Document ybpo34OrLBGaNjr2JDqaMoZ0V

NON-TOXIC PLASTICIZERS IN SYNTHETIC-RESIN ADHESIVES ir MAY 1960 I Supplement to Technical Bulletin PL-307 Plasticizers In Synthetic-Resin Adhesives f Tood packaging represents an important market tor synthetic-resin adhesives. Wherever adhesivc components can possibly migrate to food, only FDA-approved ingredients may he used. Kven though one-vear extensions have been granted to a large number of food-packaging com ponents, any material that is learned to be harmful at the effective concentration will Inbanned immediately. Accordingly, we believe that it is probably advisable to start at once to consider reformulations based on already-approved plasticizers. The following table is presented to help the compounder select appropriate nontoxic substitutes for some of the now-unapproved plasticizer?-, in many of the si formulations described in Technical bulletin 1*1,-A07. 0 05i0*09 TOWOLDMONOQ35402 O tZO tS O XX wanr-wfi F.*' rW**rtv' X X L.tfart fWe. X POSSIBLE SUBSTITUTES, WHICH ARE FDA APPROVED Plasticizer Listed in Bulletin No. PL-307 | 1 . i Santicizer - Santicizer > Santicizer pS. j j^ Santicizer* 160 Santicizer 8 Santicizer M-17 Tricresvl Phosphate HB-40* ......J 1................ .. .x x1 ! X \ Ix X 'm*rnw* X Aroclor* plasticizers X *S<mticirer. jdB-40. and Aroclor Monsanto Chemical Company trademarks. Registered in U. S. Patent Office. Te i n*or"ia*'Cn ccnta'ned in This bu-e-in 'S *C our best Itnowl. edqe. true ard accurate but a'' recommendations or suaaes'ions d'e made wi`^c>u* guarantee s:nce the conditions o- use are beyond cu' 'or'".'. Mcn$an*o Chemical Company declaims arv iab' *v m rr-nriect ' r\ wi,L uSe r i `he-e data contained harem sha': be construed as a ise any product in c-nf!ict wi`h e'istino ma'ena1 or its use MONSANTO CHEMICAL COMPANY 800 North Lindbergh Blvd. St. Louis 66, Mo. TOWOLDMONOQ35403 |tttf.|ii"i'iii i iiiVirfiiifnliWM'i'irii r'n r'fTril p CONTENTS Synthetic-Resin Adhesives--A Growing Market.--------- ---------------------------- ..-------2 Development of Synthetic-Resin Adhesives__________ _____ ______ ....... 3 Emulsion Adhesives................ .......................................................... --................ ........ 3 Polyvinyl Acelate Adhesives.._________________ ______ _________________ 4 Monsanto Plasticizers..._____ _________________ ______ .... . .... 4 Monsanto Resin Additives________________________________ ____ _____ 6 Monsanto Preservatives and Odor-masking Agents..._____________-- 6 Adhesives__________________________ __________________ ___ ..... -- 6 Polystyrene Adhesives_________________________________ ________ __ ___ 10 Hot-Melt Adhesives____________________________________________________ ..---------10 Delayed-Tack Adhesives-------------------------- ------------------------------------ --------- - . .. ..13 Solution Adhesives________________ _______________________________... .. ...... 15 Vinyl Adhesives_________ 15 Nitrocellulose Adhesives_______________________ ....16 Cellulosic Adhesives___________ __________________________________ ____ .16 Polyurethane Adhesives___________ 18 Chlorinated-Rubber Adhesives_____________ _________ _____ __________ ... 18 Zein Adhesives___________ ____ _________ __________________________ .... 19 Pressure-Sensitive Adhesives..._________ ____________________ _____ ..... .. 19 Adhesive Primers__ _________...___ __________ _______ __________ ______........ 2 I Miscellaneous Adhesives___ ____ _____ ______________ _________________ _.22 Toxicology._____________________ 23 Ingredient Index________ _____ ____ _ _______ _______ ______ ____ ______ _______ 24 Technical Literature_____ _____________ ______ 26 Shipping..._ __________ ___ ...---------------------------------------------------- - -------------- 28 wmmmm r b osiom TOWOLDMONOQ35404 SYNTHETIC-RESIN ADHESIVES-A GROWING MARKET Consumption of synthetic-resin adhesives is rapidly expanding both because of continuing dis placement of older gluing materials in steadily-growing uses and because of the introduction of many new applications for which conventional adhesives are unsuitable. Superior performance of the synthetic-resin adhesives has enabled them to supplant conventional adhesives based on natural products in many large-volume applications. Wide-spread and increasing usage of syn thetic-resin adhesives is foreseen in such diverse industries as the following: Shoe manufacturing Book binding Paper-bag and folding-box-carton manufacturing Food-container production Food packaging (labeling, sealing, wrapping, etc.) Tobacco packaging Specialty product packaging Automobile production Building construction Use of the proper plasticizer in synthetic-resin adhesives -- to best accomplish the desired pur pose of the adhesive for its intended application -- is extremely important. The plasticizer in an adhesive formulation improves film formation; imparts tack, flexibility, and gloss; decreases drying time; and lowers production costs. More svnthetic-resin adhesives are used today than ever before because: Synthetic-resin adhesives adapt well to high-speed sealing and labeling machines, thereby increasing production rates. Synthetic-resin adhesives are cleaner, easier to use. They keep maintenance costs down. Synthetic-resin adhesives resist deterioration caused by water, light, and fungus much better than the usual adhesives based on natural proteinaceous materials. Adhesive emulsions require no volatile, toxic, or flammable solvents. Emulsion properties are easily adjusted and controlled. Monsanto Chemical Company, a major supplier of plasticizers for synthetic-resin adhesives, of fers plasticizers that are efficient, heat and light stable, and non-toxic. Lack of toxicity is es pecially important now in food applications because of the 1958 amendment to the Federal Pure Food, Drug, and Cosmetic Act. Monsanto plasticizers impart excellent grease resistance and heat 2 TOWOLDMONOQ35405 sealabilitv to the adhesive. Because of the great variety of Monsanto plasticizers, customers can realize lower costs by taking advantage of mixed shipments. This bulletin suggests typical formulations for various adhesive applications and describes the benefits to be derived from the use of plasticizers in synthetic-resin adhesives. If you need additional assistance, experienced Monsanto technical representatives are always ready to help you with your special formulation problems. Since Monsanto does not have a vested interest in any particular plasticizer, you are assured of advice directed toward achievement of the best pos sible performance of your product. DEVELOPMENT OF SYNTHETIC-RESIN ADHESIVES Not long ago industrial users or consumers could choose among only a few naturally derived materials for their adhesive applications. Constant industrial demand for adhesives with greater strength, faster tack, and greater versatility for bonding many types of surfaces forced the de velopment of svnthctic-resin adhesives. With the great number of excellent adhesives now avail able, both industry and consumers have a much wider choice and are more likely to obtain suitable adhesives to fill specialized needs. Only synthetic-resin adhesives are able to tolerate extreme exposure conditions. They withstand temperatures that quickly destroy natural materials, and they bond surfaces - - such as rubber and metal - that normally defy bonding. From 1946 to 1956, synthetic-resin adhesives gained dominance among adhesives in major construction. For nearly any fastening job, a good syn thetic-resin adhesive is now available. Synthetic-resin adhesives commonly used are based on vinyl polymers (polyvinyl acetate, poly vinyl alcohol, and polyvinyl chloride); on condensation resins (urea-formaldehyde, melamineformaldehyde, phenol-formaldehyde, resorcinol-formaldehyde); on cellulose derivatives; polyes ters; elastomers; and epoxies, Addition of plasticizers generally modifies an adhesive to suit a particular need. TYPES OF RESIN-ADHESIVE FORMULATIONS The major types of plasticized svnthetic-resin-adhesive formulations are emulsion, hot-melt, delayed-tack, solution, pressure-sensitive, and adhesive primers or coatings. These types will be discussed in order. Suppliers of special ingredients are listed at the end of this bulletin. EMULSION ADHESIVES Resin-emulsion adhesives are emulsions of plasticized or unplasticized resins dispersed in a water base. T hey offer the advantages of reduced fire and toxicity hazard because of the elimi nation of volatile, flammable, and possibly toxic solvents. 3 * ; K \ ^ TOWOLDMONOQ35406 POLYVINYL ACETATE ADHESIVES The widely-used polyvinyl acetate-emulsion adhesives possess quick tack, good adhesion to many surfaces, grease resistance, non-toxicity, and many other desirable features. Monsanto Plasticizers for polyvinyl acetate-emulsion adhesives Monsanto liquid plasticizers most commonly used in the polyvinyl acetate-emulsion adhesives are Santicizer* 160, dibutyl phthalate, Aroclor* 1221, Aroclor 1232, Aroclor 1242, dimethyl phthalate, diethyl phthalate, tricresyl phosphate, Santicizer 140, Santicizer ]41, Santicizer M-17, Santicizer B-16, Santicizer E-15, and Santicizer 8. Dibutyl phthalate imparts good flexibility and softening action with relatively low volatility. Santicizer 160 is considered better than dibutyl phthalate in most applications because of lower volatility, improved moisture resistance, and film toughness. Diethyl phthalate is used for fast-tack, non-toxic applications. The Aroclor plasticizers impart quick tack, good adhesion to many surfaces, and are widely used in commercial adhesives either as extender plasticizers or alone to make versatile, lowcost adhesives. Dimethyl phthalate is preferred in polyvinyl acetate adhesives for bonding cellulose acetate film or sheeting because of its better solvency action on the cellulose acetate. Uses for this type of adhesive include covering cut-out windows in cartons or for laminating paper. Santicizer 140, Santicizer 141, and tricresyl phosphate are used when flame resistance, oil re sistance, and low volatility are desired. Santicizer 141 is most efficient in polyvinyl acetate adhesives, followed by Santicizer 140 and tricresyl phosphate. l'or bonding overlays of paper, Santicizer M-17 is frequently used for its superior light sta bility, quick tack, and solvency on cellulose acetate. Santicizer 8 imparts excellent grease resistance, good flow and wetting action, and improves the bonding of rubber to metal. Monsanto's solid plasticizers, Santicizer 1-H, Santicizer 9, diphenyl phthalate, dicyclohexyl phthal ate, and Aroclor 5460, are frequently used in polyvinyl acetate-emulsion adhesives to impart better beat-sealing characteristics. They also improve moisture and solvent resistance. For nontoxic adhesives, Santicizer B-16, Santicizer E-15, Santicizer 141, and diethyl phthalate have been accepted by the U. S. Bureau of Animal Industry and the Food and Drug Admini stration. Typical illustrations of the use of these products include adhesives for food-wrapping films, boxboard manufacture, and envelope adhesives. Table I on page 5 lists performance data of Monsanto plasticizers in polyvinyl acetate. Aroclor; Santicizer: Monsanto Chemical Company trademarks. Registered in U S, Patent Office. 4 051021* TOWOLDMONOQ35407 m Table I. PERFORMANCE OF MONSANTO PLASTICIZERS IN POLYVINYL ACETATE-EMULSION ADHESIVES Plasticiier' Volatility 20 Hours at 87 C (Activated Carbon) (per cent) Low-Temp. Flexibility (Modified Clash & Berg Test) 1- C) Oil Extraction--Weight Loss After 24 Hours at Room Temperature (per cent) Kerosene Peanut Oil Cotton-Sei Aroclor 1221 Aroclor 1232 Aroclor 1242 Triphenvl Phosphate Tricresyi Phosphate Dimethyl Phthalate Diethyl Phthalate Dibutyl Phthalate Diphenyl Phthalate Santicizer B-16 Santicizer M-17 Santicizer 1-H Santicizer 8 Santicizer 9 Santicizer 140 Santicizer 141 Santicizer 160 5.2 4.8 4.4 2.0 0.75 5.6 4.8 4.4 5.9 2.2 3.6 1.5 3.6 3.1 1.2 1.8 2.1 -5.0 4.0 5.3 5.7 3.6 -1.6 -5.0 -6.1 -- -3.9 1.5 -- 6.4 - 5.0 -3.3 1.9 0.63 0.54 0.57 0.02 0.16 0.92 0.85 0.59 1.31 0.08 0.19 0.96 0.43 1.13 0.15 0.17 0.20 --- -- 0.37 0.38 0.75 0.63 0.51 0.90 0.46 0.50 0.36 0.60 0.57 0.34 0.42 0.39 -- -- 0.38 0.46 0.93 0.82 0.59 0.98 0.36 0.48 0.53 0.64 0.63 0.36 0.31 0.34 "'Formulation: 11 part? plasticizer in 100 parts Gelva S-55 (poiy\ iny] acetate) emulsion. Film thickness 0.040 inch. STPOTSO TOWOLDMONOQ35408 Monsanto Resin Additives for Poiyvinly Acetate Adhesives Monsanto industrial resins, Santolite* MHP and Santolite MS-80%, when used to modify poly vinyl acetate adhesives, give a very tough but flexible product. They impart quick tack and adhesion to a wide variety of surfaces. Normally, they are compounded with a liquid plasti cizer, such as dibutyl phthalate or Santictzer 160, or with an eutectic mixture (1:1) of dibutyl phthalate and triphenyl phosphate. The Santolite resins are especially useful to bond cellophane or aluminum foil to paper. Monsanto Preservatives and Odor-Masking Agents for Polyvinyl Acetate Adhesives Monsanto supplies a complete line of industrial preservatives including Santobrtte*, Monsanto's Penta (pentachlorophenol), and technical sodium benzoate. These materials are useful in pre venting fungus attack on the adhesive if natural materials, subject to fungus attack, are incor porated in the formulation. Monsanto odor-masking agents for polyvinyl acetate include Saufotnasife* II, methyl salicylate, coumarin, and vanillin. Literature on these products is available on request. Polyvinyl Acetate-Adhesive Formulations Polyvinyl acetate-emulsion adhesives range in complexity from simple blends of polyvinyl ace tate and plasticizer to more complex formulations involving many ingredients. Formula No. 1, presented as a guide to general polyvinyl acetate-emulsion adhesives, illustrates the types and range of concentrations of ingredients that may be incorporated for various ad hesive applications. (An index of formulation ingredients and their suppliers begins on page 24.) Formula 1--General Polyvinyl Acetate-Emulsion Adhesive Ingredient Polyvinyl acetate emulsion (55% solids) Plasticizer Clay filler Cooked starch or dextrine Preservative Stabilizer Wetting Agent Secondary Water Defoamer Odorant (masking agent) Parts by Weight 100 10'- 50 0--30 0-- 1000 0-2 0-2 0- 0.2 0- 100 0- 2 0- 1 Santoiifc; Samobritr; Sanumas^: Monsanto Chemical Company trademarks. Registered in U.S. Patent Office. Formulas 2 through 6 illustrate five of the most widely used applications for polyvinyl acetate adhesives. Formula 2--Quick-Tack Polyvinyl Acetate-Emulsion Adhesive Ingredient Gelva S-55 polyvinyl acetate emulsion Santicizer 160 Santicizer 8 Water Parts by Weight 100 12 12 9.0 Formula 3--Polyvinyl Acetate Adhesive or Slue tor Wood Ingredient Gelva S-5S polyvinyl acetate emulsion Santicizer 160 or dibutyl phthalate Water Parts by Weight 95 3 2 Formula A--Low-Cost, Quick-Tack Polyvinyl Acetate Adhesive Ingredient Gelva S-55 polyvinyl acetate emulsion Aroclor 1232 Parts by Weight 100 11 Formula 5--Typical Polyvinyl Acetate Combining Adhesive Ingredient Polyco 117 H Dibutyl phthalate Water Solids content Viscosity 62.5 2500- 3000 centipoises Parts by Weight 64.9 26.6 8.5 7 TOWOLDMONOQ35410 Formula 6 Illustrates a Polyvinyl Acetate Adhesive for Padding Ingredient Parts by Weight Polyco 117-H Tricresyl phosphate Water Polyco 118 42.3 11.6 4.6 41.5 Add Polyco 118 to 117-H with good agitation, Then slowly add tricresyl phosphate with high-speed agitation. Blend water slowly. Solids content Viscosity 40 4000 - 5000 ccntipoises For bonding moisture-proof cellophane to aluminum foil or paper or for bonding aluminum foil to paper, Formula 7 is especially useful. Adhesion develops rapidly, and good bond strength is maintained at high temperatures. Formula 7--Polyvinyl Acetate-Emulsion Adhesive for Cellophane, Aluminum Foil, and Paper Ingredient Gelva S-55 polyvinyl acetate emulsion Santicizcr 160 Santolitc MS-80# Water Parts by Weight 100 9 13.5 13.4 Polyvinyl acetate emulsions are used for grease-proof coatings on paper. Although Formula 8, for "flatboard," and Formula 9, for "flexible board," are not used in true adhesive applications, they are included to show the versatility of Monsanto's plasticizers in polyvinyl acetate for mulations. Ingredient Parts by Weight Formula 8 Formula ' Elvacet 81-900 polyvinyl acetate emulsion Santicizer 141 York Whiting No. 7, superfine calcium carbonate Rutile titanium dioxide Tamol 731 dispersing agent (25# aq. soln.) Elvanol 71-30 polyvinyl alcohol (10% aq. soln.) Poly-G P-1200 polypropylene glycol Water 100.0 8.25 119.25 13.25 2.1 30.0 1.0 34.0 100.0 13.75 96.75 10.75 1.8 30.0 1.0 34.0 .0*10210 TOWOLDMONOQ35411 Properties Total solids Viscosity (26 C), centipoises Pigment-to-binder ratio PVAc resin-to-PVA resin ratio PVAc resin-to-plasticizer ratio Formula 8 65 1600 2:1 18:1 6.6:1 Formula 9 65 2700 1.5:1 18:1 4:1 To prepare these grease-proof coatings, the following procedure is suggested: 1. Prepare a stock solution by mixing polyvinyl alcohol in water at room temperature. Heat for 30 to 40 minutes at 185 to 190 F. The water required to adjust the solids content may be added to this stock solution. 2. Continue stirring, and add the Santicizer 141, Poly-G P-1200 defoamant, and Tamol 731 pigment-dispersant solution. 3. Add the pigments, stirring until dispersion is complete. 4. Add the polyvinyl acetate emulsion, and stir until a homogenous mixture is obtained. A grease-resistant coating for wrapping papers, such as used for bakery goods, is illustrated in Formula 10. The composition may be applied with a roller coater provided with a smoothing roll to give a uniform, continuous film. About 140 F is required for optimum film formation, if it is to be used as a laminating adhesive. Formula 10--Polyvinyl Acetate Grease-Resistant Paper Coating Ingredient Elvacet 81-900 polyvinyl acetate emulsion Santicizer B-16 Titanium dioxide Water Quilon Parts by Weight 100 3.S 7.0 15-30 0- 5 For many applications, incorporation of a solid plasticizer to provide rapid heat-sealing is de sirable. Formulas 11, 12, and 13 illustrate the technique of dispersing diphenyl phthalate, San ticizer 1-H, and triphenyl phosphate, respectively, in water, for convenient incorporation into a polyvinyl acetate adhesive. Ingredient Diphenyl phthalate Santicizer 1-H Triphenyl phosphate Water Polyvinylpyrollidone Carboxymethylcellulose Formula 11 100 -- -- 100 4.7 1.3 Parts by Weight Formula 12 -- 100 -- 100 4.4 1.3 Formula 13 -- 100 100 4.4 1.3 0510219 TOWOLDMONOQ35412 The procedure for preparation of these formulations is as follows: 1. Grind the solid plasticizer with dry ice to the desired particle size. The dry ice prevents coagulation of the solid plasticizer as a result of softening from frictional heat. 2. Add the thickening agents to the water, and agitate this mixture until solution is effected. 3. Slowly add the solid plasticizer to the water-thickener mixture with good agitation. This dispersion may be used in any desired polyvinyl acetate-emulsion formulation. POLYSTYRENE-EMULSION ADHESIVES Use of polystyrene-emulsion adhesives is increasing. Santicizer 160, HB-40*, diethyl phthalate, dibutyl phthalate, Aroclor 1242, Aroclor 1248, and Aroclor 1254 are extensively used as plas ticizers for this resin in adhesive emulsions. Formula 14 illustrates a basic styrene-emulsion adhesive that is stable and has a high degree of wet tack. The caseinate imparts stability, wet tack, and film toughness. These properties may be varied by alteration of the caseinate concentration. Formula 14--Styrene-Emulsion Adhesive Ingredient Lustrcx* Styrene 601-40 HB-40 Diethyl phthalate Triton X155 Ammonium caseinate, 15^ aqueous Parts by Weight 100 18.0 5.0 2.5 34.0 HOT-MELT ADHESIVES Hot-melt adhesives are utilized because they set rapidly after application. The molten adhesive is applied to the materials to be joined; the bond sets before the adhesive is cool. Plasticizers play an important part in the successful manufacturing and application of hot-melt adhesives. Liquid plasticizers, such as Santicizer M-17, Santicizer 160, dibutyl phthalate, San ticizer B-16, and the. Aroclor liquids, are frequently used. Solid plasticizers, such as diphenyl phthalate, dicyclohexyl phthalate, Santicizer 1-H, Santicizer 9, and Aroclor 5460, are also utilized in many applications, since they melt at the processing Lusirex: Monsanto Chemical Company trademarks, Registered in U. S. Patent Office. 0^10220 TOWOLDMONOQ35413 temperature of the hot-melt adhesive. Upon application of the adhesive to the materials to be bonded, these plasticizers solidify as the temperature is reduced, thereby overcoming the prob lem of excessive softness frequently encountered with hot-melt adhesives. Formulas 15 and 16 represent two starting formulations for bookbinding adhesives. Formula 15 Ingredient Nevillac Hard Resin Santicizcr 160 Paraffin Wax Parts by Weight 61.4 15.0 6.4 Mix and heat the ingredients at 250 to 275 F until melted. Raise temperature to 300 to 325 F and add the following with agitation: Vinylite AYAA Ethyl Cellulose 12.9 4.3 Formula 16 Ingredient Nevindene R-3 or Cumar W-l Santicizcr 8 Rosin WW Vinylite XYHL Mineral Oil Paraffin Wax Parts by Weight 30 15 35 15 5 5 Formulas 17 through 19 are good suggested starting points for the development of hot melts for application between 160 and 180 C. By changing the type of polyvinyl acetate resin utilized in the hot melt, the viscosity of the melt can be increased or decreased without changing the ratio of resin to plasticizer. For example, substitution of Gelva V-15 for Gelva Y-7 in formula tions 17 and IS increases the melt viscosity. Ingredients Gelva polyvinyl acetate resin V-7 Ethyl cellulose Gelva C-SV-16R Santicizcr 160 Rosin WW Dibutyl phthalate Aroclor 1254 Formula 17 100 -- --_ 75 30 55 Parts by Weight Formula 18 65 15 -- 16 -- -- 4 Formula -- -- 100 -- 75 30 55 Gt> 10^21 TOWOLDMONOQ35414 Polyvinyl butyral hot-melt adhesives are useful for joining cellophane, aluminum foil, glassine, and waxed glassine to themselves. The sealing temperature is usually 2000 to 350 F. The pressure can range between 0.5 psi and 30 psi. Polyvinyl butyral hot melts are extremely fast setting--usually from 0.5 to 2 seconds. The molten adhesive is usually applied to both surfaces to be bonded and allowed to cool and set. The surfaces are then brought together, and the bond is formed under heat and pressure. Formula 20--Polyvinyl Butyral Hot-Melt Adhesive Ingredients Butvar B-76 Opalwax Poly-pale Ester # 1 Staybelite Ester #10 Sanlicizcr B-16 Armid HT Parts by Weight 10.5 30.5 19.7 14.7 6.0 11.0 The procedure used to make Formula 20 is to dissolve the Butvar B-76 in ethanol. The wax is then added with agitation and slight heating until a homogeneous slurry is obtained. The alcohol is then distilled from the mixture, and the other ingredients are added to the molten Butvar-wax mix. To obtain a smooth formulation, the finished compound should be strained through two thicknesses of cheesecloth. Formula 21 is a polymethyl methacrylate hot-melt adhesive used to join cloth for inner liners, fabrics, or backings. Formula 21--Polymethyl Methacrylate Hot-Melt Adhesive Ingredients Polymethyl methacrylate Saniicizer 160 Chlorinated rubber Parts by Weight 100 10 20 A typical cellulose acetate hot-melt adhesive is shown in Formula 22: Formula 22--Cellulose Acetate Hot-Melt Adhesive Ingredients Cellulose acetate Santicizer M-17 Inert filler Parts by Weight 50 88 35 12 0*10222 e m Cellulose acetate butyrate is commonly used for hot-melt applications. Formula 23 is a typical starting formula. Formula 23--Cellulose Acetate Butyrate Hot-Melt Adhesive Ingredients Half-second cellulose acetate butyrate Aroclor 5460 Dioctyl phthalate Newport V-40 Santonox* Syn Fleur # 6 Parts by Weight 35.00 30.00 15.00 19.89 0.1 0.01 The above coating can be applied at about 350 F. Ventilation should be provided. A typical starting formulation for an ethyl cellulose hot-melt adhesive is shown in Formula 24. Formula 24--Ethyl Cellulose Hot-Melt Adhesive Ingredients Ethyl cellulose, 50 cpr Lopor No. 45 Mineral Oil Bakers No. 15 Castor Oil Epoxy soybean oil Paraffin wax (m.p. 135 F) Santonox Aroclor 5460 Parts by Weight 24 57 5 3 3 1 7 DELAYED-TACK ADHESIVES Delayed-tack adhesives differ from hot-melt adhesives, which become nontacky upon cooling. Delayed-tack adhesives are normally tack-free at ordinary temperatures, after they are spread and dried on a surface. After subsequent heat activation they maintain tackiness for from sev eral hours to several days over a fairly wide temperature range. This slow-setting property per mits necessary mechanical handling before the adhesive cools and sets. Santonox: Monsanto Chemical Company trademark. Registered in U.S. Patent Office. 13 05>1(^<;3 TOWOLDMONOQ35416 Solid plasticizers, such as diphenyl phthalate, Santicizer 1-H, and Santicizcr 9, make possible the delayed-tack properties of these unusual adhesives. The solid plasticizers are chosen for their compatibility with the base resin, their solvency action on the base resin, the tempera ture at which the adhesive is activated, their lack of disagreeable odor, and their crystallizing characteristics. The patent literature relating to delayed-tack adhesives should be investigated by those desir ing to produce them; for example, U. S. Patents 2,462,029; 2,608,542; 2,608,543; 2,613,156; and 2,613,191. Formulas 25 through 27 are quoted from the patents as indicated. Formula 25--Delayed-Tack Adhesive (U. S. Patent No. 2,462,029, Example 96) Ingredients Santicizer 1-H Vinsol Resin Thinned amine dispersant Acrysol M.R. Parts by Weight 50 50 250 10 "The thinned amine dispersant is a mixture composed of 1 part stearic acid, 1 part Poly-pale resin, a polymerized rosin containing approximately 40^ dipolymers of abietic acid (Hercules Powder Co.), 1 part 2-amino-2-methyl-l-propanol (Commer cial Solvents Corp.), and 3 parts water. This composition is designed solely as a dispersion assistant..................''(from column 10 of this patent) Formula 26--Delayed-Tack Adhesive (U. S. Patent No. 2,462,029, Example 18) Ingredients Diphenyl phthalate Nevindine R-3 Thinned amine dispersant (see formula 25) Hycar OR-25 Parts by Weight 52.5 30.0 198.0 43.5 The above formulation is non-tacky at ordinary temperatures and is heat activated at about 150 F. The compound then remains adhesive through temperatures as low as 50 K. Once set, the adhesive continues to hold at ordinary temperatures. 0510214 TOWOLDMONOQ35417 Formula 27--Polystyrene-Emulsion, Delayed-Tack Adhesive (U. S. Patent No. 2t613,I56, Example I) "Ten (10) parts polystyrene (molecular weight 10,000 to 15,000) and 40 parts di phenyl phthalate are mixed and heated together at approximately 190 F, forming a clear fluid. While still at this temperature, the fluid is poured into a solution of 6 parts of a 25c/c aqueous solution of Aerosol OT and 4.5 parts polyvinyl alcohol (of the grade sold under the trademark Elvanol 50-42) in 75.5 parts water; the solution being at a temperature of approximately 190 F, constant agitation is main tained, 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 adhesive forms a smooth, non-grainy film when spread evenly on paper and dries to a completely tack-free surface. When heated to 170 F the film becomes very tacky and powerfully adhesive. Formula 28--Polyamide Delayed-Tack Adhesive Ingredients Versamid 940 Sattltcizcr 9 Candelilla wax Isopropyl alcohol Toluene Parts by Wei 100 51.6 5.9 29.5 29.5 1 SOLUTION ADHESIVES Solution synthetic-resin adhesives differ from the emulsion adhesives in that solvents other than water carry the adhesive. The use of solution adhesives improves the "bite" or adhesion to many of the materials to be joined. Following is a discussion of various solution adhesives. VINYL ADHESIVES Formula 29 is a non-toxic, grease-resistant paper coating, which is readily heat sealable. Formula 29--Vinyl Solution Coating Ingredients Vinylite VYHH Vinylite VMCH Vinylite VAGH Santicizcr 141 or Satiticizer M-17 Acetone Methyl ethyl ketone Parts by Weight 80 10 10 20 250 100 15 0510225 TOWOLDMONOQ35418 NITROCELLULOSE ADHESIVES Nitrocellulose-lacquer coatings are frequently applied to make cellophane heat sealable and mois ture resistant. Formulas 30 and 31 illustrate starting formulations for this type of application. Formula 32 is typical of a starting formulation for a nitrocellulose cement. Formulas 30, 31, and 32--Nitrocellulose Lacquers and Cement Ingredients Nitrocellulose (j4-sec.SS) Nitrocellulose (30-40 sec.RS) Dibutvl phthalate Dicyclohexvl phthalate Santicizer 160 Santolite MHP Dammar wax Santolite MS-80% Paraffin wax Denatured alcohol Ethyl acetate Acetone Toluene Heat-Sealable Cellophane Lacquer Nitrocellulose Cement Parts by Weight Formula 30 Formula 31 Formula 32 15 50 10 87 -- 20 5 16 12 -- 0 15 50 31 104 ---- 15 50 12 -- 34 34 -- CELLULOS1C ADHESIVES Formulations 33 and 34 illustrate suggested starting formulations for cellulose acetate butyrate. Formula 33--For Sealing Paper to Paper or to Cellulose Acetate Butyrate Ingredients Parts by Weight Cellulose acetate butyrate (half second) Santolite MHP Ethyl alcohol (95%) Isobutyl acetate Toluene Hi-Flash naphtha 15 15 15 10 35 10 16 TOWOLDMONOQ35419 Formula 34--For Sealing Paper to Cellulose Acetate Ingredients Cellulose acetate butyrate (half second) SantoVue MHP Ethyl alcohol (95c/c) Isobutyl acetate Toluene Hj-Klash naphtha Parts by Weight 12 18 15 10 35 10 Formula 35 gives outstanding grease resistance and light stability. Formula 35--Grease-Resistant Coating Ingredients Cellulose acetate LL-1 Santicizer M-17 Santicizer 8 Acetone Methyl ethyl ketone Methyl cellosolve acetate Ethyl lactate Parts by Weight 20 10.2 2.5 16.8 37 7 7 A formulation useful for self adhesion of ethyl cellulose is as follows: Formula 36--For Seif Adhesion of Ethyl Cellulose Ingredients Ethyl cellulose N-14 Lewisol 28 Dibutyl phthalate Toluene-alcohol blend (4:1) Parts by Weight 10 5 1.5 83.5 17 0510*^7 TOWOLDMONOQ35420 POLYURETHANE ADHESIVES The advent of urethane foam has increased the need for adhesives to bond it to itself or to other materials. Formula 37 is an example of a good starting formulation for this application. Ingredients Multranil 176 Mondur C Ethyl acetate Aroclor 1254 Formula 37--Polyurethane Adhesive Parts by Weight 100 5 50 20 Formula 37 has a maximum work life of 48 hours. Excessive humidity or temperature shorten the work Hie. It is recommended that only enough adhesive for one day's use be mixed at a time. The formula may be diluted with acetone or ethyl acetate if desired, This adhesive may be applied by a cold method. The adhesive is applied, allowed to stand at room temperature for 10 to 30 minutes until the solvent evaporates. The pieces to be joined are compressed at 50 psi for at least 15 seconds. The adhesive surfaces may also be heated with infrared lamps to 130 F for 4 minutes to evap orate the solvent. While still warm, the pieces should be pressed together at 50 psi for 3 to 10 minutes. CHLORINATED-RUBBER ADHESIVES Chlorinated rubber is used in heat-sealing adhesives because of its low moisture-vapor transmis sion, chemical resistance, and heat sealability. Formula 38 is a suggested starting formulation for a heat-sealing chlorinated-rubber adhesive. When 5 to 7 pounds are applied to a ream of paper, this coating allows only 1/16 gram of moisture vapor to pass through 100 square inches of paper in 72 hours. Ingredients l'arlon 125-centipoise type Aroclor 1254 Aroclor 1260 Dibutyl phthalate Paraffin Wax Pentalyn H Toluene Solvent Formula 38 Heat-Sealing Chlorinated-Rubber Adhesive Formula 39 Chlorinated-Rubber Label Adhesive Parts by Weight 60 20 --6 --6 14 -- 5-- 21 -- -- as needed 68 -- 18 TOWOLDMON0035421 ZEIN ADHESIVES Formulations 40 and 41, based upon zein, illustrate the versatility of Monsanto plasticizers to produce specialty formulations with unusual characteristics. Formula 40--Zein Label Varnish Ingredients Zein Rosin WW Santolite MHP Santicizcr 8 Proprietary or 91% isopropanol Parts by Weight 100 100 20 25 190 Formula 41--Zein Foil-Tinting Base Ingredients Zein A Santolite MHP Santicizcr 8 91% Isopropanol 85% Phosphoric acid Coloring Parts by Weight 100 65 70 230 2.3 as needed PRESSURE-SENSITIVE ADHESIVES Pressure-sensitive adhesives are materials that are tacky at ordinary temperatures and require little or moderate pressure for fixing in place. Formulations 42 through 45 illustrate four pres sure-sensitive adhesives. Formula 42--Pressure-Sensitive Adhesive (calender onto fabric) Ingredients Cellulose acetate (type A-9, 40 mesh) Santicizcr 8 Santolite MHP Parts by Weight 1 2.5-5 1-2 19 0*1022') TOWOLDMONOQ35422 Formula 43--Pressure-Sensitive Adhesive (calender onto fabric) Ingredients Vinylite AYAF (polyvinyl acetate) Arofene 700 (100% phenolic resin) Santicizer B-16 Parts by Weight 5 36 18 Formula 44--Pressure-Sensitive Adhesive (hot-melt type) Ingredients Pale crepe rubber Vistanex (polyisobutylene) Ester gum S'antolite MHP Methyl abietate, Santicizer 160, dibutyl phthalate, Aroclor, or Santicizer B-16 Wax (Montan, paraffin, carnauba, or amorphous microcrystalline) Parts by Weight 15-20 5-15 20 20 25-50 1-20 Melt all components except rubber at about 210 F. Add rubber, and reduce temperature to 180 F. Stir at this temperature for 1 to 2 hours until mixture becomes smooth. Hot cast on suitable surface. Formula 45--Pressure-Sensitive Adhesive (solution type) Ingredients Parlon 1259 type Staybelite Ester #10 Dibutyl phthalate Acetone Hexane Parts by Weight 5 10 10 52.5 22.5 Qb10230 TOWOLDMONOQ35423 ADHESIVE PRIMERS Adhesive primers are used in the same fashion as paint primers; that is, one is applied as a preliminary coating so that the secondary coating can adhere better. The secondary coat may be any type of vinyl chloride, if the primer, such as the one illustrated in Formula 46, is first applied. Formula 46--Adhesive Primer (for bonding vinyl to paper or cotton cloth) Ingredients Vinylite VYMS Vinylite VMCH Santkher 160 Methyl ethyl ketone Solvesso No. 1 Parts by Weight 18 2 15 25 17 Since synthetic fabrics, such as nylon or Dacron, have particularly non-adhesive surfaces, ad hesive primers are especially useful. Formula 47 provides a very effective adhesive primer coat for nylon and Dacron, as well as for metal. Formula 47--Adhesive Primer for Synthetic Fabrics Ingredients Vinylite VMCH Vinyl Resin Dioctyl phthalate (DOP) Methyl ethyl ketone Mondur M Parts by Weight 100 60 200 5 Formula 47 is made by mixing methyl ethyl ketone with the plasticizer, then adding the resin. The shelf life of the mixture is indefinite until the Mondur M is added. Upon addition of Mondur M the adhesivity of the compound decreases by 15 to 20 percent in 10 days. Accord ingly, Mondur M is added last, just before the adhesive is to be applied; and only as much ad hesive should be finally compounded as can be used within a day or so. 21 Q5104 Ji. TOWOLDMONOQ35424 MISCELLANEOUS FORMULATIONS EPOXY-RESIN ADHESIVES Epoxy resins are widely used in adhesive applications. Monsanto Chemical Company's ModEpox* organophosphorus compound improves the bond strength of epoxy adhesives (Formulas 48, 49, and 50). Mod-Epox also reduces the viscosity of epox adhesives, maintains chemical resistance, and lowers the cost considerably. Formulas 48, 49, and 50 -- Epoxy-Resin Adhesives Ingredients Liquid epoxy resin (EV-200) Diethylenetriamine Mod-Epox Butyl glycidyl ether Formula 48 Formula 49 Formula 50 Parts by Weight 100 100 100 12 8 13 - 25 -- -- -- 13.5 Cure: 20 hours at room temperature plus 2 hours at 100 C. Tensile Shear-bond Strength Aluminum - Aluminum Steel - Steel Glass - Glass 'Cohesive failure of resin. Adhesive bond intact. Formula 48 1880 psi 2000 2750 Formula 49 2590 psi 3060 4900* Formula 50 2010 psi - _ Aroclor and Montar* chlorinated polyphenyls are frequently used to extend epoxy adhesives and coatings. The use of these materials greatly reduces costs with a minimum effect on chem ical resistance or adhesive characteristics of the compounds. Mod-Epox; Monwr: Monsanto Chemical Company trademarks. Registered in U. S. Patent Office. 22 0t>10232 ) TOWOLDMONOQ35425 i (t POLYURETHANE-RESIN ADHESIVES Polyurethane resins are commonly used in flocking adhesives. The following formulation is typi cal of a flocking adhesive: Formula 51---Polyurethane-Resin Flocking Adhesive Ingredients Part A -- Multranil FLD Aroclor 1254 Mondur C Part B -- Multranil FLD Mondur C Parts by Weight 100 20 5 100 5-10 Part A is applied to the fabric by knife coating and allowed to dry thoroughly. The fabric is then coated with Part B, and the material is flocked immediately. j____________________________________________________ TOXICOLOGICAL CHARACTERISTICS The 1958 amendment to the Pure Food, Drug, and Cosmetics Act has caused some uncertainty about the kinds of materials that can be used in adhesives. The Food and Drug Administration has ruled that it will approve any material that does not migrate from the adhesive into the food. Migration is determined by use of a suitable dye. Monsanto offers six plasticizers that are approved by the Food and Drug Administration as being non-toxic. These products are: Santicizcr 141 Santicizer B-16 Santicizer E-15 Diethyl phthalate Dioctyl phthalate ^ > (For foods with high water content only) Diisooctyl phthalate j Use of these materials as plasticizers in synthetic adhesives should greatly aid acceptance of the adhesive. 23 QblQlS* TOWOLDMONOQ35426 1 INGREDIENT INDEX Ingredient Identification Supplier Acrysol* Aluminum oxide Ammonium caseinate Armid* Arofene* Bakers castor oil Rutvar* Butyl glycidyl ether Candelilla wax Carboxymelhylcellulose Cellulose acetate Cellulose acetate butyrate Chlorinated rubber Cumar* Dammar wax Diethylenetriamine Elvacet* Epoxy soybean oil Ester gum Ethyl cellulose Gelva* Geon* Hycar* Lewisol* Lopor* No. 45 Methyl abietate Synthetic-resin emulsions Amides Modified phenolic and maleic resins Polyvinyl butyral resins Coumarone-indene resins Polyvinyl acetate emulsion Polyvinyl acetate emulsion Polyvinyl materials Resins and synthetic rubber products Rosin-modified maleates Mineral oil Rohm & Haas Co. Reynolds Metal Co. National Casein Co. Armour Industrial Chemical Co. U. S. Industrial Chemicals, Inc. Baker Castor Oil Co. Shawinigan Resins Corp. Shell Chemical Co. Concord Chemical Co. Antara Chemicals Division General Aniline & Film Corp. Eastman Chemical Products Co. Eastman Chemical Products Co. Hercules Powder Co. Allied Chemical Corp. Hathaway Allied Products Union Carbide Chemical Co. E. 1. du Pont de Nemours & Co Rohm & Haas Co. Glidden Company Hercules Powder Co. Shawinigan Resins Corp. B. F. Goodrich Chemical Co. B. F. Goodrich Chemical Co. Hercules Powder Co. Esso Standard Oil Co. Hercules Powder Co. `'Trademark rendered in U.S. Patent Office. 24 05102J4 0 TOWOLDMONOQ35427 L Ingredient Index - Continued Ingredient Identification Supplier Methyl Cellosolve* acetate Mondur* Montan wax Multranil* Nevillac* Nevindene* Newport V-40* Nitrocellulose Opalwax* Parlon* Pentalyn* Poly-G* P-1200 Poly-pale* esters Polyco* Polymethyl methacrylate Polyvinylpyrollidone Quilon* Solvesso* Staybelite* esters Syn Fleur* Triton* X-15S Versamid* Vinsol* Vinylite* Vistanex* York Whiting* Zein Union Carbide Chemical Co. Isocyanates Mobay Chemical Co. Beacon Company Synthetic resin Mobay Chemical Co. Phenol-modified coumaroneindene resins Coumarone-indene resins Neville Chemical Co. Neville Chemical Co. Pine resin Newport Industries, Inc. Hercules Powder Co. Castor oil, synthetic wax Chlorinated rubber Pentaerythritol esters of rosin Polypropylene glycol Baker Castor Oil Co. Hercules Powder Co. Hercules Powder Co. Olin Matheieson Chemical Co. Glyceryl & glycol esters of polymerized rosin Polyvinyl acetate emulsion Hercules Powder Co. The Borden Co. Rohm & Haas Co. Chrome complex Aromatic solvent Antara Chemicals Division General Aniline & Film Corp. E. I. du Pont de Nemours & Co. Esso Standard Oil Co. Hydrogenated rosin esters Hercules Powder Co. Odorant Syn Fleur Scientific Co. Wetting, emulsifying, dis persing, scouring agents Polyamide resins Rohm & Haas Co. General Mills, Inc. Pine resin Hercules Powder Co. Vinyl resins Union Carbide Plastics Co. PolyisobutyJene resin Enjay Company Superfine calcium carbonate National Gypsum Co. Corn Products Sales Co. Trademark registered in U.S. Patent Office. 25 0510235 TOWOLDMONOQ35428 r TECHNICAL LITERATURE ABOUT MONSANTO PLASTICIZERS The following technical bulletins and brochures give technical information about the properties and applications of the Monsanto plasticizers and other products that are mentioned in this bulletin. Monsanto technical literature is continuously revised to contain the most recent and reliable information possible. Your request for any literature will be promptly and cheerfully filled -without obligation, of course. General "Monsanto Plasticizers"; Booklet containing technical data about all of Monsanto's plas ticizers "Seven Plasticizers for non-toxic applications" "How you can benefit from Monsanto Solid Plasticizers" Phthalate Plasticizers Santicizer 160 (butyl benzyl phthalate): Dibutyl Phthalate; Diethyl Phthalate and Dimethyl Phthalate: Dicyclohexyl Phthalate: Di-(2-ethylhexyl) Phthalate (DOP): Diphenyl Phthalate: Technical Bulletin PL-160 Technical Bulletin PL-302 Technical Bulletin PL-303 Technical Bulletin PL-312 Technical Bulletin PL-318 Technical Bulletin PL-319 Phthalyl Glycollate Plasticizers Santicizer E-15 (Ethyl phthalyl ethyl glycollate): SoM/irizer B-16 (Butyl phthalyl butyl glycollate): Santicizer M-17 (Methyl phthalyl ethyl glycollate): Technical Bulletin PL-15 Technical Bulletin PL-16 Technical Bulletin PL-17 Phosphate Plasticizers Santicizer 140: Santicizer 141 (non-toxic plasticizer): Triphenyl Phosphate (flame-retarding plasticizer): Tricresvl Phosphate (flame-retarding plasticizer): Technical Bulletin PL-140 Technical Bulletin PL-141 Technical Bulletin PL-301 Technical Bulletin PL-305 26 TOWOLDMONOQ35429 Sulfonamide Plasticizers Santicizer 1-H: Santicizer 8: Santicizer 9: Technical. Bulletin PL-l-H Technical Bulletin PL-8 Technical Bulletin PL-9 Aroctor Plasticizers The Aroclors: Aroclors 1221, 1232, and 1242 for polyvinyl acetate emulsion adhesives: Application Data Bulletin O-P-115 Technical Bulletin PL-321 Other Plasticizers HR-40 (partially hydrogenated terphenyl): Mod-Epox (epoxy-resin modifier): Technical Bulletin 0-104 Technical Bulletin PL-313 Resin Additives Santolitc MHP and Santolite MS-80% (Monsanto industrial resins): Technical Bulletin PL-320 Preservatives and Stabilizers Santobrite and Penta for the preservation of paints and water-base adhesives: Santonox and Santonox R, antioxidants for polyethylene: Sodium Benzoate, Technical: Technical Bulletin SC-2 Technical Bulletin PL-324 Technical Data Sheet Odor-Masking Agents "Coumarin Monsanto": ``Methyl Salicylate Monsanto": Santomask 11, Odor-Control Agent for Paint, Ink, Plastics, and Other Odorous Products: "Vanillin Monsanto": folder folder Technical Bulletin PL-325 folder 27 TOWOLDMONOQ35430 SHIPPING INFORMATION Most Monsanto plasticizers are shipped in bulk in tank cars or tank trucks (within estab lished delivery zones) from six strategically-located bulk-storage stations. As supplier of the world's largest selection of plasticizers, Monsanto offers savings through mixed shipments of different plasticizers (compartmented tank cars and tank trucks or mixed trucklots of drums) for all of your plasticizer needs. No shipping limitations apply to any of Monsanto's plasticizers. Shipping classifications and net contents of standard containers are tabulated below for the plasticizers mentioned in this bulletin, Standard Containers Product Classification 55-gal. drums (lb., net] 5-gal. drums (lb., net] Dimethyl phthalate Diethyl phthalate Dibutyl phthalate Dioctyl phthalate Dicyclohexyl phthalate Diphenyl phthalate Dimethyl phthalate Diethyl phthalate Dibutyl phthalate Dioctyl phthalate Dicyclohexyl phthalate Diphenyl phthalate 530 500 475 445 350 400 40 45 40 40 _--_ Santicizer 160 Santicizer E-15 Santicizer B-16 Santicizer M-17 Butyl benzyl phthalate (Resin plasticizer) Resin plasticizer Resin plasticizer Resin plasticizer 500 535 500 550 40 45 40 50 Tricresyl phosphate Triphenyl phosphate Santicizer 140 Santicizer 141 Santicizer 1-H Arocior 1221 Aroclor 1232 Arocior 1242, 1248, 1254, 1260 Arocior 5460 I1B-40 Mod-Epox Santolitc MHP | Santolitc MS-80% A Santomask 11 Santonox Resin plasticizer Resin plasticizer Resin plasticizer Resin plasticizer Resin plasticizer Synthetic resin Synthetic resin Synthetic resins Synthetic resin Resin plasticizer Chemical, NOIBN rail: synthetic resin without filler truck: synthetic resin, solid mass Chemical, NOIBN Chemical, NOIBN ) 1 / | 28 530 45 225 -- 545 50 495 45 -- 80(* 520 -- 550 600 -- 500 - 450 40 510 45 -- 60lb 540 45 250,c 150 45 - 'corrugated carton (16" x 8" x 9") b>7 gallon c,33 gallon TOWOLDMONOQ35431 The information contained in this bulletin is to our best knowledge, true and accurate, but all recommendations or suggestions are made without guarantee, since the conditions of use ere beyond our control. The Monsanto Chemical Company disclaims any liability incurred in connection with the use of these data or suggestions. Furthermore, nothing contained herein shell be construed as a recommendation to use any product in conflict with exist ing patents covering any material or its use. THIS BULLETIN REPLACES TECHNICAL BULLETIN NO. 0-99 DATED APRIL 1953. TOWOLDMONOQ35432 TOWOLDMONOQ35433