EP2412870B1 - Composition and process for whitening paper - Google Patents
Composition and process for whitening paper Download PDFInfo
- Publication number
- EP2412870B1 EP2412870B1 EP10171451.7A EP10171451A EP2412870B1 EP 2412870 B1 EP2412870 B1 EP 2412870B1 EP 10171451 A EP10171451 A EP 10171451A EP 2412870 B1 EP2412870 B1 EP 2412870B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- paper
- component
- weight
- starch
- 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.)
- Revoked
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/09—Sulfur-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
Definitions
- the present invention relates to a composition suitable for surface treatment of paper, in particular a size press liquor, and a process for whitening paper using said composition.
- a sizing step is usually carried out for achieving good writing and printing properties and strength.
- Such a sizing step can take place, on the one hand, before the sheet formation in the paper pulp (internal sizing) and, on the other hand, after the sheet formation in the size press.
- a combination of both processes is also possible.
- whitening of the pulp or of the paper sheet is usually also carried out by means of a fluorescent whitening agent (FWA).
- FWA fluorescent whitening agent
- the size and fluorescent whitening agent are added separately to the paper pulp in the case of pulp application, whereas the fluorescent whitening agent is incorporated into the size press liquor and applied together with it to the paper sheet in the case of surface sizing.
- EP 2 135 997 Al disclose aqueous compositions containing specific bis-triazinylamino-stilbene compounds containing alkylsulfonic acid groups, a salt of a bivalent cation, and a carrier.
- the present invention relates to a composition suitable for surface treatment of paper, wherein the composition contains
- the invention further relates to a process for whitening paper, wherein a cellulose sheet is brought into contact with the above defined composition, preferably in the size press.
- a process for whitening paper wherein a cellulose sheet is brought into contact with the above defined composition, preferably in the size press.
- Fig. 1 is a diagram showing the influence of calcium chloride on the performance of different fluorescent whitening agents according to Example 1.
- the composition suitable for surface treatment of paper is a size press liquor
- the process is a process for whitening paper in the size press, wherein a cellulose sheet is brought into contact with the size press liquor.
- size press is understood as meaning a surface application unit, preferably of the paper machine, in which the cellulose sheet formed is brought into contact with a size press liquor, and in which the proportion of the liquor which is to be taken up by the sheet (liquor absorption) can preferably be adjusted by means of the roll pressure.
- the composition contains at least one bis-triazinylamino-stilbene compound of the above defined formula (I), wherein n, m, R 1 to R 4 , and M are as defined above.
- the alkyl group can be linear or branched, and the possible substituents of the alkyl group, which are alkoxy, hydroxyl and/or cyano groups, can be attached at any position of the alkyl chain.
- C 2 -C 4 alkoxyalkyl means C 2 -C 4 alkyl substituted with C 2 -C 4 alkoxy.
- n and m are integers from 1 to 2, most preferred 2.
- R 1 , R 2 , R 3 and R 4 represent, independently of each other, hydrogen, C 1 - C 4 alkyl, C 2 -C 4 cyanoalkyl, or C 2 -C 4 hydroxyalkyl, in particular propyl, cyanoethyl, or hydroxypropyl.
- the -SO 3 M groups at the terminal aromatic rings can be in o -, m-, or p -position. The preferred positions depend on the number of the -SO 3 M groups. If n or m is 1, p-position is preferred. If n or m is 2, the 2,5-position is preferred.
- R 1 , R 2 , R 3 and R 4 is propyl, cyanoethyl or hydroxypropyl.
- R 1 , R 2 , R 3 and R 4 are propyl or hydroxypropyl, in particular all are either propyl or hydroxypropyl, wherein preferably n and m are 2.
- the hydroxypropyl group is a hydroxyisopropyl group.
- n and m are 2, and the two - SO 3 M groups are in 2,5-position.
- n and m are 2, R 1 , and R 3 are hydroxyisopropyl, and R 2 and R 4 are cyanoethyl.
- At least one of R 1 , R 2 , R 3 and R 4 contains at least 3 carbon atoms.
- at least one of R 1 and R 2 and at least one of R 3 and R 4 contain at least 3 carbon atoms.
- at least one of R 1 , R 2 , R 3 and R 4 in particular at least one of R 1 and R 2 and at least one of R 3 and R 4 , represent(s) C 3 - C 4 alkyl, C 3 - C 4 alkoxyalkyl, C 3 -C 4 cyanoalkyl, or C 3 - C 4 hydroxyalkyl.
- C 3 -C 4 alkoxyalkyl means C 3 or C 4 alkyl substituted with C 3 or C 4 alkoxy.
- M are hydrogen, Na, K, Ca, Mg, in particular M is Na or K, most preferred is Na.
- the fluorescent whitening agents of formula (I) can be produced by known procedures, and are used as free acids or as salts thereof, preferably alkali metal salts.
- the compounds are prepared by reacting cyanuric chloride with 4,4'-diaminostilbene-2,2'-disulfonic acid or a salt thereof, and an appropriate aniline derivative containing a phenyl ring substituted with -SO 3 M group(s), and substituted aliphatic amines or heterocyclic compounds.
- EP 0 860 437 Al describes the preparation of such compounds.
- composition of the invention can contain more than one, preferably two or three, most preferred three, of the fluorescent whitening agents of formula (I).
- Component (a) of the composition can contain, in addition to the at least one fluorescent whitening agent of formula (I), one or more known bis-triazinylamino-stilbene or distyryl-biphenyl based fluorescent whitening agents.
- the salt of component (b) of the composition of the invention comprises bivalent cations, preferably cations of an earth alkaline metal, in particular calcium or magnesium.
- the counterions of the bivalent cations are mono- or multivalent anions, in particular halide, sulphate, hydrosulphate, phosphate, hydro-phosphate, dihydrophosphate, carbonate, hydrocarbonate, nitrate, acetate, or a mixture thereof, preferably chloride or sulphate, most preferably chloride.
- the salts disclosed in US 6,207,258 B1 are also suitable.
- a preferred salt is calcium chloride, magnesium chloride, magnesium sulphate, or a mixture thereof; more preferred is calcium chloride, magnesium chloride, or a mixture thereof; most preferred is calcium chloride.
- the carrier of component (c) is any compound known in the art to be suitable as a carrier, in particular carriers suitable for size press liquors.
- Preferred carriers are carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), starch or mixtures thereof, with starch being particularly preferred.
- Suitable carrier substances are, for example, hydrophilic polymers having the ability to form hydrogen bridge bonds.
- Preferred carrier substances are starch, polyvinyl alcohols, carboxymethyl-celluloses and polyethylene glycols having a number average molecular weight of from 200 to 8000 g/mol, as well as any desired mixtures of these substances, it being possible for these polymers optionally to be modified.
- Preferred polyvinyl alcohols are those having a degree of hydrolysis >85%, preferred carboxymethyl-celluloses are those having a degree of substitution DS of >0.5.
- Polyethylene glycols having a number average molecular weight Mn of from 200 to 8000 g/mol are particularly preferred.
- Suitable starches are based e.g., but not exclusively, on potato starch, rice starch, wheat starch, maize starch or tapioca starch. In particular, starches whose molecular weights have already been reduced by partial degradation and/or which have been obtained by derivatization are preferably used instead of natural starches. Furthermore, starches for which both modification steps have been combined, i.e. which have been partially degraded and additionally derivatized, are suitable. Typical methods for starch degradation are, for example, enzymatic, oxidative, thermal or hydrolytic treatment. Examples of suitable starch derivatives are hydroxyethyl starch or cationic starch.
- composition of the invention contains as component (d) water and, optionally, can contain sizing agents, such as alkenyl ketene dimer, alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), rosin size, styrene maleic anhydride copolymers, styrene acrylate, styrene acrylic acid copolymers, polyurethane or ethylene acrylic acid copolymers, or other common paper chemicals, such as styryl-acrylate copolymers, latex, pigments, defoamers, or salts, such as NaClor NaHCO 3 , or mixtures of two or more thereof.
- sizing agents such as alkenyl ketene dimer, alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), rosin size, styrene maleic anhydride copolymers, styrene acrylate,
- the composition of the invention contains preferably component (a) in an amount of 0.02 to 3, more preferably 0.05 to 2, most preferably 0.1 to 1, weight-% based on 100 weight-% of the composition. If fluorescent whitening agents other than those of formula (I) are used, their amount is 5 to 95 weight-% based on 100 weight-% of component (a).
- Component (b) is preferably contained in an amount of 0.2 to 8, in particular 0.5 to 6, most preferably 1 to 5, weight-% based on 100 weight-% of the composition.
- Component (c) is preferably contained in an amount of 3 to 20, in particular 5 to 15, most preferably 6 to 12, weight-% based on 100 weight-% of the composition.
- the composition of the invention contains preferably water in an amount of 75 to 96.78, in particular 79 to 94.45, most preferably 82.5 to 92.9, weight-% based on 100 weight-% of the composition.
- the composition contains a sizing agent, preferably in an amount of 0 to 5, in particular 0 to 4, most preferably 0 to 3, in each case weight-% based on 100 weight-% of the composition.
- auxiliaries such as, for example, dispersants, thickeners, antifreezes, preservatives, complexing agents, etc., or organic byproducts from the fluorescent whitening agent synthesis which were not completely removed in the working-up, may be contained in the composition of the invention.
- compositions are also described in US 6,207,258 B1 , wherein according to the invention as component (a) at least one fluorescent whitening agent of formula (I) is used.
- the production of the composition is effected by known methods and preferably effected by combining an aqueous solution of the fluorescent whitening agent used as component (a), which preferably has a suitable pH value, with the other components, such as carrier substances, sizing agents, binders, pigments, salts or standardizing agents.
- component (a) which preferably has a suitable pH value
- component (c) an aqueous preparation of carrier component (c) is prepared, to which preparation an aqueous preparation of salt component (b) is added, followed by the addition of an aqueous preparation of the fluorescent whitening agent component (a), preferably adjusted in pH value, and the other components.
- composition of the invention can be used for whitening paper, in particular for surface treatment of paper, e.g. in a size press.
- the process of the invention for whitening paper is carried out according to known processes, preferably using a size press, and is subject to no restrictions.
- the paper used is not critical and may be any cellulose sheet.
- Paper obtained by the process of the invention exhibits, in addition to improved printing performance, improved whiteness, and is in particular suitable for inkjet printing applications.
- the whiteness of the papers produced can be characterized by the CIE whiteness.
- Different fluorescent whitening agents can be compared to each other with respect to the saturation behavior when determined according to CIE whiteness. In other words, if a larger amount of fluorescent whitening agent is used and no further increase in whiteness is found, there is a saturation behavior and there may even be adverse effects on the whiteness when using higher amounts.
- the effect of saturation is also referred to as greening.
- the greening limit i.e. the point at which increasing amounts of fluorescent whitening agent used results in virtually no further increase in whiteness, can be derived, for example, from the a*-b* diagram, where a* and b* are the color coordinates in the CIE-L*a*b system.
- a 15% starch solution of neutral oxidatively degraded potato starch (Perfectamyl 4692) and a 50% calcium chloride solution were prepared.
- the fluorescent whitening agent was weighed in a glass, and 13.33 g of 15% starch solution was added. Then, 50% calcium chloride solution was weighed in, and the solution was filled up with water to 20 g, so that the tests were carried out in a 10% starch solution. After stirring for a short time the solution was applied on one side of the basepaper by a semiautomatic lab coater with a Rakel (No. 2) which should simulate a film press application. 1.7 g/m2 of dry starch was applied on that basepaper. After the drawing the paper was directly dried on a drying cylinder at about 100°C. After climatization over night the prepared side of the papers were measured with a Datacolor spectrometer (IS02469) by determining CIE, L*, a* and b*, the light source used based on ISO2469 standard.
- fluorescent whitening agent per 100g starch preparation were as indicated in Table 1 below.
- the amount of calcium chloride was 2g for each fluorescent whitening agent.
- the following fluorescent whitening agents were used:
- the results of Table 1 are also shown in Fig. 1 .
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Description
- The present invention relates to a composition suitable for surface treatment of paper, in particular a size press liquor, and a process for whitening paper using said composition.
- In the production of paper, a sizing step is usually carried out for achieving good writing and printing properties and strength. Such a sizing step can take place, on the one hand, before the sheet formation in the paper pulp (internal sizing) and, on the other hand, after the sheet formation in the size press. A combination of both processes is also possible. In one or both production stages of paper, whitening of the pulp or of the paper sheet is usually also carried out by means of a fluorescent whitening agent (FWA). Usually, the size and fluorescent whitening agent are added separately to the paper pulp in the case of pulp application, whereas the fluorescent whitening agent is incorporated into the size press liquor and applied together with it to the paper sheet in the case of surface sizing.
- The combination of surface sizing and whitening of papers is widely used in the paper-producing industry. This method is widely used particularly in the printing and writing paper segment (copy, inkjet, offset, etc.). There is a continuing trend towards surface-sized papers having high whiteness and improved printing performance and consequently there is a demand for size press liquors which are as effective as possible.
US 6,207,258 B1 discloses a composition and process for improved inkjet printing performance using a salt of a bivalent metal, in particular calcium chloride. Therefore, in order to achieve more brilliant and sharper printings, especially inkjet printings, the paper production industry uses nowadays calcium chloride in size press liquors. However, the use of that salt affects adversely the performance of the fluorescent whitening agents commonly used in size press liquors. In particular, the whitening effectiveness is decreased, the shade is moving to the greenish-yellowish direction, and additionally a loss of fluorescence is observed. -
WO 2009/150180 Al undEP 2 135 997 Al disclose aqueous compositions containing specific bis-triazinylamino-stilbene compounds containing alkylsulfonic acid groups, a salt of a bivalent cation, and a carrier. - Surprisingly, it has been found that further specific bis-triazinylamino-stilbene compounds when used in combination with salts of bivalent cations, such as calcium chloride, in compositions suitable for surface treating of paper, such as size press liquors, also overcome problems of the prior art.
- Therefore, the present invention relates to a composition suitable for surface treatment of paper, wherein the composition contains
- (a) at least one fluorescent whitening agent of formula (I)
R1, R2, R3, and R4 represent, independently of each other, hydrogen, C1-C4 alkyl, C2-C4 alkoxyalkyl, C2-C4 cyanoalkyl, or C2-C4 hydroxyalkyl; or R1 and R2 or R3 and R4 independently of each other together with N atom form morpholine, piperidine or pyrrolidine ring;
wherein at least one of R1, R2, R3 and R4 contains at least 3 carbon atoms;
M represents hydrogen, or one equivalent of a cation, in particular Li, Na, K, Ca, Mg, ammonium, or ammonium which is mono-, di-, tri- or tetra-substituted by C1 - C4 alkyl or C2- C4 hydroxyalkyl; - (b) at least one salt of a bivalent cation;
- (c) at least one carrier; and
- (d) water.
- The invention further relates to a process for whitening paper, wherein a cellulose sheet is brought into contact with the above defined composition, preferably in the size press. Preferred embodiments of the invention are described in the description hereinafter, the claims and the figure.
-
Fig. 1 is a diagram showing the influence of calcium chloride on the performance of different fluorescent whitening agents according to Example 1. - In a preferred embodiment of the invention, the composition suitable for surface treatment of paper is a size press liquor, and the process is a process for whitening paper in the size press, wherein a cellulose sheet is brought into contact with the size press liquor.
- In the context of this invention, size press is understood as meaning a surface application unit, preferably of the paper machine, in which the cellulose sheet formed is brought into contact with a size press liquor, and in which the proportion of the liquor which is to be taken up by the sheet (liquor absorption) can preferably be adjusted by means of the roll pressure.
- Recent developments of the size press or film press, namely of the Speedsizer as well as of the Symsizer as well as Gate-roll, are likewise understood as being covered by the term size press.
- According to the invention the composition contains at least one bis-triazinylamino-stilbene compound of the above defined formula (I), wherein n, m, R1 to R4, and M are as defined above. In the context of this invention, in the formula (I) the alkyl group can be linear or branched, and the possible substituents of the alkyl group, which are alkoxy, hydroxyl and/or cyano groups, can be attached at any position of the alkyl chain. In the present invention, C2-C4 alkoxyalkyl means C2-C4 alkyl substituted with C2-C4 alkoxy. In a preferred embodiment, n and m are integers from 1 to 2, most preferred 2. In another preferred embodiment, R1, R2, R3 and R4 represent, independently of each other, hydrogen, C1- C4 alkyl, C2-C4 cyanoalkyl, or C2-C4 hydroxyalkyl, in particular propyl, cyanoethyl, or hydroxypropyl. The -SO3M groups at the terminal aromatic rings can be in o-, m-, or p-position. The preferred positions depend on the number of the -SO3M groups. If n or m is 1, p-position is preferred. If n or m is 2, the 2,5-position is preferred. In a preferred embodiment, at least one of R1, R2, R3 and R4 is propyl, cyanoethyl or hydroxypropyl. In another preferred embodiment, R1, R2, R3 and R4 are propyl or hydroxypropyl, in particular all are either propyl or hydroxypropyl, wherein preferably n and m are 2. Most preferably, the hydroxypropyl group is a hydroxyisopropyl group. In another preferred embodiment, n and m are 2, and the two - SO3M groups are in 2,5-position. In a further preferred embodiment, n and m are 2, R1, and R3 are hydroxyisopropyl, and R2 and R4 are cyanoethyl.
- In the compound of formula (I), at least one of R1, R2, R3 and R4 contains at least 3 carbon atoms. Preferably, at least one of R1 and R2 and at least one of R3 and R4 contain at least 3 carbon atoms. In a further preferred embodiment, at least one of R1, R2, R3 and R4, in particular at least one of R1 and R2 and at least one of R3 and R4, represent(s) C3 - C4 alkyl, C3 - C4 alkoxyalkyl, C3-C4 cyanoalkyl, or C3- C4 hydroxyalkyl. In the present invention, C3-C4 alkoxyalkyl means C3 or C4 alkyl substituted with C3 or C4 alkoxy.
- Preferred embodiments of M are hydrogen, Na, K, Ca, Mg, in particular M is Na or K, most preferred is Na.
- The fluorescent whitening agents of formula (I) can be produced by known procedures, and are used as free acids or as salts thereof, preferably alkali metal salts. Generally, the compounds are prepared by reacting cyanuric chloride with 4,4'-diaminostilbene-2,2'-disulfonic acid or a salt thereof, and an appropriate aniline derivative containing a phenyl ring substituted with -SO3M group(s), and substituted aliphatic amines or heterocyclic compounds. For example,
EP 0 860 437 Al describes the preparation of such compounds. - The composition of the invention can contain more than one, preferably two or three, most preferred three, of the fluorescent whitening agents of formula (I).
- Component (a) of the composition can contain, in addition to the at least one fluorescent whitening agent of formula (I), one or more known bis-triazinylamino-stilbene or distyryl-biphenyl based fluorescent whitening agents.
- The salt of component (b) of the composition of the invention comprises bivalent cations, preferably cations of an earth alkaline metal, in particular calcium or magnesium. Preferably, the counterions of the bivalent cations are mono- or multivalent anions, in particular halide, sulphate, hydrosulphate, phosphate, hydro-phosphate, dihydrophosphate, carbonate, hydrocarbonate, nitrate, acetate, or a mixture thereof, preferably chloride or sulphate, most preferably chloride. The salts disclosed in
US 6,207,258 B1 are also suitable. A preferred salt is calcium chloride, magnesium chloride, magnesium sulphate, or a mixture thereof; more preferred is calcium chloride, magnesium chloride, or a mixture thereof; most preferred is calcium chloride. - The carrier of component (c) is any compound known in the art to be suitable as a carrier, in particular carriers suitable for size press liquors. Preferred carriers are carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), starch or mixtures thereof, with starch being particularly preferred. Suitable carrier substances are, for example, hydrophilic polymers having the ability to form hydrogen bridge bonds. Preferred carrier substances are starch, polyvinyl alcohols, carboxymethyl-celluloses and polyethylene glycols having a number average molecular weight of from 200 to 8000 g/mol, as well as any desired mixtures of these substances, it being possible for these polymers optionally to be modified. Preferred polyvinyl alcohols are those having a degree of hydrolysis >85%, preferred carboxymethyl-celluloses are those having a degree of substitution DS of >0.5. Polyethylene glycols having a number average molecular weight Mn of from 200 to 8000 g/mol are particularly preferred. Suitable starches are based e.g., but not exclusively, on potato starch, rice starch, wheat starch, maize starch or tapioca starch. In particular, starches whose molecular weights have already been reduced by partial degradation and/or which have been obtained by derivatization are preferably used instead of natural starches. Furthermore, starches for which both modification steps have been combined, i.e. which have been partially degraded and additionally derivatized, are suitable. Typical methods for starch degradation are, for example, enzymatic, oxidative, thermal or hydrolytic treatment. Examples of suitable starch derivatives are hydroxyethyl starch or cationic starch.
- The composition of the invention contains as component (d) water and, optionally, can contain sizing agents, such as alkenyl ketene dimer, alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), rosin size, styrene maleic anhydride copolymers, styrene acrylate, styrene acrylic acid copolymers, polyurethane or ethylene acrylic acid copolymers, or other common paper chemicals, such as styryl-acrylate copolymers, latex, pigments, defoamers, or salts, such as NaClor NaHCO3, or mixtures of two or more thereof.
- The composition of the invention contains preferably component (a) in an amount of 0.02 to 3, more preferably 0.05 to 2, most preferably 0.1 to 1, weight-% based on 100 weight-% of the composition. If fluorescent whitening agents other than those of formula (I) are used, their amount is 5 to 95 weight-% based on 100 weight-% of component (a). Component (b) is preferably contained in an amount of 0.2 to 8, in particular 0.5 to 6, most preferably 1 to 5, weight-% based on 100 weight-% of the composition. Component (c) is preferably contained in an amount of 3 to 20, in particular 5 to 15, most preferably 6 to 12, weight-% based on 100 weight-% of the composition. The composition of the invention contains preferably water in an amount of 75 to 96.78, in particular 79 to 94.45, most preferably 82.5 to 92.9, weight-% based on 100 weight-% of the composition.
- Optionally, the composition contains a sizing agent, preferably in an amount of 0 to 5, in particular 0 to 4, most preferably 0 to 3, in each case weight-% based on 100 weight-% of the composition.
- In addition, relatively small amounts, usually amounts of less than 5% by weight, of further auxiliaries, such as, for example, dispersants, thickeners, antifreezes, preservatives, complexing agents, etc., or organic byproducts from the fluorescent whitening agent synthesis which were not completely removed in the working-up, may be contained in the composition of the invention.
- Suitable compositions are also described in
US 6,207,258 B1 , wherein according to the invention as component (a) at least one fluorescent whitening agent of formula (I) is used. - The production of the composition is effected by known methods and preferably effected by combining an aqueous solution of the fluorescent whitening agent used as component (a), which preferably has a suitable pH value, with the other components, such as carrier substances, sizing agents, binders, pigments, salts or standardizing agents. Preferably, an aqueous preparation of carrier component (c) is prepared, to which preparation an aqueous preparation of salt component (b) is added, followed by the addition of an aqueous preparation of the fluorescent whitening agent component (a), preferably adjusted in pH value, and the other components.
- The composition of the invention can be used for whitening paper, in particular for surface treatment of paper, e.g. in a size press.
- The process of the invention for whitening paper is carried out according to known processes, preferably using a size press, and is subject to no restrictions. The paper used is not critical and may be any cellulose sheet.
- Paper obtained by the process of the invention exhibits, in addition to improved printing performance, improved whiteness, and is in particular suitable for inkjet printing applications.
- The whiteness of the papers produced can be characterized by the CIE whiteness. Different fluorescent whitening agents can be compared to each other with respect to the saturation behavior when determined according to CIE whiteness. In other words, if a larger amount of fluorescent whitening agent is used and no further increase in whiteness is found, there is a saturation behavior and there may even be adverse effects on the whiteness when using higher amounts. The effect of saturation is also referred to as greening. The greening limit, i.e. the point at which increasing amounts of fluorescent whitening agent used results in virtually no further increase in whiteness, can be derived, for example, from the a*-b* diagram, where a* and b* are the color coordinates in the CIE-L*a*b system.
- The following example illustrates the invention and shows preferred embodiments, without limiting the scope of protection.
- The whitening performance of different fluorescent whitening agents in the presence of calcium chloride was studied using the following test procedure for size press application.
- First, a 15% starch solution of neutral oxidatively degraded potato starch (Perfectamyl 4692) and a 50% calcium chloride solution were prepared. The paper used was a 80 g/m2 basepaper, which was a machine paper, internally sized (Cobb equals to 110 g/m2) and slightly whitened with fluorescent whitening agent to have the following optical characteristics: CIE -104.89; L* = 93.92; a* = 1.21; b* = -4.34.
- The fluorescent whitening agent was weighed in a glass, and 13.33 g of 15% starch solution was added. Then, 50% calcium chloride solution was weighed in, and the solution was filled up with water to 20 g, so that the tests were carried out in a 10% starch solution. After stirring for a short time the solution was applied on one side of the basepaper by a semiautomatic lab coater with a Rakel (No. 2) which should simulate a film press application. 1.7 g/m2 of dry starch was applied on that basepaper. After the drawing the paper was directly dried on a drying cylinder at about 100°C. After climatization over night the prepared side of the papers were measured with a Datacolor spectrometer (IS02469) by determining CIE, L*, a* and b*, the light source used based on ISO2469 standard.
-
- The results obtained are summarized in Table 1.
Table 1 FWA Amount (wt%) in starch preparation CIE whiteness L* a* b* FWA 10.8 127.41 93.92 2.14 -9.32 1.6 133.13 94.13 2.15 -10.50 2.4 135.06 94.27 1.98 -10.87 FWA2 0.8 125.94 93.87 2.11 -9.01 1.6 131.64 94.03 2.20 -10.21 2.4 133.86 94.17 2.11 -10,65 Comparative
FWA0.8 126.13 93.98 1.80 -9.01 1.6 129.95 94.19 1.54 -9.76 2.4 130.81 94.37 1.22 -9.87 - As may be taken from Table 1,
FWA 1 andFWA 2 containing certain aliphatic amine groups, namely of diisopropanolamine or dipropylamine, in combination with dimethanilic acid, showed for almost all concentrations of fluorescent whitening agent used an improvement in whiteness in the presence of calcium chloride compared to the comparative FWA which does not contain that specific combination of groups. For further illustration, the results of Table 1 are also shown inFig. 1 . - The above experimental data show that the use of bis-triazinylamino-stilbene fluorescent whitening agent compounds with a specific combination of terminal groups according to the invention results in paper of improved whiteness in the presence of a salt of a bivalent cation, such as calcium chloride.
Claims (15)
- A composition suitable for surface treatment of paper, wherein the composition contains(a) at least one fluorescent whitening agent of the formula (I)
R1, R2, R3 and R4 represent, independently of each other, hydrogen, C1 - C4 alkyl, C2 - C4 alkoxyalkyl, C2-C4 cyanoalkyl, or C2- C4 hydroxyalkyl; or R1 and R2 or R3 and R4 independently of each other together with N atom form morpholine, piperidine or pyrrolidine ring;
wherein at least one of R1, R2, R3 and R4 contains at least 3 carbon atoms;
M represents hydrogen, or one equivalent of a cation, in particular Li, Na, K, Ca, Mg, ammonium, or ammonium which is mono-, di-, tri- or tetra- substituted by C1- C4 alkyl or C2- C4 hydroxyalkyl;(b) at least one salt of a bivalent cation;(c) at least one carrier; and(d) water. - The composition of claim 1, wherein n and m each are 2, and the -SO3M groups are in 2,5-position.
- The composition of claim 1 or 2, wherein R1, R2, R3 and R4 are, independently of each other, propyl, cyanoethyl, or hydroxypropyl.
- The composition of any of claims 1 to 3, wherein n and m are 2, and R1, R2, R3 and R4 are propyl.
- The composition of any of claims 1 to 3, wherein n and m are 2, and R1, R2, R3 and R4 are hydroxypropyl, in particular hydroxyisopropyl.
- The composition of any of claims 1 to 3, wherein n and m are 2, R1 and R3 are hydroxypropyl, in particular hydroxyisopropyl, and R2 and R4 are cyanoethyl.
- The composition of any of the preceding claims, wherein M is Na or K.
- The composition of any of the preceding claims, wherein the salt of component (b) is calcium chloride.
- The composition of any of the preceding claims, wherein the carrier of component (c) is selected from carboxymethylcellulose, polyvinyl alcohol, starch, and mixtures thereof.
- The composition of claim 9, wherein the carrier is starch.
- The composition of any of the preceding claims, wherein the composition contains component (a) in an amount of 0.02 to 3 weight-%, component (b) in an amount of 0.2 to 8 weight-%, and component (c) in an amount of 3 to 20 weight-%, each based on 100 weight-% of the composition.
- The composition of any of the preceding claims, wherein the composition is a size press liquor which optionally contains a sizing agent.
- A process for whitening paper, wherein a cellulose sheet is brought into contact with a composition as defined in any of the preceding claims.
- The process of claim 13, wherein the contacting is conducted in a size press.
- A paper obtainable by the process according to claim 13 or 14.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10171451.7A EP2412870B1 (en) | 2010-07-30 | 2010-07-30 | Composition and process for whitening paper |
PCT/EP2011/062081 WO2012013513A1 (en) | 2010-07-30 | 2011-07-14 | Composition and process for whitening paper |
CA2802544A CA2802544A1 (en) | 2010-07-30 | 2011-07-14 | Composition and process for whitening paper |
US13/813,160 US20130126117A1 (en) | 2010-07-30 | 2011-07-14 | Composition and process for whitening paper |
BR112013002342A BR112013002342A2 (en) | 2010-07-30 | 2011-07-14 | paper bleaching composition and process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10171451.7A EP2412870B1 (en) | 2010-07-30 | 2010-07-30 | Composition and process for whitening paper |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2412870A1 EP2412870A1 (en) | 2012-02-01 |
EP2412870B1 true EP2412870B1 (en) | 2013-04-17 |
Family
ID=43446405
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10171451.7A Revoked EP2412870B1 (en) | 2010-07-30 | 2010-07-30 | Composition and process for whitening paper |
Country Status (5)
Country | Link |
---|---|
US (1) | US20130126117A1 (en) |
EP (1) | EP2412870B1 (en) |
BR (1) | BR112013002342A2 (en) |
CA (1) | CA2802544A1 (en) |
WO (1) | WO2012013513A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PT2781648E (en) * | 2013-03-21 | 2016-03-07 | Clariant Int Ltd | Optical brightening agents for high quality ink-jet printing |
PL2799618T3 (en) * | 2013-04-29 | 2016-12-30 | Use of micronized cellulose and fluorescent whitening agent for surface treatment of cellulosic materials | |
CN104312197B (en) * | 2014-09-05 | 2016-09-21 | 旭泰(太仓)精细化工有限公司 | A kind of hexa-sulphonic acid liquid fluorescent whitening agents and preparation method and application |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8330404D0 (en) * | 1983-11-15 | 1983-12-21 | Dow Chemical Europ | Activation of fluorescent whitening agents |
DE3502038A1 (en) * | 1985-01-23 | 1986-07-24 | Sandoz-Patent-GmbH, 7850 Lörrach | AQUEOUS BRIGHTENING DEVICES AND THEIR USE IN THE PAPER LINE |
DE19706238B4 (en) * | 1997-02-18 | 2005-09-01 | Bayer Chemicals Ag | Process for the preparation of substituted 4,4'-diaminostilbene-2,2'-disulfonic acids |
MY125712A (en) | 1997-07-31 | 2006-08-30 | Hercules Inc | Composition and method for improved ink jet printing performance |
KR100529488B1 (en) * | 1998-02-20 | 2005-11-22 | 시바 스페셜티 케미칼스 홀딩 인크. | A process for the preparation of stilbene compounds |
US6165973A (en) * | 1999-02-05 | 2000-12-26 | Ciba Specialty Chemicals Corporation | Fluorescent whitening agent, its preparation and use |
DE10149313A1 (en) * | 2001-10-05 | 2003-04-17 | Bayer Ag | Use of aqueous brightener preparations to lighten natural and synthetic materials |
DE10217677A1 (en) * | 2002-04-19 | 2003-11-06 | Bayer Ag | Use of brighteners for the production of coating slips |
US7270771B2 (en) * | 2002-07-05 | 2007-09-18 | Ciba Specialty Chemicals Corporation | Triazinylaminostilbene disulphonic acid mixtures |
EP1805361B1 (en) * | 2004-10-27 | 2009-08-26 | Basf Se | Compositions of fluorescent whitening agents |
US7682438B2 (en) * | 2005-11-01 | 2010-03-23 | International Paper Company | Paper substrate having enhanced print density |
DE602008004328D1 (en) | 2008-06-11 | 2011-02-17 | Kemira Germany Gmbh | Composition and process for paper bleaching |
US20100129553A1 (en) * | 2008-11-27 | 2010-05-27 | International Paper Company | Optical Brightening Compositions For High Quality Inkjet Printing |
-
2010
- 2010-07-30 EP EP10171451.7A patent/EP2412870B1/en not_active Revoked
-
2011
- 2011-07-14 BR BR112013002342A patent/BR112013002342A2/en not_active Application Discontinuation
- 2011-07-14 CA CA2802544A patent/CA2802544A1/en not_active Abandoned
- 2011-07-14 WO PCT/EP2011/062081 patent/WO2012013513A1/en active Application Filing
- 2011-07-14 US US13/813,160 patent/US20130126117A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
WO2012013513A1 (en) | 2012-02-02 |
BR112013002342A2 (en) | 2016-05-24 |
CA2802544A1 (en) | 2012-02-02 |
EP2412870A1 (en) | 2012-02-01 |
US20130126117A1 (en) | 2013-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2135997B1 (en) | Composition and process for whitening paper | |
US8821688B2 (en) | Optical brightening compositions | |
EP2478152B1 (en) | Disulfo-type fluorescent whitening agents in coating applications | |
CA2744837C (en) | Improved optical brightening compositions for high quality ink jet printing | |
AU2011214619B2 (en) | Aqueous sizing compositions for shading in size press applications | |
EP2412870B1 (en) | Composition and process for whitening paper | |
EP2535455A1 (en) | Use of fluorescent whitening agent compositions for whitening paper | |
AU2014259497B2 (en) | Improved optical brightening compositions | |
JP2019518746A (en) | Fluorescent whitening agents and mixtures thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
17P | Request for examination filed |
Effective date: 20100730 |
|
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 SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME RS |
|
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 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R079 Ref document number: 602010006191 Country of ref document: DE Free format text: PREVIOUS MAIN CLASS: D21H0021300000 Ipc: D21H0017070000 |
|
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: D21H 17/51 20060101ALI20120926BHEP Ipc: D21H 17/07 20060101AFI20120926BHEP Ipc: D21H 17/09 20060101ALI20120926BHEP Ipc: D21H 21/30 20060101ALI20120926BHEP Ipc: C07D 251/00 20060101ALI20120926BHEP Ipc: C09K 11/06 20060101ALI20120926BHEP |
|
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 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: 607396 Country of ref document: AT Kind code of ref document: T Effective date: 20130515 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602010006191 Country of ref document: DE Effective date: 20130613 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 607396 Country of ref document: AT Kind code of ref document: T Effective date: 20130417 |
|
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: VDEP Effective date: 20130417 |
|
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: 20130417 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: 20130417 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: 20130417 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: 20130819 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: 20130817 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: 20130718 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: 20130717 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: 20130728 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: 20130417 |
|
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: 20130417 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: 20130417 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: 20130417 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: 20130417 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: 20130717 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130417 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: 20130417 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: 20130417 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: 20130417 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
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: 20130417 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: 20130417 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: 20130417 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130417 |
|
26 | Opposition filed |
Opponent name: ARCHROMA IP GMBH Effective date: 20140116 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602010006191 Country of ref document: DE Effective date: 20140116 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PLAF | Information modified related to communication of a notice of opposition and request to file observations + time limit |
Free format text: ORIGINAL CODE: EPIDOSCOBS2 |
|
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: 20130730 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20140730 |
|
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: 20140731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140731 |
|
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: 20130417 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140730 |
|
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: 20130417 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: 20130417 |
|
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: 20130730 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: 20100730 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: 20130417 |
|
APBM | Appeal reference recorded |
Free format text: ORIGINAL CODE: EPIDOSNREFNO |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
APBM | Appeal reference recorded |
Free format text: ORIGINAL CODE: EPIDOSNREFNO |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
APBQ | Date of receipt of statement of grounds of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA3O |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
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: 20130417 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R064 Ref document number: 602010006191 Country of ref document: DE Ref country code: DE Ref legal event code: R103 Ref document number: 602010006191 Country of ref document: DE |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20190725 Year of fee payment: 10 Ref country code: FI Payment date: 20190719 Year of fee payment: 10 Ref country code: DE Payment date: 20190726 Year of fee payment: 10 Ref country code: FR Payment date: 20190724 Year of fee payment: 10 |
|
RDAF | Communication despatched that patent is revoked |
Free format text: ORIGINAL CODE: EPIDOSNREV1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
REG | Reference to a national code |
Ref country code: FI Ref legal event code: MGE |
|
27W | Patent revoked |
Effective date: 20191010 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: ECNC |