Thickeners or viscosity-modifiers for aqueous- based dye-depletion products are disclosed.

As used in this disclosure, the term "dye- depletion" refers to the bleaching, fading, altering, diluting, solvating, oxidizing, or other effect upon a dyed article or substrate wherein a dye-depletion reagent is used in changing the appearance of the dye (or other colorant) in the location where the reagent is applied.

As used in this disclosure, the term "dye- depletion reagent" refers to such things as bleaches, oxidizers, reducers, solvents, or any chemicals or chemical formulations which are used in changing the appearance, color, amount ; effect or concentration of a dye, pigment, colorant, or other such visually significant additive in or on a cloth, fabric, leather, wood, or paper or other pulp product, whether or not it

is of a woven, non-woven, sheeted, fibrous, or compressed form.

Thickeners or other viscosity-modifiers are often used in aqueous-based functional products, e.g. household products, commercial products, cleansers, disinfectants, and bleaches and in personal care products, such as soaps, lotions, face creams, hand creams, and toothpaste. Thickeners that have been used in these applications include natural and synthetic water-sensitive organic polymers, or other water- sensitive organic substances. Also, inorganic substances, such as natural clays, refined clays, synthetic clay-like materials, silicates, and aluminates have been used.

Natural clays and refined natural clays may vary from one mining location to another. The performance obtained with one batch may not exactly 0 match the performance of another batch. Colors may not match and the effect on viscosity may not be identical.

The natural clays, and even refined natural clays, may contain impurities which can produce non-uniformity _j - among batches and may create side-reactions with other ingredients in a formulation to which the clay is added.

Clays are normally anionic and can react with ingredients _' which are cationic, such as cationic surfactants used as fabric softeners. 0

. _.. Polymers or other organic thickeners are often subject. ^" to microbial attack and may lose their effectiveness if not protected with a preservative.

Some polymers do not typically have a true yield point 5 which is required to indefinitely suspend solids. Many of the polymeric thickeners also contain functional

groups which are adversely attacked by the chemicals in bleaches or other formulations, and this can cause a loss or diminishment of either the desired viscosity control or the effectiveness of the chemical.

It has now been found that certain mixed metal hydroxides, which are of layered crystalline structures exhibiting cationic surface charges, are beneficially employed as thickeners or viscosity-modifiers in various aqueous-based dye-depletion products, such as bleaches and oxidants. The inorganic mixed metal hydroxide for each occurrence of MMOH compounds are resistant to microbial attack, are cationic (which prevents interaction with cationic ingredients used in many of the formulations), and, since they are synthetic, can be made substantially of consistent quality and purity.

The crystalline mixed metal hydroxides used in the present invention conform substantially to the empirical formula

Li _m D _d T(0H)(m+2d+3+n-a)(A ⁿ ) _a - H2θ where m is zero to one, where D is at least one divalent metal cation and d is zero to *., where T is at least one trivalent metal cation, where A is at least one monovalent or polyvalent anion or negative-valence radical, a is an amount of A ions of valence n, with n«a being zero to -3, where (m+2d+3+n-a) is equal to or more than 3, where m+d is greater than zero, and where xH2θ represents excess waters of hydration, with x being zero or more. (By "excess waters of hydration" it is meant that there is more water associated with the compound than is needed to

supply the amount of hydroxyl ions required in the crystal formula.)

In the above formula, it should be noted that n, being the valence of the anion or negative-valence radical, is a negative number. Thus, n-a is a negative number.

These crystalline mixed metal hydroxides are found to be beneficial as thickeners or viscosity- modifiers for aqueous-based dye-depletion products, such as bleaches, oxidants, whiteners, color-extractants, reducing agents, and inorganic bases.

In one aspect, the present invention is a formulation of the type described, having incorporated therein the mixed metal hydroxide compounds.

In another aspect, the present invention is a means, method, or process for providing viscosity- modifiers or thickeners to the dye-depletion formulations by incorporating therein the mixed metal hydroxide compounds.

• A further aspect is that mixed metal hydroxide compounds provide a thickened product which thins readily under even very slight shear, but which rethickens ("gels") rapidly when the shear is stopped. The gelation rate is perceived as being essentially immediate.

In yet another aspect, the present invention is a method for dye-depletion by the application of the dye-depletion formulations which contain beneficial quantities of the mixed metal hydroxide compounds.

The mixed metal hydroxide compounds useful in the present invention are preferably those of the monodispersed, monolayer variety such as described in U.S. Patent 4,664,843, but can also be of the varieties disclosed in U.S. Patents 4,477,367; 4,446,201; 4,392,979; and 4,461,714. For the most part the mixed metal hydroxide compounds are prepared by the general process of forming a solution of compounds of the subject metals under conditions whereby a soluble alkaline material, e.g. ammonia or caustic, reacts with the soluble metal compounds to produce the layered crystals of mixed metal hydroxides. However in the present invention, it is often best to avoid having ammonia in the product, in which case another alkaline material, especially NaOH or KOH is used. The mixed metal hydroxide may be used as a slurry of varied solids content, or dry.

The dye-depletion reagents include, but are not limited to, metal hypochlorites and metal permanganates, such as those which contain alkali metals or alkaline earth metals such as, sodium hypochlorite, lithium hypochlorite, calcium hypochlorite, sodium permanganate, potassium permanganate, lithium permanganate, and the like.

The dye-depletion reagents also include, but are not limited to, halates, halites, peroxides, including, for example, sodium chlorite, sodium chlorate, hydrogen peroxide, sodium hydrosulfite, sodium perborate, sodium peroxide, sulfur dioxide, sodium borohydride, thiourea dioxide, chlorine dioxide, and potassium iodate.

The dyed, stained, tinted, pigmented, or otherwise colored articles, substances or substrates include, but are not limited to, fiber, yarn, thread, rope, sliver, tone, roving, and fabric of either natural or synthetic origin. This includes articles, substances or substrates which may be dyed or otherwise provided with color by using, for example, a dye or colorant administered via direct, sulfur, naphthol, fiber reactive, vat, disperse, acid, indigo, azoic, and basic dyes.

Methods of applying the mixed metal hydroxide- -modified dye-depletion reagents to the colored articles or substrates includes, but is not limited to dipping, padding, screening, roll printing, saturating (such as in a Beck dyeing machine or in a jet dyeing machine) , or tumbling with pumice stones or the like in a garment bleaching machine.

The process of using mixed metal hydroxide compounds to thicken aqueous-based dye-depletion products includes, but is not limited to the following two general ways. One method, in general, involves the activation of the mixed metal hydroxide particles by an electrolyte. In this process, the mixed metal hydroxide is first dispersed by using high shear, sonic waves or other methods known in the art to produce a high degree of dispersion of agglomerated particles. Once the material is dispersed in aqueous or partially aqueous media, a salt (electrolyte) is added either predissolved or dry. Mixing or shearing is continued until a smooth, thickened system is obtained. Other ingredients may be blended into the prethickened material. Often, one or more of the ingredients is a salt and a separate activator is not needed. The salt used for activation

can be almost any ionic substance but components containing organic anions or multivalent anions such as

CO3-2, P04-3, P3θιo~5 and the like are usually more effective.

The other general method involves interaction with other colloidal particles in such a manner that they are linked together through bridges or bonds formed by the mixed metal hydroxide. In these cases, it can be interpreted as forming an adduct with the other particles. This can produce an "extending" effect in that less material is needed for thickening. This can happen, for instance, when fumed silica or a clay is also an ingredient. This can also occur when a normally soluble material is included in the formulation beyond the point of saturation such that very small or colloidal particles are present as crystals or agglomerates. In this case, the thickening occurs when the mixed metal hydroxide and other particles are sheared together and agglomerates are broken, exposing fresh faces which react.

As used in this disclosure, the expression "thickener" when used in reference to the effect of the mixed metal hydroxide additives, means that the apparent viscosity at ambient conditions and at little or no applied shear has been increased by the addition of the mixed metal hydroxide. The expression "viscosity- modifier" is used herein to refer to the effect obtained by the addition of the mixed metal hydroxide whether or not the effect on viscosity is evident at ambient conditions or at non-ambient conditions and whether or not the effect is a thickening effect apparent under no- stress conditions or under shear. For example, changing of a Newtonian liquid to a non-Newtonian liquid, or

vice-versa, is one form of a viscosity modification. Changing the degree or extent of thixotropicity or dilatancy of a liquid is a form of viscosity modi ication.

The expression "mixed metal hydroxide" indicates that there are at least two different metals in the hydrous oxide crystals. In the present invention, it is preferred that at least one of the metals is a trivalent metal, along with at least one other metal which can be either, or both, of the divalent or monovalent (Li) varieties. The amount of the A anion (or negative-valence radical) is that which substantially satisfies the valence requirements of the cations in the crystalline material.

In the above described formula, the trivalent metal cation is preferably Al, Fe, or Ga, and can be mixtures of any of these; Al is most preferred as the trivalent metal.

The divalent metal cation is preferably Mg, Ca, Mn, Fe, Co, Ni, Cu, or Zn and can be mixtures of any of these. Ca or Mg, especially Mg, is most preferred as the divalent metal.

The anion, A, can be monovalent, divalent, trivalent, or polyvalent, and is preferably at least one of hydroxyl, halide, sulfate, nitrate, phosphate, carbonate, glycolate, lignosulfate, and polycarboxylic or negative-valence radicals. Thus, the A anion can be inorganic or a hydrophilic organic group or mixture of different anions. Preferably the A anion is inorganic, such as OH- or a combination of anions, at least one of which is 0H-.

The contents of the dye-depletion formulations that can be thickened or modified by the addition of mixed metal hydroxide compounds can be beneficially varied for particular applications. Generally, the ingredients and levels of the ingredients which are in a given formulation have a desired effect other than simply that of thickening or viscosity-modification. The versatility of the mixed metal hydroxide compounds is beneficial in that it can be added to dye-depletion

10 formulations for viscosity purposes without interfering with the other ingredients in their intended purpose. Substitutions, replacements, and/or eliminations of one or more of the components (other than the mixed metal -.,- hydroxide compound) usually have little effect on thickening or viscosity-modification.

The amount of the mixed metal hydroxide added to the aqueous-based dye-depletion formulation will 0 usually be 0.03 percent to 10 percent or more depending somewhat on temperature, the particular formulation into which it is added, the mixed metal hydroxide varieties is being used, and the extent of thickening or viscosity-modification desired. In a general sense, it 5 is preferable to use an amount of 0.5 percent to 10 percent, with 3 percent to 6 percent being most preferred. Generally, one would not expect amounts of mixed metal hydroxide of much less than 0.03 percent to give an appreciable effect on thickening or viscosity- 0 modification. Thus, an overall concentration range for the mixed metal hydroxide of 0.03 percent to 10 percent is anticipated as being a sufficient range in which to operate for most applications. 5 The dye-depletion formulations into which the mixed metal hydroxide compounds are incorporated are,

for the most part, those which rely on water or some aqueous base as a carrier and to provide fluidity to the formulation.

_ς In the following examples the expression "MAH" is in reference to certain compounds within the generic formula shown above and which conform substantially to the formula MgAl(0H)5_ _y Cly'xH20 and which are prepared from an aqueous solution containing MgCl2 and AICI3 as

10 taught, e.g., in U.S. 4,664,843. The small amount of Cl" anion present is a residual amount of the Cl~ anion which was in the starting materials. Typically, Y is zero to 1.0.

15 The following examples are given to illustrate applications of the mixed metal hydroxide in various dye-depletion formulations; however, the invention is not limited to only the examples illustrated.

20 Example 1.

Sodium hypochlorite solution is thickened for use in screen printing in accordance with the following:

25

30

In the above recipe, the MAH comprises about 5.8 percent of the total, and the active chlorine comprises about 5 percent of the total.

35 The NaOCl, the a2Cθ3, and the water are mixed until all solubles are dissolved, and the solution is

homogenous. This solution and the MAH are then pumped simultaneously through an in-line mixer at high shear conditions. The resulting mixture is free of lumps and 100 percent will pass through a 100 mesh, sieve (150 micrometers).

The following rheological data is obtained at ambient laboratory temperature after 8 weeks using a Brookfield Model RV* viscosimeter (*a trademark) having a #6 spindle.

RPM: 0^ _J O _, 2^5 5_j_0 JO 20 50 J00

Vise.** 296 123 43.2 27.2 24.6 12.3 6.4 3-35

(**viscosity, cps X1000)

With this viscosity and yield point, this thickened bleach is easily pumped through a typical print paste feed system to a print roll, and is easily screened through the roll. Once in moistened fabric, the bleach is immobilized by the rapid gellation and provides minimal migration and bleed.

Example 2.

Commercially available Kandu* laundry bleach (*a trademark) is thickened in accordance with the following:

(In the above recipe, the MAH comprises about 2.5 percent of the total and the NaOCl comprises about 3.23 percent of the total.)

The MAH, Na2Cθ3 and water are mixed until the solubles are dissolved and a smooth paste is obtained. The thickened paste is allowed to set for several minutes and the NaOCl solution is added slowly with blending until the mixture is smooth.

The following rheological data are obtained at ambient laboratory temperature using a Brookfield Model RV* viscosimeter (*a trademark):

RPM: 0_;_5 J_;_0 2^5. ^ D ^0 20 50 _. JJX) Vise.** 26.7 19.7 12.5 7.1 3.9 2.2 1.0 0.5 (**viscosity, cps X1000)

Thus it is shown that a small percent of the MAH thickens the bleach solution, but it thins easily when shear is applied. The thickened bleach solution can be applied to a print roll where it quickly re-gels and does not run off rapidly, but it is easily transferred to print fabric where, with its high yield point, the bleach is immobilized and gives minimal migration.

Example 3.

Potassium permanganate for use in garment finishing is thickened in accordance with the following:

Ingredient Grams Approx. % of Total

MAH slurry (12% MAH cone.) 2417 48.3 KMn04 250 5.0

Water 2333 46 .7

Totals: 5000 100

(In the above recipe, the MAH comprises about 5.8% of the total.)

The MAH, KMnθ4 and water are mixed until all solubles are dissolved and a smooth paste is obtained on a Hobart* blender (*a trademark). The resulting product is visually lump free. This product gives excellent results in bleaching moistened denim garments (in this instance blue jean pants) using pumice stones in a garment dyeing machine.

The following rheological data are obtained at ambient laboratory temperature using a Brookfield Model RV* viscosimeter (*a trademark):

RPM: (K5 J^ 2^5 5^0 J0_ 20_ 50_ JJ30 Vise.** 328 137 48 24.2 19.3 13.2 6.5 3.05 (**viscosity, cps X1000)

Thus a randomly patterned material is produced by the dye-reduction process. The process can be applied to the material either before or after being made into a garment.

Example 4.

In similar manner to the above laundry bleach example, thickened bleaches are prepared by using more MAH and/or by using greater concentrations of NaOCl. Furthermore, other oxidizing or reducing agents are similarly thickened, such as KMnθ4, NaC103, or Na2Sθ3 and the like, using MAH or other mixed metal hydroxide compounds.

Example 5.

The mixed metal hydroxide-thickened dye- depletion formulations, when applied to pieces of sponge, ceramic beads, stones or particles, or other porous or high surface area non-porous carriers are effective in causing the dye-depletion reagent to be applied to the dyed moistened substrate (such as cotton cloth) at the points of contact of the sponge (or other porous material) with the substrate, and the formulation does not "run" onto other portions of the substrate. Thus the dye-depletion reagent only affects the dye in the places where the fast-gelling formulation is applied by the sponge or other carrier.