EP3523413B1 - Bleichzusammensetzung - Google Patents

Bleichzusammensetzung Download PDF

Info

Publication number
EP3523413B1
EP3523413B1 EP16810082.4A EP16810082A EP3523413B1 EP 3523413 B1 EP3523413 B1 EP 3523413B1 EP 16810082 A EP16810082 A EP 16810082A EP 3523413 B1 EP3523413 B1 EP 3523413B1
Authority
EP
European Patent Office
Prior art keywords
weight
fabrics
polymer
amount
bleaching composition
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.)
Active
Application number
EP16810082.4A
Other languages
English (en)
French (fr)
Other versions
EP3523413A1 (de
Inventor
Matteo LEGA
Stefano Resta
Luca Sarcinelli
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.)
Fater SpA
Original Assignee
Fater SpA
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 Fater SpA filed Critical Fater SpA
Publication of EP3523413A1 publication Critical patent/EP3523413A1/de
Application granted granted Critical
Publication of EP3523413B1 publication Critical patent/EP3523413B1/de
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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to bleaching compositions, in particular to hypochlorite bleaching compositions, suitable for use in hard surface cleaning and laundry applications such as hand and machine laundry methods.
  • Bleaching compositions are well-known in the art. Amongst the different bleaching compositions available, those relying on bleaching by hypohalite bleaches such as hypochlorite are often preferred, mainly for performance reasons, especially at lower temperature.
  • hypochlorite based-compositions a problem encountered with the use of hypochlorite based-compositions is the resulting damage and/or yellowing of the fabrics being bleached.
  • EP0867502 discloses a bleaching composition comprising sodium tripolyphosphate (STPP).
  • Bleaching compositions comprising hybrid polymers are disclosed in US2013165572 , US5185096 and WO2013064647 .
  • hypohalite-containing composition suitable for use in laundry applications, which, maintaining the performances related to fabric whiteness, allows a better safety of fabrics treated therewith, in particular in terms of reduction of tensile strength loss.
  • compositions according to claim 1 a process according to claim 8 and a use according to claim 9.
  • a liquid bleaching composition According to a first aspect of the invention, there is provided a liquid bleaching composition.
  • the present invention also encompasses a process of treating fabrics where said fabrics are immersed in a bleaching solution formed by diluting said bleaching composition in water.
  • the present invention further encompasses the use, in a hypohalite bleaching composition, of a hybrid polymer, for providing improved fabric safety to the fabrics treated therewith while maintaining fabric whiteness comparable to that obtained with product that are free from the hybrid polymer.
  • the present invention further encompasses the use, in a hypohalite bleaching composition, of an hybrid polymer, for providing improved shine properties to hard surfaces treated therewith.
  • the present invention further encompasses the use, in a hypohalite bleaching composition with a surfactants system, of a hybrid polymer, for providing improved stability in terms of gas evolution from hypoalite degradation.
  • Hypohalite bleaches may be provided by a variety of sources, including bleaches that are oxidative bleaches and subsequently lead to the formation of positive halide ions as well as bleaches that are organic based sources of halides such as chloroisocyanurates.
  • Suitable hypohalite bleaches for use herein include alkali metal and alkaline earth metal hypochlorites, hypo-bromites, hypoiodites, chlorinated trisodium phosphate dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
  • the preferred hypohalite bleaches among the above described are the alkali metal and/or alkaline earth metal hypochlorites, more preferably selected from the group consisting of sodium, potassium, magnesium, lithium and calcium hypochlorites, and mixtures thereof, even more preferably the sodium hypochlorite.
  • the liquid compositions according to the present invention comprise said hypohalite bleach such that the content of active halide in the composition is of from 0.1% to 20% by weight, more preferably from 2% to 8% by weight, most preferably from 2.5% to 5% by weight of the composition.
  • a source of alkalinity is another essential component for the compositions of the invention.
  • the source of alkalinity ensures that the pH of the composition as it is, is typically from 12 to 14 measured at 25°C.
  • the composition of the invention is buffered to a pH value ranging from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5 after the composition has been diluted into 1 to 500 times its weight of water. It is in this alkaline range that the optimum stability and performance of the hypohalite as well as fabric whiteness and safety are obtained.
  • the pH range is suitably provided by the source of alkalinity and the hypohalite bleach mentioned hereinbefore, which are alkalis.
  • Suitable sources of alkalinity for use herein are selected from the group consisting of pH buffering agents, strong bases or mixtures thereof.
  • Preferred pH buffering agents are selected from the group consisting of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, borates, metaborates, phosphates, stannates, alluminates and mixtures thereof, and preferably are selected from the group consisting of sodium carbonate, sodium silicate, sodium borate, and mixtures thereof.
  • Preferred strong bases are selected from the group consisting of caustic alkalis such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such as sodium and/or potassium oxide and mixtures thereof, and preferably are selected from the group consisting of sodium hydroxide and potassium hydroxide.
  • the source of alkalinity is a mixture of sodium carbonate and sodium hydroxide.
  • the amount of the source of alkalinity in the composition is from 0.05% to 10% by weight of the total composition, preferably from 0.5% to 5% and more preferably from 1.0 to 4.0.
  • Typical levels of such strong bases when present, are of from 0.01% to 3.5% by weight, preferably from 0.1% to 3.0%, preferably from 0.5% to 2.8% even more preferably from 0.8 to 2.5% by weight of the composition.
  • Liquid bleaching compositions herein will contain an amount of pH buffering agent of from 0.05% to 5% by weight, preferably from 0.5% to 5% by weight, and more preferably in an amount of from 0.6% to 3% by weight of the composition.
  • a hybrid polymer component is another essential component for the compositions of the invention.
  • hybrid copolymers useful in the composition of the invention are all those disclosed in EP1746109B1 .
  • Graft copolymers are defined as a backbone of one monomer or polymer and one or more side chains derived from another monomer(s) attached on to the backbone ( Odian, George, PRINCIPLES OF POLYMERIZATION, 2nd ed., Wiley-Interscience, New York, p. 424 (1981 )). Graft copolymers (such as those described in U.S. Patent Nos. 5,854,191 , 5,223,171 , 5, 227, 446 and 5,296,470 ) typically have a natural polymer backbone and short side chains derived from synthetic monomers.
  • the hybrid copolymers of the present invention have long chains of synthetic monomers that incorporate a moiety derived from natural material at the end of the chain. From Mark, Herman F., ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, 3rd ed., Vol. 11, Wiley-Interscience, New York, p. 380 (2004 ), fragments of a chain transfer agent are incorporated into polymer chains as end groups. A transfer reaction can therefore be used to introduce specific end groups into the polymeric material.
  • the hybrid polymers of the composition of the present invention comprise a hydroxyl containing naturally derived chain transfer agent selected from the group consisting of gluconic acid, glucoheptonic acid and naturally derived mono-, di-, oligo- or polysaccharides, as the chain terminating portion of the polymer.
  • Examples of naturally derived mono-, di-, oligo- or polysaccharides include sucrose, fructose, maltose, glucose, and saccharose, as well as reaction products of saccharides such as mannitol, sorbitol and so forth.
  • the chain transfer agents include oxidatively, hydrolytically or enzymatically degraded monosaccharides, oligosaccharides and polysaccharides, as well as chemically modified monosaccharides, oligosaccharides and polysaccharides.
  • Such chemically modified derivatives include carboxylates, sulfonates, phosphates, phosphonates, aldehydes, silanes, alkyl glycosides, alkyl-hydroxyalkyls, carboxy-alkyl ethers and other derivatives.
  • Polysaccharides useful in the present invention can be derived from plant, animal and microbial sources.
  • examples of such polysaccharides include starch, cellulose, gums (e.g., gum arabic, guar and xanthan), alginates, pectin and gellan.
  • Starches include those derived from maize and conventional hybrids of maize, such as waxy maize and high amylose (greater than 40% amylose) maize, as well as other starches such as potato, tapioca, wheat, rice, pea, sago, oat, barley, rye, and amaranth, including conventional hybrids or genetically engineered materials.
  • hemicellulose or plant cell wall polysaccharides such as D-xylans.
  • plant cell wall polysaccharides include arabino-xylans such as corn fiber gum, a component of corn fiber.
  • An important feature of these polysaccharides is the abundance of hydroxyl groups. These hydroxyl groups provide sites for chain transfer during the polymerization process. The higher the number of secondary and tertiary hydroxyl groups in the molecule the more effective it will be as chain transfer agent.
  • chain transfer agents include maltodextrins, which are polymers having D-glucose units linked primarily by ⁇ -1,4 bonds and have a dextrose equivalent ('DE') of less than about 20.
  • Maltodextrins are available as a white powder or concentrated solution and are prepared by the partial hydrolysis of starch with acid and/or enzymes.
  • the chain transfer agents are maltodextrins and/or low molecular weight oxidized starches.
  • Useful chain transfer agents according to the present invention have molecular weights of less than about 20,000. In another aspect, the chain transfer agents have molecular weights of less than about 2000. In even another aspect, chain transfer agents according to the present invention have molecular weights of less than 1000.
  • Polysaccharides can be modified or derivatized by etherification (e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyltrimethylarmnonium chloride), esterification (e.g., via reaction with acetic anhydride, octenyl succinic anhydride ('OSA')), acid hydrolysis, dextrinization, oxidation or enzyme treatment (e.g., starch modified with ⁇ -amylase, ⁇ -amylase, pullanase, isoamylase or glucoamylase), or various combinations of these treatments.
  • etherification e.g., via treatment with propylene oxide, ethylene oxide, 2,3-epoxypropyltrimethylarmnonium chloride
  • esterification e.g., via reaction with acetic anhydride, octenyl succinic anhydride ('OSA')
  • acid hydrolysis e.g., via reaction with acetic an
  • the hydroxyl-contairiing naturally derived chain transfer agents can be used from about 0.1 to about 75% by weight based on total weight of the polymer. In one aspect, the range is from about 1 to about 50% by weight of chain transfer agents based on total weight of the polymer.
  • the hybrid copolymers are prepared from at least one hydrophilic acid monomer as the synthetic constituent.
  • hydrophilic acid monomers include but are not limited to acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloro-acrylic acid, ⁇ -cyano acrylic acid, ⁇ -methyl-acrylic acid (crotonic acid), ⁇ -phenyl acrylic acid, ⁇ -acryloxy propionic acid, sorbic acid, ⁇ -chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, ⁇ -styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3), itaconic acid, maleic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, tricarboxy ethylene, 2-acryloxypropionic acid, 2-acrylamido-2-methyl propane sulfonic acid, vinyl sul
  • Moieties such as maleic anhydride or acrylamide that can be derivatized to an acid containing group can be used.
  • Combinations of acid-containing hydrophilic monomers can also be used.
  • the acid-containing hydrophilic monomer is acrylic acid, maleic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid or mixtures thereof.
  • hydrophobic monomers can also be used as the synthetic constituent.
  • hydrophobic monomers include, for example, ethylenically unsaturated monomers with saturated or unsaturated alkyl, hydroxyalkyl, alkylalkoxy groups, arylalkoxy, alkarylalkoxy, aryl and aryl-alkyl groups, alkyl sulfonate, aryl sulfonate, siloxane and combinations thereof.
  • hydrophobic monomers examples include styrene, ⁇ -methyl styrene, methyl methacrylate, methyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, octyl acrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 1-vinyl naphthalene, 2-vinyl naphthalene, 3-methyl styrene, 4-propyl styrene,
  • the hybrid polymers have thus the performance properties of synthetic polymers but use lower cost, readily available and environmentally friendly materials derived from renewable sources.
  • the number average molecular weight of the hybrid copolymer is between about 1000 and about 100, 000. In another aspect, the number average molecular weight of the polymer is between about 2000 and about 25,000.
  • the hybrid polymer is present in an amount of about 0.02% to about 2% by weight of the total composition, preferably from 0.03% to 1% by weight of the total composition.
  • the polymerization process can be a solution or suspension process.
  • the process involves polymerization using free radical initiators with one or more of the above hydrophilic and/or hydrophobic monomers, and the hydroxyl containing natural products used as chain transfer agents or chain stoppers. These chain transfer agents can be added either at the beginning of the reaction or during reaction as the monomer(s) is (are) added.
  • This system makes use of typical free radical initiators. Unlike grafting systems, special redox systems such as Ce(IV) salts are not required. Instead, easy-to-use thermally activated initiators such as sodium persulfate can be used. One skilled in the art will recognize that most initiating systems are applicable here.
  • a high degree of chain transfer can lead to crosslinking and formation of an insoluble gel. In one embodiment, this can be avoided by ensuring that monomer and initiator are fed over the same approximate period of time. If initiator feed lasts much longer than monomer feed, a crosslinked gel can form, particularly when oligopolysaccharides and polysaccharides (those having a molecular weight greater than about 1000) are used as the chain transfer agent.
  • the reaction product forms a hybrid gel during manufacture of these hybrid copolymers.
  • the synthetic monomer used is extremely reactive (e.g., acrylic acid reacted at low pH (protonated form)) or if the natural chain transfer agent has a molecular weight of greater than about 1000.
  • a crosslinked gel starts to form after the monomer feed has ended and while the rest of the initiator is being fed in. This is undesirable in most cases, since the gel product cannot be diluted in water.
  • an undesirable gel starts to form during the process due to a reactive monomer, it can be eliminated in a number of ways. This includes reducing monomer reactivity by neutralizing the monomer. Alternatively, additional chain transfer agents like thiols, sodium hypophosphite and alcohols can also be used. Thiols and alcohols are particularly useful in controlling molecular weight and preventing the formation of crosslinked gels. Finally, these gels can be eliminated by shortening the initiator feeds so that the initiator and monomer feeds are pumped over the same period of time.
  • hybrid polymers examples include but not limited to 6 of EP1746109 .
  • a preferred hybrid polymer to be used in the bleaching composition of the present invention is Alcoguard H5941 from Akzo Nobel, a hybrid polymer as above described of amylose-polyacrylate having a molar ratio between the polyacrylate and the amylose of from 1:1 to 1:100, preferably from 1:1 to 1:10, more preferably from 1:2 to 1:5, even more preferably 1:3, a molecular weight of the polyacrylate between 140 and 2500 and a molecular weight of the amylose between 342 and 3400.
  • composition according to the invention may also comprise one surfactant or a mixture of surfactants, added in a quantity sufficient to give the desired cleaning effectiveness.
  • surfactant refers to a substance which is able to lower the surface tension of the water.
  • the total level of surfactants varies from 0.001 to 20% w/w of the total quantity of aqueous solution, more preferably from 0.01 to 10%, even more preferably from 0.01 to 7%, even mere preferably from 0.0125 to 5%.
  • the surfactant or the mixture of surfactants contained in the liquid composition of the present invention are preferably anionic, nonionic, cationic, zwitterionic, amphoteric, ampholytic surfactants or mixtures thereof.
  • Non-exhaustive examples of anionic surfactants suited to the present invention comprise conventional anionic surfactants.
  • a sulfate surfactant such as alkoxylate and/or non-alkoxylate alkyl sulfates, and/or sulfonated surfactants, for example, alkyl benzene sulfonates, and their hydrosoluble salts.
  • alkoxylate alkyl sulfates comprise ethoxylated, propoxylated, ethoxylated/propoxylated and butoxylated alkylsulfate surfactants.
  • the alkyl group contains approximately 7 to approximately 20 atoms of carbon.
  • anionic surfactants that can be used for the present invention are the water soluble salts of paraffin sulfonates and secondary alkane sulfonates containing approximately 7 to approximately 20 atoms of carbon; alkyl glyceryl ether sulfonates, especially alcohol ethers from C7 to C20.
  • alkyl glyceryl ether sulfonates especially alcohol ethers from C7 to C20.
  • anionic surfactants useful for the present invention are the water soluble salts of carboxylic acid, for example lauroyl sarcosinate or myristoyl sarcosinate.
  • the anionic surfactants are preferably hydrosoluble salts of alkali metals, ammonium salts and alkylammonium salts.
  • Non-exhaustive examples of nonionic surfactants suited to the present invention comprise fatty alcohol alkoxylates and alkyl amine oxides.
  • the fatty alcohol alkoxylates can be chosen from alcohol alkoxylates and alkylphenol alkoxylates with formula RO-(E) e -(P) p -H, in which
  • the alkyl amine oxides preferably have the formula R 1 R 2 R 3 NO, in which each R 1 , R 2 and R 3 groups are independently a C1-C30 alkyl group, more preferably a C1-C20 alkyl group, more preferably a C1-C18 hydrocarbon chain, even more preferably R 1 and R 2 are methyl groups, and R 3 is a C8-C18 hydrocarbon chain.
  • Non-exhaustive examples of cationic surfactants suitable for the present invention comprise quaternary ammonium surfactants, which can have up to 26 carbon atoms , alkoxylated surfactants of quaternary ammonium, such as hydroxyethyl dimethyl quaternary ammonium, hydroxyethyl lauryl dimethyl ammonium chloride.
  • Non-exhaustive examples of zwitterionic surfactants suitable for the present invention comprise derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium quaternary phosphonium or compounds of tertiary sulphonium salts.
  • Non-exhaustive examples of ampholytic and/or amphoteric surfactants suitable for the present invention include derivatives of secondary or tertiary aliphatic amines, or heterocyclic aliphatic derivatives of secondary and tertiary amines in which the aliphatic radical can be linear or branched.
  • One of the aliphatic substituents can contain at least 8 atoms of carbon, for example 8 to 18 atoms of carbon, and at least one contains an anionic water solubilising group, for example carbonyl, sulfonate or sulfate.
  • At least one surfactant chosen from the group consisting of soluble salts of alkyl sulfates (primary or secondary ⁇ , soluble salts of alkyl sulfonates (primary or secondary ⁇ , paraffin sulfonates and secondary alkane sulfonates, linear or branched ethoxylated alcohols, amine alkyl oxides or quaternary ammonium surfactants is particularly preferred.
  • composition according to the invention may also comprise further optional components such as perfumes, bleach-stable surfactants, organic or inorganic alkalis, pigments, dyes, optical brighteners, solvents, chelating agents, radical scavengers and mixtures thereof.
  • perfumes bleach-stable surfactants, organic or inorganic alkalis, pigments, dyes, optical brighteners, solvents, chelating agents, radical scavengers and mixtures thereof.
  • the bleaching compositions of the invention are used in diluted form in laundry applications.
  • the expression "used in diluted form” herein includes dilution by the user, which occurs for instance in handwash laundry applications, as well as dilution by other means, such as in a washing machine.
  • the bleaching composition is diluted into 5 to 500 times its weight of water for hand laundry application and 10 to 500 times its weight of water in a washing machine.
  • hypohalite bleaching composition of an hybrid polymer for providing improved safety to the fabrics treated therewith while maintaining whiteness properties comparable to those of bleaching compositions that do not comprise the hybrid polymer.
  • improved safety it is meant that hypohalite bleaching compositions, with the hybrid polymer, provide better safety, i.e. less tensile strength loss, compared to hypohalite bleaching compositions which do not comprise said hybrid polymer ingredient.
  • Example 5 as well as examples 1, 2, 6, and 13 are not within the scope of current invention and they are therefore reference examples.
  • Table 1 sample %AvCl %NaOH %Na 2 CO 3 %STPP %Alcoguard H5941 %water 1 3.00 1.00 1.75 --- --- Complement to 100% 2 3.00 1.00 1.75 0.049 --- Complement to 100% 3 3.00 1.00 1.75 --- 0.049 Complement to 100% 4 5.00 1.00 1.75 --- 0.200 Complement to 100% 5 (not within the invention) 2.00 1.00 1.75 --- 0.01 Complement to 100% 6 3.00 1.20 1.20 0.049 --- complement to 100% 7 3.00 1.20 1.20 --- 0.049 Complement to 100% 8 3.00 1.20 1.20 --- 0.10 Complement to 100% 9 3.00 1.20 1.20 0.049 0.049 Complement to 100% 10 3.00 4.00 4.00 --- 0.049 Complement to 100% 11 3.00 0.15 0.15 --- 0.049 Complement to 100% 12 3.00 0.15 4.00 --- 0.0
  • RAT Rapid Aging Test
  • Example 2 performances in terms of whiteness and mechanical properties in laundry applications - knitted cotton
  • each formulation was diluted in 500 mL of tap water (dilution 7.5/500; pH TW>10), having a Fe content of 61.3 ppb, a Mn content of 2.6 ppb and a total hardness of 26°f (260 mg/L) .
  • the fabrics were analyzed by spectrophotometer in order to assess whiteness (WI Ganz).
  • Example 3 performances in terms of whiteness and mechanical properties in laundry applications-woven cotton
  • the test was repeated changing the key experimental conditions, namely: type of cotton, simulated wash condition and product formula.
  • type of cotton used determines the type of resistance test performed on fabric: burst test (UNI EN ISO 13938-2:2001) for knitted cotton or tear test (UNI EN ISO 13934-1:2000) for woven cotton.
  • formulations 6 and 7 were tested. The following procedure was used: 1.0 g of formulations 6 and 7 was diluted in 200 mL of tap water (dilution 2.5/500; pH TW>10). For every formulation, 5 fabrics (standard woven cotton provided by equest, 20x20 cm, in total ⁇ 40 g) were added to the solution. After 20 minutes, fabrics were rinsed 3 times and dried by tumble dryer.
  • the wash cycle was repeated for 20 times.
  • the fabrics were analyzed by spectrophotometer in order to assess whiteness (WI Ganz).
  • Table 5 Sample WI Ganz 6 (0.049 STPP) 228 7 (0.049 ALC) 222 untreated fabric (woven cotton) 263
  • Results for sample 7 clearly show a recovery in tensile strength loss about 50% compared with sample 6, confirming the beneficial effect.
  • Example 4 performances in terms of whiteness and mechanical properties in laundry applications-woven cotton
  • the fabrics were analyzed by spectrophotometer in order to assess whiteness (WI Ganz), and not relevant differences between Alcoguard and STPP were observed.
  • Example 5 performances in terms of whiteness and mechanical properties in laundry applications-woven cotton
  • compositions 6 0.049 STPP
  • 7 0.049 Alcoguard
  • Multicycle test (20 cycle) were performed in washing machine (Ariston Hotpoint ARXF 109) at 30°C.
  • the test procedure was the following:
  • composition of the invention still allows a reduction of the loss in tensile strength of the treated fabrics.
  • Example 6 performances in terms of whiteness and mechanical properties in laundry applications- ISO cotton
  • compositions 6 0.049 STPP
  • 7 0.049 Alcoguard
  • composition of the invention allows a reduction of the loss in tensile strength of the fabrics treated according to standard procedures.
  • Example 7 performances on shine in hard surface cleaning applications
  • the procedure was the following: 15 mL of products were diluted in 500 mL of water. A soft, previously conditioned, sponge was soaked in the solution, then wringed up to a water uptake of 2 g.
  • the sponge was rubbed uniformly on the surface of a black, conditioned ceramic tile. The operation was repeated 3 times in different directions. The tail was left to dry for 10 minutes before evaluation of 4 trained graders.
  • compositions were tested (Table 12). Composition 10 has been taken as reference.
  • Examples 17 and 18 are not in accordance to the current invention and they are therefore reference examples.
  • Table 12 Sample %AvCl %NaOH %Na2CO3 %STPP %Alcoguard %water 17 3.00 1.2 1.2 0.049 --- Complement to 100 18 3.00 1.1 1.1 0.049 --- Complement to 100 19 3.00 1.1 1.1 --- 0.049 Complement to 100
  • Alcoguard delivers a benefit in surface care in terms of shine and residues.
  • a reasonable mechanism is the improved dispersion ability towards salt residues on the surface, which allows less visible strokes.
  • Examples 20, 21, and 24-27 are not in accordance to the current invention and they are therefore reference examples.
  • Table 14 Compositions 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 Sodium hypochlorite 3 3 3 3 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 0.7 1 1.5 3 3
  • hypochlorite-containing formulations develops molecular oxygen as main degradation product of the oxidant.
  • This reaction is catalytically enhanced by metal impurities which are usually present in water, such as copper and iron.
  • metal impurities which are usually present in water, such as copper and iron.
  • This phenomenon is very relevant for bleach products, because large values of gas evolution rate may cause bulging of bottles, which would cause drawbacks in terms of aesthetics and safety of the packaging. For this reason, GER is a key parameter for the assessment of the robustness of new formulations.
  • the Gas Evolution Rate test has been performed measuring the pressure increase in a close bottle containing a known volume of product at 50°C ( ⁇ 0.5°C).
  • the pressure increase and the gas evolution rate were related on the basis of the following equation:
  • composition from 13 to 16 were tested also with a contamination of iron (400 ppb) and copper (200 ppb), which was added on top of the product.
  • the product already contains about 200 ppb of iron and 200 ppb of copper coming from raw materials.
  • Example 9 performances in terms of whiteness and mechanical properties in laundry applications for woven and ISO cotton
  • compositions 13, 14 and 15 have been tested in a laundry test.
  • Multicycle test (20 cycle) were performed in washing machine (Ariston Hotpoint ARXF 109) at 30°C.
  • the test procedure was the following:
  • composition of the invention still allows a reduction of the loss in tensile strength of the treated fabrics.

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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (9)

  1. Flüssigbleichzusammensetzung umfassend:
    - Hypohalitbleiche in einer Menge von 2,5 bis 5 Gewichtsprozent der Gesamtzusammensetzung,
    - eine Alkalinitätsquelle in einer Menge von 0,05 bis 10 Gew.-% der Gesamtzusammensetzung, wobei die Alkalinitätsquelle eine Mischung aus Natriumcarbonat und Natriumhydroxid ist, und
    - ein Hybridpolymer in einer Menge von 0,02% bis 2 Gew.-% der Gesamtzusammensetzung, das Hybridpolymer umfassend:
    ein synthetisches Polymer als Rückgrat des Hybridpolymers und
    ein Kettentransfermittel ausgewählt aus der Gruppe bestehend aus Gluconsäure,
    Glucoheptonsäure und natürlich abgeleiteten Mono-, Di-, Oligo- oder Polysacchariden als Kettenabschlussteil des Polymers.
  2. Flüssigbleichzusammensetzung nach Anspruch 1, wobei es sich bei der Hypohalitbleiche um ein Alkalimetall oder ein Alkali-Erdmetall-Hypochlorit handelt.
  3. Flüssigbleichzusammensetzung nach einem der Ansprüche 1 oder 2, wobei der Hypohalit, basierend auf aktivem Halogenid, in einer Menge von 0,1% bis 20 Gew.-% vorhanden ist.
  4. Flüssigbleichzusammensetzung nach Anspruch 1, wobei die Menge des Hybridpolymers 0,02 % bis etwa 2 Gew.-% der Gesamtzusammensetzung beträgt.
  5. Flüssigbleichzusammensetzung nach Anspruch 1, wobei das Hybridpolymer Polyacrylat als synthetisches Polymer und Amylose als Kettentransfermittel umfasst.
  6. Flüssigbleichzusammensetzung nach Anspruch 5, wobei das Molverhältnis zwischen der Menge an Polyacrylat und der Menge an Amylose von 1:1 bis 1:100, vorzugsweise von 1:1 bis 1:10, besonders bevorzugt von 1:2 bis 1:5, noch bevorzugter 1:3, das Molekulargewicht des Polyacrylats von 1600 und das Molekulargewicht der Amylose zwischen 342 und 3400 beträgt.
  7. Flüssigbleichzusammensetzung nach einem der vorhergehenden Ansprüche, wobei ein oder mehrere Tenside vorhanden sind und zwischen 0,01 % und 10 Gew.-% der Gesamtzusammensetzung umfassen.
  8. Ein Verfahren zum Bleichen von Stoffen mit einer Bleichzusammensetzung nach einem der Ansprüche 1 bis 7, wobei die Stoffe in eine Bleichlösung eingetaucht werden, die durch Verdünnen dieser Bleichzusammensetzung in Wasser gebildet ist.
  9. Verwendung, in einer Hypohalit-Bleichzusammensetzung wie in den Ansprüchen 1 bis 7 definiert, eines Hybridpolymers in einer Menge von 0,02 bis 2 Gew.-% der Gesamtzusammensetzung, wobei das Hybridpolymer umfasst:
    - ein synthetisches Polymer als Rückgrat des Hybridpolymers und
    - ein Kettentransfermittel, ausgewählt aus der Gruppe bestehend aus Gluconsäure, Glucoheptonsäure und natürlich abgeleiteten Mono-, Di-, Oligo- oder Polysacchariden, als Kettenabschlussteil des Polymers
    für eine verbesserte Sicherheit der damit behandelten Stoffe oder für einen verbesserten Glanz der damit behandelten harten Oberfläche.
EP16810082.4A 2016-10-05 2016-10-05 Bleichzusammensetzung Active EP3523413B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2016/000228 WO2018066006A1 (en) 2016-10-05 2016-10-05 Bleaching composition

Publications (2)

Publication Number Publication Date
EP3523413A1 EP3523413A1 (de) 2019-08-14
EP3523413B1 true EP3523413B1 (de) 2021-05-12

Family

ID=57543113

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16810082.4A Active EP3523413B1 (de) 2016-10-05 2016-10-05 Bleichzusammensetzung

Country Status (3)

Country Link
EP (1) EP3523413B1 (de)
PT (1) PT3523413T (de)
WO (1) WO2018066006A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7446413B2 (ja) 2019-09-26 2024-03-08 エコラボ ユーエスエー インコーポレイティド 主要な増粘系としてジウタンガムを使用した高アルカリ溶剤ベースの脱脂剤およびクリーナー

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2574551B1 (fr) 1984-12-12 1986-12-26 Commissariat Energie Atomique Procede de generation et de traitement de signaux pour l'obtention par resonance magnetique nucleaire d'une image exempte de distorsions a partir d'un champ de polarisation inhomogene
US5185096A (en) * 1991-03-20 1993-02-09 Colgate-Palmolive Co. Aqueous liquid automatic dishwashing detergent composition comprising hypochlorite bleach and bleach stabilizer
DE4003172A1 (de) 1990-02-03 1991-08-08 Basf Ag Pfropfcopolymerisate von monosacchariden, oligosacchariden, polysacchariden und modifizierten polysacchariden, verfahren zu ihrer herstellung und ihre verwendung
FR2663940B1 (fr) 1990-07-02 1994-04-08 Rhone Poulenc Chimie Polysaccharides greffes, leur procede de preparation et leur application comme agents de sequestration.
FR2663948B1 (fr) 1990-07-02 1994-06-03 Rhone Poulenc Chimie Composition detergente contenant un polysaccharide greffe biodegradable.
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
ATE282687T1 (de) 1997-03-27 2004-12-15 Procter & Gamble Bleichmittelzusammensetzungen
US7666963B2 (en) 2005-07-21 2010-02-23 Akzo Nobel N.V. Hybrid copolymers
US9309435B2 (en) * 2010-03-29 2016-04-12 The Clorox Company Precursor polyelectrolyte complexes compositions comprising oxidants
EP2773320B1 (de) * 2011-11-04 2016-02-03 Akzo Nobel Chemicals International B.V. Hybriddendrit-copolymere, zusammensetzungen daraus und verfahren zu ihrer herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
WO2018066006A1 (en) 2018-04-12
PT3523413T (pt) 2021-07-06
EP3523413A1 (de) 2019-08-14

Similar Documents

Publication Publication Date Title
EP2773320B1 (de) Hybriddendrit-copolymere, zusammensetzungen daraus und verfahren zu ihrer herstellung
US9051406B2 (en) Graft dendrite copolymers, and methods for producing the same
US7666963B2 (en) Hybrid copolymers
US20130137799A1 (en) Graft copolymers
SK395A3 (en) Graft copolymers of unsaturated monomers and sugars, process for producing the same and their use
DE4343993A1 (de) Pfropf-Copolymerisate von ungesättigten Monomeren und Polyhydroxyverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
JPS63260994A (ja) ポリアルキレンオキシドを基礎とするグラフト重合体を有効成分とする洗濯用灰色化防止剤
JPS63260996A (ja) ポリアルキレンオキシドを基礎とするグラフト重合体を有効成分とする洗濯用灰色化防止剤
WO2007089001A1 (en) (meth)acrylic acid-based copolymer, method for producing the same and detergent composition using the same
SA113340825B1 (ar) بوليمر يحتوي على مجموعة كربوكسيل وتركيبة تحتوي عليه
EP3523413B1 (de) Bleichzusammensetzung
EP0867502B1 (de) Bleichmittelzusammensetzungen
JP3165159B2 (ja) 漂白組成物
EP1167505B1 (de) Verdickte Bleichmittelzusammensetzungen mit kontrollierter Freisetzung und verbesserte Viskositätstabilität bei hohen Temperaturen
EP0824147A1 (de) Bleichmittelzusammensetzungen
US6153120A (en) Bleaching compositions
JP2012057085A (ja) アクリル酸エステル系重合体及びその製造方法
JP2012057086A (ja) アクリル酸エステル系重合体及びその製造方法
JP5982145B2 (ja) ポリカルボン酸系重合体組成物およびその製造方法
JP5661741B2 (ja) ２−メチレングルタル酸系共重合体およびその製造方法
JP2012072278A (ja) ポリカルボン酸系系重合体およびその製造方法
ITVA20000041A1 (it) Soluzioni acquose per la sbianca di fibre cellulosiche.
MXPA99001524A (en) Bleaching compositions

Legal Events

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

Free format text: STATUS: UNKNOWN

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: 20190415

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200717

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 3/37 20060101ALI20201103BHEP

Ipc: C11D 3/395 20060101ALI20201103BHEP

Ipc: C11D 3/10 20060101ALI20201103BHEP

Ipc: C11D 3/08 20060101ALI20201103BHEP

Ipc: C11D 3/20 20060101ALI20201103BHEP

Ipc: C11D 3/22 20060101ALI20201103BHEP

Ipc: C11D 11/00 20060101ALI20201103BHEP

Ipc: C11D 3/06 20060101ALI20201103BHEP

Ipc: C11D 3/04 20060101AFI20201103BHEP

INTG Intention to grant announced

Effective date: 20201202

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

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FATER S.P.A.

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: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016057813

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1392191

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210615

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 3523413

Country of ref document: PT

Date of ref document: 20210706

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20210629

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1392191

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210512

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210512

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: 20210812

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: 20210512

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: 20210512

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: 20210512

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: 20210512

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

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: 20210512

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: 20210512

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: 20210812

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: 20210512

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: 20210912

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: 20210512

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: 20210813

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: 20210512

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

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: 20210512

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: 20210512

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: 20210512

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: 20210512

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: 20210512

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: 20210512

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016057813

Country of ref document: DE

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

26N No opposition filed

Effective date: 20220215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602016057813

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

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: 20210912

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: 20210512

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211031

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20211005

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: 20210512

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

Ref country code: LU

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

Effective date: 20211005

Ref country code: GB

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

Effective date: 20211005

Ref country code: DE

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

Effective date: 20220503

Ref country code: BE

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

Effective date: 20211031

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

Ref country code: LI

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

Effective date: 20211031

Ref country code: CH

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

Effective date: 20211031

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

Ref country code: FR

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

Effective date: 20211031

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: 20211005

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230329

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: 20210512

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: 20161005

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

Ref country code: RO

Payment date: 20230915

Year of fee payment: 8

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

Ref country code: IT

Payment date: 20231003

Year of fee payment: 8

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: 20210512

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

Ref country code: TR

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: 20210512

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

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: 20210512

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

Ref country code: PT

Payment date: 20240916

Year of fee payment: 9