[go: up one dir, main page]

EP2855653A1 - Stabilization of phthalimido percarboxylic with lithium salts - Google Patents

Stabilization of phthalimido percarboxylic with lithium salts

Info

Publication number
EP2855653A1
EP2855653A1 EP12725048.8A EP12725048A EP2855653A1 EP 2855653 A1 EP2855653 A1 EP 2855653A1 EP 12725048 A EP12725048 A EP 12725048A EP 2855653 A1 EP2855653 A1 EP 2855653A1
Authority
EP
European Patent Office
Prior art keywords
lithium
phthalimido
acid
mixture
mixture according
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
EP12725048.8A
Other languages
German (de)
French (fr)
Other versions
EP2855653B8 (en
EP2855653B1 (en
Inventor
Amila Bilic
Johannes Georg Winter
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.)
Ecolab USA Inc
Original Assignee
Ecolab USA Inc
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 Ecolab USA Inc filed Critical Ecolab USA Inc
Publication of EP2855653A1 publication Critical patent/EP2855653A1/en
Application granted granted Critical
Publication of EP2855653B1 publication Critical patent/EP2855653B1/en
Publication of EP2855653B8 publication Critical patent/EP2855653B8/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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds

Definitions

  • the present invention relates to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt, to a detergent composition comprising said mixture, and to the use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.
  • organic peracids have encountered increasing interest in the industrial field, among others due to their excellent properties as bleaching agents in detergent formulations. Therefore, a large number of publications are concerned with organic peracid compounds endowed with the required property of sufficient bleaching activity, said characteristic being essential for an industrial application and a widespread use of such compounds.
  • organic straight-chain or cyclic mono- or dipercarboxylic acids are known and used, e.g. in detergent compositions.
  • boric acid As boric acid has become a chemical of high concern, it is to be expected that boric acid will be banned from use in domestic applications in the near future.
  • the present invention satisfies this need by providing a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
  • a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
  • phthalimido percarboxylic acids can be stabilized by lithium salts. This is rather surprising since it was suggested by the prior art that phthalimido percarboxylic acids if not stabilized degrade following a radical reaction pathway.
  • phthalimido peroxyhexanoic acid phthalimido percaproic acid, PAP
  • PAP phthalimido percaproic acid
  • nucleophilic reaction sites at PAP and/or by catching nucleophiles with electrophiles other than PAP.
  • the present invention is directed to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
  • the at least one lithium salt may be either organic or inorganic.
  • the at least one lithium salt may be hydrous or anhydrous.
  • the present invention also relates to the mixture described above, characterized in that it comprises at least one inorganic lithium salt.
  • the present invention further relates to the mixture described above, characterized in that it comprises at least one organic lithium salt.
  • the anion of the at least one lithium salt is rather non-nucleophilic. If the anion in question is too nuc!eophilic, it is assumed to compete against the lithium cation for interaction with the phthalimido percarboxylic acid.
  • Suitable non-nucleophilic anions for use according to the present invention are hexafluorosilicate (SiF 6 2" ), sulfite (S0 3 2” ), hydrogensulfite (HS0 3 ⁇ ), organosulfite (RS0 3 ⁇ ), sulfate (S0 4 2” ), hydrogensulfate (HS0 4 " ), organosulfate (RS0 4 " ), phosphate (PO4 3 ), hydrogenphosphate (HPO4 2” ).
  • R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof, wherein the sulfate anion represents the most preferred anion.
  • the present invention also relates to the mixture described above, characterized in that it comprises at least one lithium salt is selected from the group consisting of lithium hexafluorosilicate (L ⁇ SiFe), lithium sulfite (U2SO3), lithium hydrogensulfite (L1HSO3), lithium organosulfite (Li 2 RS0 3 ), lithium sulfate (Li 2 S0 4 ), lithium hydrogensulfate (LJHSO4), lithium organosulfate (LiRS0 4 ), lithium phosphate (Li 3 P0 4 ), lithium hydrogenphosphate ⁇ U2HPO4), lithium dihydrogenphosphate
  • LiPF 6 lithium hexachloro aluminate
  • Li 3 AICI 6 lithium hexabromo aluminate
  • Li 3 AIBr 6 lithium salt of an organic acid
  • R is selected from the group of Ci to C 30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof.
  • the present invention further relates to the mixture as described above, characterized in that it comprises lithium sulfate. Also, there is no restriction as concerns the chemical nature of the at least one phthalimido percarboxylic acid. Suitable phthalimido percarboxylic acids for use according to the present invention may be selected from the phthalimido
  • n is an integer of from 1 to 5:
  • phthalimido percaproic acid phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP)
  • the present invention also relates to the mixture described above, characterized in that it comprises at least one phthalimido percarboxylic acid selected from the phthalimido percarboxylic acids of the general formula (I) above, where n is an integer of from 1 to 5.
  • the present invention further relates to the mixture described above, characterized in that it comprises phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP).
  • Phthalimido percarboxylic acids and especially phthalimido peroxycarproic acid may be prepared as described in EP 0 325 288 A1 and EP 0 349 940 B1 , respectively.
  • a substrate selected from phthalimido carboxylic acids and anhydrides thereof having a structure corresponding to the desired percarboxylic acid, e.g. of the general formula (I) may be reacted with concentrated H2O2 in a reaction medium selected from concentrated H 2 S0 4 and CH3SO3H or in an alkaline medium, and the
  • percarboxylic acid is then separated from the reaction mixture by conventional and known techniques.
  • the content of lithium salt in the mixture should range between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
  • the present invention also relates to the mixture described above, characterized in that the content of lithium salt is between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
  • the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1 :1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
  • the present invention also relates to the mixture described above, characterized in that the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1:1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
  • An especially expedient mixture for use as a bleaching agent comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
  • the present invention also relates to the mixture described above, characterized in that it comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
  • phthalimido peroxyhexanoic acid phthalimido percaproic acid, PAP
  • lithium sulfate based on the total weight of the mixture.
  • the mixture comprising the at least one phthalimido percarboxylic acid and the at least one lithium salt according to the present invention may be manufactured in the form of an aqueous solution, gel, emulsion, paste, dispersion, powder, flake, granules, scales, pearls, tablets, solid block form, extrudates and other forms known in the art, but preferably represents a powder or a flake.
  • the present invention also relates to the mixture described above, characterized in that the mixture is in the form of a powder or a flake.
  • the mixture according to the present invention is particularly suitable as effective bleaching agent in detergent formulations.
  • the present invention is also directed to the use of a mixture described above as a bleaching agent.
  • the present invention is further directed to a detergent composition comprising a mixture described above.
  • the detergent composition may contain any additive or active ingredient commonly used in corresponding washing, cleansing and/or disinfecting agents like builders, surfactants, soaps, zeolites, hydrotropic agents, corrosion inhibitors, enzymes, optical brighteners, stabilizers, abrasives, perfumes, coloring agents.
  • inventive mixture may be incorporated into the detergent composition either as such or in combination with further additives, for example phosphates, carbonates, zeolites, carboxymethylcellulose or filmbuilding agents like fatty acids, fatty acid amides or esters etc. in the forms mentioned above for the mixture.
  • further additives for example phosphates, carbonates, zeolites, carboxymethylcellulose or filmbuilding agents like fatty acids, fatty acid amides or esters etc.
  • the detergent composition is substantially free of boric acid, i.e. comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
  • the present invention also relates to the detergent composition described before, characterized in that it comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
  • the detergent composition may be used as a laundry detergent, preferably as a textile detergent, and is not only suitable for generally washing laundry, but as well for disinfecting.
  • the detergent according to the present application may be used as cleanser and/or disinfectant for cleansing and disinfecting various kinds of hard surfaces like, for example, in the medicinal or institutional field, in the food preparing, processing and/or selling industry, in agriculture, in hotel business, catering trade and/or in public buildings and/or institutions. It may as well be useful in further applications in which a disinfected surface is required or desired and which are not explicitly mentioned herein.
  • the surfaces supposed to become disinfected may be made of common materials mentioned in the state of the art like, for example, metal, glass, ceramic, plastic, (coated) wood.
  • the present invention relates to the use of at least one lithium salt for stabilizing a phthalimido percarboxy!ic acid in a detergent composition.
  • a mixture for use as a bleaching agent comprising 86 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and 14 % by weight of a stabilizing agent (example 1a: boric acid (comparative); example 1 b: sodium sulfate (comparative); example 1c: lithium sulfate) was tested for its long-term stability. Therefore, the amount of chemically active PAP in the respective mixture was determined after storage by 40 °C at 1 , 3, 7, 14, 21 , 28, 49, 84, 119, 161 and 2 0 days, respectively.
  • a mixture comprising lithium sulfate shows a significantly higher long-term stability of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) than a mixture comprising sodium sulfate (example 1b).
  • phthalimido peroxyhexanoic acid phthalimido percaproic acid, PAP
  • a lithium salt according to the present invention example 1c
  • boric acid conventionally used example 1a

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)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention relates to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt, to a detergent composition comprising said mixture, and to the use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.

Description

Stabilization of phthalimido percarboxylic acids with lithium salts
FIELD OF THE INVENTION
The present invention relates to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt, to a detergent composition comprising said mixture, and to the use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.
BACKGROUND OF THE INVENTION
In the past, organic peracids have encountered increasing interest in the industrial field, among others due to their excellent properties as bleaching agents in detergent formulations. Therefore, a large number of publications are concerned with organic peracid compounds endowed with the required property of sufficient bleaching activity, said characteristic being essential for an industrial application and a widespread use of such compounds. Thus, many organic straight-chain or cyclic mono- or dipercarboxylic acids are known and used, e.g. in detergent compositions.
A problem with the widespread use of organic peracids arises from their low thermal stability, which makes it necessary to physically or chemically stabilize these compounds. The organic peracids known so far show a significant decrease of active oxygen, even under conventional storage conditions. This is also the case with imido percarboxylic acids as described already in J. Chem. Soc. 1962, 3821 and Chem. Ind. 1961 , 469. Among the imido percarboxylic acids, phthalimido percarboxylic acids have gained a widespread use in industry, especially as bleaching agents in detergent compositions. However, addition of boric acid to phthalimido percarboxylic acids is considered necessary to guarantee a sufficient long-term stability.
As boric acid has become a chemical of high concern, it is to be expected that boric acid will be banned from use in domestic applications in the near future.
Consequently, there is a need for alternative ways of stabilizing phthalimido percarboxylic acids in detergent compositions without making use of boric acid. SUMMARY OF THE INVENTION
The present invention satisfies this need by providing a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt. With the present invention, it is possible to stabilize phthalimido percarboxylic acids so as to minimize a decrease of oxygen under conventional storage conditions, but to avoid the use of boric acid. Thus, detergent compositions may be obtained showing sufficient bleaching activity over time.
DETAILED DESCRIPTION OF THE INVENTION
After extensive studies, the inventors have found that phthalimido percarboxylic acids can be stabilized by lithium salts. This is rather surprising since it was suggested by the prior art that phthalimido percarboxylic acids if not stabilized degrade following a radical reaction pathway.
Without wishing to be bound to any theory, it is assumed that phthalimido
percarboxylic acids in fact degrade by attack of nucleophiles. A plausible degradation scheme of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) in alkaline conditions is shown in figure 1. According to figure 1 , PAP is degraded to 4- phthalimido-1-hexanol and carbon dioxide via an electrocyclic reaction. As a consequence, the presence of at least one lithium salt would prevent nucleophiles from degrading PAP either by excluding reactive nucleophiles, by blocking
nucleophilic reaction sites at PAP and/or by catching nucleophiles with electrophiles other than PAP.
Therefore, the present invention is directed to a mixture for use as a bleaching agent comprising at least one phthalimido percarboxylic acid and at least one lithium salt.
There is no restriction as concerns the chemical nature of the at least one lithium salt. Thus, the at least one lithium salt may be either organic or inorganic. Besides, the at least one lithium salt may be hydrous or anhydrous.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises at least one inorganic lithium salt. The present invention further relates to the mixture described above, characterized in that it comprises at least one organic lithium salt.
According to the present invention, it is preferred that the anion of the at least one lithium salt is rather non-nucleophilic. If the anion in question is too nuc!eophilic, it is assumed to compete against the lithium cation for interaction with the phthalimido percarboxylic acid. Suitable non-nucleophilic anions for use according to the present invention are hexafluorosilicate (SiF6 2"), sulfite (S03 2"), hydrogensulfite (HS03 ~), organosulfite (RS03 ~), sulfate (S04 2"), hydrogensulfate (HS04 "), organosulfate (RS04 "), phosphate (PO43 ), hydrogenphosphate (HPO42"). dihydrogenphosphate (H2P04 "), tetrafluoro borate (BF4 ~), tetrachloro borate (BCI4"), tetrabromo borate (BBr4_ ), tetraiodo borate (Bl4 "), tetraphenyl borate (B[C6H5]4"), tetra(pentafluoro)pheny! borate (B[C6F5]4"), hexafluorophosphate (PF6 ~), hexachloro aluminate (AICI6 3"), hexabromo aluminate {AIBr6 3'), corresponding anion of an organic acid {OC[0]R'), wherein R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof, wherein the sulfate anion represents the most preferred anion.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises at least one lithium salt is selected from the group consisting of lithium hexafluorosilicate (L^SiFe), lithium sulfite (U2SO3), lithium hydrogensulfite (L1HSO3), lithium organosulfite (Li2RS03), lithium sulfate (Li2S04), lithium hydrogensulfate (LJHSO4), lithium organosulfate (LiRS04), lithium phosphate (Li3P04), lithium hydrogenphosphate {U2HPO4), lithium dihydrogenphosphate
(UH2PO4), lithium tetrafluoro borate (UBF4), lithium tetrachloro borate (LiBCI4), lithium tetrabromo borate (LiBB^), lithium tetraiodo borate (UBI4), lithium tetraphenyl borate (LiB[C6H5]4), lithium tetra(pentafluoro)phenyl borate (LiB[C6F5]4), lithium
hexafluorophosphate (LiPF6), lithium hexachloro aluminate (Li3AICI6), lithium hexabromo aluminate (Li3AIBr6), lithium salt of an organic acid (LiOC[0]R), wherein R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl, and combinations thereof. The present invention further relates to the mixture as described above, characterized in that it comprises lithium sulfate. Also, there is no restriction as concerns the chemical nature of the at least one phthalimido percarboxylic acid. Suitable phthalimido percarboxylic acids for use according to the present invention may be selected from the phthalimido
percarboxylic acids of the general formula (1), where n is an integer of from 1 to 5:
Thus, suitable phthalimido percarboxylic acids for use according to the present invention may be selected from the group consisting of phthalimido peracetic acid (n=1 ), phthalimido perpropionic acid (n=2), phthalimido perbutyirc acid (n=3), phthalimido peramylic acid (n=4) and phthalimido percaproic acid (n=5), wherein phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP) represents the most preferred phthalimido percarboxylic acid.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises at least one phthalimido percarboxylic acid selected from the phthalimido percarboxylic acids of the general formula (I) above, where n is an integer of from 1 to 5. The present invention further relates to the mixture described above, characterized in that it comprises phthalimido percaproic acid (phthalimido peroxyhexanoic acid, PAP).
Phthalimido percarboxylic acids and especially phthalimido peroxycarproic acid may be prepared as described in EP 0 325 288 A1 and EP 0 349 940 B1 , respectively. Thus, a substrate selected from phthalimido carboxylic acids and anhydrides thereof having a structure corresponding to the desired percarboxylic acid, e.g. of the general formula (I), may be reacted with concentrated H2O2 in a reaction medium selected from concentrated H2S04 and CH3SO3H or in an alkaline medium, and the
percarboxylic acid is then separated from the reaction mixture by conventional and known techniques.
In order to obtain optimum stabilization of the at least one phthalimido percarboxylic acid, the content of lithium salt in the mixture should range between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
Therefore, the present invention also relates to the mixture described above, characterized in that the content of lithium salt is between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
Advantageously, the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1 :1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
Therefore, the present invention also relates to the mixture described above, characterized in that the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1:1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
An especially expedient mixture for use as a bleaching agent comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
Therefore, the present invention also relates to the mixture described above, characterized in that it comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
The mixture comprising the at least one phthalimido percarboxylic acid and the at least one lithium salt according to the present invention may be manufactured in the form of an aqueous solution, gel, emulsion, paste, dispersion, powder, flake, granules, scales, pearls, tablets, solid block form, extrudates and other forms known in the art, but preferably represents a powder or a flake.
Therefore, the present invention also relates to the mixture described above, characterized in that the mixture is in the form of a powder or a flake. The mixture according to the present invention is particularly suitable as effective bleaching agent in detergent formulations.
Therefore, the present invention is also directed to the use of a mixture described above as a bleaching agent.
The present invention is further directed to a detergent composition comprising a mixture described above. The detergent composition may contain any additive or active ingredient commonly used in corresponding washing, cleansing and/or disinfecting agents like builders, surfactants, soaps, zeolites, hydrotropic agents, corrosion inhibitors, enzymes, optical brighteners, stabilizers, abrasives, perfumes, coloring agents.
The inventive mixture may be incorporated into the detergent composition either as such or in combination with further additives, for example phosphates, carbonates, zeolites, carboxymethylcellulose or filmbuilding agents like fatty acids, fatty acid amides or esters etc. in the forms mentioned above for the mixture.
It is preferred that the detergent composition is substantially free of boric acid, i.e. comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
Therefore, the present invention also relates to the detergent composition described before, characterized in that it comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
The detergent composition may be used as a laundry detergent, preferably as a textile detergent, and is not only suitable for generally washing laundry, but as well for disinfecting.
Besides, the detergent according to the present application may be used as cleanser and/or disinfectant for cleansing and disinfecting various kinds of hard surfaces like, for example, in the medicinal or institutional field, in the food preparing, processing and/or selling industry, in agriculture, in hotel business, catering trade and/or in public buildings and/or institutions. It may as well be useful in further applications in which a disinfected surface is required or desired and which are not explicitly mentioned herein. The surfaces supposed to become disinfected may be made of common materials mentioned in the state of the art like, for example, metal, glass, ceramic, plastic, (coated) wood.
Finally, the present invention relates to the use of at least one lithium salt for stabilizing a phthalimido percarboxy!ic acid in a detergent composition.
In the following, the stabilization of phthalimido peroxycarboxylic acids with lithium salts will be demonstrated without being restricted to these examples.
EXAMPLES
Example 1 :
A mixture for use as a bleaching agent comprising 86 % by weight of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) and 14 % by weight of a stabilizing agent (example 1a: boric acid (comparative); example 1 b: sodium sulfate (comparative); example 1c: lithium sulfate) was tested for its long-term stability. Therefore, the amount of chemically active PAP in the respective mixture was determined after storage by 40 °C at 1 , 3, 7, 14, 21 , 28, 49, 84, 119, 161 and 2 0 days, respectively.
As can be taken from Table 1 , a mixture comprising lithium sulfate (example 1c) shows a significantly higher long-term stability of phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) than a mixture comprising sodium sulfate (example 1b).
Table 1 :
Activity of PAP %
Moreover, as can be taken from Figure 2, phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP) can even more effectively be stabilized by a lithium salt according to the present invention (example 1c) than by boric acid conventionally used (example 1a).

Claims

Claims
1. Mixture for use as a bleaching agent comprising at least one phthalimido
percarboxylic acid and at least one lithium salt.
2. Mixture according to claim 1 , characterized in that it comprises at least one inorganic lithium salt.
3. Mixture according to claim 1 or 2, characterized in that it comprises at least one organic lithium salt.
4. Mixture according to any of claims 1 to 3, characterized in that it comprises at least one lithium salt selected from the group consisting of lithium
hexafluorosilicate (Li2SiF6), lithium sulfite {U2SO3), lithium hydrogensulfite (LJHSO3), lithium organosulfite (Li2RS03), lithium sulfate (Li2S04), lithium hydrogensulfate (LiHS04), lithium organosulfate (L1RSO4), lithium phosphate (Li3P0 ), lithium hydrogenphosphate (Li2HP04), lithium dihydrogenphosphate (LiH2P04), lithium tetrafluoro borate (L1BF4), lithium tetrachloro borate (LiBCU), lithium tetrabromo borate (LiBBr ), lithium tetraiodo borate (LiBU), lithium tetraphenyl borate (LiBfCeHsk), lithium tetra(pentafluoro)phenyi borate
(LiB[C6F5]4), lithium hexafiuorophosphate (LiPFe), lithium hexachloro aluminate (Li3AICI6), lithium hexabromo aluminate (Li3AIBr6), lithium salt of an organic acid (LiOC[0]R), wherein R is selected from the group of Ci to C30 substituted and unsubstituted, linear, branched, cyclic alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl and combinations thereof.
5. Mixture according to any of claims 1 to 4, characterized in that it comprises lithium sulfate.
6. Mixture according to any of claims 1 to 5, characterized in that it comprises at least one phthalimido percarboxylic acid is selected from the phthalimido percarboxylic acids of the general formula (I)
where n is an integer of from 1 to 5.
7. Mixture according to any of claims 1 to 6, characterized in that it comprises phthalimido peroxyhexanoic acid (phthalimido percaproic acid, PAP).
8. Mixture according to any of claims 1 to 7, characterized in that the content of lithium salt is between 1 and 50 % by weight, preferably between 1 and 25 % by weight, more preferably between 1 and 10 % by weight, most preferably between 2 and 5 % by weight based on the total weight of the mixture.
9. Mixture according to any of claims 1 to 8, characterized in that the weight ratio of phthalimido percarboxylic acid to lithium salt is between 20:1 and 1 :1 , preferably between 10:1 and 1 :1 , more preferably between 5:1 and 1 :1 , most preferably between 2:1 and 1 :1.
10. Mixture according to any of claims 1 to 9, characterized in that it comprises between 10 and 25 % by weight of phthalimido peroxyhexanoic acid
(phthalimido percaproic acid, PAP) and between 2 and 5 % by weight of lithium sulfate based on the total weight of the mixture.
11. Mixture according to any of claims 1 to 10, characterized in that the mixture is in the form of a powder or a flake,
13. Detergent composition comprising the mixture according to any of claims 1 to 11.
14. Detergent composition according to claim 13, characterized in that it
comprises less than 10 ppm, preferably less than 5 ppm, even more preferably less than 1 ppm, and most preferably less than 0,1 ppm boric acid.
15. Use of at least one lithium salt for stabilizing a phthalimido percarboxylic acid in a detergent composition.
EP12725048.8A 2012-06-01 2012-06-01 Stabilization of phthalimido percarboxylic acid with lithium salts Active EP2855653B8 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2012/060448 WO2013178289A1 (en) 2012-06-01 2012-06-01 Stabilization of phthalimido percarboxylic with lithium salts

Publications (3)

Publication Number Publication Date
EP2855653A1 true EP2855653A1 (en) 2015-04-08
EP2855653B1 EP2855653B1 (en) 2016-07-20
EP2855653B8 EP2855653B8 (en) 2016-12-07

Family

ID=46201675

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12725048.8A Active EP2855653B8 (en) 2012-06-01 2012-06-01 Stabilization of phthalimido percarboxylic acid with lithium salts

Country Status (3)

Country Link
EP (1) EP2855653B8 (en)
ES (1) ES2595180T3 (en)
WO (1) WO2013178289A1 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1233846B (en) 1988-01-20 1992-04-21 Ausimont Spa IMMEDIATE AROMATIC PEROXIDES
DE3823172C2 (en) 1988-07-08 1998-01-22 Hoechst Ag Omega-phthalimidoperoxihexanoic acid, process for its preparation and its use
EP1586628A1 (en) * 2004-04-05 2005-10-19 The Procter & Gamble Company Particulate bleaching compositions
DE102004030900A1 (en) * 2004-06-25 2006-01-26 Henkel Kgaa Preparation of particulate peroxycarboxylic acid compositions
GB0509377D0 (en) * 2005-05-09 2005-06-15 Reckitt Benckiser Nv Detergent composition
JP2010138268A (en) * 2008-12-11 2010-06-24 Kao Corp Liquid bleaching detergent composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013178289A1 *

Also Published As

Publication number Publication date
ES2595180T3 (en) 2016-12-28
EP2855653B8 (en) 2016-12-07
WO2013178289A1 (en) 2013-12-05
EP2855653B1 (en) 2016-07-20

Similar Documents

Publication Publication Date Title
CA2786573C (en) Hydrogen peroxide compositions and cleaning formulations prepared therefrom
US10226048B2 (en) Disinfecting detergent
EP0376704B1 (en) Bleaching composition
EP0667392A2 (en) Bleach compositions
EP0008475B2 (en) A process for preparing peroxide-based bleach media and concentrated bleach compositions for use in carrying out that process
US4131562A (en) Stabilized particulate peroxygen compounds
US4681696A (en) Solid stabilized active halogen-containing detergent compositions and methods
WO1996006912A1 (en) Peroxide activation method and peroxide composition
KR20150081280A (en) Method for producing equilibrium peracetic acid and equilibrium peracetic acid obtainable by the method
KR20050114707A (en) Composition for bactericide production and process for producing organic peracid
CA1226502A (en) Detergent bleach composition
EP2855653A1 (en) Stabilization of phthalimido percarboxylic with lithium salts
JPH04349109A (en) Alkaline aqueous hydrogen peroxide solution and method for stabilizing same
WO2020243915A1 (en) Formula and method for immediately and quickly generating peracetic acid disinfectant
EP2855654A1 (en) Stabilization of phthalimido percarboxylic acids with disaccharides
WO2014183795A1 (en) Stabilization of phthalimido percarboxylic acids with aminoalkanesulfonic acids
US4738794A (en) Aqueous dispersion of potassium salt of 4-sulpho-peroxybenzoic acid stabilized with a potassium salt
CA1231612A (en) Stabilized active halogen-containing detergent compositions and methods
WO2014187485A1 (en) Stabilization of phthalimido percarboxylic acids with dicarboxylic acids
CA2010465A1 (en) Hydroxamate bleach stabilizer
CN104686572A (en) Acidic disinfectant and preparation method thereof
EP0315204A3 (en) Bleaching composition
FR2751634A1 (en) HYDROGEN PEROXIDE STABILIZED AND STAMPED SOLUTION, PROCESS FOR PRODUCING THE SAME AND USE THEREOF FOR DECONTAMINATING CONTACT LENSES
US8735339B2 (en) Liquid composition comprising ethylenediamine disuccinic acid salt
US3415752A (en) Detergent compositions

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20141218

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

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 3/22 20060101AFI20160125BHEP

Ipc: C11D 17/06 20060101ALI20160125BHEP

Ipc: C11D 3/04 20060101ALI20160125BHEP

Ipc: C11D 3/06 20060101ALI20160125BHEP

Ipc: C11D 3/39 20060101ALI20160125BHEP

INTG Intention to grant announced

Effective date: 20160215

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 814127

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012020720

Country of ref document: DE

GRAT Correction requested after decision to grant or after decision to maintain patent in amended form

Free format text: ORIGINAL CODE: EPIDOSNCDEC

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160720

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 814127

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160720

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2595180

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20161228

RAP4 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: ECOLAB USA INC.

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

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: 20160720

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: 20160720

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: 20160720

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: 20160720

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: 20161120

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: 20161020

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: 20160720

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

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: 20161021

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: 20160720

Ref country code: BE

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: 20160720

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: 20160720

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: 20160720

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: 20161121

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: 20160720

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012020720

Country of ref document: DE

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: 20160720

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: 20160720

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

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: 20160720

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: 20160720

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: 20160720

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: 20161020

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: 20160720

26N No opposition filed

Effective date: 20170421

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: 20160720

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: 20160720

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

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: 20170630

Ref country code: IE

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

Effective date: 20170601

Ref country code: LI

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

Effective date: 20170630

Ref country code: LU

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

Effective date: 20170601

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 NON-PAYMENT OF DUE FEES

Effective date: 20170601

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

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: 20160720

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: 20120601

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: 20160720

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: 20160720

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: 20160720

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

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

Ref country code: DE

Payment date: 20250402

Year of fee payment: 14

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

Ref country code: GB

Payment date: 20250401

Year of fee payment: 14

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

Ref country code: IT

Payment date: 20250522

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20250401

Year of fee payment: 14

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

Ref country code: ES

Payment date: 20250704

Year of fee payment: 14