Document JJRqzyN1ND1Mm8yr0po7JLzz6

Marvinol 50, an all-purpose PVC plastisol and organosol dispersion resin. Dwmtcal Divtsion U.f. RUBBER URL 14468 2 Marvinol50 isidealforawide range c of plastisol and organosol applications. URL 14469 Since the introduction of the pvc dispersion resin technique. many industries have utilized plastisols and organosols for the enchancement of their existing products and in the development of entirely new products. With the growth of these new products, it was inevitable that different types of vinyl dispersion resins would be made available with various end applications best served by specific resins. Marvinol 50 is an all-purpose pvc plastisol and organosol dispersion resin developed by U.S. Rubber. It rapidly gained wide acceptance in the fabric, paper, and organosol coating fields where high and low-shear rheological properties are of such great importance. Outstanding properties of Marvinol 50 include its controlledrheological properties at high and low rates ofshear, thus adapting it for a wide variety of molding, dipping, spreading and spraying applications. Its high glossand clarity are ideal for many flooring and coat ed cloth products. Its high degree of taste and odor integrity makes Marvinol 50 very useful in food clo sure work. Marvinol 50 meets F.D.A. requirements for food contact applications. Marvinol 50 is a homopolymer of vinyl chloride. Its typical resin characteristics are as follows: Specific gravjn Specific viscosity* Moisture and volatiles (max.) Apparent density Methanol extract 0 o 1.4 0.50 17 Ibs'cubic feet l-3"o U.S. Rubber registered tradename for its PVC resin. ASTM D-1243-60 Method B 3 n V Marvinol 50 can be supplied : to meetyour viscosity requirements. UfiL 14471 Since dispersion resins by definition are processed as liquids at room temperatures, the ability of the resin to meet the rheological needs of the processor is of axiomatic importance. Marvinol 50 can be supplied to meet a wide range of viscosity requirements. Becauseofthe infinite number and widely divergent types of formulations in which dispersion resin may be used, it is a challenge to completely predict the performanceofa resin from a single test recipe. However, experience has taught that in the high-shear rate coat ing of plastisols and organosols on cloth, paper, wire, glass yam, etc., high-shear viscosity properties can be characterized by high-shear measurements made on a relatively simple plastisol formulation. The diagram below is a plot of typical high-shear viscosity properties for Marvinol 50. This curve illustratesthereason Marvinol 50processes so well at highshear rates. Low high-shear viscosities and the mainte nance ofNewtonian-like properties over a wide range of shear allow for rapid, dilatant-free coating. The low high-shear viscosity properties of Marvi nol 50 also enable the formulator to lower his plasti cizer level without resorting to the organosol or modi fied plastisol techniques. This property assumes great importance in the casting of tough, low plasticizer level films at film thicknesses that preclude the use of volatile diluent. The diagram below is a plot of Severs viscosity ver sus plasticizer concentration. This curve illustrates the unusually low plasticizer levels available to formulators using Marvinol 50. 200 - $ 150 Ic 1100 Severs viscositt properties of Marvinol 50. Marvinol 50 ................. DOP................................. Sample age: Test temperature: 100 parts 60 parts 2hours 25aC 50 500 1000 1500 2000 Shear rate in seconds-1 2500 5 How viscosity of Marvinol 50 varies with temperature and age. f URL 14472 One very important facet of high-shear rheology associated with plastisol formulations is the large vis cosity response to changes in plastisol temperature. From the data in the diagram below (left) it can be seen that normal seasonal changes in ambient temper ature will produce viscosity variations that could re quire formulating adjustments. This viscosity variation is actually due to the change in plasticizer viscosity w ith temperature. Consequent ly, a study of the plasticizers used in a formulation with respect to their viscosity-temperature relation ship may become essential. These data are supplied in several plasticizer manuals. The viscosity-tempera ture data for dop, a typical plasticizer, are shown in the diagram below. In high-shear applications with only a few special exceptions low viscosity at high-shear is a desirable property. With regard to a plaslisol's low -shear properties, the preceding statement does not necessarily apply, i.eM I 6 c * plastisols formulated for cold dipping or fabric coat ing would find too low a low-shear viscosity trouble some. Since many applications require unique lowshearviscosityproperties,itisnoteworthy that through theuseofsurfactants, gelling agents, and diluents basic low-shear properties of Marvinol 50 can be altered to aconsiderableextent. The diagrams below illustrate the general type of low-shear properties associated with Marvinol 50 as measured with a Brookfield viscometer. The diagram at left illustrates the normal increase in viscosity with age andhowa share of this increase is due to thixotropic buildup. Thediagram at right illustrates the plastic and pseudoplasticnature of plastisols at low-shear. These flow properties are typical of many plastisol resins includ ing those in the Marvinol series. It is possible to supply Marvinol 50 resin for appli cations requiring a wide range of specialized viscosity properties. URL 14473 i URL 14474 8 Marvinol 50 can be fused overa wide range of temperatures Oncethe plastisol is cast or applied, it is then neces sary to fuse it into a useful product. This is done by exposing the plastisol to some suitable temperature in the 300F to 400 F range and holding it there long enough to insure that the plastisol itself reaches its fu sion temperature. The diagramatlowerleft illustrates the development ofa plastisol's fusion properties at two plasticizer lev els as measured by ultimate tensile strength. The diagram at lower right illustrates the develop ment of an organosol's fusion properties as both a function of temperature and time. The reduced tensiles obtained at five minutes reveal that the films have not yet reached the indicated oven air tempera ture and that for the particular oven involved ap proximately ten minutes is actually required. The con tinual increase in tensile at 400 F is the result of plasti cizer volatilization from the film which is evidenced by a rapid weight loss of the film under these excessive fusion conditions. Certain material or equipment limitations require reduced fusion temperatures, below the 325F indi cated by these data. In this event, the use of solvating plasticizerssuch asTCPis suggested. A comprehensive study covering "The Influence of Resin on Plastisol Fusion" is available on request. URL 14475 9 URL 14476 10 Marvinol 50 is compatible with a wide range of compounding ingredients. jit-m a n A single resin falls short ofencompassing all the in dividual processor's detailed needs. For this reason US. Rubber has developed a family of dispersion grade resins where specific resins have been designed to meet specific requirements. A list of these resins is shown on page 16 and their use is described in the table of formulations on page 18. The art of plastisol and organosol compounding may be put on a more scientific basis by the exercise of a few formulating principles. A typical recipe may consistofresin, plasticizers, stabilizers, a volatile dilu ent, fillers, pigments, and miscellaneous ingredients. Here is a briefoutline on the selection of the various components that go into a dispersion recipe: Resins. Dispersion type resins are homopolymers of pvc and copolymers of vinyl chloride with smaller amounts of comonomers. Resins vary in a number of important respects such as their non-pvc content, molecular weight, etc. The major difference between resins, how ever, is their ability to process in a satisfactory manner. The following lists some of the major rheological plus other processing features the formulator is con cerned w ith for some typical applications: Fabric coating: (1) Low high-shear viscosity for ease of coating. (2) Medium low-shear viscosity for cloth penetration control. Wire and yarn coating: (1) Low high-shear viscosity for ease of coating. (2) Medium low-shear viscosity forresistancetodrippingpriortogelation and fusion. Slush molding: (1) Low' low-shear viscosity for good drainage. (2) Good air release. (3) Low gela tion temperature for rapid buildup in mold. (4) Dry surface. Rotational molding: (1) Low low-shear viscosity for uniform distribution in mold. (2) Good air release, (3) Medium-high gel temperature. Organosols: (1) Low high-shear viscosity for ease ofcoating. (2) Low low-shear viscosity for good flowout.(3) Compatibility with diluents. (4) High clarity and gloss. Plasticizers. Once a resin best suited to the end application has been selected, it must then be blended with plasticizers ofthe correct type and level. Blends of plasticizers will frequently impart the desired properties rather than one alone. The following lists some general characteristics as sociated with each plasticizer type although not all the plasticizers in each group will actually possess these properties: Phthlates: good compatibility, good balance of all properties (dop, diop, dcp, ddp and mixed esters). Phosphates: good flame resistance, reduced fusion temperature (TCP). Polymeries: low extraction, high viscosity. Epoxy (soybean type): enhances heal stability. Epoxy (tallate type): enhances heat stability and low temperature flexibility. Azelates, adipates: good low- temperature flexibil ity, limited compatibility, low viscosity (doz. doa). Extenders: low cost, low' viscosity, limited compati bility. Although the resin generally imparts to the plastisol its basic rheological properties, the plasticizer is occa sionally selected for its affect on viscosity. An example of this is the use of the low viscosity types for rigid plastisol molding work. H (This discussion of compounding ingredients and aromatics as was the case with the early copol for Marvinol 50 is continued from the previous page.) ymer organosol resins. Aliphatic naphthas, such as Stabilizers. VM&P and mineral spirits, etc., are recommended The stabilizer has the function of minimizing color along with those aliphatic diluents whose aromatic development during fusion or any subsequent expo* components have been removed. The latter mate sure to heat and light. This may be one of a number of rials made primarily for the odorless paint field, al proprietary lead, tin, barium, cadmium, or zinc com though slightly more expensive are excellent for pounds sold for this purpose. maintaining good viscosity stability. The most widely used stabilizer systems in plastisol The boiling range of the diluent selected w ill be de and organosol work are based on combinations of pendent upon the plastisol's processing conditions. In barium, cadmium and zinc compounds and are gen the case where there is considerable exposure of the erally sold as a single blend. It is important to remem unfused organosol prior to coating or w here there is ber that it is always necessary to include a small the danger ofrapid fusion trapping diluent in the film, amount of epoxy, generally epoxy plasticizer (ca. a slow evaporating or high boiling diluent is desir 5 phr) to prevent the compound from suddenly dark able. On the other hand, too high a boiling range ening during fusion as a result of the inclusion of zinc may result in some diluent remaining in the film in the stabilizer system. after fusion. Barium: Holds color for long-term heat exposure. Another consideration in diluent selection is the Cadmium: Good color during early fusion stages. compatibility of the diluent with the plasticizer sys Zinc: Similar to cadmium but will darken com tem. Many polymeric type plasticizers are not com pound quickly unless balanced with epoxy; used to patible with aliphatic hydrocarbons and, in such minimize sulfur staining. an instance, diluent blends high in aromatic content Lead: Excellent for long term heat stability; has are required. pigmenting effect; excellent activator for foams Fillers. based on Celogen az. Mineral fillers are many times added to reduce per Volatile diluents. pound costs. It should be recognized, however, that I n the preparation of organosols based on Marvinol the pound-volume cost is not reduced as dramatically 50, it is not necessary to use the highly polar ketones asthepoundcost due to the higher density of the filler U S Rubber registered tradename for its blowing agents. 12 URL 14479 in comparison with the plastisol: for example, 2.6 for calcium carbonate versus 1.2 for a typical plastisol compound. Although fillers are selected primarily on the basis ofcost, a few additional considerations are of impor tance. Their effect on viscosity may be minimized by the selection of a low oil absorption type. They must not be excessively coarse so as to cause any wear on processing equipment such as mixers and paint mills. Such wear on equipment will also result in a graying ofthe plastisol due to the presence of the particles of eroded metal. Fillers used in plastisol work are generally of the calciumcarbonate type which are available at low cost in a variety ofparticle sizes and surface treatments. Pigments. The selection ofpigments must be made on the basis oftheir ability to withstand color changes during the fusion cycle and the exposure to which the plastisol will be subjected in use. Such information is available in considerable detail from pigment manufacturers. Of practical importance to many plastisol users who are not in a position to prepare their own pig ment dispersion is the availability from several sup pliers ofpigments dispersed in plasticizer, made espe cially for the plastisol field. Miscellaneous ingredients. Through the use of various formulating ingredients in addition to those just discussed the plastisol com- pounderis capable of applying considerable finesse to his work. Some of these materials are high oil absorption pig ments, surfactants, thermosetting plasticizers and toners. The functions ofthese miscellaneous ingredi ents are described below. High oil absorption pigments are used in small quantities to build yield value in plastisols for cold dip type applications and to prevent cloth penetration in glove dipping and spread coating. Another approach to the development of yield value in plastisols is through resin selection. Here MarvinolX6215Sand blends with Marvinol 50 may be utilized to build yield value.' Surfactants are used as viscosity depressants. A typ ical surfactant is Polyethylene glycol 400 dioleate. Thermosetting plasticizers are used to produce rigid plastisols without resorting to the use of volatile dilu ents. They also impart good heat distortion proper ties. These systems are generally handicapped by high cost and poor heat and viscosity stability. Toners are violet dyes or fluorescent agents that help offset the yellowish cast developed in many clear plastisols on fusion. This is of particular value in the clear plastisol boot field. A typical toner is Alizarine Irisol (General Aniline & Film Corp: Dyestuff & Chemical Division). 13 URL 14480 14 Marvinol 50 is readily compounded with standard mixing equipment, techniques. The relative ease with which dispersion resin may be blended with plasticizers and other formulating in gredients partially accounts for the rapid growth of this field. Consequently, a briefdiscussion on the vari ous mixing techniques available is in order. Forthe bulk of plastisol and organosol compound ing, the change can or pony type mixer pictured here is quite adequate. A normal mixing cycle would involve charging the mixerwithsufficient plasticizer, or plasticizer and dilu ent in the case of an organosol, to wet the resin into a fairly heavy paste. This allows for the effective trans mission of shear forces throughout the mix. When all the resin has been thoroughly wetted and dispersed, the balance of the plasticizer or diluent and other for mulating ingredients can then be blended in slow ly. From this point the batch may be further processed through paint mills and deaerators, ifnecessary. This low speed, high-shear mixing technique may be satisfactorily applied to virtually all types of plastisol and organosol compounds. In the manufacture of organosols and plastisols of the low viscosity type, it is possible to utilize another type mixer which does away with the necessity of keepingthe paste in a heavy stage for effective mixing. Known as a "high-speed, high-shear'' mixer, it is best used for low viscosity plastisols and organosols. Since the high-shear mixing action takes place in the immediate vicinity of the rotating blade, it is nec essary to have rapid circulation of the compound to prevent localized overheating and consequent gelation of the material, thus requiring compounds w ith low viscosity properties. Consequently, all the liquid in gredients would be first blended in the mixer after which the resin is added in increments. Ball and pebble mills used so extensively in the paint field are still occasionally used to compound plastisols and organosols. Since no real grinding ac tion is required, just a deagglomeration of the soft resin clusters, considerably more latitude w ith respect to ball or pebble charges and compound loading may be tolerated compared with paints. Frequently deaer ation can be accomplished in the same mill by rigging it for vacuum. Occasionally, inadequate mixing or improper mix* ingprocedureswill allow for undispersed resin agglom erates working their way into the finished compound. In such instances a single, loose pass through a threeroll paint mill is sufficient to disperse any such resin clusters. When deaeration is necessary, a variety of vacuum set-ups will accomplish this. 15 There are seven other Marvinol plastisol resins and three different blending resins. i URL 14482 In addition to Marvinol 50, LJ.S. Rubber can supply in the future, all meeting industry's sophisticated de any of the following plastisol resins with more to come mands for specialty dispersion resins. Dispersion resins Blending resins Marvinol SI Marvinol S3 Marvinol 55(X-6116) Marvinol 56 Marvinol X-6085 Marvinol X-621SS Marvinol X-6501 Marvinol 10 Marvinol 24PL Marvinol IS Readily stirred into plasticizers to form plastisols with low Brookfield viscosity and outstanding air release properties. Excellent for slush molding, rota tional casting, chemically blown plastisol foam. Readily stirred into plasticizers to form plastisols of outstanding quality with respect to chemically blown foam. Also, well-suited to processing condi tions requiring reduced gelation time, low viscosity and excellent air release, e.g. slush molding, rotational casting, hot and cold dipping, etc. A stir-in copolymer dispersion resin designed for lower fusion temperature applications. High viscosity and rapid gelation features control cloth penetration. A stir-in copolymer plastisol resin combining low Brookfield and Severs vis cosity properties with rapid gelation and low fusion temperature properties. Ideally suited for a wide variety of plastisol casting, molding, and adhesive applications, where a combination of low temperature fusion and low appli cation viscosity is required for more rapid processing or in the coating of heat sensitive substrates. A stir-in homopolymer w ith uniquely low viscosity properties. Also provides excellent gloss control. A plastisol resin that'swell-adaptedtohigh plasticizer level compounds where high viscosityandyieldarc required to develop strike-through resistance. Ex cellent for chemically blown foam. A stir-in copolymer dispersion with uniquely low-viscosity properties com bined with low-fusion temperatures. High molecularweight resin. Reduces viscosity, enhances air release in plasti sol formulations. Alowcost blending resin for plastisol compounds. Reduces viscosity and en hances air release. Excellent for chemically blown foam compounds. A low cost blending resin for plastisol compounds where paint mill processability is desired. Reduces viscosity and enhances air release. Excellent for chemically blown foam compounds. 16 Recipes to use as a guide. URL 1^483 When discussing plastisol and organosol formula tions, it is only possible to present them in a most gen eral manner. The actual production recipe will, in many cases, bear only a slight resemblance to the "starting point" recipe. As a guide, however, the fol lowing recipes are presented. Perhaps their greatest value will be to illustrate the principles behind the use of the various ingredients. Further details on these formulations for other applications are available through our technical sales representatives. The use of Marvinol resins other than 50 has been indicated w here such resins were specifically designed for that particular application. A. Paper and fabric coating. This is a basic recipe for high gloss and general pur pose coating onto paper, fabric and other substrates. The use of diluent for high-shear viscosity adjustment will depend upon coating speed and thickness, plasti cizer level and type, etc. Generally an intermediate low-shear (Brookfield) viscosity provides an optimum for vacuum deaeration, pigment floatation resistance and fabric penetration control. A balanced stabilizer system including epoxy plasticizer is used. B. Low cost, low gloss coating. For paper and fabric coating, the use of a controlled partidesize blending resin and filler lower compound gloss as well as cost with only a minimal loss in phys ical properties. C. Organosols. The use ofaliphatic diluent and surface active agent enables the formulation of low-stable viscosities at low plastidzer levels. Here again the high gloss characteristicsofMarvinol50makeit an exceptional resin for flooring and paper coating. D. Slush and rotational molding. Marvinol 51 and 10 combine to provide excep tionally low viscosity, excellent air release, high hot strength and high physical properties at room tem perature. Marvinol 10 provides a roughened air sur face which is essential in footwear. E. Foam. High temperature blowing agents (Celogen AZ ) are most popularly used in vinyl foam. Here Marvinol 53 used alone or combined with a high viscosity resin. Marvinol X6215S for cloth penetration control pro vides an optimum in foam quality and physical prop erties. F. Semi-rigid plastisol. A unique resin, Marvinol X6085 combined with Marvinol 24PL provides exceptionally low viscosity . This enables a marked reduction in plasticizer level. G and H. Low fusion temperature. A copolymer dispersion resin, Marvinol 56 com bined with a high solvating plasticizer provides ex ceptionally low fusion temperatures. Through the useof Marvinol X6501, low fusion is combined with low gloss and ultra-low viscosity. I. Food closure and non-fog. Marvinol 50 and X6085 have unusually good taste and odor integrity for a variety of food closure 17 3 applications. These resins are equally useful in non-fog automotive applications. These qualities result from the low level and careful selection of the non-pvc in gredients used in these resins. Marvinol 50 may be combined with Marvinol 10 in these applications for a further enhancement of properties plus improve ments in air release, viscosity and cost. Of course plas ticizer and stabilizer selection are equally important. APPLICATION - AB C D Paper and Low gloss. Slush and fabric low cost Organosol. rotational coating. coating. molding. Marvinol 50 100 70 100 ____ Marvinol 51 -- -- -- 70 Marvinol 53 ___ ___ ___ ___ Marvinol 56 -------- Marvinol X6085 ___ ___ ____ ___ Marvinol X62I5S Marvinol X650I Marvinol 10 Marvinol 1$ Marvinol 24PL TCP DOP DCP Extender plasticizer Epoxy plasticizer Aliphatic diluent Dibasic lead phihalateO) Ba, Cd, Zn stabilizer PEG 400 dioleale Celogen AZ Ca COa filler Pigmentation (I) Dyihal-Nauonal Lead Company -- ---- ---- -- ------ -- 30 -- ------ ------ 60 60 30 -- ---- ------ 55 5 2- 10 -- ---- 333 ---- 1 -- ---- -- 20 -- 5 5-- -- -- 30 -- -- -- 35 35 -- 5 -- -- 3 -- -- -- -- E Foam. ___ ___ 70 _ _ 30 ___ -- -- -- -- 95 -- -- 5 - 3 -- -- 3 -- -- FG H Semi-rigid plastisol. Low fusion. Low fusion. low gloss, low viscosity. ___ ___ ___ -- ___ -- ___ ___ -- ___ 100 60 __ ____ -- ___ ---- ---- 40 -- -- 60 ___ ___ -- 100 -- -- -- 60 ---- 35 -- -- 10 55 -- -- -- -- 10 5 -- ---- 33 ___ -- -- 3 -- ---- -- ---- ---- -- -- URL 14484 ) Where to get more information. fan If you'd like more information about our products venient to you. Or if you prefer, write directly to our please call or write the district sales office most con division headquarters. Northeast Akron Chicago Dallas Dalton Detroit Gastonia Los Angeles New York Division headquarters: U S Rubber Company, Chemical Division, Naugatuck, Connecticut To contact Naugatuck from Boston To contact Naugatuck from New Jersey To contact Naugatuck from Philadelphia District sales offices: U.S. Rubber Company, Chemical Division, 1815 West Market Street. Akron. Ohio 44313 U.S. Rubber Company. Chemical Division, 4135 South Pulaski Rd., Chicago, Illinois 60632' U.S. Rubber Company. Chemical Division. 1011 Regal Row, Dallas, Texas 75247 U.S. RubberCompany, Chemical Division. P. O. Box 37). Dalton, Georgia 30720 U.S. Rubber Company, Automotive sales office, 4500 Enterprise Drive, Allen Park, Michigan 48101 U.S. Rubber Company. Chemical Division. 214 West Ruby Avenue, Gastonia, North Carolina 28053 U.S. Rubber Company. Chemical Division, 5901 Telegraph Road, Los Angeles, California 90022 Foreign sales offices: Naugatuck Chemical International, 1230 Avenue ofthe Americas, New York 10020 Cable address: UNIROYAL. New York 203-729-5241 326-6000 -846-9100 -368-6445 216-864-2145 312-254-5700 214-631-2310 404-278-19)1 313-274-3700 704-864-34)1 213-723-9971 212-247-5000 The recommendations for the use of our products are bated on lest! believed to be reliable. However, we do not guarantee the results to be obtained by others under different conditions. Nothing in this brochure is intended as a recommendation to use our products ao as to infringe on any patent. 19 UNITED STATES RUBBER COMPANY Chemical Dtytaian Naugatuck. Connecticut 06770