Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
  • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
  • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
  • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
  • B29K2309/08—Glass
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
  • Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
  • Y10T156/1043—Subsequent to assembly
  • Y10T156/1044—Subsequent to assembly of parallel stacked sheets only
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31739—Nylon type
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31761—Next to aldehyde or ketone condensation product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31942—Of aldehyde or ketone condensation product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
  • Y10T442/3472—Woven fabric including an additional woven fabric layer
  • Y10T442/3504—Woven fabric layers comprise chemically different strand material
  • Y10T442/3512—Three or more fabric layers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
  • Y10T442/3472—Woven fabric including an additional woven fabric layer
  • Y10T442/3528—Three or more fabric layers
  • Y10T442/3569—Woven fabric layers impregnated with a thermosetting resin
  • Y10T442/3577—Phenolic resin

Definitions

• Certain fire-resistant resins such as melamine formaldehyde resins,--arenot only substantially more expensiyejthanphenolic resins, but when applied to cellulosic fibrousmaterials, their moisture resistance is poor.
• the dielectric strength of melamines is not as high as vthat of other cheaper laminates, and thick sections, that is overone-quarter of an inch, tend to crack badly on :aging, particularly at temperatures of 100 C. For examplega melamine formaldehyde laminatell z inches thick when heated to 100 C. had cracked badly in one :day.
• test equipment comprises a ventilated'box approximately l8inches square in cross section and about 3 feet high with an opening at the top .in which there is disposed a constant speed exhaust fan to withdrawgases 'from the box.
• a four-jawed chuck adapted to hold in a vertical position laminate specimens having dimensions of /2 inch 'by cinch-by 5 inches in length.
• a heating coil composed of nickel-chromium alloy wound on a 1 .inch diameter of a length of Z'inchesgis located with its center. about the specimen held-in the chuck. Above the top.turn of this heating coil are disposed two automobile spark plugs with their ignition-electrode tips approximately of an inch away from two opposite sides of ,the laminatesample'tobe tested.
• a rod of the .sample machined to dimensions of /2 inch by /2 inch by 5 inches in length is insertedin-the chuck, andtheheat- .ingcoil iszenergized with 55 amperes of electrical cur- .rent and the spark plugs are energized with electrical cur- .rentso that an electrical .arc plays .across .the ignition electrodes continuously.
• the ignition time is the United States Patent 0 elapsed time from the start of energization of the coil and the arcing of the spark plugs until a flame settles upon the sample.
• the object of this invention is to provide for thermosettable resinous reaction products comprising phenol, dicyandiamide and formaldehyde, which when applied to fibrous sheet material and cured under heat and pressure result in resinous laminates that are highly fire resistant.
• thermoset laminates comprising a fibrous sheet material and a .thermoset reaction product of phenol, dicyandiamide and formaldehyde, which laminate has a high fire resistance, good electrical insulating properties and high physical strength.
• thermoset resinous laminates may be prepared from a resinous prodnot derived by reacting phenol, dicyanidiamide and formaldehyde in the proportions of 1 mole of the phenol, from 0.8 to 2 moles of dicyandiamide and from.0.9 to 1.5 moles of formaldehydelper mole. of the phenol and. dicyandiamide. Water is present, being usually furnished as a part of aqueous formaldehyde solution (37% .to 40%.), and amounting to at leastv 10% of the weight of the reactants, and ordinarily should not exceed the weight of the reactants.
• the mixture is reactedunder alkaline conditions for at least /2 hour, and preferably by refluxing from 1 to 2 hours, and then is vacuum dehydrated at a temperature not exceeding C. until substantially all of the water is removed and then a volatile solvent is applied to produce an impregnating varnish.
• Tie varnish may include a small proportion of the order of 2% to 10% by weight of finely divided solids such assilica, aluminum oxide, antimony oxide and the like refrac-torysolids to impart better flame resistance.
• The-impregnating varnish' is applied tofibrous sheet materials andparticularly cellulosic fibrous materials,- such as kraft paper, alpha paper and cotton cloth. Exceptional flame resistant properties and high strengths are obtained using such cellulosic materials.
• cellulosic fibrous materials such as kraft paper, alpha paper and cotton cloth.
• other fibrous materials may be used, such as glass cloth, glass mat,
• asbestos cloth, nylon cloth and other synthetic resinous fibrousmaterial ispassed through an oven or other dryer after each dipto remove the volatile .solvent.
• the heat treatment of the applied phenol-.dicyandiamide-formaldehyde resin at this stage is conducted so that the resulting treated fabric has a green ness offrom 0.5 to 10%.
• the greenness is determined byplacing a small piece of the-resin treated sheet mate- .rial in-aIhot-press at atemperature of C. and a pressure of 1,000 pounds per square inch for 5 minutes, .and then measuring the amount of resin that'is forced out or by employing water-alcohol mixtures as the solvent.
• a greenness of is relatively high and is desirable for the making of certain products, such as tubes which require a considerable flow of resin between laminations in order that the laminations bond adequately.
• a greenness of about 0.5% on the other hand is relatively low but is essential for the purpose of making thick flat laminates, for example, V inch thickness and greater. For preparing laminates of thicknesses of V8 inch, a greenness of from 1% to 3 is adequate.
• the sheet fibrous material with the applied B stage phenol-dicyandiamide-formaldehyde resinous product thereon, may be molded into laminates, tubes and other members by superimposing a plurality of layers of the treated sheet material and compressing it at pressures of from 150 to 5,000 pounds per square inch at temperatures of from 135 C. to 165 C. It will be appreciated that the fibrous sheet material may be chopped or macerated, or otherwise treated, and members molded fromv such comminuted fibrous material. Of course, the highest strength products are secured with laminates made from superimposed layers of the impregnated fibrous sheet material.
• the ammonia and the formaldehyde were admixed before being introduced into the kettle with the remainder of the ingredients, the mixture having a pH of approximately 8.5.
• the mixture was slowly heated, and at 80 C. an exothermic reaction took place that carried the temperature to approximately 95 C. Additional heat was then supplied in order to cause the reaction mixture to reflux.
• the mixture was refluxed for 90 minutes and then dehydrated under a vacuum of 28 inches of mercury, and the temperature gradually increased to approximately 75 C. during dehydration. Substantially all the water had been removed.
• reaction 4 (2) 5 mil thick kratt paper, the treated paper contain- 1 ing 98% of its weight of resin solids, the greenness being (3) 6 /2 ounce bleached cambric, the resin solids being equal to the weight of the cambric, the greenness being 0.5%.
• Laminates were prepared from each of these three impregnated materials by superimposing a sufficient number of laminations to produce consolidated members of various thicknesses of up to V2 inch. The superimposed layers were consolidated at 1,000 pounds per square inch with the temperature of the press platens slowly rising to a final temperature of 165 C.
• the following table sets forth the ignition time and burning time in seconds of the laminates, and includes a standard XXX-grade phenolic laminate prepared from alpha cellulose paper for comparison purposes.
• OOHdllilOD O-96/23/96 After 96 hours at 23 0. and 96% relative humidity.
• Condition D-24/23" Tested after 24 hours immersion in distilled water at 23 C.
• Laminates made from kraft paper treated with the resin of Example I to a resin content exhibited tensile strengths of 22,800 p. s. i., flexural strength of 28,050 p. s. i., compressive strength of 51,320 p. s. i., and izod impactof 2.2 ft. 1bs. per-inch width flatwise (XXX grade phenolic having an izodimpact of 1.4 ft. lbs. per inch .width flatwise)
• EXAMPLE II The procedureof Example I was employed in reacting the J following:
• the mixture was dehydrated under a vacuum of 27 inches of mercury and a final. temperature of 70 C.
• the resulting reactionproduct was then dissolved in a solvent mixture comprising 90gallonsof 95% ethanol and 35 gallons of water.
• the resulting varnish had a viscosity of approximately 250 centipoises and between 52% and .55 by weight of recoverable resin solids.
• the set time 'goods are treated with solvents and the like to remove naturallypresent-waxes and the like.
• the dielectric strength of the grey goods laminates was 522 volts per mil thickness for the inch laminate and 372 volts per mil thickness for the Ms inch laminate. These dielectric strength values are excellent and equal to those of the best phenolic laminates available in the trade.
• the resinous compositions of this invention may be prepared by substituting cresol for a part or all of the phenol. Furthermore, the phenol, dicyandiamide and formaldehyde may be reacted with other alkali catalysts than ammonia, and in some cases, we have found that the reaction will occur without the extraneous addition of any catalysts whatever.
• Suitable alkali catalysts are sodium hydroxide, sodium carbonate, disodium phosphate, calcium oxide and barium oxide. The catalysts may be employed in an amount of up to based on the weight of the phenol.
• the laminates of this invention have been applied with considerable success to circuit interrupters.
• arc barriers, splitters, channels and tubes and insulating supports for conductors, as well as the covers, bases and other structural parts not necessarily subject to full voltage of the conductors have been prepared from the laminates of this invention.
• Fuse tubes and other fuse elements may be advantageously made from the laminates. Switchboards and cubicles containing electrical members subject to considerable .and arcing members.
• thermoset resinous laminates comprising impregnating a sheet fibrous material with a solution of a thermosettable resinous product derived by reacting onlyone mole of a phenol, from 0.8 to 2.0 moles of dicyandiamide, and
• the volatile solvent comprises a mixture of ethanol and Water in the proportions of from 20% to 80% by weight of ethanol.
• the sheet fibrous material comprises cellulose and the volatile solvent in a mixture of water and ethanol in the proportions of from 20% to 80% by weight of ethanol.
• An impregnating varnish comprising in combination (a) from 30% to 60% by weight of a thermosettable resinous product derived by reacting only one mole of a phenol, from 0.8 to 2.0 moles of dicyandiamide, and from 0.9 to 1.5 moles of formaldehyde per mole of the phenol and dicyandiamide in the presence of water and an alkali catalyst in an amount of up to 5% of the weight of the phenol, the mixture being refluxed for at least /2 hour, and then vacuum dehydrated at a temperature not exceeding C., and (b) from 70% to 40% by Weight of a volatile solvent comprising amixture of ethanol and water, the ethanol comprising from 20% to 80% by weight of the volatile solvent.
• thermoset laminate comprising a plurality of layers of sheet fibrous material and a thermoset resin impregnating each of the layers, the thermoset resin also uniting the layers, the thermoset resin comprising from 0.7 to 2 times the weight of the sheet fibrous material, the thermoset resin comprising the cured resinous product derived by reacting only one mole of a phenol, from 0.8 to 2.0 moles of dicyandiamide, and from 0.9 to 1.5 moles of formaldehyde per mole of the phenol and dicyandiamide in the presence of water and an alkali catalyst in an amount of up to 5% of the weight of the phenol, the mixture being refluxed for at least /2 hour, and then vacuum dehydrated at a temperature not exceeding 100 C.
• thermoset laminate comprising a plurality of layers of cotton fabric and a thermoset resin uniting the layers, the thermoset resin comprising from 0.7 to 2 times the weight of the sheet fibrous material, the thermoset resin comprising the cured resinous product derived by reacting only one mole of a phenol, from 0.8 to 2.0 moles of dicyandiamide, and from 0.9 to 1.5 moles of'formaldehyde per mole of the phenol and dicyandiamide in the presence of water and an alkali catalyst in an amount of up to 5% of the Weight of the phenol, the mixture being refluxed for at least /2 hour, and then vacuum dehydrated at a temperature not exceeding 100 C., the resulting resinous reaction product being dissolved in a mixture of water and ethanol, the solution being applied to the cotton fabric and dried to evaporate the solvent and to advance the reaction product to the B stage.
• an insulating member comprising a fire-resistant thermoset laminate comprising a plurality of layers of sheet fibrous material and a thermoset resin uniting the layers
• an insulating member comprising a fire-resistant themoset laminate comprising a plurality of layers of sheet fibrous material and a thermoset resin uniting the layers, the thermoset resin uniting the layers, the thermoset resin comprising from 0.7 to 2 times the weight of the sheet fibrous material, the thermoset resin comprising the cured resinous product derived by reacting only one mole of a phenol, from 0.8 to 2.0 moles of dicyandiamide, and from 0.9 to 1.5 moles of formaldehyde per mole of the phenol and dicyandiamide in the presence of water and an alkali catalyst in an amount of up to 5% of the weight of the phenol, the mixture being refluxed for at least /2 hour, and then vacuum dehydrated at a temperature not exceeding 100 C., said insulating member having a high resistance to ignition due to the high temperatures and being rapidly self-extinguishing.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Composite Materials (AREA)
• Mechanical Engineering (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Mathematical Physics (AREA)
• Laminated Bodies (AREA)
• Reinforced Plastic Materials (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Organic Insulating Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (6)

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Publications (1)

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Cited By (10)

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Citations (6)

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• 1954
  • 1954-07-15 US US443720A patent/US2801672A/en not_active Expired - Lifetime
• 1955
  • 1955-07-08 FR FR1135352D patent/FR1135352A/fr not_active Expired
  • 1955-07-08 GB GB1978355A patent/GB785731A/en not_active Expired
  • 1955-07-14 DE DEW17098A patent/DE1040781B/de active Pending
  • 1955-07-14 CH CH353896D patent/CH353896A/de unknown
  • 1955-07-15 JP JP1918655A patent/JPS33797B1/ja active Pending

Patent Citations (6)

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