JPH0320439B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to granular detergent compositions containing an anionic surfactant and an anionic water-soluble polymer in intimate admixture. The composition disperses and dissolves in the wash liquor more quickly than similar compositions having only surfactants. The dispersibility and solubility of granular detergent compositions presents challenges and dilemmas to those who formulate and process these types of compositions. Spray-dried forms of compositions of this type generally provide satisfactory dispersibility and solubility when the individual components are soluble or dispersible in water. However, spray-dried forms require tolerance for relatively low densities of about 0.4-0.5 g/ml or less to obtain substantial porosity. Of course, porosity provides dissolution rate benefits. Various mechanical mixing methods and agglomerations
Although dense granular detergent compositions can be prepared by the tion method, the dissolution rate is generally unsatisfactory. It is an object of the present invention to improve the dispersibility and solubility of granular detergent compositions prepared by a method that provides a higher density than that obtained from conventional spray drying methods. However, the invention is applicable to any detergent composition within the broad scope of the invention. BACKGROUND ART US Pat. No. 4,072,621 discloses the addition of water-soluble copolymers of vinyl compounds and maleic anhydride to granular detergents containing aluminosilicate builders. GB 2048841 discloses the use of polymeric acrylamide to stabilize aqueous suspensions of zeolites. The suspension is said to be suitable for spray drying to obtain detergent compositions. U.S. Pat. No. 3,933,673 describes the use of partial alkali metal salts of homopolymers or copolymers of unsaturated aliphatic monocarboxylic or polycarboxylic acids as builders to provide improved storage properties. There is. U.S. Pat. No. 3,794,605 discloses a mixture of 0.1% to 20% of a salt of cellulose sulfate and a copolymer of a vinyl compound and maleic anhydride to impart whiteness maintenance benefits to detergent compositions. Regarding the use of . US Pat. No. 3,380,922 discloses film-forming resinous polymers useful as builders to improve the mechanical properties of detergents. US Pat. No. 3,803,285 describes granular detergents containing various starch derivatives. The granulate is said to be film-forming, cake-resistant, and rapidly soluble in water. US Pat. No. 3,922,230 discloses detergent compositions containing polyacrylate oligomers. US Pat. No. 4,031,022 discloses detergent compositions containing copolymers of alpha-hydroxyacrylic acid and acrylic acid. US Pat. No. 4,076,643 discloses a method for preparing free-flowing granular premixes for use in detergent compositions. The premix contains one or more liquid or paste-like surfactants and a water-soluble hydroxycarboxylic acid polymer or copolymer. GB 1333915 discloses that polyacrylic acid with 5 to 55% of its carboxyl groups neutralized as sodium salt and having a molecular weight greater than 1000 is a free-flowing powder useful as a detergent builder. are doing. GB 1380402 relates to the addition of small amounts of reactive and non-reactive polymers to provide free-flowing granular detergents containing non-ionic surfactants. US Patent No. 3,920,570 relates to the use of poly-alpha-hydroxy acrylates as sequestering agents for detergent compositions. U.S. Patent Application No. filed April 22, 1981
No. 256,454 discloses adding soluble film-forming polymers to low phosphate and silicate granular detergents with aluminosilicate builders to impart free-flowing and solubility properties. U.S. Patent Application No. filed April 22, 1981
No. 256453 specifies organic surfactants, water-soluble salts,
Granular detergent compositions containing an aluminosilicate ion exchange material, a low percentage of silicate, and a film-forming copolymer of acrylamide and acrylate are disclosed. SUMMARY OF THE INVENTION The present invention provides: (a) a non-soap anionic surfactant from about 3% to about 40%;
(b) from about 5 to about 85% by weight of a water-soluble neutral or alkaline salt or mixture thereof, and (c) having an average molecular weight of from about 300 to about 15,000 and at least one ionic per 200 units of molecular weight. from about 1% to about 50% by weight of a non-soap anionic surfactant having an ionizable site, the surfactant and polymer comprising the other ingredients of the granular detergent composition. A granular detergent composition characterized in that it is produced by preparing a mixture of the surfactant and the polymer prior to contacting the bulk. DETAILED DESCRIPTION OF THE INVENTION The granular detergent composition of the present invention contains the following essential components: (1) a non-soap anionic surfactant, (2) a water-soluble salt, and (3) a water-soluble anionic polymer. The composition is prepared by any suitable method that produces an intimate mixture of surfactant and polymer. Intimate mixing can be achieved by drying the solution or slurry containing the polymer and surfactant or their precursors. Post-processing, such as incorporation of water-soluble salts and optional ingredients, should avoid steps that would result in significant dissolution of the polymer/surfactant mixture in the presence of other water-soluble ingredients. The surfactant and polymer mixture can be mixed with other ingredients prior to spray drying, provided that the total water content in the resulting paste or slurry does not contain more than about 50% water by weight. Under these types of conditions, intimate mixing of surfactant and polymer is maintained. Agglomeration and dry mixing techniques are particularly preferred in the practice of this invention to prepare complete granular detergent compositions while maintaining intimate mixing of surfactant and polymer. Without being limited to any particular theory, the polymers useful in the compositions of the present invention are highly viscous "gum"s of water and anionic surfactants that act to retard the dissolution of particulates. It is believed that they confer their benefits by eliminating or delaying phase formation. Surfactants The detergent compositions of the present invention contain from about 3% to about 40%, preferably from about 4% to about 35% by weight, non-soap anionic surfactants.
% by weight, more preferably from about 5 to about 30% by weight. In relatively high foaming detergent compositions,
Non-soap anionic surfactants generally represent about 10 to about 35%, preferably about 12 to about 30% by weight of the detergent composition. Surfactants useful in the present invention are described in US Pat. No. 3,664,961 and US Pat. No. 3,919,678. Also useful non-soap anionic surfactants are:
For example, water-soluble salts of organic sulfuric acid reaction products having an alkyl group of about 10 to about 20 carbon atoms and a sulfonic acid ester group or a sulfuric acid ester group in their molecular structure, preferably alkali metal salts, ammonium salts and alkanol ammonium salts. (the term "alkyl" includes the alkyl portion of an acyl group). Examples of this group of synthetic surfactants are:
Sodium alkyl sulfates and potassium alkyl sulfates, especially those obtained by sulfating higher alcohols (carbon number _C8 to _C18 ), such as those produced by reducing the glycerides of tallow or coconut oil Sodium alkylbenzenesulfonates and potassium alkylbenzenesulfonates in which the alkyl group has from about 9 to about 15 carbon atoms in a straight or branched chain configuration, such as U.S. Pat. Nos. 2,220,099 and 2,477,383. It is of the type described in . Of particular value are linear straight-chain alkylbenzene sulfonates, abbreviated C _11-13 LAS, with an average number of carbon atoms in the alkyl group of about 11-13. Other anionic surfactants are sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonate and sodium coconut oil fatty acid monoglyceride sulfate; 1 molecule Sodium or potassium salts of alkyl phenol ethylene oxide ether sulfuric acid containing about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl group has about 8 to about 12 carbon atoms; and about 1 to about 10 units of ethylene oxide per molecule; It is a sodium salt or potassium salt of an alkyl ethylene oxide ether sulfate containing the following, and whose alkyl group has about 10 to about 20 carbon atoms. Other anionic surfactants useful in the present invention include, for example, water-soluble salts of esters of alpha-sulfonated fatty acids having about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group; Approximately 2 carbon atoms in the acyl group
~9, water-soluble salt of 2-acyloxy-alkane-1-sulfonic acid having about 9 to about 23 carbon atoms in the alkane moiety; about 10 to 20 carbon atoms, about 1 in the alkyl group
an alkyl ether sulfate having ~30 moles of ethylene oxide; a water-soluble salt of olefin sulfonic acid having about 12 to 24 carbon atoms; and about 1 to about 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane moiety. It is a β-alkyloxyalkanesulfonate having the following formula. Anionic sulfonate surfactants are particularly preferred in the compositions of the present invention because they offer very substantial solubility benefits. Particularly preferred anionic surfactants in the present invention are:
For example, linear alkylbenzene sulfonates having an average number of carbon atoms in the alkyl group of about 11 to 14; tallow alkyl sulfates; coconut alkyl glyceryl ether sulfonates; Approximately 1
-4 alkyl ether sulfates, and olefin sulfonates or paraffin sulfonates having about 12 to 16 carbon atoms. Particular surfactants preferred for use in the present invention include, for example, linear sodium C _11-13 alkylbenzene sulfonates and C _12-18 alcohols
It is the sodium salt of a sulfated condensate with 4 moles of ethylene oxide. The advantages obtained with the compositions and methods of the present invention are particularly apparent when the compositions contain a non-soap anionic surfactant selected from the group consisting of alkylbenzene sulfonates, olefin sulfonates and paraffin sulfonates. Water-soluble neutral or alkaline salts The granular detergents of the present invention contain from about 5 to about 85% by weight water-soluble neutral or alkaline salts, preferably from about 10 to about
70% by weight, more preferably about 30 to about 65% by weight. Neutral or alkaline salts have a PH of 7 or higher in solution and can be either organic or inorganic. The salt helps impart the desired density and bulk to the detergent granules of the present invention. Some salts are inert, but many also act as detergency builders. Neutral or alkaline water-soluble salts useful in the practice of this invention are considered suitable for use in granular detergent compositions from standpoints such as biological safety, environmental impact, and physical and chemical properties. It is an ivy substance. Sodium and potassium salts are particularly useful for reasons of cost and physical properties. Suitable salts can be inorganic or organic monomers or polymers. Examples of neutral water-soluble salts are, for example, alkali metal, ammonium or substituted ammonium chlorides and sulphates. alkali metal salts of the foregoing;
Particularly preferred are sodium salts. Sodium sulfate is typically used in detergent granules and is a particularly preferred salt in the present invention. Other useful water-soluble salts are, for example, compounds commonly known as detergent builder substances. Builders are generally alkali metal, ammonium or substituted ammonium water-soluble phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, selected from carboxylic acid salts, and polycarboxylic acid salts. Preference is given to the alkali metal salts of those mentioned above, especially the sodium salts. Particular examples of inorganic phosphate builders are sodium and potassium tripolyphosphates, pyrophosphates, polymeric metaphosphates with a degree of polymerization of about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and ethane-1,1,2-
Sodium and potassium salts of triphosphonic acid. Other phosphorus builder compounds are described in U.S. Pat.
Specification No. 3159581, Specification No. 3213030, No.
Specification No. 3422021, Specification No. 3422137, No.
It is disclosed in specification No. 3400176 and specification No. 3400148. Examples of phosphorus-free inorganic builders are sodium and potassium carbonates, bicarbonates, sesquicarbonates, tetraborates + hydrates, and _SiO2 to alkali metal oxide weight ratios of about 0.5 to about 4.0, preferably Approximately 1.0~
It is a silicate with a value of about 2.4. Water-soluble phosphorus-free organic builders useful in the present invention include:
For example, various alkali metals, ammonium and substituted ammonium polyacetates, carboxylates,
Polycarboxylate and polyhydroxysulfonate. Examples of polyacetate and polycarboxylate builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, and sodium, potassium, lithium, ammonium, and substituted ammonium salts of citric acid. It's salt. Salts of nitrilotriacetic acid, such as sodium nitrilotriacetate, are particularly preferred. The polymeric polycarboxylate builder has a U.S. patent
It is described in the specification of No. 3308067. Substances of this type are water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Some of these materials are useful as water-soluble anionic polymers, but only in intimate admixture with non-soap anionic surfactants. Other builders useful in the present invention are sodium and potassium carboxymethyl oxymalonate, carboxymethyl succinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate. , and copolymers of maleic anhydride and vinyl methyl ether or ethylene. Other polycarboxylate salts suitable for use in the present invention are the polyacetal carboxylates described in US Pat. No. 4,144,226 and US Pat. No. 4,246,495. These polyacetal carboxylates can be produced as follows. The ester of glyoxylic acid and the polymerization initiator are placed together under polymerization conditions. The resulting polyacetal carboxylic ester is then coupled with chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solutions, converted to the corresponding salt, and incorporated into detergent compositions. Added. The water-soluble silicate solid is represented by the formula _SiO2.M2O , where M is _an alkali metal and has a _SiO2 : _M2O weight ratio of about 0.5 to about 4.0.
From about 2% to about 2% on a dry weight basis in the compositions of the invention
Salts are useful in amounts of about 15%, preferably about 3% to about 8%. Anhydrous or hydrated particulate silicates are available. In one embodiment of the water invention, an aqueous silicate solution containing about 35% to about 55% silicate solids can be used as an agglomerating agent. Water Soluble Anionic Polymers The compositions of the present invention can be used in intimate admixture with a non-soap anionic detergent surfactant, preferably from about 1 to about 50% by weight of the non-soap anionic detergent surfactant. about 30% by weight, more preferably from about 5 to about 20% by weight, of a water-soluble anionic polymer having at least one ionic site per 200 units of molecular weight, preferably at least one ionic site per 100 units of molecular weight. Also contains. The average molecular weight is preferably between about 300 and about 15,000, although some dispersion advantage is obtained with polymers with average molecular weights as high as 50,000.
Most preferably from about 1000 to about 5000. The water-soluble anionic polymer is also preferably a substantially or completely neutralized water-soluble salt. Average molecular weight herein is based on polymer weight. Polymers suitable for the present invention are homopolymers and copolymers of unsaturated aliphatic monocarboxylic or polycarboxylic acids. Suitable carboxylic acids are acrylic acid, hydroxyacrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, crotonic acid, and citraconic acid. Polycarboxylic acids (eg, maleic acid) can be polymerized in their anhydride form and then hydrolyzed. Copolymers can be produced from mixtures of unsaturated carboxylic acids and other copolymerizable monomers (with or without), or from a single unsaturated carboxylic acid and other copolymerizable monomers. can. In either case, the weight percent of polymer units derived from non-carboxylic acids is preferably less than about 50%. Suitable copolymerizable monomers include, for example, vinyl chloride, vinyl alcohol, furan, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate,
These are styrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and 3-butenoic acid. Homopolymers and copolymers of suitable monomers, such as sulfonates, sulfates, and phosphates, such as styrene, vinyl alcohol, vinyl chloride, and the like, are particularly useful in the practice of this invention. Approximately 2000~
Polystyrene sulfonates having molecular weights within the range of about 6000 are particularly useful in the practice of this invention. Other preferred polymers are homopolymers and copolymers of acrylic acid, hydroxyacrylic acid, or methacrylic acid, and their salts, with at least about 50 acid-derived units in the case of copolymers.
% by weight, preferably at least about 80% by weight. Particularly preferred polymers are sodium polyacrylate and sodium polyhydroxyacrylate. Most preferred is sodium polyacrylate. Other particularly preferred polymers are homopolymers and copolymers of maleic anhydride, particularly copolymers of maleic anhydride with ethylene, styrene and vinyl methyl ether. These polymers are commercially available under trade names such as Gantrez AN. Polymerization of acrylic acid homopolymers and copolymers can be accomplished using free radical initiators such as alkali metal persulfates, acyl and aryl peroxides, acyl and aryl peresters, and aliphatic azo compounds. The reaction can be carried out in situ or in an aqueous or non-aqueous solution or suspension. Chain terminators can be added to control molecular weight. Copolymers of maleic anhydride can be synthesized using free radical initiators of the type described above in an inert atmosphere in a suitable solvent such as benzene or acetone or in the absence of a solvent. These polymerization techniques are well known in the art. It will be appreciated that instead of using a single polymeric aliphatic carboxylic acid, a mixture of two or more polymeric aliphatic carboxylic acids can be used to form the polymer. In general, natural polymers such as pectyl, alginic acid, gum arabic and carrageenan and cellulose derivatives such as cellulose sulfate, carboxymethyl cellulose, hydroxypropyl cellulose and hydroxybutyl cellulose are not particularly useful in the practice of this invention. Building polymers that do not have sufficient ionic sites are also not particularly effective. Generally, these defects appear to be the result of a low ratio of ionic sites to molecular weight or too high a molecular weight. Optional Ingredients Nonionic surfactants can be present in the compositions of the invention. Nonionic substances of this type are, for example, compounds produced by condensation of an alkylene oxide group (hydrophilic) with an aliphatic or alkyl aromatic organic hydrophobic compound. The chain length of the polyoxyalkylene group that is fused with a particular hydrophobic group can be easily adjusted to produce a compound with the desired balance of hydrophilic and hydrophobic elements. Suitable nonionic surfactants are, for example, polyethylene oxide condensates of alkylphenols, such as those having 6 carbon atoms in either a straight or branched configuration.
Alkylphenols having alkyl groups having ~15 and about 3 to about 1 mole of alkylphenol
It is a condensate with 12 moles of ethylene oxide. Preferred nonionic surfactants include aliphatic alcohols having from 8 to 22 carbon atoms in either a straight or branched chain configuration and from about 3 to 22 carbon atoms per mole of alcohol.
It is a water-soluble condensate with about 12 moles of ethylene oxide. Alcohols with alkyl groups having about 9 to 15 carbon atoms and about 4 to 8 per mole of alcohol
Particular preference is given to condensates of molar ethylene oxide. Suitable semipolar nonionic surfactants include, for example (1)
a water-soluble amine oxide containing one alkyl moiety having about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to about 3 carbon atoms; 10-18
(3) a water-soluble phosphine oxide containing one alkyl moiety of and two moieties selected from the group consisting of alkyl groups having about 1 to 3 carbon atoms and hydroxyalkyl groups; A water-soluble sulfoxide containing one alkyl moiety and one moiety selected from the group consisting of alkyl moieties having about 1 to 3 carbon atoms and hydroxyalkyl moieties. Water-soluble salts of higher fatty acids, or "soaps", can be used in the present compositions. These are, for example, alkali metal soaps, such as the sodium, potassium, ammonium and alkanol ammonium salts of higher fatty acids having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be produced by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, ie, sodium or potassium tallow soaps and coconut soaps. Cationic surfactants can be utilized in the compositions of the present invention. Preferred cationic surfactants are quaternary ammonium compounds having one long-chain alkyl and three short-chain alkyl groups, such as dodecyltrimethylammonium chloride. The optional surfactant is preferably separated from the intimate mixture of non-soap anionic surfactant and polymer, but in non-interfering amounts such that the overall anionic character of the mixture is maintained. can be present in the mixture. Detergent compositions of the present invention have the formula Na _z [(CAlO ₂ ) _z ·(SiO ₂ ) _y ]·xH ₂ O, where z and y are at least about 6;
The molar ratio of z to y is about 1.0 to about 0.5, and x
from about 10 to about 264). Amorphous hydrated aluminosilicate materials useful in the present invention have the empirical formula M _z (zAlO ₂ .ySiO ₂ ), where M is sodium, potassium, ammonium, or substituted ammonium, and z is about 0.5
~2 and y is 1), and the material has a magnesium ion exchange capacity of at least about 50 milliquivalents of CaCO ₃ hardness per gram of anhydrous aluminosilicate. Aluminosilicate ion exchange builder materials are in hydrated form and when crystalline contain approximately 10 to
It contains about 28% by weight, and potentially even more if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain about 18% to about 22% water within their crystalline matrix. Crystalline aluminosilicate ion exchange materials are further characterized by a particle size of about 0.1 microns to about 10 microns. Amorphous materials are often smaller, for example smaller than about 0.01 microns.
Preferred ion exchange materials are about 0.2 microns to about 4
It has a particle size of microns. As used herein, "particle size" refers to the average particle size of a given ion exchange material as determined by conventional analytical techniques, such as microscopic measurements utilizing scanning electron microscopy. The crystalline aluminosilicate ion exchange material has a water hardness of at least 200 mg equivalent _CaCO3 /calculated on an anhydrous basis.
1g of aluminosilicate, typically about 300mg
They are usually further characterized by their calcium ion exchange capacity which is within the range of eq/g to about 352 mgeq/g. The aluminosilicate ion exchange material contains at least about 2 grains Ca ⁺⁺ /gal/min/
g/gal aluminate (anhydrous basis) and generally ranges from about 2 grains/gal/g/gal to about 6 grains/gal/gal based on calcium ion hardness.
They are still further characterized by their calcium ion exchange rate which is in the range of minutes/g/gallon. Aluminosilicates of choice for builders exhibit calcium ion exchange rates of at least about 4 grains/gal/min/g/gal. Amorphous aluminosilicate ion exchange materials typically contain at least about 50 mgeqCaCO ₃ /g (12 mgMg ⁺⁺ /
g) and ^{an Mg++ exchange} rate of at least about 1 grain/gal/min/g/gal. The amorphous material shows no observable diffraction pattern when examined by Cu irradiation (1.54 Å units). Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. Aluminosilicates useful in the present invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or can be synthetically produced. A method for making aluminosilicate ion exchange materials is described in US Pat. No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are available under the names Zeolite A, Zeolite B, and Zeolite X. In particularly preferred embodiments, the crystalline aluminosilicate ion exchange material has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O, where x is from about 20 to about 30, especially about 27 ). Other ingredients commonly used in detergent compositions can be incorporated into the compositions of the present invention. These include, for example, color speckles, bleaching agents such as perborates and percarbonates and whitening agent activators,
Foam enhancers or foam inhibitors, anticorrosion agents and corrosion inhibitors, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, fungicides, PH regulators, non-builder alkali sources, hydrotropes, Examples are toluene sulfonate and xylene sulfonate, enzymes, enzyme stabilizers, fragrances and water. The detergent composition of the present invention can form part of a composition containing a variety of materials suitable for detergent or other uses. The following non-limiting examples illustrate detergent compositions of the present invention. All percentages, parts and ratios used herein are by weight unless otherwise specified. Example 1 Copolymer of acrylamide and acrylate with 30% sodium salt of linear _C13 alkylbenzene sulfonic acid (sodium _C13 LAS), a molecular weight of about 15000 and an acrylamide content of about 12% 3
A slurry containing 15% sodium sulfate and 52% water was prepared. The slurry was spray dried to prepare granules containing sodium C ₁₃ LAS and an intimate mixture of acrylamide and acrylate copolymer. The water content was reduced to less than 10% by weight. A granular detergent composition containing the following ingredients was prepared.

[Table] NTA, sodium carbonate and sodium silicate in dry granular form in mullion mixer model
I put it in 2030. After mixing for 1 minute, add C _12-13 alcohol 6.5 ethoxylate as a spray,
It was then made to act as an agglomeration agent. The appropriate amount of the granular mixture of sodium C ₁₃ LAS, polymer and sodium sulfate was then added, followed by the addition of the hydrated silica. The resulting granular detergent product was sieved to remove large lumps in some cases, and the final product had a density of 0.67 g/ml. Entrapment Test This method is used to measure the entrapment potential of a granular detergent product relative to another comparison product. The comparison product is preferably a predetermined standard having a consumer-relevant entrapment profile. Tests are set to high stress conditions (low agitation, low temperature, high product to fabric ratio) to maximize visual differences between products. The entrapment test measures the ability or inability of granular detergent to dissolve or disperse from a closed fabric pocket during a gentle wash cycle in a full-scale washing machine. Equipment Full size washing machine - Kenmore or GE Black fabric - 4" x 6" (approx. 10.2cm x approx.
15.2 cm) Rectangular Stapler Operation Entrapment testing was performed in a full-size washing machine (17.5 gallon fill) in tap water at 60°C for 10 minutes on a gentle wash cycle (Kenmore 4848rpm; GE60rpm). ). 1 Make the four fabric pockets as follows. Create an open pocket by pinning two 4-inch x 6-inch (about 10.2 cm x 15.2 cm) rectangular black fabric pieces together along three sides. 2 Place 1/4 of the recommended use of the product to be tested into each of the four fabric pockets. 3. Each of the fabric pockets was stapled closed along the fourth side to create an airtight pocket. 4. Fill the washing machine with tap water at 60°C (approximately 15.6℃) and add the 4 pockets to the washing machine when starting stirring. 5 Remove the two pockets from the washer at the end of the wash-spin cycle. The other two pockets are removed at the end of the rinse-spin cycle. 6 Gently squeeze the pocket to remove excess water and blot between paper towels to remove additional water. 7 Open the pocket along three sides, then unfold and air dry. Comparisons between products are made after the pockets are completely dry. An entrapment test is used to make visual comparisons between products to determine relative solubility and solubility. The example composition was compared to a composition prepared by the same method but without the acrylamide/acrylate copolymer. The example compositions had substantial benefits as measured by the entrapment test. EXAMPLES Example compositions were prepared in an Aeromatic atomized granulator fluidized bed. An example slurry containing sodium C ₁₃ LAS and acrylamide/acrylate copolymer was sprayed onto a fluidized bed of suspended NTA and sodium carbonate with heated air. cooling the fluidized bed;
Then the remaining ingredients were added. The resulting granular detergent compositions have physical properties equivalent to the example compositions, such as dissolution rate and density, and substantial solubility advantages over products prepared without incorporating the polymer. EXAMPLE Dispersibility test for surfactants By adding 1 g of granules to 400 ml of room temperature water gently stirred with a magnetic stirrer, the acrylamide/acrylate copolymer of the example with sodium sulfate is tested. A sample of spray-dried C ₁₃ LAS without (10%) was tested. The time required to dissolve the sample without polymer was twice as long (25 minutes) as the sample with polymer (12 minutes). Additional evaluations obtained using the same procedure showed the following results. Table C ₁₃ LAS Polyacrylic acid (MW2000)% Dispersion time (min) 0 19 13.2 11 26.4 5 52.9 0.33

【table】

[Table] Example Sodium C ₁₃ LAS with polyacrylic acid at a concentration of 40.7% polymer in the paste
The following molecular weight dependence of the dispersibility of MW of Polyacrylic Acid Dispersion Time (min) Less than 1000 1/2 2000 1/2 5000 41/2 104000 28 1250000 75 Example The following composition was prepared by spray drying an aqueous clutter mixture of the following ingredients: did.
The moisture content of the clutcher mixture was about 38% and was reduced to about 8% by spray drying. Sodium polyacrylate having a molecular weight of 2000 was mixed with the anionic surfactant paste before adding the remaining ingredients to the clutcher.

Table: The resulting spray dried granules were dry mixed with the following ingredients: Ingredients Part Tetrasodium pyrophosphate 41.26 Sodium carbonate 5.21 Fragrance, enzyme, dust control agent 1.43 47.9 parts The water dispersibility of the resulting composition shows that it contains the same ingredients except that it does not contain sodium polyacrylate (average molecular weight 2000) and a composition containing the same ingredients but with sodium polyacrylate (average molecular weight
2000) was substantially superior to compositions that were not mixed with the anionic surfactant paste before mixing with other ingredients. Example The following composition was prepared.

【table】

[Table] Sodium silicate, sodium tripolyphosphate, maleic anhydride copolymer, CMC, magnesium sulfate and phosphor were first made into a clutter mixture with a water content of 42% and then spray dried to determine the density.
It gave a granular powder of 650-670 g/ml and a moisture content of 7%. This granular base powder has a diameter of 3 inches (about 7.6 cm).
Patterson-Kerich bird blender and the non-ionic surfactant was sprayed on for 2 minutes at a temperature of 40°C. When mixing was continued for another 8 minutes, the powder density was 800-830g/
It was hot. Sodium perborate, foam suppressor components, and enzymes are then dry mixed into the nonionic surfactant-containing powder using a Vertomix in-line mixer (manufactured by Babkotsk Gardner Limited) to determine the density. 790~800g/
powder. Pass the product through a 20 mesh sieve,
Those that were too large were then recycled to further reduce their size. LAS/SPA flakes were made from an aqueous slurry with a solids content of 50% by weight. The solids consisted of 90% LAS paste and 10% sodium polyacrylate (Goodrite K-759, sodium polyacrylate with a molecular weight of 2100 manufactured by the Gudryutsch Chemical Group). The slurry was dried on a heated roller with 35 psi steam and 80% LAS, 10% sodium polyacrylate, 7% sodium sulfate.
%, and was removed as a 0.25 mm thick flake with a moisture content of 3%. The flakes were broken up by stirring for 10 minutes in a cube mixer and the portion passing through a 20 mesh sieve was used as dry additive in the product. Add LAS to the rest of the product using the same operations as for dry mixing with other ingredients.
Addition of SPA flakes was carried out in a belt mixer to give a final product density of 750 g/. The final product had the following particle size distribution: On 14 mesh tiler 0% On 20 mesh 2.8% On 36 mesh 18.5% On 72 mesh 39.2% On 100 mesh 14.1% On 150 mesh 18.4% Through 150 mesh 7.0% The dispersion and solubility of the final product in water is excellent. Ta. LAS/SPA flake thickness of 0.10mm and 0.50mm
The example product is manufactured using LAS/SPA flake thickness. Comparable dispersion and solubility are obtained. EXAMPLE The present invention also helps reduce product loss at the sump or drain plug connection of front-load washing machines. In this type of washing machine, the sump comprises a drain plug located at the lowest point of the washing machine and a short length of piping connecting the plug to either the external casing or a member of the wash water recirculation system. are doing. The product is added to the washing machine via a dispenser and its contents are flushed into the outer casing of the washing machine by a stream of cold water at the beginning of the cycle. Product components that have low dissolution rates in cold water tend to collect in the sump, and this tendency is enhanced by the formation of a viscous surfactant phase that causes agglomeration of other components.
This tendency is particularly pronounced when the anionic surfactant is dry mixed with the remaining ingredients of the formulation, and the compositions of the present invention can be shown to overcome this problem. The following compositions were prepared. (a) Flaked composition NaLAS 88.9% Na ₂ SO ₄ + trace components 7.8% H ₂ O 3.3% (b) Flaked composition NaLAS 80% consisting of the following components Polyacrylic acid with a molecular weight of 2000 Sodium 10% Na ₂ SO ₄ + Minor 7% H ₂ O 3% Both flake compositions were prepared as in the previous examples. In a model test using a funnel fitted with a length of tubing simulating a washing machine sump and suitable for trapping undissolved material,
The percentage of original formulation remaining as residue in the sample was: Sample (a) 17.1% Sample (b) 4.5%

Claims (1)

[Claims] 1 (a) Non-soap anionic surfactant 3% to 40%
(b) 5 to 85% by weight of water-soluble neutral or alkaline salts or mixtures thereof; and (c) non-soap having an average molecular weight of 300 to 15,000 and at least one ionic point per 200 units of molecular weight. 1 to 50% by weight of an anionic surfactant of a water-soluble anionic polymer; A granular detergent composition, characterized in that it is produced by preparing an intimate mixture with said polymer. 2. The composition of claim 1, wherein the non-soap anionic surfactant comprises an alkali metal salt of a _C11-13 alkylbenzene sulfonic acid. 3. Claim 1, wherein the water-soluble anionic polymer is selected from the group consisting of polyacrylic acid and its water-soluble salts, copolymers of acrylamide and acrylates, polystyrene sulfonate polymers, and mixtures thereof. Composition of. 4. The composition of claim 1, wherein the water-soluble anionic polymer is in an amount of 5 to 20% by weight of the non-soap anionic surfactant. 5. The composition according to claim 1, wherein the water-soluble anionic polymer has a molecular weight of 1000 to 5000. 6. Claim 1, wherein the non-soap anionic surfactant is in an amount of 12 to 30% by weight of the granular detergent composition.
The composition described in Section. 7. Claims 1 and 2, wherein the water-soluble neutral or alkaline salt is a substance selected from the group consisting of alkali metal polyphosphates, alkali metal nitrilotriacetates, alkali metal sulfates, and mixtures thereof. The composition according to item 1, 3 or 6. 8. According to claim 1, wherein said intimate mixture of said non-soap anionic surfactant and said water-soluble polymer is agglomerated with said water-soluble neutral or alkaline salt or mixtures thereof. Composition of. 9. The intimate mixture of the non-soap anionic surfactant and the water-soluble polymer is mixed into an aqueous slurry also containing the water-soluble neutral or alkaline salt or mixtures thereof, provided that the slurry is
2. A composition according to claim 1, wherein the composition is spray-dried from a composition containing not more than % water by weight. 10 Claim 3, wherein the polymer is a substantially or completely neutralized salt of polyacrylic acid.
The composition according to item 1, item 8 or item 9.