Document JN0eKZJJ8O38X8nE4aXo9gv06

vj IMonsanto; ** PLASTICIZERS Jn \ is YNTHET/C-RESIN \ . ... ' * -gjitty 4 ADHESIVES ' .si -g* ' ........................*' TECHNICAL BULLETIN No PL.J07 ' OFCFMBEP 19*9 1 &" ` ^ ' S. `5 4, v ` NON-TOXIC PLASTICIZERS IN SYNTHETIC-RESIN ADHESIVES r MAY 1060 Supplement to Technical Bulletin PL-307 ;- Plestlelzere In Synthetle-Reeln Adhesives December 1969 t? f Food |Mtfkaninj represents an ini|M>rtant market tor synthetic-resin adhesives. Wherever adheive components can jmsMbly migrate to food, only FDA-approved ingredients may he used Kven though one year eMlensmns have l>een yarned o> a lare number id iood-pac^kayintf com [Ninenis, any materia) thal is learned to lx* harmful ai I he ettertive comentraiion \ull be banned immrdiaieh. Accordingly. we believe lhal it is probably advisable to start at once to con-ider reionmilaiinnbasetl on already-approved plasticizers. The lolloumj; table is presented to help the compounder -elect appropriate mmioNir substitutes {or some oi' the now-unapproved plasticizers in many ni the si formulation- describetl in Technical Kulletin IM.-W. 0 HONS 076524 X X X XX HONS 0 7 8 5 2 5 POSSIBLE SUBSTITUTES, WHICH ARE FDA APPROVED PUtticixer Listtd in Bulletin No. PL-307 Sunticizir* IftO Si 3 Senticrzer - . ; p Santicixer " \ Santicixer i f. SuHtiazrr 8 Santiciztr M-17 Tricresyl Phor-phate HR-40* plasticizers i 5 |X ______i__ ><__ 1______I______ X X X1X jX Sanocirrr HB-40 and Arodo' Monsanto Chemical Company trademarks Registered in U $ Patent Office T- cc^ta^ed ^ s fcu >$ *c au' bei' kno* e3a? f'ut ard ac:urafe bo* a1 e<c'T''^e',ae*-ors sr iuaa*i` c <j'c --ado - Qus'ari'Ce i -'e ike c:"3'! ;"> o* use a be.'*3 l'u' Mc"i"`o C*e*" ca1 Co'r'caf'v d-ioa11 a1-. ab ' r ' ''>ec* n use 1 `Sep oa Cu' rj^K.ig ;anta-ned Ke"* * s^a' be comfruos as --.ng4- - f, ? an, c'>duri n c* MONSANTO CHEMICAL COMPANY tOO North Lindbarqh llvd. St. Louis 66. Mo. CONTENTS Synthetic-Resin Adhesives--A Growing Marie*...................... --. _ Development of Synthetic-Resin Adhesives... .. ..................... . ... ... 2 ] Emulsion Adhesives. . ..... --.... ................................................. .3 Polyvinyl Acetate Adhesives ........................... ..................... ...... . .. 4 Monsanto Plastifirers . ....... .................. .4 Monsanto Resin Additives______ _____________________ .. 6 Monsanto Preservatives and Odor-masking Agents.. ... .6 Adhesives.......... ...... .............. .......................... .................. 6 Polystyrene Adhesives....._____ _________________ _________ _ ... 10 Hot-Melt Adhesives. ................................ ..................... ...... .......... .......... ... . 10 DelayedTack Adhosivos........ ............. ............. ................... --............... ... . . .13 Solution Adhesives......... ....................................... . . .............. ... ... .15 Vinyl Adhesives...................................... ........... .......................... . . .. IS Nitrocellulose Adhesives.... _______________ __ ________________ 16 Cellulosic Adhesives....................................... .................................................... 16 Polyurethane Adhesives.................... ........................................................... . .. 18 Chlorinated-Rubber Adhesives......... ................ ........................... ................. .18 Zein Adhesives . .................. .............................. ............... ............. . 19 Pressure-Sensitive Adhesives.. .. .. ................................. ........... 19 Adhesivo Primers. ........ ........................... .. ...................... .. .. 21 Miscellaneous Adhesives...................... ........................................ . . 22 Toxicology............... ..................................... .......... ................. ...... .. ..... . 23 Ingredient Index.. . . .. ...................... ........... 24 Technical Literature ....... .............. .......................... .... .. 26 Shipping ...... ......... . . ............................... .............. ........... . .28 HONS 078526 SYNTHETIC RESIN AOHESIVES-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 (he adhesive for its intended application -- is extremely important. The plasticizer in an adhesive formulation improves film formation; imparts t8ck, flexibility, and gloss; decreases drying time; and lowers production costs. More synthetic-resin adhesives are used today than ever before because: Synthetic-resin adhesives adapt well to high-speed sealing and labeling machines, thrreby 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 bused 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 MONS 078527 sralabilitv 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 ad ditional 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 |>crformancc of vour 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 lack, anti greater versatility for bonding many types of surfaces forced the de velopment of synthetic-resin adhesives. With the great number of excellent adhesives now avail able, both industry anti consumers have a much wider choice and are more likely to obtain suitable adhesives to fill s|)eciaiized needs. Only synthetic-resin adhesives are able to tolerate extreme exposure conditions. They withstand temperature* 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 comntonly used are based on vinyl jwlymers (polyvinyl acetate, poly vinyl alcohol, and polyvinyl chloride); on condensation resins (urea-formaldehyde, melamine formaldehyde, 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 synthelic-resln-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 arc listed at the end of this bulletin. EMULSION ADHESIVES l Resin-emulsion adhesives are emulsions of plasticized or unplasticized resins dispersed in a water base. They offer the advantages of reduced fire and toxicity hazard because of the elimi nation of volatile, flammable, and possibly toxic solvents. 3 HONS 078528 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 Plasticiser* (or polyvinyl acafate-amultion adhasivas Monsanto liquid plasticisers most commonly used in the polyvinyl acetate-emulsion adhesives are Santicizer* 160, dibutyl phthalate, Aroclor* 1221, Aroclor 1232, Aroclor 1242, dimethyl phthalate, diethyl phthalate, iricresyl phosphate, Santicizer 140, Santicizer 141, Santicizer M-17, Santicizer B-16, Santicizer -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, Santicizrr 141, and Iricresyl 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. For bonding overlays of paper, Santicizer M-17 is frequently used for its superior light sta bility, quick tack, and solvency on cellulose acetate. Santicizer S 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 S460, are frequently used in polyvinyl acetate-emulsion adhesives to impart better heat-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 ol Animal Industry and the Food and Drug Admini stration. Typical illustrations of the use of these products include adhesives lor food-wrapping films, boxboard manufacture, and envelope adhesives. Table f on page 5 lists performance data of Monsanto plasticizers in polyvinyl acetate. Aroclor. Santiciser: Motmnto Chemical Company trademarks. Regtetered in U S. Patent Office A HONS 07B529 Table i. PERFORMANCE OF MONSANTO PLASTICIZERS IN POLYVINYL ACETATE-EMULSION ADHESIVES Plasticiier'* Arodor 1221 Aroclor 1232 Arodor 1242 Triphenyl Phosphate Tricresyl Phosphate Dimethyl Phthalate Diethyl Phthalate Dibutyl Phthalate Diphenyl Phthalate Santicizer B-16 Santicizer M-17 Santidzer 1-H Santicizer 8 Santicizer 9 Santicizer 140 Santicizer 141 Santicizer 160 Volatility 20 Hour? at 87 C (Activated Carbon) (per cent) 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 Low-Temp. ReribiEty (Modified Clash A Berg Test) (C| -5.0 4.0 5.3 5.7 3.6 -1.6 -5.0 -6.1 -- -3.9 1.5 -- 6.4 50 -3.3 1.9 Oil Extraction--Weight Loss After 24 Hours at Room Temperature (per cent) Kerosene 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 Peenut OH _ -- -- 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 Cotton-Seed OH -- -- 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 pan* flawticiicr in 100 pares Gelva S-55 (polyvi nyl acetate) emulsion Fiirri thickness 0 040 inch. Momenta Resin Additive* for Polyvinly 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 diet, such as dibulyt phthalate or Santictzer 160, or with an eutectic mixture (1:1) of dibutyl phthalate and tripheny) phosphate. The Santolite resins are especially useful to bond cellophane or aluminum foil to paper. Monsanto Preservatives end Odor-Maiking Agents for Polyvinyl Acetate Adhesives Monsanto supplies a complete line of industrial preservatives including Santobrite*, Monsanto's Penla (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 Santomask* 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 I---Genera! 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 O- 30 0-1000 0-2 0-2 0-0.2 0-100 0-2 0- 1 S*tnftr, Sawcotmw, SantomAtk Monaanto Chemical Company trademark?. Registered in \J.S Patent Office. 6 MOMS 078531 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 Geiva S- 55 polyvinyl acetate emulsion Santiciter 160 Sanliciter 8 Water Part* by Weight 100 12 12 9.0 Formula 3--Polyvinyl Acatato Adhasiva or Gluo for Wood Ingradiont Geiva S-55 polyvinyl acetate emulsion Santkitcr 160 or dibulyl phthalate Water Part* by Weight 95 3 2 Formula 4---Low-Cost, Quiek-Taek Polyvinyl Acetate Adhesive Ingredient Geiva S-55 polyvinyl acetate emulsion Araclor 1232 Parts by Weight 100 11 Formula 6--Typical Polyvinyl Aeetata Combining Adhesive Ingredient Polyco 117 H Dibuty! phthalate Water Solids content 62.5 Viscosity 2500 - 3000 centipoises Part* by Weight 64.9 26.6 8.5 7 M0NS 073532 Formula 6 Illustrates a Polyvinyl Acetate Adhailva for Padding Ingredient Paris by Waight Polyco 117-H Tricrcsyl phosphate Water Polyco lift 42.3 11.6 4.6 41.5 Add Polyco lift to 117-H with good agitation. Then slowly add tricresy! 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, end Paper Ingredient Gelva S-55 polyvinyl acetate emulsion Santicixcr 160 Santolife 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. Ingradiant Parts by Waight Formula 8 Formula 1 Elvacet 81-900 polyvinyl acetate emulsion Santicixer 141 York Whiting No. 7, superfine calcium carbonate Rutile titanium dioxide Tamol 731 dispersing agent (25r/c 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 078533 HONS Properties Total solids Viscosity (26C), ceotipoises Pigment-to-binder ratio PVAc resin-to-PVA resin ratio PYAc 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 (he solids content may be added to this stock solution. 2. Continue stirring, and add the Santicizer Ml, Poly-G P-1200 Hefoamant, 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 Greeje-Reiiitant Paper Coating Ingradiant Elvacet 81-900 polyvinyl acetate emulsion Santicizer B-16 Titanium dioxide Water Quilon Parts by Weight 100 3.5 7.0 15-30 05 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, Sonticizcr 1-H, and triphenyl phosphate, respectively, in water, for convenient incorporation into a polyvinyl acetate adhesive. Ingradient Diphenyl phthalate Sonfirtser 1-H Triphenyl phosphate Water Polyvinylpyrollidone Carboxymethylcellulose Formula 11 too -- -- 100 4.7 1.3 Part* by Weight Formula 12 _ 100 -- 100 4.4 1.3 Formula 13 -- -- 100 100 4.4 1.3 HONS 07B534 The procedure for preparation of these formulations is as follows: 1. Crind 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. Santicizcr 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 styTene-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--Styrtns-Emulsion Adhesive Ingredient Lustrcx* Styrene 601-40 HB-40 Diethyl phthalate Triton X1S5 Ammonium caseinate, lS'/r 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 SatUicizcr M-17, Santicizer 160, dibutyl phthalate, Soulirizcr B-16, and the Aroclor liquids, are frequently used. Solid plasticizers, such as diphenyl phthalate, dicyclohexyl phthalate, Sonluiztr 1-H, Sonitrizcr 9, and Aroclor 5460, are also utilized in many applications, since they melt at the processing H1MO, Lunrex Monsanto Chemical Company trademark*. Registered in l) S Patent Office. 10 MOHS 078535 f# Icmprrnturc of the hot melt adhesive. Upon application of the adhesive to the materials to he bonded, these plasticizers solidify as the temperature is reduced, thereby overcoming the prob lem of excessive soilness frequently encountered with hot-melt adhesives. Formulas 15 and 16 represent two starting formulations for bookbinding adhesives. Formula 15 Ingredient Kevillac Hard Resin Satilicizcr 160 Paraffin Wax Part* by Weight 61.4 15.0 6.4 Mix and heat ihe ingredients at 250 to 275 0 F until melted. Raise temperature to 300 to 525 I*' ami add the following with agitation: Yinylite AYAA Ethyl Cellulose 12.9 4.3 Formula 16 Ingredient Nevindcnc R-3 or Cumar W-l Sanlidtcr 8 Rosin WW Yinylite XYHL Mineral Oil Paraffin Wax Pert* 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 100 and 180 C. By changing the type of polyvinyl acetate resin utilized in ihc hot melt, (he viscosity of the melt can be increased or decreased without changing the ratio of resin to plasticizer. For example, substitution nf Gelva Y-15 for Gelva Y-7 in formula tions 17 and 18 increases the melt viscosity. Ingredients Gelva polyvinyl acetate resin V-7 Ethyl cellulose Gelva C-SV-16R Satiliritcr 160 Rosin WW Dihulyl phthalate Aror.lnr 1254 Formula 17 100 -- -- -- 75 30 55 Part* by Weight Formula 18 65 15 -- 16 -- -- 4 Formula -- too -- 75 30 55 HONS 078536 Polyvinyl butyral hot-melt adhesives are useful for joining cellophane, aluminum foil, glassine, and waxed glassine to themselves. The sealing temperature is usually 200 to 350 F. The pressure can range between 0.5 psi and 30 psi. Polyvinyl butyral hot melts are extremely fast sclling--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-Malt Adhesive Ingredients Butvar B-76 Opalwax Poly-pale Ester # 1 Staybelite Ester # 10 Sunticncr 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 arc 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 Sanfiriacr 160 Chlorinated rubber Parts by Weight 100 10 20 A typical cellulose acetate bol-meh adhesive is shown in Formula 22: Formula 22--Cellulose Acetate Hot-Melt Adhesive Ingredients Cellulose acetate Sanliciier M*17 Inert filler Parts by Weight 50 88 35 HONS 078537 Cellulose acetate butyrate is commonly used for hot-melt applications. Formula 23 is a typical starting formula. Formula 23---Calluloia Aeatata Butyrate Hot-Malt 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 coaling 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 Ilakers 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 DELAYEDTACK 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: Monaanto Chemical Company trademark Regiitered in U.S. Patent Office. 13 MOMS 078538 Solid plasticisers, such as diphenyl phthalate, Santiciter I H, and SantUizcr 9, make possible the deiayed-tack properties of these unusual adhesives. The solid plasticizers are chosen lor 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; 2,608,54.}; 2,61.}, 156; and 2,613,191. Formulas 25 through 27 are quoted from (he patents as indicated. Formula 25--Dalayad-Tack Adhasiva (l). S. Patent No. 2,462,029, Example 96) Ingredients Sanlicitrr 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 polymerised rosin containing approximately 40^ dipolymers of abietic acid (Hercules Powder Co.), I part 2-amino-2-metbyl-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--Dalayed-Tack Adhasiva (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 F. Once set, the adhesive continues to hold at ordinary temperatures. 14 MGNS 078539 Formula 27--Polystyrene-Emulsion, Delayed-Taeli Adhesive (U. S. Patent No. 2,613,156, Example 1) "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 llr/c aqueous solution of Aerosol OT and 4.5 ]>arts 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 (ieon 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 very tacky and powerfully adhesive. Formula 20--Polyamide Dalayad-Taek Adhesive Ingredients Versamid 940 Santicizrr 9 Candelilla wax Isopropyl alcohol Toluene Parts by Weight 100 31.6 5.9 29.5 29.5 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 Vlnylite VMCH Vinylite VAGH Sattlkizr.r 141 or Santicner M-17 Acetone Methyl ethyl ketone Parts by Weight 80 10 10 20 250 100 15 HONS G785AG 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 (or a nitrocellulose cement. Formulas 30, 31, and 32-~Nitrocellulose Lacquers and Cement Ingredients Nitrocellulose (^-sec.SS) Nitrocellulose (30-40 sec.RS) Dibutyl phthalate Dicyclohexyl phthalate Santiciner 160 5a/efrfc 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 -- 87 -- 20 --- 16 12 --8 ---- --3 15 50 31 104 --15 50 10 5 -- 12 -- 34 34 -- CELLULOSIC ADHESIVES Formulations 33 and 34 illustrate suggested starting formulations for cellulose acetate butyrate. Formula 33--For Seeling Paper to Paper or to Cellulose Acetete Butyrate Ingredients Perts by Weight Cellulose acetate butyrate (half second) Santolitc MHP Ethyl alcohol <959fc) Isobutyl acetate Toluene Hi-Flash naphtha 15 15 15 10 35 10 16 MOMS 070541 Formula 34--For Sealing Paper to Cellulose Acetate Ingredients Cellulose acetate butyrate (hall second) Santolite MHP Ethyl alcohol (95%) Isobutyl acetate Toluene Hi-Flash naphtha Parts by Weight 12 18 15 10 35 10 Formula .15 gives outstanding grease resistance and light stability. Formula 35--Grease-Resistant Coating Ingredients Cellulose acetate LL-1 Santiazcr M-17 Santicixcr 8 Acetone Methyl ethyl ketone Methyl ceilosolve 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 Self 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 MOMS 076542 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 Arochr 1254 Formula 37--Polyurethane Adhesive Parts by Weight 100 5 50 20 Formula .17 has a maximum work life of 48 hours. Excessive humidity or temperature shorten the work life. 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 (cm|>eralure for 10 to 30 minutes until the solvent evaporates. The pieces to be joined are compressed at 50 psi lor at least 15 seconds. The adhesive surfaces may also be heated with infrared lamps to 130 V for 4 minutes to evap orate (he 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 scalability. 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, t!is coating allows only 1/16 gram of moisture vapor to pass through 100 square inches of paper in 72 hours. Ingredients l'arlon 125-crntipotsc 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 -- 14 5 21 -- as needed 20 6 6 - 6ft 19 MGNS 078543 > ZEIN ADHESIVES Formulations 40 and 41, based upon zein, illustrate the versatility of Monsanto plasticizers to produce specialty formulations with unusual characteristics. Formula 40--Z#!n Label Varnish Ingredients Zein Rosin WW Sanfolitr MHP Sanlicizer 8 Proprietary or 91% isopropanol Part* by Weight 100 100 20 25 190 Formula 41--Zein Foil-Tinting Base ingredients Zein A Santolitc MHP Santiciicr 8 91% Isopropanol 85% Phosphoric acid Coloring Pactt 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 (calendar onto fabric) Ingradianti Cellulose acetate (type A-9, 40 mesh) Sanlicizer 8 Sautolilc MHP Parts by Weight I 2.5-5 1-2 19 HONS 076544 Formula 43--Presiure-Seniitive Adhesive (calender onto fabric) Ingredients Vinylite AYAF (polyvinyl acetate) Arofene 700 (100% phenolic resin) Santicizer B*16 Parts by Waight S 36 IS Formula 44 Pressure-Sensitive Adhesive (Kot-malt typo) Ingrediants Pale crepe rubber Yistanex (polyisobutylene) Ester gum Santolitc MHP Methyl abietate, Santicizer 160, dibutyl phthalate, Aroclor, or Santicizer B-16 Wax (Montan, paraffin, camauba, or amorphous microcrystalline) Parts by Weight 15-20 5-15 " 20 20 25-50 1-20 Malt 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 Parkm 1259 type Stoybcllte Ester # 10 Dibutyl phthalate Acetone Hexane Parts by Waight 5 10 to 52.5 22.5 (HONS 078545 P_J 1 ADHESIVE PRIMERS Adhesive primers are used in (he 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 allied. Formula 46--Adhesive Primer (for bonding vinyl fo paper or cotton cloth) Ingredients Vinylite VYMS Vinyllte VMCH Sunth izrr 160 Methyl ethyl ketone Solvesso No. 1 Parts by 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 ii for nylon and Dacron, as well as for metal. Formula 47--Adhesive Primer for Synthetic Fabrics Ingredients Yinylite VMCH Vinyl Resin Dioctyl phthalate (DOP) Methyl ethyl ketone Mondur M Parts by Weight 100 60 200 5 Formula 47 in made by mixing methyl ethyl ketone with the plasticizer, then adding the resin. Ihe shelf life of the mixture is indefinite until the Mondur M is added. Upon addition of Mondur M the adhesivlly of the compound decreases by IS 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. HONS 076546 T 4 I MISCELLANEOUS FORMULATIONS EPOXY-RESIN ADHESIVES E|x>xy resins are widely used in adhesive applications. Monsanto Chemical Company's ModEpox* organopbosphoniR compound improves the bond strength of epoxy adhesives (Formulas 48, 49, and 50). Afod-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-ZOQ) Difthylenetriamine Mod-Epox Butyl glycidyl ether Formula 48 Formula 49 Formula 60 Parts by Weight too too 100 12 8 13 25 -- - - 13.5 Cure: 20 hours at room temperature plus 2 hours at 100 C. Tensile Sheer-bond Strength Aluminum Aluminum Steel - Steel Glass - Glass Cohesive failure of retin. Adhesive bond intact. Formula 48 1880 psi 2000 2750 Formula 49 2590 psi 3060 4900* Formula 50 2010 psi - _ Arodor 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. Md-Epox; Monur: Montanto Chemical Company trademark*. Regiatered m U. 5. Patent Office. 22 0785'*7 KQNS pa.a ( POLYURETHANE-RESIN ADHESIVES Polyurethane resin* are commonly used in flocking adhesives. The following formulation is typi cal of a flocking adhesive: Formula SI--Polyurathane-Rasln Flocking Adhesive Ingredients Part A -- Multranil FLD Arocfor 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. TOXICOLOGICAL CHARACTERISTICS I 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 plasticisers that are approved by the Food and Drug Administration as being non-toxic. These products are: Saniicizer 141 Santicizer B-16 Santicizer E-l 5 Diethyl phthalate Dioctyl phthalate "j > (For foods with high water content only) Diisooctyl phthalate j Use of these materials as plasticisers in synthetic adhesives should greatly aid acceptance of the adhesive. 23 HONS 078548 INGREDIENT INDEX Ingredient Identification Supplier Acrysol* Aluminum oxide Ammonium caseinate Armid* Arofene* Bakers castor oi) Bulvar* Butyl glycidyl ether Candclilla wax Carboxymeihylcellulose Synthetic-resin emulsions Amides Modified phenolic and maleic resins Polyvinyl butyral resins Cellulose acetate Cellulose acetate butyrate Chlorinated rubber Cumar* Dammar wax Coumarone-indene resins Diethyienetriamine Elvacet* Polyvinyl acetate emulsion Epoxy soybean oil Ester gum Ethyl cellulose Gelva* Polyvinyl acetate emulsion Geon* Polyvinyl materials Hycar* Lewisol* Resins and synthetic rubber products Rosin-modified maieates l,opor* No. 45 Mineral oil Methyl abietate 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. I. du Pont de Nemours & Co. Rohm A- Haas Co. Glidden Company Hercules Powder Co. Shawinigan Resins Corp. 11 F Goodrich Chemical Co. B. F. Goodrich Chemical Co. Hercules Powder Co. Esso Standard Oil Co. Hercules Powder Co. reniMertd in U S. Patent Office. 24 HONS 07854S Ingredient Inde* - Continued Ingredient Identification Supplier Methyl Cellosolve* acetate Mondur* Montan wax Mullranil* Nevillac* Nevindene* Newport V-40* Nitrocellulose Opalwax* Parlon* Pentalyn* Poly-G* P-1200 Poly-pale* esters Polyco* Polymethyl methacrylate Polyvinylpyrollldone Quilon* Solves*)* Staybellte* esters Syn Fleur* Triton* X-155 Veraamid* Vinsol* Vinylite* Vistanex* York Whiting* Zein Isocyanates Union Carbide Chemical Co. Mobay Chemical Co. Beacon Company Synthetic resin Mobay Chemical Co. Phenol-modified cottmaroneindene 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 polymerised rosin Polyvinyl acetate emulsion Hercules Powder Co. The Borden Co. Rohm & Haas Co. Chrome complex Aromatic solvent Hydrogenated rosin esters Odorant Antara Chemicals Division General Aniline & Film Corp. E. I. du Pont de Nemours & Co. Esso Standard Oil Co. Hercules Powder Co. Syn Fleur Scientific Co. Welting, emulsifying, dis persing, scouring agents Polyamide resins Pine resin Vinyl resins Polyisobutylene resin Superfine calcium carbonate Rohm & Haas Co. General Mills, Inc. Hercules Powder Co. Union Carbide Plastics Co. Enjay Company National Gypsum Co. Corn Products Sales Co. *Tradcmik registered in U.5. Patent Office. 25 MGNS 078550 r TECHNICAL LITERATURE ABOUT MONSANTO PLASTICIZERS The following technical bulletins and brochures give technical information about the pro|)erties and a|>plications of the Monsanto plasticizers and other products that are mentioned in this bulletin. Monsanto technical literature is continuously revised to contain (he 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 I'lasticizers for non-toxic applications" "How you can benefit from Monsanto Solid Plasticizers" Phthalate Plasticizers Satiltchi'r 160 (butyl benzyl phthalate): Dibutyl Phthalate: Diethyl Phthalate and Dimethyl Phthalate: Dicyclohexyl Phthalate: Di-(Z-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 Sauticizrr E-1S (Ethyl phthalyl ethyl glycollate): Santicizcr B-16 (Butyl phthalyl butyl glycollate): Santicizcr M-17 (Methyl phthalyl ethyl glycollate): Technical Bulletin PL-IS Technical Bulletin PL-16 Technical Bulletin PL-17 Phosphate Plasticizers Santicizcr 140: Santicizcr 141 (non-toxic plasticizer): Triphcnyl Phosphate (flame-retarding plasticizer): Tricresvl Phosphate (flame-retarding plasticizer): Technical Bulletin PL-140 Technical Bulletin PL-141 Technical Bulletin PL-301 Technical Bulletin PI.-305 26 o ZB55L Sulfonamlda Plasticiiors Sarttiriser 1-H: Sautirizer 8: Sauticiter 9: Technical. Bulletin PL-l-H Technical Bulletin FL-8 Technical Bulletin PL-9 Aroclor Plasticiiars The Aroclors: Aroclors 1221, 1232, and 1242 for polyvinyl acetate emulsion adhesives: Application Data Bulletin O-P-115 Technical Bulletin PL-321 Other Plaiticixars I1B-40 (partially hydrogenated terphenyl): Mod-Epox (epoxy-resin modifier): Rosin Additives Santo/ile MHP and Santolite MS-fiO^f (Monsanto industrial resins): Technical Bulletin 0-104 Technical Bulletin PL-313 Technical Bulletin PL-320 Preservatives and Stabilisers San/obrUe and Penia for the preservation of paints and water-base adhesives: Santonox and Santonox R, antioxidants for polyethylene: Sodium Bensoate, 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 lor Paint, Ink, Hastics, and Other Odorous Products: "Vanillin Monsanto": folder folder Technical Bulletin PL-325 folder 27 MOh,s 07a552 SHIPPING INFORMATION Most Monsanto plasticizers are shipped in bulk in tank cars or lank 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 phihalate Diethyl phthalate Dibutyl phthalate Dioctyl phthalate Dkyciohexyl phthalate Diphenyl phthalate Santieiztr 160 Santiciter E-15 Senfictzer B-16 Santicizcr M-17 Dimethyl phthalate Diethyl phihalate Dibutyl phihalate Dioctyl phthalate Dicyclohexyi phthalate Diphenyl phthalate Rutyl benzyl phthalate (Resin plasticizer) Resin plasticizer Resin plasticizer Resin plasticizer 530 500 475 445 350 400 500 535 500 550 40 45 40 40 -- -- 40 45 40 50 Tricresyl phosphate Triphenyl phosphate Santicizcr MO Santtetter Ml Santicizcr 1-H Aroclor 1221 Aroclor 1232 Aroclor 1242, 1248, 1254, 1260 Aroclor 5460 Resin plasticizer Resin plasticizer Resin plasticizer Resin plasticizer Resin plasticizer Synthetic resin Synthetic resin Synthetic resins Synthetic resin 530 45 225 -- 545 50 495 45 --- HO'* 520 550 600 -- 500 HB-10 Mod-Epox SantohIf' MHP SantolUv MS-80^ Santomask 11 Santonor Resin plasticizer Chemical, N01BN | rail: synthetic resin without filler i / j truck: synthetic resin, f solid mass | Chemical, NOIBN Chemical, NOIBN 29 450 40 510 45 -- 60lb 540 45 2501c 150 45 'corrucatcd carlmi (1<T * 8" * S>`) b>7 gallon c,l$ cation MGNS 078553 Tha information containad in this bullatin it to our bait knowtadga, trua and aceurata, but all racommandations or suggestions ara mada without guarantee. since tha conditions of use ara bayond our control. Tha Montanto Chamicai Company disclaim* any liability incurrad in connaction with tha usa of thasa data or suggestion*. Furthermore. nothing containad herein ihalt ba comtruad a* a racommandation to via any product in conflict with mist ing patents eovarinq any matariai or its usa. THIS BULLETIN REPLACES TECHNICAL BULLETIN NO. 0 99 DATED APRIL 1953. *QNS