CA1124609A - Slurried laundry detergent - Google Patents

Abstract

U. S. Serial No. 24,800 Filed March 28, 1979 Ref. 5647 SLURRIED LAUNDRY DETERGENT
Abstract of the Disclosure Heavy duty built laundry washing product in slurry form containing alkali metal hydroxide, detergents, sodium polyacrylate, a modified polyacrylic acid salt, and water insoluble aluminosilicate ion exchange material and/or complex phosphates, also optionally optical brightener, coloring agent, carboxymethyl cellulose and salts thereof, and perfume.

Description

4~

The invention is directeA to a hiqhly concentrated heavy duty built launclrv washing product in a form amenable to mechanieal metering (i.e., in slurry form), eontaining Na or K
hydroxides, detergents, water-insoluble aluminosilicate ion exchange material, or sodium tripolyphosphate or mix~ures theleof, sodium polyacrylate, a modified polyaerylie aeid salt and water and optionally optical brightener, coloring agent, sodium carhoxymethyl cellulose and perfume.
Both granular and liquid laundry products have a number of inherent deficiencies.
Granular products are subject to caking in their package or in t:he dispenser from which they are fed into the laundry machine. Thev contain bulk aids or fillers which serve no direct purpose in launclering fahric.
On the other hand, conventional liquid laundry washing prc~dlcts are limited in the amount of active in~redients which can ~-e clissolved in water ancl still provide a stable system.
We have discovered that incorporating the best properties of the liquid launclry deterqent and the granular laundry detergent into a single new laundry product was best achieved by using a novel blend in a slurry form.
The slurry form eliminates the eaking and the dusting of powclerecl launclry detergents and provides a positive means of mechanically dispensing into the laundry machine. It also provicles improved performance over liquid products, which are

- 2 -limited in concentration by the mutual compatibility of its ingredients. ~he use o~ a slurry allows the use of materials normally incompatible and/or insoluble since in a slurry, no true solution need he formed. Rather, a semi-fluid, essentially homogeneous mass is the only prerequisite for a satisfactory product.
Our new composition is particularly useful in areas where the water supply contains high calcium and magnesium hardness.
Our product has high physical stability. Kept at 120F~ for two weeks it shows only very slight separation. It i5 easily metered using a peristaltic dispensing pump.
Table 1 gives preferred and operable ranges for the components. Most of the components are discussed further below, particularly as to their preferred formsO

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o o o ô o o o O O Oo. 0 3, ~ ,~ n ~,, :: r ,~ o -~
1 ~ ~ ~ ~ u~ o ~
~s .~, ~ 3 3 I r D O
O N N O O ~; o o ~ ~o V ~ 3 ~ N

N r In .,1 L~ n ~: w 3 Q"J~ Q, 3.~
lo ~ o o o o o u~ C o a~ v ~L
¦~i ~ ~. O N~r ~ CO ~1 0 0 V O ~: a~ ~ V ~ N
1~ l l l l l l l Q, ~ ID ~,, ~ 3 ~ S '' o~1 o u~ o oo ~1 o o o Ir~ X ~1 o a~ s ~J ~ ¦ O _i Ui N O _i 0 0 0 0 0 ~ Ll Sl,s O ~ o ~ fi Ul 'J ~ S -e ~ r~d SV'o ~ ~ G ~ la ,1,~
¦ ~ o ~ : a~ o ~ 3 J
~. Iv ~ ~ c ~ ID O ~ L~ S ~ ~rl ~rl r ''I ~o ~r) ~ o o o. . . ~ 111 S U~ ~ o o ~
, 2~ ~ U ~ ~ I P' Q U
a~ 1 c o o ~ ~ ul Q) ~1 0 ~. ~
I e v ~ c ~ c ~ E S ~
a~ U ~ Q, ,~ U , 3 L U~ Ul ~ e ~ o ~ ~ v, v ~ c ~ ~
.,, m c ~ o ~ v ~ ~ ~ ~ e O r1 0 ~ S O ID 11) Ll O
U 1~ 'D~ C ~ O ~ ~ O SO ~ V N C U ~n U _ ~ ~ D O ' O rl v ~ ~ U~ ~ D ~ c U d~ I O ~ IS c U Itl v cl V ~ a ul ~ e m ~ al u c r1 n~ Ul V D 'O C Q ' ''~
v ~ a a C ~ ~ D, c al o ~ ~ s U~

~ v~ ~ J ~ C X Q~ ~ U u~ 3 e~ .C ul t~ 'ol ~ ,- e ~ Y a~ C~ o e ~

~ U ~ C o~' Q ff~ a S ~ ~ O UJ ~''~ U ~'V ~ S
,~ ~ ,' o ~ e ~ e E ", u~'o V ~,s ~ ~ ~ 'c'o ~

3 ~ ~ 3 z ~ ~ ~ o ~ ~ ~1 u fi ~ ~ 3 ~ ~ a ~ G s:~

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Example 1 A slurried detergent was prepared as follows. The lngredients as given in Column 1 of Tahle 1 were added in order to a kettle equipped with a jacket capable of heating and cooling and a mixer capable of running at a minimum of 150 rpm. Sufficient ingredients were used to make a 1000 pound mix. The water was added first, at 50 - 80 F. Next the modified polyacrylic acid was added, using a funnel disperser.
This component was added slowly to avoid lumping. It was admixed into the water with high agitation until dissolved.
The liquid caustic soda was added next and mixed for ten minutes. The alizarine blue dye was predissolved in three quarts of hot tap water and added to the batch. The ethoxylated alcohol detergent (non-ionic surfactant) was added slowly and mixed for ten minutes with maximum agitation. At this point water is run through the kettle jacket to provide cooling to 120 or less. The sodium tripolyphosphate was added slowly through a four-to-the-inch screen with the mixer going at the highest speed. A good rate of addition is five minutes per 100 pounds with a five-minute pause between each 100 pounds added. If the powder floats or otherwise does not mix or wet, allow more time between additions. The rate of addition of the sodium tripolyphosphate is very important for good mixing.
After all of the sodium tripolyphosphate is added, mix one hour. The temperature is maintained at 120 F or ]ess after the addition of the sodium tripolyphosphate. At the end of that time pull a sample for inspection. The sample should flow like a lotion with no curding. If curding occurs~ mix an additional hour and recheck. Continue mixing until smooth.

~2~6~3 Next add the sodium polyacrylate and mix for fifteen minutes.
Next add the ~odecyl benzene sulfonic acid ancl mix for fifteen minutes. Next add the sulfostyryl derivative and mix or one hour. This completes preparation of the composition.
In compositions that include sodium aluminosilicate and/or sodium carboxymethylcellulose, these should be stirred into the vesse] in similar fashion, with a view to eliminating lumps and sediment.
This slurried laundry product uses a water softener system suspended in a base thickened with a modified polyacrylic acid salt and a polyacrylic acid salt. The modified polyacrylic aci~ salt and the polyacrylic aci~ salt act as suspending aids to keep the water softener (zeolite, sodium tripolyphosphate or a variety of other water softeners known to the trade) suspended uniformly for pro]onged periods of storage.

Example 2 In order to make modified polyacry]ic acid polymers of the type of Example l, solution polymerization using the following reaction mixture can be used:
Raw MaterialParts by Weight -Acrylic acid98.75 Polyallyl sucrose l.25 Azoisobutyronitrile l.0 Benzene 880.0 The polymerization is carried out under autogenous pressure at 50 C until the reaction is complete, which may require 20 hours. The polymer formed is a fine friab]e powder~ The pow(ler, freed from solvent, is in the acid form, and is ready to use. Molecular weight is about 1,000,000. Preferably the product is neut{alized with alkali, e.g., NaOH or KOH, to develop its thickening properties in formu]ations. Such alkali is provided in the formulations in Tahle 1.
The polyallyl sucrose can be made by the allylation of sucrose. The sucrose is dissolved in concentrated aqueous sodium hydroxide solution, one and one-half equivalent weights of allyl chloride for every hydroxyl group in the sucrose molecule added and the mixture sealed in a reaction autoclave.
The autoclave and its contents are heated to 80 to 83 C for ahout five ho~lrs until no further drop in pressure occurs. The autoclave is cooled and the contents diluted with water until all precipitated salts are dicsolved. An organic layer separates out and is isolated and steam distilled. The crude product resulting from steam distillation is then washed with a large volume of ~ater. The wet polyallyl sucrose is then dissolved in toluene, decolori~ed with "Darco" activated charcoal and drie~ with sodium sulfate. The toluene is finally removed by distillation under reduced pressure at 100 C. The re~idue remaining is a polyallyl polyether of sucrose. It has an average of 5.~ allyl groups and 1.97 hydroxyl groups per molec-lle. The yield is ahout 91%.
The polymers formed from the reaction of polyallyl sucrose and acrylic acid as in Example 5 of U. S. Patent 2 798 053 are suitable as the allyl sucrose modified polyacrylic acid component of our composition.
Similar procedures for makinq the same or suhstantially the same acrylic-allyl sucrose copolvmers are given in U. S. Patent 4 130 401.

~2~6~9 Carhopol 941, a mo~ified polyacrylic acid available commercially from s. F. ~oodrich, is considered similar to that of Example 2 of our instant specification and is especially suitahle.
The above procedure (our Example 2) gives a polyacrylic acid modified hy slight cross-linking with polyallyl sucrose.
The molecular wei~ht is about 500,000 - 10,000,000, typically l,000,000. This material is herein referred to as allyl sucrose modified polyacrylic acid or (for purposes of hrevity, e.q., in Table 1) simply modified polyacrylic thickening agent.
~ ore comprehensively stated, the modified polyacrylic acid thickening agent can operably be the genus defined as a water dispersihle copolymer of an alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acid crosslinked with a polyether of a polyol selected from the class consisting of oliqo sacchari~es, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol, the hydroxyl groups of said polyol which are modifie~ heing etherified with allyl groups, said polyol having at least two allyl groups per polyol molecule, water ~isp~rsions of which are suitahle for use as suspension aids by adjustinq the P~ to the proper range. Examples of commercially availahle memhers of this class of resin are the Carhopol resins, i.e., Carhopol 934, Carbopol 940 and Carbopol 941, manufactured by B. F. Goodrich Chemical Company, Akron, Ohio.
~, ~
Particularly preferred is Carbopol 941. The Carbopol resins can he made by the process of IJ. S. Patent 2 798 053, above referenced.

2~

Some or the other components of our composition are herein described as follows.
The non-ionic suri:actant is preferably the reaction product of a linear Cl2- Cl5 alcohol with 3-12 moles of ethylene oxide. The 7 mole ethoxylate is preferred. Other nonionic detergents or mixtures thereof known to the trade are also suitably incorporated.
Sodium polyacrylate can have a molecular weight in the range 50,000 - 200,000. Typically the molecular weight is ahout 90,000. It is availahle as PSK-20 from Dearborn Div., Chemed Corp. (Molecular weights herein given are weight average unless otherwise stated.) The sodium polyacrylate is preferahly added in liquid form in solution, e.g., in water.
We prefer a 20% solution in water. Other monovalent polyacrylic acid salts are also suitable, as are monovalent polymethacrylic acid salts.
The alkyl aryl sulfonic acid and salts thereof are well known surfactant detergents and are available commercially as compounds of the formula alkyl - ~ SO3R, where the alkyl grou~ is C8 - Cl8 and R is Na, K, or H. The preferred product is linear dodecylben~ene sulfonic acid. Other anionic deter~ents or mixtures thereof known to the trade are also suitahly incorporated.
The optical hrightener or whitener is suitably 4,4'-di(2-sulfostyryl biphenyl), disodium salt, available commercially as Tinopal CBS from Ciha-Geiqy Corp. Numerous other suitable optical hriqhteners are commercially availahle, _ g _ ~ ,Z~

and the type is not critical, except that it be ~hemically staL>le in the medium of the composi~ion. A typical optical hrightener for laundry use is made hy dia~otization of 4-aminostllhene- 2-s~lfonic acld, fol]owed hy coupling with e.g., a naphthylamine derivative, and oxidation to the triazole compound.
The zeolite, a sodium aluminosilicate of the formula 12~(A12)12(Si2)121-XH2~ is availahle commercially as zeolite 4A from various sourcesr e.g., as Sylosiv 100 from W. R. Grace & Co. with X = 0-2, typically 1 or 2. When it is put in water, it rapidly hydrates until X =
aho~lt 20-30. I~ence, operationally, X = 0-30.
As for the polYphosphate, there are several well-known polyphosphates useful as Lui]ders in laundry operations, e.q., thP alkali metal pyrophosphates, sodium hexametaphosphate, s~dium tripolyphosphate, and the like. These are also known as complexin~ or condensed phosphates. When we use a polyphosphate, we prefer sodium tripolyphosphate, in powdered form.

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Claims (4)

WE CLAIM

1. A slurry detergent consisting essentially of:
Components Wt.
Water 25.0 - 80.
Water dispersible cross-linked interpolymer of a monomeric mixture comprising a monomeric polymerizable alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acid, and a polyether of a polyol selected from the class consisting of oligo saccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol, the hydroxyl groups of said polyol which are modified being etherified with allyl groups,said polyol having at least two allyl ether groups per polyol molecule 0.1 - 3.0 NaOH or KOH, dry basis 2.5 -25.0 Non-ionic detergent 0.0 -12.0 Polyphosphate 0. -30.0 Sodium polyacrylate, dry basis 0.2 - 4.0 Alkyl aryl sulfonic acid 0.0 -10.0 Optical brightener 0. - 2.0 Sodium aluminosilicate 0. -30.0 Sodium carboxymethylcellulose 0. - 2Ø

2. Slurry detergent according to Claim 1 consisting essentially of:
Components Wt. %
Water 45.0 - 73.00 Allyl sucrose modified polyacrylic acid made by co-polymerizing about 98-99.5 parts by weight of acrylic acid with about 0.5 - 2.0 parts of polyallyl polyether of sucrose having about 4-8 allyl groups per molecule 0.3 - 1.3 Liquid caustic soda 50% active 11.0 - 39.0 (Dry Basis) (5.5 - 19.5) Ethoxylated alcohol detergent, 3-10 moles ethylene oxide per mole of primary saturated C12-C15 alcohols 2.0 - 8.0 Sodium tripolyphosphate, powdered 0.0 - 20.0 Sodium polyacrylate, 20% soln. in water 1.0 - 10.0 Linear dodecyl benzene sulfonic acid 0.0 - 4.0 4,4'-di(2-sulfostyryl-biphenyl, disodium salt 0.05- 1.00 Sodium aluminosilicate, Na12[A102)12 (Si02)12]? XH20, where x = about 0-30 0.0 - 18.0 Sodium carboxymethylcellulose 0.5 - 1.5 ?

3. Slurry detergent according to Claim 2 consisting essentially of:
Components Amount Water 45.4 Wt.
Allyl sucrose modified polyacrylic acid made by co-polymerizing about 98.75 parts by weight of acrylic acid with about 1.25 parts of poly allyl polyether of sucrose having about 5.6 allyl groups per molecule 0.5 "
Liquid caustic soda 50% active 25.0 "
Brilliant alizarine milling blue BL 15 g./1000 lbs.
of formula Ethoxylated alcohol detergent, 7 moles ethylene oxide per mole of primary saturated C12- C15 alcohols 5.0 Wt. %
Sodium tripolyphosphate, powdered 16.0 "
Sodium polyacrylate, 20% soln. in water 6.0 "
Linear dodecyl benzene sulfonic acid 2.0 "

4,4' -di(2-sulfostyryl-biphenyl), disodium salt 0.1 "