Water-soluble light-projecting materials.
Abstract
Compounds of formula I. U (̵SOL) n '(I), wherein n 'is a number from 1 to 4, U is a radical of a UV absorber of the hydroxyphenyl-benzotriazole, cinnamic acid or triazine type and SOL is a group of the formula lamean. The symbols in the formula la have the meaning given in claim 1. The compounds, some of which are new, are suitable as light stabilizers, in particular for recording materials and inks for inkjet printing.

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Projected expiry passed 15 December 2009, 16.8 years ago.
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38 claims: 38 independent, 0 dependent
- 1Recording material containing at least one compound of the formula I as stabilizerwhere n is a number from 1 to 4,U is a residue of a UV absorber of the type hydroxyphenyl benzotriazole, cinnamic acid or hydroxyphenyl triazine,SOL, the same or different, is a group of the formula lameans whatg represents 0 or 1,A a direct bond, C1-C6Alkylene or alkylidene, or a group of the formula Ibmeans, where p is a number from 1 to 6,Y is a direct bond or one of the following groups:-CO-, -COO-, -OOC-, -CO-N (R ') -, - (R') N-CO-, -S02-N (R ') -, - (R') N-S02-, B represents a direct bond or a C optionally substituted with OH2-Cs alkylene or alkylidene, which may be replaced by one -O- or by one or two - (R ')2- is interrupted, or a group of formula Icis, or the grouprepresents a saturated or unsaturated 1 to 3-nucleus N-heterocycle which contains 1-4 N atoms as ring members, of which at least one is quaternized, under the conditions thata) in the case of g = 1, A, Y and B do not simultaneously mean a direct bond;b) in the case of g = 1 and A = direct bond, Y is -CO- or a direct bond;andc) in the case of B = a direct bond, also Y is a direct bond;R is hydrogen, C1-C4-Alkyl or C2-C3-Hydroxyalkyl, B ° - (CH2)̵m or one of the following groups means:where m and r are independently 2 or 3,R33 a meaning of R3 has or for a group of formulas Id and lewhere g, p, B, Y, A and U have the meaning given above,R1, R2 and R3 independently of one another hydrogen, C1-C8-Alkyl, C substituted by a -COOR or 1 to 3 OH1-C8-Alkyl, interrupted by one or more -O- C2-Cs-Hydroxyalkyl, substituted with an OH - (C1-C8) Alkylene-COO⊖, - (C1-C8) Alkylidene COO⊖, - (C2-C8) Alkylene SO or - (C2-C8) Alkylidene- SO⊖3, C3-C5Alkenyl, C5-C7-Cycloalkyl, phenyl, tolyl, benzyl or glycidyl, or R1 together with R2 and optionally with R3 as well as together with the Atom to which they are attached form an N-heterocycle which may contain 1-3 N atoms or a 0 atom as ring members,R "is hydrogen or C1-C4-Alkyl is, andX8, if not in R1, R2, R3 or R33 present, means a colorless organic or inorganic anion. 1. Aufzeichnungsmaterial enthaltend als Stabilisator mindestens eine Verbindung der Formel I U-(SOL)n (I), worin n eine Zahl von 1 bis 4 bedeutet,U ein Rest eines UV-Absorbers vom Typ Hydroxyphenyl-benztriazol, Zimtsäure oder Hydroxyphenyl-Triazin ist,SOL, gleich oder verschieden, eine Gruppe der Formel la bedeutet, woring für 0 oder 1 steht,A eine direkte Bindung, C1-C6-Alkylen oder -Alkyliden, oder eine Gruppe der Formel Ib bedeutet, wobei p eine Zahl von 1 bis 6 ist,Y eine direkte Bindung oder eine der folgenden Gruppen ist:-CO-, -COO-, -OOC-, -CO-N(R')-, -(R)N-CO-, -S02-N(R')-, -(R')N-S02-, B eine direkte Bindung bedeutet oder ein gegebenenfalls mit OH substituiertes C2-Cs-Alkylen oder -Alkyliden ist, welches gegebenenfalls durch ein -O- oder durch ein oder zwei - X⊖(R')2- unterbrochen ist, oder eine Gruppe der Formel Ic ist, oder die Gruppe für einen gesättigten oder ungesättigten 1 bis 3-kernigen N-Heterocyklus steht, der 1-4 N-Atome als Ringglieder enthält, von denen mindestens eines quaterniert ist, unter den Bedingungen, dass a) im Falle g = 1, A, Y und B nicht gleichzeitig eine direkte Bindung bedeuten;b) im Falle g = 1 und A = direkte Bindung, Y -CO- oder eine direkte Bindung bedeutet;undc) im Falle B = eine direkte Bindung, auch Y eine direkte Bindung ist;R' Wasserstoff, C1-C4-Alkyl oder C2-C3-Hydroxyalkyl ist,B° -(CH2)m- oder eine der folgenden Gruppen bedeutet: wobei m und r unabhängig voneinander 2 oder 3 bedeuten,R33 eine Bedeutung von R3 hat oder für eine Gruppe der Formeln Id und le steht, worin g, p, B, Y, A und U die zuvor genannte Bedeutung haben, R1, R2 und R3 unabhängig voneinander Wasserstoff, C1-C8-Alkyl, durch ein -COOR" oder 1 bis 3 OH substituiertes C1-C8-Alkyl, durch ein oder mehrere -O- unterbrochenes C2-C8-Hydroxyalkyl, mit einem OH substituiertes -(C1-C8)Alkylen-COOe, -(C1-C8)Alkyliden-COO⊖, -(C2-C8)Alkylen-SO oder -(C2-C8)Alkyliden-SO, C3-Cs-Alkenyl, C5-C7-Cycloalkyl, Phenyl, Tolyl, Benzyl oder Glycidyl bedeuten, oder R1 zusammen mit R2 und gegebenenfalls mit R3 sowie zusammen mit dem -Atom, an das sie gebunden sind, einen N-Heterocyklus bilden, der gegebenenfalls 1-3 N-Atome oder ein 0-Atom als Ringglieder enthält,R" Wasserstoff oder C1-C4-Alkyl ist, undXe, falls nicht in R1, R2, R3 oder R33 vorhanden, ein farbloses organisches oder anorganisches Anion bedeutet. 1. Aufzeichnungsmaterial enthaltend als Stabilisator mindestens eine verbindung der Formel I worin n eine Zahl von 1 bis 4 bedeutet, U ein Rest eines UV-Absorbers vom Typ Hydroxyphenyl-benztriazol, Zimtsäure oder Hydroxyphenyl-Triazin ist,SOL, gleich oder verschieden, eine Gruppe der Formel la bedeutet, woring für 0 oder 1 steht,A eine direkte Bindung, C1-C6-Alkylen oder -Alkyliden, oder eine Gruppe der Formel Ib bedeutet, wobei p eine Zahl von 1 bis 6 ist,Y eine direkte Bindung oder eine der folgenden Gruppen ist:-CO-, -COO-, -OOC-, -CO-N(R')-, -(R')N-CO-, -S02-N(R')-, -(R')N-S02-, B eine direkte Bindung bedeutet oder ein gegebenenfalls mit OH substituiertes C2-Cs-Alkylen oder -Alkyliden ist, welches gegebenenfalls durch ein -O- oder durch ein oder zwei - (R')2- unterbrochen ist, oder eine Gruppe der Formel Ic ist, oder die Gruppe für einen gesättigten oder ungesättigten 1 bis 3-kernigen N-Heterocyklus steht, der 1-4 N-Atome als Ringglieder enthält, von denen mindestens eines quaterniert ist, unter den Bedingungen, dassa) im Falle g = 1, A, Y und B nicht gleichzeitig eine direkte Bindung bedeuten;b) im Falle g = 1 und A = direkte Bindung, Y -CO- oder eine direkte Bindung bedeutet;undc) im Falle B = eine direkte Bindung, auch Y eine direkte Bindung ist;R Wasserstoff, C1-C4-Alkyl oder C2-C3-Hydroxyalkyl ist, B° -(CH2)̵m oder eine der folgenden Gruppen bedeutet: wobei m und r unabhängig voneinander 2 oder 3 bedeuten,R33 eine Bedeutung von R3 hat oder für eine Gruppe der Formeln Id und le steht, worin g, p, B, Y, A und U die zuvor genannte Bedeutung haben,R1, R2 und R3 unabhängig voneinander Wasserstoff, C1-C8-Alkyl, durch ein -COOR oder 1 bis 3 OH substituiertes C1-C8-Alkyl, durch ein oder mehrere -O- unterbrochenes C2-Cs-Hydroxyalkyl, mit einem OH substituiertes -(C1-C8)Alkylen-COO⊖, -(C1-C8)Alkyliden-COO⊖, -(C2-C8)Alkylen-SO oder -(C2-C8)Alkyliden- SO⊖3, C3-C5-Alkenyl, C5-C7-Cycloalkyl, Phenyl, Tolyl, Benzyl oder Glycidyl bedeuten, oder R1 zusammen mit R2 und gegebenenfalls mit R3 sowie zusammen mit dem -Atom, an das sie gebunden sind, einen N-Heterocyklus bilden, der gegebenenfalls 1-3 N-Atome oder ein 0-Atom als Ringglieder enthält,R" Wasserstoff oder C1-C4-Alkyl ist, undX8, falls nicht in R1, R2, R3 oder R33 vorhanden, ein farbloses organisches oder anorganisches Anion bedeutet.
- 2Aufzeichnungsmaterial gemäss Anspruch 1 von Verbindungen der Formel I, worin in der Formel la g = 0 ist. 2. Aufzeichnungsmaterial gemäss Anspruch 1 von Verbindungen der Formel I, worin in der Formel la g = 0 ist. 2nd Recording material according to claim 1 of compounds of formula I, wherein in the formula la g = 0.
- 3Aufzeichnungsmaterial gemäss Anspruch 2, worin R33 in der Formel la eine Bedeutung von R3 hat. 3. Aufzeichnungsmaterial gemäss Anspruch 2, worin R33 in der Formel la eine Bedeutung von R3 hat. 3rd Recording material according to claim 2, wherein R33 in the formula la a meaning of R3 Has.
- 4Aufzeichnungsmaterial gemäss Anspruch 3, worin die Formel la einer Gruppe der Formel If Y° -COO-, -CONH- oder bedeutet, y eine Zahl von 0 bis 6 ist, und p, B°, R1, R2 und R3 die in Anspruch 1 genannte Bedeutung haben. 4. Aufzeichnungsmaterial gemäss Anspruch 3, worin die Formel la einer Gruppe der Formel If Y° -COO-, CONH- oder bedeutet, y eine Zahl von 0 bis 6 ist, und p, B°, Ri, R2 und R3 die in Anspruch I genannte Bedeutung haben. 4th Recording material according to claim 3, wherein the formula la of a group of the formula IfY ° -COO-, -CONH- ormeans y is a number from 0 to 6, and p, B °, R1, R2 and R3 have the meaning given in claim 1.
- 5Recording material according to claim 1, wherein the compound of the formula I is a compound of the formula II or IIIcorresponds to whatR4 Halogen, C1-C4-Alkoxy, C1-C8-Alkyl, C5-C6-Cycloalkyl, phenyl, phenyl-C1-C4Is alkyl or a group of the formula Ia,Rs and R6 are independently hydrogen, or a meaning of R4 to have,R7 OH, C1-C8Alkoxy, which can be substituted by 1 to 3 OH or 1 to 2 -COOH, C1-C8Alkanoyloxy, a group of the formula la with g = 1 or glycidyloxy,provided that at least one of R4, Rs and R6 in formula II and at least one of Rs and R7 in formula III stands for a group of formula la. 5. Aufzeichnungsmaterial gemäss Anspruch 1, worin die Verbindung der Formel I einer Verbindung der Formel II oder III entspricht, worin R4 Halogen, C1-C4-Alkoxy, C1-C8-Alkyl, C5-C6-Cycloalkyl, Phenyl, Phenyl-C1-C4-Alkyl oder eine Gruppe der Formel la ist,Rs und R6 unabhängig voneinander Wasserstoff sind, oder eine Bedeutung von R4 haben,R7 OH, C1-C8-Alkoxy, welches durch 1 bis 3 OH oder 1 bis 2 -COOH substituiert sein kann, C1-C8-Alkanoyloxy, eine Gruppe der Formel la mit g = 1 oder Glycidyloxy ist,unter der Bedingung, dass mindestens eines von R4, Rs und R6 in der Formel II und mindestens eines von Rs und R7 in der Formel III für eine Gruppe der Formel la steht. 5. Aufzeichnungsmaterial gemäss Anspruch 1, worin die Verbindung der Formel I einer Verbindung der Formel II oder III entspricht, worin R4 Halogen, C1-C4-Alkoxy, C1-C8-Alkyl, Cs-C6-Cycloalkyl, Phenyl, Phenyl-C1-C4-Alkyl oder eine Gruppe der Formel la ist,R5 und R6 unabhängig voneinander Wasserstoff sind, oder eine Bedeutung von R4 haben,R7 OH, C1-C8-Alkoxy, welches durch 1 bis 3 OH oder 1 bis 2 -COOH substituiert sein kann, C1-C8-Alkanoyloxy, eine Gruppe der Formel la mit g = 1 oder Glycidyloxy ist,unter der Bedingung, dass mindestens eines von R4, R5 und R6 in der Formel II und mindestens eines von R6 und R7 in der Formel III für eine Gruppe der Formel la steht.
- 6Recording material according to claim 5, wherein R4 Halogen, C1-C5-Alkyl, cyclohexyl or a group of the formula la, Rs is hydrogen or has a meaning of R4, R6 represents hydrogen, halogen or a group of the formula Ia, and R7 OH, C optionally substituted with 1 to 3 OH1-C4-Alkoxy, glycidyloxy, C2-C3-Alkanoyloxy or a group of the formula Ia with g = 1. 6. Aufzeichnungsmaterial gemäss Anspruch 5, worin R4 Halogen, C1-C5-Alkyl, Cyclohexyl oder eine Gruppe der Formel la ist, Rs Wasserstoff ist oder eine Bedeutung von R4 hat, R6 für Wasserstoff, Halogen oder eine Gruppe der Formel la steht, und R7 OH, gegebenenfalls mit 1 bis 3 OH substituiertes C1-C4-Alkoxy, Glycidyloxy, C2-C3-Alkanoyloxy oder eine Gruppe der Formel la mit g = 1 bedeutet. 6. Aufzeichnungsmaterial gemäss Anspruch 5, worin R4 Halogen, C1-C5-Alkyl, Cyclohexyl oder eine Gruppe der Formel la ist, Rs Wasserstoff ist oder eine Bedeutung von R4 hat, R6 für Wasserstoff, Halogen oder eine Gruppe der Formel la steht, und R7 OH, gegebenenfalls mit 1 bis 3 OH substituiertes C1-C4-Alkoxy, Glycidyloxy, C2-C3-Alkanoyloxy oder eine Gruppe der Formel la mit g = 1 bedeutet.
- 7Recording material according to claim 6, wherein in the formula II R4 C1-C4-Alkyl or a group of the formula If Rs is hydrogen, C1-C4Is alkyl or a group If, and R6 Is hydrogen, CI or a group If, where y is 0, provided that at least one of R4, R5 and R6 represents a group of formula If. 7. Aufzeichnungsmaterial gemäss Anspruch 6, worin in der Formel II R4 C1-C4-Alkyl oder eine Gruppe der Formel If bedeutet, Rs Wasserstoff, C1-C4-Alkyl oder eine Gruppe If ist, und R6 Wasserstoff, CI oder eine Gruppe If bedeutet, worin y für 0 steht, unter der Bedingung, dass mindestens eines von R4, R5 und R6 eine Gruppe der Formel If darstellt. 7. Aufzeichnungsmaterial gemäss Anspruch 6, worin in der Formel II R4. C1-C4-Alkyl oder eine Gruppe der Formel If bedeutet, R5 Wasserstoff, C1-C4-Alkyl oder eine Gruppe If ist, und Rs Wasserstoff, CI oder eine Gruppe If bedeutet, worin y für 0 steht, unter der Bedingung, dass mindestens eines von R4, R5 und Rs eine Gruppe der Formel If darstellt.
- 8Aufzeichnungsmaterial gemäss Anspruch 1, worin die Verbindung der Formel I einer Verbindung der Formel V entspricht, worin R13 Wasserstoff, C1-C8-Alkyl, C3-C8-Alkenyl, Phenyl-C1-C4-Alkyl oder eine Gruppe der Formel bedeutet, R14 und R15 unabhängig voneinander -C≡N, -CO-Ci-C4-Alkyl, -COO-R19 oder -CO-NR20R21 bedeuten, R16, R17, R18, R'16, R'17 und R'18 unabhängig voneinander für Wasserstoff, C1-C4-Alkyl, Phenyl, Glycidyl, OH, Halogen, gegebenenfalls mit 1 bis 3 OH substituiertes C1-C4-Alkoxy, Phenoxy, Benzyloxy oder eine Gruppe der Formel la stehen, undR19, R20 und R21 unabhängig voneinander Wasserstoff, C1-C4-Alkyl, welches gegebenenfalls mit 1 bis 3 OH substituiert ist, C5-C7-Cycloalkyl, Phenyl, Benzyl, Tolyl, Glycidyl oder eine Gruppe der Formel Ig bedeuten, worin B°, Ri, R2 und R3 die in Anspruch 1 genannte Bedeutung haben,unter der Bedingung, dass mindestens eines von R16, R17, R18, R'16, R'17 oder R'18 eine Gruppe der Formel la oder mindestens eines von R19, R20 oder R21 eine Gruppe der Formel Ig bedeuten. 8. Aufzeichnungsmaterial gemäss Anspruch 1, worin die Verbindung der Formel I einer Verbindung der Formel V entspricht, worin R13 Wasserstoff, C1-C8-Alkyl, C3-Cs-Alkenyl, Phenyl-C1-C4-Alkyl oder eine Gruppe der Formel bedeutet, R14 und R15 unabhängig voneinander C≡N, -CO-C1-C4-Alkyl, -COO-R19 oder -CO-NR2oR21 bedeuten, R16, R17, R18R'16, R'17 und R'18 unabhängig voneinander für Wasserstoff, C1-C4-Alkyl, Phenyl, Glycidyl, OH, Halogen, gegebenenfalls mit 1 bis 3 OH substituiertes Cl-C4-Alkoxy, Phenoxy, Benzyloxy oder eine Gruppe der Formel la stehen, und R19, R20 oder R21 unabhängig voneinander Wasserstoff, C1-C4-Alkyl, welches gegebenenfalls mit 1 bis 3 OH substituiert ist, C5-C7-Cycloalkyl, Phenyl, Benzyl, Tolyl, Glycidyl oder eine Gruppe der Formel Ig bedeuten, worin B°, R1, R2 und R3 die in Anspruch 1 genannte Bedeutung haben,unter der Bedingung, dass mindestens eines von R16, R17, R18, R'16, R'17 oder R'18 eine Gruppe der Formel la oder mindestens eines von R19, R20 oder R21 eine Gruppe der Formel Ig bedeuten. 8th. Recording material according to Claim 1, in which the compound of the formula I is a compound of the formula Vcorresponds to whatR13 Hydrogen, C1-C8-Alkyl, C3-C8-Alkenyl, phenyl-C1-C4-Alkyl or a group of the formulameans R14 and R15 independently of one another -C≡N, -CO-Ci-C4-Alkyl, -COO-R19 or -CO-NO20R21 mean R16, R17, R18, R '16, R '17 and R '18 independently for hydrogen, C1-C4-Alkyl, phenyl, glycidyl, OH, halogen, optionally substituted with 1 to 3 OH1-C4-Alkoxy, phenoxy, benzyloxy or a group of the formula la, andR19, R20 and R21 independently of one another hydrogen, C1-C4Alkyl, which is optionally substituted by 1 to 3 OH, C5-C7-Cycloalkyl, phenyl, benzyl, tolyl, glycidyl or a group of the formula Igmean, where B °, Ri, R2 and R3 have the meaning given in claim 1,provided that at least one of R16, R17, R18, R '16, R '17 or R '18 a group of the formula la or at least one of R19, R20 or R21 mean a group of the formula Ig.
- 9A recording material according to claim 8, wherein the compound of formula V is a compound of formula Vacorresponds to whatR13 Hydrogen, C1-C4-Alkyl or a grouprepresents, and R14, R15, R16, R17, R18, R '16, R '17 and R '18 have the meaning given in claim 10. 9. Aufzeichnungsmaterial gemäss Anspruch 8, worin die Verbindung der Formel V einer Verbindung der Formel Va entspricht, worin R13 Wasserstoff, C1-C4-Alkyl oder eine Gruppe darstellt, und R14, R15, R16, R17, R18, R'16, R'17 und R'18 die in Anspruch 10 genannte Bedeutung haben. 9. Aufzeichnungsmaterial gemäss Anspruch 8, worin die Verbindung der Formel V einer Verbindung der Formel Va entspricht, worin R13 Wasserstoff, C1-C4-Alkyl oder eine Gruppe darstellt, und R14, R15, R16, R17, R18, R'16, R'17 und R'18 die in Anspruch 10 genannte Bedeutung haben.
- 10Aufzeichnungsmaterial gemäss Anspruch 1, worin die Verbindung der Formel I einer Verbindung der Formel VI entspricht, worin R22 eine Gruppe der Formel la mit g = 1 ist und R23, R24, R25, R23, R24 und R25 für Wasserstoff, OH, Halogen, C1-C4-Alkoxy, C1-C4-Alkyl, Phenyl oder eine Gruppe der Formel la mit g = 1 stehen. 10. Aufzeichnungsmaterial gemäss Anspruch 1, worin die Verbindung der Formel I einer Verbindung der Formel VI entspricht, worin R22 eine Gruppe der Formel la mit g = 1 ist und R23, R24, R25, R'23, R'24 und R'25 für Wasserstoff, OH, Halogen, C,-C4-Alkoxy, C1-C4-Alkyl, Phenyl oder eine Gruppe der Formel la mit g = 1 stehen. 10th Recording material according to Claim 1, in which the compound of the formula I is a compound of the formula VIcorresponds to whatR22 is a group of formula la with g = 1 and R23, R24, R25, R '23, R '24 and R '25 for hydrogen, OH, halogen, C, -C4-Alkoxy, C1-C4-Alkyl, phenyl or a group of formula la with g = 1.
- 11A recording material according to claim 10, wherein the compound of formula VI is a compound of formula Vlacorresponds, and R22 stands for a group of formula la with g = 1. 11. Aufzeichnungsmaterial gemäss Anspruch 10, worin die Verbindung der Formel VI einer Verbindung der Formel Vla entspricht, und R22 für eine Gruppe der Formel la mit g = 1 steht. 11. Aufzeichnungsmaterial gemäss Anspruch 10, worin die Verbindung der Formel VI einer Verbindung der Formel Vla entspricht, und R22 für eine Gruppe der Formel la mit g = 1 steht.
- 12Aufzeichnungsmaterial gemäss Anspruch 1, worin Xe in der Formel la ist Chlorid oder Bromid, C1-C4-Alkyl-COO⊖, C1-C4-Alkyl-OSO oder R0-SO bedeutet, wobei R° für Methyl, Tolyl oder -CF3 steht. 12. Aufzeichnungsmaterial gemäss Anspruch 1, worin Xe in der Formel la ist Chlorid oder Bromid, C1-C4-Alkyl-COO⊖, C1-C4-Alkyl-OSO oder Ro-SO bedeutet, wobei R° für Methyl, Tolyl oder -CF3 steht. 12th Recording material according to claim 1, wherein Xe in the formula la is chloride or bromide, C1-C4-Alkyl-COO⊖, C1-C4-Alkyl-OSO or RO-SO means, where R ° is methyl, tolyl or -CF3 stands.
- 13Recording material according to claim 1, characterized in that the recording material is suitable for ink jet printing. 13. Aufzeichnungsmaterial gemäss Anspruch 1, dadurch gekennzeichnet, dass das Aufzeichnungsmaterial für Tintenstrahldruck geeignet ist. 13. Aufzeichnungsmaterial gemäss Anspruch 1, dadurch gekennzeichnet, dass das Aufzeichnungsmaterial für Tintenstrahldruck geeignet ist.
- 14Recording material according to claim 13, characterized in that it consists of a carrier material with a surface printable by ink jet. 14. Aufzeichnungsmaterial gemäss Anspruch 13, dadurch gekennzeichnet, dass es aus einem Trägermaterial mit einer durch Tintenstrahl bedruckbaren Oberfläche besteht. 14. Aufzeichnungsmaterial gemäss Anspruch 13, dadurch gekennzeichnet, dass es aus einem Trägermaterial mit einer durch Tintenstrahl bedruckbaren Oberfläche besteht.
- 15Recording material according to claim 14, characterized in that it is a coated paper. 15. Aufzeichnungsmaterial gemäss Anspruch 14, dadurch gekennzeichnet, dass es ein beschichtetes Papier ist. 15. Aufzeichnungsmaterial gemäss Anspruch 14, dadurch gekennzeichnet, dass es ein beschichtetes Papier ist.
- 16Process for the production of a recording material for inkjet printing, stabilized against light damage, characterized in that a two-dimensional support is coated with a coating composition which contains at least one compound of the formula I according to claim 1. 16. Verfahren zur Herstellung eines gegen Lichtschädigung stabilisierten Aufzeichnungsmaterials für den Tintenstrahldruck, dadurch gekennzeichnet, dass man einen zweidimensionalen Träger mit einer Beschichtungsmasse beschichtet, welche mindestens eine Verbindung der Formel I gemäss Anspruch 1 enthält. 16. Verfahren zur Herstellung eines gegen Lichtschädigung stabilisierten Aufzeichnungsmaterials für den Tintenstrahldruck, dadurch gekennzeichnet, dass man einen zweidimensionalen Träger mit einer Beschichtungsmasse beschichtet, welche mindestens eine Verbindung der Formel I gemäss Anspruch 1 enthält.
- 17Verwendung von Verbindungen der Formel I gemäss Anspruch 1 als Lichtschutzmittel für Aufzeichnungsmaterialien. 17. Verwendung von Verbindungen der Formel I gemäss Anspruch 1 als Lichtschutzmittel für Aufzeichnungsmaterialien. 17th Use of compounds of the formula I according to claim 1 as light stabilizers for recording materials.
- 18Tinte enthaltend als Stabilisator mindestens eine Verbindung der Formel I U-(SOL)n (I),worin n eine Zahl von 1 bis 4 bedeutet,U ein Rest eines UV-Absorbers vom Typ Hydroxyphenyl-benztriazol, Zimtsäure oder Hydroxyphenyl-Triazin ist,SOL, gleich oder verschieden, eine Gruppe der Formel la bedeutet, woring für 0 oder 1 steht,A eine direkte Bindung, C1-C6-Alkylen oder -Alkyliden, oder eine Gruppe der Formel lb bedeutet, wobei p eine Zahl von 1 bis 6 ist,Y eine direkte Bindung oder eine der folgenden Gruppen ist:B eine direkte Bindung bedeutet oder ein gegebenenfalls mit OH substituiertes C2-C6-Alkylen oder -Alkyliden ist, welches gegebenenfalls durch ein -0- oder durch ein oder zwei - X⊖(R')2- unterbrochen ist, oder eine Gruppe der Formel Ic ist, oder die Gruppe für einen gesättigten oder ungesättigten 1 bis 3-kernigen N-Heterocyklus steht, der 1-4 N-Atome als Ringglieder enthält, von denen mindestens eines quaterniert ist, unter den Bedingungen, dass a) im Falle g = 1, A, Y und B nicht gleichzeitig eine direkte Bindung bedeuten;b) im Falle g = 1 und A = direkte Bindung, Y -CO- oder eine direkte Bindung bedeutet;undc) im Falle B = eine direkte Bindung, auch Y eine direkte Bindung ist;R' Wasserstoff, C1-C4-Alkyl oder C2-C3-Hydroxyalkyl ist,B° -(CH2)m- oder eine der folgenden Gruppen bedeutet: wobei m und r unabhängig voneinander 2 oder 3 bedeuten,R33 eine Bedeutung von R3 hat oder für eine Gruppe der Formeln Id und le steht, worin g, p, B, Y, A und U die zuvor genannte Bedeutung haben, Ri, R2 und R3 unabhängig voneinander C1-C8-Alkyl, durch ein -COOR" oder 1 bis 3 OH substituiertes C1-C8-Alkyl, durch ein oder mehrere -O- unterbrochenes C2-C8-Hydroxyalkyl, mit einem OH substituiertes -(C1-C8)-Alkylen-COO⊖, -(C1-Cs)Alkyliden-COOe, -(C2-C8)Alkylen-SO oder -(C2-C8)Alkyliden-SO⊖3, C3-C5-Alkenyl, C5-C7-Cycloalkyl, Phenyl, Tolyl, Benzyl oder Glycidyl bedeuten, oder R, zusammen mit R2 und gegebenenfalls mit R3 sowie zusammen mit dem -Atom, an das sie gebunden sind, einen N-Heterocyklus bilden, der gegebenenfalls 1-3 N-Atome oder ein 0-Atom als Ringglieder enthält, R Wasserstoff oder C1-C4-Alkyl ist, und X⊖, falls nicht in R1, R2, R3 oder R33 vorhanden, ein farbloses organisches oder anorganisches Anion bedeutet. 18. Verbindung der Formel IoU-(SOLo)n' (1°),worin n eine Zahl von 1 bis 4 bedeutet,U ein Rest eines UV-Absorbers vom Typ Hydroxyphenyl-benztriazol, Zimtsäure oder Triazin ist,SOL°, gleich oder verschieden, eine Gruppe der Formel Ioa bedeutet, woring für 0 oder 1 steht,A eine direkte Bindung, C1-C6-Alkylen oder eine Gruppe der Formel Iob bedeutet, wobei p eine Zahl von 1 bis 6 ist,Y eine direkte Bindung oder eine der folgenden Gruppen ist:-CO-, -COO-, -OOC-, -CO-N(R')-, -(R')N-CO-, -S02-N(R')-, -(R')N-S02-, B eine direkte Bindung bedeutet oder ein gegebenenfalls mit OH substituiertes C2-C6-Alkylen ist, welches gegebenenfalls durch ein -0- oder durch ein oder zwei - X⊖(R')2- unterbrochen ist, oder eine Gruppe der Formeln I°c oder I°C ist, oder die Gruppe für einen gesättigten oder ungesättigten 1 bis 3-kernigen N-Heterocyklus steht, der 1-4 N-Atome als Ringglieder enthält, von denen mindestens eines quaterniert ist, unter den Bedingungen, dass a) im Falle g = 1, A, Y und B nicht gleichzeitig eine direkte Bindung bedeuten;b) im Falle g = 1 und A = direkte Bindung, Y -CO- oder eine direkte Bindung bedeutet: undc) im Falle B = eine direkte Bindung, auch Y eine direkte Bindung ist;R' Wasserstoff, C1-C4-Alkyl oder C2-C3-Hydroxyalkyl ist,B° -(CH2)-m oder eine der folgenden Gruppen bedeutet: wobei m und r unabhängig voneinander 2 oder 3 bedeuten,R33 eine Bedeutung von R3 hat oder für eine Gruppe der Formeln Iod und Ioe steht, worin g, p, B, Y, A und U die zuvor genannte Bedeutung haben, R1, R2 und R3 unabhängig voneinander C1-C8-Alkyl oder durch ein -COOR" oder 1 bis 3 OH substituiertes C1-C8-Alkyl, durch ein oder mehrere -0- unterbrochenes C2-C8-Hydroxyalkyl, mit einem OH substituiertes -(C1-C8)Alkylen-COO⊖, -(C1-C8)Alkyliden-COO⊖, -(C2-C8)Alkylen-SO oder -(C2-C8)Alkyliden-SO , C3-Cs-Alkenyl, C5-C7-Cycloalkyl, Phenyl, Tolyl, Benzyl oder Glycidyl bedeuten, oder R, zusammen mit R2 und gegebenenfalls mit R3 sowie zusammen mit dem -Atom, an das sie gebunden sind, einen N-Heterocyklus bilden, der gegebenenfalls 1-3 N-Atome oder ein O-Atom als Ringglieder enthält,R" Wasserstoff oder C1-C4-Alkyl ist, undX8, falls nicht in Ri, R2, R3 oder R33 vorhanden, ein farbloses organisches oder anorganisches Anion bedeutet, unter den Bedingungen, dass A) im Falle U für einen Rest vom Typ Hydroxyphenyl-Benztriazol steht und n in der Formel I° 1 bedeutet, Y in der Formel 1° die Bedeutung von Y1 hat, wobei Y1 eine der folgenden Gruppen ist B) im Falle U für einen Rest vom Typ Hydroxybenzophenon steht und n in der Formel Ioa 1 oder 2 bedeutet, g = 0 ist;C) im Falle U für einen Zimtsäurerest mit 1 oder 2 -C≡N-Gruppen steht, n in der Formel I° 3 oder 4 ist;oderD) im Falle U für einen Hydroxyphenyl-Triazinrest steht und in der Formel Ioa g = 1, A = Alkylen und Y eine direkte Bindung bedeuten, B nicht für eine direkte Bindung oder Alkylen stehen kann, oder wenn g = 1 und A eine direkte Bindung bedeuten, Y nicht -CO- sein kann. 18th Compound of formula I.OU- (SOLO)n' (1°),where n is a number from 1 to 4,U is a residue of a UV absorber of the hydroxyphenyl-benzotriazole, cinnamic acid or triazine type,SOL °, identical or different, a group of formula I.Oameans whatg represents 0 or 1,A a direct bond, C1-C6Alkylene or a group of formula I.Obmeans, where p is a number from 1 to 6,Y is a direct bond or one of the following groups:-CO-, -COO-, -OOC-, -CO-N (R ') -, - (R') N-CO-, -S02-N (R ') -, - (R') N-S02-, B represents a direct bond or a C optionally substituted with OH2-C6-Alkylene, which may be replaced by one -0- or one or two - X⊖(R ')2- is interrupted, or a group of the formulas I ° C or I ° Cis, or the grouprepresents a saturated or unsaturated 1 to 3-nucleus N-heterocycle which contains 1-4 N atoms as ring members, of which at least one is quaternized, under the conditions thata) in the case of g = 1, A, Y and B do not simultaneously mean a direct bond;b) in the case of g = 1 and A = direct bond, Y is -CO- or a direct bond means: andc) in the case of B = a direct bond, also Y is a direct bond;R 'is hydrogen, C1-C4-Alkyl or C2-C3-Hydroxyalkyl is,B ° - (CH2)-m or one of the following groups means: where m and r are independently 2 or 3,R33 a meaning of R3 has or for a group of formulas IOd and IOewhere g, p, B, Y, A and U have the meaning given above, R1, R2 and R3 independently of each other C1-C8-Alkyl or by a -COOR "or 1 to 3 OH substituted C1-C8-Alkyl, interrupted by one or more -0- C2-C8-Hydroxyalkyl, substituted with an OH - (C1-C8) Alkylene-COO⊖, - (C1-C8) Alkylidene-COO⊖, - (C2-C8) Alkylene SO or - (C2-C8) Alkylidene SO , C3-CsAlkenyl, C5-C7-Cycloalkyl, phenyl, tolyl, benzyl or glycidyl, or R together with R.2 and optionally with R3 as well as together with the Atom to which they are attached form an N-heterocycle which may contain 1-3 N atoms or an O atom as ring members,R "is hydrogen or C1-C4-Alkyl is, andX8, if not in Ri, R2, R3 or R33 is a colorless organic or inorganic anion,under the conditions thatA) in the case of U represents a radical of the hydroxyphenyl-benzotriazole type and n in the formula is 1 °, Y in the 1 ° formula is Y1 where Y1 is one of the following groupsB) in the case of U represents a radical of the hydroxybenzophenone type and n in the formula I.Oa represents 1 or 2, g = 0;C) in the case of U represents a cinnamic acid residue with 1 or 2 -C≡N groups, n in the formula I ° 3 or 4;orD) in the case of U represents a hydroxyphenyl triazine residue and in the formula I.Oag = 1, A = alkylene and Y mean a direct bond, B cannot stand for a direct bond or alkylene, or if g = 1 and A signify a direct bond, Y cannot be -CO-.
- 19Tinte gemäss Anspruch 18, dadurch gekennzeichnet, dass die Tinte für den Tintenstrahldruck verwendet wird. 19. Verbindung gemäss Anspruch 18, worin die Verbindung der Formel Io einer Verbindung der Formel IIo oder IIIoentspricht, worin R4 Halogen, C1-C4-Alkoxy, C1-C8-Alkyl, C5-C6-Cycloalkyl, Phenyl, Phenyl-Ci-C4-Alkyl oder eine Gruppe der Formel Ioa ist,R5 und R6 unabhängig voneinander Wasserstoff sind, oder eine Bedeutung von R4 haben,R7 OH, C1-C8-Alkoxy, welches durch 1 bis 3 OH oder 1 bis 2 -COOH substituiert sein kann, C1-C8-Alkanoyloxy, eine Gruppe der Formel la mit g = 1 oder Glycidyloxy ist,unter der Bedingung, dass mindestens eines von R4, Rs und R6 in der Formel IIo und mindestens eines von R6 und R7 in der Formel IIIo für eine Gruppe der Formel Ioa steht, undin der Formel Ioa falls g = 0 und A = Alkylen bedeuten, Y nicht eine direkte Bindung, -COO- oder -CONHsein kann, oderfalls g = 1, A = Alkylen und Y eine direkte Bindung bedeuten, B nicht für eine direkte Bindung oder Alkylen stehen kann. 19th A compound according to claim 18, wherein the compound of formula IO a compound of formula IIO or IIIOcorresponds to whatR4 Halogen, C1-C4-Alkoxy, C1-C8-Alkyl, C5-C6-Cycloalkyl, phenyl, phenyl-Ci-C4-Alkyl or a group of formula I.Oa isR5 and R6 are independently hydrogen or have a meaning of R4,R7 OH, C1-C8Alkoxy, which can be substituted by 1 to 3 OH or 1 to 2 -COOH, C1-C8Alkanoyloxy, a group of the formula la with g = 1 or glycidyloxy,provided that at least one of R4, Rs and R6 in formula IIO and at least one of R6 and R7 in formula IIIO for a group of formula I.Oa stands, andin formula I.Oa if g = 0 and A = alkylene, Y cannot be a direct bond, -COO- or -CONH, orif g = 1, A = alkylene and Y mean a direct bond, B cannot stand for a direct bond or alkylene.
- 20Tinte gemäss Anspruch 18, dadurch gekennzeichnet, dass die Tinte Wasser enthält. 20. Verbindung gemäss Anspruch 19, worin R4 Halogen, C1-C5-Alkyl, Cyclohexyl oder eine Gruppe der Formel Ioa ist, Rs Wasserstoff ist, oder eine Bedeutung von R4 hat, R6 für Wasserstoff, Halogen oder eine Gruppe der Formel Ioa steht, und R7 OH, gegebenenfalls mit 1 bis 3 OH oder mit 1 bis 2 COOH substituiertes C1-C4-Alkoxy, Glycidyloxy, C2-C3-Alkanoyloxy oder eine Gruppe der Formel Io a mit g = 1 bedeutet. 20th A compound according to claim 19, wherein R4 Halogen, C1-C5-Alkyl, cyclohexyl or a group of formula I.Oa is, Rs is hydrogen, or a meaning of R4 has, R6 for hydrogen, halogen or a group of formula I.Oa stands, and R7 OH, C optionally substituted with 1 to 3 OH or with 1 to 2 COOH1-C4-Alkoxy, glycidyloxy, C2-C3Alkanoyloxy or a group of formula I.O a with g = 1 means.
- 21A compound according to claim 20, wherein in formula IIO R4 C.1-C4-Alkyl or a group of formula I ° fmeans Rs is hydrogen, C1-C4-Alkyl or a group IOis f and Rs Hydrogen, CI or a group I.Of means where y is 0, provided that at least one of R4, Rs and R6 a group of formula I.Of represents. 21. Tinte gemäss Anspruch 18, dadurch gekennzeichnet, dass diese den Stabilisator der Formel I in einer Konzentration von 0,01 bis 20 Gew.-%, insbesondere von 0,5 bis 10 Gew.-%, enthält. 21. Verbindung gemäss Anspruch 20, worin in der Formel IIo R4 C1-C4-Alkyl oder eine Gruppe der Formel I°f bedeutet, Rs Wasserstoff, C1-C4-Alkyl oder eine Gruppe Iof ist, und Rs Wasserstoff, CI oder eine Gruppe Iof bedeutet, worin y für 0 steht, unter der Bedingung, dass mindestens eines von R4, Rs und R6 eine Gruppe der Formel Iof darstellt.
- 22A compound according to claim 18, wherein the compound of formula IO a compound of formula V °where R13 Hydrogen, C1-C8-Alkyl, C3-C8-Alkenyl, phenyl-C1-C4-Alkyl or a group of the formulameans R14 and R15 independently of one another -C≡N, -CO-C1-C4-Alkyl, -COO-R19 or -CO-NO2oR21 mean R,6, R17, R18, R '16, R '17 and R '18 independently for hydrogen, C1-C4-Alkyl, phenyl, glycidyl, OH, halogen, optionally substituted with 1 to 3 OH1-C4-Alkoxy, phenoxy, benzyloxy or a group of formula I.Oa stand, and R19, R20 or R21 independently of one another hydrogen, C1-C4Alkyl, which is optionally substituted by 1 to 3 OH, C5-C7-Cycloalkyl, phenyl, benzyl, tolyl, glycidyl or a group of formula I.OGmean, where B °, Ri, R2 and R3 have the meaning given in claim 20, under the conditions that at least one of R16, R17, R18, R '16, R '17 and R '18 a group of formula I.Oa or at least one of R19, R20 or R21 a group of formula I.Omean g and if R14 and / or R15 represent -C≡N, at least 3 groups of the formula I.Oa and / or IOg are present. 22. Tinte gemäss Anspruch 21, dadurch gekennzeichnet, dass diese zusätzlich mindestens einen wasserlöslichen Azofarbstoff enthält. 22. Verbindung gemäss Anspruch 18, worin die Verbindung der Formel Io einer Verbindung der Formel V° entspricht, worin R13 Wasserstoff, C1-C8-Alkyl, C3-C8-Alkenyl, Phenyl-C1-C4-Alkyl oder eine Gruppe der Formel bedeutet, R14 und R15 unabhängig voneinander -C≡N, -CO-C1-C4-Alkyl, -COO-R19 oder -CO-NR2oR21 bedeuten, R,6, R17, R18, R'16, R'17 und R'18 unabhängig voneinander für Wasserstoff, C1-C4-Alkyl, Phenyl, Glycidyl, OH, Halogen, gegebenenfalls mit 1 bis 3 OH substituiertes C1-C4-Alkoxy, Phenoxy, Benzyloxy oder eine Gruppe der Formel Ioa stehen, und R19, R20 oder R21 unabhängig voneinander Wasserstoff, C1-C4-Alkyl, welches gegebenenfalls mit 1 bis 3 OH substituiert ist, C5-C7-Cycloalkyl, Phenyl, Benzyl, Tolyl, Glycidyl oder eine Gruppe der Formel Iog bedeuten, worin B°, Ri, R2 und R3 die in Anspruch 20 genannte Bedeutung haben, unter den Bedingungen, dass mindestens eines von R16, R17, R18, R'16, R'17 und R'18 eine Gruppe der Formel Ioa oder mindestens eines von R19, R20 oder R21 eine Gruppe der Formel Iog bedeuten, und falls R14 und/oder R15 für -C≡N stehen, mindestens 3 Gruppen der Formel Ioa und/oder Iog vorhanden sind.
- 23A compound according to claim 22, wherein the compound of formula V ° a compound of formula VOawhere R13 Hydrogen, C1-C4-Alkyl or a grouprepresents, and R14, R15, R16, R17, R18, R '16, R '17 and R '18 have the meaning given in claim 22. 23. Verbindung gemäss Anspruch 22, worin die Verbindung der Formel V° einer Verbindung der Formel Voa entspricht, worin R13 Wasserstoff, C1-C4-Alkyl oder eine Gruppe darstellt, und R14, R15, R16, R17, R18, R'16, R'17 und R'18 die in Anspruch 22 genannte Bedeutung haben. 23. Verwendung von Verbindungen der Formel I gemäss Anspruch 18 als Stabilisator für organische Materialien.
- 24Verbindung gemäss Anspruch 18, worin die Verbindung der Formel Io einer Verbindung der Formel VIoentspricht, worin R22 eine Gruppe der Formel I°a mit g = 1 ist und R23, R24, R25, R'23, R'24 und R'25 für Wasserstoff, OH, Halogen, C1-C4-Alkoxy, C1-C4-Alkyl, Phenyl oder eine Gruppe der Formel I°a mit g = 1 stehen, unter der Bedingung, dass falls in der Formel I°a g = 1, A = Alkylen und Y eine direkte Bindung bedeuten, B nicht für eine direkte Bindung oder Alkylen steht, oder falls g = 1 und A eine direkte Bindung bedeuten, Y nicht -CO- sein kann. 24. Verwendung gemäss Anspruch 23 als Stabilisator für Aufzeichnungsmaterialien für den Tintenstrahldruck. 24th A compound according to claim 18, wherein the compound of formula IO a compound of formula VIOwhere R22 is a group of formula I ° a with g = 1 and R23, R24, R25, R '23, R '24 and R '25 for hydrogen, OH, halogen, C1-C4-Alkoxy, C1-C4-Alkyl, phenyl or a group of the formula I ° a with g = 1, provided that if in the formula I ° ag = 1, A = alkylene and Y are a direct bond, B is not a direct bond or Alkylene, or if g = 1 and A signify a direct bond, Y cannot be -CO-.
- 25Verbindung gemäss Anspruch 24, worin die Verbindung der Formel VI° einer Verbindung der Formel VI°a entspricht, und R22 für eine Gruppe der Formel 10a mit g = 1 steht. 25. Verwendung gemäss Anspruch 23 als Stabilisator für Tinten für den Tintenstrahldruck. 25th A compound according to claim 24, wherein the compound of formula VI ° a compound of formula VI ° acorresponds, and R22 for a group of Formula 10a stands with g = 1.
- 26Compounds according to claim 18, wherein X8 in the formula la halogens, C1-C4-Alkyl-COO⊖, C1-C4-Alkyl-OSO or R0-SO means, where R ° is methyl, tolyl or -CF3 stands. 26. Verbindungen gemäss Anspruch 18, worin X8 in der Formel la Halogene, C1-C4-Alkyl-COO⊖, C1-C4-Alkyl-OSO oder R0-SO bedeutet, wobei R° für Methyl, Tolyl oder -CF3 steht. 26. Zusammensetzung enthaltend ein organisches Material und mindestens eine Verbindung der Formel I gemäss Anspruch 18 als Stabilisator.
- 2727 Use of compounds of formula I ° according to claim 18 as a stabilizer for organic materials. 27. Verwendung von Verbindungen der Formel I° gemäss Anspruch 18 als Stabilisator für organische Materialien. 27. Zusammensetzung gemäss Anspruch 26, dadurch gekennzeichnet, dass das organische Material ein synthetisches Polymer ist.
- 2828 Use according to claim 27 as a stabilizer for recording materials for inkjet printing. 28. Verwendung gemäss Anspruch 27 als Stabilisator für Aufzeichnungsmaterialien für den Tintenstrahldruck. 28. Zusammensetzung gemäss Anspruch 26, dadurch gekennzeichnet, dass das organische Material ein Lack ist.
- 29Use according to claim 27 as a stabilizer for inks for ink jet printing. 29. Verwendung gemäss Anspruch 27 als Stabilisator für Tinten für den Tintenstrahldruck.
- 30Zusammensetzung enthaltend ein organisches Material und mindestens eine Verbindung der Formel I° gemäss Anspruch 18 als Stabilisator. 30th Composition containing an organic material and at least one compound of formula I ° according to claim 18 as a stabilizer.
- 3131 Composition according to claim 30, characterized in that the organic material is a synthetic polymer. 31. Zusammensetzung gemäss Anspruch 30, dadurch gekennzeichnet, dass das organische Material ein synthetisches Polymer ist.
- 32Composition according to claim 30, characterized in that the organic material is a lacquer. 32. Zusammensetzung gemäss Anspruch 30, dadurch gekennzeichnet, dass das organische Material ein Lack ist.
- 33Composition according to claim 30, characterized in that the organic material is an ink. 33. Zusammensetzung gemäss Anspruch 30, dadurch gekennzeichnet, dass das organische Material eine Tinte ist.
- 34Ink containing at least one compound of the formula I as stabilizerU- (SOL)n (I),where n is a number from 1 to 4,U is a residue of a UV absorber of the type hydroxyphenyl benzotriazole, cinnamic acid or hydroxyphenyl triazine,SOL, the same or different, is a group of the formula lameans whatg represents 0 or 1,A a direct bond, C1-C6Alkylene or alkylidene, or a group of the formula Ibmeans, where p is a number from 1 to 6,Y is a direct bond or one of the following groups:-CO-, -COO-, -OOC-, -CO-N (R ') -, - (R') N-CO-, -SO2-N (R ') -, - (R') N-SO2-, B is a direct bond or a C which is optionally substituted by OH2-C6Alkylene or alkylidene, which may be replaced by an --O-- or by one or two - X⊖(R ')2- is interrupted, or a group of formula Icis, or the grouprepresents a saturated or unsaturated 1 to 3-nucleus N-heterocycle which contains 1-4 N atoms as ring members, of which at least one is quaternized, under the conditions thata) in the case of g = 1, A, Y and B do not simultaneously mean a direct bond;b) in the case of g = 1 and A = direct bond, Y is -CO- or a direct bond;andc) in the case of B = a direct bond, also Y is a direct bond;R 'is hydrogen, C1-C4-Alkyl or C2-C3-Hydroxyalkyl is,B ° - (CH2)m- or one of the following groups means:where m and r are independently 2 or 3, R33 a meaning of R3 has or for a group of formulas Id and lewhere g, p, B, Y, A and U have the meaning given above,R1, R2 and R3 independently of one another Ci-Cs-alkyl, by a -COOR "of 1 to 3 OH substituted C1-Cs alkyl, interrupted by one or more -0- C2-Cs-Hydroxyalkyl, substituted with an OH - (C1-C8) -Alkylene-COO⊖, - (C1-C8) Alkylidene-COO⊖, - (C2-C8) Alkylene SO or - (C2-C8) Alkylidene SO, C3-C5Alkenyl, C5-C7-Cycloalkyl, phenyl, tolyl, benzyl or glycidyl, or R1 together with R2 and optionally with R3 as well as together with the Atom to which they are attached form an N-heterocycle which may contain 1-3 N atoms or a 0 atom as ring members,R "is hydrogen or C1-C4-Alkyl is, andXe, if not in R1, R2, R3 or R33 present, means a colorless organic or inorganic anion. 34. Tinte enthaltend als Stabilisator mindestens eine Verbindung der Formel I U-(SOL)n (I),worin n eine Zahl von 1 bis 4 bedeutet,U ein Rest eines UV-Absorbers vom Typ Hydroxyphenyl-benztriazol, Zimtsäure oder Hydroxyphenyl-Triazin ist,SOL, gleich oder verschieden, eine Gruppe der Formel la bedeutet, woring für 0 oder 1 steht,A eine direkte Bindung, C1-C6-Alkylen oder -Alkyliden, oder eine Gruppe der Formel Ib bedeutet, wobei p eine Zahl von 1 bis 6 ist,Y eine direkte Bindung oder eine der folgenden Gruppen ist:-CO-, -COO-, -OOC-, -CO-N(R')-, -(R')N-CO-, -SO2-N(R')-, -(R')N-SO2-, B eine direkte Bindung bedeutet oder ein gegebenenfalls mit OH substituiert C2-C6-Alkylen oder -Alkyliden ist, welches gegebenenfalls durch ein -O- oder durch ein oder zwei - X⊖(R')2- unterbrochen ist, oder eine Gruppe der Formel Ic ist, oder die Gruppe für einen gesättigten oder ungesättigten 1 bis 3-kernigen N-Heterocyklus steht, der 1-4 N-Atome als Ringglieder enthält, von denen mindestens eines quaterniert ist, unter den Bedingungen, dass a) im Falle g = 1, A, Y und B nicht gleichzeitig eine direkte Bindung bedeuten;b) im Falle g = 1 und A = direkte Bindung, Y -CO- oder eine direkte Bindung bedeutet;undc) im Falle B = eine direkte Bindung, auch Y eine direkte Bindung ist;R' Wasserstoff, C1-C4-Alkyl oder C2-C3-Hydroxyalkyl ist,B° -(CH2)m- oder eine der folgenden Gruppen bedeutet: wobei m und r unabhängig voneinander 2 oder 3 bedeuten, R33 eine Bedeutung von R3 hat oder für eine Gruppe der Formeln Id und le steht, worin g, p, B, Y, A und U die zuvor genannte Bedeutung haben,R1, R2 und R3 unabhängig voneinander Ci-Cs-Alkyl, durch ein -COOR" der 1 bis 3 OH substituiertes C1-Cs-Alkyl, durch ein oder mehrere -0- unterbrochenes C2-Cs-Hydroxyalkyl, mit einem OH substituiertes --(C1-C8)-Alkylen-COO⊖, -(C1-C8)Alkyliden-COO⊖, -(C2-C8)Alkylen-SO oder -(C2-C8)Alkyliden-SO, C3-C5-Alkenyl, C5-C7-Cycloalkyl, Phenyl, Tolyl, Benzyl oder Glycidyl bedeuten, oder R1 zusammen mit R2 und gegebenenfalls mit R3 sowie zusammen mit dem -Atom, an das sie gebunden sind, einen N-Heterocyklus bilden, der gegebenenfalls 1-3 N-Atome oder ein 0-Atom als Ringglieder enthält,R" Wasserstoff oder C1-C4-Alkyl ist, undXe, falls nicht in R1, R2, R3 oder R33 vorhanden, ein farbloses organisches oder anorganisches Anion bedeutet.
- 35Ink according to claim 34, characterized in that the ink is used for ink jet printing. 35. Tinte gemäss Anspruch 34, dadurch gekennzeichnet, dass die Tinte für den Tintenstrahldruck verwendet wird.
- 36Ink according to claim 34, characterized in that the ink contains water. 36. Tinte gemäss Anspruch 34, dadurch gekennzeichnet, dass die Tinte Wasser enthält.
- 37Ink according to claim 34, characterized in that it contains the stabilizer of formula I in a concentration of 0.01 to 20 wt .-%, in particular from 0.5 to 10 wt .-%. 37. Tinte gemäss Anspruch 34, dadurch gekennzeichnet, dass diese den Stabilisator der Formel I in einer Konzentration von 0,01 bis 20 Gew.-%, insbesondere von 0,5 bis 10 Gew.-%, enthält.
- 38Ink according to claim 37, characterized in that it additionally contains at least one water-soluble azo dye. 38. Tinte gemäss Anspruch 37, dadurch gekennzeichnet, dass diese zusätzlich mindestens einen wasserlöslichen Azofarbstoff enthält.
Independent claims38
215 paragraphs, as filed
The present invention relates to the light stabilization of recording materials for ink jet printing by adding water-soluble stabilizers and new compounds and their use as stabilizers.
Inkjet printing is a printing process that can be controlled by electrical signals. A fine jet of ink droplets is sprayed through a nozzle onto the recording material. The ink is a solution of a dye in an aqueous or non-aqueous solvent. The recording material should quickly and permanently absorb the dye of the ink. Usually specially prepared papers or plastic foils with a dye-binding layer are used for this. Because of the fineness of the nozzles, pigments are hardly used, but mainly dyes that are completely dissolved in the inkjet medium. However, these dyes generally have a lower light fastness than the color pigments common in conventional printing inks. As a result, records made in inkjet printing can only be stored for a limited period under the influence of light. When stored in the light for a long time, they begin to fade or change color. To solve this problem, it has been proposed, for example, in US-A-4,256,493 to add a water-soluble UV absorber to the ink. Anionic UV absorbers of the benzophenone class, which contain sulphonate groups, were used to ensure compatibility with the mostly anionic dyes in the ink. However, such benzophenone derivatives and their salts have the disadvantage that they cause discoloration with certain dyes, especially black dyes. Furthermore, the addition of such additives can cause a reduction in the water resistance of the print, since the anionic UV absorbers compete with the anionic dye for the cationic mordants in the recording material.
Another problem with ink jet printing is the resistance of the printed recording material to water, which is related to the light fastness. If no or only inadequate countermeasures are taken, the dyes come off the recording material on contact with water and run. Furthermore, a diffusion of the dyes due to moisture can take place during the storage of the printed recording material. This leads to a reduction in the image quality.
It is also important that the inks, which are sprayed onto the recording material in rapid succession, as is the case, for example, with 4-color inkjet printing, do not run into one another and cause an unsharp image.
In order to solve the problem of water resistance, DE-A-3 640 359 proposes to provide an ink-receiving layer which contains a water-soluble polymer containing 2 to 30% by weight of a cationic resin. The cationic charges fix the mostly anionic dyes of the ink in the ink receiving layer. In US Pat. Nos. 4,659,382, 4,664,708, 4,680,332 and 4,705,567, it has already been proposed to react the anionic dyes with a cationic polymer. The insoluble product is then dispersed in the ink medium to give the resulting ink jet prints good water resistance. However, these undissolved, polymer-bound dyes increase the tendency to clog the ink nozzles.
From US Pat. No. 4,685,968 and EP-A-0 224 909 and 0 262 861 it is known that the nations can be replaced by an anionic dye and replaced by quaternary amines such as ammonium, quaternary alkanolamine and Amidoamine ions, an ink with improved water resistance and reduced tendency to nozzle clogging.
All previous proposals for the provision of a waterproof recording material for inkjet printing could only be achieved at the expense of lightfastness (see GF Bradley and HS Laver: Fastness of Ink-Jet Prints from Water-based inks, The Soc. Of Electrophotography of Japan, Japan, pp 167-169) 1988.
It has now been found that certain stabilizers which contain at least one quaternary ammonium group are effective light stabilizers and are particularly suitable for the stabilization of recording materials and inks, in particular for inkjet printing.
Cationic UV absorbers which contain at least one quaternary ammonium group are known. For example, JP-A-61-192 781 and 50-121 178 describe benztriazole type cationic UV absorbers, JP-A-61-192 778 benzophenone type and JP-A-61-192 780 2-cyanocinnamic acid -Type. They are used to protect coatings, varnishes, dyes, cosmetics and in cationic electroplating.
The present invention relates to a recording material containing at least one compound of the formula I as stabilizer<ul id="ul0001" list-style="none"><li>U (̵SOL) n '(I),</li><li>where n is a number from 1 to 4,</li><li>U is a residue of a UV absorber of the type hydroxyphenyl benzotriazole, cinnamic acid or hydroxyphenyl triazine,</li><li>SOL, the same or different, is a group of the formula la<chemistry id="chem0001" num="0001"><img file="EP0374751A2_D0001.tif" /></chemistry>means what</li><li>g represents 0 or 1,</li><li>A a direct bond, C<sub>1</sub>-C<sub>6</sub>Alkylene or alkylidene or a group of the formula Ib<chemistry id="chem0002" num="0002"><img file="EP0374751A2_D0002.tif" /></chemistry>means, where p is a number from 1 to 6,</li><li>Y is a direct bond or one of the following groups: -CO-, -COO-, -OOC-, -CO-N (R ') -, - (R') N-CO-, -S0<sub>2</sub>-N (R ') -, - (R') N-S0<sub>2</sub>-, <chemistry id="chem0003" num="0003"><img file="EP0374751A2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0374751A2_D0004.tif" /></chemistry>where n is a number from 1 to 4, B is a direct bond or a C which is optionally substituted by OH<sub>2</sub>-C<sub>6</sub>Alkylene or alkylidene, which may be replaced by one -O- or by one or two - <img file="EP0374751A2_D0005.tif" />X<sup>⊖</sup>(R ')<sub>2</sub>- is interrupted, or a group of formulas Ic or IC<chemistry id="chem0005" num="0005"><img file="EP0374751A2_D0006.tif" /></chemistry>is, or the group<chemistry id="chem0006" num="0006"><img file="EP0374751A2_D0007.tif" /></chemistry>represents a saturated or unsaturated 1 to 3-nucleus N-heterocycle which contains 1-4 N atoms as ring members, of which at least one is quaternized, under the conditions that</li></ul>
a) in the case of g = 1, A, Y and B do not simultaneously mean a direct bond;<ul id="ul0002" list-style="none"><li>b) in the case of g = 1 and A = direct bond, Y is -CO- or a direct bond; and</li><li>c) in the case of B = direct bond, Y is also a direct bond; R 'is hydrogen, C<sub>1</sub>-C<sub>4</sub>-Alkyl or C<sub>2</sub>-C<sub>3</sub>-Hydroxyalkyl is,<ul id="ul0003" list-style="none"><li>B ° - (CH2) ̵<sub>m</sub> or one of the following groups means:<chemistry id="chem0007" num="0007"><img file="EP0374751A2_D0008.tif" /></chemistry>where m and r are independently 2 or 3,</li><li>R<sub>33</sub> a meaning of R<sub>3</sub> has or for a group of formulas Id and le<chemistry id="chem0008" num="0008"><img file="EP0374751A2_D0009.tif" /></chemistry>where g, p, B, Y, A and U have the meaning given above,</li><li>R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> independently of one another hydrogen, Ci-Cs-alkyl or C substituted by a -COOR "or 1 to 3 OH<sub>1</sub>-C<sub>8</sub>-Alkyl, interrupted by one or more -O- C<sub>2</sub>-C<sub>8</sub>-Hydroxyalkyl, substituted with an OH - (C<sub>1</sub>-C<sub>8</sub>) Alkylene-COO⊖, - (C<sub>1</sub>-C<sub>8</sub>) Alkylidene COOe, - (C<sub>2</sub>-C<sub>8</sub>) Alkylene SO<sub>3</sub> or - (C<sub>2</sub>-C<sub>8</sub>) Alkylidene SO<img file="EP0374751A2_D0010.tif" />, C<sub>3</sub>-C<sub>5</sub>Alkenyl, C<sub>5</sub>-C<sub>7</sub>-Cycloalkyl, phenyl, tolyl, benzy or glycidyl, or Ri together with R.<sub>2</sub> and optionally with R<sub>3</sub>, together with the N atom to which they are bonded, form an N heterocycle which may contain 1-3 N atoms or an O atom as ring members,</li><li>R "is hydrogen or C<sub>1</sub>-C<sub>4</sub>-Alkyl is, and</li><li>X<sup>e</sup>, if not in Ri, R<sub>2</sub>, R<sub>3</sub> or R<sub>33</sub> present, means a colorless organic or inorganic anion.</li></ul></li></ul>
Preference is given to recording materials comprising a compound of the formula I in which I = 0 in the formula I, and in particular in which R33 in the formula Ia is an meaning of R.<sub>3</sub> Has. Very particularly preferred are those in which the formula Ia of a group of the formula If<chemistry id="chem0009" num="0009"><img file="EP0374751A2_D0011.tif" /></chemistry>corresponds, whereby Y ° -COO-, -CONH- or<chemistry id="chem0010" num="0010"><img file="EP0374751A2_D0012.tif" /></chemistry>means y is a number from 0 to 6, and p, B °, R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> have the aforementioned meaning.
Also preferred are recording materials in which the compound of the formula I is a compound of the formula II or III<chemistry id="chem0011" num="0011"><img file="EP0374751A2_D0013.tif" /></chemistry>corresponds to what<ul id="ul0004" list-style="none"><li>R<sub>4</sub> Halogen, C<sub>1</sub>-C<sub>4</sub>-Alkoxy, C<sub>1</sub>-C<sub>8</sub>-Alkyl, C<sub>5</sub>-C<sub>6</sub>-Cycloalkyl, phenyl, phenyl-C<sub>1</sub>-C<sub>4</sub>Is alkyl or a group of the formula Ia,</li><li>Rs and R<sub>6</sub> are independently hydrogen, or a meaning of R<sub>4</sub> to have,</li><li>R<sub>7</sub> OH, C<sub>1</sub>-C<sub>8</sub>Alkoxy, which can be substituted by 1 to 3 OH or 1 to 2 -COOH, C<sub>1</sub>-C<sub>8</sub>Alkanoyloxy, a group of the formula la with g = 1 or glycidyloxy,</li><li>provided that at least one of R<sub>4</sub>, Rs and R<sub>6</sub> in formula II and at least one of R<sub>6</sub> and R<sub>7</sub> in formula III stands for a group of formula la.</li></ul>
From this group, particular preference is given to those in which R<sub>4</sub> Halogen, C<sub>1</sub>-C<sub>5</sub>Is alkyl, cyclohexyl or a group of the formula Ia, R<sub>5</sub> Is hydrogen or a meaning of R<sub>4</sub> has, R<sub>6</sub> represents hydrogen, halogen or a group of the formula Ia, and R<sub>7</sub> OH, C optionally substituted with 1 to 3 OH<sub>1</sub>-C<sub>4</sub>-Alkoxy, glycidyloxy, C<sub>2</sub>-C<sub>3</sub>-Alkanoyloxy or a group of the formula Ia with g = 1.
Those in which in formula II R<sub>4</sub> C.<sub>1</sub>-C<sub>4</sub>-Alkyl or a group of the formula If<chemistry id="chem0012" num="0012"><img file="EP0374751A2_D0014.tif" /></chemistry>means Rs is hydrogen, C<sub>1</sub>-C<sub>4</sub>Is alkyl or a group If, and R<sub>6</sub> Is hydrogen, CI or the group If, in which y is O, and B °, Y °, Ri, R<sub>2</sub> and R<sub>3</sub> have the aforementioned meaning, provided that at least one of R<sub>4</sub>, Rs and R<sub>6</sub> represents a group of formula If.
Also of interest are recording materials in which the compound of formula I is a compound of formula V<chemistry id="chem0013" num="0013"><img file="EP0374751A2_D0015.tif" /></chemistry>corresponds to what<ul id="ul0005" list-style="none"><li>R,<sub>3</sub> Hydrogen, C<sub>1</sub>-C<sub>8</sub>-Alkyl, C<sub>3</sub>-Cs alkenyl, phenyl-Ci-C<sub>4</sub>-Alkyl or a group of the formula<chemistry id="chem0014" num="0014"><img file="EP0374751A2_D0016.tif" /></chemistry>means R<sub>14</sub> and R<sub>15</sub> independently of one another -C≡N, -CO-alkyl (C<sub>1</sub>-C<sub>4</sub>), -COO-R<sub>19</sub> or -CO-NO<sub>20</sub>R<sub>21</sub> mean R<sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>, R '<sub>16</sub>, R '<sub>17</sub> and R '<sub>18</sub> independently for hydrogen, C<sub>1</sub>-C<sub>4</sub>-Alkyl, phenyl, glycidyl, OH, halogen, optionally substituted with 1 to 3 OH<sub>1</sub>-C<sub>4</sub>-Alkoxy, phenoxy, benzyloxy or a group of the formula la, and</li><li>R<sub>19</sub>, R<sub>20</sub> and R<sub>21</sub> independently of one another hydrogen, C<sub>1</sub>-C<sub>4</sub>Alkyl, which is optionally substituted by 1 to 3 OH, C<sub>5</sub>-C<sub>7</sub>Cycloalkyl, phenyl, benzyl, tolyl, glycidyl or a group of the formula lg<chemistry id="chem0015" num="0015"><img file="EP0374751A2_D0017.tif" /></chemistry>mean, where B °, Ri, R<sub>2</sub> and R<sub>3</sub> have the aforementioned meaning, provided that at least one of R<sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>, R '<sub>16</sub>, R '<sub>17</sub> or R '<sub>18</sub> a group of the formula la or at least one of R<sub>19</sub>, R<sub>20</sub> or R<sub>21</sub> mean a group of the formula Ig.</li></ul>
Of particular interest are recording materials in which the compound of the formula V is a compound of the formula Va<chemistry id="chem0016" num="0016"><img file="EP0374751A2_D0018.tif" /></chemistry>corresponds to what<ul id="ul0006" list-style="none"><li>R<sub>13</sub> Hydrogen, C<sub>1</sub>-C<sub>4</sub>-Alkyl or a group<chemistry id="chem0017" num="0017"><img file="EP0374751A2_D0019.tif" /></chemistry>represents, and R<sub>14</sub>, R<sub>15</sub>, R<sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>, R '<sub>16</sub> R '<sub>17</sub> and R '<sub>18</sub> have the aforementioned meaning.</li></ul>
Also preferred are recording materials in which the compound of formula I is a compound of formula VI<chemistry id="chem0018" num="0018"><img file="EP0374751A2_D0020.tif" /></chemistry>where R<sub>22</sub> is a group of formula la with g = 1 and R<sub>23</sub>, R<sub>24</sub>, R<sub>25</sub>, R '<sub>23</sub>, R '<sub>24</sub> and R '<sub>25</sub> for hydrogen, OH, halogen, C<sub>1</sub>-C<sub>4</sub>-Alkoxy, C<sub>1</sub>-C<sub>4</sub>-Alkyl, phenyl or a group of formula la with g = 1.
Of these, recording materials are particularly preferred in which the compound of the formula VI is a compound of the formula Via<chemistry id="chem0019" num="0019"><img file="EP0374751A2_D0021.tif" /></chemistry>corresponds, and R<sub>22</sub> stands for a group of formula la with g = 1.
X<sup>e</sup> in the formula la preferably means halogens, in particular Cl<sup>⊖</sup> or Br<sup>e</sup>, C<sub>1</sub>-C<sub>4</sub>-Alkyl-COO<sup>⊖</sup>, C<sub>1</sub>-C<sub>4</sub>-Alkyl-OSO<img file="EP0374751A2_D0010.tif" /> or R<sup>O</sup>-SO<img file="EP0374751A2_D0010.tif" />, where R ° is methyl, tolyl or -CF<sub>3</sub> stands.
Any alkyl residues as C<sub>1</sub>-C<sub>4</sub>Alkyl means, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or t-butyl.
Any alkyl residues as C<sub>1</sub>-C<sub>8</sub>In addition to the meanings mentioned, alkyl can be, for example, n-pentyl, t-amyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl or 1,1,3,3-tetramethylbutyl.
R 'as C<sub>2</sub>-C<sub>3</sub>Hydroxyalkyl means, for example, 2-hydroxyethyl or 2-hydroxypropyl.
Any residues as C optionally substituted by 1 to 3 OH<sub>1</sub>-C<sub>8</sub>In addition to the meanings of R, alkyl can be, for example, hydroxymethyl, 3-hydr.oxybutyl, 2,3-dihydroxypropyl, 2,2-di (hydroxymethyl) propyl, 4-hydroxybutyl, 6-hydroxyhexyl, 8-hydroxyoctyl, 1, 2,4-trihydroxybut-2-yl, 1,2,6-trihydroxy-hex-2-yl, 1,2,3-trihydroxy-prop-2-yl.
R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> or R<sub>33</sub> as C interrupted by one or more -0-<sub>2</sub>-C<sub>8</sub>Hydroxyalkyl means, for example, 4-hydroxy-3-oxapropyl, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl or 11-hydroxy-3,6,9-trioxaundecyl.
B as C<sub>2</sub>-C<sub>6</sub>Alkylene of the alkylidene means, for example, ethylene, ethylidene, tri, tetra, penta- or hexamethylene, 1,2-propylene, 2,2-propylidene, 2,2-butylidene, 1,2-butylene or 2,2- Dimethyl-1,3-propylene.
A as C<sub>1</sub>-C<sub>6</sub>In addition to the meanings of B, alkylene or alkylidene can also be methylene.
Stand Ri, R<sub>2</sub> and R<sub>3</sub> for - (C<sub>2</sub>-C<sub>8</sub>) Alkylene SO<sub>3</sub>-, the alkylene radical can have the meaning of B and additionally mean heptamethylene, octamethylene or 3,3-dimethyl-1,5-pentylene.
Any alkoxy radicals can be, for example, methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, n-hexoxy, 2-ethylhexyloxy or n-octyloxy.
Any phenyl-C<sub>1</sub>-C<sub>4</sub>Alkyl radicals can be, for example, benzyl, 2-phenylethyl, 1-phenylethyl, 3-phenylpropyl or 2-phenylpropyl-2.
Means the group<chemistry id="chem0020" num="0020"><img file="EP0374751A2_D0022.tif" /></chemistry>an N-heterocycle, for example the following heterocycles are possible:<chemistry id="chem0021" num="0021"><img file="EP0374751A2_D0023.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP0374751A2_D0024.tif" /></chemistry>
Mean R, and R<sub>2</sub>, if necessary with R<sub>3</sub> together, an N-heterocycle, for example the following heterocycles are possible:<chemistry id="chem0023" num="0023"><img file="EP0374751A2_D0025.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP0374751A2_D0026.tif" /></chemistry>
Stand Ri, R<sub>2</sub> and R<sub>3</sub> for a -COOR "substituted C<sub>1</sub>-C<sub>8</sub>-Alkyl, the meaning of A as C can be for the alkyl part<sub>1</sub>-C<sub>6</sub>Alkylene or alkylidene come into question and additionally heptamethylene, octamethylene, 3-methyl-1,1-butylidene or 2-methyl-1,1-butylidene.
B as an optionally substituted with OH<sub>2</sub>-C<sub>s</sub>Alkylene or alkylidene, which may be replaced by one or one or two <img file="EP0374751A2_D0005.tif" />(R ')<sub>2</sub>- is interrupted means a residue in which between 2 X<sup>⊖</sup>-Heteroatoms are at least 2 carbon atoms, such as 3-oxa-1,5-pentylene, 4-oxa-1,7-heptylene, 3-0xa-2,4-dimethyl-1,5-pentylene, 2 -Hydroxy-1,3-propylene, 3-hydroxy-1,5-pentylene, 4-hydroxy-1,6-hexylene, quaternized 3-aza-1,5-pentylene, 4-aza-1,7-heptylene, 2,5-diaza-1,6-hexylene, 2,5-diaza-1,7-heptylene, 3,5-diaza-1,6-hexylene or 3,6-diaza-1,8-octylene, 4- Oxa-2,6-dihydroxy-1,7-heptylene, 3-oxa-5-hydroxy-1,6-hexylene, quaternized 3,6-diaza-5-hydroxy-1,8-octylene or 2-hydroxy-4-aza-1,7-heptylene.
R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> as a substituted by an OH - (C<sub>1</sub>-C<sub>8</sub>) Alkylene COO<sup>⊖</sup> or - (C<sub>1</sub>-C<sub>8</sub>) Alkylidene COO<sup>⊖</sup> mean, for example, 1-hydroxy-3-carboxypropylene, 2-hydroxy-4-carboxy-butylene, 1-carboxy-2-hydroxyethyl-1-idene, 1-carboxy-2-hydroxypropyl-1-idene or 2-hydroxy- 8-carboxyoctylene.
R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> as C<sub>3</sub>-C<sub>5</sub>Alkenyl means, for example, allyl, methallyl, n-but-2-enyl, 2-methyl-prop-2-enyl or n-pent-2-enyl. Any C<sub>3</sub>-C<sub>8</sub>-Alkenyl radicals can additionally be n-hexenyl, n-heptenyl, n-octenyl or 2,5-dimethyl-3-hexenyl.
Any cycloalkyl radicals as C<sub>5</sub>-C<sub>7</sub>Cycloalkyl mean, for example, cyclopentyl, cyclooctyl, cyclohexyl or cycloheptyl.
The following examples of compounds of formula I illustrate the invention:<chemistry id="chem0025" num="0025"><img file="EP0374751A2_D0027.tif" /></chemistry><tables id="tabl0001" num="0001"><img file="EP0374751A2_D0028.tif" /></tables><chemistry id="chem0026" num="0026"><img file="EP0374751A2_D0029.tif" /></chemistry>Further examples:<chemistry id="chem0027" num="0027"><img file="EP0374751A2_D0030.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP0374751A2_D0031.tif" /></chemistry>
The water-soluble compounds of formula I can be prepared, for example, by 1 molar equivalent of a compound of formula Ih<chemistry id="chem0029" num="0029"><img file="EP0374751A2_D0032.tif" /></chemistry>with n molar equivalent of a quaternizing agent of the formula R.<sub>33</sub>-X quaternized, where U, A, Y, B, R<sub>1</sub>, R<sub>2</sub>, R<sub>33</sub>, X, g and n have the meaning given above.
The quaternization can be carried out at temperatures of 0-1800 C, preferably at 30-140 C.
As quaternizing agent R<sub>33</sub>The following compounds are suitable, for example: alkyl halides, such as methyl chloride, ethyl bromide, butyl bromide or benzyl chloride, dialkyl sulfates, such as dimethyl or diethyl sulfate, sulfonic acid esters, such as methyl or ethyl toluene or benzosulfonate, or epichlorohydrin, alkyl chlorides being particularly preferred.
The quaternization with alkyl halides, dialkyl sulfates or sulfonic acid esters to give the compounds of the formula I is expediently carried out in a solvent or solvent mixture which is inert to the quaternizing agent. Suitable solvents are, for example Hydrocarbons, such as benzene, toluene and xylene, halogenated aliphatic or aromatic hydrocarbons, such as methylene chloride, chloroform, ethylene chloride, chlorobenzene and dichlorobenzene, alcohols, such as ethanol, butanol and ethylene glycol, ethers, such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether and dioxane, amides, such as dimethylformamide and N-methylpoxide or ketones, such as acetone.
The quaternization with epichlorohydrin is carried out at the temperatures mentioned in an acidic medium, advantageously in the presence of an organic acid such as formic acid, acetic acid, propionic acid or benzoic acid, but inorganic acids such as sulfuric acid, phosphoric acid or hydrohalic acids can also be used for this. These inorganic acids can be used in concentrated, commercially available form as dilute aqueous solutions or in a mixture with the organic solvents mentioned, if appropriate with the addition of water. If the reaction is carried out in the presence of organic acids, the concentrated form of these acids is usually used, if appropriate in a mixture with the organic solvents mentioned.
Some of the starting compounds of the formula Ih are commercially available or can be prepared by known methods.
The recording materials according to the invention are suitable for pressure-sensitive copying systems, photocopying systems with microcapsules, heat-sensitive copying systems, photographic materials and preferably for inkjet printing.
The recording materials according to the invention are characterized by unexpected quality improvements. Inkjet printing can take place without coagulation of the casting compound, while at the same time improving the lightfastness and washfastness.
The recording materials according to the invention have the structure known for the respective application. They consist of a common carrier, for example paper or plastic film, which is coated with one or more layers. Depending on the type of material, these layers contain the necessary components, such as in the case of photographic materials, silver halide emulsions, color couplers, dyes, etc. Material which is particularly suitable for inkjet printing has a layer which is particularly receptive to ink on a conventional carrier.
Uncoated inkjet paper can also be used. Here the paper serves both as a carrier material and an ink receiving layer.
The recording material can also be transparent, as in the case of projection foils.
The compounds of the formula I can already be incorporated into the carrier material during the production thereof, for example when adding paper to the paper pulp. A second method of application is spraying the carrier material with an aqueous solution of the compounds of the formula I.
Usually, however, a dye-affine layer is applied to the carrier material and in this case the compounds of formula I are added to this coating composition. The coating compositions usually consist of a solid filler and a binder, as well as smaller proportions of additives.
The filler is the main quantitative component of the coating composition. Examples of fillers that can be used are silica, kaolin, talc, clay, Ca, Mg or Al silicates, gypsum, zeolite, bentonite, diatomaceous earth, vermiculite, starch or those described in JP-A-60-260 377 described surface-modified silica. Small amounts of white pigments, such as Titanium dioxide, barite, magnesium oxide, lime, chalk or magnesium carbonate can be used with the filler in the coating composition, provided that they do not reduce the density of the ink jet print too much.
Coating compositions intended for transparent, projection-capable recording materials cannot contain light-scattering particles, such as pigments and fillers.
The binder binds the fillers to themselves and to the carrier material. Examples of common binders are water-soluble polymers, such as Polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, cellulose ether, polyvinyl pyrrolidone and its copolymers, polyethylene oxide, salts of polyacrylic acid, sodium alginate, oxidized starch, gelatin, casein, vegetable rubber, dextrin, albumin, dispersions of polyacrylates or acrylate-methacrylate copolymers, latices of Natural or synthetic rubber, poly (meth) acrylamide, polyvinyl ether, polyvinyl ester, copolymers of maleic acid, melamine resins, Urea resins or chemically modified polyvinyl alcohols, as described in JP-A-61-134 290 or 61-134 291.
Although the compounds of the formula I impart washfastness to inkjet printing, an additional dye receptor or mordant can be added to the binder, which fix the dye more firmly to the coating. Dye receptors for acid dyes are cationic or amphoteric in nature. Examples of cationic receptors are polymeric ammonium compounds, such as Polyvinylbenzyl trimethyl ammonium chloride, polydiallyl dimethyl ammonium chloride, polymethacryloxyethyl dimethyl<sub>-</sub>hydroxyethylammonium chloride, polyvinylbenzylmethylimidazolium chloride, polyvinylbenzylpicolinium chloride or polyvinylbenzyltributylammonium chloride. Other examples are basic polymers, such as Poly (dimethylaminoethyl) methacrylate, polyalkylene polyamines and their condensation products with dicyandiamide, amine-epichlorohydrin polycondensates or those described in JP-A-57-36 692, 57-64 591, 57-187 289, 57-191 084, 58-177 390, 58-208 357, 59-20 696, 59-33 176, 59-96 987, 59-198 188, 60-49 990, 60-71 796, 60-72 785, 60-161 188, 60-187 582, 60-189 481, 60-189 482, 61-14 979, 61-43 593, 61-57 379, 61-57 380, 61-58 788, 61-61 887, 61-63 477, 61-72 581, 61-95 977, 61-134 291 or in the compounds described in US-4,547,405 and 4,554,181 and in DE-A-3,417,582. An example of amphoteric dye receptors is gelatin.
The dye-binding coating can contain a number of other additives, such as, for example, antioxidants, light stabilizers (including UV absorbers which do not belong to the UV absorbers according to the invention), viscosity improvers, optical brighteners, biocides or / and antistatic agents.
Examples of suitable antioxidants are, in particular, sterically hindered phenols and hydroquinones, such as, for example, the antioxidants listed in GB-A-2 088 777 or JP-A-60-72 785, 60-72 786 and 60-71 796.
Examples of suitable light stabilizers are in particular organic nickel compounds and sterically hindered amines, such as, for example, those in JP-A-58-152 072, 61-146 591, 61-163 886, 60-72 785 and 61-146 591 or those in GB-A-2 088 777, JP-A-59-169 883 and 61-177 279 mentioned light stabilizers.
Additional UV absorbers can be added to the coating composition for inkjet printing, for example UV absorbers as described in Research Disclosure No. 24239 (1984) p. 284, GB-A-2 088 777 and EP-A-0 280 650.
In most cases, however, thanks to the high light fastness conferred by the compounds of formula I, an additional UV absorber can be dispensed with.
In order to ensure a good dispersion of the fillers and additives or to influence the casting properties or the rheology of the coating composition, surfactants can be added to the latter. Suitable surfactants are only those of a nonionic, amphoteric or cationic nature, but not anionic, since the compounds of the formula I themselves are cationic.
Examples of non-ionic surfactants are esters or ethers of polyethylene oxides or polypropylene oxides or of their copolymers, fatty acid alkanolamides, ethoxylated alkanolamides, partial fatty acid esters of polyols (for example of glycerol, polyglycerol, sorbitol, pentaerythritol or sucrose), N-alkylmorpholines or long-chain amine oxides .
Examples of amphoteric surfactants are fatty acid amidoalkyl betaine, fatty acid amidoalkyl sultaine, fatty acid imidazoline betaine, N-alkyl-ß-aminopropionic acid or alkylene bis (amidoalkylglycinate).
Examples of cationic surfactants are the quaternary ammonium salts of long-chain fatty amines and benzylamines, imidazolinium, pyridinium, picolinium or morpholinium salts with long-chain alkyl radicals, quaternary ammonium salts of long-chain alkylamido-alkylamines or bis-ammonium salts of quaternary diamines.
The coating composition is usually prepared as follows: the water-soluble components, such as the binder, are dissolved in water and stirred together. The solid components, such as fillers and other additives already described, are dispersed in this aqueous medium. The dispersion is advantageously carried out with the aid of devices such as ultrasound samples. Turbo stirrers, homogenizers, colloid mills, bead mills, sand mills, high speed stirrers and the like.
It is a particular advantage of the compounds of the formula I that they can be easily incorporated into the coating composition. Since they are water-soluble, the compounds of the formula I can simply be added to the binder solution or stirred directly into the coating composition. The shredding process or emulsification process, as is necessary with conventional UV absorbers, is not required here.
The coating composition is applied to the carrier, which is usually paper, and dried by heating. As already mentioned, the compounds of the formula I can also be applied to the recording material as an aqueous solution in a separate operation, alone or together with other components already described. It can be applied by spraying, gluing in a gluing press, a separate casting process or by immersing it in a tub. After such post-treatment of the recording material, an additional drying process is of course necessary.
The process for the preparation of the recording material for inkjet printing, which is stabilized against light damage, is also an object of the present invention and is characterized in that a two-dimensional support is coated with a coating composition which comprises at least one compound of the formula I. This recording material not only has a good absorption capacity for inkjet printing inks, it also gives the printed dye high lightfastness and water resistance.
The recording material thus prepared preferably contains 1 to 5000 mg / m<sup>2</sup>, in particular 50-1200 mg / m<sup>2</sup>, a compound of formula I.
With the recording materials according to the invention, it does not matter what type the ink and the dye dissolved in it and what type of printing device (printer) is used.
In the printers used today, a distinction is made between those with a continuous ink jet and drop-on-demand printers, especially bubble-jet printers. The recording material according to the invention can be used for all of these apparatus methods.
The inks are mostly aqueous inks, but they can also be solutions of the dye in an organic solvent or in a molten wax. Aqueous inks usually still contain water-soluble solvents, such as Mono-, di-, tri- or higher ethylene glycols, propylene glycol, 1,4-butanediol, or ethers of such glycols, thiodiglycol, glycerol and its ethers and esters, polyglycerol, mono-, di- and triethanolamine, propanolamine, dimethylformamide, dimethyl sulfoxide, Dimethylacetamide, N-methylpyrrolidone, 1,3-dimethylimidazolidone, methanol, ethanol, isopropanol, n-propanol, diacetone alcohol, acetone, methyl ethyl ketone or propylene carbonate.
Aqueous inks contain water-soluble dyes, which are also known for dyeing natural fibers. These can be, for example, monoazo, diazo or polyazo dyes or reactive dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes. Examples include CI Food Black 2, CI Direct Black 19, CI Direct Black 38, CI Direct Black 168, CI Sulfur Black 1, GI Acid Red 35, CI Acid Red 249, CI Direct Red 227, CI Acid Yellow 23, CI Direct Yellow 86, CI Acid Blue 9, CI Direct Blue 86 or CI Direct Blue 199, CI Acid Red 14, CI Acid Red 52, CI Reactive Red 40, CI Direct Yellow 107, CI Direct Black 154.
Aqueous inks can also contain various additives in smaller quantities, such as binders, surfactants, biocides, corrosion inhibitors, sequestering agents, pH buffers or conductivity additives. They can also contain anionic water-soluble UV absorbers or other water-soluble light stabilizers. In general, however, the addition of a UV absorber according to the invention to the recording material is sufficient.
If the ink is a non-aqueous ink, it is a solution of the dye in an organic solvent or solvent mixture. Examples of solvents used for this are alkyl carbitols, alkyl cellosolves, dialkylformamides, dialkylacetamides, alcohols, especially alcohols with 1-4 C atoms, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, di-isopropyl ketone, dibutyl ketone, dioxane, ethyl butyrate, ethyl isovalerate, diethyl malonate, diethyl succinate, methyl pelargonate, butyl acetate, triethyl phosphate, ethyl glycol acetate, toluene, xylene, tetralin, gasoline fractions. Examples of solid waxes as solvents are stearic or palmitic acid.
Such solvent-based inks contain soluble dyes such as solvent red, solvent yellow, solvent orange, solvent blue, solvent green, solvent violet, solvent brown or solvent black. Such inks can also contain other additives, such as binders, antioxidants or biocides.
As already mentioned, the recording materials according to the invention encompass a wide field. The compounds of formula I can be used, for example, in pressure-sensitive copying systems. They can be introduced into the paper in order to protect the microcapsulated dye precursors from light there, and also into the binder of the developer layer in order to protect the dyes which are formed there.
Photocopier systems with photosensitive microcapsules that are developed with printing are described in U.S. Patents 4,416,966, 4,483,912, 4,532,200, 4,535,050, 4,565,463, 4,551,407, 4,562,137, 4,608,330 and in EP-A-139 479, EP-A-162 664, EP-A-164-931, EP-A-237 024, EP-A-237 025 or EP-A-260 129. In all of these systems, the compounds of formula 1 can be used in the dye-receiving layer. However, the compounds of the formula I can also be used in the donor layer in order to protect the color formers from light.
Photographic materials that can be stabilized are photographic dyes and layers containing such dyes or their precursors, for example photographic papers and films. The compounds of the formula I act here as antistatic agents, which increase the conductivity of the gelatin layer, and at the same time as a UV filter against electrostatic flashes. In color photographic materials, couplers and dyes are also protected against photochemical degradation.
The compounds of the formula I can also be used in recording materials which are based on the principles of photopolymerization, photoplastification or the breaking of microcapsules, or where heat- and light-sensitive diazonium salts, leuco dyes with oxidizing agents or dye lactones with Lewis acids are used.
They can also be used in recording materials for dye diffusion transfer, thermal wax transfer and dot matrix printing, and for use with electrostatic, electrographic, electrophoretic, magnetographic and laser electrophotographic printers and pen plotters.
The compounds of the formula I can also be used in inks, preferably for ink jet printing. The water resistance of inkjet printing is surprisingly improved. This fact is probably due to the formation of a poorly soluble salt from the anionic dye and the cationic stabilizer of the formula I. It has been found that aqueous inkjet printing inks can be prepared from one or more anionic dyes and one or more compounds of the formula I, in particular if either the anionic or the cationic components are present in sufficient excess.
It is therefore a further subject of the present invention an ink containing as a stabilizer at least one compound of formula I.
The ink, especially for inkjet printing, preferably contains water. Inks which contain the stabilizer of the formula I in a concentration of 0.01 to 20% by weight, in particular 0.5 to 10% by weight, are also preferred.
In the inks according to the invention, preference is given to using those compounds of the formula I which have also been indicated as preferred for the recording materials described above.
Some of the compounds of the formula I in the recording materials according to the invention are new and are therefore also an object of the present invention.
The invention therefore relates to compounds of the formula I °<ul id="ul0007" list-style="none"><li>U (̵SOL °)<sub>n</sub> (I °),</li><li>where n is a number from 1 to 4,</li><li>U is a residue of a UV absorber of the hydroxyphenyl-benzotriazole, hydroxybenzophenone, cinnamic acid or hydroxyphenyl-triazine type,</li><li>SOL °, identical or different, a group of formula I ° a<chemistry id="chem0030" num="0030"><img file="EP0374751A2_D0033.tif" /></chemistry>means what</li><li>g represents 0 or 1,</li><li>A a direct bond, C<sub>1</sub>-C<sub>6</sub>-Alkylene or a group of formula I ° b<chemistry id="chem0031" num="0031"><img file="EP0374751A2_D0034.tif" /></chemistry>means, where p is a number from 1 to 6,</li><li>Y is a direct bond or one of the following groups:</li><li>-CO-, -COO-, -OOC-, -CO-N (R ') -, - (R') N-CO-, -S0<sub>2</sub>-N (R ') -, - (R') N-S0<sub>2</sub>-, <chemistry id="chem0032" num="0032"><img file="EP0374751A2_D0035.tif" /></chemistry>or<chemistry id="chem0033" num="0033"><img file="EP0374751A2_D0036.tif" /></chemistry>B is a direct bond or a C optionally substituted with OH<sub>2</sub>-C<sub>6</sub>-Alkylene, which may be replaced by one -O- or by one or two - <img file="EP0374751A2_D0005.tif" />X<sup>⊖</sup>(R ')<sub>2</sub>- is interrupted, or a group of the formulas I ° C or I ° C<chemistry id="chem0034" num="0034"><img file="EP0374751A2_D0037.tif" /></chemistry>is, or the group<chemistry id="chem0035" num="0035"><img file="EP0374751A2_D0038.tif" /></chemistry>represents a saturated or unsaturated 1 to 3-nucleus N-heterocycle which contains 1-4 N atoms as ring members, at least one of which is quaternized, forms a heterocycle which contains 1 to 3 N atoms, under the conditions that<ul id="ul0008" list-style="none"><li>a) in the case of g = 1, A, Y and B do not simultaneously mean a direct bond;</li><li>b) in the case of g = 1 and A = direct bond, Y is -CO- or a direct bond; and</li><li>c) in the case of B = a direct bond, also Y is a direct bond, R is hydrogen, C<sub>1</sub>-C<sub>4</sub>-Alkyl or C<sub>2</sub>-C<sub>3</sub>-Hydroxyalkyl is,</li></ul></li><li>B ° - (CH<sub>2</sub>)̵<sub>m</sub> or one of the following groups means:<chemistry id="chem0036" num="0036"><img file="EP0374751A2_D0039.tif" /></chemistry>where m and r are independently 2 or 3,</li><li>R<sub>33</sub> a meaning of R<sub>3</sub> has or for a group of the formulas I ° d and I ° e<chemistry id="chem0037" num="0037"><img file="EP0374751A2_D0040.tif" /></chemistry>where g, p, B, Y, A and U have the meaning given above, R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> independently of each other C<sub>1</sub>-C<sub>8</sub>-Alkyl, or C-substituted by a -COOR or 1 to 3 OH<sub>1</sub>-C<sub>8</sub>-Alkyl, interrupted by one or more -0-C<sub>2</sub>-C<sub>8</sub>-Hydroxyalkyl, optionally substituted with an OH - (C<sub>1</sub>-C<sub>8</sub>) Alkylene COO<sup>e</sup>, - (C<sub>1</sub>-C<sub>8</sub>) Alkylidene COO<sup>⊖</sup>, - (C<sub>2</sub>-C<sub>8</sub>) Alkylene SO<img file="EP0374751A2_D0010.tif" /> or - (C<sub>2</sub>-C<sub>8</sub>) Alkylidene SO<img file="EP0374751A2_D0041.tif" />, C<sub>3</sub>-C<sub>5</sub>Alkenyl, C<sub>5</sub>-C<sub>7</sub>-Cycloalkyl, P henyl, tolyl, benzyl or glycidyl, or R<sub>1</sub> together with R<sub>2</sub> and optionally with R<sub>3</sub> as well as together with the <img file="EP0374751A2_D0005.tif" />Atom to which they are attached form an N-heterocycle which may contain 1-3 N atoms or a 0 atom as ring members,</li><li>R "is hydrogen or C<sub>1</sub>-C<sub>4</sub>-Alkyl is, and</li><li>X<sup>e</sup>, if not in R<sub>1</sub>, R<sub>2</sub>, R<sub>3</sub> or R<sub>33</sub> present, an organic or inorganic anion means, under the conditions that<ul id="ul0009" list-style="none"><li>A) in the case of U is a radical of the hydroxyphenyl-benzotriazole type and n in the formula is 1 °, Y in the formula Ia is Y.<sub>1</sub> where Y<sub>1</sub> is one of the following groups:<chemistry id="chem0038" num="0038"><img file="EP0374751A2_D0042.tif" /></chemistry><chemistry id="chem0039" num="0039"><img file="EP0374751A2_D0043.tif" /></chemistry></li><li>B) in the case of U is a radical of the hydroxybenzophenone type and n in the formula I ° 1 or 2, g = 0;</li><li>C) in the case of U represents a cinnamic acid residue with 1 or 2 -C≡N groups, n in the formula I ° 3 or 4; or</li><li>D) in the case of U stands for a hydroxyphenyl-triazine residue and in the formula I ° ag = 1, A = alkylene and Y mean a direct bond, B cannot stand for a direct bond or alkylene, or if g = 1 and A one mean direct bond, Y cannot be -CO-.</li></ul></li></ul>
The possible meanings for R given above under the formula<sub>1</sub>, R<sub>2</sub>, R<sub>3</sub>"R ', R", A, Y and B also apply here.
Compounds of the formula I ° are preferred, those of a compound of the formula II ° or III °<chemistry id="chem0040" num="0040"><img file="EP0374751A2_D0044.tif" /></chemistry>correspond to what<ul id="ul0010" list-style="none"><li>R<sub>4</sub> Halogen, C<sub>1</sub>-C<sub>4</sub>-Alkoxy, C<sub>1</sub>-C<sub>8</sub>-Alkyl, C<sub>5</sub>-C<sub>6</sub>-Cycloalkyl, phenyl, phenyl-C<sub>1</sub>-C<sub>4</sub>Is alkyl or a group of the formula I ° a,</li><li>R<sub>5</sub> and R<sub>6</sub> are independently hydrogen or a meaning of R<sub>4</sub> to have,</li><li>R<sub>7</sub> OH, C<sub>1</sub>-C<sub>8</sub>Alkoxy, which can be substituted by 1 to 3 OH or 1 to 2 -COOH, C<sub>1</sub>-C<sub>8</sub>Alkanoyloxy, a group of the formula I ° a with g = 1 or glycidyloxy,</li><li>provided that at least one of R<sub>4</sub>, Rs and R<sub>6</sub> in the formula II ° and at least one of R<sub>s</sub> and R<sub>7</sub> in formula III stands for a group of formula I ° a.</li></ul>
Among these, particular preference is given to those compounds of the formula I ° in which R<sub>4</sub> Halogen, C<sub>1</sub>-C<sub>5</sub>-Alkyl, cyclohexyl or a group of the formula I ° a, R<sub>5</sub> Is hydrogen or a meaning of R<sub>4</sub> has, R<sub>s</sub> represents hydrogen, halogen or a group of the formula I ° a, and R<sub>7</sub> OH, C optionally substituted with 1 to 3 OH or with 1 to 2 COOH<sub>1</sub>-C<sub>4</sub>-Alkoxy, glycidyloxy, C<sub>2</sub>-C<sub>3</sub>-Alkanoyloxy or a group of the formula I ° a with g = 1, and in particular in which in the formula II ° R<sub>4</sub> C.<sub>1</sub>-C<sub>4</sub>-Alkyl or a group of formula I ° f<chemistry id="chem0041" num="0041"><img file="EP0374751A2_D0045.tif" /></chemistry>means<ul id="ul0011" list-style="none"><li>R<sub>s</sub> Hydrogen, C<sub>1</sub>-C<sub>4</sub>-Alkyl or a group I ° f, and R<sub>s</sub> Is hydrogen, CI or a group I ° f, where y is 0, provided that at least one of R<sub>4</sub>, R<sub>5</sub> and R<sub>6</sub> represents a group I ° f.</li></ul>
Also of interest are V-compounds of the formula I °, those of a compound of the formula V °<chemistry id="chem0042" num="0042"><img file="EP0374751A2_D0046.tif" /></chemistry>correspond to what<ul id="ul0012" list-style="none"><li>R<sub>13</sub> Hydrogen, C<sub>1</sub>-C<sub>8</sub>-Alkyl, C<sub>3</sub>-C<sub>8</sub>-Alkenyl, phenyl-C<sub>1</sub>-C<sub>4</sub>-Alkyl or a group of the formula<chemistry id="chem0043" num="0043"><img file="EP0374751A2_D0047.tif" /></chemistry>means R<sub>14</sub> and R<sub>15</sub> independently of one another -C≡N, -CO-C<sub>1</sub>-C<sub>4</sub>-Alkyl, -COO-R<sub>19</sub> or -CO-NO<sub>20</sub>R<sub>21</sub> mean R<sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>, R '<sub>16</sub>, R '<sub>17</sub> and R '<sub>18</sub> independently for hydrogen, C<sub>1</sub>-C<sub>4</sub>-Alkyl, phenyl, glycidyl, OH, halogen, optionally substituted with 1 to 3 OH<sub>1</sub>-C<sub>4</sub>-Alkoxy, phenoxy, benzyloxy or a group of the formula I ° a, and</li><li>R<sub>19</sub>, R<sub>20</sub> and R<sub>21</sub> independently of one another hydrogen, C<sub>1</sub>-C<sub>4</sub>Alkyl, which is optionally substituted by 1 to 3 OH, C<sub>s</sub>-C<sub>7</sub>-Cycloalkyl, phenyl, benzyl, tolyl, glycidyl or a group of formula I ° g<chemistry id="chem0044" num="0044"><img file="EP0374751A2_D0048.tif" /></chemistry>mean, where B °, Ri, R<sub>2</sub> and R<sub>3</sub> have the aforementioned meaning, provided that at least one of R<sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>, R '<sub>16</sub>, R '<sub>17</sub> or R '<sub>18</sub> a group of formula I ° a and at least one of R<sub>19</sub>, R<sub>20</sub> or R<sub>21</sub> is a group of the formula I ° g, and if R<sub>14</sub> and / or R<sub>15</sub> represent -C≡N, at least 3 groups of the formula I ° a and / or I ° g are present.</li></ul>
Of particular interest are those that a compound of formula V ° a<chemistry id="chem0045" num="0045"><img file="EP0374751A2_D0049.tif" /></chemistry>correspond to what<ul id="ul0013" list-style="none"><li>R<sub>13</sub> Hydrogen, C<sub>1</sub>-C<sub>4</sub>-Alkyl or a group<chemistry id="chem0046" num="0046"><img file="EP0374751A2_D0050.tif" /></chemistry>represents, and R<sub>14</sub>, R<sub>15</sub>, R<sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>, R '<sub>16</sub>, R '<sub>17</sub> and R '<sub>18</sub> have the aforementioned meaning.</li></ul>
Also of interest are compounds of formula 1 °, those of a compound of formula VI °<chemistry id="chem0047" num="0047"><img file="EP0374751A2_D0051.tif" /></chemistry>correspond in which R<sub>22</sub> is a group of formula I ° a with g = 1 and R<sub>23</sub>, R<sub>24</sub>, R<sub>25</sub>, R<sub>23</sub>, R<sub>24</sub> and R '<sub>25</sub> for hydrogen, OH, halogen, C<sub>1</sub>-C<sub>4</sub>-Alkoxy, C<sub>1</sub>-C<sub>4</sub>-Alkyl, phenyl or a group of the formula I ° a with g = 1, provided that if in the formula I ° ag = 1, A = alkylene and Y are a direct bond, B is not a direct bond or Alkylene, or if g = 1 and A signify a direct bond, Y cannot be -CO-.
Of particular interest are those that a compound of formula VI ° a<chemistry id="chem0048" num="0048"><img file="EP0374751A2_D0052.tif" /></chemistry>correspond, and R<sub>22</sub> for a group of Formula 1<sup>0</sup>a stands with g = 1.
Compounds of the formula I ° are preferred in which X<sup>S</sup> in the formula I ° a halogens, C<sub>1</sub>-C<sub>4</sub>-Alkyl-COO<sup>⊖</sup>, C<sub>1</sub>-C<sub>4</sub>-Alkyl-OSO<img file="EP0374751A2_D0010.tif" /> or R<sup>0</sup>-SO<img file="EP0374751A2_D0010.tif" /> means, where R ° is methyl, tolyl or -CF<sub>3</sub> stands.
As already described, the new compounds of the formula I ° can be prepared by methods known per se.
The new compounds of formula I ° can be used as stabilizers for organic materials, in particular against their damage by light, oxygen and heat. The materials to be stabilized can be, for example, oils, fats, waxes, cosmetics, dyes or polymers. Due to their structure, they are advantageous for cathodic electrophoretic coating as well as in water-based paints and protective coatings.
The new compounds of the formula I ° are preferably used as stabilizers for recording materials or inks for inkjet printing.
Examples of polymers which can advantageously be stabilized with the compounds of the formula I according to the invention are:<ul id="ul0014" list-style="none"><li>1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene and polymers of cycloolefins such as cyclopentene or norbornene; also polyethylene (which may or may not be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE).</li><li>2nd Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).</li><li>3rd Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as, for example Ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene Copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; furthermore mixtures of such copolymers with one another and with polymers mentioned under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers and LLDPE / ethylene Aerylic acid copolymers.</li><li>3a. Hydrocarbon resins (e.g. Cs-Cs) including hydrogenated modifications thereof (e.g. tackifier resins).</li><li>4th Polystyrene, poly- (p-methylstyrene), poly- (a-methylstyrene).</li><li>5. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, a polyarylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene ..</li><li>6. Graft copolymers of styrene or a-methylstyrene, such as styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene, styrene and alkyl acrylates or Alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkylacrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their mixtures with the copolymers mentioned under 5), as described, for example, as so-called ABS, MBS, ASA or AES polymers are known.</li><li>7. Halogen-containing polymers, such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, in particular polymers made from halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl. acetate.</li><li>8th. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.</li><li>9. Copolymers of the monomers mentioned under 8) with one another or with other unsaturated monomers, such as, for example, acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene-butadiene.</li><li>10th Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallylphthalate, polyallylmelamine; as well as their copolymers with olefins mentioned in point 1.</li><li>11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers.</li><li>12th Polyacetals, such as polyoxymethylene, and also those polyoxymethylenes which contain comonomers, such as, for example, ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.</li><li>13. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides.</li><li>14. Polyurethanes derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and their precursors.</li><li>15. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides made from hexamethylenediamine and iso- and / or terephthalic acid and optionally an elastomer as a modifier, for example Poly-2,4,4-trimethylhexamethylene terephthalamide, poly-m-phenylene-isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomeric or chemically bonded or grafted elastomers; or with polyethers, such as with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Furthermore, polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (“RIM polyamide systems”).</li><li>16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.</li><li>17th Polyesters which are derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters which are derived from polyethers having hydroxyl end groups; furthermore polyesters modified with polycarbonates or MBS.</li><li>18th Polycarbonates and polyester carbonates.</li><li>19th Polysulfones, polyether sulfones and polyether ketones.</li><li>20th Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.</li><li>21. Drying and non-drying alkyd resins.</li><li>22. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications.</li><li>23. Crosslinkable acrylic resins derived from substituted acrylic esters, such as epoxy acrylates, urethane acrylates or polyester acrylates.</li><li>24th Alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.</li><li>25th Crosslinked epoxy resins derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic diepoxides.</li><li>26. Natural polymers, such as cellulose, natural rubber, gelatin, and their polymer-homologously chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose; as well as rosins and derivatives.</li><li>27 Mixtures (polyblends) of the aforementioned polymers, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.</li><li>28 Natural and synthetic organic substances, which are pure monomeric compounds or mixtures thereof, for example mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates), as well as Mixtures of synthetic esters with mineral oils in any weight ratios, such as those used as spin finishes, and their aqueous emulsions.</li><li>29. Aqueous emulsions of natural or synthetic rubbers, such as natural rubber latex or latices of carboxylated styrene-butadiene copolymers.</li></ul>
The stabilizers according to the invention are expediently added to the polymers in a concentration of 0.01-10% by weight, calculated on the material to be stabilized. Preferably 0.05 to 5.0 wt .-%, particularly preferably 0.1 to 2.0 wt .-% of the compounds of formula 1, calculated on the material to be stabilized, incorporated into this.
The incorporation can be carried out, for example, by mixing in the stabilizers according to the invention and, if appropriate, further additives by the methods customary in industry, before or during shaping, or else by applying the dissolved or dispersed compounds to the polymer, if appropriate with subsequent evaporation of the solvent. The stabilizers according to the invention can also be added to the plastics to be stabilized in the form of a masterbatch which contains the stabilizer, for example in a concentration of 2.5 to 25% by weight.
The compounds of the formula I ° can also be added before or during the polymerization or the crosslinking reaction. In this way, directly stabilized polymers are obtained.
The materials stabilized in this way can be used in a wide variety of forms, for example as films, fibers, tapes, molding compounds, profiles or as binders for paints, adhesives or putties.
The use of the compounds according to the invention is particularly preferred in lacquers of all kinds. These can be pigmented or unpigmented lacquers or metallic effect lacquers. They can contain an organic solvent or be solvent-free or be aqueous lacquers. Of particular importance is the use of aqueous lacquers, such as those used for electrophoretic coatings or for wood lacquering.
The paints can contain at least one of the polymers listed above as a binder.
Examples of varnishes with special binders are the following:<ul id="ul0015" list-style="none"><li>1. Paints based on cold or hot crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, optionally with the addition of an acidic curing catalyst;</li><li>2nd Two-component polyurethane lacquers based on acrylate, polyester or polyether resins containing hydroxyl groups and aliphatic or aromatic polyisocyanates;</li><li>3rd One-component polyurethane varnishes based on blocked polyisocyanates, which are deblocked during baking;</li><li>4th Two-component paints based on (poly) ketimines and aliphatic or aromatic polyisocyanates;</li><li>5. Two-component paints based on (poly) ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methyl acrylamidoglycolate methyl ester;</li><li>6. Two-component lacquers based on polyacrylates and polyepoxides containing carboxyl or amino groups;</li><li>7. Two-component paints based on acrylate resins containing anhydride groups and a polyhydroxy or polyamino component;</li><li>8th. Two-component paints based on (poly) oxazolidines and acrylate resins containing anhydride groups or unsaturated acrylate resins or aliphatic or aromatic polyisocyanates.</li><li>9. Two-component paints based on unsaturated polyacrylates and polymalonates;</li><li>10th thermoplastic polyacrylate varnishes based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins;</li><li>11. Lacquer systems based on siloxane-modified acrylic resins.</li></ul>
The paints can also be radiation-curable paints. In this case, the binding agent consists of monomeric or oligomeric compounds which contain ethylenic double bonds and are converted into a crosslinked high-molecular form by irradiation with actinic light or with electron beams. This is usually a mixture of such compounds.
The lacquers can be applied as single-layer or two-layer lacquers, the stabilizers according to the invention preferably being added to the unpigmented top layer. In addition to the stabilizers according to the invention, such paints can also contain the additives listed in the following sections 1 to 10. In particular, combinations of these stabilizers with those under 2.7. sterically hindered amines mentioned have good stabilizing effects.
The lacquers can be applied to the substrates (metal, plastic, wood, etc.) by the usual methods, for example by brushing, spraying, pouring, dipping or electrophoresis.
In practice, the stabilizers according to the invention can be used together with other stabilizers.
Examples of further additives with which the stabilizers used according to the invention can be used are:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di- tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6- dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol.
1.2. Alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-di-phenyl- 4-octadecyloxyphenol.
1.3. Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4.4 thio-bis- (6th -tert.butyl-3-methylphenol), 4,4'-thio-bis- (6-tert.buty) -2-methylphenol).
1.4. Alkylidene bisphenols, e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2-methylene-bis- [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4 -methylphenol), 2,2'-methylene-bis- (4,6-di-tert.butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert.butylphenol), 2,2 ' -Ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4.4 '-Methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis- (3rd -tert.butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert.butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenz<sup>y</sup>l) -6-tert-butyl-4-methylphenyl] terephthalate.
1.5 benzyl compounds, e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, bis- (3,5-di-tert-butyl-4-hydroxybenzyl) - sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, 1,3,5-tris - (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3.5 Di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyloster, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.6. Acylaminophenols, e.g. 4-hydroxylauric anilide, 4-hydroxystearic anilide, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, N- (3, 5-di-tert.butyl-4-hydroxyphenyl) carbamic acid octyl ester.
1.7. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol , Tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.
1.8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such as with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol , Tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.
1.9. Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris ( hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.
1.10. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N , N -Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
2nd Other UV absorbers and light stabilizers
2.1. 2- (2'-Hydroxyphenyl) benzotriazoles such as 5'-methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5' - (1,1,3 , 3-tetramethylbutyl) -, 5-chloro-3, 5-di-tert.butyl-, 5-chloro-3'-tert.butyl-5'-methyl-, 3'-sec-butyl-5'-tert .butyl, 4 -Octoxy-, 3, 5'-di-tert.amyl-, 3 5 -Bis- (a, a-dimethylbenzyl) derivative. Mixtures of ß- [3- (2-H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl] propionic acid polyethylene glycol 300 ester and bis- {ß- [3- (2-H- benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl] propionic acid} polyethylene glycol 300 ester.
2.2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2, 4-trihydroxy, 2'-hydroxy -4,4'-dimethoxy derivative.
2.3. Esters of optionally substituted benzoic acids, such as, for example, 4-tert-butylphenyisalicylate, phenylsalicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert.butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4- 2,4-di-tert-butylphenyl hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, such as, for example, a-cyano-ß, ß-diphenylacrylic acid ethyl ester or isooctyl ester, a-carbomethoxy cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, a-carbomethoxy-p-methoxy cinnamic acid methyl ester, N- (ß-carbomethoxy-ß-cyanovinyl) -2-methyl-indoline.
2.5. Nickel compounds, such as Nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n -Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as methyl or ethyl ester, nickel complexes of ketoximes, such as 2-hydroxy-4- methyl-phenyl-undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
2.6. 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 -octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6- bis (2,4-dimethylphenyl) -1, 3,5-triazine.
2.7. Sterically hindered amines, such as Bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4- hydroxybenzyl-malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product from N, N '-Bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris- (2.2 , 6,6-tetramethyl-4-piperidyl) nitrilotriacetate, Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraoate, 1,1 - (1,2-ethanediyl) -bis- (3,3,5,5 -tetramethyl-piperazinone).
2.8. Oxalic acid diamides, such as 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2-di-dodecyloxy-5,5 di- tert-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2- Ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide, mixtures of o- and p-methoxy and of o- and p-ethoxy-di-substituted oxanilides.
2.9.1. Cationic UV absorbers which contain at least one quaternary ammonium group, for example those described in JP-A-61-19278, 61-192 778, 61-192 780 and FR-A-1 464 919.
2.9.2. Anionic UV absorbers and their salts, as described, for example, in JP-A-54-085 804, 54-068 303, 62-106 971, 63-046 277, 59-027 972 and 59-169 883.
3rd Metal deactivators such as N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert.butyl -4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide.
4th Phosphites and phosphonites, such as Triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris- (nonylphenyl) -phosphite, trilaurylphosphite, trioctadecylphosphite, distearyl-pentaerythritol-diphosphite, tris- (2,4-di-tert.butylphenyl) -phosphite, diisodhritol-diisodhritol-diphosphite - tert.butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert.butylphenyl) -4,4'-biphenylene diphosphonite, 3,9-bis- (2,4-di- tert.butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] -undecane.
5. Peroxide-destroying compounds, such as, for example, esters of β-thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide dodecodecapro (pentacrylic acid) propionate.
6. Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
7. Basic co-stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na -Ricinoleate, K-palmitate, antimony catecholate or tin catecholate.
8th. Nucleating agents, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
10th Other additives, such as plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
The following examples further illustrate the invention. Percentages refer to the weight, unless otherwise stated.
Manufacturing examples
Example 1:
a) Preparation of [1,3-bis (N, N-dimethylamino) -2-propyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionate
<chemistry id="chem0049" num="0049"><img file="EP0374751A2_D0053.tif" /></chemistry>100 g of 3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionic acid are suspended in 600 ml of toluene. 10 ml of dimethylformamide (DMF) are added and the mixture is heated to 70 ° C. 70.1 g of thionyl chloride are then added dropwise to the mixture. One observes HCI and SO<sub>2</sub>-Development. The solution is stirred at 80 ° C. for 4 hours. Finally, the excess thionyl chloride is removed by distillation. 50.9 g of 1,3-bis (N, N-dimethylamino) propan-2-ol are added dropwise to the solution at 80 ° C., producing HCI.
The reaction mixture is stirred at 80 ° C. for 8 hours and then cooled to 10 ° C. The HCl precipitate is filtered, washed with ether, then dissolved in 1 1 water and 10 ml conc. NH<sub>3</sub> (NH<sub>3</sub> with 25% H<sub>2</sub>0) neutralized. The product is extracted with methylene chloride.
The organic phase, which contains the crude product, is washed with aqueous NaCi solution, over MgS0<sub>4</sub> dried and concentrated. The residue is recrystallized from a petroleum ether / ethyl acetate mixture.
54.4 g of [1,3-bis (N, N-dimethylamino) -2-propyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionate are obtained as white crystals (mp 79-80 C).
b) Preparation of [1,3-bis (N, N, N-trimethylammonium) -2-propyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionate di -monomethyl sulfate
<chemistry id="chem0050" num="0050"><img file="EP0374751A2_D0054.tif" /></chemistry>20 g [1,3-bis (N, N-dimethylamino) -2-propyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionate are dissolved in 200 ml of acetone and 21.6 g of dimethyl sulfate were added dropwise. An exothermic reaction takes place, producing a white precipitate. The reaction mixture is heated to reflux for one hour. The precipitate is then filtered and washed with acetone. After recrystallization from methanol, 17.4 g of [1,3-bis (N, N, N-trimethylammonium) -2-propyl] -3- [3- (2-benzotriazole) -4-hydroxy-5- t-butylphenyl] propionate di-monomethyl sulfate as white crystals (mp. 196-203 C).
Example 2: [1,3-bis (N, N, N-trimethylammonium) -2-propyl] -3- [3- (2-benzotriazole) -4-hydroxy-5-t-butylphenyl] propionate- dichloride
<chemistry id="chem0051" num="0051"><img file="EP0374751A2_D0055.tif" /></chemistry>20 g [1,3-bis (N, N-dimethylamino) -2-propyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionate are dissolved in 360 ml acetone / methylene chloride (4: 1 parts by volume) solved. Methyl chloride is passed through the solution for 30 minutes, then the bottle is closed and left to stand overnight. The resulting precipitate is filtered, washed with about 100 ml of petroleum ether and dried. After recrystallization from a methylene chloride / petroleum ether mixture, 24.0 g of [1,3-bis (N, N, N-trimethylammonium) -2-propyl] -3- [3- (2-benzotriazolyl) -4 are obtained -hydroxy-5-t-butylphenyl] propionate dichloride as white crystals (mp. 105-110 ° C, associated with decomposition).
Example 3:
a) Preparation of 3,5-bis {5 '- [2 "- (N, N-dimethylamino) ethoxycarbonyl] -2'-methylpent-2'-yl} -2-hydroxyphenyl-benzotriazole
<chemistry id="chem0052" num="0052"><img file="EP0374751A2_D0056.tif" /></chemistry>
The procedure is as in Example 1 a), but 23.4 g (0.05 mol) of the corresponding dicarboxylic acid are used. 33.5 g (0.049 mol) of the bishydrochloride (98% of theory; mp. 195-198 C) are obtained. The product is then neutralized and purified by chromatography (Alex type E with acetoacetic ester / petroleum ether in a 1: 3 volume ratio). 23.5 g (0.039 mol) of the diamine are obtained as a slightly yellowish oil (80% of theory).<tables id="tabl0002" num="0002"><img file="EP0374751A2_D0057.tif" /></tables>b) Preparation of 3,5-bis {5 '- [2 "- (N, N, N-trimethylammonium) ethoxycarbonyl] -2'-methylpent-2'-yl} -2-hydroxyphenyl-benzotriazole-bis-monomethyl sulfate<chemistry id="chem0053" num="0053"><img file="EP0374751A2_D0058.tif" /></chemistry>
The procedure is analogous to Example 1 b), 3.0 g of the product from Example 1 a) being used.
3.5 g of the desired substance are obtained as white crystals (mp. 50-65 ° C.)
Example 4: Preparation of [1,3-bis (N, N, N-trimethylammonium) -2-propyl] -3- [3- (5-chloro-2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl ] propionate diiodide
<chemistry id="chem0054" num="0054"><img file="EP0374751A2_D0059.tif" /></chemistry>
The procedure is analogous to Examples 1 and 2, but using 100 g of the corresponding carboxylic acid and methyl iodide instead of methyl chloride. 43 g of the product are obtained as slightly yellowish crystals (mp. 180-187 C).
Example 5: Preparation of {3- [4- (2-benzotriazolyl) -3-hydroxyphenoxy] -2-hydroxy-1-propyl} -N, N, N-trimethylammonium chloride
<chemistry id="chem0055" num="0055"><img file="EP0374751A2_D0060.tif" /></chemistry>11.4 g (0.05 mol) of 2- (2,4-dihydroxyphenyl) benzotriazole are heated with 7.75 g (0.051 mol) of glycidyltrimethylammonium chloride in 100 ml of acetonitrile at 50-60 ° C. for 24 hours.
The precipitate is filtered and heated to reflux in 20 ml of acetonitrile. After cooling and filtering, 3.7 g of a light yellow solid (mp. 225-228 ° C.) are obtained.
Example 6: Preparation of [1,3-bis (N, N, N-trimethylammonium) -2-propyl] -2-cyano-3,3-diphenyl acrylate bis-monomethyl sulfate
<chemistry id="chem0056" num="0056"><img file="EP0374751A2_D0061.tif" /></chemistry>
The procedure is analogous to Example 1, but 12.5 g of 2-cyano-3,3-diphenylacrylic acid are used. 7.1 g of the product are obtained as white crystals (mp. 189-191 ° C.).
Example 7: Preparation of 2- [3,5-di-tert-butyl-2-hydroxyphenyl] -5-benzotriazolecarboxylic acid 2-N, N-dimethylaminoethyl ester
<chemistry id="chem0057" num="0057"><img file="EP0374751A2_D0062.tif" /></chemistry>
The procedure is analogous to Example 1, but 36.7 g of 2- [3,5-di-tert-butyl-2-hydroxyphenyl] -5-benzotriazole-carboxylic acid and 9.8 g of 2-N, N-dimethylaminoethanol are used. 37.0 g (89% of theory) of the product are obtained in the form of slightly yellowish crystals (mp. 127-129 ° C.).
Example 8: Preparation of 2- [3,5-di-tert-butyl-2-hydroxyphenyl] -5- [2- (N-2-hydroxypropyl-N, N-dimethylammonium) ethoxycarbonyl] benzotriazole bromide
<chemistry id="chem0058" num="0058"><img file="EP0374751A2_D0063.tif" /></chemistry>17.5 g of 2- [3,5-di-tert-butyl-2-hydroxyphenyl] -5-benzotriazolecarboxylic acid 2-N, N-dimethylaminoethyl ester are dissolved in 70 ml of toluene. 25 g of 2-bromoethanol are added and the solution is refluxed for 15 hours. Then let it cool down, whereby the product fails. It is filtered, washed with diethyl ether and dried in vacuo. 17.0 g (75% of theory) of the product are obtained in the form of yellowish crystals (mp. 222-224 ° C.).
Example 9: Preparation of [N, N-bis-2-chloroethyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl) propionamide
<chemistry id="chem0059" num="0059"><img file="EP0374751A2_D0064.tif" /></chemistry>
The procedure is analogous to Example 1, but 33.9 g of 3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionic acid and 19.6 g of bis (2-chloroethyl) amine are used. The product is purified chromatographically (Alex type E, ethyl acetate / petroleum ether 1: 4 v / v). 5 g of the product are obtained in the form of white crystals (mp 90-93 ° C.).
Example 10: Preparation of [N, N-bis [(N, N, N-trimethylammonium) -2-ethyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionane dichloride
<chemistry id="chem0060" num="0060"><img file="EP0374751A2_D0065.tif" /></chemistry>1.16 g of [N, N-bis-2-chloroethyl] -3- [3- (2-benzotriazolyl) -4-hydroxy-5-t-butylphenyl] propionamide are dissolved in 10 ml of toluene. 4.8 ml of a solution of trimethylamine (4.2 M) in ethanol and 0.1 ml of DMF are added and heated in a bomb tube at 100 ° C. for 24 hours. Then let it cool down, whereby the product fails. After washing with diethyl ether and drying in vacuo, 1.3 g (84% of theory) of the dichloride are obtained in the form of white hygroscopic crystals (mp. 110-120 ° C.).
Application example 1:
Manufacture of inkjet coatings
<ul id="ul0016" list-style="none"><li>A. Coating without stabilizer:<ul id="ul0017" list-style="none"><li>16.4 g of a 10% aqueous solution of polyvinyl alcohol are mixed with 0.03 g of di-t-octylphenol polyethylene oxide wetting agent, 0.3 g of Polyfix @ 601 (Showa High Polymer Co.) mordant and with water to 27.0 g replenished.</li><li>2.0 g of silica (Syloid® type 244, Grace & Co.) are stirred into the solution and dispersed using ultrasound. The pH of the dispersion is adjusted to 7.0 with 2N NaOH.</li></ul></li><li>B. Coating containing a stabilizer: A dispersion is prepared analogously to the description under A, but the Polyfixo601 mordant is mixed with 0.6 g of the compound from Example 1 b)<chemistry id="chem0061" num="0061"><img file="EP0374751A2_D0066.tif" /></chemistry>replaced. The total amount of the aqueous phase is 32.4 g.</li></ul>
The casting mixtures A and B obtained are applied with a wire spiral to photographic paper in a thickness of 50 μm.
The coatings obtained after drying have a dry weight of 7 g / m<sup>2</sup>, of which BI g / m<sup>2</sup> contains the stabilizer.
The recording materials prepared in this way are each printed with a purple-red ink in an inkjet printing device of the "Think-Jet" type (Hewlett-Packard). The inks have the following composition:<ul id="ul0018" list-style="none"><li>5 Share CI Acid Red 35 or CI Acid Red 249</li><li>50 Parts of diethylene glycol and</li><li>45 Parts of water.</li></ul>
The inks are filtered through an ultrafilter with a pore size of 0.3 μm and filled into the ink cartridge of the "Think-Jet" device. Printed samples are made with a dot density of 192 x 96 dots per inch.
The color density (intensity) of the printed samples is now determined using a densitometer (Macbeth TR 924) using a Status A filter.
Lightfastness test
In order to test the lightfastness of the printed samples, the samples are irradiated in an Atlas Weatherometer with a xenon lamp with an illuminance of 81 klux behind a filter made of 6 mm thick window glass.
The color density is measured again to determine the percentage loss of color density.
The results are summarized in Table 1 below. Lower values mean higher lightfastness.<tables id="tabl0003" num="0003"><img file="EP0374751A2_D0067.tif" /></tables>
Testing the fastness to washing
The printed sample with coating B is washed in a drum processor (Jobo Autolab ATL-1). (This device is typically used to develop photographic materials).
The printed sample is washed in the drum processor 10 times for 30 seconds with water at 25 ° C. The drum speed is the minimum to avoid mechanical damage to the sample coating.
The sample is then dried and its color density measured in order to determine the percentage of color loss during the washing process. The results are summarized below.<tables id="tabl0004" num="0004"><img file="EP0374751A2_D0068.tif" /></tables>
It can be seen from the results obtained that the recording materials according to the invention, which contain a compound of the formula I as a stabilizer, have excellent lightfastness and, at the same time, washfastness.
Example of use 2:
A solution (A) of the dye GI Acid Yellow 23, which has extremely poor water resistance in titanjet prints, is prepared as follows:<ul id="ul0019" list-style="none"><li>3rd g CI Acid Yellow 23</li><li>30th g diethylene glycol and</li><li>67 g of water.</li></ul>
A second solution (B) is made from:<ul id="ul0020" list-style="none"><li>3rd g of the compound from Example Ib</li><li>30th g diethylene glycol and</li><li>67 g of water.</li></ul>
Inks for ink jet printing can be made by either adding solution A to solution B or vice versa. 3.1 g of solution A can thus be added to 10 g of solution B with stirring before the onset of turbidity. Similarly, 10 g of solution B can be added to 10 g of solution A without forming a precipitate.
The two solution mixtures are filtered through a filter with a pore size of 0.3 μm and used as ink for ink jet printing analogous to Application Example 1.
Two blank samples are also made. They consist of solution A and solution C in the same mixing ratios as the inks from solution A and solution B.
Solution C is prepared as follows:<ul id="ul0021" list-style="none"><li>3rd g Solution A</li><li>30th g diethylene glycol and</li><li>67 g of water.</li></ul>
A paper with a 5 g / m<sup>2</sup> Coating consisting of 2.24 g / m<sup>2</sup> Polyvinyl alcohol, 2.73 g / m<sup>2</sup> Silica and 0.03 g / m<sup>2</sup> Di-t-octylphenyl polyethylene oxide (8EO) was used. This paper is printed with the inks as described in application example 1 and checked for its wash fastness. The results are summarized in Table 3. Low values mean higher fastness to washing.<tables id="tabl0005" num="0005"><img file="EP0374751A2_D0069.tif" /></tables>
This example shows that the compounds of formula I can be added directly to the ink for ink jet printing and that these inks provide improved water resistance to ink jet prints.
Example of use 3:
Coating compositions for inkjet printing papers are made analogously to Application Example 1 from 16.4 g of a 10% polyvinyl alcohol solution (Riedel de Haen), 0.015 g Invadin® JFC wetting agent (Ciba-Geigy), 0.52 g of a UV absorber according to the invention, 2.0 g Silica (Syloid®, type 244, WR Grace) and water up to 33.2 g. The pH is adjusted to 7.0 using lithium hydroxide. The mass obtained in this way is applied to a polyethylene coating paper using a 60 μm rack casting machine and dried. The paper now has an order of 8 g / m<sup>2</sup>, of which 1 g / m<sup>2</sup> the UV absorber is used.
As a comparison, papers are produced with 0.52 g of a 10% mordant solution instead of the 0.52 g UV absorber. This corresponds to a pickling agent application of approx. 0.1 g / m<sup>2</sup>.
The products used are Polyfix 601 (Showa High Polymer Co.), Merquat 100 (Chemviron), Tinofix EW (Ciba-Geigy AG) and Polyallylamine HCI (Nitto Boseki Col.), which are described, for example, in DE 3 640 359 and JP 61061 887 are described.
These papers are printed as described in application example 1 with an ink which consists of 4 g of CI Acid Red 35 in a mixture of 48 g of water and 48 g of diethylene glycol (cf. application example 1). Then the light and wash fastnesses are determined as in application example 1. The results are summarized in Table 3.<tables id="tabl0006" num="0006"><img file="EP0374751A2_D0070.tif" /></tables>
Example of use 4
This example shows that even smaller amounts of UV absorbers according to the invention in inkjet printing papers bring about an improvement in light fastness.
Coating compositions are made from 14.9 g of a 10% solution of polyvinyl alcohol, 0.015 g Invadin® JFC wetting agent, 0.24 g UV absorber according to the invention, 0.27 g Polyfix 601 solution (Showa High Polymer Co.), 2, 0 g silica and water made up to 30.5 g. The coating compositions are applied on a paper support. After drying, the papers thus obtained are printed with the ink-jet ink based on Acid Red 35 in accordance with Application Example 3. The light fastness of the printed samples is then tested as described in application example 1. The results are summarized in Table 4.<tables id="tabl0007" num="0007"><img file="EP0374751A2_D0071.tif" /></tables>
Application example 5:
An aqueous clear coat of the following composition is produced:<tables id="tabl0008" num="0008"><img file="EP0374751A2_D0072.tif" /></tables>1.5% stabilizer (based on solid paint) are worked into the clear coat at 3000 rpm for 5 minutes. The resulting paint is adjusted to spray resistance with deionized water and sprayed onto a prepared substrate (coil coat sheet with filter and aqueous silver metallic basecoat). The sheet is fired at 80 ° C. for 10 minutes and then at 140 ° C. for 30 minutes. The sheet thus obtained is tested in Florida after outdoor exposure.
A corresponding lacquer without stabilizer, with which an identical sheet was coated in the manner described above, serves as a comparison. Table 5 shows the results.<tables id="tabl0009" num="0009"><img file="EP0374751A2_D0073.tif" /></tables><chemistry id="chem0062" num="0062"><img file="EP0374751A2_D0074.tif" /></chemistry>
179 sheets
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Every citation, both ways
| Document | Relation | Office | Category | Cited during |
|---|---|---|---|---|
| EP0415880A2 | Cited by | European Patent Office (EPO) | – | Search report |
| US5543083A | Cited by | United States of America | – | Search report |
| EP0425429A3 | Cited by | European Patent Office (EPO) | – | Search report |
| EP0415880A3 | Cited by | European Patent Office (EPO) | – | Search report |
| US5723435A | Cited by | United States of America | – | Search report |
| US5723435A | Cited by | United States of America | – | Search report |
| US7897556B2 | Cited by | United States of America | – | Applicant |
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| EP0451813A1 | Cited by | European Patent Office (EPO) | – | Examiner |
| US5474691A | Cited by | United States of America | – | Search report |
| US5733855A | Cited by | United States of America | – | Search report |
| FR2698870A1 | Cited by | France | – | Search report |
| BE1006797A5 | Cited by | Belgium | – | Search report |
| US5869443A | Cited by | United States of America | – | Search report |
| EP0425429A2 | Cited by | European Patent Office (EPO) | – | Search report |
| EP0075202A2 | Cites | European Patent Office (EPO) | A | Search report |
| EP0165608A2 | Cites | European Patent Office (EPO) | A | Search report |
| EP0272576A1 | Cites | European Patent Office (EPO) | AD | Search report |
| EP0357545A2 | Cites | European Patent Office (EPO) | E | Search report |
9 members in 7 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 467488 | Switzerland | – | |
| 467488 | Switzerland | A | |
| 467488 | Switzerland | A | |
| 467488 | – | – | – |
| CH19880004674 | – | – | – |
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| Document | Office | Kind | |
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| CA2005651A1 | Canada | A1 | |
| EP0374751A2This record | European Patent Office (EPO) | A2 | |
| KR900009306A | Republic of Korea | A | |
| CN1043728A | China | A | |
| BR8906545A | Brazil | A | |
| BR8906545A | Brazil | A | |
| JPH02222457A | Japan | A | |
| US5096781A | United States of America | A | |
| EP0374751A3 | European Patent Office (EPO) | A3 |
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Numbers
- Publication
- 0374751
- Publication, DOCDB
- 0374751
- Publication, EPODOC
- EP0374751
- Application
- 89123224
- Application, DOCDB
- 89123224
- Application, EPODOC
- EP19890123224
Titles3
- German
- Wasserlösliche Verbindungen als Lichtschutzmittel
- English
- Water-soluble light-projecting materials
- French
- Agents hydrosolubles protégeant de la lumière
Classification
- CPC, 6
- G03C11/10
- B41M5/00
- B41M5/0035
- C07D249/20
- C09D11/38
- G03C1/8155
- IPC, 12
- B41M1 36
- B41M7 02
- C07D249 20
- C08K5 3475
- C08K5 3477
- C08K5 3492
- C08L101 00
- C09D7 12
- C08K5 3472
- C09D11 38
- G03C1 815
- G03C11 10
Designated states7
- Contracting states, 7
- Belgium
- Germany
- Spain
- France
- United Kingdom
- Italy
- Netherlands (Kingdom of the)