WO2017005386A1

WO2017005386A1 - Large particles

Info

Publication number: WO2017005386A1
Application number: PCT/EP2016/059426
Authority: WO
Inventors: Stephen Thomas Keningley; David Moorfield; Jonathan Osler; David Christopher Thorley
Original assignee: Unilever Plc; Unilever N.V.; Conopco, Inc., D/B/A Unilever
Priority date: 2015-07-08
Filing date: 2016-04-27
Publication date: 2017-01-12
Also published as: EP3320076B1; CN107771211A; CL2018000022A1; ZA201708393B; PH12017502304B1; EP3320076A1; CN107771211B; BR112018000313A2; BR112018000313B1; PH12017502304A1; TR201901001T4

Abstract

The present invention large bleaching particle adjunct to use with similar sized detergent particles.

Description

LARGE PARTICLES

Field of the Invention

The present invention provides for a bleaching adjunct for incorporation in a large particle formulation.

Background of the Invention

The following published applications describe large particles of detergent material:

WO/2012/048950; WO/2012/048947; WO/2012/048949; WO/2012/048951 ;

WO/2012/048948; WO/2012/049178; WO/2012/048926; WO/2012/048945;

WO/2012/048909; WO/2012/049033; WO/2012/048910; WO2013/149754;

WO2013/149755; WO2013/149753; WO2013/149752; and, WO2014/048857.

We have found that the use of a large particle adjunct with a specific bleach reduces spotting over that with smaller particles.

Summary of the Invention

It is usual that larger particles exhibit localised spotting in contrast to larger particles.

In one aspect the present invention provides a bleach adjunct particle having

perpendicular dimensions x, y and z, wherein x is from 0.5 to 2 mm, y is from 2 to 8mm, and z is from 2 to 8 mm, wherein the particle comprises: (i) from 40 to 95 wt % a composition susceptible to aqueous attack, wherein said composition is selected from water-soluble materials, partially water soluble materials, water-dispersible materials, water-disintegrating materials, and mixtures thereof; and, (ii) from 5 to 60 wt % dispersed in the composition susceptible to aqueous attack particles of PAP having a size from 10 micron to 200 microns, preferably 20 to 50 microns, most preferably 20 to 40 microns, wherein when 1 gm of the bleach adjunct particle is dissolved in 100 ml of demineralised water the pH to the solution is in the range from 3 to 6, preferably 3 to 5.

In another aspect the present invention provides a laundry detergent comprising from 5 to 40 %, preferably 10 to 25 wt %, of the bleach adjunct particle as defined in any one of the preceding claims together with from 60 to 95 wt %, preferably 90 to 75 w%, of a coated detergent particle having perpendicular dimensions x, y and z, wherein x is from 0.5 to 2 mm, y is from 2 to 8mm, and z is from 2 to 8 mm, wherein the particle comprises:

(i) from 20 to 50 wt % of a surfactant selected from: anionic and non-ionic surfactants; (ii) from 10 to 40 wt % of inorganic salts selected from: sodium carbonate and/or

sodium sulphate of which at least 5 wt % of the inorganic salt is sodium carbonate; and, wherein the inorganic salts and are present on the detergent particle as a coating and the surfactant is present as a core. Other adjunct particles of similar size may be present. These other adjunct particles may be aesthetic or functional.

Detailed Description of the Invention

Shape

Preferably the bleach adjunct particle and the coated laundry detergent particle are substantially the same shape and size. Preferably the bleach adjunct particle and the coated laundry detergent particle are curved.

The particle may be lenticular (shaped like a whole dried lentil), an oblate ellipsoid, where z and y are the equatorial diameters and x is the polar diameter; preferably y = z.

The particle may be shaped as a disc. Preferably the particle does not have hole; that is to say, the coated laundry detergent particle does not have a conduit passing there though that passes through the core, i.e., the particle has a topologic genus of zero. Bleach Adjunct Particle

The Bleach Adjunct Particle is preferably uncoated in contrast to the laundry detergent particle.

The Bleaching agent

The bleaching agent used in the adjunct particle is phthalimido-peroxy-hexanoic-acid (CAS 128275-31 -0) (PAP). The particle size of the PAP is from 10 to 200 microns, preferably 20 to 50 microns. The adjunct particle is susceptible to aqueous attack. The particles of PAP contain are PAP on a carrier such as starch, cellulose, methyl cellulose, ethyl cellulose and propyl cellulose; cellulose ethers; cellulose esters; cellulose amides polysaccharides including starch, modified starch; gelatin; alginates; xyloglucans, other hemicellulosic polysaccharides including xylan, glucuronoxylan, methylcellulose, carboxymethylcellulose sodium, modified carboxy-methylcellulose, dextrin, ethylcellulose, propylcellulose, hydroxyethyl cellulose and silica. For a powder, the particle size is measured using a standard sieve set vibrated at an amplitude of 1 .2 mm for 4 mins, the weight retained on each sieve is then recorded as a percentage. For the lenticular disks, the key parameter is the thickness and thickness distribution, this is measured using a micrometer. A Composition Susceptible to Aqueous Attack

The composition susceptible to aqueous attack is selected from water-soluble materials, partially water soluble materials, water-dispersible materials, water-disintegrating materials, and mixtures thereof. Dispersed throughout the composition susceptible to aqueous attack is a bleaching agent. The bleaching agent in the adjuncts is from 5 to 60 wt %, preferably 20 to 40 wt %.

The composition susceptible to aqueous attack comprises a water-soluble or partially water-soluble material. As used herein, water-soluble materials include partially water- soluble materials. Where a water-soluble material is used, the functionalized substrate has a water-solubility of at least 50%, alternatively at least 75%, or even at least 95%, as measured by the Water-Solubility Method as provided herein.

Suitable water-soluble materials include water-soluble polymeric materials (polymers) which can be formed into a film or sheet or laminate or extruded (or extruded or pressed into a 3-deminsional shape).

Examples of polymers, copolymers or derivatives thereof suitable for use as water- soluble material include but are not limited to polyvinyl alcohols (PVA), modified PVAs; polyvinyl pyrrolidone; PVA copolymers such as PVA polyvinyl pyrrolidone; partially hydrolyzed polyvinyl acetate; polyalkylene oxides such as polyethylene oxide; acrylamide; acrylic acid; cellulose, alkyl cellulosics such as methyl cellulose, ethyl cellulose and propyl cellulose; cellulose ethers; cellulose esters; cellulose amides; polyvinyl acetates;

polycarboxylic acids and salts; polyaminoacids or peptides; polyamides; polyacryl amide; copolymers of maleic/acrylic acids; polysaccharides including starch, modified starch; gelatin; alginates; xyloglucans, other hemicellulosic polysaccharides including xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan and galactoglucomannan; and natural gums such as pectin, xanthan, and carrageenan, locus bean, arabic, tragacanth; and combinations thereof. In one embodiment the polymer comprises polyacrylates, especially sulfonated polyacrylates and water-soluble acrylate copolymers; and alkylhydroxy cellulosics such as methylcellulose, carboxymethylcellulose sodium, modified carboxy-methylcellulose, dextrin, ethylcellulose, propylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates. In yet another embodiment the polymer comprises PVA; PVA copolymers; hydroxypropyl methyl cellulose (HPMC); and mixtures thereof. Where the composition comprises PVA, the functionalized substrate comprises a rapid dissolution rate, as defined herein, where the functionalized substrate at least partially dissolves in an aqueous solution at cold temperatures, i.e., less than about 5°C or 10°C during the wash cycle and/or the rinse cycle. Typical wash and/or rinse cycles should take about 10 minutes, alternatively about 5 minutes. In one embodiment, the entire functionalized substrate dissolves in during the wash and/or rinse cycles. In one embodiment, PVA is mixed or blended with another polymer to obtain the desired dissolution rate. It is believed that selecting polymers based on average molecular weight and/or degree of hydrolysis allows for different dissolution rates. In one embodiment, the functionalized substrate comprises a PVA film. Suitable PVA films are known under the trade reference MonoSol M8630, as sold by MonoSol. Other films suitable for use herein include films known under the trade reference PT film or the K-series of films supplied by Aicello, or VF-HP film supplied by Kuraray.

It is further believed that specific blends of polymers provide dissolving films or foams with dissolution rates of the present invention, which can be produced with good mechanical properties for subsequent handling and converting into manufactured articles. For instance, a blend containing at least two types of polymers that have disparate molecular weights, can be used to prepare substrate that dissolves at a dissolution rate as disclosed herein under cold water conditions. In one embodiment, such blends contain at least a first polymer comprising a molecular weight greater than about 50,000, alternatively greater than about 60,000, and alternatively greater than about 70,000, and a second polymer or mixture of polymers comprising an average molecular weight of less than about 30,000, alternatively less than about 15,000, and alternatively less than about 10,000.

The composition may comprises a polymer blend.

Blends of high and low molecular weight polymers at ratios of 80/20, 60/40, and 50/50 mixtures of low to high molecular weight polymers can be evaluated for specific applications. In one embodiment, the composition comprises a blend of at least one PVA having a molecular weight of about 78,000 and higher and a second PVA about 6,000 or lower. This embodiment has been found to produce a film which dissolves at a rate as defined herein under cold water conditions. Additional suitable solubility modifiers that are soluble in a given pH range are based on methacrylic acid co-polymers, styrene hydroxystyrene co-polymers, acrylate co-polymers, polyethylene glycol polyvinyl acetate, diethylphtalate, dioctyl sodium sulfocuccinate, poly- dl-lactide-co-glycolide (PLG), vinylpyridine/styrene co-polymers. Solubility modifiers that are soluble in a specific chemistry environment are also commercially available. For instance caustic soluble barrier agents are commercially available from Alcoa under the trade name Hydra-Coat-5. Water dispersible barrier agents are based on sodium starch glycolate, polyplasdone and are commercially available from FMC Corporation under the trade name Ac-di-sol, from Edward Mendell Corporation under the trade name Explotab, from ISP under the trade name

Crospovidone. Polyacrylate-type mat function as a structurant and comprise in particular polyacrylate polymers and copolymers of acrylate and methacrylate. An example of a suitable polyacrylate type structurant is Carbopol Aqua 30 available from B. F. Goodridge

Company. Examples of polymeric gums which may be used as structurant herein can be characterized as marine plant, terrestrial plant, microbial polysaccharides and

polysaccharide derivatives. Examples of marine plant gums include agar, alginates, carrageenan and furcellaran. Examples of terrestrial plant gums include guar gum, gum arable, gum tragacenth, karaya gum, locust bean gum and pectin. Examples of microbial polysaccharides include dextrin, gellan gum, rhamsan gum, welan gum and xanthan gum. Examples of polysaccharide derivatives include carboxymethyl cellulose, methyl hydroxypropyl cellulose, hydroxy propyl cellulose, hydroxyethyl cellulose, propylene glycol alginate and hydroxypropyl guar. The second structurant is selected from the above list or a combination thereof. Acceptable polymeric gums include pectin, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, Diutan® gum (ex. CP Kelco), and guar gum. If polymeric gum structurant is employed herein, an

acceptable material of this type is gellan gum. Gellan gum is a tetrasaccharide repeat unit, containing glucose, and glucurronic acid, glucose.

The functionalized substrate may further comprise a plasticizer, for example glycerol, dipropylene glycol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof. Glycerol is one preferred plasticizer. Other useful additives include disintegrating aids.

Preferably the composition susceptible to aqueous attack comprises sodium citrate/citric acid, polyvinyl alcohol, maleic acid/acrylic acid copolymer sodium salt (preferably Sokolan CP5), methylglycinediacetic acid (MGDA), starch, silicone antifoam and/or carboxymethyl cellulose. The Coated Detergent Particle

The coated detergent particle is described in the following patent applications:

WO/2012/048950; WO/2012/048947; WO/2012/048949; WO/2012/048951 ;

WO/2012/048948; WO/2012/049178; WO/2012/048926; WO/2012/048945;

WO/2012/048909; WO/2012/049033; WO/2012/048910; WO2013/149754;

WO2013/149755; WO2013/149753; WO2013/149752; and, WO2014/048857. In particular, WO2010/122050 describes a process for the preparation of a coated detergent particle.

Experimental

Impact of format on dye damage

The use of bleach is commonly associated with dye damage on susceptible textiles. In using a compacted format we have shown that this damage can be minimised in comparison with PAP containing powder of a smaller granule.

Two comparative samples were prepared in the extruder, in one case the product from the extruder was controlled to be a powder/granule in the alternate the product was formed into a lenticular shape by extrusion under pressure and cutting the product into a lenticular shape. This is to exemplify how the physical form of the product can influence the degree of damage caused to a fabric.

Formulations of adjunct granule/adjunct

Control A B C

GP-4427 Powdered Antifoam 31 % 20% 0% 0% (ex Dow Corning)

Sodium citrate (dihydrate) 38% 25% 15% 0%

Maleic acid/acrylic acid copolymer sodium 15% 10% 40% 40% salt (BASF Sokolan CP5)

Polymer Repel-O-Tex® (ex Rhodia) SF2 8% 5% 0 0

Eureco (TM) WM1 (PAP) (ex Solvay) 0% 35% 35% 50%

Citric acid 8% 5%. 10% 10% The above formulation was mixed with water to form a soft solid as it was processed through an extruder at 40 to 50°C, as disclosed in WO2010/122050, to provide lenticular adjunct particles having the following size range 1 mm thickness and 5mm diameter. A Subsample was added to a screen mill to produce a powder.

Particle size data on powder sample

Weight percent via sieving (4mins sieving @ 1.2 amplitude, std sieve shaker)

Thickness of crystal form (average of 8 measurements using digital calliper)

Dye damage assessment

Bleach-containing products were compared to a non-bleach containing control product at equivalent levels in a static contact test. Average measurements of colour change using the CIE DE^* scale were recorded as shown.

The granule/adjunct was added to a standard non-bio detergent formulation in a ratio of 70 parts detergent base to 30 parts adjunct granule to produce a detergent product. One 10x10cm piece of woven cotton fabric dyed with CI sulphur black 1 (CAS#1326-82-5) was placed into a shallow tray and 5ml water (26°FH) was added. 0.5g of formulation in either adjunct or powdered form was evenly applied over a central area that measured 25cm2. A further 10ml water was applied to a separate 10x10cm piece of heavy-construct knitted cotton then this was placed on top of the dyed monitor in order to hold the product in position. A further 50ml water was added to the tray and this was incubated at 21 °C for 120 minutes. After this time the dye monitor was rinsed in clean water and allowed to air dry in the dark before the colour change of the central region was measured by reflectometry with values calculated for the colour change (DE^*) with reference to the initial state.

It can clearly be seen that the colour change for the lenticular product is much less than that for the powdered sample.

Claims

1. A bleach adjunct particle having perpendicular dimensions x, y and z, wherein x is from 0.5 to 2 mm, y is from 2 to 8mm, and z is from 2 to 8 mm, wherein the particle comprises:

(i) from 40 to 95 wt % a composition susceptible to aqueous attack, wherein said composition is selected from water-soluble materials, partially water soluble materials, water-dispersible materials, water-disintegrating materials, and mixtures thereof; and, from 5 to 60 wt % dispersed in the composition susceptible to aqueous attack particles of PAP having a size from 10 micron to 200 microns, preferably 20 to 50 microns, most preferably 20 to 40 microns, wherein when 1 gm of the bleach adjunct particle is dissolved in 100 ml of demineralised water the pH to the solution is in the range from 3 to 6, preferably 3 to 5.

2. A bleach adjunct particle according to claim 1 , wherein the bleach adjunct particle comprises from 5 wt% to 30 wt % maleic acid/acrylic acid copolymer sodium salt.

3. A bleach adjunct particle according to claim 1 or 2, wherein the bleach adjunct

particle comprises an acidic component selected from: citric acid; and

methylglycinediacetic acid.

4. A bleach adjunct particle according to any one of the preceding claims, wherein the particle comprises from 0 to 15 wt % water.

5. A bleach adjunct particle according to claim 4, wherein the particle comprises from 1 to 5 wt % water.

6. A laundry detergent comprising from 5 to 40 %, preferably 10 to 25 wt %, of the bleach adjunct particle as defined in any one of the preceding claims together with from 60 to 95 wt %, preferably 90 to 75 w%, of a coated detergent particle having perpendicular dimensions x, y and z, wherein x is from 0.5 to 2 mm, y is from 2 to 8mm, and z is from 2 to 8 mm, wherein the particle comprises:

(i) from 20 to 50 wt % of a surfactant selected from: anionic and non-ionic

surfactants;

(ii) from 10 to 40 wt % of inorganic salts selected from: sodium carbonate and/or sodium sulphate of which at least 5 wt % of the inorganic salt is sodium carbonate; and, wherein the inorganic salts and are present on the detergent particle as a coating and the surfactant is present as a core.

7. A plurality of particles according to any one of the preceding claims, wherein at least 90 to 100 % of the particles in the in the x, y and z dimensions are within a 20 % variable from the largest to the smallest particle.