Aminofunctional polyvinylacetals
View Patent ↗Polyvinyl acetals which contain acetal moieties derived by acetalizing polyvinyl alcohol with both aliphatic aldehydes or their derivatives and with amino- and/or ammonium-substituted aldehydes display exceptional substrate adhesion when used in printing ink as binders, allowing inks without adhesion promoters to be produced.
1. In a printing ink composition comprising at least one pigment and a binder, the improvement comprising incorporating into the composition a binder comprising at least one polyvinyl acetal modified with amino or ammonium groups, prepared by acetalizing fully or partially hydrolyzed vinyl ester polymers containing ≧50 mol % of vinyl alcohol units in an aqueous medium with
a) one or more aliphatic aldehydes having 1 to 15 carbon atoms, or an acetal, hemiacetal, or mixture thereof, and
b) at least one aldehyde containing amino or ammonium group(s), or a hydrate, acetal, hemiacetal, or mixture thereof,
wherein the degree of acetalization of the fully or partially hydrolyzed vinyl ester polymers with aliphatic aldehyde(s) is from 40 mol % to 80 mol %, and
separating the polyvinyl acetal modified with amino or ammonium groups contained as a solid from the aqueous medium.
2. The printing ink composition of claim 1 , wherein the at least one aldehyde containing amino or ammonium groups is selected from the group consisting of
I) (R) 2 N—(CH 2 ) n —CH(OR) 2 ,
II) (R) 2 N—(CH 2 ) n —CH═O,
III) X − (R) 3 N + —(CH 2 ) n —CH(OR) 2 , and
IV) X − (R) 3 N + —(CH 2 ) n —CH═O,
in each of which R is identical or different and is hydrogen or a branched or unbranched, saturated or unsaturated, alkyl radical having 1 to 12 carbon atoms, X − is an anion, and n is a number from 0 to 40.
3. The printing ink composition of claim 1 , wherein the at least one aldehyde component containing amino or ammonium groups is selected from the group consisting of formamide, aminoacetaldehyde dimethyl acetal, aminoacetaldehyde diethyl acetal, aminopropionaldehyde dimethyl acetal, aminopropionaldehyde diethyl acetal, aminobutyraldehyde dimethyl acetal, aminobutyraldehyde diethyl acetal, and cationic ammonium salts thereof.
4. The printing ink composition of claim 1 , wherein the aliphatic aldehyde comprises butyraldehyde or a mixture of butyraldehyde and acetaldehyde.
5. The printing ink composition of claim 1 , wherein the aldehyde(s) containing amino or ammonium groups are used in an amount such that the amount of amino- and ammonium-containing acetal units, relative to the total amount of acetal units, is 0.001% to 95%, in mol %.
6. The printing ink composition of claim 1 , wherein the nitrogen content of the polyvinyl acetal is from 0.001 to 5 weight percent based on the total weight of the polyvinyl acetal.
7. The printing ink composition of claim 1 , wherein the nitrogen content of the polyvinyl acetal is from 0.01 to 1 weight percent based on the total weight of the polyvinyl acetal.
8. The printing ink composition of claim 1 , wherein the nitrogen content of the polyvinyl acetal is from 0.02 to 0.9 weight percent based on the total weight of the polyvinyl acetal.
9. The printing ink composition of claim 1 , wherein the polyvinyl acetal is prepared by acetalization of polyvinyl alcohol with butyraldehyde, acetaldehyde, their acetals, hemiacetals, or mixtures thereof, and at least one of aminoacetaldehyde dimethyl acetal, aminopropionaldehyde dimethyl acetal, aminobutyraldehyde dimethyl acetal, or their cationic ammonium salts.
10. The printing ink composition of claim 9 , wherein the polyvinyl acetal modified with amino or ammonium groups has a nitrogen content in the range of 0.01 to 1 weight percent, based on the weight of the polyvinyl acetal modified with amino or ammonium groups.
11. The printing ink composition of claim 9 , further comprising at least one organic solvent.
12. The printing ink composition of claim 11 , wherein the at least one organic solvent is an alcohol or an alcohol ester.
13. The printing ink composition of claim 11 , wherein the at least one solvent is ethyl acetate or ethanol.
14. The printing ink composition of claim 1 , comprising 5 to 25 weight percent of one or more pigments based on the total weight of the printing ink composition.
15. The printing ink composition of claim 1 , comprising 5 to 25 weight percent of binder based on the total weight of the printing ink composition.
16. The printing ink composition of claim 1 , which is free of adhesion promoters.
17. The printing ink composition of claim 1 , wherein the at least one aldehyde containing amino or ammonium groups is selected from the group consisting of
I) (R) 2 N—(CH 2 ) n —CH(OR) 2 ,
II) (R) 2 N—(CH 2 ) n —CH═O,
in each of which R is identical or different and is hydrogen or a branched or unbranched, saturated or unsaturated, alkyl radical having 1 to 12 carbon atoms,
and n is a number from 0 to 40.
18. The printing ink composition of claim 1 , wherein the at least one aldehyde containing amino or ammonium groups is selected from the group consisting of
III) X − (R) 3 N + —(CH 2 )—CH(OR) 2 , and
IV) X − (R) 3 N + —(CH 2 ) n —CH═O,
in each of which R is identical or different and is hydrogen or a branched or unbranched, saturated or unsaturated, alkyl radical having 1 to 12 carbon atoms,
X − is an anion, and n is a number from 0 to 40.