.S. Pat. No. 3,985°669. I'm being teased. Preferred synthetic crystalline aluminosilicate ion exchange useful herein The substances are named Zeolite A, Zeolite B1 Zeolite X1 Zeolite I (S or and mixtures thereof. In a particularly preferred embodiment, crystalline aluminum The nosilicate ion exchange material is zeolite A and has the formula %. (wherein X is 20 to 30, especially 27). formula %formula% Zeolite X also has the formula Na ((A102)6 (SiO2)ii)7.5H20 of zeolite H5 and Equally suitable.

Water-soluble monomeric or oligomeric organic carboxylate chelators are available in a wide range of The first carboxyl logarithmic acidity constant ( pKl) less than 9, preferably from 2 to 8.5, more preferably from 4 to 7.5.

The logarithmic acidity constant is defined by reference to equilibrium, where A is the builder salt fully ionized carboxylate anion) Therefore, the equilibrium constant is:

and pK-1OgloK0 ■ For purposes of this specification, acidity constants are defined at 25° C. and zero ionic strength. Literature value are taken where possible (stability constants of metal ion complexes, Special Pub. licagesidine N11L25, The Chemical Society, London), suspected If they occur, they can be measured by potentiometric titration using a glass electrode. do.

Preferred carboxylates are also carboxylates defined similarly to pKl by the formula It can be defined by the sium ion stability constant (pKca++).

Preferably, the polycarboxylate has a pKca++ of about 2 to about 7, especially about 3 to about It has 6. Once again, literature values for stability constants are taken where possible. stable The degree constant was developed by Anders Ringbom in the field of Complexation in Analytical Chemistry. (1963) at 25°C and zero ionic strength. Defined by

Monomeric polycarboxylates are generally preferred for cost and performance reasons, but Carboxylate or polycarboxylate builders can be monomeric or oligomeric in type. Can be a ligomer.

The monomer and oligomer builder are represented by the general formula [wherein R is H, C alkyl or Alkenyl 1 1-30 (optionally substituted with hydroxy, carboxy, sulfo or phosphoni groups) or to a polyethyleneoxy moiety containing up to 20 ethyleneoxy groups) Representation: R is H, C alkyl, alkenyl or hydro2 1-4 represents a xyalkyl, or alkaryl, sulfo, or phosphono group; X represents a single bond; 0; S; So; So; or NR; Y is H; carboxy; hydroxy; carboxymethyloxy; or C alkyl or alkenyl (if 1-80 (substituted with hydroxy or carboxy group); Z represents H; or carboxy; m is an integer from 1 to 10; n is an integer from 3 to 6; p, q are integers from 0 to 6, p+q is from 1 to 6; XSY and Z are each When repeated with a given molecular formula, have the same or different, at least one in the molecule Y or Z contains a carboxyl group] Choose from acyclic, alicyclic, heterocyclic and aromatic carboxylates with Can be done.

Suitable carboxylates containing one carboxy group include lactic acid, glycosyl acid and Belgian patents 831.368 and 821.369 No. 821,370 and their ether derivatives as disclosed in U.S. Pat. can be lost. As the polycarboxylate containing two carboxy groups, Citric acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, Water-soluble salts of tartaric acid, tartronic acid and fumaric acid, and German Offenleg enschrlft No. 2.446°686 and No. 2,446,687 and U.S. Pat. No. 3,935,257. Xylate and sulfinyl as described in Belgian Patent No. 840°623 Examples include carboxylates. Polycarboxy containing 3 carboxy groups In particular, water-soluble citrate, aconitrate and citracone as well as succinate derivatives, such as British Patent No. 1.379,241. Carboxymethyloxysuccinate described in British Patent No. 1,389,73 Lactoxysuccinate as described in Specification No. 2 and Dutch Application No. 72058 Aminosuccinates as described in No. 73 and British Patent No. 1.387.44 2-oxa-1゜1,3-propanetricarboxylate described in Specification No. 7 Which oxypolycarboxylate materials may be mentioned.

As a polycarboxylate containing four carboxy groups, British Patent No. 1. 261.829, oxydisuccinate, 1.1,2.2-etha tetracarboxylate, 1,1.3.3-propane tetracarboxylate and 1,1,2,3-propane tetracarboxylate. Sulho As polycarboxylates containing substituents, British Patent No. 1°398.42 1 and 1,398,422 and U.S. Pat. No. 3,936, 448 and British Patent No. 1°08. While the sulfonated pyrolytic citrate described in 2.179 is mentioned, Polycarboxylates containing phosphono substituents are described in British Patent No. 1.439.00. It is disclosed in the specification of No. 0.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis , cis, cis-tetracarboxylate, cyclopentadienide bentacar Boxylate, 2゜3.4.5-tetrahydrofuran-cis, cls, cis -tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate Sylate, 2.2,5.5-tetrahydrofuran-tetracarboxylate, 1 ．． 2,3,4°5.6-hexane-hexacarboxylate and sorbitol , carboxymethyl derivatives of polyhydric alcohols such as mannitol, xylitol, etc. can be mentioned. Aromatic polycarboxylates include mellitic acid and pyromellitic acid. and phthalic acid derivatives disclosed in British Patent No. 1,425,343. It will be done.

Among the above, preferred polycarboxylates contain up to 3 carboxylates per molecule. Hydroxy carboxylates containing xyl groups, more particularly citrates.

Monomeric or oligomeric polycarboxylate chelating agent parent acids or Mixtures of salts such as citric acid or citrate/citric acid mixtures are also suitable for use with the present invention. It is intended as a component of a clear and useful builder system.

The third element of the builder type is the general formula % formula % (where M is sodium or hydrogen, X is a number from 1.9 to 4, and y is 0 ~20). this kind of crystal layered sodium silicate is disclosed in EP-A 0164514. and their manufacturing methods are described in DE-A No. 3417649 and DE-A No. 3. It is disclosed in the specification of No. 742043. For the purposes of the present invention, X in the general formula above is , 2.3 or 4, preferably 2. More preferably, M is nat and y is O, and a preferred example of this formula is α-1 of Na2Si2O5. Consists of β-1γ and δ forms.

These substances are Na5KS-5 and Na5K from Hoechst AG FRG, respectively. Available as S-7, Na5KS-11 and Na5KS-6. most preferred Examples of such substances are δ-Na2Si205 and Na5KS-6.

Other detersive builder substances may form part of the builder system; These are not required elements. Such substances may be organic or inorganic in nature. I can do it.

For the purposes of the present invention, inorganic builder substances which can constitute any element of the builder system These include alkali metal carbonates, bicarbonates and silicates. preferred organic Substances include organic phosphonates and aminopolyalkylene phosphonates. However, if minimizing phosphorus compounds in the composition is desired, these substances may be used. The quality is not very good.

Other suitable water-soluble organic salts are those in which the polycarboxylic acids are separated by no more than two carbon atoms. a homopolymer or copolymer containing at least two carboxyl groups separated into Polycarboxylic acids or their salts. Polymers of the latter type are described in British Patent No. , 596,756. Examples of such salts include molecular weight 2000 ~5000 polyacrylates and their copolymers with maleic anhydride. and such copolymers have a molecular weight of 20,000 to 70,000, particularly about 40,000. has. These substances usually represent 0.5 to 10% by weight of the composition, more preferably is used in an amount of 0.75 to 8% by weight, most preferably 1 to 6% by weight.

Optional builder materials, if present, generally total up to 25% by weight of the composition. It will be less than 20% by weight, most usually less than 15% by weight.

For the purposes of the composition according to the invention, the builder system comprises from 10 to 95% by weight of the composition and more. Preferably it will account for 20-60% by weight. Within the builder system, Alumino Kei The acid sodium zeolite will account for 20-60% by weight of the mixture, and the monomer The carboxylate or oligomeric carboxylate may account for 10 to 30% by weight of the mixture. The wax, crystalline layered silicate, will represent 10-65% by weight of the mixture.

More preferably, the zeolite is present in an amount of 25% to 50% and is free from monomers or oligomers. Sesame carboxylate accounts for 15% to 25%, and layered silicates are builder-based It accounts for 20 to 50% by weight. Preferably, the builder system also contains up to 25% Auxiliary inorganic compounds such as sodium carbonate and maleic anhydride/acrylic acid copolymer formulating a combination of a builder and an organic builder.

The composition according to the present invention comprises a non-surfactant non-detergent builder component 40 as an optional ingredient. It can also contain up to %. Anti-redeposition agent, anti-staining agent, optical brightener, Stain release agents, dyes and pigments are examples of such optional ingredients and can be added as desired. It can be added in an amount of

Suitable anti-redeposition agents and anti-staining agents include methyl cellulose, Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose conductors, and homopolymer or copolymer polycarboxylic acids or their salts. It will be done. This type of polymer includes maleic anhydride, ethylene, and methyl vinyl ester. copolymer with ester, acrylic acid or methacrylic acid (maleic anhydride is a copolymer make up at least 20 mol% of the body). These substances are usually 0.5-10% by weight of the composition, more preferably 0.75-8%, most preferably It is used in an amount of 1 to 6% by weight.

Other useful polymeric materials include polyethylene glycol, especially molecular weight 1000-10 000, more particularly between 2000 and 8000, most preferably about 4000. . These may be present in amounts of 0.20 to 5% by weight, more preferably 0.25 to 2.5% by weight. used in These polymers and the homopolymer or copolymer polycarboxylic phosphate salts are useful for whiteness maintenance, fabric ash adhesion, and viscosity in the presence of transition metal impurities. Valued for improving cleaning performance against soil, protein and oxidative soils There is.

However, one advantage of the compositions according to the invention is that they contain a reduced amount of polymeric polycarbonate. With xylate builders/anti-redeposition agents or in preferred compositions of the invention suspends insoluble particulate solids (ash) even without the presence of polymeric polycarboxylates. It is the ability to maintain. Thus, the amount of polymeric polycarboxylic acid in a typical product of 5% The rate can be halved, i.e. 2.5%, without increasing the amount of fabric ash in the composition according to the invention. It can be done. If all the high molecular weight polycarboxylate is removed, polymerization In contrast to the virtual doubling of the ash amount when removing the body from normal formulations, the Only a slight increase occurs.

The composition according to the invention is prepared under insufficiently built conditions, i.e. due to the mineral hardness present. hardness when insufficient cleanability builders are available to control all of the It also shows the robustness of control. This benefit is especially strong in the context of poor builder participation. Ability of ternary builder system components to redistribute sium and magnesium hardness ions (due to an increase in crystalline layered silicate components relative to magnesium ions) be believed to take advantage of the affinities).

Still other benefits conferred by the composition according to the invention arise from the cleaning process. This reduces damage to the fabric.

This loss is due to the loss of heavy metal ions deposited on the fabric during the cleaning process with oxygen bleach. It is believed to arise from interaction. The fabric washed with the composition of the present invention has a crystalline weight compared to compositions in which the layered silicate component is replaced with ordinary amorphous silicate. Showing metal ion coverage and reduced tensile strength loss.

Preferred optical brighteners are anionic in character, examples of which include 4,41-bis-( 2-jetanolamino-4-anilitsu-triazin-6-ylamino)su Tilbene-2: 21-disulfonic acid disodium, 4,41-bis-(2-mol Holino-4-anilino-5-triazin-6-ylamino)stilbene-2=2 Disodium l-disulfonate, 4,4'-bis-(2,4-dianilino-s- Triazin-6-ylamino)stilbene-2: 21-disulfonic acid dinato 4,4bis-(2,4-dianilino-s-triazin-6-ylamino) ) stilbene-2-sulfonic acid-sodium, 4.41-bis-(2-anilino -4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6 -ylamino)stilbene-2,21-disulfonic acid disodium, 4,41- Bis-(4-phenyl-2゜1.3-triazol-2-yl)stilbene-2 ゜21-Disulfonic acid disodium, 4,4'-bis(2-anilino-4-(l) -Methyl-2-hydroxyethylamino)-S-)riazin-6-ylamino) Disodium stilbene-2,21-disulfonate and 2(S11).

Tiruvil-4l1-(naphtho-1,2,4,5)-1゜2.3-triazole- 211-sodium sulfonate.

Soil release agents useful in the compositions of the present invention typically include terephthalic acid and ethyl alcohol in various configurations. Copolymers with lene glycol units and/or propylene glycol units or is a terpolymer. Examples of such polymers are disclosed in commonly assigned U.S. Pat. 16885 and 4711730 and European Published Patent Application No. It is disclosed in the specification of No. 0272033. EP-A No. 0272033 specification Particularly preferred polymers according to the formula %) (wherein, PEG is -(OC2H4)0-, po is (QCHO), and T is a polymeric substance consisting of (pcOc6H4Co), for example, typically with a molecular weight of 500 0 to 20,000, preferably 10,000 to 15,000 polyvinylpyrrolidone , an agent useful in preventing the transfer of labile dyes between fabrics during the cleaning process. to be accomplished.

Another optional but highly preferred ingredient is a granular inorganic perhydrate bleach. Ru. Any particulate inorganic verhydrate bleach may be present in amounts ranging from 3 to 40% by weight of the composition. preferably in an amount of 8 to 25% by weight, most preferably 12 to 20% by weight. Ru. Preferred examples of such bleaching agents are sodium perborate monohydrate and tetrahydrate. and mixtures thereof.

Another preferred ingredient is a peroxycarboxylic acid bleach precursor (commonly referred to as a bleach activator). ). It is preferably added in prilled or agglomerated form. this species Examples of suitable compounds include GB 1,586,769 and GB 21,432. No. 31 and the method of forming the prilled form is disclosed in the European published patent application. It is described in the specification of No. 0062523. Preferred examples of such compounds are triacetylethylenediamine and 3,5.5-trimethylhexanoyloxy Sodium cybenzenesulfonate.

The bleach activator usually comprises 0.5 to 10% by weight of the composition, more preferably 1 to 8% by weight of the composition. %, preferably from 2 to 6% by weight.

Other optional ingredients are exemplified by silicones and silica-silicone mixtures. It is a foam suppressant. Silicones are generally made of alkylated polysiloxane materials. While silica is typically used in finely divided form, it is commonly used in silica aerogels and and xerogels and various hydrophobic silicas. These substances are , formulated as granules. Here, the foam suppressor is preferably water-soluble or water-dispersible. The composition is releasably formulated in a substantially non-surface-active, detergent-impermeable carrier. Or, the foam suppressant is , by dissolving or dispersing it in a liquid carrier and spraying it onto one or more of the other ingredients. can be applied.

As noted above, useful silicone antifoam agents include alkylated siloxanes of the type described above. and solid silica. Such mixtures contain silicone Manufactured by adhering to the surface of solid silica. Preferred silicone antifoam agent has a particle size Ions~20n1 and a specific surface area higher than 50rrr/g. Hydrophobic silanized (most preferably trimethylsilanated) silica with a molecular weight of about 500 ~200,000 dimethyl silicone fluid and silicone vs. silanized silicone It is represented by an intimate mixture of 1:1 to about 1:2 by weight of Rika.

Preferred silicone antifoam agents are those disclosed in Paltrotsuta et al., U.S. Pat. No. 3,933,672. It is disclosed in the specification of No.

Other particularly useful foam suppressants include German patent application DTOS No. 1, published April 28, 1977. 2.646,126, a self-emulsifying silicone foam suppressor. Kaka An example of a compound available from Dow Corning is DC-544 (siloxane). Sun/glycol copolymer).

The foam suppressor usually accounts for 0.001 to 0.5% by weight of the composition, preferably 0.01% by weight of the composition. It is used in an amount of ~0.1% by weight.

A preferred method of formulation is to form a liquid form by spraying onto one or more of the main components of the composition. The application of a foaming agent or alternatively the forming of a foam suppressor into separate granules, the granules then being can be mixed with other solid components of the composition. The formulation of foam control agents as separate granules is , other antifoam substances that would otherwise adversely affect the dispersibility of the matrix. , for example, C20"""24 fatty acids, microcrystalline wax and ethi A high molecular weight copolymer of ren oxide and propylene oxide can be added thereto. Make it. Techniques for forming such foam-modifying granules include the above-mentioned Pultodotuta, etc. Disclosed in US Pat. No. 3',933,672.

Another optional ingredient useful in the invention is one or more enzymes.

Preferred enzyme substances include commercially available amylases that are commonly included in detergent compositions. , neutral and alkaline proteases, lipases, esterases and cellular Examples include ze. Suitable enzymes are described in U.S. Pat. No. 3,519,570 and No. 3,533.139.

Fabric softeners can also be included in detergent compositions according to the invention.

These agents may be inorganic or organic in type.

Inorganic softeners include smectite viscosity disclosed in British Patent No. 1,400,898. Illustrated by earth. As an organic fabric softener, British Patent No. 1514276 water-insoluble tertiary as disclosed in the specification and EP-B No. 0011340; Examples include amines. A combination of them and a mono C12-C14 quaternary ammonium salt The combination is based on EP-B No. 0026527 and No. 0026528. It is disclosed in the book. Other useful organic fabric softeners include EP-B No. 0242919 di-long chain amides as disclosed in the specification. Additional organic components in fabric softening systems and According to EP-A No. 0299575 and EP-A No. 0313146, High molecular weight polyethylene oxide materials such as those disclosed are included.

The amount of smectite clay is usually 5 to 15% by weight, more preferably 8 to 12% by weight. % and the material is added to the rest of the formulation as a dry mix component. Mizufu Organic fabric softeners such as soluble tertiary amines, di-long chain amide materials, etc. %, usually 1 to 3% by weight, while high molecular weight polyethylene oxide material and water-soluble cationic substances, 0.1 to 2% by weight, usually 0.15 to 1.5% by weight. Add in the amount of When spray-drying a portion of the composition, dry blending may be used in some cases. Adding as a granule or spraying as a molten liquid onto other solid components of the composition may be more convenient, but these substances may be It can be added to the slurry.

The compositions of the invention can be processed by a variety of methods including dry blending, spray drying, agglomeration and granulation. Preparable and preferred methods therefore include a combination of these techniques. set The preferred method of preparation of the composition is a combination of spray drying and agglomeration in a high speed mixer and dry mixing. Includes combinations.

Preferred detergent compositions according to the invention also include at least two particulate multicomponent components. . The first component is at least 20% by weight of the composition, usually 30-70%, more preferably Preferably, it accounts for 40% by weight or less, and the second component accounts for 1 to 50% by weight of the composition, and more Preferably it accounts for 10 to 40% by weight.

The first component is an anionic surfactant and powder in an amount of 0.75-35% by weight of the powder. one or more inorganic and/or organic salts in an amount of 99.25 to 65% by weight of Consists of granules. Granules may be in any suitable form, e.g. granules, flakes, prills, mulch. can have garume or noodles, but preferably in granular form. be. The granules themselves are processed by pan or drum agglomeration or into an in-line mixer. Although the agglomerates may be more prepared, it is preferable that the aqueous slurry of the components be With spray-dried particles prepared by atomization in a hot air stream to remove water in minutes be. In the method, the spray-dried granules constituting the first component, before reagglomeration, are They themselves are subjected to a densification process, e.g. by a high speed cutter mixer. The density may be increased over time. For purposes of illustration, the first component is the preferred It is referred to below as a spray-dried powder.

The important properties of the main anionic surfactant in the first component are the Low dissolution rate in aqueous media at water temperatures widely used in the liquid filling process It is something that should be done with great care. Regarding European cleaning habits, The water temperature used is typically between 5°C and 20°C, more usually between 7°C and 12°C.

Anionic surfactants suitable for the purpose of the first component have an average of 16 to 22 alkyl groups. linear alkyl sulfates with carbon atoms and an average of 16 to 24 alkyl groups. It was found to be a linear alkyl carboxylate having a carbon atom.

The alkyl groups for both types of surfactants are preferably derived from natural fats such as tallow. . A mixture of alkyl moieties (more than 40% of which have 14 or fewer carbon atoms) short-chain alkyl sulfates or carboxylic acids derived from sources containing Sylates are less preferred as the first component causes a gel-like mass to form upon dissolution. .

The amount of anionic surfactant in the spray-dried powder constituting the first component is between 0.75 and 4 0% by weight, more usually 2.5-25% by weight, preferably 3-20% by weight, most preferably Preferably, it is 5 to 15% by weight. Water-soluble such as linear alkylbenzene sulfonates Surfactants can be incorporated or subsequently spray-dried by spray-on. It may also be applied as a powder.

The other main components of the spray-dried powder are one or more inorganic salts or It is an organic salt. The inorganic and/or organic salts may be water-soluble or water-insoluble. The latter type is often composed of water-insoluble building blocks or water-insoluble building blocks. and these form part of the builder system. Suitable water soluble inorganic Salts include C, alkali metal carbonates, bicarbonates, sulfates and borates. It will be done. If the aluminosilicate does not form part of the spray drying ingredients, the alkali Rimetallic silicates can also be present in the spray dried granules.

incorporating at least a portion of the aluminosilicate builder into the spray-dried granules; is preferred and as mentioned above, if this occurs, any existing Silicates should also not form part of the spray-drying ingredients in these situations. , silicates can be formulated in several ways, e.g. by separate silicate-containing spray drying. By preparing granules, it is possible to incorporate silicates into aggregates of other components. or more preferably by adding the silicate as a dry mixed solid component. more achievable.

Any of the above optional builder salts can be incorporated into the spray-dried powder that constitutes the first component. . Spray-dried powder chelated with water-soluble monomers or oligomers carboxylates 1111 (this means that this It is less preferred since it tends to inhibit rapid dissolution of the components. organic salts and /or inorganic salt, 60-90% by weight of the first component, more preferably 70-90% % by weight, most preferably 75-85% by weight.

Additionally, spray-dried powders typically contain up to 15% by weight of miscellaneous components.

In preferred compositions where the first component is a spray-dried powder, the first component includes The optional ingredients used in the spray drying process must be heat stable to the extent necessary to withstand the temperatures encountered in the spray drying process It should be sexual. If the first component is a spray-dried powder, typically the spray-dried Dry to a moisture content of 7 to 11%, more preferably 8 to 10% by weight of the powder. Dew. The moisture content of powders produced by other methods, e.g. agglomeration, is lower. The amount may be within the range of 1 to 10% by weight.

The particle size of the first component is normal and preferably 5% by weight or less is 1.4+am or more while below 10% by weight the maximum dimension is less than 0.15i+m Should.

Preferably at least 60%, most preferably at least 80% by weight of the powder The size is 0.7 mm to 0.25 mm. In the case of spray-dried powders, the particle The bulk density should be in the range of 350 g/D to 650 g/Ill, but Regularly 540g/l~600gzJ! is within the range of 600-650g/N Bulk densities in the upper part of the range are particularly useful when the production of so-called concentrated products is desired. be. Bulk densities higher than this range may result in the spray-dried powder being subjected to further processing, e.g. , if the powder is compacted after being subjected to size reduction in a high speed cutter mixer. Sometimes. Alternatively, methods other than spray drying can be used to form the powder. Good too.

The second component of the preferred composition according to the invention is a granular material containing a water-soluble surfactant. It is.

This can be anionic surfactants, nonionic surfactants, cationic surfactants or It may be a semi-polar surfactant or a mixture of any of these. suitable interface Although the surfactants are described above, preferred surfactants are linear C1, ~C alkylbenzes. sulfonates and fatty CI4-C18 methyl ester sulfonates.

The second component may have any suitable physical form, i.e. flakes, prills, etc. , quince, noodle, ribbon, or granule form. they are gushing It may be a mist-dried or non-spray-dried agglomerate. The second component is theoretically soluble in water. may consist of a surfactant alone, but in practice at least one organic salt or or inorganic salts are added to facilitate processing. This means that the crystallinity, organic salts or inorganic salts present in the first component. It may be one or more types of salt.

The particle size range of the second component is not critical, but the particle size range of the spray-dried first component during blending is It should be such as to avoid segregation from children. Thus, less than 5% by weight Should be larger than 1.4mm, while below 10% the maximum dimension is 0.15 Should be less than mm.

The bulk density of the second component will be a function of the method of preparation. Thus, in spray-dried granular form The second component may have a density of 350 g/l to 650 g/l, but more Preferably it will be within the range of 500g/l to 630g/l. However, preferred The second component in a new form is a pan agglomerator, A Z-blade mixer or more preferably an in-line mixer, such as an oran Da's Lely Stud 29 Chrome Strat 8211AS Shugi (Holland ) BV and FRG Bostfach 2050 Elsenerstrasse 7-9D- 4790 Badenborn 1 Gebruder Rodige Maschinenban Gmb Mechanically mixed aggregates may be prepared by adding H. this By means of 650 g/j in the second component! ~1190g, Q.

More preferably, the bulk density is within the range of 750 g/N to 850 g/I. can. This is particularly useful when formulating so-called "concentrate" products.

Preferred compositions include from 3 to 15%, more preferably from 5 to 12%, by weight of the composition. the amount of alkali metal carbonate in the second component that corresponds to the amount. This is the second component The amount of carbonate in the carbonate will be 20-40% by weight.

Also, highly preferred components of the second component are present at 10-35% by weight of the second component. The synthetic zeolite-type hydrated water-insoluble aluminosilicate ion exchange material Ru.

The amount of water-insoluble aluminosilicate material incorporated in this manner may range from 1 to 10% of the composition. It is 10% by weight, more preferably 2 to 8% by weight. If you spray dry the second component For example, the second component contains both a silicate component and an aluminosilicate component for the above reason. It is important that it does not contain. Under such circumstances, the silicate becomes the first component. may be blended or other dry formulas if it also contains aluminosilicates. It may be added as a solid to the first component and the second component together with the mixed material.

In one method for preparing the second component, the surfactant salt is added in-line. Generate on the fly in a mixer. The liquid acid type surfactant is Rosige KM mixer. Granular anhydrous sodium carbonate and hydrated aluminosilicate in continuous high-speed blending such as In addition to the mixture with sodium, it neutralizes and adds surface activity while maintaining the granular nature of the mixture. Produces sex drug salts. The resulting agglomerated mixture prepares the second component and then this second component. The second ingredient is added to the other ingredients of the product. In a variation of this method, the surfactant salt is Pre-neutralize and add to the mixture of other ingredients as a viscous paste. This modified smell In other words, the mixer simply serves to agglomerate the ingredients to prepare the second ingredient.

In a particularly preferred method of preparing the composition according to the invention, a jet comprising a first particulate component is provided. A portion of the mist-dried product is diverted and treated with a low level of non-ionic surfactant before re-blending with the remainder. Attach to sex agent spray-on. The second particulate component is prepared using the preferred method described above. do. Other dry mix ingredients are then added, such as carboxylate chelating agents, Along with machine peroxygen bleaches, bleach activators, soil release polymers, silicates and enzymes The first component and the second component are fed to a conveyor belt and the conveyor belt to a horizontally rotating drum where the fragrance and silicone suds suppressor are processed. Spray on the product. In highly preferred compositions, a small amount (approximately 2% by weight) of Introducing ground crystalline aluminosilicate to increase density and improve granular flow properties An additional drum drying step is used.

The composition according to the invention can be applied to the product overflow in the drum of an automatic washing machine at the beginning of the washing cycle. Provides a high localized concentration across the entire washing machine, thereby reducing the Delivery (del1) which also avoids problems associated with product loss in lup) very) system.

Delivery to drums is most easily accomplished by compounding the composition into bags or containers. can. The composition is then subjected to agitation, increased temperature or immersion in wash water in a drum. Therefore, it can be released quickly at the beginning of the cleaning cycle. Or the washing machine itself, e.g. For example, the composition can be added directly to the drum by a dispensing device at the access door. May be adapted to make it possible.

Products consisting of detergent compositions enclosed in bags or containers typically have container integrity. Although kept dry to prevent extraction of contents during drying, immersion in aqueous solutions is usually Designed in a manner that accommodates the release of container contents into the cleaning environment during exposure. It will be done.

Typically, containers such as bags, pouches, etc. will be flexible.

The bag has a fibrous structure coated with an impermeable protective material to retain the contents. For example, the one disclosed in European Published Patent Application No. 0018678 It may be. Or it is European Published Patent Application No. 0011500 No. 0011501, No. 0011502, and No. 00119 Edge seams designed to rupture in aqueous media as disclosed in No. 68 may be formed from a water-insoluble synthetic polymeric material provided with a seal or closure. . Advantageous forms of water brittle closures include non-woven materials such as polyethylene, polypropylene, etc. disposed along one edge of a pouch formed from a water-permeable polymeric film and Consisting of a water-soluble adhesive that binds.

In a variation of the bag or container product form, the central flexible layer is impregnated with the composition and and/or coat the central flexible layer with the composition and then apply one or more outer layers to create a fabric-like appearance. Laminated sheet products that produce a decorative effect can be used. Layers remain bonded during use May be sealed together to facilitate release of coated or impregnated substances It may separate on contact with water in order to

Another laminate form is a series of pouch-like containers, each containing a predetermined amount of detergent ingredients. pouch-like when the second layer is on top of the first layer and the two layers are in contact. embossed or deformed to give it a seal) in the area between the containers It has one layer. The ingredients may be applied in granular, paste or molten form and The laminate layer should prevent extraction of the contents of the pouch-like container before addition to water . The layers may separate upon contact with water or remain bound together. Well, the only requirement is that the structure allows rapid release of the contents of the pouch-like container into solution. This is what should be done. The number of pouch-like containers per unit area of the substrate is selected However, it will usually vary from 500 to 25,000 per go.

Suitable materials that can be used for the flexible laminate layer in this aspect of the invention include: , inter alia sponges, paper and woven and non-woven fabrics.

However, the preferred implementation of the present invention is to use solids that are permeable to liquids but The composition is dispensed by a reusable dispensing device with walls that are impermeable to the composition. The process involves introducing an object into the liquid surrounding the fabric in the drum.

Devices of this kind are described in European Patent Applications Nos. 0343069 and 0343 It is disclosed in the specification of No. 070. The latter application includes a support line defining an orifice. A device comprising a flexible sheath in the form of a bag extending from the orifice (the orifice is Suitable for bagging enough product for one wash cycle) is disclosed. A portion of the cleaning medium flows into the bag through the orifice and the solution is then passed outward through the orifice to reach the cleaning medium. Ru. The support ring has a masking device to prevent the extraction of wet undissolved product. This device typically has a spoked wheel shape with a diameter extending from a central boss. Consisting of directionally extending walls or similar structures in which the walls are helical.

The invention is illustrated by the following non-limiting examples. All percentages here are weighted unless otherwise noted. It is based on quantity.

In detergent compositions, abbreviated component identifications have the following meanings: CLAS Bilinear C12 Sodium Alkylbenzene Sulfonate TAS: Tallow alcohol sodium sulfate C14/15AS” 14-C15 Sodium alkyl sulfate TAE: n moles of ethyne per mole of alcohol Tallow alcohol 45E7 ethoxylated with oxide: average of 7 moles of ethyl C4-C15 mainly linear primary alcohol CAE condensed with ren oxide ・Condensation with 6.5 moles of ethylene oxide E6.5゜ C12-C13 primary alcohol PEG: polyethylene glycol ( Molecular weight usually below) TAED: Tetraacetylethylenediamine silicate: Amorphous sodium silicate (Sl 02:Na 20 ratio usually below) NaSKS-6: Crystal columnar layered silicate with formula δ-N a S t 205 Carbonate: Anhydrous sodium carbonate CMC: Sodium carboxymethyl cellulose zeolite A: - Missing particle size 1 formula% with ~10μm Sodium minosilicate Polyacrylate diacrylic acid homopolymer with a molecular weight of 4000 Cytrate: Sodium citrate trihydrate Photoactivated bleach: Tetrasulfonate Zinc phthalocyanide MA/AA: Maleic acid/acrylic acid l:4 copolymer , average molecular weight approximately 80,000 MVEMA: Maleic anhydride believed to have an average molecular weight of 240,000 /vinyl methyl ether copolymer. This material was pre-hydrolyzed with NaOH before addition. did.

Belborate: Nominal formula Sodium perborate tetrahydrate of NaBO'3HO'H2O2 Berborate monohydrate: Empirical formula N a B O2/H2O2 Anhydrous Sodium Perborate Bleach Enzyme 2 Novo I Mixed proteolytic/amylolytic fermentation marketed by Industries AS Prime brightener: 4,4'-bis(2-morpholino-4-7nilino-s7triazine- 6-ylamino)stilbene-2:2'-disulfonic acid disodium DETP MP: Product name Dequest 2060 by Monsanto Diethylenetriaminepenta(methylenephosphonic acid) commercially available in Mixed foam suppressor: 25% paraffin wax with melting point 50”C, 17% hydrophobic silica, foam Raffin oil 58%.

Example I A granular detergent product was prepared having the composition shown below (41 parts).

A13 Zeolite A 18.2 g, O N a S K S -6-11,0 Site rate 9.25 8.0 M A / A A 4.9 4.9 T A E D 5.0 5.0 Belborate 10.0 10.0 Berborate monohydrate 8.0- 13. QD E T P M P O, 19 0.19 enzyme 1.40 1.40 Silicate (ratio 2.0) 4. Q - Carbonate 15.5 9.0 Foam suppressant 0.55 0.55 CM COJ O,8 Light activated bleach 20ppm 20ppm Fragrance 0.43 0.43 Brightener Q, 24 0.24 Moisture and miscellaneous components 10.34 6.29 Spray drying, flocculation and dry blending of both products. It was prepared by combination with synthetic technique. All of TAS, about 174 of LAS, Maleic anhydride/acrylic acid copolymer, DETPMPSCMC and brightener Spray drying with carbonate and a portion of zeolite virgool A powder was prepared. In the case of product A, approximately 82% of zeolite and carbonate In the case of product B, approximately 65% of zeolite was incorporated into the spray-dried part. 60% of carbonate and 45% of carbonate were added in this way. spray dried products Passed through Rosige KM high speed mixer/cutter and added 45E7 non-ionic surfactant. Sprayed onto the granules. The treated granules were then transferred to a conveyor belt.

LAS, carbonate and the remainder of the zeolite in a Rosige KM high speed mixer. Processed to form agglomerated particles, these agglomerated particles were fed to a conveyor belt.

Other dry solid ingredients, namely citrates, silicates, verborates and bleaches. An activator was also added to the belt at the same time. Finally, the mixed granules are placed in a mixing drum with low strength The finished product is subjected to a blending process in which fragrance and foam suppressants are sprayed onto the granules. was formed.

These products are then compared in a split bundle cleaning test program to This makes it possible to evaluate stain removal performance. Design a test program and ensure sufficient It included repeated experiments and allowed for statistical treatment of the results. 95g/load of product A while product B was used in an amount of 79 g/load. The difference is product 810 to reflect a higher concentration of ingredients per part 0, thus giving the same amount of non-builder ingredients. reflects the need to use less weight. The test program is Fkl, 2 AEG Lava at 980 automatic washing machine set to cycle used. The washing machine was charged with 25″ German hardness water with a Ca:Ma ratio of 3:1. . The test was carried out at three temperatures, namely 40°C, 60°C and 95°C, and each Fabric loads of 1.81 kg, 2.25 kg and 2.72 kg were used.

Each load was tested for each type of stain, to enable evaluation of whiteness and stain removal performance. That is, samples soiled with grease stains, clay stains (enzyme-degradable and bleachable) and It consisted of a mixture of naturally stained white cotton fabric articles. Each swatch consists of a pair of halves. and the other half was washed in the same machine using a comparison product. After washing, The fabric was dried at room temperature and then graded on a 1-5 chef scale. Product A and Product B at a given temperature using spring rings determined by experts. The differences in whiteness and stain removal performance between the two were characterized.

The spring ring shows that Product B is resistant to grease stains and clay stains at 40°C. showed a significant advantage over product A against clay stains at 95°C, and the overall Stain removal performance was otherwise statistically indistinguishable.

Therefore, useful performance advantages are derived from the builder systems of the present invention over prior art compositions. It is present in the case of compositions containing Furthermore, such benefits are achieved by reducing the amount of builder ingredients. can be obtained with a significant reduction (13.0 parts).

Example■ A comparison of the amount of deposited inorganic substances on fabrics that have been washed multiple times shows that product B in Example Laundry detergent (produced in the UK by Brocter & Gamble Limited) The cleaning conditions were Mlele Hydromatic. ) W698 (Ca: Mg-3: 1) main cleaning cycle and cleaning temperature It was 95 degrees Celsius. Each product uses 2.7 new cotton terry towel fabrics A load consisting of 2 kg was washed and each wash load was then washed an additional 14 times completely. It was subjected to a thorough cleaning cycle.

A sample of fabric from each load is then weighed, incinerated, and the residue weighed and placed in the wash cycle. The value of the inorganic substances deposited during rolling was given.

The results were as follows.

Product Dosage/Cleaning (g) Ash (wt%) Ariel Ultra 125 g 0, 698% Product 8 102g 0.483% The results show that the composition according to the invention has a higher concentration of inorganic salts obtained using commercially available phosphate-free detergent products. This indicates that the amount of inorganic salt deposited is smaller than the amount of deposited inorganic salt.

Example■ The following compositions are according to the invention and prepared in a similar manner to product B of Example I. Ru.

N a S K S -611,00 Berborate monohydrate 12.50 D E T P M P 0.19 Photoactivated bleach 2OppII Brightener 0,24 Foam suppressant 0.49 Fragrance 0.43 Moisture and miscellaneous components 8.70 Example ■ Three detergents having the same composition as composition B of Example I except for the builder system differences indicated below. Products C, D and E were prepared according to the method of composition B of Example I (values are in parts by weight in the composition). ).

CD E Zeolite A I3.0 13.0 13.0 Site rate 13.0 6.0 B, ON a S K S 6 11.0 11.0 -Silicate (ratio 2 ．． 0)★--13,75M A/A A 4.25 2.0 2.0★Active Modern washing machine testing using product supplied as 80% water content (11.0 parts on an anhydrous basis) I did it. In this test, a clean fabric ballast load of 4) cg was applied to a terry towel cotton swatch. The heavy metal ions that accumulate on fabrics after repeated washings are The amounts of carbon (Fe and Mn) and total air (inorganic salt) were measured. F e C13 and 2.5 ppm of Fe as Mn and 0.5 ppm of Mn as C12. 2ppm A heavy metal ion "spike" was added to the water supplied to the washing machine.

The washing conditions were as follows.

Washing machine type Mier Hydromatic W698 washing machine cycle 95℃ cotton Two knees adjusted to give German hardness 25″ with water hardness Ca:Mg ratio 3:1 Castle upon Tyne (UK) tap water (this water source is typically CuO ~Contains Bpp layer) Artificial stain 20g mixture consisting of the following / Loaded palmitic acid 250g Stearic acid 250g Garden clay 200g Dirty motor oil 150g Glyceryl trioleate 150g Iron oxide (Fe20a) 5, 36g sample washed 25 times and then the heavy metal ion content (ppIll) and total inorganic salt content (ash) Analyze about. The latter involves placing a weighed terry towel fabric swatch in a flame for 3 minutes. It required calcining at 800° C. for 2.5 hours after combustion. Then put the ashes down The following elements were analyzed and reported as a fraction of the original sample weight.

The results were as follows.

D.E. F e ppm 8.8 9,9 27.2 Mn ppm 1.9 3.5 1 2.4Cu ppm 1.4 2.3 7.0Ca + M g% 0.42 0.46 1.05Si & A1% 0.18 0.27 0.49 Composition of the present invention Cotton fabrics washed with product C+D, which consists of It can be seen that it shows the amount. However, the composition The present invention contains an amount of polymeric polycarboxylate co-builder which is 50%. The use of a three-component builder system is shown to impart increased toughness to detergent compositions.

The results of product C are similar to those of the conventional builder system when compared with those of comparative product E. It also shows a reduction in the amount of deposited inorganic salts (ash) resulting from the use of ternary builder systems compared to vinegar.

More specifically, the comparison between product C+D and product E is based on the results obtained from the use of the composition of the invention. shows a significant reduction in the amount of heavy metal ions on the fabric. Inorganic Berhide on the surface of fabric Fabric heavy metal ion content believed to result from catalytic decomposition of rate bleaching agents can be directly correlated with tensile strength loss during

international search report Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, NL, SE), 0A ( BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, TG), AT, AU, BB, BG, BR, CA, CH, C3, DE, D.K.

ES, FI, GB, HU, JP, KP, KR, LK, LU, MC, MG, MW, NL, No, PL, RO, SD, SE, 5U (72) Inventor: Birdy, Ball, Andrew Belgium, Oberice, Russia Zeerens Steenbeek, 97

Claims (1)

[Claims] 1. (a) One or more anionic surfactants, nonionic surfactants, amphoteric surfactants 5-50% by weight of an agent or a cationic surfactant or a mixture of any of them; (b) (i) 20-60% by weight of the mixture of sodium aluminosilicate zeolite; and, (ii) 10-30% by weight of the mixture of water-soluble monomers or oligomeric organic carboxylic acids; xylate chelating agent and (iii) 10 to 65% by weight of the mixture of composition Na MSixO2x+1, yH2O (where M is sodium or hydrogen, x is 1.9 to 4, and y is a number from 0 to 20) with thorium a detersive builder system consisting of a mixture of 10% to 95%; and (c) a granular form characterized by containing 0 to 40% of a non-surfactant, non-builder detergent component; Detergent composition. 2. Granular detergent according to claim 1, wherein in component (b)(iii) x has a value of 2. Composition. 3. Any of claims 1 and 2, wherein in component (b)(iii), M is sodium. The detergent composition according to item 1. 4. Component (b) (iii) is α, β, γ or δ-Na2Si2O5, A detergent composition according to any one of claims 1 to 3. 5. Sodium aluminosilicate zeolite is calculated as zeolite 1 on an anhydrous basis. Calcium ion exchange capacity of at least 200 mgeq CaCO3 water hardness per g 5. A hydrated synthetic zeolite having an amount of detergent composition. 6. Synthetic hydrated zeolite has a unit cell formula Naz[(AlO2)z(SiO2)y ], xH2O (where z and y are at least 6 and the ratio of z to y is 1.0 ~0.5 and x is at least 5, preferably from 7.5 to 276) The detergent composition according to any one of claims 1 to 5, comprising: 7. Sodium aluminosilicate zeolite is hydrated zeolite A, X, B or The detergent composition according to any one of claims 1 to 6, which is HS. 8. A monomeric or oligomeric organic carboxylate chelating agent according to any one of the preceding claims, having a xyl logarithmic acidity constant (pK1) of less than 9. Detergent compositions as described. 9. The monomeric or oligomeric organic carboxylate chelating agent has a pK of 12 to 8.5, preferably between 4 and 7.5. Detergent compositions. 10. Claim 1 wherein component (b)(ii) consists of a monomeric polycarboxylate. 10. The detergent composition according to any one of items 1 to 9. 11. Component (b)(ii) is an aliphatic monomer containing 2 to 4 carboxyl groups 11. The composition according to claim 1, wherein the polycarboxylate is made of polycarboxylate. Detergent composition. 12. Component (b)(ii) is citric acid, water-soluble citrate or a mixture thereof 12. A detergent composition according to any one of claims 1 to 11, comprising: 13. Any of the preceding claims, wherein component (b) also includes one or more auxiliary builders. The detergent composition according to item 1. 14. Auxiliary builders include aminopolyalkylene phosphonates, alkali metal carbonates, salts and bicarbonates, homopolymer/copolymer polycarboxylic acids or their selected from salts and mixtures thereof, the polycarboxylic acid having no more than 2 carbon atoms. 14. Thus comprising at least two carboxyl groups separated from each other. Detergent compositions as described. 15. Component (a) 5% to 30%, component (b) 20% to 60% and other detergent components A detergent composition according to any one of the preceding claims, comprising from 20% to 40%. 16. 16. A detergent composition according to claim 15, wherein component (c) consists of an oxygen bleach. 17. The detergent set according to claim 16, wherein the oxygen bleach is an inorganic perhydrate. A product. 18. 17. and wherein the oxygen bleach comprises an organic peroxy acid precursor. 18. The detergent composition according to any one of Item 17. 19. according to any one of the preceding claims, wherein component (c) comprises a detergent enzyme. Detergent composition. 20. Crystalline layered sodium silicate (b) (iii) as component (a) and component (b) one or more particulate solids comprising (i) and (ii) and component (c) if present; Any one of claims 1 to 19, characterized in that it is added to the body as a finely ground particulate solid. A method for producing a detergent composition according to item 1.