EP3320076A1 - Large particles - Google Patents

Large particles

Info

Publication number
EP3320076A1
EP3320076A1 EP16719075.0A EP16719075A EP3320076A1 EP 3320076 A1 EP3320076 A1 EP 3320076A1 EP 16719075 A EP16719075 A EP 16719075A EP 3320076 A1 EP3320076 A1 EP 3320076A1
Authority
EP
European Patent Office
Prior art keywords
particle
water
bleach
adjunct
bleach adjunct
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16719075.0A
Other languages
German (de)
French (fr)
Other versions
EP3320076B1 (en
Inventor
Stephen Thomas Keningley
David Moorfield
Jonathan Osler
David Christopher Thorley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP3320076A1 publication Critical patent/EP3320076A1/en
Application granted granted Critical
Publication of EP3320076B1 publication Critical patent/EP3320076B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents

Definitions

  • the present invention provides for a bleaching adjunct for incorporation in a large particle formulation.
  • the present invention provides a bleach adjunct particle having
  • 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.
  • 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:
  • a surfactant selected from: anionic and non-ionic surfactants;
  • inorganic salts selected from: sodium carbonate and/or
  • adjunct particles 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.
  • the bleach adjunct particle and the coated laundry detergent particle are substantially the same shape and size.
  • the bleach adjunct particle and the coated laundry detergent particle are curved.
  • the particle may be shaped as a disc.
  • 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.
  • the Bleach Adjunct Particle is preferably uncoated in contrast to the laundry detergent particle.
  • the bleaching agent used in the adjunct particle is phthalimido-peroxy-hexanoic-acid (CAS 128275-31 -0) (PAP).
  • PAP phthalimido-peroxy-hexanoic-acid
  • 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.
  • a carrier such as starch, cellulose, methyl cellulose, ethyl cellulose and propyl cellulose
  • cellulose ethers such as starch, cellulose, methyl cellulose, ethyl cellulose and propyl cellulose
  • cellulose esters include cellulose amides polysaccharides including starch, modified starch; gelatin; alginates;
  • 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.
  • the key parameter is the thickness and thickness distribution, this is measured using a micrometer.
  • 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.
  • water-soluble materials include partially water- soluble materials.
  • 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).
  • 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.
  • 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.
  • the polymer comprises PVA; PVA copolymers; hydroxypropyl methyl cellulose (HPMC); and mixtures thereof.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • polymeric gums which may be used as structurant herein can be characterized as marine plant, terrestrial plant, microbial polysaccharides and
  • polysaccharide derivatives examples include 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
  • 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.
  • 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.
  • 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 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 is described in the following patent applications:
  • WO2013/149755 describes a process for the preparation of a coated detergent particle.
  • WO2013/149753 describes a process for the preparation of a coated detergent particle.
  • WO2013/149752 describes a process for the preparation of a coated detergent particle.
  • 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.
  • Citric acid 8% 5% 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

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.
EP16719075.0A 2015-07-08 2016-04-27 Large particles Active EP3320076B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15175808 2015-07-08
PCT/EP2016/059426 WO2017005386A1 (en) 2015-07-08 2016-04-27 Large particles

Publications (2)

Publication Number Publication Date
EP3320076A1 true EP3320076A1 (en) 2018-05-16
EP3320076B1 EP3320076B1 (en) 2019-01-02

Family

ID=53541534

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16719075.0A Active EP3320076B1 (en) 2015-07-08 2016-04-27 Large particles

Country Status (8)

Country Link
EP (1) EP3320076B1 (en)
CN (1) CN107771211B (en)
BR (1) BR112018000313B1 (en)
CL (1) CL2018000022A1 (en)
PH (1) PH12017502304A1 (en)
TR (1) TR201901001T4 (en)
WO (1) WO2017005386A1 (en)
ZA (1) ZA201708393B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020109227A1 (en) 2018-11-28 2020-06-04 Unilever N.V. Large particles

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1289155B1 (en) * 1997-01-03 1998-09-29 Ausimont Spa GRANULAR COMPOSITIONS OF PEROXYESANOIC E-PHTHALYMIDIC ACID
GB2406338A (en) * 2003-09-22 2005-03-30 Reckitt Benckiser Nv Package comprising a detergent composition
PL1601753T3 (en) * 2003-03-11 2007-12-31 Reckitt Benckiser Nv Package comprising a detergent composition
ITMI20040498A1 (en) * 2004-03-16 2004-06-16 Solvay Solexis Spa GRANULAR COMPOSITIONS
GB0509377D0 (en) * 2005-05-09 2005-06-15 Reckitt Benckiser Nv Detergent composition
ES2537714T3 (en) * 2010-10-14 2015-06-11 Unilever N.V. Laundry detergent particles
IN2013MN00622A (en) * 2010-10-14 2015-06-12 Unilever Plc
GB201019628D0 (en) * 2010-11-19 2010-12-29 Reckitt Benckiser Nv Dyed coated bleach materials

Also Published As

Publication number Publication date
EP3320076B1 (en) 2019-01-02
CN107771211A (en) 2018-03-06
CL2018000022A1 (en) 2018-07-06
ZA201708393B (en) 2019-06-26
PH12017502304B1 (en) 2018-06-25
WO2017005386A1 (en) 2017-01-12
CN107771211B (en) 2020-07-07
BR112018000313A2 (en) 2018-09-04
BR112018000313B1 (en) 2022-08-30
PH12017502304A1 (en) 2018-06-25
TR201901001T4 (en) 2019-02-21

Similar Documents

Publication Publication Date Title
JP5620105B2 (en) Water-soluble film
EP1355977B1 (en) Water dissolvable polymer film forming compositions and articles made therefrom
CN103946360A (en) Solid and liquid textile-treating compositions
US20080110370A1 (en) Water-soluble film
US20080146481A1 (en) Water-soluble detergent pouch
JP2017500376A5 (en)
JPH06504811A (en) Cold water soluble films and film-forming compositions
KR102642561B1 (en) Sheet for laundry
EP3320076B1 (en) Large particles
WO2018231885A1 (en) Water-soluble unit dose article comprising a solid laundry detergent composition
EP1553930A1 (en) Capsule and film-forming composition comprising gum arabic
JP2004026861A (en) Water-soluble cellulose ether of high filterability and its selection method
JP5196151B2 (en) Method for selecting hydroxyalkylalkylcellulose
JP2001098090A (en) Method for production of film
EP4176039A1 (en) Particulate laundry composition
WO2018231679A1 (en) Water-soluble unit dose article comprising a solid laundry detergent composition
JP2018162232A (en) Covered chlorine agent tablet and chlorine agent tablet package
WO2000063341A1 (en) Process for making non-staining colored particles for improving aesthetics of a liquid automatic dishwashing detergent product, the particles, and a composition
JP2004307598A (en) Water-soluble resin composition and film

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20171207

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
INTG Intention to grant announced

Effective date: 20180821

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1084380

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190115

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016009012

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190102

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1084380

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190402

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190502

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190402

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190502

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190403

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016009012

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20191003

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160427

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602016009012

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

Free format text: FORMER OWNER: UNILEVER NV, ROTTERDAM, NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20220127 AND 20220202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230424

Year of fee payment: 8

Ref country code: DE

Payment date: 20220620

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20230424

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230419

Year of fee payment: 8