# US 4,391,640 A · Process for producing oil-modified and rosin-modified phenolic resin for printing inks > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,391,640 A - Document ID: US4391640A - Status: Granted - Kind: A - Application number: 06/270,021 - Filed: 1981-06-03 - Granted: 1983-07-05 - Earliest claimed: 1980-06-05 - Assignees: Dainippon Ink and Chemicals, Inc. - Inventors: Noboru Okoshi; Kin-ichi Kudo; Shoichi Shimoyama - Web page: https://patentgrep.com/patent/US4391640A ## CPC - C09D 11/103: of aldehydes, e.g. phenol-formaldehyde resins - C08G 8/28: Chemically modified polycondensates - C08L 61/14: Modified phenol-aldehyde condensates - Y10S 260/38: Ink - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A process for producing an animal or vegetable oil-modified and rosin-modified phenolic resin for printing inks, which comprises: [I] reacting (a) a resol-type phenol/formaldehyde initial condensation product, (b) an animal or vegetable oil having an iodine value of 100 to 210 or containing a hydroxyl group, (c) a rosin and (d) an alchohol, and if required, (e) an acid or (f) a hydrocarbon resin; or [II] reacting the condensation product (a) and the animal or vegetable oil (b) with a rosin ester obtained by the reaction of the rosin (c) and the alcohol (d) and if required, the acid (e) or the hydrocarbon resin (f) in advance. ## Claims ### Claim 1 A process for producing an animal or vegetable oil-modified and rosin-modified phenolic resin for printing inks, which comprises: (I) reacting (a) a resol phenol/formaldehyde initial condensation product, (b) an animal or vegetable oil having an iodine value of 100 to 210 or containing a hydroxyl group, (c) a rosin and (d) an alcohol; or (II) reacting the condensation product (a) and the animal or vegetable oil (b) with a rosin ester obtained by the reaction of the rosin (c) and the alcohol (d). ### Claim 2 (depends on 1) The process of claim 1 wherein the animal or vegetable oil-modified and rosin-modified phenolic resin has an acid value of not more than 30 and a softening point of at least 70.degree. C. ### Claim 3 (depends on 2) The process of claim 2 wherein the animal or vegetable-modified and rosin-modified phenolic resin has a softening point of from 100.degree. to 150.degree. C. ### Claim 4 (depends on 1) The process of claim 1 wherein the resol phenol/formaldehyde initial condensation product (a) is a product obtained by reacting a phenol selected from the group consisting of phenol, cresol, p-tert-butylphenol, p-octylphenol, p-nonylphenol and bisphenol A with a formaldehyde-yielding substance selected from the group consisting of formalin and paraformaldehyde in the presence of an alkaline catalyst, and neutralizing the reaction product with an acid. ### Claim 5 (depends on 1) The process of claim 1 wherein the resol phenol/formaldehyde initial condensation product is a mixture of a compound of the formula (A) ##STR4## wherein R represents a hydrogen atom or an alkyl group, as the main component, and at least one compound selected from compounds of the formula (B) and (C); ##STR5## wherein R is as defined above, ##STR6## wherein R is as defined above. ### Claim 6 (depends on 1) The process of claim 1 wherein the animal or vegetable oil (b) is at least one member selected from the group consisting of tall oil, cotton seed oil, soybean oil, safflower oil, dehydrated castor oil, linseed oil, tung oil, cattlefish oil, sardine oil, castor oil and stand oil or the fatty acids thereof. ### Claim 7 (depends on 1) The process of claim 1 wherein from 10 to 35 parts by weight of the resol phenol/formaldehyde initial condensation production (a) per 100 parts by weight of the entire resin-forming components and from 5 to 40 parts by weight of the animal or vegetable oil (b), per 100 parts by weight of the entire resin-forming components are reacted to form the reaction product (I) or (II). ### Claim 8 (depends on 1) The process of claim 1 wherein said rosin (c) is selected from the group consisting of gum rosin, wood rosin, tall oil rosin and hardened rosin and the alcohol (d) is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, hexanediol, hexanetriol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, hexyl alcohol, nonyl alcohol and octyl alcohol. ### Claim 9 (depends on 1, 10) The process of claim 1 or 10 wherein said oil-modified and rosin-modified phenolic resin is prepared by adding the initial condensation product (a) dropwise continuously or intermittently at a temperature of 120.degree. to 180.degree. C. for a period of from 1 to 5 hours to a mixture of the rosin (c) and animal or vegetable oil (b) and esterifying the resulting reaction product with the alcohol (d) at 200.degree. to 280.degree. C. ### Claim 10 A process for producing an animal or vegetable oil-modified and rosin-modified phenolic resin useful in preparing varnishes for printing inks having both high gloss and fast set which comprises reacting (a) a resol phenol/formaldehyde initial condensation product comprised predominantly of a compound of the formula (a) ##STR7## wherein R represents a hydrogen atom or an alkyl group, (b) at least one animal or vegetable oil having an iodine value of 100 to 210 or containing an hydroxyl group; (c) a rosin, and (d) a trihydric aliphatic alcohol or higher aliphatic monohydric alcohol; and, up to not more than 30 parts by weight per 100 parts by weight of the total resin-forming components of an aliphatic, aromatic or alicyclic resin having a number average molecular weight of about 500 to 5,000 and a softening point of at least 70.degree. C.; the amounts of (a) and (b) being, respectively, from about 10 to about 35 parts, and about 5 to about 45 parts, each based on 100 parts by weight of the resin-forming components; and the amount of the alcohol (d) providing an equivalent ratio of hydroxyl groups to the total carboxylic acid of from 0.7:1 to 1.3:1; said oil-modified and rosin-modified phenolic resin having a softening point of 100.degree. to 150.degree. C. and an acid value of not more than 30 and a number average molecular weight of from about 500 to about 5,000 calculated in terms of polystyrene. ### Claim 11 A process for producing an animal or vegetable oil-modified and rosin-modified phenolic resin useful in preparing varnishes for printing inks having both high gloss and fast set which comprises reacting (a) a resol phenol/formaldehyde initial condensation product comprised predominantly of a compound of the formula (A) ##STR8## wherein R represents a hydrogen atom or an alkyl group, (b) at least one animal or vegetable oil having an iodine value of 100 to 210 or containing an hydroxyl group; (c) a rosin, (d) a trihydric aliphatic alcohol or higher aliphatic monohydric alcohol, and at least one of the following components (e) and (f): (e) a monobasic or polybasic carboxylic acid, (f) an aliphatic, aromatic or alicyclic resin having a number average molecular weight of about 500 to 5,000 and a softening point of at least 70.degree. C., the amount of (f) being up to not more than 30 parts by weight per 100 parts by weight of the total resin-forming components; the amounts of (a) and (b) being, respectively, from about 10 to about 35 parts, and about 5 to about 45 parts, each based on 100 parts by weight of the resin-forming components; and the amount of the alcohol (d) providing an equivalent ratio of hydroxyl groups to the total carboxylic acid of from 0.7:1 to 1.3:1; said oil-modified and rosin-modified phenolic resin having a softening point of 100.degree. to 150.degree. C. and an acid value of not more than 30 and a number average molecular weight of from about 500 to about 5,000 calculated in terms of polystyrene. ### Claim 12 (depends on 11) The process of claim 11 wherein component (e) is present. ### Claim 13 (depends on 11) The process of claim 11 wherein component (f) is present. ### Claim 14 A process for producing an animal or vegetable oil-modified and rosin-modified phenolic resin for printing inks, which comprises (I) reacting (a) a resol phenol/formaldehyde initial condensation product, (b) an animal or vegetable oil having an iodine value of 100 to 210 or containing a hydroxyl group, (c) a rosin and (d) an alcohol; or (II) reacting the condensation product (a) and the animal or vegetable oil (b) with a rosin ester formed by reacting the rosin (c) and the alcohol (d); and further reacting the reaction product (I) or (II) with a carboxylic acid (e) or a hydrocarbon resin (f) selected from the group consisting of aliphatic, aromatic and alicyclic resins having a number average molecular weight of from about 500 to about 5,000 and a softening point of at least 70.degree. C. ### Claim 15 (depends on 14) The process of claim 14 wherein the reaction product (I) is reacted with the carboxylic acid (e). ### Claim 16 (depends on 14) The process of claim 14 wherein the reaction product (I) is further reacted with the hydrocarbon resin (f). ### Claim 17 (depends on 14) The process of claim 14 wherein the reaction product (II) is further reacted with the carboxylic acid (e). ### Claim 18 (depends on 14) The process of claim 14 wherein the reaction product (II) is further reacted with the hydrocarbon resin (f).