JPS6052192B2 - detergent composition - Google Patents

Description

[Detailed description of the invention] Background of the invention This invention relates to aluminosilicate ion exchange materials.

More particularly, the present invention relates to aluminosilicate ion exchange materials that rapidly and effectively remove divalent and polyvalent cations from water. Aluminosilicates are rapid and effective water softeners and can be used in detergent compositions as detergent builders to replace water-soluble builders traditionally used in detergent compositions. Various naturally produced aluminosilicates, usually viscous! It has long been recognized that earth mineral forms of aluminosilicates can sequester or remove calcium hardness from water.

For example, 1 SOAP Volume 3, #3, 3-1
Rao i (RaO) described on page 3 (1950)
Report on Surface Active Agents and Detergents by Schwartz et al.
2, pp. 297 et seq. (1966). It has been proposed to use zeolites, particularly naturally occurring aluminosilicate zeolites, in laundry compositions.

See US Pat. No. 2,213,641 and US Pat. No. 2,264,103. Various aluminosilicates,
It has been proposed for use as an additive in or with detergent compositions.

For example, US Patent Nos. 9238 and 1419625, British Patent Nos.
See the specifications of No. 62591 and No. 522097. A synthetic zeolite aluminosilicate particularly suitable for gas adsorption is described in US Pat. No. 2,882,243.

US Pat. No. 3,310,373 describes a method for producing crystalline aluminosilicate. US Patent No. 36
74426, the above-mentioned U.S. Patent No. 28822
No. 43 describes the use of heavy metal oxyacids to enhance the adsorption properties of synthetic biolites. However, the synthetic zeolite aluminosilicates described in the prior art are calcined to have optimal gas adsorption properties. Such materials do not have the requisite cation exchange rates and exchange capacities necessary to be effective water softeners and detergent builders. US patent application Ser.

Although this complex crystalline aluminosilicate is useful for its intended purpose, it is somewhat limited in that they only sequester calcium sulfide ions and have virtually no effect on hydride magnesium ions. . U.S. Patent Application No. 3
No. 59,923 describes overcoming these difficulties by using an auxiliary water-soluble builder material with the aluminosilicate to control mixed hydride. It can be seen from the above that a variety of methods have been used in the past to remove water-hardening cations from water. Particular attention is paid to removing water-hardening cations from aqueous laundry systems simultaneously with the wash cycle of domestic laundry operations. To be truly useful in laundry detergent compositions, an ion exchange material must have sufficient cation exchange capacity to significantly reduce water hardness in the laundry bath without the need for excessive amounts of ion exchanger. must have. Furthermore, the ion exchange material must act quickly. That is, water-hardening cations in aqueous laundry baths must be reduced to acceptable levels within the limited amount of time available (approximately 10-12 minutes) during the wash cycle of a home laundry operation. Optimally, the effective ion exchange material contains about 65 to 130 mg (about 1 to 2 grains) of both calcium and magnesium hydride per gallon during the first 1 to 3 minutes of the wash cycle. It should be possible to reduce the Finally, useful cation exchange builders are desirably substantially water-insoluble inorganic materials that present little or no ecological problem in sewage. Certain amorphous aluminosilicate materials and amorphous monocrystalline mixed aluminosilicate materials exhibit the high ion exchange capacity and rapid ion exchange rate necessary for cation exchange builder materials useful in laundry detergent compositions. It has now been found that it has both.

Additionally, amorphous aluminosilicates and amorphous-crystalline mixed aluminosilicates have been found to control both calcium and magnesium hydration cations without the need for supplemental water-soluble builders. It is therefore an object of the present invention to provide an aluminosilicate ion exchange material that sequesters both calcium and magnesium ions from aqueous solutions.

Another object of the present invention is to provide an aluminosilicate ion exchange material having sufficient ion exchange capacity and rate for both calcium and magnesium ions to be useful as a detergent builder. It is a further object of the present invention to provide detergent compositions containing insoluble amorphous inorganic aluminosilicate ion exchange materials that control both Ca++ and Mg++ water hardening without the need for auxiliary builders.

Optionally, the detergent composition may also contain crystalline aluminosilicates. These and other objects are achieved by the present invention as will be seen from the following description.

SUMMARY OF THE INVENTION The present invention contemplates an aluminosilicate ion exchange material that can rapidly reduce the content of both calcium and magnesium metal ions (mixed hydride) in aqueous solutions.

There are two types of aluminosilicate materials in this invention, each useful as a detergent builder.

The first type of material has an empirical formula (wherein X is a number from 1.0 to 1.2) and has a water hardening CacO
3 as 50-150m9 equivalent Mg+1 exchange capacity, 1
Approximately 65 mg to approximately 195 mg (1 to 3 grains) per y/y
Mg++ exchange rate of 3.785' (1 gallon)/min, 1
200 to 352 m9 equivalent of Ca+8 exchange capacity as water hardening CacO3 per y and about 130 to about 390 m per y
g (2-6 grains)/3.785e (1 gallon)/min calcium exchange rate, characterized by a particle size of approximately 0.01-5μ in diameter, insoluble in water containing 10-2% water by weight is an amorphous hydrated aluminosilicate ion exchange builder material.

The second type of aluminosilicate builder material consists of an amorphous monocrystalline mixed aluminosilicate ion exchange builder material comprising: (a) the general formula (where x
is an integer from about 20 to about 301, preferably 27), with a particle size of about 1 to about 10 microns in diameter and at least about 200 mg equivalents of hardened CacO3 per y aluminosilicate/y, calculated on an anhydrous basis, generally is about 300 to about 35
characterized by a calcium ion exchange capacity of 2m9 equivalents and further containing at least about 130 mg (about 2 grains)/3.78 as Ca++ per y of aluminosilicate on an anhydrous basis.
5' (1 gallon)/min, generally a calcium ion exchange rate of about 2 to about 6 grains/Gal/min/g based on hardened calcium ions.
(b) a water-insoluble crystalline aluminosilicate ion-exchange material characterized by: 50-150 as water hardening CacO3 per 1V
Mg++ exchange capacity for Tn9 equivalents, about 65 to about 1 per gram
95m9 (1-3 grains)/3.785e (1 gal)/min Mg+8 exchange rate, water hardening CacO3 per y
as 200 to 352 mg equivalent Ca++ exchange capacity and about 130 to about 390 m9 (about 2 to 6 grains per y).
/3.785e (1 gallon)/min calcium exchange rate, characterized by a particle size of about 0.01-5μ in diameter, 10-2
water-insoluble amorphous hydrated aluminosilicate ion exchange builder material containing 1:4 to about 4:1, preferably about 1
:1 weight ratio of amorphous aluminosilicate to crystalline aluminosilicate.

DETAILED DESCRIPTION OF THE INVENTION The amorphous and mixed amorphous monocrystalline aluminosilicate ion exchange builders of the present invention are characterized by a process that produces materials particularly suitable for use as cleaning builder and water softener agents. made with

Specifically, the aluminosilicate of the present invention has a higher calcium ion exchange capacity and a higher exchange rate than similar materials previously proposed as cleaning bilters. Furthermore,
The aluminosilicates of this invention sequester magnesium ions sufficiently to be useful as builders for cleaning applications. It is clear that the desirable ion exchange properties of the aluminosilicates of this invention are a function of several interrelated factors resulting from their preparation.

Amorphous aluminosilicate exhibits both Ca++ and Mg++ control, amorphous monocrystalline mixed aluminosilicate also exhibits both Ca++ and Mg++ control, whereas pure crystalline aluminosilicate exhibits both Ca++ and Mg++ control.
Indicates a + only control. Therefore, to control mixed hydride, the ion exchange material of the present invention can be used as a substantially pure amorphous aluminosilicate and in a substantial proportion of . It is provided as a mixture containing a combination of the above amorphous aluminosilicate and crystalline aluminosilicate. The amorphous aluminosilicate provided by the present invention can control hydride in the mixture. It can be seen from the above that it is recognized and preferred as a 5-ion exchange builder due to its properties.

However, it is difficult to produce pure amorphous materials on an industrial scale. Amorphous monocrystalline mixed aluminosilicates are more easily obtained and, when made with the appropriate amorphous to crystalline ratios described above, exhibit excellent control of mixed hydrides. The first essential characteristic of both the amorphous and mixed amorphous monocrystalline ion exchange builder materials of the present invention is that they are in monosodium form.

For example, it has surprisingly been found that the potassium and hydrogen forms of the aluminosilicate do not exhibit the exchange rates or exchange capacities necessary for optimal builder applications. A second essential property of the ion exchange builder materials of the present invention is that they are in hydrated form, ie, contain from about 10 to about 2 weight percent water.

The highly preferred aluminosilicate of the present invention has a theoretical maximum amount of water in its crystal matrix of about 18 to
Contains about 2% by amount. For example, it has been found that less preferred hydrated aluminosilicates, such as those having about 6% water, do not function effectively as ion exchange builders when used in laundry detergent compositions. Additionally, the amorphous aluminosilicates of the present invention are stable under processing conditions commonly used in the manufacture of spray-dried detergent compositions.

That is, the amorphous aluminosilicate of the present invention has a
It retains mixed hydride control properties even after being heated to 00°C. This is unusual since other amorphous aluminosilicates lose their ion exchange properties when heated. A third essential characteristic of the ion exchange builder materials of the present invention is particle size range.

Of course, the amorphous aluminosilicate of the present invention has an inherently small particle size (approximately 0.01-5 micron diameter). It is desirable that the crystalline portion of the amorphous-crystalline mixed material has a small particle size within the above range. Proper selection of small particle size results in a long-lasting and extremely effective builder material. Additionally, the small particle size of the aluminosilicates of the present invention probably accounts for the fact that they are less likely to be deposited on fabrics from aqueous wash liquors. Of course, it is desirable that this precipitation not occur when aluminosilicate is used as a detergent builder. The method described below for making the aluminosilicates of the present invention is specifically designed to make such materials in an amorphous state.

In particular, the method uses highly concentrated solutions, which tend to favor rapid production of amorphous particles. The concentration of the solution is
Limited only by the need to inject and effectively mix the reactants. Additionally, the method takes into account all of the following essential elements for making an effective aluminosilicate builder material.

First, the method avoids contamination of the aluminosilicate product with cations other than sodium. Second, the process is designed to form the aluminosilicate in its most highly hydrated form. Therefore, avoid high temperature heating and high temperature drying. Third, the method is designed to form the aluminosilicate material as a finely divided state with a narrow range of small particle sizes. Of course, additional milling operations can be used to further reduce the particle size. However, the need for such mechanical downsizing steps is substantially reduced by the method described below. The chemical reactions involved in making the aluminosilicate of the present invention are complex due to the large number of possible reactions that can occur when mixing aluminate and silicate in an aqueous basic medium.

Under the reaction conditions used for this reaction, each reactant initially appears to form an amorphous aluminosilicate material that undergoes further rearrangements before being converted to a crystalline aluminosilicate. So the amorphous-crystalline conversion is not stepwise, but occurs throughout the process because the reaction system is in a dynamic state. Although it is theoretically possible to mix the reactants and cool the reaction at a suitable temperature to ensure only the desired amorphous aluminosilicate, this is not feasible in large scale manufacturing. In practice, the method produces a mixture of amorphous aluminosilicate and crystalline aluminosilicate at a point where a substantial portion (approximately 50 and more) of the amorphous material has not yet been converted to the crystalline form. Designed to stop the reaction. These desirable results are obtained by using highly concentrated mixtures of each reactant in the method described below and by carefully controlling the reaction times. After producing the amorphous-crystalline mixture, the mixture can be separated by suspending it in water. The crystalline material then settles and the amorphous material remains suspended. The aluminosilicate ion exchange builder and water softener material of the present invention is made by the following method: (a) Sodium aluminate (Na,AlO2) and sodium hydroxide are mixed in water with the following weights of each component: Form a mixture with the ratio (preferred ratio): H2O/NaAlO2 = 29:1H
20/NaOH = 5.2:1 NaA102/NaOH = 1.8:1 If made at lower temperatures, the mixture of aluminate and sodium hydroxide is not a true solution but contains small amounts of finely dispersed particulate matter. .

The temperature of the mixture is adjusted to about 20-70°C, preferably about 50°C. (b) Sodium silicate solution (solid content = approximately 3% by weight, SlO2:Na2O = 3.2:1) in the process (
Add quickly to the mixture in a).

This rapid mixing step can be carried out using a vessel equipped with an effective stirrer. Alternatively, the mixture of the two at the desired temperature can be metered into an in-line mixer, which can be part of the main tank system, for a continuous process. The ratio of NaAlO2 to sodium silicate (on an anhydrous basis) is about 1.6:1, which is in excess of NaA]02 with respect to the composition of the aluminosilicate builder material. (C) The mixture of step (b) is rapidly heated to 75-95°C.
(preferably 80-85 bC), and at this temperature 1
Maintain 0 to 6 particles (preferably 10 to 2 particles).

(d) The slurry obtained in step (c) is cooled to about 50°C and filtered.

The resulting filter cake is collected and washed in water with sufficient water to obtain a wash water to solids (anhydrous basis) weight ratio of about 2.0:1 (preferred ratio). Repeat the above cleaning and washing operations. The filter cake made by the above method comprises an approximately 1:1 (weight ratio) mixture of crystalline aluminosilicate and amorphous aluminosilicate. The material obtained from the filter cake shows rapid and efficient absorption of both Ca+8 and Mg++ ions. The filter cake itself is useful as an ion exchange material. For use in powder or granular detergent compositions, the filter cake is dried to an ice content of about 10 to about 2 percent by weight using a drying temperature of less than about 175° C. to avoid excessive dehydration. is preferred. Preferably, the drying is carried out at 100-105°C. If desired, the amorphous aluminosilicate of the present invention can be separated from the amorphous-crystalline mixture made by the above method by simply suspending the filter cake mixture in water.

When suspended in this manner, the crystalline portion of the mixture settles out (over a period of about 1 to 6 hours), whereas the amorphous material remains suspended in the aqueous medium. The amorphous material can be separated by decantation or other physical means. Of course, low speed centrifugation can be used to more quickly separate the amorphous component of the mixture from the crystalline component. The aluminosilicate made by the above method is a mixture of amorphous and crystalline materials.

The crystalline part of the aluminosilicate is characterized by a cubic crystal structure. Of course, amorphous materials have irregular structures,
Not amenable to analysis by X-ray diffraction. Both crystalline and amorphous aluminosilicate ion exchangers have a calcium ion exchange capacity of at least 200 m9 equivalents of hardened CacO3 per y of aluminosilicate, generally from about 300 to about 352 m9 equivalents, calculated on an anhydrous basis. Further features.

The ion exchange material in the present invention further comprises (on an anhydrous basis)
At least 130 TrLg (2 grains)/3.785' (1 gallon) per y of aluminosilicate (as Ca++), typically from about 130 to about 390 mg (from about 2 to about 6 grains) based on hardened calcium ions. )/
It is characterized by a calcium ion exchange rate of Gal/min/da. Aluminosilicates of choice as builders contain at least about 25 ymg (4 grains)/Gal/min/y of Ca.
+8 indicates exchange rate. The aluminosilicate ion exchanger further has aluminosilicate 1y calculated on an anhydrous basis.
It is characterized by a magnesium exchange capacity of at least about 50 m9 equivalents, and generally about 50 to 150 m9 equivalents, per water hardening CacO3. Furthermore, the ion exchange material
(anhydrous standard) per 19 aluminosilicate (Mg++
) at least approximately 65 m9 (1 grain)/Gal/
minutes, generally 65 to about 195 m9 (1 to about 3 grains)/Gal/minute/based on hardened magnesium ions.
It is characterized by the magnesium ion exchange rate of y.

Aluminosilicates of choice as builders exhibit a magnesium exchange rate of at least about 130 m9 (2 grains)/Gal/min/y. The ion exchange properties of aluminosilicates are conveniently determined by calcium ion electrodes and divalent ion electrodes.

In this technique, the absorption rate and capacity of Ca++ and Mg+1 from an aqueous solution containing known amounts of Ca++ and Mg++ are determined as a function of the amount of aluminosilicate ion exchange material added to the solution. More specifically, the ion exchange rate of each amorphous and amorphous monocrystalline mixed aluminosilicate is determined as follows. The aluminosilicate prepared by the above method was in sodium form at a concentration of 0.06% by weight, PHLO. O, (Ca
3.785e (measured as cO3) per gallon.
05 m9 (4.7 grains) of Ca++ and 156 m9 (
150 ml of an aqueous solution containing Mg+8 (2.4 grains)
Add the solution to the solution with gentle stirring. The consumption rate of calcium is measured using a calcium electrode [Orion (0rj0n) available commercially], and the total consumption rate of calcium and magnesium is determined using a general divalent cation electrode. The removal of magnesium ions is then determined by the difference between those readings. Depletion rates are determined by measuring each cation at appropriate time intervals. Calculate the total depletion from the solution after 1 sip. This 10 minutes corresponds to the normal washing time in an aqueous washing method. Curves for the depletion rate of calcium, the depletion rate of magnesium, and the combined depletion rate of calcium and magnesium are plotted as Mg (grains)/time versus time.
′ (gallons). The calcium exchange capacity of aluminosilicate is determined by a simple titration method.

In practice, an aluminosilicate sample is treated with a known excess of Ca+
Equilibrate at 1. After equilibration and adsorption of calcium ions, excess calcium ions remaining in the solution are removed using a standard Eriochrome Black T indicator (
EriOchrOmeBlackTIndjcatOr
) by standard titration with EDTA. The magnesium ion exchange capacity is determined titrimetrically in a similar manner. As mentioned above, both the crystalline and amorphous components of the aluminosilicate exhibit excellent exchange rates and exchange capacities for calcium ions.

Moreover, the amorphous material additionally provides rapid and effective absorption of magnesium ions. Therefore, the mixture of crystalline and amorphous materials is hardened with "Ca++ and Mg++".
and provide control of the mixture. The following example is a typical pilot plant scale production of an amorphous monocrystalline mixed aluminosilicate ion exchange builder.

As mentioned above, amorphous aluminosilicate is easily removed from crystalline aluminosilicate by suspending the filter cake in water. The crystalline portion of the mixture settles out (on standing for about 1-6 hours) and the amorphous portion remains suspended in the water. The parts can be separated by decantation or other mechanical means. Example 1 Typical charges used in the pilot plant were as follows: The pilot plant consisted of a 208f (55 gallon) adiabatic reactor with a wall plate and a recycler with a Lightnin propeller-type mixer. It consisted of a side arm heat exchanger equipped for circulation and fed by a gear pump.

The pump had a rated capacity of 18.9' (5 gallons) per minute. The effluent stream from the reactor is passed through another heat exchanger where the effluent stream is cooled and then vacuum rotated? was fed to the filter. The cake from the filter was placed in a tank equipped with a Lightnin propeller mixer in which the cake was reslurried with wash water. The slurry was then fed to a vacuum rotary strainer and the cake was collected or rewashed as desired. A metering pump was included as an auxiliary device to supply the silicate raw material solution at the desired rate. Water was charged to the reactor, followed by sodium aluminate and sodium hydroxide.

The mixture was stirred until the aluminate was dissolved. The temperature was adjusted to 50°C. Sodium silicate at 50° C. was then metered into the aluminate solution at a rate of about 35'b per minute. Maximum agitation was required at this stage of the operation to prevent solidification of the slurry. The slurry was stirred for about 1 minute to break up any lumps and ensure complete contact between each reactant. The slurry is then passed through a measuring arm heat exchanger to reduce its temperature to about 80-1
00°C and maintained in this temperature range for approximately 1 hour.
The slurry was then passed through another heat exchanger, cooled to about 3rC and filtered. The cake was washed several times with water. The aluminosilicate prepared by the above method consisted of an approximately 50:50 (weight ratio) mixture of the following two components:
a) Formula 1 - 1 - - Particle size of 1 to 20μ, approximately 324m9 (5 grains)
/Gal/min/g Ca++ exchange rate and approximately 300 mg
and (b) a crystalline hydrated aluminosilicate having a Ca+8 exchange capacity of equivalent/y; and (b) having a general formula (wherein Amorphous aluminosilicate characterized by a magnesium ion exchange capacity of 125 mg equivalent.

suspending the mixed filter cake material in water for about 6 hours;
Next, the upper layer liquid containing the amorphous substance was taken out and dried to separate the amorphous aluminosilicate from the crystalline aluminosilicate.

The detergent compositions of the present invention may contain all embodiments of water-soluble organic detergent compounds.

Because it's aluminosil. This is because gated ion exchangers are compatible with all such materials. Typical examples of the types of detergent compounds useful in the present invention are U.S. Pat.
It is described in the specification of No. 961. The patent specification is hereby incorporated by reference. The detergent compounds and mixtures described below that may be used in the compositions of the present invention are representative of, but not limited to, such materials. Water-soluble salts of higher fatty acids, ie, soaps, are useful as detergent ingredients in the compositions of this invention.

Detergents of this type include common alkali metal salts such as sodium, potassium, ammonium and alkyl ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 100 carbon atoms. There is soap. Soaps are made by direct saponification of fats and oils or by neutralization of fatty acids. Particularly preferred are the sodium and potassium salts of fatty acid mixtures derived from tallow and tallow, ie tallow and tallow based sodium or potassium soaps. Other types of detergents include water-soluble salts of organic sulfuric acid reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and an ester group of sulfonic acid or sulfuric acid, especially alkali metals. salts, ammonium salts and alkylolammonium salts. The term 1-alkylo above also includes the alkyl portion of an acyl group).

Examples of synthetic detergents of this group which form part of the detergent compositions of the invention are the sodium and potassium salts of alkyl sulphates, especially higher (C8-Cl8) alcohols made by reducing the glycerides of tallow or apricot oil. and sodium and potassium salts of alkylbenzene sulfonic acids in which the alkyl group has from about 9 to about b carbon atoms in a straight or branched configuration;
For example, U.S. Pat. Nos. 2,220,0 and 2,477
, No. 383. Of particular value are linear straight chain alkylbenzene sulfonates (abbreviated as Cl3LAS) in which the average number of carbon atoms in the alkyl group is about 13. Other anionic detergent compounds include: sodium alkyl glyceryl ether sulfonates, especially these ethers of higher alcohols derived from tallow and castor oil; sodium salts of sulfonic and sulphate esters of castor oil fatty acid monoglycerides; and A sodium or potassium salt of an alkylphenol ethylene oxide ether sulfate containing about 1 to about 1 position of ethylene oxide per molecule, the alkyl group containing about 8 to about 12 carbon atoms.

Water-soluble nonionic synthetic detergents are also useful as detergent components of the compositions of the present invention. Generally speaking, such non-ionic detergent materials are compounds made by the condensation of an alkyl oxide group (hydrophilic) with an organic hydrophobic compound (which may be aliphatic or alkyl aromatic). can be defined. The chain length of the polyoxyalkylene group condensed with any particular hydrophobic group can be easily adjusted to yield a water-soluble compound with the desired balance of hydrophilicity and hydrophobicity. for example,
A well-known non-ionic synthetic detergent is Pluronik (PlLlr).
'0niC). It is available on the market under the trade name J. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol. Other suitable nonionic synthetic detergents include condensates of alkylphenols and polyethylene oxide, such as alkylphenols with alkyl groups in the form of straight or branched chains containing about 6 to 12 carbon atoms and ethylene oxide. , in which the ethylene oxide is present in an amount of 5 to 25 moles per mole of alkylphenol. Water-soluble condensation products of aliphatic alcohols in linear or branched chain form with 8 to 22 carbon atoms and ethylene oxide, e.g. An oil-based alcohol-ethylene oxide condensate, in which the oil-based alcohol moiety is 10 to 14
Those with 5 carbon atoms are also useful nonionic detergents.

Semipolar nonionic detergents include one alkyl group having about 10 to 28 carbon atoms and two groups selected from the group consisting of alkyl groups containing from 1 to 3 carbon atoms and hydroxyalkyl groups. a water-soluble amine oxide containing one alkyl group having about 10 to 28 carbon atoms and about 1 to 28 carbon atoms;
a water-soluble phosphine oxide detergent containing two groups selected from the group consisting of an alkyl group containing 3 carbon atoms and a hydroxyalkyl group: and one alkyl group having about 10 to 28 carbon atoms. and two groups selected from the group consisting of alkyl groups containing 1 to 3 carbon atoms and hydroxyalkyl groups.

Amphoteric detergents include derivatives of aliphatic heterocyclic secondary and tertiary amines in which the aliphatic groups are straight or branched and one of the aliphatic substitutions is about 8 to 18 carbon atoms and at least one of its aliphatic substitutions
Some contain anionic water-solubilizing groups.

Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds;
the aliphatic group is straight or branched and contains one or about 8 to 18 carbon atoms of the aliphatic substituents, and one of the aliphatic substituents carries an anionic water-solubilizing group; There are some things that it contains.

Other useful detergent compounds include about 6 in the fatty acid group.
~20 carbon atoms and about 1 in the ester group
Water-soluble salts of esters of alpha-sulfonated fatty acids containing ~W carbon atoms: about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane group water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing; alkyl ether sulfates containing about 10 to 2 carbon atoms in the alkyl group and containing about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonic acids containing 12 to 24 carbon atoms;
There are β-alkyloxyalkane sulfonates containing about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane group. Preferred water-soluble organic detergent compounds include about 11 to 1 in the alkyl group.
Linear alkylbenzene sulfonates containing 4 carbon atoms; tallow-based alkyl sulfates; oil-based alkyl glyceryl sulfonates; alkyl ether sulfates, the alkyl group of which contains about 14 to 18 carbon atoms; whose average degree of ethoxylation is 1 to 6; sulfated condensation products of tallow alcohols and about 3 to 10 moles of ethylene oxide; olefin sulfonates containing about 14 to 16 carbon atoms; alkyl dimethyl An amine oxide, the alkyl group of which contains about 11 to 1 carbon atoms. Alkyldimethyl-ammoniopropane-sulfonates and alkyldimethyl-ammoniohydroxypropane-sulfonates in which the alkyl group contains about 14 to 1 carbon atom: Soaps as described above:
There are condensation products of tallow fatty alcohols and about 11 moles of ethylene oxide: and condensation products of Cl3 (average) secondary alcohols and 9 moles of ethylene oxide.

Particularly preferred detergents for use in the present invention include: linear ClO-Cl8 alkylbenzene sulfonate sodium di-ClO-Cl8 alkylbenzene sulfonate triethanolamine; tallow-based sodium alkyl sulfate; oil-based alkyl glyceryl ether sulfone. Sodium salt of a sulfated condensation product of a tallow alcohol and about 3 to about 10 moles of ethylene oxide; a condensation product of an oil fatty alcohol and about 6 moles of ethylene oxide;
Condensation product with moles of ethylene oxide: 3-(N,N
-dimethyl-N-alkylammonio)-2-
Hydroxypropane-1-sulfonate; 3-(N,N
-dimethyl-N-amphialkyl ammonio)-propane-1-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; dodecyldimethylamine oxide; Water-soluble sodium and potassium salts of higher fatty acids containing 24 carbon atoms.

It should be appreciated that any of the detergents mentioned above may be used separately or as a mixture.

Examples of preferred detergent mixtures are as follows. A particularly preferred alkyl ether sulfate detergent component of the compositions of the present invention is a mixture of alkyl ether sulfates having an average (arithmetic mean) of about 12 to 16 carbon atoms, preferably about 14 to about 1,000 carbon atoms. It has a carbon atom and an average (arithmetic mean) degree of ethoxylation of about 1 to 4 moles of ethylene oxide, preferably about 2 to 3 moles.

U.S. Patent No. 306,3 (filed November 13, 2019)
9) Please refer to the specification.

The application specification is incorporated herein as a reference document. In particular, such preferred mixtures include Cl2~
Mixture of 13 compounds about 0.05-5% by weight, Cl4-1
55-70% by weight of a mixture of 5 compounds, about 25-40% by weight of a mixture of Cl6-17 compounds, and about 0.1-5% by weight of a mixture of Cl8-19 compounds. Furthermore, such preferred alkyl ether sulfate mixtures include 0
about 15-25% by weight of a mixture of compounds with a degree of ethoxylation of from 1 to 4, about 50-65% by weight of a mixture of compounds with a degree of ethoxylation of from 5 to 8, about 12-25% by weight of a mixture of compounds with a degree of ethoxylation of from 5 to 8. 2 weight percent, and about 0.5 to 1 weight percent of a mixture of compounds with a degree of ethoxylation greater than 8. Examples of alkyl ether sulfate mixtures falling within the ranges specified above are shown in Table 1.

Preferred olefin sulfonate detergent mixtures useful in the present invention include olefin sulfonates containing from about 10 to about 24 carbon atoms.

Such materials are made by sulfonating alpha-olefins with uncomplexed sulfur dioxide and then neutralizing under conditions such that any sultone present is hydrolyzed to the corresponding hydroxy-alkanesulfonate. That α-
The olefinic starting material preferably has 14 to 1 carbon atoms. The preferred alpha-olefin sulfonates are described in U.S. Pat. No. 3,332,880.
The patent specification is hereby incorporated by reference. Preferred α-olefin sulfonate mixtures consist essentially of the following: from about 30% to about 70% by weight of Component A, from about 20% to about 70% by weight of Component B, and from about 2% to about 15% by weight of Component C: (a) the components; A is a double bond regioisomeric mixture of a water-soluble salt of an alkene-1-sulfonic acid containing from about 10 to about 24 carbon atoms, and the regioisomeric mixture is about the α-β unsaturated isomer. 10 to about 25%, about 30 to about 70% β-γ unsaturated isomers, about 5 to about 2 γ-δ unsaturated isomers
(b) component B contains from about 10 to about 24 carbon atoms and contains difunctionally substituted sulfur; It is a mixture of water-soluble salts of saturated aliphatic compounds containing a mixture of water-soluble salts of saturated aliphatic compounds, the functional units of which are a hydroxyl group and a sulfonate group, the sulfonate group always being on the terminal carbon, and the hydroxyl group being at least the number of carbon atoms from the terminal carbon atom. bonded to two carbon atoms apart and at least 90% of its hydroxyl substitutions
% in the 3, 4, and 5 positions; and (c) the component C is about 30 to 95% a water-soluble salt of an alkene disulfonate containing from about 10 to about 24 carbon atoms; and from about 10 to 95%; A mixture containing from about 5 to about 70% of a water-soluble salt of a hydroxy disulfonate containing about 24 carbon atoms, wherein the alkened disulfonate includes a sulfonate bonded to a terminal carbon atom and a number of carbon atoms from the terminal carbon atom. a second sulfonate group attached to internal carbon atoms that are no more than about 6 apart, the alkene double bond being between the terminal carbon atom and approximately the 7th carbon atom, and the hydroxydisulfonate is a sulfonate group attached to a terminal carbon atom,
A second sulfonate group bonded to an internal carbon atom that is about 6 or less carbon atoms away from the terminal carbon atom, and bonded to a carbon atom that is about 4 or less carbon atoms away from the bonding position of the second sulfonate group. It is a saturated aliphatic compound with a hydroxyl group.

In addition to the aluminosilicate ion exchange builders, the detergent compositions of the present invention may also contain supplementary water-soluble builders such as those commonly considered for use in detergent compositions. Such auxiliary builders are used to aid in the sequestration of water hardening ions in the wash liquor and to improve the pH of the wash liquor.
Used to help regulate. Such co-builders are present at concentrations of from about 5 to about 5 weight percent, preferably from about 10 to about 35 percent by weight of the detergent compositions of the present invention, so as to provide their co-builder and PH regulating effects. used. As auxiliary builders there are any customary inorganic and organic water-soluble builder salts. Such an auxiliary builder is
For example, water-soluble salts of phosphoric acid, pyrophosphoric acid, orthophosphoric acid, polyphosphoric acid, phosphonic acid, carbonic acid, polyhydroxysulfonic acid, silicic acid, polyacetic acid, carboxylic acid, polycarboxylic acid, and succinic acid can be used.

Specific examples of inorganic phosphates include the sodium and potassium salts of tripolyphosphoric acid, phosphoric acid, and hexametaphosphoric acid. Specifically, polyphosphonates include, for example, sodium and potassium salts of ethylenediphosphonic acid, sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and ethane-1,1,
There are sodium and potassium salts of 2-triphosphonic acid. Examples of these and other phosphorus-based builder compounds are given in U.S. Patent No. 3,159,581;
9) No. 3,422,021, No. 3,422,13
No. 7, No. 3,400,176 and No. 3,400,14
It is described in each specification of No. 8. These US patent specifications are hereby incorporated by reference.
Phosphorus-free sequestering agents may also be selected as co-builders for use in the present invention.

Specific examples of non-phosphorous inorganic supplemental detergent builder components include water-soluble inorganic carbonates, bicarbonates, and silicates.

Particularly useful are the alkali metal salts of carbonic, bicarbonate, and silicic acids, such as the sodium and potassium salts. Water-soluble organic co-builders are also useful in the present invention.

For example, alkali metal, ammonium and substituted ammonium salts of polyacetic acids, carboxylic acids, polycarboxylic acids and polyhydroxysulfonic acids are useful co-builders in the compositions of this invention. Specific examples of polyacetate and polycarboxylate builders include the sodium salts of ethylenediaminetetraacetic acid, nitriloacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acid, and citric acid;
There are potassium salts, lithium salts, ammonium salts and substituted ammonium salts. Highly preferred non-phosphorus co-builder materials include sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, and mixtures thereof.

Another highly preferred auxiliary builder is U.S. Pat.
It is a polycarboxylate builder described in US Pat. No. 08067. The patent specification is hereby incorporated by reference. Examples of such materials 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. Additional preferred auxiliary builders include:
Water-soluble salts of carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and chloroglucinoltrisulfonic acid, especially the sodium and potassium salts.

The detergent compositions of the present invention may contain all types of additive materials commonly found in laundry and cleaning compositions.

For example, the compositions of the invention may include thickening agents and soil suspending agents such as carboxymethyl cellulose and the like. Enzymes commonly used in laundry detergent compositions, particularly proteolytic and lipolytic enzymes, may also be present in the compositions of the present invention.Various fragrances, fluorescent brighteners, fillers, anti-caking agents, fabrics. Softeners and the like may also be present in the composition in order to obtain the usual benefits derived from the use of such materials in detergent compositions. It should be appreciated that such materials are useful in the present invention because they are compatible with, and stable in the presence of, ion exchange builders. made by any of several known methods for.

For example, the composition can be made by simply mixing an aluminosilicate ion exchange material and a water-soluble organic detergent compound. If desired, optional builder substances and auxiliary ingredients can be simply mixed therewith. Another method is to spray dry an aqueous slurry of aluminosilicate ion exchange builder containing dissolved water-soluble organic detergent compounds and optional auxiliary substances in a column to obtain a granular composition. I can do it. Such spray-dried detergent composition granules contain an aluminosilicate ion exchange builder, an organic detergent compound, and optional materials. Ion-exchanged aluminosilicates can also be used in combination with standard cationic softeners for fabrics during fabric rinsing.

When so used, the aluminosilicate removes water-hardening cations, resulting in a softer catalytic effect on the softened fabric. Typical fabric cationic softeners useful in combination with aluminosilicate ion exchangers include tallow trimethylammonium bromide, tallow trimethylammonium chloride, ditallow dimethyl ammonium bromide, and ditallow dimethyl ammonium chloride. . Aqueous fabric softener compositions containing aluminosilicate ion exchangers include from about 5 to about 95 weight percent amorphous aluminosilicate and from about 1 to about 35 weight percent cationic fabric softener. The detergent compositions of the present invention can be applied as an aqueous solution using any of the standard laundry and cleaning techniques.
Used to clean surfaces, especially fabric surfaces.

For example, the compositions of the present invention can be washed in a standard automatic washer with approximately 0.0
It is particularly suitable for use at concentrations of 1 to about 0.50% by weight. Compositions of the present invention may be used in an aqueous laundry bath at least about 0.0%.
Optimal results are obtained when used at a level of 1% saliva volume. As is the case with most commercial detergent compositions, the dry compositions of the present invention typically contain about 1 ml per 17 gallons of wash water.
．． It is added to a conventional aqueous laundry solution at the rate of 0 cups. Aluminosilicate ion exchange builder materials have a wide range of P
Hydrogenated calcium and magnesium ions act to remove calcium and magnesium ions over a period of about 8.5%, but detergent compositions containing such materials have a concentration of about 1.2% in solution.
It is preferred to exhibit a pH within the range of 0 to about 11, preferably about 9.5 to about 10.5.

As with other standard detergent compositions, the compositions of the present invention work best within the basic pH range for removing soils and triglyceride stains. Although aluminosilicates inherently result in basic solutions, detergent compositions containing aluminosilicates and organic detergent compounds can additionally contain from about 5 to about 25 weight percent of a PH modifier. Of course, such compositions can optionally include water-soluble builders and adjuvants as described above. The PH adjusting agent used in such compositions is selected such that the PH of the 0.05% by weight aqueous mixture of the composition is in the range of about 9.5 to about 10.5. P, an optional component useful in the present invention
The H regulator can be any of the water-soluble basic materials commonly used in detergent compositions. Typical examples of such water-soluble substances include sodium phosphate, sodium silicate, sodium hydroxide, potassium hydroxide, triethanolamine, diethanolamine, ammonium hydroxide, and the like.
Preferred pH adjusting agents include sodium hydroxide, triethanolamine and sodium silicate. The use of aluminosilicate materials as water softeners and detergent builders is illustrated below: Example: Insensitivity to hard water containing aluminosilicates. The laundry soaps are as follows:
★． A 50:50 (by weight) mixture of amorphous aluminosilicate and crystalline aluminosilicate prepared in Example 1.

The above soap composition is 3.785e (1 gallon) per 7
Water hardening Ca++ and Mg up to 78 m9 (12 prenes)
Provides excellent cleaning and foaming performance in hard water containing a mixture of ++. Fabrics washed in an aqueous bath containing 0.15% by weight of the above built soap are not coated with soap stains caused by the formation of insoluble Ca++ and Mg++ soap precipitates. In the above composition, replacing the amorphous monocrystalline mixed aluminosilicate builder with an equal amount of the amorphous aluminosilicate builder made in Example 1 gives equivalent results.

In the above composition, a 50:5 mixture of amorphous aluminosilicate and crystalline aluminosilicate is mixed with an 80:5 mixture of amorphous aluminosilicate and crystalline aluminosilicate.
:20,70:30,60:40,40:60,30:
Good hard water washability can be obtained by replacing them with 70:80, 20:80 and 10:90 (weight ratio) mixtures, respectively.

The following example illustrates the use of aluminosilicates in laundry detergent compositions containing synthetic detergents:★
A 50:50 (by weight) mixture of amorphous aluminosilicate and crystalline aluminosilicate made in Example 1.

Example Make a mist-dried detergent composition with the following composition:★
Made using the method described in Example 1.

The above composition is 454 g/3.785e (1 gallon)
mg (7 grains) of water-hardening Mg++ and Ca++ when used under conventional home laundry conditions in a laundry liquor containing a mixture of hardened Mg++ and Ca++ at a composition concentration of about 0.1% by weight in the laundry liquor. Gives the fabric excellent washing performance.

Under such conditions, the foaming and cleaning performance of the example compositions is comparable to that of conventional, fully built, high foaming anionic detergent formulations. Such compositions are pourable and can be made in conventional spray drying equipment. In the above example compositions, sodium tallowalkyl sulfate is equal to potassium tallow alkyl sulfate, sodium oleic alkyl sulfate, potassium oleic alkyl sulfate, sodium decylbenzenesulfonate, sodium undecylbenzenesulfonate, tridecyl sodium benzenesulfonate,
Replace with sodium tetradecylbenzenesulfonate, sodium tetrapropylenebenzenesulfonate, potassium decylbenzenesulfonate, potassium undecylbenzenesulfonate, potassium tridecylbenzenesulfonate, potassium tetradecylbenzenesulfonate, and potassium tetrapropylenebenzenesulfonate, respectively. Sometimes compositions with substantially similar performance characteristics are obtained.

In the example composition described above, an equal amount of the condensation product of Cl5 secondary alcohol and 9 moles of ethylene oxide is
Condensation product of tridecyl alcohol and about 6 moles of ethylene oxide (IIL, B=11.4) Condensation product of an oil fatty alcohol and about 6 moles of ethylene oxide (
I(L,B=12.0)NeOdOl)
23-6.5 (HL, B=12); Neodol 25-9
(HLB=13.1) and Tergitol (Tergi
tOl) 15-S-9 (1LB=13.3), compositions with substantially similar performance properties, physical properties, and processability are obtained.

Example V A spray-dried detergent composition useful in hard water containing both Ca++ and Mg++ is made having the following composition:
1. Made using the method described in Example 1.

The composition of Example V is 454 g/gal.
m9 (7 grains) in a wash liquor containing a mixture of hardened Mg++ and Ca++ under conventional domestic washing conditions.
When used at a composition concentration in the wash liquor of about 0.1% by weight, it provides excellent cleaning performance of fabrics.

The pH of the composition as a solution is approximately 10.2 at this concentration.
It is. Under such conditions, the foaming performance of the composition of Example V is comparable to that of conventional, fully built, high foaming anionic detergent formulations. Such compositions are easily pourable, storage stable, and made in conventional spray drying equipment. In the above composition, sodium silicate is added in equal amounts to sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium oxydisuccinate, sodium mellitate, monosodium nitrilotriacetate, sodium ethylenediaminetetraacetate, sodium polymaleate, sodium polyitaconate, Sodium polymethaconate, sodium polyfumarate, sodium polyaconitate, sodium polycitraconate, polymethylene-
When replacing sodium malonate, and mixtures thereof, respectively, compositions with substantially similar performance characteristics, physical properties, and processability are obtained.

In the composition of Example V above, all of its components are left in the same relative proportions and the sodium perborate solids! Approximately 3% by weight
Upon incorporation, compositions with substantially similar performance characteristics, physical properties, and processability are obtained.

Such perborate-loaded compositions are particularly suitable for use under laundry conditions commonly encountered in Europe. Excellent cleaning performance is obtained in the above compositions when the entire surfactant system is replaced by equal amounts of the alkyl ether sulfate mixtures 1, and, shown in Table 1, respectively.

Example: Make a phosphorus-free detergent composition having the following composition: ★ The above surfactant system consists essentially of the following: Component A about 30 to about 7% by weight, Component B about 20 to about 7% by weight, and component C about 2 to about 1
5% by weight of an alpha-olefin sulfonate mixture: (a) said component A is a double bond regioisomeric mixture of a water-soluble salt of an alkene-1-sulfonic acid containing from about 10 to about 24 carbon atoms; The mixture of positional isomers includes about 10% to about 25% α-β unsaturated isomers, about 30% to about 70% β-γ unsaturated isomers, and about 5% to about 25% γ-δ unsaturated isomers.
, and about 5 to about 10% of the delta-topically unsaturated isomer; (
b) said component B contains about 10 to about 24 carbon atoms;
It is a mixture of water-soluble salts of difunctionally substituted sulfur-containing saturated aliphatic compounds, the functional units of which are hydroxy and sulfonate groups, the sulfonate group always being on the terminal carbon and the hydroxy group being on the terminal carbon. It is bonded to a carbon atom at least two carbon atoms away from a carbon atom, and at least 90% of its hydroxy group substitutions are 3,
4, and 5 positions: and (c) said component C is about 10
~ about 30% to about 95% water soluble salts of alkene disulfonates containing about 24 carbon atoms, and about 5% to about 70% water soluble salts of hydroxydisulfonates containing about 10 to 24 carbon atoms a mixture, the alkene disulfonate containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom that is no more than about 6 carbon atoms away from the terminal carbon atom; Its alkene double bond connects to the terminal carbon atom approximately at the 7th
a sulfonate group attached to a terminal carbon atom, a second sulfonate group attached to an internal carbon atom that is no more than about 6 carbon atoms away from the terminal carbon atom, and It is a saturated aliphatic compound having a hydroquine group bonded to a carbon atom that is about 4 carbon atoms or less away from the bonding site of the second sulfonate group.

★★Made as described in Example 1 above.

The composition of the example was placed in an aqueous bath at 43° C. (110° C.) at 0.15° C.
It is added in a proportion of % by weight and used for washing oil-stained fabrics. 454-778m per 3.785e (1 gallon)
Excellent cleaning results are obtained under initial hard water conditions containing 9 (7-12 grains) of mixed hydride. In the above composition, the surfactant system is combined with an equal amount of linear ClO to about 18 alkylbenzene sulfonate; tallow-based sodium alkyl sulfate; castor oil-based sodium alkyl glyceryl ether sulfonate; tallow-based alcohol and about 3 to about 1
Sodium salt of sulfated condensation product with 0 mol of ethylene oxide; condensation product of oil-based fatty alcohol with about 6 mol of ethylene oxide; condensation product of tallow fatty alcohol with about 11 mol of ethylene oxide; 3-( N
, N-dimethyl-N-alkylammonio)-
2-hydroxypropane-1-sulfonate; 3-(N
, N-dimethyl-N-alkylammonio)-
propane-1-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; tridodecyldimethylamine oxide; alkyl dimethylamine oxide based on oil; and higher Equivalent results are obtained by respectively replacing water-soluble sodium and potassium salts of fatty acids: and mixtures thereof. In the above composition, the surfactant system is mixed with an equal amount of 0.05 to 5 ml of a mixture of Cl2-13 compounds.
% by weight, mixture of Cl4-15 compounds about 55-7% by weight
, about 25-40% by weight of a mixture of Cl6-17 compounds, C
About 0.1-5% by weight of a mixture of l8-,9 compounds, about 15-25% by weight of a mixture of compounds with a degree of ethoxylation of 0
, a mixture of compounds with a degree of ethoxylation from 1 to 4 about 50
~65% by weight, about 12-2% by weight of a mixture of compounds with a degree of ethoxylation of 5-8, and about 0.5-10% by weight of a mixture of compounds with a degree of ethoxylation greater than 8. Equivalent results can be obtained by substituting mixtures of compounds. In the above composition, sodium sulfate is combined with equal amounts of sodium carbonate, sodium bicarbonate, sodium silicate, sodium oxydisuccinate, sodium mellitate, sodium nitrilolyacetate, and as described in U.S. Pat. No. 3,308,067. Replacement of polymeric carboxylates, as well as mixtures thereof, provides effective hard water detergency.

Example: Make a soap-based laundry granule with the following composition: (1) 90% tallow soap and 1 part oil-based soap.
Soap mixture containing 0%.

(2) Sodium salt of ethoxylated tallowalkyl sulfate with an average of about 3 units of ethylene oxide per molecule.

(3) Sodium salt of a linear alkylbenzene sulfonic acid with an average alkyl chain length of about 12 carbon atoms. 75 parts by weight of the soap-based granules produced above,
Mix with 25 parts by weight of amorphous aluminosilicate prepared as described in Example 1.

When the composition is used at 0.1 weight percent of the washing liquid, 3.7
85e (648 mg (10 grains) per gallon) of mixed hydride gives the fabric excellent cleaning and foaming properties in water. The composition of the example is modified by the addition of 3 parts by weight of sodium perborate to give an excellent hot water [49
~87C (120-180F) cleaning performance is obtained.

In addition to the foregoing, it has been found that additional whiteness maintenance benefits are obtained when polyethylene glycols of molecular weight from about 400 to about 800, preferably about 6000, are used in the detergent compositions of the present invention. The use of polyethylene glycols in detergents is shown in US Pat. No. 2,806,001. Such materials may be added to about 0% of any of the detergent compositions described above.
．． Desirable whiteness benefits are obtained when used at concentrations of 1 to about 3% by weight, preferably 0.5 to 1.5% by weight. The following examples illustrate preferred detergent compositions containing polyethylene glycol. Example Linear sodium alkylbenzene sulfonate whose alkyl groups have an average chain length of 11.8 carbon atoms: 20% condensation product of 1 mole of an oil fatty alcohol and about 6 moles of ethylene oxide :4.7% (Weight ratio of anion and nonion = 4.26:1) ★Above example - 1÷? I made it as I did.

The above composition is used to launder fabrics at a concentration of 1 cup per 17 gallons of water. Its composition is
454 m9 (7 grains) per 3.785' (1 gallon)
Shows good fabric cleaning and excellent whiteness maintenance in water with mixed hydrides. As can be seen from the foregoing, amorphous aluminosilicate ion exchange builder materials can be used in all types of cleaning compositions.

The fact that aluminosilicate is an inorganic substance may be due to
This explains why they are stable and compatible with all kinds of ingredients used in detergent compositions. Depending on the user's wishes, it may, of course, be useful to add the aluminosilicate builder material to the wash or rinse liquor separately from the detergent composition. Such separate use provides the user with flexibility in selecting the detergent composition to be used while providing the desired benefits of the material. Alternatively, aluminosilicates can be used in standard water softeners to pre-soften wash water. The separate use of aluminosilicate builders to pre-soften wash water is fully contemplated by the present invention. The highly desirable ion exchange rates and ion exchange capacities of amorphous aluminosilicate materials make them particularly desirable when such materials are used to pre-soften laundry fluids.
easily recognized.

To be suitable for such use, the material must not have a slow exchange rate that would require a long dwell time before adding the laundry detergent composition to the laundry liquor. Additionally, it is equally undesirable for the user to have to utilize materials with low ion exchange capacities that require unreasonably large quantities to effectively sequester water hardening ions. Finally, if the substance is a water-hardening mixed polyvalent cation, e.g. Ca++9
It is desirable to sequester Mg++9Fe+10 and Fe+++. Amorphous aluminosilicate builders are useful in all types of cleaning compositions.

In addition to those mentioned above, they may be usefully used in detergent-containing floor cleaners, polish cleaners, etc. where hard water presents cleaning problems. Typical polishing cleaners include, for example, from about 25 to about 95% by weight of a polishing material (e.g., silica), from about 10 to about 35% by weight of an amorphous aluminosilicate builder, such as those described above, and from about 0 to about 30% by weight of ancillary builders, such as those described above. about 2% rut weight, and 0.2% to about 10% by weight of an organic detergent compound. Excellent cleaning performance is obtained when an amorphous monocrystalline mixed aluminosilicate is used in place of the amorphous aluminosilicate of Examples.

An amorphous monocrystalline mixed aluminosilicate is prepared in the manner described in Example 1.

Claims (1)

[Scope of Claims] 1. A detergent composition capable of rapidly reducing the content of free polyvalent metal ions in an aqueous solution, characterized in that it contains: (a) Empirical formula Nax(xAlO_2·SiO_2) (formula (inside
g equivalent of Mg^+^+exchange capacity, approximately 65mg per 1g~
Approximately 195 mg (1-3 grains) / 3.785 l) (1
gallon)/min Mg^+^+ exchange rate, 200-352 mg equivalent of Ca^+ as water hardening CaCO_3 per gram
^+ Exchange capacity and about 130 to about 390 mg per 1g (2
Water-insoluble amorphous containing 10-22% water by weight, characterized by a calcium exchange rate of ~6 grains)/3.785 l (1 gal)/min, particle size of approximately 0.01-5μ in diameter from about 5% to about 95% by weight of a hydrated aluminosilicate ion exchange builder material; and (b) a water-soluble organic selected from the group consisting of anionic detergents, nonionic detergents, zwitterionic detergents, and zwitterionic detergents and mixtures thereof. From about 5% to about 95% by weight detergent compound. 2. A detergent composition capable of rapidly reducing the content of free polyvalent metal ions in an aqueous solution, characterized in that it comprises: (i) an amorphous-crystalline mixed alumino consisting essentially of: Silicate ion exchange builder material: (a) Formula Na_1_2(AlO_2・SiO_2)_1_2・x
H_2O (wherein x is an integer from about 20 to about 30), particle size from about 1 to about 10 microns in diameter, 200 to 3 as hardened CaCO_3 per gram of aluminosilicate on an anhydrous basis.
Features a calcium ion exchange capacity of 52 mg equivalent,
Furthermore, on an anhydrous basis, about 130 per gram of aluminosilicate
~390mg (2-6 grains)/3.785l (1
(b) a water-insoluble crystalline aluminosilicate ion exchange material characterized by a calcium ion exchange rate of (expressed as CaCO_3)/min (expressed as CaCO_3); and (b) an empirical formula Nax(xAlO_2.SiO_2), where x is 1. 0 to 1.2), and 50 to 150 m as hard water CaCO_3 per 1 g on anhydrous basis.
g equivalent of Mg^+^+exchange capacity, about 65 to about 1 per gram
95mg (1-3 grains)/3.785L (1 gallon)/min Mg^+^+exchange rate, per gram of hardened CaC
Ca^+^+ exchange capacity of 200 to 352 mg equivalent as O_3 and calcium exchange rate of about 130 to about 390 mg (2 to 6 grains)/3.785 l (1 gal)/min, diameter about 0.01 to 5 μ characterized by a particle size of
Water-insoluble amorphous hydrated aluminosilicate ion-exchange builder material containing 10-22% water by weight:
The amorphous-crystalline mixed builder material has a weight ratio of amorphous aluminosilicate to crystalline aluminosilicate of about 1:4.
and (ii) a water-soluble organic detergent compound selected from the group consisting of anionic detergents, nonionic detergents, amphoteric detergents, zwitterionic detergents, and mixtures thereof.
~about 95% by weight.