Production of novel resins and their uses in printing ink compositions

A maleic-modified hydrocarbon/tall oil resin suitable for use in heat-set and gravure printing ink compositions, which resin has a Ring and Ball softening point of from about 130.degree. C to 170.degree. C, a color (Barrett) of up to about two, and Acid Number of from about fifteen to about 30, and Gardner-Holdt solution viscosities at about 25.degree. C (bubble seconds) of from about 2.65 to about 8.0 (60% in 47 Kauri butanol gravure ink solvent) and from about 20 to about 60 (50% in 31 Kauri butanol heat set ink solvent), and which resin consists essentially of

• the reaction product of from about three to five parts maleic anhydride with about ninety-seven to ninety-five parts of a base resin consisting essentially of a polymerized mixture of:
• (a) from about fifty to about seventy-five percent of dicyclopentadiene or a dicyclopentadiene-rich hydrocarbon fraction containing at least about seventy percent dicyclopentadiene and minor amounts of methyl dicyclopentadiene and codimers of cyclopentadiene and methyl cyclopentadiene;
• (b) from about five to about twenty percent of a mixture consisting essentially of from about seventy to about ninety percent dimers of isoprene, cis-piperylene and trans-piperylene and codimers, trimers and cotrimers of isoprene, cis-piperylene, trans-piperylene and cyclopentadiene and from about thirty to ten percent higher polymers of isoprene, cis-piperylene, trans-piperylene and cyclopentadiene;
• and (c) from about ten to about thirty percent refined tall oil consisting essentially of a predominant amount of tall oil fatty acids and a lesser amount of tall oil rosin acids.

A process for producing a dibasic acid-modified hydrocarbon/tall oil resin suitable for use in heatset and gravure printing ink compositions, which process comprises:

• 1. copolymerizing a reaction mixture consisting essentially of:
• a. a predominant amount of dicyclopentadiene;
• and lesser amounts of
• b. a mixture consisting essentially of dimerized aliphatic cyclic and non-cyclic dienes of five carbon atoms, and
• c. tall oil,
• to form a base resin;
• and
• 2. reacting the base resin with at least one ethylenically unsaturated lower aliphatic dicarboxylic acid or anhydride in an amount sufficient to produce a modified resin having an acid number higher than the acid number of the base resin, the modified resin having Gardner-Holdt solution viscosities at about 25.degree. C (bubble seconds) of from about 1.65 to about 9.0 (60% in 47 Kauri butanol gravure ink solvent) and from about 10 to about 1000 (50% in 31 Kauri butanol heat set ink solvent).

A process for producing a maleic-modified hydrocarbon/tall oil resin suitable for use in heat-set and gravure printing ink compositions, which process comprises:

• (1) at a temperature of from about 230.degree. C to 270.degree. C and at autogenous pressure and under agitation, reacting a mixture consisting essentially of:
• (a) from about fifty to about seventy-five percent of dicyclopentadiene or a dicyclopentadiene-rich hydrocarbon fraction containing at least about seventy percent dicyclopentadiene and minor amounts of methyl dicyclopentadiene and codimers of cyclopentadiene and methyl cyclopentadiene;
• (b) from about five to about twenty percent of a mixture consisting essentially of from about seventy to about ninety percent dimers of isoprene, cis-piperylene and trans-piperylene and codimers, trimers and cotrimers of isoprene, cis-piperylene, trans-piperylene and cyclopentadiene;
• and (c) from about ten to about thirty percent refined tall oil consisting essentially of a predominate amount of tall oil fatty acids and a lesser amount of tall oil rosin acids, to produce a base resin having a Ring and Ball softening point of from about 130.degree. C to about 160.degree. C and an Acid Number of less than about five;
• and (2) reacting at a temperature of from about 200.degree. C to about 240.degree. C and under an inert gas blanket from about three to five parts of maleic anhydride and about ninety-seven to ninety-five parts of the base resin until a maleic-modified resin having a maleic-modified hydrocarbon/tall oil resin suitable for use in heat-set and gravure printing ink compositions, which resin has a Ring and Ball softening point of from about 130.degree. C to 170.degree. C, a color (Barrett) of up to about two, and Acid Number of from about fifteen to about 30, and Gardner-Holdt solution viscosities at about 25.degree. C (bubble seconds) of from about 2.65 to about 8.0 (60% in 47 Kauri butanol gravure ink solvent) and from about 20 to about 60 (50% in 31 Kauri butanol heat set ink solvent) is produced.

A base resin suitable for use in heat-set and gravure printing ink compositions, and which base resin consists essentially of a polymerized mixture of:

• (a) from about fifty to about seventy-five percent of dicyclopentadiene or a dicyclopentadiene-rich hydrocarbon fraction containing at least about seventy percent dicyclopentadiene and minor amounts of methyl dicyclopentadiene and codimers of cyclopentadiene and methyl cyclopentadiene;
• (b) from about five to about twenty percent of a mixture consisting essentially of from about seventy to about ninety percent dimers of isoprene, cis-piperylene and trans-piperylene and codimers, trimers and cotrimers of isoprene, cis-piperylene, trans-piperylene and cyclopentadiene and from about thirty to ten percent higher polymers of isoprene, cis-piperylene, trans-piperylene and cyclopentadiene;
• and (c) from about ten to about thirty percent refined tall oil consisting essentially of a predominant amount of tall oil fatty acids and a lesser amount of tall oil rosin acids o produce a base resin having a Ring and Ball softening point of from about 130.degree. C to about 160.degree. C and an Acid Number of less than about five;
• and having Gardner-Holdt solution viscosities at about 25.degree. C (bubble seconds) of from about 1.65 to about 9.0 (60% in 47 Kauri butanol gravure ink solvent) and from about 10 to about 1000 (50% in 31 Kauri butanol heat set ink solvent).

A process of producing a base resin suitable for use in heat-set and gravure printing ink compositions, which process comprises:

• copolymerizing a reaction mixture consisting essentially of:
• a. a predominant amount of dicyclopentadiene;
• and lesser amounts of
• b. a mixture consisting essentially of dimerized aliphatic cyclic and non-cyclic dienes of five carbon atoms, and
• c. tall oil,
• form a base resin having Gardner-Holdt solution viscosities at about 25.degree. C (bubble seconds) of from about 1.65 to about 9.0 (60% in 47 Kauri butanol gravure ink solvent) and from about 10 to about 1000 (50% in 31 Kauri butanol heat set ink solvent).

A process for producing a base resin suitable for use in heat-set and gravure printing ink compositions, which process comprises:

• at a temperature of from about 230.degree. C to 270.degree. C and at autogenous pressure and under agitation, reacting a mixture consisting essentially of:
• (a) about fifty to about seventy-five percent of dicyclopentadiene or a dicyclopentadiene-rich hydrocarbon fraction containing at least about seventy percent dicyclopentadiene and minor amounts of methyl dicyclopentadiene and codimers of cyclopentadiene and methyl cyclopentadiene;
• (b) from about five to about twenty percent of a mixture consisting essentially of from about seventy to about ninety percent dimers of isoprene, cis-piperylene and trans-piperylene and codimers, trimers and cotrimers of isoprene, cis-piperylene, trans-piperylene and cyclopentadiene;
• and (c) from about ten to about thirty percent refined tall oil consisting essentially of a predominant amount of tall oil fatty acids and a lesser amount of tall oil rosin acids, to produce a base resin having a Ring and Ball softening point of from about 130.degree. C to about 160.degree. C and an Acid Number of less than about five;
• and Gardner-Holdt solution viscosities at about 25.degree. C (bubble seconds) of from about 1.65 to about 9.0 (60% in 47 Kauri butanol gravure ink solvent) and from about 10 to about 1000 (50% in 31 Kauri butanol heat set ink solvent).