# US 4,393,189 A · Method of preparing a phenolic aldehyde resin and resin composition for an adhesive system to be applied to glass fibers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,393,189 A - Document ID: US4393189A - Status: Granted - Kind: A - Application number: 06/321,971 - Filed: 1981-11-16 - Granted: 1983-07-12 - Earliest claimed: 1978-10-30 - Assignees: PPG Industries, Inc. - Inventors: Mikhail M. Girgis - Web page: https://patentgrep.com/patent/US4393189A ## CPC - C08J 5/08: glass fibres - C08G 8/08: of formaldehyde, e.g. of formaldehyde formed in situ - C08L 61/06: of aldehydes with phenols - C09J 121/02: Latex - C09J 161/06: of aldehydes with phenols - C08J 2321/00: Characterised by the use of unspecified rubbers - C08L 2666/16: Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof - Y10S 156/91: Bonding tire cord and elastomer: improved adhesive system - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - 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) - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A method of preparing a thermoplastic, water-soluble, phenolic aldehyde resin and the composition are provided to enhance the flexibility and resistance to compression fatigue breakage of glass fibers to which the resin has been applied. The method involves two steps. In the first step, the phenolic compound and the aldehyde are reacted to less than 100 percent completion in an amount so that the aldehyde to phenolic compound ratio is in the range of about 0.6 to about 1.5 and at an acidic pH and for a period of time equivalent to about 3 hours to about 10 hours when the temperature is in the range of about 55.degree. F. (13.degree. C.) to about 90.degree. F. (32.degree. C.) to produce a resinous mixture. In the second stage the pH of the reaction is adjusted within the range above about 7.0 to about 7.5 and the reaction is continued between the unreacted phenolic compound and aldehyde and resinous mixture to produce a resinous mixture composition that is thermoplastic, and water soluble and has trimer polymer with slight cross-linking and dimer and no higher oligomer polymers. The phenolic aldehyde resin mixture is processed into an adhesive system by combining it with one or more elastomeric latex and various latex additives. The adhesive system is aged and has added to it an amine or ammonia to tie up any unreacted aldehyde. Also additional phenolic compound may be added. The adhesive system is used to coat filamentary materials and the coated filamentary materials are dried to produce reinforcement material for rubber. ## Claims ### Claim 1 An improved flexible and tough resorcinolic or resorcinolic and phenolic aldehyde resin, comprising a thermoplastic, water soluble, resorcinol or resorcinol and a phenolic aldehyde resin that is a mixture of polymers having trimer polymer and dimer polymer and no higher non-water soluble oligomers produced by: a. reacting to less than 100 percent completion a resorcinol or resorcinol and phenolic compound with an aldehyde in an amount of aldehyde to resorcinol or aldehyde to mixture of resorcinol and phenolic compound in mole ratio in the range of about 0.8 to about 1.5 and at a pH in the range of about 3.5 to about 5.5 to limit formation of resorcinol and phenolic alcohols and for a period of time equivalent to a period of time in the range of about 3 hours to about 10 hours at a temperature in the range of about 55.degree. F. (13.degree. C.) to about 90.degree. F. (32.degree. C.) to produce a resinous polymer mixture along with unreacted resorcinol, or resorcinol and phenolic compound and aldehyde in the polymer mixture, and b. continuing the resin reaction at a pH maintained above 7 to about 7.5 at a temperature in the range of 55.degree. F. (13.degree. C.) to 90.degree. F. (32.degree. C.) when the residence time is in the range of 0.5 hours to about 10 hours thereby producing a thermoplastic, water soluble, resorcinolic or resorcinolic and phenolic aldehyde resin mixture with improved flexibility and with toughness, since it has a substantial amount of trimer and dimer polymers without any higher oligomers and has only slight cross-linking and is capable of further reaction. ### Claim 2 (depends on 1) Composition according to claim 1 wherein the phenolic compound is a mixture of resorcinol and phenol. ### Claim 3 (depends on 1) Composition according to claim 1 wherein the aldehyde is formaldehyde. ### Claim 4 (depends on 3) Composition according to claim 3 wherein the formaldehyde is in the form of formalin. ### Claim 5 (depends on 4) Composition of claim 4 wherein the slightly cross-linked, thermoplastic water soluble resorcinolic or resorcinolic and phenolic aldehyde resin mixture has up to 20 percent unreacted aldehyde. ### Claim 6 (depends on 1) Composition of claim 1 wherein an acid catalyst was used to obtain a pH of about 3.5 to about 5.5.