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Y MONSANTO PL\s / .'Ss L._ MONSANTO PLASTICIZERS in Synthetic <%e*in c4dhe*ive* Monsanto Tochnical Bvllotin No. 0-99 April, 1953 Monsanto Chemical Company, Organic Chemicals Division, St. Louis 1, Mo* MONSANTO PLASTICIZERS ( M o n s a n to T o c h n ic a l B u lle tin N o . in Synthetic Resin Adhesives | INTRODUCTION The superior properties of plasticized synthetic resin adhesives are causing these pre parations to rapidly displace or supplement conventional animal and vegetable base adhesives. The synthetic resin adhesives referred to are primarily adhesives based on polyvinyl acetate and its co-polymers with polyvinyl chloride or polyvinyl alcohol, but also included are adhesives with such bases as nitrocellulose, zein, casein, acry lates, polystyrene, cellulose and other polymers. Synthetic resin adhesives find a wide and increasing usage in such diverse industries as the following: Shoe industry Book binding industry Paper bag and folding box carton manufacturing Sanitary food container producers Laminators and converters of packaging products Tobacco industry (packaging) Automotive industry Food industry (for labels and carton sealing), etc. Factors contributing to the rapid increase in the quantity use of synthetic resin ad hesives are these: 1) Synthetics are better adapted to high speed machinery operation and make up their increased cost over other adhesive types by the resultant increases in production rates. 2) Synthetic adhesives are cleaner and easier to use from a production and maintenance standpoint. 3) Synthetic adhesives have superior water, mold and fungus resistance and better light stability than conventional organic adhesives. Also, any degree of flexibility can be obtained. 4) Adhesive emulsions obviate the use of volatile, toxic or flammable solvents. Emulsion properties can be carefully adjusted and controlled for specific needs. Plasticizers are essential in synthetic resin adhesives for improving film formation, imparting tack, decreasing drying time, imparting flexibility and gloss and reducing costs. Production rates are often increased several hundred percent by switching from ordinary pastes and glues to synthetic resin adhesives. Emulsion adhesive costs are reduced because plasticizers increase emulsion viscosities to such an extent that water is often used to thin down the formulation, with a net reduction in cost even though a relatively expensive plasticizer is used. Monsanto is a major supplier of the plasticizers used in synthetic resin adhesives and also supplies such necessities as preservatives, wetting agents, odorant or masking agents, and in some instances -- the resins themselves. Monsanto plasticizers meet the demands of being efficient, heat and light stable, and nontoxic. They possess excellent grease resistance and are of moderate to low cost. Typical formulations of various synthetic resin adhesives are given in this bulletin, with discussion emphasis on their plasticizer content. Th Ch*mic*l construed rtcovnmt iy product in conflict with A p ril, 1953 06i<t7a5 TOWOLDMONOQ38862 TYPES OF RESIN ADHESIVE FORMULATIONS The major types of plasticized synthetic resin adhesive formulations are A, Emulsion; B, Hot-melt; C, Delayed-tack; D, Solvent; E, Pressure Sensitive and F, Adhesive Primers or Coatings. These will be discussed in order. Units for all formulations are weight percent or parts by weight. Sources of ingredients are listed at the back of this bulletin. , A. fmuliion Adhesives Resin emulsion adhesives are emulsions of plasticized resins dispersed in a water base. They are often ex tended with materials like starch paste and thus require the incorporation of a preservative. The resin most commonly used in emulsion adhesives is polyvinyl acetate. The following is a typical polyvinyl acetate emul sion adhesive formula: A.-l. Polyvinyl acetate emulsion (55% solids) Plasticizer Clay Filler Cooked starch or dextrine Preservative Stabilizer Wetting Agent Secondary water Defoamer Odorant (masking agent) 100 10 -50 0 -30 0 - 1,000 1 -2 1 -2 0 -0.2 75 -100 1 -2 0 -1 The plasticizers most commonly used in polyvinyl acetate emulsion adhesives are dibutyl phthalate and orthonitrobiphenyl (ONB). Dibutyl phthalate imparts good flexibility and softening action with relatively low volatility. ONB is not quite as efficient as dibutyl phthalate as a plasticizer, but is widely used because of its economy as either an "extender" plasticizer or as the sole primary plasticizer. Dimethyl phthaLte is used in some cases because of its low cost and because it is a better solvent for bond ing to cellulose acetate film or sheeting where this material is used in making windows in or laminations to paper. Tricresyl phosphate and Santicizer* 140 are used where flame resistance, oil resistance and low vola tility are desired. Santicizer 140 is more efficient than TCP and has better light stability and less odor. Santicizer M-17 is an excellent plasticizer for bonding acetate overlays to paper, because of its superior light stability. Santicizer 8 imparts good flow and wetting action and has excellent grease resistance. Santicizer 160 is considered better in some applications than dibutyl phthalate because of its lower volatility, greater film toughness and improved moisture resistance. Santicizer products B-16, E-15 and 141 are used for nontoxic applications (food wrapping films, etc.) and have been granted approval for such uses by the U. S. Bureau of Animal Industry and the U. S. Food and Drug Administration. aANTlCIUR: IUf. VM. P*t. Off. 06 l A ?ti6 TOWOLDMONOQ38863 A. Emulsion Adhesives (continued) Monsanto industrial resins, Santolite* MHP and MS-80%, are the best resin additives lor use with poly vinyl acetate for imparting quick tack. They are being used successfully for bonding cellophane to cello phane and aluminum foil to paper. These resins make a very tough but flexible adhesive and are normally compounded with some liquid plasticizer like dibutyl phthalate, or with an eutectic mixture (1:1) of dibutyl phthalate and triphenyl phosphate. The table on page 5 gives data evaluating various Monsanto plasticizers in combination with polyvinyl ace tate. Properties evaluated are compatibility, volatility, low temperature flexibility and grease resistance. It will be noted that the typical emulsion adhesive formulation A.-l requires a preservative. Monsanto sup plies an excellent line of industrial preservatives which includes Santobrite*, Santophen* 20, Milmer*I and these masking agents: methyl salicylate, Santomask*, saccharin, coumarin and vanillin. Literature on these products is available. At the back of this bulletin is a listing of the various trade marked products men tioned in succeeding formulas. Formulas A.-2 and A.-3 below are more examples of polyvinyl acetate (PVA) emulsion adhesives. A.-2. Quick Tack PVA Emulsion Adhesive Gelva Emulsion S-56 (51% solids) Dibutyl Phthalate Santicizer* 8 Water 100 11.8 11.8 9.4 Through the use of other additives, adhesives designed for specialized purposes may be formulated. As an example, the following formulation shows good properties as an adhesive for bonding moistureproof cello phane to aluminum foil or to paper; or for bonding aluminum foil to paper. A.-3. Polyvinyl Acetate Emulsion Adhesive Gelva Emulsion S 55** Dibutyl Phthalate Santolite* MS-80% Water 100 9 13.5 13.4 This formulation shows rapid development of adhesion and maintains good bond strength at elevated temperatures. The following formula is an example of a low molecular weight styrene polymer candnon adheeive. SANTOUTE, OAlfTOBRrrS. BANTOPHEN, MlLkCSt, SANTOMAMC. OAlfTlCIZKR: Beg. U.S. ft. Off. a** mibi p<t a. -2- ObiHlQl TOWOLDMONOQ38864 A. Emulsion Adhesives (continued) Styrene Emulsion Adhesive HB-40* Diethyl Phthalate Triton X155** Lustrex* Styrene 601-40 Ammonia Caseinate, 15% 18.0 6.0 2.5 100.0 34.0 Formula A.-4. illustrates a basic, stable composition which possesses a high degree of wet tack. Such prop erties as stability, wet tack, and film toughness are imparted to this composition by the caseinate present and are varied by changes in the caseinate ratio., * The following formulation is suggested as a grease-resistant coating for paper products for wrapping such items as bakery goods. A.-5. Polyvinyl Acetate Grease-resistant Paper Coating Elvacet 81-900** Santicizer* B-16 Tri-Pure **(titanium dioxide) Water Quilon** 100 3.5 7.0 15-30 0-5 "Hie above composition is applied with a roll coater provided with a smoothing roll to develop a uniform con tinuous film. If used as a laminating adhesive, about 140F. heat is required for optimum film formation. B. Hot-melt Adhesives Hot-melt adhesives may be made with either liquid or solid plasticizers, depending upon the properties desired . *** e"d product. Santicizers* M-17 and 160 and dibutyl phthalate are favored because of their excellent t stability and mild odor. Of the solid plasticizers, diphenyl phthalate and Santicizer 1-H are preferred Decause they have the least odor and are in the proper melting point range for most applications. Three ulations are given (all parts are by weight or in weight percent). Hot-melt Coating Cellulose Acetate Santicizer* M-17 Inert fillers 50 88 35 Hot-meft Bookbinding Adhesive Neville Hard Resin** Santicizer 160* Paraffin wax 61.4% 15.0% 6.4% Raise temperature to 300-325F. and agitate after adding: Vinylite AYAA (polyvinyl acetate) Ethyl cellulose 12.9% 4.3% Bookbinding Hot Melt (application temp.: 165175F.) Copolymer C-3 Aroclor* 1254 Dibutyl Phthalate or Santicizer 160 Clay Fluxing resins (Bell-Ro or Rosin WW) 100 50-70 20-35 20-35 75 Mix and heat at 250o-Z7SF. until melted. MttIMt iigy,"-*1 MWTREX: R.f. UJ. P.t. Ott. MDIUMto product. -3- 0bl'i7llb TOWOLDMON0038865 C. Delayed-tack Adhesives These preparations. after they are spread and dried on a surface, are normally tack-free at ordinary tempera tures. They are activated by heat and possess the property of maintaining tackiness over a fairly wide tem perature range from several hours to several days. This permits the necessary mechanical handling, while two surfaces arc being united, before the adhesive becomes nontacky by cooling and setting. Thus, the action of delayed-tack adhesives differs from that of hot-melt adhesives where tackiness terminates on cooling alone. ^olid plasticizers, such as diphenyl phthalate and Santicizers* 1-H and 9, make possible the "delayed-tack" feature of these unusual adhesives. Plasticizers are selected on the basis of their effect on the base resin (i.e., the temperatures at which the adhesive quality inactivated and de-activated), and for their heat and light stability, odor, nontoxicity where required, etc. Much of this art is described in the patent literature (for example. I'.S. patents numbered 2.462.029; 2,608.54'; 2.608,545; 2.615,156 and 2,613.191) which should be investigated by those desiring to produce delayed-tack adhesives. Sample formulations below were taken from such patents, as indicated. C.-l. Example 9b Delayed-tack Adhesive (from l\S. Patent No. 2,462,029) Santicizer* 1-H Vinsol Ke.-in Thinned Amine Dispersant Acrysol M.R. 50 50 240 10 The thinned amine dispersant is a mixture composed of 1 part stearic acid, 1 part "polypale resin", a polymerized rosin containing approximately 40% dipolymers of abietic acid (Hercules Powder Co.). 1 pan of 2amino-2methvl-1 propanol (Commercial Solvents Corp.) and 5 parts of water. This com position is designed solely as a dispersing assistant . . ." --From Column 10 of above patent. C.-2. Example 18 Delayed Tack Adhesive (from U.S. Patent No. 2.462,029) Diphenyl Phthalate Nevindine R-3 'I'hinned aminedispersant (see above) Hycar OR-25 52.5 30.0 198.0 43.5 The above formulation is nontacky at ordinary temperatures and is heat activated at about 150F. T he compound will then remain adhesive through temperatures as low as 50F. Once set. the ad hesive continues to hold at ordinary temperatures. C.-3. Polystyrene Emulsion Delayed-tack Adhesive (Example 1 of C.S. Pat. No. 2,613,156) "Ten (10) parts polystyrene (molecular weight 10,000 15,000) and 40 parts diphenyl phthalate are mixed and heated together at approximately 190F.. forming a clear fluid. While still at this temperature, the fluid is poured into a solution of 6 parts of a 25% aqueous solution of Aerosol OT and 4.5 parts polyvinyl alcohol (of the grade sold under the trade name of Elvanol 50-42) in 75.5 parts water; the solution being at a temperature of approximately 190F., constant agitation is maintained, resulting in a homogeneous emulsion. The emulsion is then permitted to cool." (This formulation is improved by the addition, after cooling, of 8 parts of Geon polyblend 550X20.) This will form a smooth nongrainy film when spread evenly on paper and will dry to a completely tack-free surface. When heated to 170F., the film becomes very tacky and powerfully adhesive, retaining these prop erties for as long as 70 seconds while cooling. *8ANT1CIZER: UJ9. Pot. Off. Monunto Product, product llttlag on p*f* 4- 0614769 TOWOLDMONOQ38866 EVALUATION OF MONSANTO PLASTICIZERS IN COMBINATION WITH POLYVINYL ACETATE EMULSION PLASTICIZER* VOLATILITY 24 Hours at 87C. [Activated Carbon) LOW TEMP. FLEXIBILITY, C. Modified Clash & Berg Test OIL EXTRACTION -- /a Weigh! Loss After 24 Hours at Room Temperature KEROSENE PEANUT OIL COTTON SEED OIL Dimethyl Phthalate Diethyl Phthalate 5.6% 4.8 -- 1.6C. -- 5.0 0.9 2*+ 0.85 0.75% 0.63 Dibutyl Phthalate 4.4 -6.1 0.59 0.51 ' Diphenyl Phthalate 59 1.31 0.90 ' Santicizer 160 2.1 + 1.9 0.20 0.39 Tricresyl Phosphate 0.75 + 3.6 0.16 0.38 Triphenyl Phosphate 2.0 + 5.7 0.02 0.37 Santicizer** 140 1.2 + 5.0 0.15 0.34 Santicizer 141 1.8 -- 3.3 0.17 0.42 Santicizer 8 5.6 + 6.4 0.43 0.60 Santicizer 1-H 1.5 0.96 0.36 Santicizer 9 3.1 1.13 0.57 Santicizer B-16 2.2 -- 3.9 0.08 0.46 Santicizer M-17 3.6 + 1.5 0.19 0.50 Ortho-Nitrobiphenyl 5.2 + 3.7 0.69 0.72 FORMULATION: 11 parts of plasticiser In 100 ports Shawlnlgan 8-55 Oelva (polyvinyl acetatei emulsion Film thickness 0 040 Inches BANTICrZKR: Trade Mark Reg U 8. Pat Off. 0.93% 0.82 0.59 0.98 0.34 0.46 0.38 0.36 0.31 0.64 0.53 0.63 0.36 0.48 0.68 0614790 TOWOLDMONOQ38867 D. Solvent Type Adhesives In this type of synthetic resin adhesive, solvents are used to carry the adhesive instead of water as in the emulsion type. Two typical formulations follow. D.-l. Heat Sailing NBroceNutose Lacquar Nitrocellulose (V** sec.) Santolite* MHP resin Dibutyl phthalate Denatured alcohol Ethyl acetate Toluol 15% 16% 8% 15% 31% 15% Formulation D,-l is suitable for bonding cellophane* to cellophane or as a lacquer coating which can be heat sealed. D.-2. Nontoxic, Greese-rosistent Paper Coating Vinylite VYHH** Vinylite VMCH Vinylite VAGH Santicizer* 141 orM-17 Acetone Methyl ethyl ketone 80 10 10 20 250 100 The above formulation can be used as a nontoxic, grease-resistant paper coating or heat sealing lacquer. E. Pressure Sensitive Adhosives These adhesives are tacky at ordinary temperatures and require moderate finger or roller pressure when placing coated matenals. E.-l. E.-2. Pressure Sensitive Adhesive (calender onto fabric) Cellulose acetate (Type A-9, Tennesee Eastman Corp., 40 mesh) Santicizer 8 Santolitet MHP resin Pressure Sensitive Adhesive (calender onto fabric) Vinylite AYAF (polyvinyl acetate) Rauzene N100 (100% phenolic resin) Santicizer B-16 1 2.5 - 5 1-2 5 36 18 E.-3. Pressure Sensitive Adhesive (hot-melt type) Rubber or pale crepe rubber Vistanex (polyisobutylene) Santolite MHP resin Ester gum Methyl abietate, dibutyl phthalate, Aroclor* or Santicizer B-16 Wax (Montan, paraffin, camauba or amorphous microcrystalline) 15 - 25 5 - 15 20 20 25 - 50 1 - 20 Melt all components except rubber at about 210F. Add rubber and drop temperature to 180F. Stir at this temperature for 1 to 2 hours until smooth. Hot cast on suitable surface. J\ Adhesive Primers These preparations are used in the same fashion as paint primers; i.e., they are applied as a preliminary coating to make following coats adhere better. In this case, the follower coat may be any type of adhesive. F.-l. Adhesive Primer (for bonding vinyls to paper or cloth) Vinylite VYNS Vinylite VMCH Santicizer 160 Methyl ethyl ketone Solvesso No. 1 18 2 15 25 17 SAKTOLTO. SANTICIZER. AROCLOR: R*filUrl Tridl Mark. MoBMBto product*. "Sm product luting on pact *6- 0bl`t?91 TOWOLDMON0038868 Miscellaneous Formulations The following formulations are representative of the numerous synthetic adhesive preparations based on other than the polyvinyl acetate and PVA co-polymer resin bases mentioned in the introduction. Here a zein base is plasticized to give specialty products. Zein Label Varnish Zein Rosin WW Santolite MHP Santicizer 8 Proprietary or 91# isopropyl alcohol 100 100 20 25 190 Zein Foil Tintin9 Base Zein A Santolite MHP Santicizer 8 91# Isopropanol 85# Phosphoric Acid Coloring 100 65 70 230 2.3 As needed Santicizers* 141, B-16 and E-15 are Monsanto plasticizers which have been given full approval by the U.S. Bureau of Animal Industry and the U.S. Food and Drug Administration for use in food wrapping films and other products where a nontoxic plasticizer is required. These Santicizers are particularly recommended for any adhesives which must meet similar requirements. **** LITERATURE AVAILABLE ON MONSANTO PLASTICIZERS THE AROCLORS -- Physical Properties and Suggested Applications: Technical Bulletin P-115. AROCLOR* 1254 -- Co-plasticizer With DOP: Technical Bulletin P-134. DIOCTYL PHTHALATE (DOP): Technical Bulletin 0-82. HB-40*: Technical Bulletin P-104. ORTHO-NITROBIPHENYL-- Plasticizer and Chemical Intermediate: Technical Bulletin 0-78. ORTHO-NITROBIPHENYL-- Toxicity Data: Technical Bulletin O-D-700. SANTICIZER* 3: Technical Bulletin 0-81. SANTICIZER 8: Use in Adhesives; Use in Coatings; Use in Moldings: Three Separate Technical Data Sheets. SANTICIZER 140: Technical Bulletin 0-88. SANTICIZER 141 The Nontoxic Plasticizer: Technical Bulletin O-D-114. SANTICIZER 160: Technical Bulletin 0-92. THE BULK TANK STORAGE OF PLASTICIZERS: Technical Bulletin 0-69. FASTER PROCESSING OF POLYVINYL CHLORIDE WITH MONSANTO PLASTICIZERS: Booklet. MONSANTO PLASTICIZERS In Polyvinyl Chloride Film and Sheeting: Technical Bulletin 0-70. An 80 page booklet entitled "Monsanto Plasticizers" presents much data and general information on the following products: Dibuty)-, Diethyl-, Dimethyl- and Diphenyl Phthalates; Santicizers 1-H, 3, 8, 9, B-16, E-15, M-17, 140, 141 and 160; Tricresyl Phosphate and Triphenyl Phosphate. This booklet is available on request. OTHER MONSANTO LITERATURE ON RELATED PRODUCTS SANTOBRITE* For The Preservation of Water Base Adhesives: Technical Bulletin 0-1. SANTOMASK* II For "After-Odor" Control of Interior Paint, Printing Ink and Other Odorous Composi tions: Technical Bulletin 0-16. TRIPHENYL PHOSPHATE Application In Alkyd Resins: Technical Bulletin 0-65. BENTHAL* Application in Alkyd Resins: Technical Bulletin O-D-503. SANTOLITE* MHP and MS-80% -- Monsanto Industrial Resins: Technical Bulletin 0-94. *lUf. UJ. Pftt. Off. kSftBMBtO product*. -7- 06 IA 79 2 TOWOLDMON0038869 Listed below are the suppliers of special ingredients of the formulations presented in this bulletin. Most of the products are trade mark items. MANUFACTURER FORMULATION INGREDIENTS SUPPLIED BAKELITE DIV., UNION CARBIDE AND CARBON CORP. New York, New York BEACON CO. Boston, Mass. B. F. GOODRICH CHEMICAL CO. Akron, Ohio E. I. DU PONT de NEMOURS & CO. Wilmington, Delaware ' ENJAY CO. (ESSO STANDARD OIL CO.) New York, New York ESSO STANDARD OIL CO. New York, New York HERCULES POWDER COMPANY Wilmington, Delaware MONSANTO CHEMICAL CO. Plastics Division Springfield, Mass. Organic Chemicals Division St. Louis, Missouri VINYLITE vinyl resins. MONTAN wax. HYCAR resins and rubber products. ELVACET polyvinyl acetate resins, TRl-PURE titanium dioxide opacifiers, QUILON resin insolubilizer. VTSTANEX polyisobutylene resin. SOLYESSO aromatic solvents. * VINSOL ROSIN WW and BEL-RO rosin products. LUXTREX* heat resistant polystyrenes. SANTICIZERS* 3, 8, 9, 107 (DOP), MO, 141, 160, 1-H, E-1S, B-16, M-17 resin plasticizers; SANTOLITES* MHP and MS-80% industrial resins; TRICRESYL PHOSPHATE, DIBUTYL-, DI ETHYL- DIMETHYL- and DIPHENYL PHTHALATES, TRIPHENYL PHOSPHATE and ORTHO-NITROBIPHENYL resin plasti cizers; SANTOBRITE* water soluble preservatives; SANTOMASK* odor masking agent and coumarin and vanillin derivatives. Phosphate Division St. Louis, Missouri AROCLOR* plasticizers; HB-40* plasticizer. NEVILLE CO. Pittsburgh, Pa. NEVILLAC hard resin and NEYTNDINE resin. ROHM and HAAS CO. Philadelphia, Pa. TRITON wetting, emulsifying and dis persing agents. SHAW1NIGAN RESINS CORP. Springfield, Mass. ACRYSOL, acrylic resin emulsions. GELVA and CO-POLYMER polyvinyl acetate resins. . *TrMk Mark R*f. QJ. rat. Off. Obi*'7'53 TOWOLDMONOQ38870 AVAILABILITY OF MONSANTO PLASTICIZERS Monsanto plasticizers are available in SS gallon black iron drums and in full or compartment loads in tank cars and tank trucks. Because so many plasticizers are available from Monsanto, full advantage can be taken of the savings resulting from mixed shipments. ** MB; 9 PRINTED IM ` 0 bl^*. TOWOLDMONOQ38871 Mberta-Barfcley'-- Research Library 3t. Louis < ..... tt) ` (WfJ r Monsanto Chemicals-Plastics _____ft For further information on the product! described in thi* bulletin contact the naarait Montanto offica. MONSANTO CHEMICAL COMPANY ST. LOUIS AKRON BIRMINGHAM BOSTON CHARLOTTE CHICAGO NEW YORK PHILADELPHIA PORTLAND (Or..) SAN FRANCISCO CINCINNATI CLEVELAND DETROIT HOUSTON LOS ANGELES SEATTLE TWIN CITIES MONSANTO CHEMICALS LTD. London MONSANTO CANADA LTD. Montreal Toronto V.ncouv.r MONSANTO CHEMICALS (AUSTRALIA) LTD. Melbourne R.prowntotivoi in the Principal Clti.i of th. World ^0 TOWOLDMONOQ38872