Fluorescent whitening agents and mixtures thereof

A composition comprising

• at least one compound of formula (1)
• wherein n is 0, 1, or 2;
• and wherein R1, R2, R3, R4, R5, R6, R7 and Rs independently of each other are H, linear or branched C1-C4 alkyl, linear or branched C2-C4 hydroxyalkyl, linear or branched C1-C4 alkoxyalkyl, linear or branched C2-C4 cyanoalkyl, phenyl substituted with 803″, —(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM, —(CH2)k—COOR9, —(CH2)k—CONH2, —(CH2)k—OR9, wherein i is an integer from 1 to 3, k is an integer from 1 to 4, and R9 is linear or branched C1-C3 alkyl;
• or R1 and R2, or R3 and R4, or Rs and R6, or R7 and R8 independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and wherein M represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, Mg2+, ammonium, C1-C4 tetraalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p+with Rio being C1-C4 alkyl and R11 being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2, and o≠p, alkyl is linear or branched;
• and mixtures of said cations or of formula (1a):
• and wherein Rx and Ry independently of each other are H, linear or branched C1-C4 alkyl, linear or branched C2-C4 hydroxyalkyl, linear or branched C1-C4 alkoxyalkyl, linear or branched C2-C4 cyanoalkyl, or —(CH2)i—SO3—, —(CH2)i-phenyl, —(CH2)k—COOM1—(CH2—1k-COOR9, —(CH2)k—CONH2, —(CR2)k—OR9, wherein i is an integer from 1 to 3 and wherein k is an integer from 1 to 4, R9 is linear or branched C1-C3 alkyl, or Rx and Ry independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• or a mixture of said amines.
• and
• at least one further fluorescent whitening agent (FWA) selected from the compound of formula (4) and the compound of formula (9):
• wherein n=0, 1, or 2, Rx and Ry independently of each other are H, C1-C4 alkyl, C2−C4 hydroxyalkyl, C1-C4 alkoxyalkyl, C2-C4 cyanoalkyl, wherein the alkyl residue is linear or branched, or -(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM1, —(CH2)k—COOR9, —(CH2)k—CONH2, —(CH2)k—OR9, wherein i is an integer from 1 to 3 and wherein k is an integer from 1 to 4, R9 is linear or branched C1-C3 alkyl, or Rx and Ry independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and
• wherein M1 represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, ammonium, C1-C4 tetraalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p+with R10 being C1-C4 alkyl and Ru being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2 and o≠p, and alkyl is linear or branched;
• and mixtures of said cations.

A coating color comprising

• at least one comound of formula (1):
• wherein n is 0 1 or 2and wherein R1, R2, R3, R4, R5, R6, R7 and R8 independentlyof each other are H, linear or branched C1-C4 alkyl, linear or branched C2-C4 hydroxyalkyl, linear or branched C1-C4 alkoxyalkyl, linear or branched C2-C4 cyanoalkyl, phenyl substituted with SO3−, —(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM, —(CH2)k—COOR9, —(CH2)k—CONH2, —(CH2)k—OR9, wherein i is an integer from 1 to 3, k is an integer from 1 to 4, and R9 is linear or branched C1-C3 alkyl;
• or R1 and R2, or R3 and R4, or R5 and R6, or R7 and R8 independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and wherein M represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, Mg2+, ammonium, C1-C4 tetraalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p+ with R10 being C1-C4 alkyl and R11 being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2, and o≠p, alkyl is linear or branched;
• and mixtures of said cations,
• or a composition comprising the compound of foitaula (1) and at least one further fluorescent whitening agent (FWA) selected from the compound of formula (4) and the compound of formula (9):
• wherein n=0, 1, or 2, Rx and Ry independently of each other are H, C1-C4 alkyl, C2-C4 hydroxyalkyl, C1-C4 alkoxyalkyl, C2-C4 cyanoalkyl, wherein the alkyl residue is linear or branched, or —(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM1, —(CH2)k—COOR9, —(CH2)k—CONH2, —(CH2)k—ORS, wherein i is an integer from 1 to 3 and wherein k is an integer from 1 to 4, R9 is linear or branched C1-C3 alkyl, or Rx and Ry independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and
• wherein M1 represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, ammonium, C1-C4 tetraalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p±with R10 being Ci-C4 alkyl and R11 being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2 and o≠p, and alkyl is linear or branched;
• and mixtures of said cations,
• at least one white pigment, and
• at least one binder.

A size press or film press liquor comprising at least one compound of formula (1):

• wherein n is 0, 1, or 2;
• and wherein R1, R2, R3, R4, R5, R, R7 and R8 independently of each other are H, linear or branched C1-C4 alkyl, linear or branched C2-C4 hydroxyalkyl, linear or branched C1-C4 alkoxyalkyl, linear or branched C2-C4 cyanoalkyl, phenyl substituted with SO3−, —(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM, —(CH2)k—COOR9, —(CH2)k—CONH7, —(CH1)k—OR9, wherein i is an integer from 1 to 3, k is an integer from 1 to 4, and R9 is linear or branched C1-C3 alkyl;
• or R1 and R2, or R3 and R4, or R5 and R6, or R7 and 128 independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and wherein M represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, Mg2+, ammonium, C1-C4 tetraalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p+ with R10 being C1-C4 alkyl and R11 being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2, and o≠p, alkyl is linear or branched;
• and mixtures of said cations,
• or a composition comprising the compound of formula (1) and at least one further fluorescent whitening agent (FWA) selected from the compound of formula (4) and the compound of formula (9):
• wherein n=0, 1, or 2, Rx and Ry independently of each other are H, C1-C4 alkyl, C2-C4 hydroxyalkyl, C1-C4 alkoxyalkyl, C2-C4 cyanoalkyl, wherein the alkyl residue is linear or branched or —(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM1, —(CH2)k—COOR9, —(CH2)k—CONH2, —(CH2)k—OR9, wherein i is an integer from 1 to 3 and wherein k is an integer from 1 to 4, R9 is linear or branched C1-C3 alkyl, or Rx and Ry independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and
• wherein Mi represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, ammonium, C1-C4 tetraalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p+ with R10 being C1-C4 alkyl and Ru being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2 and o≠p, and alkyl is linear or branched;
• and mixtures of said cations,
• and
• at least one sizing agent.

A method for optically whitening cellulose-based materials comprising treating the cellulose-based material with at least one compound of formula (1):

• wherein n is 0, 1, or 2;
• and wherein R1, R2, R3, R4, R5, R6, R7 and R8 independently of each other are H, linear or branched C1-C4 alkyl, linear or branched C2-C4 hydroxyalkyl, linear or branched C1-C4 alkoxyalkyl, linear or branched C2-C4 cyanoalkyl, phenyl substituted with SO3−, —(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM, —(CH2)k—COOR9, —(CH2)k—CONH2, —(CH2)k—OR9, wherein i is an integer from 1 to 3, k is an integer from 1 to 4, and R9 is linear or branched C1-C3 alkyl;
• or R1 and R2, or R3 and R4, or R5 and R6, or R7 and R8 independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and wherein M represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, Mg2+, ammonium, C1-C4 tetraalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p+ with R10 being C1-C4 alkyl and R11 being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2, and o≠p, alkyl is linear or branched;
• and mixtures of said cations
• or a composition comprising the compound of formula (1) and at least one further fluorescent whitening agent (FWA) selected from the compound of formula (4) and the compound of formula (9):
• wherein n=0, 1, or 2, Rx and Ry independently of each other are H, C1-C4 alkyl, C2-C4 hydroxyalkyl, C1-C4 alkoxyalkyl, C2-C4 cyanoalkyl, wherein the alkyl residue is linear or branched, or —(CH2)i—SO3−, —(CH2)i-phenyl, —(CH2)k—COOM1, —(CH2)k—COOR9, —(CH2)k—CONH2, —(CH2)k—OR9, wherein i is an integer from 1 to 3 and wherein k is an integer from 1 to 4, R9 is linear or branched C1-C3 alkyl, or Rx and Ry independently of each other together with the nitrogen atom form a morpholine, a piperidine or a pyrrolidine ring;
• and
• wherein M1 represents the corresponding cationic charge equivalent selected from the cations H+, alkali metal cation, Ca2+, ammonium, C1-C4 tehaalkyl ammonium, ammonium which is mono-, di-, tri- or tetra-substituted by C2-C3 hydroxyalkyl radicals, and NH(R10)o(R11)p+ with R10 being C1-C4 alkyl and R11 being C2-C3 hydroxyalkyl, wherein both o and p are an integer of 1 or 2 and o≠p, and alkyl is linear or branched;
• and mixtures of said cations.