JPS62169900A - Granular detergent composition having improved solubility - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to granular detergent compositions containing specific mixtures of alkylbenzene sulfonate surfactants, alkyl sulfate surfactants, alkali metal silicates, and water-soluble sulfates. The composition is prepared by drying, preferably by spray drying, an aqueous slurry containing the ingredients. The composition preferably also contains detergent builder materials, but the portion of the composition prepared by drying the slurry containing the sulfonate and sulfate surfactants, silicates and sulfates contains pyrophosphate or anhydrous Form I tripolymer. There should be relatively little or no phosphate builder.

Mixtures of alkylbenzene sulfonate and alkyl sulfate surfactants are desirable for optimal cleaning performance. However, such a mixture
It has a tendency to gel on contact with water. This can result in poor solubility of granules, especially when granules containing large amounts of alkylbenzene sulfonate and alkyl sulfate surfactants are incorporated into dense detergent compositions. be.

Highly soluble granular detergent compositions containing large amounts of alkylbenzene sulfonate surfactants and alkyl sulfate surfactants have a surfactant to silicate weight ratio of about 1.5:1 to about 6:1. It has now been found that detergent builder agents, silicates, sulfates and relatively little or no pyrophosphate or anhydrous Form I tripolyphosphate detergent builder material can be obtained by drying an aqueous slurry. In preferred compositions, these soluble detergent granules are mixed or agglomerated with the builder and any other detergent ingredients. Particularly preferred compositions include mixing the soluble granules with the builder and applying the mixture to relatively low pressures (e.g., about 20 to about 200 ps).
i) by compacting coa+pact) and optionally mixing with additional builders and other ingredients to give the final granular composition.

Background Art U.S. Pat. No. 4,028,283 discloses a granular detergent containing a surfactant with a tendency to caking and an anti-caking agent produced by reacting polyethylene glycol with an acid anhydride. are doing. The composition can also contain other surfactants such as alkylbenzene sulfonates. Spray-dried detergents containing mixtures of alkylbenzene sulfonate and alkyl ethoxy sulfate surfactants, silicates and builders are exemplified.

US Pat. No. 4,141,841 discloses granular detergents containing granular antistatic/softening additives.

In Example 8, the particles are mixed with a spray-dried base granule containing about 27% a mixture of alkylbenzene sulfonate and alkyl ethoxysulfate surfactants, 18% silicate, and about 22% sodium tripolyphosphate. ing.

JP-A-54-106509 discloses surfactants 15 to 15.
40%, silicate 5-20% and phosphene) 12%
Discloses a spray-dried granular detergent containing: The composition is said to have good physical properties and does not deposit significant amounts of insoluble matter on the fabric.

JP-A-60-72998 and JP-A-60-72
No. 999 discloses a compact compound prepared by neutralizing alkylbenzene sulfates and alkyl sulfates by high-shear mixing with sodium carbonate and water, mixing other ingredients such as builders, and then crushing and granulating the mixture. A granular detergent is disclosed.

SUMMARY OF THE INVENTION The present invention provides (1) by weight: (a) CII-013 in a weight ratio of sulfonate surfactant to sulfate surfactant of about 4:1 to about 1:4;
Alkylbenzene sulfonate surfactant and C12~0
Mixture with 1B alkyl sulfate surfactant approx.
(b) an alkali metal silicate ((
(c) about 10% to about 60% water-soluble sulfate; and (d) pyrophosphate or anhydrous Form I tripolyphosphate detergent. 0% builder substances or mixtures thereof
(2) preparing a base granule by drying an aqueous slurry containing the above ingredients to prepare a base granule containing 0 to about 30% of the base granule;
(3) consolidating said mixture at a pressure of about 20 to about 200 ps i; (4) granulating the resulting consolidated mixture; Prepared by mixing about 300% by weight of additional detergent builder material and has a bulk density of about 0.55
~about 1.2g/cc and uniform diameter of about 20 to about 1500
The present invention relates to a granular detergent composition having μ.

DETAILED DESCRIPTION OF THE INVENTION The granular detergent compositions of the present invention contain a weight ratio of Lefe-1 surfactant to sulfonate surfactant of from about 4:1 to about 1:
4, preferably from about 3:1 to about 1:3, more preferably from about 2:1 to about 1:2, of a mixture of CII-C13 alkylbenzene sulfonate surfactant and C12-01G alkyl sulfate surfactant. Approximately 85ffi
ffi%, preferably about 35 to about 60%ffi, more preferably about 40 to about 50%ffi.

Sulfonate surfactants useful in the present invention include water-soluble salts of alkylbenzene sulfonic acids in which the alkyl group has from about 11 to about 13 carbon atoms in a straight or branched configuration, particularly alkali metal salts, ammonium salts and alkanol ammonium salts. (e.g. monoethanolammonium salt or triethanolammonium salt), e.g. U.S. Pat.
．． 220,099 and 2.477.383. Linear straight chain alkylbenzene sulfonates having an average number of carbon atoms in the alkyl group of about 12 to about 13 are preferred.

Useful alkyl sulfate surfactants include C1° to C
16 Water-soluble, salts of linear or branched alkyl sulfates, especially alkali metal salts, ammonium salts and alkanol ammonium salts (eg monoethanol ammonium salt or triethanol ammonium salt). C-C, especially those containing a C14-12 15ゝC15 linear alkyl group are preferred.

The compositions may also contain trace amounts of other detergent surfactants known in the art (generally less than about 30%, preferably less than about 15% by weight of the sulfonate and sulfate surfactants). These include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants, such as those disclosed in U.S. Pat. No. 3,919,678. can be mentioned.

The compositions of the present invention also have a molar ratio of SiO2 to alkali metal oxide of about 1.0 to about 3.2, preferably about 1.6.
~2.4.

In particular, sodium silicate having a molar ratio of about 1.6 to about 2.2 is preferred.

Alkali metal silicates can be purchased either in liquid or granular form. Silicate solutions or slurries can be conveniently used to avoid having to dissolve the dry form into an aqueous slurry (eg, a clarification mix) of the ingredients of the invention.

Further, the weight ratio of alkylbenzene sulfonate + alkyl sulfate surfactant to alkali metal silicate of the present invention is from about 1.5:1 to about 6:1, preferably about 2:1.
1 to about 4:1, more preferably about 2.5:1 to about 3
．． Should be 5:1.

The composition further comprises about 10 to about 60% by weight water-soluble sulfate (preferably sodium sulfate), preferably about 2% by weight.
0 to about 50% by weight. Sodium sulfate is typically produced in the sulfation/sulfonation and neutralization steps in the production of the alkylbenzene sulfonates and alkyl sulfonate surfactants of the present invention.

The composition is prepared by drying an aqueous slurry containing the above ingredients. Slurry is generally about 25% water.
~70%, preferably about 40% to about 60%,
Dry granules, on the other hand, initially contain about 1% to about 10% water, preferably about 1% to about 3% water. The drying step can be accomplished by any convenient means, such as by using spray drying towers (both counter-current and co-current), fluidized beds, flash dryers, or industrial microwave dryers or oven dryers. It can be achieved. These are U.S. Pat.
, 019,998 (especially column 14, line 19 to column 15, line 9).

The granular detergents of the present invention are highly soluble in wash water even though they contain polyalkylbenzene sulfonate surfactants and alkyl sulfate-1 surfactants. Good solubility is obtained when the weight ratio of total sulfonate plus sulfate surfactant to silicate is within the aforementioned range of about 1.5:1 to about 6:1. Without wishing to be limited by theory, it is believed that this relatively high amount of silicate provides structure and helps maintain the integrity of the high surfactant granules, which allows the surfactant to is believed to minimize gelation when in contact with wash water. However, if the amount of silicate becomes too large (e.g.
Surfactant to silicate ratio of 1:1), the overall solubility may deteriorate due to the formation of silicate insolubles. on the other hand,
For example, granules with a surfactant to silicate ratio of 8:1 tend to have insufficient structure and be too crab-like at these high surfactant levels.

For good solubility, the pyrophosphate in the part of the granular detergent obtained by drying the aqueous slurry of the essential ingredients of the present invention should also be minimized. It is. Thus, the composition may contain from 0 to about 20%, preferably from 0 to about 15% by weight, of such detergent builder materials or mixtures thereof.
% by weight, more preferably from 0 to about 10% by weight. Most preferably, the composition is substantially free of such detergent builders (eg, contains less than about 5% by weight builder, preferably less than about 3% by weight).

The compositions may also be formulated with other detergent builders, such as U.S. Pat.
up to about 60% by weight of those described in No. 25,262;
Preferably, it can contain from about 1 to about 45% by weight. Builders generally include various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxysulfonates, polyacetates, selected from carboxylic acid salts and polycarboxylic acid salts. The alkali metal salts of the foregoing are preferred, especially the sodium salts.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphates (form ■ or hydrated form I)
, a polymeric metaphosphate having a degree of polymerization of about 6 to 21, and an orthophosphate.

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 the sodium salts of ethane-1゜1,2-triphosphonic acid. salt and potassium salt. Other phosphorus and luda compounds are described in U.S. Pat. No. 3,159,581; U.S. Pat. No. 3,213.030; No. 3,400.176, and No. 3,400,
No. 148.

Examples of phosphorus-free inorganic builders are sodium and potassium carbonates, bicarbonates, sesquicarbonates, and tetraborate decahydrates.

Water-soluble phosphorus-free organic builders useful in the present invention include various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, and the sodium, potassium, and lithium salts of citric acid,
ammonium salts and substituted ammonium salts.

High-molecular polycarboxylate builder also has U.S. Pat.
, 308,067. Such substances include 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.

Other builders of use in the present invention are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopenkunetetracarboxylate, phloroglucinol tricarboxylate. sulfonic acid salts, and copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are U.S. Pat.
44,226 and U.S. Pat. No. 4.246.4
It is a polyacetal carboxylate described in No. 95 specification. These polyacetal carboxylates are
It can be generated as follows. The ester of glyoxylic acid and the polymerization initiator are placed together under polymerization conditions. The resulting polyacetal carboxylic ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solutions and convert it into the corresponding salt.

A preferred phosphate builder is sodium tripolyphosphate (STP), preferably anhydrous. A preferred builder for use in compositions that are substantially free of phosphate builders is sodium citrate.

When mixed, the builder of the present invention should have the same particle size as the rest of the composition, as described below.

The granular detergent composition can be used as is as a final detergent composition or as a detergent additive composition. However, they are preferably used as detergent-based granules (hereinafter referred to as detergent-based granules). These detergent base granules are then mixed or agglomerated with builder substances and other optional ingredients to give a final detergent composition exhibiting good solubility. Such compositions contain from about 5% to about 50%, preferably from about 10% to about 40%, more preferably from about 100 to about 25%, by weight, of the alkylbenzene sulfonate and alkyl sulfate surfactants of the present invention.
and from about 5% to about 95% detergent builder substances as described above.
, preferably about 10% to about 85%, more preferably about 1
00 to about 75%. However, for best solubility, the amounts of pyrophosphate and anhydrous Form I tripolyphosphate should be minimized. That is, the final composition preferably contains from 0% to about 20%, preferably from 0% to about 10% of such materials, or mixtures thereof.

The composition may also contain trace amounts (generally less than 30% by weight, preferably 20% by weight) of other ingredients normally incorporated into detergent compositions.
(less than) can be contained. These ingredients include auxiliary detergent surfactant, color speckle (color 5peck)
les), bleaching agents, and bleach activators, foam enhancers or foam inhibitors, anti-tarnish agents and anti-corrosion agents, l
Includes tri-precipitation inhibitors, tri-stripping agents, dyes, fillers, optical brighteners, disinfectants, pH adjusters, non-builder alkalinity sources, enzymes, enzyme stabilizers, and six ingredients.

Agglomeration can be carried out by stirring in the presence of a suitable binder (e.g. in a fluidized bed, tumble mixer, or rotating drum or pan) or by mechanical mixing under pressure (e.g. extrusion, press , machine kneading, consolidation or pelletizing). Final sizing can then be achieved by grinding and sieving.

In a preferred embodiment, the detergent base granules contain from 0% to about 300%, preferably from about 25% to about 200%, more preferably from about 50% to about 150%, by weight of the base granules, of a detergent builder material as described above. Mix with. The resulting mixture is then preferably heated to about 20% to about 200%, preferably about 4%
Consolidate at a relatively low pressure of 0 to about 150, more preferably about 50 to about 100 bonds per square inch (psl).

The composition is then preferably applied at a concentration of 0 to about 300% of the base granules.
% by weight of additional detergent builder material, preferably from about 25 to about 200%, more preferably from about 50 to about 150%. The size and type of builder material and compaction pressure are preferably such that the final detergent composition has a bulk density of about 0.
．． 55 to about 162, preferably about 0.65 to about 1.1,
More preferably about 0.7 to about 0.9 g/cc and average particle size of about 20 to about 1500 microns, preferably about 50 to about 12
00μ, more preferably about 100 to about 800μ.

The consolidation step is preferably accomplished by using a device that applies a relatively uniform consolidation pressure, such as by using a consolidation roller having a smooth or non-corrugated surface. After consolidation, the composition is preferably granulated and sieved to provide an average particle size similar to the desired average particle size in the final composition.

The following non-limiting examples illustrate detergent compositions of the present invention.

All percentages, parts and ratios refer to
It is based on weight.

Example I The following granular detergent composition was prepared.

Final set heavy metal % per use of base granule Acid g Sodium C13 linear alkylbenzenesulfonate 22.1 5.110
0 Alkyl sulfate 14-15 Thorium 22.1 5.11
0 Sodium silicate (ratio 1.0) 13.7 3.
172 Sodium sulfate 32.2 7.4
55 polyethylene glycol (molecular weight 8000) 1.5 0.
340 Sodium polyacrylate (molecule ff14500) 2.0
0.453C alcohol poly 12-13 ethoxylate (8) 3.0 0.6
80 Diethylenetriamine Sodium Pentaacetate 1.5 0.340
Moisture 2.0 0.462 23.122 Preblend base granules 23.122 Sodium tripolyphosphate hexahydrate (powder form) 20.578
43.698 Mixture preblend 43.098 Sodium tripolyphosphate hexahydrate (granular) 19.42
9 Dye 0.003 Brightener 0.813 Foam suppressor Prill consisting of dimethyl silicone, silica, sodium tripolyphosphate and polyethylene glycol (molecule 08000) 1.703 Protease
2.044 Sodium carbonate
4.00071.490 Spray-on Mixture 71.490 Mineral Oil 0.710 72.200 Claracha - Using a temperature of 200 (approx. 93°C), a size 3 nozzle to prepare fine granules, and a silicone defoamer. By spray drying the aqueous clarification mix of ingredients in a 10 foot tower,
A base granule was prepared. If the base granules contained more than 2% moisture, a second drying step in a continuous fluidized bed was performed to reduce the moisture to 2%.

The base granules were then mixed with powdered STP hexahydrate to prepare a preblend. The preblend was consolidated in a 4 inch by 10 inch chllsonator at 50 psig roll pressure and sieved to -14(i)
A particle size cut (Tyler mesh) of i68μ)/+65 (208μ) was selected. Collect excessive particles, 14
Granulated in a Pltzaill using mesh sieves and low rprrl. Sort this through a sieve-
Particle size cuts of 20 (833μ)/148 (295μ) were selected. Both materials were dedusted by blowing away the fines in a fluid bed dryer using ambient air.

Blend the mixture in a drum mixer to 400 lbs.
1.4 kg)/batch. carbonate, granular STP
(dye sprayed), brighteners, enzymes, and foam suppressor prills were blended with the consolidated mainstream product cuts and regranulated overs (ovcrs).

The mainstream product cut to over weight ratio was 7:1. Forberg Mixer
) to add 30 to 40 pounds of mineral oil (approximately 13.6
~18.1 kg) was sprayed onto the final mixture in a 1% amount in batches.

The composition of Example 1 is preferably formulated into a laminated laundry product formed from two plies of water-insoluble tissue (at least 19 of which are water permeable) that are laminated together. At least nineteen of the plies have a cup-shaped recess surrounded by a rim, the other ply being joined to the first ply at the rim to physically separate the cups. - In embodiments, the laminate is
Made from plies of tissue paper as specified in the issue specification.

The tissue had good breathability as described in US Pat. No. 4,170,565. There are 12 cups each having a capacity of about 20 cc and at least 8 of the cups contain 9 cc of detergent composition.
g (llcc) and fill the other cups with at least 19 detergent aids. Other materials that can be used to form suitable laminates and methods of forming suitable laminates are described in 198
No. 728,070, filed April 29, 1984, and US Patent Application No. 675,804, filed November 28, 1984.

The composition of Example I exhibits excellent solubility when incorporated into the laminated laundry products.

EXAMPLE ■ The following granular detergent composition can be prepared and used according to Example I.

Final set weight % per base granule use Acid g Sodium C13 linear alkylbenzene sulfonate 15.75 6.81
C14-15 alkyl sodium sulfate 15°75 G,
81 Sodium silicate (ratio 1.6) 7.88 3.
41 Sodium sulfate IJ UA 23.01
9.95 Polyethylene glycol (molecular weight 8000) 0.78 0
44 Sodium polyacrylate (molecules! 14500) 1.05
0.46C12-13 alcohol polyethoxylate (8) 1,57 0.6
8 Sodium citrate 32.15 13.9
0 unreacted material 0.35 0.15
Moisture 1.7 0.73 43.23 Preblend base granules 43.23 Sodium aluminosilicate (hydrated zeolite A1 average diameter 3μ) 14.90 Sodium carbonate 3.00G1.1
3 mixture preblend et, ta brightener o, 53 foam suppressor capsule consisting of dimethyl silicone, silica, sodium tripolyphosphate and polyethylene glycol (molecule fik 8000) 0.91 protease 1.0083.57

Claims (1)

Claims: 1. (1) C_1_1 to C_1 in a weight ratio of (a) sulfonate surfactant to sulfate surfactant from about 4:1 to about 1:4;
_3 alkylbenzene sulfonate surfactant and C_1
_2 to about 30% to about 85% mixture with C_1_6 alkyl sulfate surfactant; (b) molar ratio of SiO_2 to alkali metal oxide of about 1.
(a) to about 3.2 (weight ratio of (a) to (b) from about 1.5:1 to about 6:1); (c) water-soluble sulfate from about 10% to about 60%; %, and (d) pyrophosphate or anhydrous form I tripolyphosphate detergent builder substances or mixtures thereof from 0%
(2) prepare a base granule containing about 20% (said base granule by drying an aqueous slurry containing the above ingredients); (3) consolidating said mixture at a pressure of about 20 to about 200 psi; (4) granulating the resulting consolidated mixture; and (5) 0 to about 300% by weight of the base granule. with a bulk density of about 0.55 to about 1.2 g.
/cc and an average particle size of about 20 to about 1500μ. 2. The base granules contain from about 35% to about 60% sulfonate and sulfate surfactants in a weight ratio of sulfonate surfactant to sulfate surfactant of about 2:1 to about 1:2.
% of the composition of claim 1. 3. Sulfonate surfactants are C_1_2 to C_1_3
3. The composition of claim 2, wherein the composition is a sodium linear alkylbenzene sulfonate and the sulfate surfactant is a C_1_4 to C_1_5 linear sodium alkyl sulfate. 4. The weight ratio of (a) to (b) is about 2.5:1 to about 3
．． 5:1 composition according to claim 1. 5. The weight ratio of (a) to (b) is about 2:1 to about 4:1, and the alkali metal silicate has a molar ratio of SiO_2 to alkali metal oxide of about 1.6 to about 2.4. 4. A composition according to claim 3, which is a sodium silicate comprising: 6. Base granules are pyrophosphate or anhydrous I
A composition according to claim 1 comprising from 0 to about 10% of a tripolyphosphate detergent builder material or mixture thereof. 7. Base granules are pyrophosphate or anhydrous I
6. The composition of claim 5, which is substantially free of tripolyphosphate detergent builder materials. 8. The composition of claim 1, wherein the base granules are mixed in step (c) with from about 50 to about 150% by weight of the base granules of a detergent builder material. 9. The detergent builder substance is sodium tripolyphosphate6.
The composition according to claim 8, which comprises a hydrate. 10. The composition of claim 1, wherein the mixture of step (2) is consolidated at a pressure of about 40 to about 150 psi. 11. The composition of claim 10, wherein the mixture of step (2) is compacted at a pressure of about 50 to about 100 psi. 12. Add the compacted mixture of step (3) to about 50 to 50% of the base granules.
11. The composition of claim 10 in admixture with about 150% by weight of additional detergent builder material. 13. The composition of claim 1 having a bulk density of about 0.7 to about 0.9 g/cc. 14. The composition of claim 8, wherein the mixture of step (2) is compacted at a pressure of about 40 to about 150 psi. 15. Add the compacted mixture of step (3) to about 50~
15. The composition of claim 14 in admixture with about 150% by weight of additional detergent builder material. 16. Approximately 50~
A composition according to claim 7 in admixture with about 150% by weight of sodium tripolyphosphate. 17. The composition of claim 16, wherein the mixture of step (2) is compacted at a pressure of about 50 to about 100 psi. 18. The compaction mixture of step (3) is added to the base granules at about 50 to
18. The composition of claim 17 in admixture with about 150% by weight of additional detergent builder material. 19. The composition of claim 18 having a bulk density of about 0.7 to about 0.9 g/cc. 20. The composition of claim 1, wherein the base granule further comprises up to about 60% by weight of a detergent builder material other than pyrophosphate or anhydrous Form I tripolyphosphate builder. 21. Base granules are pyrophosphate or anhydrous
I about 1 to about 45 tripolyphosphate or anhydrous detergent builder substances other than tripolyphosphate builder
21. A composition according to claim 20, comprising % by weight. 22. The composition of claim 1, which is substantially free of phosphate builder substances. 23. The composition of claim 22 further comprising sodium citrate. 24. A laminated selection product consisting of two plies of water-insoluble tissue, wherein: (1) at least one ply is water permeable; and (2)
At least one ply defines more than one cup (each cup is surrounded by the rim of that ply). (3) the second ply is sealed to the first ply at least at the rim of the cup to physically separate the cup so that the contents of the cup remain in place; (a) C_1_1 to C_1 with a weight ratio of sulfonate surfactant to sulfate surfactant of about 4:1 to about 1:4;
_3 alkylbenzene sulfonate surfactant and C_1
_2 to about 30% to about 85% mixture with C_1_6 alkyl sulfate surfactant; (b) molar ratio of SiO_2 to alkali metal oxide of about 1.
(a) to about 3.2 (weight ratio of (a) to (b) from about 1.5:1 to about 6:1); (c) water-soluble sulfate from about 10% to about 60%; %, and (d) pyrophosphate or anhydrous form I tripolyphosphate detergent builder substances or mixtures thereof from 0%
(ii) preparing a base granule containing from about 20% to about 300% by weight of the base granule (the base granule being prepared by drying an aqueous slurry containing the ingredients); (iii) consolidating said mixture at a pressure of from about 20 to about 200 psi; (iv) granulating the resulting consolidated mixture; and (v) from 0 to about 300% by weight of the base granule. Prepared by mixing additional detergent builder materials with a bulk density of about 0.55 to about 1.2 g
/cc and an average particle size of about 20 to about 1500 microns.