EP1624105B1 - Alkanol-ammonia containing triazinylflavonat brightener - Google Patents

Alkanol-ammonia containing triazinylflavonat brightener Download PDF

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Publication number
EP1624105B1
EP1624105B1 EP05016038A EP05016038A EP1624105B1 EP 1624105 B1 EP1624105 B1 EP 1624105B1 EP 05016038 A EP05016038 A EP 05016038A EP 05016038 A EP05016038 A EP 05016038A EP 1624105 B1 EP1624105 B1 EP 1624105B1
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Prior art keywords
formula
alkyl
brightener
weight
size press
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EP05016038A
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German (de)
French (fr)
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EP1624105A1 (en
Inventor
Heinz Dr. Giesecke
Bernhard Hunke
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Kemira Oyj
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Kemira Agro Oy
Kemira Oyj
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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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • a sizing step is generally carried out to achieve good writability and strength, which can be done on the one hand before sheet formation in the pulp (engine sizing), on the other hand after sheet formation in the size press.
  • a combination of these two methods is possible.
  • a brightening of the paper pulp or of the paper sheet is usually carried out by optical brighteners, wherein usually in the mass application, the sizing agent and the brightener of the pulp are fed separately, while incorporated in surface sizing the brightener in the size press liquor and applied together with this on the paper sheet.
  • the combination of surface sizing and whitening of papers is widely used in the paper making industry. Especially in the paper segment Printing & Writing (Copy, Inkjet, Offset, etc.) this method is widely used. In addition to the more efficient lightening, a faster correction (online measurement) of the whiteness levels to be achieved is also possible. Furthermore, with the surface application, the wet end of additional anionic freights (whiteners) spared.
  • Triazinylflavonataufheller are already described as K or Na salts as optical brighteners in the size press method for lightening paper. However, these still have some application disadvantages, in particular in the whiteness.
  • brighteners containing more than 50% by weight, preferably more than 60% by weight, preferably more than 75% by weight, in particular more than 95% by weight, of a brightener Formula I exist.
  • the brightener of the formula (I) may additionally be present in excess alkanolamine or alkanolammonium in the form of the free bases or corresponding salts with other, inorganic or organic, anions in the size press liquor.
  • the brighteners are already prepared and / or formulated in the form of their alkanolammonium salts or mixed salts of their alkanolammonium salts with their salts of inorganic bases and are finally incorporated into size press liquors in such a form which are then applied in the described preferred pH range.
  • the use can, however, e.g. also be effected by reacting with an inorganic counterion, e.g.
  • Lithium, sodium, potassium, calcium, magnesium, or ammonium whitening agent is contacted with the salt of an inorganic or organic acid of an alkanolamine, for example, an alkanolamine hydrochloride or alkanolamine sulfate, and this mixture is then applied in a size press liquor of suitable pH, or e.g. in that this matching only happens in the size press fleet, or z.
  • an alkanolamine underlying the alkanolamine is introduced in free form at any time and at any point in the manufacturing or processing and neutralized in the course with a suitable inorganic or organic acid. This of course also applies to the opposite case, namely that first the inorganic or organic acid and only then the alkanolamine is introduced.
  • the use according to the invention is preferably carried out by introducing into the size press liquor an aqueous solution of the brightener of suitable pH, which may possibly contain additional substances, such as carrier substances, salts or setting agents.
  • carrier-free or carrier-containing formulations in smaller amounts, usually in amounts below 5 wt .-%, other auxiliaries such.
  • other auxiliaries such as dispersants, thickeners, antifreeze, preservatives, complexing agents, etc., or organic by-products from the brightener synthesis, which were not completely removed in the workup, may be included.
  • the brightener with only inorganic cations shows a saturation behavior with respect to the CIE from certain brightener addition amounts.
  • Whiteness ie larger amounts do not lead to whiteness build-up any more and can even have a negative effect on the whiteness.
  • This saturation behavior occurs when using the alkanolammonium brightener only at much higher levels, compared to the salt with only inorganic cations, on.
  • the effect of saturation is also called greening.
  • the greening border i. the point above which increasing brightener amounts cause virtually no increase in whiteness can e.g. are derived from the a * -b * diagram, where a * and b * are the color coordinates in the CIE-L * a * b * system.
  • Aqueous whitener preparations are usually characterized by the so-called E1 / 1 value.
  • E1 / 1 value the extinction of a highly diluted solution of the preparation is determined by the usual and known to the expert methods of UV / Vis spectroscopy in a 1 cm cuvette at a specific wavelength. This wavelength corresponds to the long-wavelength absorption maximum of the respective brightener molecule. For flavonate brighteners it is about 350 nm.
  • the E1 / 1 value then corresponds to the imaginary extinction value extrapolated to a 1% solution of the sample to be determined.
  • the preparations according to the invention can preferably be used in the lightening process according to the invention.
  • aqueous whitener preparations comprising at least one brightener of the formula (I), in particular (Ia).
  • the size press liquor may contain inorganic or organic salts, in addition free alkanolamine, in addition alkanolamine salts, carriers and other substances.
  • the proportion of surface sizing agent, in particular starch, based on the size press liquor is preferably from 2 to 25% by weight, in particular from 5 to 15% by weight.
  • the water content of the size press liquor is preferably at least 70% by weight.
  • Comparative Examples 2a, b corresponds to Comparative Example 1 with the difference that in addition different amounts of free triethanolamine are present
  • 229 g of the membrane-filtered aqueous concentrate from Comparative Example 1 are mixed with stirring at room temperature with a) 15.0 b) 30.0 and a) 56 gb) 41 g demineralized water and then stirred for 10 min.
  • Triethanolamine-containing brightener preparations having an E1 / 1 value of 113 in the form of yellow-brownish homogeneous liquids are obtained. This corresponds to a content of brightener of about 21% and a content of triethanolamine of a) 5% b) 10%.
  • Comparative Example 3 corresponds to Example 2 WO 00 46336 .
  • the procedure is up to and including the introduction of the crystals as described for Example 1b. After dissolution of the crystals, 15 g of polyethylene glycol 1500 are added, the mixture is stirred until dissolved and determines the E1 / 1 value. The mixture is then diluted at room temperature with demineralized water to a calculated E1 / 1 value of 113.
  • the test of the individual brightener preparations is then carried out by diluting the respective preparation as a concentration series to a further 50.0 g of the same starch solution, diluted to 100.0 g with water, thoroughly mixed, and the resulting brightener-containing size press liquors as described above Help the Apply the laboratory size press to further test paper sheets. Finally, the papers so finished in the drying cylinder at about 100 ° C dried.
  • the above concentration series refers to preparations with an E1 / 1 value of 113. If preparations with a deviating E1 / 1 value are to be tested, their E1 / 1 value deviation from the guide value 113 must additionally be compensated for by: changing the concentration series in inverse proportion (for example, at an E1 / 1 value of 105, 0.538 wt% preparation is equivalent to 0.5% preparation of E1 / 1 value 113, etc.).
  • Table 1 Brightener preparation from Comparative Example 1 Amount (%) CIE whiteness L * a * b * 0.50 138.08 95.95 2.96 -10.83 1.00 144.11 96.12 3.04 -12.13 1.50 145.80 96.28 2.87 -12.44 2.00 146.46 96.32 2.69 -12.57
  • Table 4 Brightener preparation from Example la Amount (%) CIE whiteness L * a * b * 0.50 138.12 96.05 2.95 -10.80 1.00 145.36 96.31 3.09 -12.33 1.50 146.98 96.34 2.96 -12.68 2.00 148.48 96.57 2.79 -12.92
  • Table 5 Brightener preparation from Example 1b Amount (%) CIE whiteness L * a * b * 0.50 138.33 95.96 2.98 -10.88 1.00 145.58 96.26 3.12 -12.40 1.50 147.59 96.25 3.03 -12
  • Table 5 Brightener preparation from Example 1b Amount (%) CIE whiteness L * a * b * 0.50 138.33 95.96 2.98 -10.88 1.00 145.58 96.26 3.12 -12.40 1.50 147.59 96.25 3.03 -12.86 2.00 148.26 96.46 2.80 -12.92
  • Table 6 Brightener preparation from Example 2 Amount (%) CIE whiteness L * a * b * 0.50 138.69 95.96 3.02 -10.97 1.00 145.83 96.23 3.16 -12.47 1.50 148.12 96.41 3.08 -12.92 2.00 148.74 96,39 2.86 -13.06

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  • Paper (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Method for whitening paper in the size press comprises a size press fleet containing an alkanolammonium containing triazinyl flavone compound (I) as the optical whitener. Method for whitening paper in the size press comprises a size press fleet containing an alkanolammonium containing triazinyl flavone compound of formula (I) as the optical whitener. X : alkyl compounds of formula (a) or (b); either R 1>, R-1a : 1-6C alkyl; and R 2>, R-2a : H; or R 3>, R-3a : H, CH 3, CH 2CH 3, CH 2CH 2OH or CH 2CH 2OCH 3; R 4>H or 1-4C alkyl; M : an equivalent inorganic cation (preferably Li, Na, K, Ca, Mg or ammonium) or a substituted ammonium of formula (II) (where at least 10 mol.% of all cation corresponds to formula (II)); R 5>-R 7>H, 1-4C alkyl or optionally substituted 2-4C hydroxyalkyl; and R 8>optionally further substituted 2-4C hydroxy alkyl. Independent claims are also included for: (1) an optical whitener preparation comprising more than 50 (preferably more than 95) wt.% of (I); and (2) a size press fleet comprising (I) or an optical whitener preparation and at least a surface sizing agent (preferably starch). [Image] [Image] [Image].

Description

Die Erfindung betrifft ein Verfahren zum Aufhellen von Papier in der Leimpresse, Aufhellerpräparationen sowie Leimpressenflotten.The invention relates to a process for lightening paper in the size press, whitener preparations and size press liquors.

Bei der Herstellung von Papier wird zur Erzielung von guter Beschreibbarkeit und Festigkeit in der Regel ein Leimungsschritt durchgeführt, der einerseits vor der Blattbildung in der Papiermasse erfolgen kann (Masseleimung), andererseits nach der Blattbildung in der Leimpresse. Auch eine Kombination dieser beiden Verfahren ist möglich. In einer oder beiden Herstellungsstufen des Papiers wird üblicherweise auch eine Aufhellung der Papiermasse bzw. des Papierblatts durch optische Aufheller vorgenommen, wobei in der Regel bei der Masseanwendung das Leimungsmittel und der Aufheller der Papiermasse getrennt zugeführt werden, während bei Oberflächenleimung der Aufheller in die Leimpressenflotte eingearbeitet und mit dieser zusammen auf das Papierblatt aufgebracht wird.In the production of paper, a sizing step is generally carried out to achieve good writability and strength, which can be done on the one hand before sheet formation in the pulp (engine sizing), on the other hand after sheet formation in the size press. A combination of these two methods is possible. In one or both stages of manufacture of the paper, a brightening of the paper pulp or of the paper sheet is usually carried out by optical brighteners, wherein usually in the mass application, the sizing agent and the brightener of the pulp are fed separately, while incorporated in surface sizing the brightener in the size press liquor and applied together with this on the paper sheet.

Die Kombination von Oberflächenleimung und Aufhellung von Papieren ist bei der papiererzeugenden Industrie weit verbreitet. Besonders im Papiersegment Printing&Writing (Copy, Ink Jet, Offset etc.) findet diese Methode breite Anwendung. Neben der effizienteren Aufhellung ist auch eine schnellere Korrektur (Online-Messung) der zu erzielenden Weißgrade möglich. Des Weiteren wird mit der Oberflächenapplikation die Nasspartie von zusätzlichen anionischen Frachten (Weißtöner) verschont.The combination of surface sizing and whitening of papers is widely used in the paper making industry. Especially in the paper segment Printing & Writing (Copy, Inkjet, Offset, etc.) this method is widely used. In addition to the more efficient lightening, a faster correction (online measurement) of the whiteness levels to be achieved is also possible. Furthermore, with the surface application, the wet end of additional anionic freights (whiteners) spared.

In GB-A-896 533 werden bereits Triazinylflavonataufheller als K oder Na-Salze als optische Aufheller im Leimpressenverfahren zum Aufhellen von Papier beschrieben. Diese haben aber noch einige anwendungstechnische Nachteile, insbesondere im Weißgrad.In GB-A-896,533 Triazinylflavonataufheller are already described as K or Na salts as optical brighteners in the size press method for lightening paper. However, these still have some application disadvantages, in particular in the whiteness.

Es besteht ein fortgesetzter Trend zu obenflächengeleimten Papieren mit hohen Weißgraden und daher der Wunsch nach möglichst effektiven optischen Aufhellern als Leimpressenflottenbestandteil, insbesondere solchen Aufhellern, die die Nachteile des Standes der Technik nicht besitzen.There is a continuing trend for top-grade papers with high levels of whiteness and, therefore, the desire for most effective optical brighteners as size press liquor component, especially those brighteners that do not have the disadvantages of the prior art.

Die Erfindung betrifft daher ein Verfahren zum Aufhellen von Papier in der Leimpresse, dadurch gekennzeichnet, dass eine Leimpressenflotte enthaltend einen Aufheller der Formel I ,

Figure imgb0001
worin

X
unabhängig voneinander einen Rest der Formel
Figure imgb0002
 oder
Figure imgb0003
bedeutet und
R1
für C1-C6-Alkyl und
R2
für H, oder
R1
für H und
R2
für C1-C6-Alkyl steht, und unabhängig davon
R3
für H, Methyl, Ethyl, CH2CH2OH oder CH2CH2OCH3 steht,
R1'
für C1-C6-Alkyl und
R2'
für H, oder
R1'
für H und
R2'
für C1-C6-Alkyl steht, und unabhängig davon
R3'
für H, Methyl, Ethyl, CH2CH2OH oder CH2CH2OCH3 sowie
R4
für C1-C4-Alkyl steht und
M
H, ein Äquivalent eines anorganischen Kations, insbesondere Li, Na, K, Ca, Mg oder Ammonium, oder ein substituiertes Ammonium der Formel II
Figure imgb0004
bedeutet, wobei
R5 bis R7
unabhängig voneinander Wasserstoff, einen C1-C4-Alkylrest oder einen ggf. weiter substituierten C2-C4-Hydroxyalkylrest bedeuten, und R8 einen ggf. weiter substituierten C2-C4-Hydroxyalkylrest bedeutet,
wobei wenigstens 10 mol-% aller Kationen M der Formel II entsprechen beim Leimungsschritt verwendet wird.The invention therefore relates to a method for lightening paper in the size press, characterized in that a size press liquor comprising a brightener of the formula I,
Figure imgb0001
 wherein
X
independently of one another a radical of the formula
Figure imgb0002
 or
Figure imgb0003
means and
R 1
for C 1 -C 6 -alkyl and
R 2
for H, or
R 1
for H and
R 2
is C 1 -C 6 -alkyl, and independently thereof
R 3
is H, methyl, ethyl, CH 2 CH 2 OH or CH 2 CH 2 OCH 3 ,
R 1 '
for C 1 -C 6 -alkyl and
R 2 '
for H, or
R 1 '
for H and
R 2 '
is C 1 -C 6 -alkyl, and independently thereof
R 3 '
for H, methyl, ethyl, CH 2 CH 2 OH or CH 2 CH 2 OCH 3 as well
R 4
is C 1 -C 4 -alkyl and
M
H, one equivalent of an inorganic cation, in particular Li, Na, K, Ca, Mg or ammonium, or a substituted ammonium of the formula II
Figure imgb0004
means, where
R 5 to R 7
independently of one another are hydrogen, a C 1 -C 4 -alkyl radical or an optionally further substituted C 2 -C 4 -hydroxyalkyl radical, and R 8 is an optionally further substituted C 2 -C 4 -hydroxyalkyl radical,
wherein at least 10 mol% of all cations M of formula II are used in the sizing step.

Bevorzugt besitzen wenigstens 20 mol-%, insbesondere mehr als 50 mol-%, ganz besonders bevorzugt mehr als 80 mol-% aller Kationen M die Bedeutung der Formel II.Preferably, at least 20 mol%, in particular more than 50 mol%, very particularly preferably more than 80 mol% of all cations M have the meaning of the formula II.

Ganz besonders bevorzugt ist es, Aufheller zu verwenden, die zu mehr als 50 Gew.-%, bevorzugt mehr als 60 Gew.-%, vorzugsweise mehr als 75 Gew.-%, insbesondere mehr als 95 Gew.-% aus einem Aufheller der Formel I bestehen.It is very particularly preferred to use brighteners containing more than 50% by weight, preferably more than 60% by weight, preferably more than 75% by weight, in particular more than 95% by weight, of a brightener Formula I exist.

Bevorzugte optische Aufheller entsprechen der Formel (I) mit

  • R1 = H,
  • R2 = lineares C1-C6-Alkyl sowie
  • R3 = H;
weiterhin der Formel (I) mit
  • R1' = H,
  • R2' = lineares C1-C6-Alkyl sowie
  • R3' = H und R4 = H oder Methyl,
in denen M jeweils eine Mischung von Kationen enthaltend Alkanolammoniumionen der Formel II, wobei die Reste R5 für H; R6 für H oder C2-C4-Hydroxyalkyl und R7 und R8 für C2-C4-Hydroxyalkyl stehen und Na- oder K-Ionen bedeutet.Preferred optical brighteners correspond to the formula (I) with
  • R 1 = H,
  • R 2 = linear C 1 -C 6 -alkyl and
  • R 3 = H;
furthermore of the formula (I)
  • R 1 ' = H,
  • R 2 ' = linear C 1 -C 6 -alkyl and
  • R 3 ' = H and R 4 = H or methyl,
in which M is in each case a mixture of cations containing alkanolammonium ions of the formula II, where the radicals R 5 are H; R 6 is H or C 2 -C 4 hydroxyalkyl and R 7 and R 8 are C 2 -C 4 hydroxyalkyl and denote Na or K ions.

Besonders bevorzugt ist der Aufheller der Formel (Ia)

Figure imgb0005
worin

M
eine Mischung enthaltend das Kation der Formel II
Figure imgb0006
und Na+ oder K+ bedeutet.The brightener of the formula (Ia) is particularly preferably
Figure imgb0005
 wherein
M
a mixture containing the cation of formula II
Figure imgb0006
and Na + or K + means.

Die besondere Eignung der alkanolammoniumhaltigen Aufheller der Formel I für die erfindungsgemäße Verwendung bedeutet, dass für den Fall, dass mindestens einer der Reste R5-R7 Wasserstoff ist, der pH-Wert in der Leimpressenflotte vorzugsweise so eingestellt wird, dass eine für die vorliegende Menge an Aufhelleranionen optimale Mindestmenge an protoniertem Alkanolamin zur Verfügung steht. Dies ist im Allgemeinen im Bereich von pH <= 7,5 der Fall; vorzugsweise wird im Anwendungsmedium ein pH-Wert eingestellt, bei dem möglichst alles vorliegende Alkanolamin protoniert ist, d.h. ein pH-Bereich von 4-7.The particular suitability of the alkanolammonium brightener of formula I for the inventive use means that in the event that at least one of R 5 -R 7 is hydrogen, the pH in the size press liquor is preferably adjusted so that one for the present Amount of Aufhelleranionen optimal minimum amount of protonated alkanolamine is available. This is generally the case in the range of pH <= 7.5; preferably adjusted in the application medium, a pH at which as far as possible all present alkanolamine is protonated, ie, a pH range of 4-7.

Bei der erfindungsgemäßen Verwendung der Aufheller der Formel (I) kann zusätzlich überschüssiges Alkanolamin bzw. Alkanolammonium in Form der freien Basen bzw. entsprechender Salze mit anderen, anorganischen oder organischen, Anionen in der Leimpressenflotte anwesend sein.In the inventive use of the brightener of the formula (I) may additionally be present in excess alkanolamine or alkanolammonium in the form of the free bases or corresponding salts with other, inorganic or organic, anions in the size press liquor.

Unter Leimpresse wird im Rahmen dieser Erfindung ein Oberflächenauftragungsaggregat vorzugsweise der Papiermaschine verstanden, in dem das gebildete Celluloseblatt mit einer wässrigen Flotte, enthaltend wenigstens ein Oberflächenleimungsmittel, insbesondere Stärke, beispielsweise native, derivatisierte oder abgebaute, vorzugsweise oxidativ abgebaute Stärke, der sogenannten Leimpressenflotte in Kontakt gebracht wird, und in dem der Anteil der Flotte, der von dem Blatt aufgenommen werden soll (Flottenaufnahme) vorzugsweise durch den Walzenpressdruck eingestellt werden kann.Under size press is understood in the context of this invention, a surface application unit preferably the paper machine in which the cellulose sheet formed with an aqueous liquor containing at least one surface sizing agent, in particular starch, for example, native, derivatized or degraded, preferably oxidatively degraded starch, the so-called size press liquor brought into contact is, and in which the proportion of the fleet, which is to be absorbed by the sheet (liquor pickup) can be preferably adjusted by the roll pressure.

Neuere Entwicklungen der Leimpresse namentlich der Speedsizer als auch der Symsizer werden ebenfalls unter dem Begriff Leimpresse verstanden.Recent developments in the size press, namely the Speedsizer as well as the Symsizer are also understood by the term size press.

So können z.B. die Aufheller bereits in Form ihrer Alkanolammoniumsalze oder Mischsalze ihrer Alkanolammoniumsalze mit ihren Salzen anorganischer Basen hergestellt und / oder formuliert werden und in einer solchen Form schließlich in Leimpressenflotten eingebracht werden, die dann in dem beschriebenen bevorzugten pH-Bereich angewendet werden. Die Verwendung kann aber z.B. auch dadurch erfolgen, dass ein mit einem anorganischen Gegenion, wie z.B. Lithium, Natrium, Kalium, Calcium, Magnesium, oder Ammonium vorliegender Aufheller mit dem Salz einer anorganischen oder organischen Säure eines Alkanolamins zusammengebracht wird, beispielsweise einem Alkanolaminhydrochlorid oder Alkanolaminsulfat, und diese Mischung dann in einer Leimpressenflotte von geeignetem pH-Wert angewendet wird, oder z.B. dadurch, dass dieses Zusammenbringen erst in der Leimpressenflotte geschieht, oder z. B. auch dadurch, dass das dem Alkanolaminsalz zu Grunde liegende Alkanolamin in freier Form zu einem beliebigen Zeitpunkt und an einer beliebigen Stelle in den Herstellungs- oder Verarbeitungsgang eingebracht und im weiteren Verlauf mit einer geeigneten anorganischen oder organischen Säure neutralisiert wird. Dies gilt natürlich auch für den umgekehrten Fall, dass nämlich zuerst die anorganische oder organische Säure und erst danach das Alkanolamin eingebracht wird.Thus, e.g. the brighteners are already prepared and / or formulated in the form of their alkanolammonium salts or mixed salts of their alkanolammonium salts with their salts of inorganic bases and are finally incorporated into size press liquors in such a form which are then applied in the described preferred pH range. The use can, however, e.g. also be effected by reacting with an inorganic counterion, e.g. Lithium, sodium, potassium, calcium, magnesium, or ammonium whitening agent is contacted with the salt of an inorganic or organic acid of an alkanolamine, for example, an alkanolamine hydrochloride or alkanolamine sulfate, and this mixture is then applied in a size press liquor of suitable pH, or e.g. in that this matching only happens in the size press fleet, or z. B. also in that the alkanolamine underlying the alkanolamine is introduced in free form at any time and at any point in the manufacturing or processing and neutralized in the course with a suitable inorganic or organic acid. This of course also applies to the opposite case, namely that first the inorganic or organic acid and only then the alkanolamine is introduced.

Bevorzugt erfolgt die erfindungsgemäße Verwendung dadurch, dass eine wässrige Lösung des erfindungsgemäß eingesetzten Aufhellers von geeignetem pH-Wert, die ggf. zusätzliche Stoffe enthalten kann, wie z.B. Carriersubstanzen, Salze oder Stellmittel, in die Leimpressenflotte eingebracht wird.The use according to the invention is preferably carried out by introducing into the size press liquor an aqueous solution of the brightener of suitable pH, which may possibly contain additional substances, such as carrier substances, salts or setting agents.

Als Carriersubstanzen kommen beispielsweise hydrophile Polymere mit der Fähigkeit zur Ausbildung von Wasserstoffbrückenbindungen in Frage. Bevorzugte Carriersubstanzen sind Polyvinylalkohole, Carboxymethylcellulosen sowie Polyethylenglykole mit einem zahlenmittleren Molgewicht von 200 bis 8000 g/mol, als auch beliebige Mischungen dieser Substanzen, wobei diese Polymere gegebenenfalls modifiziert sein können. Bevorzugte Polyvinylalkohole sind solche mit einem Hydrolysegrad >85%, bevorzugte Carboxymethylcellulosen solche mit einem Substitutionsgrad DS von >0,5. Besonders bevorzugt sind Polyethylenglykole mit einem zahlenmittleren Molgewicht Mn von 200 bis 8000 g/mol.Suitable carrier substances are, for example, hydrophilic polymers capable of forming hydrogen bonds. Preferred carrier substances are polyvinyl alcohols, carboxymethylcelluloses 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, these polymers optionally being able to be modified. Preferred polyvinyl alcohols are those with a degree of hydrolysis> 85%, preferred carboxymethylcelluloses are those with a degree of substitution DS of> 0.5. Particularly preferred are polyethylene glycols having a number average molecular weight Mn of 200 to 8000 g / mol.

Mit solchen Formulierungen können in der Regel günstigere Weißgradaufbaukurven und höhere Vergrünungsgrenzen realisiert werden als mit carrierfreien Aufhellerpräparationen.With such formulations, generally more favorable whiteness build-up curves and higher greening limits can be realized than with carrier-free whitener preparations.

Zusätzlich können in den carrierfreien oder auch carrierhaltigen Formulierungen in kleineren Mengen, üblicherweise in Mengen unter 5 Gew.-%, weitere Hilfsstoffe wie z. B. Dispergiermittel, Verdicker, Frostschutzmittel, Konservierungsmittel, Komplexbildner etc. oder auch organische Nebenprodukte aus der Aufhellersynthese, die bei der Aufarbeitung nicht vollständig entfernt wurden, enthalten sein.In addition, in the carrier-free or carrier-containing formulations in smaller amounts, usually in amounts below 5 wt .-%, other auxiliaries such. As dispersants, thickeners, antifreeze, preservatives, complexing agents, etc., or organic by-products from the brightener synthesis, which were not completely removed in the workup, may be included.

Vergleicht man den extinktionsgleichen Einsatz der in Formel (I) gezeigten Aufheller in einer Leimpressenanwendung in Form ihrer Salze, worin M nur anorganische Kationen sind, mit ihren alkanolammoniumhaltigen Salzen, so zeigt ab bestimmten Aufhellerzusatzmengen der Aufheller mit nur anorganischen Kationen ein Sättigungsverhalten bezüglich des CIE-Weißgrades, d.h. größere Einsatzmengen führen zu keinem Weißgradaufbau mehr und können sich sogar negativ auf den Weißgrad auswirken. Dieses Sättigungsverhalten tritt bei Verwendung der alkanolammoniumhaltigen Aufheller erst bei deutlich höheren Einsatzmengen, verglichen zum Salz mit nur anorganischen Kationen, auf. Dadurch können mit den alkanolammoniumhaltigen Formulierungen überraschend höhere Weißgrade realisiert werden als mit Formulierungen, die lediglich anorganische Kationen enthalten. Der Effekt der Sättigung wird auch als Vergrünung bezeichnet. Die Vergrünungsgrenze, d.h. der Punkt, ab dem steigende Aufheller-Einsatzmengen praktisch keinen Weißgradzuwachs mehr bewirken, kann z.B. aus dem a*-b*-Diagramm abgeleitet werden, wobei a* und b* die Farbkoordinaten im CIE-L*a*b*-System sind.If one compares the extinction-like use of the brighteners shown in formula (I) in a size press application in the form of their salts, where M are only inorganic cations, with their alkanolammonium-containing salts, the brightener with only inorganic cations shows a saturation behavior with respect to the CIE from certain brightener addition amounts. Whiteness, ie larger amounts do not lead to whiteness build-up any more and can even have a negative effect on the whiteness. This saturation behavior occurs when using the alkanolammonium brightener only at much higher levels, compared to the salt with only inorganic cations, on. As a result, it is possible with the alkanolammonium-containing formulations to achieve surprisingly higher degrees of whiteness than with formulations which contain only inorganic cations. The effect of saturation is also called greening. The greening border, i. the point above which increasing brightener amounts cause virtually no increase in whiteness can e.g. are derived from the a * -b * diagram, where a * and b * are the color coordinates in the CIE-L * a * b * system.

Wässrige Aufhellerzubereitungen werden üblicherweise durch den sogenannten E1/1-Wert charakterisiert. Dazu wird die Extinktion einer stark verdünnten Lösung der Zubereitung nach den üblichen und dem Fachmann bekannten Methoden der UV/Vis-Spektroskopie in einer lcm-Küvette bei einer bestimmten Wellenlänge bestimmt. Diese Wellenlänge entspricht dem langwelligen Absorptionsmaximum des jeweiligen Aufhellermoleküls. Bei Flavonataufhellern beträgt sie ca. 350 nm. Der E1/1-Wert entspricht dann dem fiktiven, auf eine 1 %ige Lösung der zu bestimmenden Probe hochgerechneten Extinktionswert.Aqueous whitener preparations are usually characterized by the so-called E1 / 1 value. For this purpose, the extinction of a highly diluted solution of the preparation is determined by the usual and known to the expert methods of UV / Vis spectroscopy in a 1 cm cuvette at a specific wavelength. This wavelength corresponds to the long-wavelength absorption maximum of the respective brightener molecule. For flavonate brighteners it is about 350 nm. The E1 / 1 value then corresponds to the imaginary extinction value extrapolated to a 1% solution of the sample to be determined.

Da die Vergrünung der alkanolammoniumhaltigen Typen erst bei relativ hohen Einsatzmengen auftritt, eignet sich ihre erfindungsgemäße Verwendung besonders zur Herstellung hochweißer Papiere. Die genauen Einsatzbedingungen, bei denen die Vergrünung in der Leimpressenanwendung einsetzt, hängen von der Zusammensetzung der jeweiligen Leimpressenflotte ab.Since the greening of alkanolammoniumhaltigen types only occurs at relatively high levels, their use according to the invention is particularly suitable for the production of high white papers. The exact conditions of use in which the greening in the size press application depends on the composition of the respective size press liquor.

In EP-A-1355004 werden ebenfalls Aufheller der Formel (I) beschrieben, allerdings werden sie dort lediglich im Zusammenhang mit der Verwendung in Streichmassen erwähnt.In EP-A-1355004 also brightener of formula (I) are described, but they are mentioned there only in connection with the use in coating slips.

In WO 0046336 werden Mischungen von Aufhellern beschrieben, die unter Anderem bis zu 45 mol-% Aufheller der Formel (I) mit R1=R3=H; R2= Methyl; M = Na, Li, Ca, Mg, Ammonium oder Ammonium, das mono-, di-, tri- oder tetrasubstituiert ist durch C1-C4-Alkyl oder C1-C4-Hydroxyalkyl, enthalten können , unter Anderem zur Aufhellung von Papier. Ob diese Mischungen besonders gut für eine Anwendung in der Leimpresse geeignet sind, wird jedoch nirgends erwähnt. Darüber hinaus konnte durch vergleichende Untersuchungen gezeigt werden, dass die in der vorliegenden Erfindung beschriebenen Aufheller der Formel Ia (entspricht 1b aus WO 00/46336 ), wenn man sie gemäß der in WO 0046336 , Beispiel 2 beschriebenen Methode als Einzelverbindung herstellt, in der Leimpressenanwendung eine deutlich besser aufhellende Wirkung zeigt als die auf ebensolche Weise hergestellte Mischung gemäß WO 0046336 , und dass sich diese Wirkung nochmals steigern lässt, wenn man das vorliegende überschüssige Alkanolamin neutralisiert.In WO 0046336 describes mixtures of brighteners which, inter alia, up to 45 mol% brightener of formula (I) with R 1 = R 3 = H; R 2 = methyl; M = Na, Li, Ca, Mg, ammonium or ammonium which is mono-, di-, tri-, or tetra-substituted by C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl, which may contain, inter alia to lighten of paper. Whether these mixtures are particularly well suited for use in the size press, however, is nowhere mentioned. In addition, it could be shown by comparative investigations that the brightener described in the present invention of the formula Ia (corresponds to 1b WO 00/46336 ), if you do it according to the in WO 0046336 Example 2 method produces as a single compound, in the size press application shows a much better brightening effect than the prepared in such a way mixture according to WO 0046336 , And that this effect can be further increased when neutralized the present excess alkanolamine.

Die Erfindung betrifft daher weiterhin Aufhellerpräparation enthaltend Aufheller, die zu mehr als 50 Gew.-%, bevorzugt mehr als 60 Gew.-%, vorzugsweise zu mehr als 75 Gew.-%, insbesondere zu mehr als 95 Gew.-% aus einem Aufheller der Formel I bestehen. Bevorzugt sind wässrige Aufhellerpräparationen die gegebenenfalls noch zusätzliche Stoffe enthalten können, wie sie beispielsweise oben bereits genannt sind.The invention therefore furthermore relates to a whitener preparation comprising brighteners which contain more than 50% by weight, preferably more than 60% by weight, preferably more than 75% by weight, in particular more than 95% by weight, of a brightener of the formula I exist. Preference is given to aqueous whitener preparations which may optionally contain additional substances, such as those already mentioned, for example, above.

Die erfindungsgemäßen Präparationen lassen sich vorzugsweise in dem erfindungsgemäßen Aufhellungsverfahren einsetzen.The preparations according to the invention can preferably be used in the lightening process according to the invention.

Besonders bevorzugt sind wässrige Aufhellerpräparationen, enthaltend wenigstens einen Aufheller der Formel (I) insbesondere (Ia).Particular preference is given to aqueous whitener preparations comprising at least one brightener of the formula (I), in particular (Ia).

Bevorzugt enthalten die erfindungsgemäßen, vorzugsweise wässrigen Aufhellerpräparation wenigstens 2,5 Gew.-% an Aufheller, besonders bevorzugt 5 bis 40 Gew.-%, insbesondere 10 bis 30 Gew.-%.The inventive, preferably aqueous brightener preparation preferably contains at least 2.5% by weight of brightener, particularly preferably 5 to 40% by weight, in particular 10 to 30% by weight.

Weiterhin können die erfindungsgemäßen Aufhellerpräparationen anorganische oder organische Salze, zusätzlich freies Alkanolamin, zusätzlich Alkanolaminsalze, Carrier sowie weitere Stoffe enthalten.Furthermore, the brightener preparations according to the invention may contain inorganic or organic salts, in addition free alkanolamine, in addition alkanolamine salts, carriers and other substances.

Ein weiterer Gegenstand der Erfindung sind Leimpressenflotten, enthaltend

  1. a) wenigstens einen Aufheller der Formel (I) insbesondere (Ia) oder eine erfindungsgemäße Aufhellerpräparation und
  2. b) wenigstens ein Oberflächenleimungsmittel, vorzugsweise Stärke.
Another object of the invention are size press liquors, containing
  1. a) at least one brightener of the formula (I) in particular (Ia) or a whitener preparation according to the invention and
  2. b) at least one surface sizing agent, preferably starch.

Weiterhin kann die Leimpressenflotte anorganische oder organische Salze, zusätzlich freies Alkanolamin, zusätzlich Alkanolaminsalze, Carrier sowie weitere Stoffe enthalten.Furthermore, the size press liquor may contain inorganic or organic salts, in addition free alkanolamine, in addition alkanolamine salts, carriers and other substances.

Bevorzugt enthält die Leimpressenflotte weniger als 2,5 Gew.-% Aufheller, insbesondere von 0,01 bis 2,0 Gew.-%. Der Gesamtaufheller besteht dabei vorzugsweise wie bereits für die Aufhellerpräparation beschrieben, zu mehr als 50 Gew.-%, bevorzugt mehr als 60 Gew.-%, vorzugsweise mehr als 75 Gew.-%, insbesondere zu mehr als 95 Gew.-% aus einem Aufheller der Formel I.Preferably, the size press liquor contains less than 2.5% by weight of brightener, in particular from 0.01 to 2.0% by weight. The total brightener preferably consists, as already described for the whitener preparation, of more than 50% by weight, preferably more than 60% by weight, preferably more than 75% by weight, in particular more than 95% by weight, of one Brightener of formula I.

Der Anteil an Oberflächenleimungsmittel, insbesondere Stärke, bezogen auf die Leimpressenflotte, beträgt vorzugsweise 2 bis 25 Gew.-%, insbesondere 5 bis 15 Gew.-%.The proportion of surface sizing agent, in particular starch, based on the size press liquor, is preferably from 2 to 25% by weight, in particular from 5 to 15% by weight.

Der Wasseranteil der Leimpressenflotte beträgt vorzugsweise wenigstens 70 Gew.-%.The water content of the size press liquor is preferably at least 70% by weight.

BeispieleExamples

Vergleichsbeispiel 1 (Aufheller aus GB 896533 , Beispiel 2, Zeilen 118-122 ; entspricht Aufheller der Formel I der vorliegenden Anmeldung, wobei die beiden anilingebundenen Sulfogruppen p-ständig sind, mit R1= R3 = H, R2 = CH3, M ausschließlich Na:
229 g eines membranfiltrierten wässrigen Konzentrats mit einem E1/1-Wert von 148 und einem pH-Wert von 8,5, das den Aufheller der Formel I mit R1= R3 = H, R2 = CH3 , M ausschließlich Na enthält, wobei die beiden anilingebundenen Sulfogruppen p-ständig sind, werden unter Rühren bei Raumtemperatur mit 71g demineralisiertem Wasser versetzt und mit ca. 10 %iger Natronlauge auf pH 9,0 gestellt. Man erhält eine wässrige Aufhellerpräparation mit einem E1/1-Wert von 113 in Form einer gelb-bräunlichen homogenen Flüssigkeit. Dies entspricht einem Gehalt an Aufheller von ca. 21% Comparative Example 1 (brightener GB 896533 Example 2, lines 118-122; corresponds to brightener of the formula I of the present application, wherein the two anilino bonded sulfo groups are p-type, with R 1 = R 3 = H, R 2 = CH 3 , M exclusively Na:
229 g of a membrane-filtered aqueous concentrate having an E1 / 1 value of 148 and a pH of 8.5, which contains the brightener of formula I with R 1 = R 3 = H, R 2 = CH 3 , M exclusively Na , wherein the two aniloxed sulfo groups are p-type, are added with stirring at room temperature with 71 g of demineralized water and adjusted to pH 9.0 with about 10% sodium hydroxide solution. This gives an aqueous brightener preparation with an E1 / 1 value of 113 in the form of a yellow-brownish homogeneous liquid. This corresponds to a brightener content of approx. 21%

Vergleichsbeispiele 2a, b (entspricht Vergleichsbeispiel 1 mit dem Unterschied, dass zusätzlich unterschiedliche Mengen freies Triethanolamin anwesend sind):
Je 229 g des membranfiltrierten wässrigen Konzentrats aus Vergleichsbeispiel 1 werden unter Rühren bei Raumtemperatur mit a) 15,0 b) 30,0 sowie a) 56 g b) 41 g demineralisiertem Wasser versetzt und anschließend 10 min verrührt. Man erhält triethanolaminhaltige Aufhellerpräparationen mit einem E1/1-Wert von 113 in Form von gelb-bräunlichen homogenen Flüssigkeiten. Dies entspricht einem Gehalt an Aufheller von ca. 21 % und einem Gehalt an Triethanolamin von a) 5 % b) 10 %. Comparative Examples 2a, b (corresponds to Comparative Example 1 with the difference that in addition different amounts of free triethanolamine are present):
229 g of the membrane-filtered aqueous concentrate from Comparative Example 1 are mixed with stirring at room temperature with a) 15.0 b) 30.0 and a) 56 gb) 41 g demineralized water and then stirred for 10 min. Triethanolamine-containing brightener preparations having an E1 / 1 value of 113 in the form of yellow-brownish homogeneous liquids are obtained. This corresponds to a content of brightener of about 21% and a content of triethanolamine of a) 5% b) 10%.

Vergleichsbeispiel 3 entspricht Beispiel 2 aus WO 00 46336 . Comparative Example 3 corresponds to Example 2 WO 00 46336 ,

Beispiele 1a, 1b:Examples 1a, 1b:

1200 g des membranfiltrierten wässrigen Konzentrats aus Vergleichsbeispiel 1 werden im Vakuum eingedampft. Das erhaltene Kristallisat hat nach Homogenisierung einen E1/1-Wert von 472.1200 g of the membrane-filtered aqueous concentrate from Comparative Example 1 are evaporated in vacuo. The crystallizate obtained has an E1 / 1 value of 472 after homogenization.

Jeweils eine Mischung aus a) 140g demineralisiertem Wasser und 15 g Triethanolamin, b) 90 g demineralisiertem Wasser und 30 g Triethanolamin, wird durch Zusatz von a) ca. 36 g b) ca. 73 g, 10 %iger Salzsäure auf pH 6 eingestellt. Anschließend trägt man bei ca. 60°C unter Rühren jeweils 71,8 g des oben beschriebenen Kristallisats ein. Man rührt bis zur Auflösung des Kristallisats nach, bestimmt den jeweiligen E1/1-Wert und verdünnt anschließend bei Raumtemperatur mit demineralisiertem Wasser jeweils auf den gleichen rechnerischen E1/1-Wert von 113.In each case a mixture of a) 140 g demineralized water and 15 g of triethanolamine, b) 90 g of demineralized water and 30 g of triethanolamine is adjusted to pH 6 by addition of a) about 36 g b) about 73 g, 10% hydrochloric acid. Subsequently, 71.8 g of the above-described crystals are introduced at about 60 ° C. with stirring. The mixture is stirred until the crystals have dissolved, the respective E1 / 1 value is determined, and the mixture is then diluted at room temperature with demineralized water to the same calculated E1 / 1 value of 113.

Man erhält jeweils ca. 300 g einer Aufhellereinstellung, welche die gleiche Molzahl Aufheller wie die Vergleichsbeispiele 1 bzw. 2a, 2b und a) ca. 5 Gew.-% (entspricht einem M mit ca. 50 mol-% Triethanolammonium Rest Na+) b) ca. 10 Gew.-% (entspricht einem M mit ca. 100 mol-% Triethanolammonium) Triethanolammoniumionen enthält.In each case about 300 g of a brightener setting is obtained which contains the same number of moles of brightener as comparative examples 1 or 2a, 2b and a) about 5% by weight (corresponds to an M with about 50 mol%). Triethanolammonium residue Na + ) b) about 10 wt .-% (corresponding to a M with about 100 mol% triethanolammonium) triethanolammonium ions.

Beispiel 2Example 2

Man verfährt bis einschließlich des Eintragens des Kristallisats wie für Beispiel 1b beschrieben. Nach Auflösen des Kristallisats trägt man 15g Polyethylenglykol 1500 ein, verrührt bis zu dessen Auflösung und bestimmt den E1/1-Wert. Anschließend verdünnt man bei Raumtemperatur mit demineralisiertem Wasser auf einen rechnerischen E1/1-Wert von 113.The procedure is up to and including the introduction of the crystals as described for Example 1b. After dissolution of the crystals, 15 g of polyethylene glycol 1500 are added, the mixture is stirred until dissolved and determines the E1 / 1 value. The mixture is then diluted at room temperature with demineralized water to a calculated E1 / 1 value of 113.

Man erhält ca. 300 g einer Aufhellerformulierung, welche die gleiche Molzahl Aufheller und Triethanolammoniumionen wie im Beispiel 1b und außerdem 5 % Polyethylenglykol 1500 als Carrier enthält.This gives about 300 g of a brightener formulation which contains the same number of moles of brighteners and triethanolammonium ions as in Example 1b and also 5% polyethylene glycol 1500 as a carrier.

Beispiel 3 entspricht Beispiel 2 aus WO 0046336 mit dem Unterschied, dass die Herstellung der Stufe 2 nicht mit dem dort beschriebenen Gemisch aus Diethanolamin und Diisopropanolamin erfolgt, sondern mit einer diesem Gemisch äquimolaren Menge Diisopropanolamin. (M = ca. 50 mol-% Triethanolammonium). Example 3 corresponds to Example 2 WO 0046336 with the difference that the preparation of stage 2 is not carried out with the mixture of diethanolamine and diisopropanolamine described therein, but with an equimolar amount of this mixture diisopropanolamine. (M = about 50 mol% triethanolammonium).

Beispiel 4 (entspricht Beispiel 2 aus WO 0046336 mit dem Unterschied, dass die Herstellung der Stufe 2 nicht mit dem dort beschriebenen Gemisch aus Diethanolamin und Diisopropanolamin erfolgt, sondern mit einer dem Gemisch äquimolaren Menge Diisopropanolamin, und zusätzlich überschüssiges Triethanolamin durch Einstellung von pH 6 mit Salzsäure neutralisiert worden ist. (M = ca. 100 mol-% Triethanolammonium) Example 4 (corresponds to Example 2 from WO 0046336 with the difference that the preparation of stage 2 is not carried out with the mixture of diethanolamine and diisopropanolamine described therein, but with a mixture equimolar amount of diisopropanolamine, and additionally excess triethanolamine has been neutralized by adjustment of pH 6 with hydrochloric acid. (M = approx. 100 mol% triethanolammonium)

Anwendungsbeispiele:Application examples: Allgemeine Beschreibung der Aufhellerprüfung / Leimpressenanwendung (gilt für alle Anwendungsbeispiele):General description of the brightener test / glue press application (applies to all application examples): 1. Gerätschaften und Hilfsmittel1. Equipment and aids

Stärkelösung 10 %ig:Starch solution 10%:
Perfectamyl A 4692 der Fa. Avebe (oxidativ abgebaute Kartoffelstärke)Perfectamyl A 4692 from Avebe (oxidatively degraded potato starch)
Prüfpapier:test paper:
Schleicher und Schuell MicroSience 3014, Zuschnitte 240X250 mm, Ref. Nr. 10344684Schleicher and Schuell MicroSience 3014, blanks 240X250 mm, Ref. No. 10344684
Laborleimpresse, Foulard:Laboratory size press, padder:
Fa. Mathis, Typ HF 52499, Zürich Oberhasli, SchweizFa. Mathis, type HF 52499, Zurich Oberhasli, Switzerland
2. Herstellung der Stärkelösung2. Preparation of the starch solution

Ca. 120 g Perfectamyl A 4692 werden mit ca. 200 ml kaltem Wasser klumpenfrei angeschlämmt. Anschl. gibt man unter Rühren ca. 700 ml heißes Wasser zur Vorlage und rührt so lange nach, bis eine klare Stärkelösung entsteht. Nach dem Abkühlen auf Raumtemperatur erfolgt eine Konzentrations-Kontrolle per Handrefraktometer. Evtl. durch zusätzliche Wasserzugabe auf 10 % einstellen.Approximately 120 g of Perfectamyl A 4692 are slurried with approx. 200 ml of cold water without lumps. Conn. About 700 ml of hot water are added with stirring to the initial charge and stirring is continued until a clear starch solution is formed. After cooling to room temperature, a concentration control by hand refractometer. Possibly. set by adding additional water to 10%.

3. Ausrüstung der Papiere3. Equipment of the papers

Zunächst wird in einer separaten Bestimmung das Flottenaufnahmeverhältnis des Prüfpapiers bestimmt.First, the liquor pick-up ratio of the test paper is determined in a separate determination.

Dazu verdünnt man 50,0 g der 10 %igen Stärkelösung mit Wasser auf 100,0 g, durchmischt gründlich, überführt die Lösung in die Laborleimpresse und führt ein abgewogenes Blatt (Gewicht 1 = m1 g) des o.b. Prüfpapiers durch die Leimpresse. Dabei sollte die Leimpressengeschwindigkeit bei ca. 4m/min und der Walzenanpressdruck bei ca. 3 bar liegen. Unmittelbar nach dem Durchgang durch die Leimpresse wird das nun feuchte Blatt erneut abgewogen (Gewicht 2 = m2 g). Die Differenz m2-m1 ergibt die aufgenommene Flottenmenge; bezogen auf das Gewicht des eingesetzten Blattes erhält man das Flottenaufnahmeverhältnis = (m2-m1) / m1.For this purpose, 50.0 g of the 10% strength starch solution are diluted to 100.0 g with water, mixed thoroughly, the solution is transferred to the laboratory size press and a weighed sheet (weight 1 = m 1 g) of the test paper is passed through the size press. The glue press speed should be around 4m / min and the roller contact pressure should be around 3 bar. Immediately after passing through the size press, the now moist sheet is weighed again (weight 2 = m 2 g). The difference m 2 -m 1 gives the amount of liquor absorbed; Based on the weight of the sheet used, the liquor pickup ratio = (m 2 -m 1 ) / m 1 is obtained .

Anschließend erfolgt die Prüfung der einzelnen Aufhellerpräparationen dadurch, dass man die betreffende Präparation als Konzentrationsreihe zu jeweils weiteren 50,0 g der selben Stärkelösung gibt, mit Wasser auf 100,0 g verdünnt, gründlich durchmischt, und die erhaltenen, aufhellerhaltigen Leimpressenflotten wie oben beschrieben mit Hilfe der Laborleimpresse auf weitere Prüfpapierblätter aufbringt. Zum Schluss werden die so ausgerüsteten Papiere im Trockenzylinder bei ca. 100°C getrocknet.The test of the individual brightener preparations is then carried out by diluting the respective preparation as a concentration series to a further 50.0 g of the same starch solution, diluted to 100.0 g with water, thoroughly mixed, and the resulting brightener-containing size press liquors as described above Help the Apply the laboratory size press to further test paper sheets. Finally, the papers so finished in the drying cylinder at about 100 ° C dried.

Die zu vergleichenden Aufhellerpräparationen werden jeweils in einer Konzentrationsreihe von 0,5 Gew.% / 1,0 Gew.% / 1,5 Gew.% / 2,0 Gew.% eingesetzt, bezogen auf das Gewicht des verwendeten Prüfpapiers. Der Zusammenhang der Konzentrationen der Aufhellerpräparationen in Bezug auf das Gewicht des Prüfpapiers zu den entsprechenden Konzentrationen in Bezug auf die Leimpressenflottenmenge wird über das vorher separat ermittelte Flottenaufnahmeverhältnis hergestellt. So müssen beispielsweise bei einem Flottenaufnahmeverhältnis von 0,9 im oben beschriebenen Versuch ohne Aufheller die Werte der obigen Konzentrationsreihe noch durch den Divisor 0,9 geteilt werden, um ihre Werte in Bezug auf die Leimpressenflottenmenge zu erhalten.The brightener preparations to be compared are each used in a concentration range of 0.5% by weight / 1.0% by weight / 1.5% by weight / 2.0% by weight, based on the weight of the test paper used. The relationship of the concentrations of brightener preparations in relation to the weight of the test paper to the corresponding concentrations in relation to the size of liquor press liquor is established using the previously separately determined liquor pick-up ratio. For example, at a liquor pick-up ratio of 0.9 in the experiment without brightener described above, the values of the above concentration series must still be divided by the divisor 0.9 to obtain their values in terms of size press liquor quantity.

So ergibt sich beispielsweise bei Einsatz von 0,5 Gew.-% Aufhellerpräparation bezogen auf Prüfpapier, bei einen Flottenaufnahmeverhältnis von 0,9 eine Menge von 0,55 Gew.-% Aufhellerpräparation, bezogen auf die Menge an Leimpressenflotte.Thus, for example, when using 0.5% by weight of whitener preparation based on test paper, at a liquor pick-up ratio of 0.9, an amount of 0.55% by weight of whitener preparation, based on the amount of size press liquor, results.

Des Weiteren bezieht sich obige Konzentrationsreihe auf Präparationen mit einem E1/1-Wert von 113. Wenn Präparationen mit einem abweichenden E1/1-Wert zu prüfen sind, muss zusätzlich deren E1/1-Wert-Abweichung vom Richtwert 113 dadurch kompensiert werden, dass man die Konzentrationsreihe im umgekehrt proportionalen Verhältnis abändert (Beispiel: bei einem E1/1-Wert von 105 sind 0,538 Gew.-% Präparation äquivalent zu 0,5 % Präparation vom E1/1-Wert 113 usw.).Furthermore, the above concentration series refers to preparations with an E1 / 1 value of 113. If preparations with a deviating E1 / 1 value are to be tested, their E1 / 1 value deviation from the guide value 113 must additionally be compensated for by: changing the concentration series in inverse proportion (for example, at an E1 / 1 value of 105, 0.538 wt% preparation is equivalent to 0.5% preparation of E1 / 1 value 113, etc.).

Anwendungsbeispiel 1:Application Example 1

Tabelle 1: Aufhellerpräparation aus Vergleichsbeispiel 1 Table 1: Brightener preparation from Comparative Example 1 Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 138,08138.08 95,9595.95 2,962.96 -10,83-10.83 1,001.00 144,11144.11 96,1296.12 3,043.04 -12,13-12.13 1,501.50 145,80145.80 96,2896.28 2,872.87 -12,44-12.44 2,002.00 146,46146.46 96,3296.32 2,692.69 -12,57-12.57 Tabelle 2: Aufhellerpräparation aus Vergleichsbeispiel 2a Table 2: Brightener preparation from Comparative Example 2a Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 135,50135.50 95,9295.92 2,832.83 -10,26-10.26 1,001.00 142,76142.76 96,1296.12 2,982.98 -11,82-11.82 1,501.50 144,48144.48 96,2896.28 2,832.83 -12,14-12.14 2,002.00 145,87145.87 96,3396.33 2,692.69 -12,43-12.43 Tabelle 3: Aufhellerpräparation aus Vergleichsbeispiel 2b Table 3: Brightener preparation from Comparative Example 2b Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 135,40135.40 95,8295.82 2,842.84 -10,28-10.28 1,001.00 142,37142.37 96,1196.11 2,972.97 -11,73-11.73 1,501.50 144,24144.24 96,2296.22 2,872.87 -12,11-12.11 2,002.00 145,10145.10 96,3196.31 2,692.69 -12,26-12.26

Man erkennt, dass die Anwesenheit von Triethanolamin in Form der freien Base keine Verbesserung der Aufhellung bewirkt.It can be seen that the presence of triethanolamine in the form of the free base does not improve the lightening.

Anwendungsbeispiel 2:Application Example 2:

Tabelle 1: Aufhellerpräparation aus Vergleichsbeispiel 1 Table 1: Brightener preparation from Comparative Example 1 Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 138,08138.08 95,9595.95 2,962.96 -10,83-10.83 1,001.00 144,11144.11 96,1296.12 3,043.04 -12,13-12.13 1,501.50 145,80145.80 96,2896.28 2,872.87 -12,44-12.44 2,002.00 146,46146.46 96,3296.32 2,692.69 -12,57-12.57 Tabelle 4: Aufhellerpräparation aus Beispiel la Table 4: Brightener preparation from Example la Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 138,12138.12 96,0596.05 2,952.95 -10,80-10.80 1,001.00 145,36145.36 96,3196.31 3,093.09 -12,33-12.33 1,501.50 146,98146.98 96,3496.34 2,962.96 -12,68-12.68 2,002.00 148,48148.48 96,5796.57 2,792.79 -12,92-12.92 Tabelle 5: Aufhellerpräparation aus Beispiel 1b Table 5: Brightener preparation from Example 1b Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 138,33138.33 95,9695.96 2,982.98 -10,88-10.88 1,001.00 145,58145.58 96,2696.26 3,123.12 -12,40-12.40 1,501.50 147,59147.59 96,2596.25 3,033.03 -12,86-12.86 2,002.00 148,26148.26 96,4696.46 2,802.80 -12,92-12.92

Man erkennt, dass die Anwesenheit von Triethanolammonium eine deutliche Verbesserung der Aufhellung bewirkt.It can be seen that the presence of triethanolammonium causes a significant improvement in lightening.

Anwendungsbeispiel 3:Application Example 3

Tabelle 5: Aufhellerpräparation aus Beispiel 1b Table 5: Brightener preparation from Example 1b Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 138,33138.33 95,9695.96 2,982.98 -10,88-10.88 1,001.00 145,58145.58 96,2696.26 3,123.12 -12,40-12.40 1,501.50 147,59147.59 96,2596.25 3,033.03 -12,86-12.86 2,002.00 148,26148.26 96,4696.46 2,802.80 -12,92-12.92 Tabelle 6: Aufhellerpräparation aus Beispiel 2 Table 6 : Brightener preparation from Example 2 Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 138,69138.69 95,9695.96 3,023.02 -10,97-10.97 1,001.00 145,83145.83 96,2396.23 3,163.16 -12,47-12.47 1,501.50 148,12148.12 96,4196.41 3,083.08 -12,92-12.92 2,002.00 148,74148.74 96,3996,39 2,862.86 -13,06-13.06

Man erkennt, dass der durch Triethanolammonium verbesserte Aufhelleffekt durch Zusatz von Polyglykol weiter gesteigert werden kann.It can be seen that the lightening effect improved by triethanolammonium can be further increased by adding polyglycol.

Anwendungsbeispiel 4: (alle Einsatzmengen sind bezogen auf einen E1/1-Wert von 113) Application Example 4: (all amounts used are based on an E 1/1 value of 113)

Tabelle 7: Aufhellerpräparation aus Vergleichsbeispiel 3 Table 7: Brightener preparation from Comparative Example 3 Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 137,64137.64 95,9595.95 2,892.89 -10,73-10.73 1,001.00 144,62144.62 96,2996.29 2,952.95 -12,16-12.16 1,501.50 146,04146.04 96,3796.37 2,782.78 -12,45-12.45 2,002.00 147,17147.17 96,596.5 2,562.56 -12,65-12.65 Tabelle 8: Aufhellerpräparation aus Beispiel 3 Table 8: Brightener preparation from Example 3 Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 137,8137.8 95,9395.93 2,942.94 -10,78-10.78 1,001.00 145,6145.6 96,2196.21 3,113.11 -12,43-12.43 1,501.50 147,6147.6 96,3296.32 2,962.96 -12,82-12.82 2,002.00 148,9148.9 96,4396.43 2,792.79 -13,08-13.08 Tabelle 9: Aufhellerpräparation aus Beispiel 4 Table 9: Brightener preparation from Example 4 Menge (%)Amount (%) CIE-WeißgradCIE whiteness L*L * a*a * b*b * 0,500.50 138,9138.9 95,9495.94 2,992.99 -11,02-11.02 1,001.00 146,3146.3 96,2996.29 3,113.11 -12,55-12.55 1,501.50 148,4148.4 96,3996,39 2,972.97 -12,98-12.98 2,002.00 149,6149.6 96,5396.53 2,802.80 -13,19-13.19

Man erkennt einerseits, dass bei extinktionsgleichem Einsatz eine Aufhellerpräparation, die den Aufheller der Formel Ia enthält (mit Diisopropanolaminresten an den Triazinringen, hergestellt analog Beispiel 2 der WO 0046336 ) eine bessere Aufhellwirkung zeigt als die Aufhellerpräparation des Beispiels 2 der WO 0046336 , die ein Aufhellergemisch enthält, das zusätzlich einen mit Diethanolaminresten an den Triazinringen substituierten Aufheller und einen unsymmetrisch mit Diisopropanolaminresten und Diethanolaminresten an den Triazinringen substituierten Aufheller enthält, und andererseits, dass sich der Aufhelleffekt zusätzlich steigern lässt, wenn das freie Triethanolamin, das in der analog Beispiel 2 der WO 0046336 hergestellten Aufhellerpräparation, die den Aufheller der Formel Ia enthält , enthalten ist, durch Zusatz von Säure neutralisiert wird.On the one hand, it can be seen that in the case of extinction-identical use, a brightener preparation which contains the brightener of the formula Ia (with diisopropanolamine radicals on the triazine rings, prepared analogously to Example 2 of US Pat WO 0046336 ) shows a better whitening effect than the whitener preparation of Example 2 of WO 0046336 which contains a whitener mixture which additionally contains a brightener substituted with diethanolamine radicals on the triazine rings and a brightener unsymmetrically substituted with diisopropanolamine radicals and diethanolamine radicals on the triazine rings, and on the other hand that the whitening effect can be additionally increased if the free triethanolamine, which in the analogous Example 2 of WO 0046336 prepared whitener preparation containing the brightener of formula Ia, is neutralized by the addition of acid.

Claims (6)

  1. A process for whitening paper in the size press, characterized in that a size press liquor containing a whitener of the formula I
    Figure imgb0017
     in which
    X, independently of one another, denote a radical of the formula
    Figure imgb0018
     or
    Figure imgb0019
     and
    R1 represents C1-C6-alkyl and
    R2 represents H, or
    R1 represents H and
    R2 represents C1-C6-alkyl, and, independently thereof,
    R3 represents H, methyl, ethyl, CH2CH2OH or CH2CH2OCH3,
    R1' represents C1-C6-alkyl and
    R2' represents H, or
    R1' represents H and
    R2' represents C1-C6-alkyl, and, independently thereof,
    R3' represents H, methyl, ethyl, CH2CH2OH or CH2CH2OCH3 and
    R4 represents C1-C4-alkyl and
    M denotes H, one equivalent of an inorganic cation, in particular Li, Na, K, Ca, Mg or ammonium, or a substituted ammonium of the formula II
    Figure imgb0020
     in which
    R5 to R7, independently of one another, denote hydrogen, a C1-C4-alkyl radical or an optionally further substituted C2-C4-hydroxyalkyl radical, and R8 denotes an optionally further substituted C2-C4-hydroxyalkyl radical,
    at least 10 mol% of all cations M corresponding to the formula II, is used in the sizing step.
  2. The process according to claim 1, characterized in that the size press liquor contains whiteners which consist of more than 50% by weight, preferably more than 60% by weight, preferably more than 75% by weight, in particular more than 95% by weight, of a whitener of the formula I.
  3. The process according to at least one of claims 1 or 2, characterized in that
    R1= H,
    R2= linear C1-C6-alkyl and
    R3= H;
    furthermore to the formula (I) in which
    R1'= H,
    R2'= linear C1-C6-alkyl and
    R3'= H and R4 = H or methyl,
    in which M in each case denotes a mixture of cations containing alkanolammonium ions of the formula II, in which the radicals R5 represent H; R6 represent H or C2-C4-hydroxyalkyl and R7 and R8 represent C2-C4-hydroxyalkyl, and Na or K ions.
  4. The process according to at least one of claims 1 to 4, characterized in that a whitener of the formula Ia is used
    Figure imgb0021
     in which
    M denotes a mixture containing the cation of the formula II
    Figure imgb0022
     and Na+ or K+.
  5. A whitener preparation containing whiteners which consist of more than 50% by weight, preferably more than 60% by weight, preferably more than 75% by weight, in particular more than 95% by weight, of a whitener of the formula I
    Figure imgb0023
     in which
    X, independently of one another, denote a radical of the formula
    Figure imgb0024
     or
    Figure imgb0025
     and
    R1 represents C1-C6-alkyl and
    R2 represents H, or
    R1 represents H and
    R2 represents C1-C6-alkyl, and, independently thereof,
    R3 represents H, methyl, ethyl, CH2CH2OH or CH2CH2OCH3,
    R1' represents C1-C6-alkyl and
    R2' represents H, or
    R1' represents H and
    R2' represents C1-C6-alkyl, and, independently thereof,
    R3' represents H, methyl, ethyl, CH2CH2OH or CH2CH2OCH3 and
    R4 represents C1-C4-alkyl and
    M denotes H, one equivalent of an inorganic cation, in particular Li, Na, K, Ca, Mg or ammonium, or a substituted ammonium of the formula II
    Figure imgb0026
    in which
    R5 to R7, independently of one another, denote hydrogen, a C1-C4-alkyl radical or an optionally further substituted C2-C4-hydroxyalkyl radical, and R8 denotes an optionally further substituted C2-C4-hydroxyalkyl radical,
    at least 10 mol% of all cations M corresponding to the formula II.
  6. A size press liquor containing
    a) at least one whitener of the formula (I), in particular of the formula (Ia), or a whitener preparation according to claim 5, and
    b) at least one surface size, in particular starch.
EP05016038A 2004-08-06 2005-07-23 Alkanol-ammonia containing triazinylflavonat brightener Active EP1624105B1 (en)

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WO2005049682A1 (en) * 2003-11-18 2005-06-02 Ciba Specialty Chemicals Holding Inc. Fluorescent whiteninig pigments
PT2135997E (en) * 2008-06-11 2011-03-10 Blankophor Gmbh & Co Kg Composition and process for whitening paper
PT2192230E (en) † 2008-11-27 2012-10-09 Clariant Finance Bvi Ltd Optical brightening compositions for high quality inkjet printing
CN101922124A (en) * 2010-07-21 2010-12-22 东营市联成化工有限责任公司 Formula and production process of liquid brightener
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GB896533A (en) * 1958-11-05 1962-05-16 Sandoz Ltd New stilbene derivatives and process for their manufacture
ES366464A1 (en) * 1968-04-26 1971-03-16 Geigy Ag J R Asymmetrically substituted bistriazinylamino stilbene compounds
CH583212A5 (en) * 1973-07-02 1976-12-31 Sandoz Ag
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