Pigment dispersants with modified copolymers
The present invention pertains to salt modified copolymers wherein one of the monomer units contains a quaternized N-atom structure with a polar substituent. The invention further relates to the use of said copolymers as dispersant especially for color filters. The copolymer is made by controlled polymerization or by conventional polymerization and comprises at least one monomer (MA r ) selected from unsaturated monomers out of the group of acrylates, methacrylates, acrylamides, methacrylamides, styrenic monomers, at least one monomer (MB s ) selected from unsaturated monomers out of the group of acrylates, methacrylates, acrylamides, methacrylamides, styrenic monomers wherein the monomer MB has a quaternized N-atom structure with a polar substituent selected from polyether, polyamine, nitrile, amide, imine, imide, ester, ketone, nitrile, aldehyde, diketone, ketoester, ketoamide, carbonate, carbamate, carbamide, sulfoxide, sulfone, carboxylic acid, sulfonic acid, phosphoric acid groups; or carboxylic acid anion, sulfonic acid anion or phosphoric acid anion groups which is formed as betaine structure r denotes the total number of monomers MA within the structural element (MA r ) and r is >5, preferred 10-1000, most preferred 10-500; s denotes the total number of monomers MB within the structural element (MB s ) and s is >1, preferred 2-100, most preferred 2-50.
1. A copolymer made by nitroxide mediated controlled polymerisation comprising,
at least one monomer (MA r ) selected from unsaturated monomers out of the group of acrylates, methacrylates, acrylamides, methacrylamides, styrenic monomers,
at least one monomer (MB s ) selected from unsaturated monomers out of the group of acrylates, methacrylates, acrylamides, methacrylamides, styrenic monomers
wherein the monomer MB has a quaternized N-atom structure with a polar substituent selected from polyether, polyamine, nitrile, amide, imine, imide, ester, ketone, nitrile, aldehyde, diketone, ketoester, ketoamide, carbonate, carbamate, carbamide, sulfoxide, sulfone, carboxylic acid, sulfonic acid, phosphoric acid groups; or carboxylic acid anion, sulfonic acid anion or phosphoric acid anion groups which is formed as betaine structure,
wherein
r denotes the total number of monomers MA within the structural element (MA r ) and r is >5;
s denotes the total number of monomers MB within the structural element (MB s ) and s is >1,
a fragment In of an initiator In-E capable to initiate radical polymerisation, and
a group E bearing at least one stable free nitroxyl radical which is bound via the oxygen atom to the copolymer.
2. A copolymer according to claim 1 , wherein MA-monomers are selected from CH 2 ═CH—C(O)OR 2 , CH 2 ═C(CH 3 )—C(O)OR 2 , CH 2 ═C(R 1 )—C(O)OR 2 CH 2 ═CH—C(O)NR 4 R 5 , CH 2 ═C(CH 3 )—C(O)NR 4 R 5 CH 2 ═C(R 1 )—C(O)NR 4 R 5 or CH 2 ═C(R 10 )—Ar,
wherein
R 1 is halogen or cyano or R 1 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 3 -C 18 cycloalkyl, C 4 -C 18 cycloalkenyl, C 6 -C 24 aryl, C 1 -C 12 alkyl-C 6 -C 24 aryl or C 2 -C 12 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen or OR 3 , SR 3 or NR 4 R 5 ; and/or optionally is interrupted by one or more —O—, —S—, —NR 4 —,
R 2 is hydrogen; or R 2 is C 1 -C 40 alkyl, C 2 -C 40 alkenyl, C 3 -C 40 cycloalkyl, C 4 -C 40 cycloalkenyl, C 6 -C 24 aryl, C 1 -C 20 alkyl-C 6 -C 24 aryl or C 2 -C 20 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen, OR 3 , SR 3 , NR 4 R 5 , NH—CO—OR 20 with R20 is —C 2 -C 6 alkylene-NR 4 R 5 or is a polyester residue and/or optionally is interrupted by one or more —O—, —S—, —NR 4 —, —C(O)—, —C(O)O—, —C(O)NR 4 — or —OC(O)NR 4 —
R 3 is hydrogen; or R 3 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkenyl, C 6 -C 24 aryl, C 1 -C 20 alkyl-C 6 -C 24 aryl or C 2 -C 20 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen, OC 1 -C 12 alkyl, SC 1 -C 12 alkyl or NR 4 R 5 ; and/or each of which is optionally interrupted by one or more —O—, —C(O)—, —C(O)O—, —S—, —NR 4 —,
R 4 , R 5 independently of each other are hydrogen; or R 4 , R 5 independently of each other are C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkenyl, C 6 -C 18 aryl, C 1 -C 20 alkyl-C 6 -C 24 aryl or C 2 -C 20 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen, OR 3 , SR 3 , C(O)R 3 , N(C 1 -C 12 alkyl) 2 ; and/or optionally is interrupted by one or more —O—, —S—, —C(O)— or —NC 1 -C 12 alkyl; R 4 and R 5 can optionally form 5-, 6- or 7-membered rings with each other;
R 10 is hydrogen, halogen or cyano; or R 10 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 3 -C 18 cycloalkyl, C 4 -C 18 cycloalkenyl, C 6 -C 24 aryl, C 1 -C 12 alkyl-C 6 -C 24 aryl or C 2 -C 12 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen or OR 3 , SR 3 or NR 4 R 5 ; and/or optionally is interrupted by one or more —O—, —S—, —NR 4 —,
Ar is pyridyl or imidazolyl, or C 6 -C 24 aryl which optionally is substituted by one or more halogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, OR 3 , SR 3 , NR 4 R 5 , C(O)R 3 , C(O)OR 3 , C(O)SR 3 or C(O)NR 4 R 5 .
3. A copolymer according to claim 1 , wherein MA-monomers are selected from CH 2 ═CH—C(O)OR 2 , CH 2 ═C(CH 3 )—C(O)OR 2 , CH 2 ═CH—C(O)NR 4 R 5 , CH 2 ═C(CH 3 )—C(O)NR 4 R 5 or CH 2 ═CH—Ar wherein R 2 , R 4 , R 5 and Ar are as defined in claim 2 .
4. A copolymer according to claim 3 , wherein R 2 is linear or branched C 1 -C 40 alkyl, or C 1 -C 4 alkyl substituted by one or more halogen, OH, —N(C 1 -C 20 alkyl) 2 , —NH—CO—O—C 2 -C 6 alkylene-N(C 1 -C 20 alkyl) 2 , —NH—CO—O—C 1 -C 40 alkylene interrupted by one or more —O—, and Ar is phenyl, tolueneyl, pyridyl, imidazolyl.
5. A copolymer according to claim 1 , wherein the monomer MB has the general formula CH 2 ═C(R 11 )—W—Y—Z
wherein
R 11 is hydrogen, halogen or cyano; or R 1 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 3 -C 18 cycloalkyl, C 4 -C 18 cycloalkenyl, C 6 -C 24 aryl, C 1 -C 12 alkyl-C 6 -C 24 aryl or C 2 -C 12 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen or OR 3 , SR 3 or NR 4 R 5 ; and/or optionally is interrupted by one or more —O—, —S—, —NR 4 —;
R 3 is hydrogen; or R 3 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkenyl, C 6 -C 24 aryl, C 1 -C 20 alkyl-C 6 -C 24 aryl or C 2 -C 20 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen, OC 1 -C 12 alkyl, SC 1 -C 12 alkyl or NR 4 R 5 ; and/or each of which is optionally interrupted by one or more —O—, —C(O)—, —C(O)O—, —S—, —NR 4 —
R 4 , R 5 independently of each other are hydrogen; or R 4 , R 5 independently of each other are C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkenyl, C 6 -C 18 aryl, C 1 -C 20 alkyl-C 6 -C 24 aryl or C 2 -C 20 alkenyl-C 6 -C 24 aryl each of which optionally is substituted by one or more halogen, OR 3 , SR 3 , C(O)R 3 , N(C 1 -C 12 alkyl) 2 ; and/or optionally is interrupted by one or more —O—, —S—, —C(O)— or —NC 1 -C 12 alkyl; R 4 and R 5 can be optionally form 5-, 6- or 7-membered rings with each other and/or R 3 or R 6
W is direct bond or C(O)—X; or W is C 1 -C 16 alkylene, C 1 -C 16 alkenylene, C 6 -C 18 arylene, each of which optionally is interrupted by one or more —O—, —S—, —NR 4 —,
X is OC 1 -C 16 alkylene, OC 1 -C 16 alkenylene, —OC 1 -C 16 alkylene-NH—CO—OC 1 -C 16 alkylene —SC 1 -C 16 alkylene, —SC 1 -C 16 alkenylene, —NR 4 C 1 -C 16 alkylene, —NR 4 C 1 -C 16 alkenylene, —OC 6 -C 18 arylene, —SC 6 -C 18 arylene, —NR 4 C 6 -C 18 arylene each of which optionally is interrupted by one or more —O—, —S—, —NR 4 —, —NR 4 C(O)O—, —NR 4 C(O)S— or —NR 4 C(O)NR 4 —
Y is C 2 -C 24 cyclicammonium + -R 6 or N + R 4 R 5 R 6
R 6 is C 1 -C 20 alkyl, C 1 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkenyl, C 6 -C 18 aryl, C 1 -C 20 alkyl-C 6 -C 24 aryl or C 2 -C 20 alkenyl-C 6 -C 24 aryl each of which is substituted one or more than once by CN, O[C 2 -C 8 alkyleneO] m R 3 , S[C 2 -C 8 alkyleneO] m R 3 , O[C 2 -C 8 alkyleneS] m R 3 , O[C 2 -C 8 alkyleneN] m R 4 R 5 , NR 4 R 5 [C 2 -C 8 alkyleneN] m R 4 R 5 , C(O)R 3 , C(O)OR 3 , C(O)SR 3 , C(O)NR 4 R 5 , S(O)R 3 , S(O) 2 R 3 , S(O) 2 OR 3 , S(O) 2 NR 4 R 5 , OS(O) 2 R 3 , OS(O) 2 OR 3 , P(O)(OR 3 ) 2 , OP(O)(OR 3 ) 2 , OC(O)R 3 , OC(O)OR 3 , OC(O)SR 3 , OC(O)NR 4 R 5 , SC(O)OR 3 , SC(O)SR 3 , SC(O)NR 4 R 5 , NR 4 C(O)R 3 , NR 4 C(O)OR 3 , NR 4 C(O)SR 3 , NR 4 C(O)NR 4 R 5 , C(O)C(O)R 3 , C(O)C(O)OR 3 , C(O)C(O)SR 3 , C(O)C(O)NR 4 R 5 , C(O)O − , S(O) 2 O − or P(O)OR 3 O − , provided that
if R 6 is C 1 -C 20 alkyl, C 1 -C 20 alkenyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkenyl, C 6 -C 18 aryl, C 1 -C 20 alkyl-C 6 -C 24 aryl or C 2 -C 20 alkenyl-C 6 -C 24 aryl each of which is substituted by one or more C(O)O − , S(O) 2 O − or P(O)OR 3 O − , Z is not existing,
Z is PF 6 − , BF 4 − , OH − , F − , Cl − , Br − or I − ; or Z is C 1 -C 40 alkyl[C(O)O − ] n ,C 1 -C 40 alkenyl[C(O)O − ] n , C 3 -C 40 cycloalkylC(O)O − , C 4 -C 40 cycloalkenylC(O)O − , C 6 -C 24 aryl[C(O)O − ] n , C 1 -C 40 alkyl[S(O) 2 O − ] n , C 1 -C 40 alkenyl[S(O) 2 O − ] n , C 3 -C 40 cycloalkylS(O) 2 O − , C 4 -C 40 cycloalkenylS(O) 2 O − , C 6 -C 24 aryl[S(O) 2 O − ] n , C 1 -C 40 alkyl[P(O)OR 3 O − ] n , C 1 -C 40 alkenyl[P(O)OR 3 O − ] n , C 3 -C 40 cycloalkylP(O)OR 3 O − , C 3 -C 40 cycloalkenylP(O)OR 3 O − or C 6 -C 24 aryl[P(O)OR 3 O − ] n each of which optionally is interrupted by one or more —O—, —S—, —NR 4 —, —C(O)—, —C(O)O—, —C(O)S—, —C(O)NR 4 —, —OC(O)O—, —SC(O)O—, —SC(O)S—, —SC(O)NR 4 —, —OC(O)NR 4 — or —NR 4 C(O)NR 4 —;
m is >1,
n is >1.
6. A copolymer according to claim 1 , wherein the monomer MB has the general formula CH 2 ═CH—W—YZ or CH 2 ═C(CH 3 )—W—YZ wherein W is a direct bond or C(O)X and X is —OC 1 -C 16 alkylene or —OC 1 -C 16 alkylene-NH—CO—OC 1 -C 16 alkylene or is —NHC 1 -C 16 alkylene and Y and Z are as defined in claim 5 .
7. A copolymer according to claim 1 wherein the monomer MB is selected from
wherein R 1 is hydrogen or methyl and
R 6 is —(CH 2 ) 1-18 CN, —(CH 2 ) 1-18 SO 3 − , —(CH 2 ) 1-18 C(O)O − , —CH 2 —O[C 2 -C 8 alkyleneO] m H, —CH 2 C(O)CH 3 , —CH 2 CHO, —CH 2 C(O)OC 1 -C 18 alkyl, —CH 2 C(O)OH, —CH 2 C(O)NH 2 , —CH 2 C(O)N(C 1 -C 18 alkyl) 2 , —CH 2 C(O)C(O)OC 1 -C 18 alkyl, —CH 2 C(O)CH 2 C(O)OC 1 -C 18 alkyl, —CH 2 CH 2 NHC(O)NH 2 , or
Z is Cl − , Br − or I − ; or Z is C 1 -C 40 alkylC(O)O − , C 1 -C 40 alkenylC(O)O − , C 6 -C 10 arylC(O)O − , C 1 -C 40 alkylS(O) 2 O − , C 1 -C 40 alkenylS(O) 2 O − , C 6 -C 10 arylS(O) 2 O − , C 1 -C 40 alkylP(O)OR 3 O − each of which optionally is interrupted by one or more —O—.
8. A copolymer MA r -MB s according to claim 1 which comprises further monomers MB′ s′ of the general formula
wherein R 1 is hydrogen or methyl and
R 70 is hydrogen, benzyl, o-chlorbenzyl, o,p-chlorbenzyl, 1-naphtyl, C 1 -C 4 alkyl, C 1 -C 4 alkenyl
Z is Cl − , Br − or I − ; or Z is C 1 -C 40 alkylC(O)O − ,C 1 -C 40 alkenylC(O)O − , C 6 -C 10 arylC(O)O − , C 1 -C 40 alkylS(O) 2 O − , C 1 -C 40 alkenylS(O) 2 O − , C 6 -C 10 arylS(O) 2 O − , C 1 -C 40 alkylP(O)OR 3 O − each of which optionally is interrupted by one or more —O—.
9. A copolymer according to claim 1 made by nitroxide mediated controlled polymerization and having the general formula
In-[(MA r -MB s )-(E)z]t
wherein
In is an initiator fragment capable to initiate radical polymerisation,
E is a group bearing at least one stable free nitroxyl radical, which is bound via the oxygen atom to the copolymer,
z=>1
t=1 to 20.
10. A copolymer according to claim 9 made by nitroxide mediated controlled polymerization and having the general formula
In-(MA r -MB s )-E
wherein
In is an initiator fragment capable to initiate radical polymerisation,
E is a group bearing at least one stable free nitroxyl radical, which is bound via the oxygen atom to the copolymer.
11. A copolymer made by controlled polymerisation or by conventional polymerization comprising
at least one monomer (MA r ) selected from unsaturated monomers out of the group of acrylates, methacrylates, acrylamides, methacrylamides, styrenic monomers,
at least one monomer (MB s ) selected from unsaturated monomers out of the group of acrylates, methacrylates, acrylamides, methacrylamides, styrenic monomers wherein the monomer MB has a quaternized N-atom structure with a polar substituent selected from polyether, polyamine, nitrile, amide, imine, imide, ester, ketone, nitrile, aldehyde, diketone, ketoester, ketoamide, carbonate, carbamate, carbamide, sulfoxide, sulfone, carboxylic acid, sulfonic acid, phosphoric acid groups; or carboxylic acid anion, sulfonic acid anion or phosphoric acid anion groups which is formed as betaine structure,
wherein
r denotes the total number of monomers MA within the structural element (MA r ) and r is >5;
s denotes the total number of monomers MB within the structural element (MB s ) and s is >1.
12. A pigment dispersion in organic solvent dispersed by means of a copolymer of claim 1 .
13. A coating composition comprising:
a) film forming binder,
b) pigment,
c) optionally other conventional coating components and/or additives,
d) dispersant which is copolymer of claim 1 , and
e) an organic solvent.
14. A composition comprising
a) photo resist binder,
b) transparent pigment,
c) optionally an organic solvent and/or optionally a photoinitiator or a photolatent catalyst,
d) dispersant which is copolymer of claim 1 for producing a color filter.
15. A copolymer according to claim 1 in preparation of paints, printing inks, inkjet inks, color resists and inkjet inks for color filters.
16. A copolymer according to claim 1 as a dispersant for pigments in an organic solvent.
17. The copolymer according to claim 5 ,
wherein
m is 1-120; and
n is 1-5.
18. The copolymer according to claim 17 ,
wherein
m is 1-40; and
n is 1-2.
19. The copolymer according to claim 1 ,
wherein
r within the structural element (MA r ) is 10-1000; and
s within the structural element (MB s ) is 2-100.
20. The copolymer according to claim 19 ,
wherein
r within the structural element (MA r ) is 10-500; and
s within the structural element (MB s ) is 2-50.