CN107771211B

CN107771211B - Large particle

Info

Publication number: CN107771211B
Application number: CN201680036562.9A
Authority: CN
Inventors: S·T·科宁利; D·穆尔菲尔德; J·奥斯勒; D·C·索利
Original assignee: Unilever PLC
Current assignee: Unilever IP Holdings BV
Priority date: 2015-07-08
Filing date: 2016-04-27
Publication date: 2020-07-07
Anticipated expiration: 2036-04-27
Also published as: EP3320076B1; CN107771211A; CL2018000022A1; ZA201708393B; PH12017502304B1; WO2017005386A1; EP3320076A1; BR112018000313A2; BR112018000313B1; PH12017502304A1; TR201901001T4

Abstract

The present invention relates to large bleach particle builders for use with similarly sized detergent particles.

Description

Large particle

Technical Field

The present invention provides bleaching aids for incorporation into large particle formulations.

Background

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; WO 2013/149754; WO 2013/149755; WO 2013/149753; WO 2013/149752; and WO 2014/048857.

We have found that the use of large particle builders with specific bleaching agents reduces spotting (spotting) compared to the use of specific bleaching agents with smaller particles.

Disclosure of Invention

Larger particles generally exhibit localized spotting as compared to larger particles.

In one aspect, the present invention provides a bleach adjunct particle having orthogonal dimensions x, y and z, wherein x is from 0.5 to 2mm, y is from 2 to 8mm and z is from 2 to 8mm, wherein the particle comprises:

(i) from 40 to 95 weight percent of a composition that is susceptible to water attack (aqueous attack), wherein the composition is selected from the group consisting of water soluble materials, partially water soluble materials, water dispersible materials, water disintegrable materials, and mixtures thereof; and the combination of (a) and (b),

(ii)5 to 60% by weight of PAP particles dispersed in said water susceptible composition, said PAP particles having a size of 10 to 200 microns, preferably 20 to 50 microns, most preferably 20 to 40 microns,

wherein when 1 gram of said bleach adjunct particles are dissolved in 100ml demineralised water, the pH of the solution is in the range of from 3 to 6, preferably from 3 to 5.

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

(i)20 to 50 wt% of a surfactant selected from anionic and nonionic surfactants;

(ii)10 to 40 wt% of an inorganic salt selected from sodium carbonate and/or sodium sulphate, wherein at least 5 wt% of the inorganic salt is sodium carbonate; and the combination of (a) and (b),

wherein the inorganic salts are present on the detergent particle as a coating and the surfactant is present as a core.

Other adjuvant particles of similar size may be present. These other adjunct particles may be aesthetic or functional.

Detailed Description

Shape of

Preferably, the bleach adjunct particles and the coated laundry detergent particles have substantially the same shape and size. Preferably, the bleach adjunct particles and the coated laundry detergent particles are curved.

The particles may be lenticular (shaped like whole dry lentils), i.e. oblate ellipsoids, where z and y are the equatorial diameters and x is the polar diameter; preferably y ═ z.

The particles may be disc-shaped.

Preferably, the particles have no pores; that is, the coated laundry detergent particle has no conduits penetrating between them through the core, i.e. the topological genus of the particle is zero.

Bleaching aid particles

In contrast to laundry detergent particles, the bleach adjunct particles are preferably uncoated.

Bleaching agent

The bleaching agent used in the co-particles was phthalimido-peroxy-hexanoic acid (CAS 128275-31-0) (PAP). The particle size of the PAP is 10 to 200 microns, preferably 20 to 50 microns. The adjuvant particles are susceptible to attack by water. PAP particles contain PAP on a carrier such as starch, cellulose, methyl cellulose, ethyl cellulose, and propyl cellulose; a cellulose ether; cellulose esters; a cellulose amide; polysaccharides, including starch, modified starch; gelatin; an alginate; xyloglucan, other hemicellulose polysaccharides including xylan, glucuronoxylan, methyl cellulose, sodium carboxymethyl cellulose, modified carboxymethyl cellulose, dextrin, ethyl cellulose, propyl cellulose, hydroxyethyl cellulose and silica.

For the powder, the particle size was measured using a standard set of sieves vibrated at an amplitude of 1.2mm for 4 minutes, and then the weight retained on each sieve was recorded as a percentage. For lentil-shaped discs, the key parameters are thickness and thickness distribution, which is measured using a micrometer.

Composition susceptible to water attack

The composition susceptible to water attack is selected from the group consisting of water soluble materials, partially water soluble materials, water dispersible materials, water disintegrable materials, and mixtures thereof. Dispersed throughout the composition susceptible to water attack is a bleaching agent. The bleaching agent in the adjuvant is 5 to 60% by weight, preferably 20 to 40% by weight.

Compositions susceptible to water attack comprise water soluble or partially water soluble materials. As used herein, water-soluble materials include partially water-soluble materials. In the case of water-soluble materials, the functionalized substrate has a water solubility of at least 50%, or at least 75%, or even at least 95%, as measured by the water-soluble methods provided herein.

Suitable water-soluble materials include water-soluble polymeric materials (polymers) that can be formed into films or sheets or laminates or extrudates (or extruded or pressed into three-dimensional shapes).

Examples of polymers, copolymers or derivatives thereof suitable for use as water-soluble materials include, but are not limited to, polyvinyl alcohol (PVA), modified PVA; polyvinylpyrrolidone; PVA copolymers, such as PVA/polyvinylpyrrolidone; partially hydrolyzed polyvinyl acetate; polyalkylene oxides, such as polyethylene oxide; (ii) acrylamide; acrylic acid; cellulose, alkyl cellulose materials such as methyl cellulose, ethyl cellulose and propyl cellulose; a cellulose ether; cellulose esters; a cellulose amide; polyvinyl acetate; polycarboxylic acids and salts; a polyamino acid or peptide; a polyamide; polyacrylamide; maleic/acrylic acid copolymers; polysaccharides, including starch, modified starch; gelatin; an alginate; xyloglucan, other hemicellulose polysaccharides including xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan and galactoglucomannan; and natural gums such as pectin, xanthan gum and carrageenan, locust bean gum (gum bean), gum arabic, tragacanth gum; and combinations thereof. In one embodiment, the polymer comprises a polyacrylate, particularly a sulfonated polyacrylate and a water soluble acrylate copolymer; and alkylhydroxycellulose materials such as methylcellulose, sodium carboxymethylcellulose, modified carboxymethylcellulose, dextrin, ethylcellulose, propylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylates. In yet another embodiment, the polymer comprises PVA; a PVA copolymer; hydroxypropylmethylcellulose (HPMC); and mixtures thereof.

Where the composition comprises PVA, the functionalized substrate comprises a rapid dissolution rate as defined herein, wherein the functionalized substrate is at least partially dissolved in an aqueous solution during the wash cycle and/or rinse cycle at cold temperatures (i.e., less than about 5 ℃ or 10 ℃). A typical wash and/or rinse cycle should take about 10 minutes, or about 5 minutes. In one embodiment, the entire functionalized substrate is dissolved during the wash and/or rinse cycle. In one embodiment, PVA is mixed or blended with additional polymers to achieve the desired dissolution rate. It is believed that selecting the polymer 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 name MonoSol m8630, as sold by MonoSol. Other membranes suitable for use herein include those known under the trade name PT membranes or K-series membranes supplied by Aicello or VF-HP membranes supplied by Kuraray.

It is further believed that the particular blend of polymers provides a dissolved film or foam having the dissolution rate of the present invention, which can be prepared with good mechanical properties for subsequent processing and conversion into a finished product. For example, a blend containing at least two types of polymers having different molecular weights can be used to prepare a substrate that dissolves at the dissolution rates disclosed herein under cold water conditions. In one embodiment, such a blend contains at least a first polymer comprising a molecular weight greater than about 50,000, alternatively greater than about 60,000, alternatively greater than about 70,000, and a second polymer or mixture of polymers comprising an average molecular weight less than about 30,000, alternatively less than about 15,000, alternatively less than about 10,000.

The composition may comprise a polymer blend.

Blends of high and low molecular weight polymers of mixtures with low to high molecular weight polymer ratios of 80/20, 60/40, and 50/50 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 greater and a second PVA having a molecular weight of about 6,000 or less. This embodiment has been found to produce a film that dissolves at the rate defined herein under cold water conditions.

Further suitable solubility modifiers which are soluble in the given pH range are based on methacrylic acid copolymers, styrene hydroxystyrene copolymers, acrylate copolymers, polyethylene glycol polyvinyl acetate, diethyl phthalate, dioctyl sodium sulfosuccinate, poly dl-lactide-co-glycolide (PLG), vinylpyridine/styrene copolymers.

Solubility modifiers that are soluble in a particular chemical environment are also commercially available. For example, a caustic soluble barrier agent (caustic soluble barrier agent) is commercially available from Alcoa under the trade name Hydra-Coat-5. The water dispersible barrier agent is sodium starch glycolate, Crospovidone based, and is commercially available from FMC Corporation under the tradename Ac-di-sol, Edward Mendell Corporation under the tradename Explotab, and ISP under the tradename Croospovidone.

Polyacrylate-type mats (mat) function as structuring agents and include, in particular, polyacrylate polymers and copolymers of acrylates and methacrylates. An example of a suitable polyacrylate type structurant is Carbopol Aqua30 available from b.f. goodridge Company. Examples of polymer gums useful as structurants herein can be characterized as marine plants, terrestrial plants, microbial polysaccharides, and polysaccharide derivatives. Examples of marine vegetable gums include agar, alginate, carrageenan, and furcellaran. Examples of terrestrial plant gums include guar gum, gum arabic, gum tragacanth, 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, hydroxyethyl cellulose, propylene glycol alginate and hydroxypropyl guar. The second structurant is selected from the above list or combinations thereof. Acceptable polymer gums include pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum,

Gums (from CP Kelco) and guar gum. If a polymer cement structurant is used herein, an acceptable material of this type is gellan gum. Gellan gum has a tetrasaccharide repeat unit and contains glucose, and glucuronic acid, glucose.

The functionalized substrate may further comprise a plasticizer, such as glycerol, dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, and mixtures thereof. Glycerol is a preferred plasticizer. Other useful additives include disintegration aids.

Preferably, the water-susceptible composition comprises sodium citrate/citric acid, polyvinyl alcohol, maleic/acrylic acid copolymer sodium salt (preferably Sokolan CP5), methylglycinediacetic acid (MGDA), starch, silicone antifoam and/or carboxymethyl cellulose.

Coated detergent particle

Coated detergent particles are 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; WO 2013/149754; WO 2013/149755; WO 2013/149753; WO 2013/149752; and WO 2014/048857. In particular, WO2010/122050 describes a process for preparing coated detergent particles.

Experiment of

Effect of form on dye Damage

The use of bleach is often associated with dye damage on susceptible textiles. When using a compacted form, we have shown that this damage can be minimised compared to powders containing smaller particles of PAP.

Two comparative samples were prepared in an extruder, in one case the product from the extruder was controlled to powder/granules, in the other the product was shaped into lentil shape by extrusion under pressure and cutting the product into lentil shape. This is to illustrate how the physical form of the product may affect the degree of damage caused to the fabric.

Adjuvant particle/adjuvant formulations

The above formulation was mixed with water to form a soft solid which when processed through an extruder at 40 to 50 ℃, as disclosed in WO2010/122050, to provide lentil-like adjuvant particles having the following size ranges: 1mm thickness and 5mm diameter. The subsamples were added to a sieve type mill to produce a powder.

Particle size data of powder samples

Weight percent by sieve (4 minutes sieve at 1.2 amplitude, standard sieve shaker)

Crystal form thickness (average of 8 measurements using digital calipers)

Dye damage assessment

In the static contact test, a product containing bleach is compared to a control product without bleach at an equivalent level. The average measurement of color change using the CIE DE scale was recorded as shown.

A10 × 10cm piece of woven cotton fabric dyed with CI Sulfur Black 1(CAS #1326-82-5) was placed in a light tray and 5ml of water (26 ℃ FH) was added 0.5g of the formulation in adjuvant or powdered form was applied uniformly over a measuring 25cm of the formulation measured as 25 @²To a separate 10 × 10cm piece of heavy-duty (heavy-constract) knitted cotton, which was then placed on top of the dyed monitor to hold the product in place, an additional 50ml of water was added to the tray and incubated at 21 ℃ for 120 minutes, after which time the dyed monitor was rinsed in clear water and allowed to air dry in the dark, and the color change in the central area was then measured by reflectometry, the value of the color change (DE) was calculated with reference to the initial state.

It can clearly be seen that the color change of the lentil-shaped product is much smaller than the color change of the powdered sample.

Claims

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

(i) from 40 to 95 weight percent of a composition susceptible to attack by water, wherein the composition is selected from the group consisting of water-soluble materials, partially water-soluble materials, water-dispersible materials, water-disintegrating materials, and mixtures thereof; and the combination of (a) and (b),

(ii)5 to 60% by weight of phthalimido-peroxy-hexanoic acid particles dispersed in the composition susceptible to attack by water, the phthalimido-peroxy-hexanoic acid particles having a size of 10 to 200 microns,

wherein when 1 gram of said bleach adjunct particles are dissolved in 100ml demineralised water, the pH of the solution is in the range 3 to 6.

2. The bleach adjunct particle of claim 1, wherein said bleach adjunct particle comprises from 5% to 30% by weight of a sodium salt of a maleic/acrylic acid copolymer.

3. The bleach adjunct particle of claim 1 or 2, wherein the bleach adjunct particle comprises an acidic component selected from citric acid and methylglycinediacetic acid.

4. The bleach adjunct particle of claim 1 or 2, wherein the particle comprises from 0 to 15% by weight water.

5. The bleach adjunct particle of claim 4, wherein said particle comprises from 1 to 5% by weight water.

6. The bleach adjunct particle of claim 1, wherein the phthalimido-peroxy-hexanoic acid particle has a size of 20 to 50 microns.

7. The bleach adjunct particle of claim 1, wherein the phthalimido-peroxy-hexanoic acid particle has a size of 20 to 40 microns.

8. The bleach adjunct particle of claim 1, wherein the pH of the solution is in the range of 3 to 5 when 1 gram of said bleach adjunct particle is dissolved in 100ml demineralised water.

9. A laundry detergent comprising from 5 to 40 wt% of a bleach adjunct particle as defined in any one of the preceding claims and from 60 to 95 wt% of a coated detergent particle having orthogonal dimensions x, y and z, wherein x is from 0.5 to 2mm, y is from 2 to 8mm and z is from 2 to 8mm, wherein the particle comprises:

(i)20 to 50 wt% of a surfactant selected from anionic and nonionic surfactants;

10. A laundry detergent according to claim 9 comprising from 10 to 25 wt% of the bleach adjunct particle as defined in any one of the preceding claims.

11. A laundry detergent according to claim 9 comprising from 90 to 75 wt% of coated detergent particles having orthogonal dimensions x, y and z.

12. A plurality of particles according to any one of claims 1-8, wherein at least 90 to 100% of the particles are within a 20% variation in the x, y and z dimensions from largest to smallest particles.