C E C E C E C E C E C E C E C E C E C E

AQUALON Ethylcellulose (EC)

Physical and Chemical Properties

AQUALON EC
A Specialty Polymer With Broad Stability and Compatibility

CONTENTS
COMPOSITION OF ETHYLCELLULOSE

PAGE
RESINS . . . . . . . . . . . . . . . . . . . . . . . . . . Effects of Ethoxyl Content . . . . . . . . . . . Compatibility With N-Type Ethylcellulose Compatibility With K-Type Ethylcellulose PLASTICIZERS . . . . . . . . . . . . . . . . . . . . Water-Sensitive Plasticizers . . . . . . . . . Oils as Ethylcellulose Plasticizers . . . . . Gasoline- and Oil-Resistant Plasticizers SPECIFIC APPLICATIONS LACQUERS . . . . . . . . . . . . . . . . . . Hard Lacquers for Rigid Surfaces Tough Lacquer . . . . . . . . . . . . . . Bronzing Lacquer . . . . . . . . . . . . Lacquer for Polystyrene Plastic . . Lacquer for Rubber . . . . . . . . . . . Specialty Wood Finishes . . . . . . . Water-White Wood Finish . . . . . . Alkali-Resistant Lacquer . . . . . . . Paper Lacquers . . . . . . . . . . . . . Flowback High-Gloss Lacquer . . . Solvent-Based Strip Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 21 21 22 22 25 25 26 27 27 27 27 27 27 28 28 28 28 28 28

TYPES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 FDA STATUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 OUTSTANDING CHARACTERISTICS Color . . . . . . . . . . . . . . . . . . . . . . . Compatibility . . . . . . . . . . . . . . . . . Density . . . . . . . . . . . . . . . . . . . . . Electrical Properties . . . . . . . . . . . . Flexibility . . . . . . . . . . . . . . . . . . . . Flammability . . . . . . . . . . . . . . . . . Softening Point . . . . . . . . . . . . . . . Solubility . . . . . . . . . . . . . . . . . . . . Stability to Chemicals . . . . . . . . . . Stability to Water . . . . . . . . . . . . . . Stability to Light . . . . . . . . . . . . . . . Stability to Heat . . . . . . . . . . . . . . . Taste . . . . . . . . . . . . . . . . . . . . . . . Thermoplasticity . . . . . . . . . . . . . . Toughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 5 5 5 5 5 5 5 5 5 5 6 6 6 6 6

PHYSICAL PROPERTIES (EFFECTS OF ETHOXYL CONTENT AND VISCOSITY) . . . . . . . . . . . . . . . . . . . . . . 7 VISCOSITY-CONCENTRATION RELATIONSHIPS . . . . . . . . . . . . . . . . . . . . . . 8 BLENDING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 How to Use the Blending Chart . . . . . . . . . . . . 8 Limitations of Blending . . . . . . . . . . . . . . . . . . . 9 FORMULATION STABILIZATION OF ETHYLCELLULOSE Hot-Melts . . . . . . . . . . . . . . . . . . . . . . Plastics . . . . . . . . . . . . . . . . . . . . . . . . Clear Films . . . . . . . . . . . . . . . . . . . . . SOLVENTS AND SOLUBILITY . . . . Solubility Parameters . . . . . . . . . Effects of Ethoxyl Content . . . . . . Solvents for N-Type . . . . . . . . . . . Effects of Alcohols . . . . . . . . . . . Dilution With Petroleum Thinners . Rule 442Exempt Solvents . . . . Economy Through Solvent Choice Effects of Solvent Composition on Film Properties . . . . . . . . . . . . Gasoline Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 13 13 13 13 13 13 14 14 15 15 16

EMULSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 INKS . . . . . . . . . . . . . . . . . . . . . Screen-Process Inks . . . . . . . . Magnetic Inks . . . . . . . . . . . . . Gravure and Flexographic Inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 28 28 28

VARNISHES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 ADHESIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 HOT-MELT APPLICATIONS . . . . . . . . . . . . . . . . 29 CASTING PLASTICS . . . . . . . . . . . . . . . . . . . . . 29 PIGMENT-GRINDING BASE . . . . . . . . . . . . . . . . 29 FILM AND FOIL . . . . . . . . . . . . . . . . . . . . . . . . . 29 PLASTICS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 FOOD CONTACT AND PHARMACEUTICALS TabletsCoatings . . . . . . . . . . . . . . . . . . . TabletsBinding . . . . . . . . . . . . . . . . . . . . Encapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 30 30 30

. . . . . . . . . . 19 . . . . . . . . . . 21

APPENDIX PRODUCT LISTING SUPPLEMENT . . . . . . . . . . 31 METHODS OF ANALYSIS . . . . . . . . . . . . . . . . . 32 PRODUCT SAFETY . . . . . . . . . . . . . . . . . . . . . . 32

Aqualon, 2002.

AQUALON EC A Specialty Polymer

With Broad Stability and Compatibility

Ethylcellulose is a cellulose ether distinguished by its versatility. It is very tough, soluble in a wide range of solvents, and flexible at low temperatures. Ethylcellulose can be formulated into lacquers, varnishes, inks, films, foils, adhesives, and plastics, and for food contact, animal feeds, and pharmaceutical goods.

Ethylcellulose is also characterized by low flammability and resistance to discoloration in sunlight. Ethylcellulose toughens, hardens, and reduces or even eliminates the surface tack of compositions in which it is compatible.

COMPOSITION OF ETHYLCELLULOSE

Ethylcellulose is a cellulose ether made by the reaction of ethyl chloride with alkali cellulose, as expressed by the reaction: RONa + C2H5CI ROC2H5 + NaCI, where R represents the cellulose radical. The structure that is most widely accepted for the cellulose molecule is a chain of anhydroglucose units joined together by acetal linkages. This is indicated in Figure 1a. These long, oxygen-linked anhydroglucose-unit chains have great strength, which is passed on to cellulose derivatives such as nitrocellulose, cellulose acetate, and ethylcellulose. The properties of flexibility and toughness in these derivatives are directly attributable to this long-chain structure. From Figure 1a., it is seen that each anhydroglucose unit has three replaceable OH groups, all or part of which may react as indicated in the reaction cited earlier. Complete substitution of all three groups would give the triethyl ether possessing a substitution value of 3, or 54.88% ethoxyl, which is illustrated in Figure 1b. The completely substituted triethylcellulose has no commercial significance, however, because it lacks strength and flexibility, is not thermoplastic, and shows extremely limited compatibility and solubility. The commercial product, which exhibits the remarkable combination of useful properties cited in the introductory paragraphs, has a substitution value between 2.25 and 2.60 ethoxyl groups per anhydroglucose unit, or 44-52% ethoxyl content.

TYPES
Aqualon ethylcellulose is available in four ethoxyl types. These are listed in Table I, along with their degree of substitution. Each of these ethoxyl types is subdivided into viscosity types, as indicated in Table II. The viscosity designation indicates the nominal viscosity in centipoises for a 5% weight concentration in the Standard Viscosity Solvent. (See footnote (b), Table II.) For example, K100 ethylcellulose would refer to K-type of 45.0-47.2% ethoxyl content, and a viscosity of 100 cps in 5% solution. Thus, ethoxyl and viscosity types can be readily specified as K100, N7, T200, and so forth.

TABLE IETHOXYL TYPES

Ethoxyl Content, % 45.0-47.2 48.0-49.5 49.6-51.5 50.5-52.5 Degree of Substitution of Ethoxyl Groups per Anhydroglucose Unit 2.22-2.41 2.46-2.58 2.58-2.73 2.65-2.81

Type K-type N-type T-type X-type

FIGURE 1 COMPOSITION OF ETHYLCELLULOSE

H HO H OH H

OH H H O O H

CH2OH O H OH H H OH -2 H O H

H OH H

OH H H OH O

CH2OH
Figure 1a. Structural Formula of Cellulose

CH2OH

H HO H OC2H5 H

OC2H5 H H O H

CH2OC2H5 O H OC2H5 H H OC2H5 H O H

H OC2H5 H

OC2H5 H H OH

-2 Figure 1b. Structural Formula of Ethylcellulose With Complete (54.88%) Ethoxyl Substitution
3

O CH2OC2H5

O CH2OC2H5

FDA STATUS
Aqualon K-, N-, and T-types of ethylcellulose(1) are in compliance with requirements of the U.S. Food and Drug Administration for use in food and food-contact applications. These requirements are specified in the Code of Federal Regulations, Title 21, subject to the limitations and requirements of each regulation under the following Sections: 175.105 175.300 175.390 176.170 176.180 Adhesives Resinous and polymeric coatings Zinc-silicon dioxide matrix coatings Components of paper and paperboard in contact with aqueous and fatty foods Components of paper and paperboard in contact with dry food 73.1001

tablet form, gum, and confectionery; inks for marking fruits and vegetables; diluents in color additive mixtures for coloring shell eggs Diluents in color additive mixtures for drug use exempt from certification: ingested drugs; inks for branding pharmaceutical forms; externally applied drugs Ethylcellulosefor use as a binder and filler in dry vitamin preparations, as a component of protective coatings for vitamin and mineral tablets, and as a fixative in flavoring compounds

172.868

177.1210 Closures with sealing gaskets for food containers 182.90 573.420
(1)Except

Ethylcellulose NF types also meet monograph requirements in the National Formulary, current edition, and the United States Food Chemicals Codex for Ethylcellulose. Ethylcellulose is included in the Cosmetic, Toiletry, and Fragrance Associations (CTFA) cosmetic ingredients dictionary. The available types of NF ethylcellulose are:
NF Type N7 N10 N14 N22 N50 N100
(d)Determined

Substances migrating to food from paper and paperboard productsethylcellulose Binder or filler in dry vitamin preparations to be incorporated into animal feed

Viscosity(d) Range, cps 5.6 to 8.0 8.0 to 11 12 to 16 18 to 24 40 to 52 80 to 105

plastic-peel-stabilized N100PP and N50S types.

In addition to the foregoing, the special NF drug grade of N-type ethylcellulose meets other code requirements, allowing it to be used in other food contact and in pharmaceutical applications. These requirements are specified in the Code of Federal Regulations, Title 21, subject to the limitations and requirements of each regulation under the following Sections: 73.1(b) Diluents in color additive mixtures for marking food: inks for marking food supplements in

using 5% ethylcellulose in 80 parts toluene: 20 parts ethanol by weight.

(See section on Food Contact and Pharmaceuticals for additional details.)

TABLE IIETHOXYL AND VISCOSITY TYPES OF AQUALON ETHYLCELLULOSE

Ethoxyl Types ( refers to types now produced)(a) K N T X 45.0-47.2% 48.0-49.5% 49.6-51.5% 50.5-52.5% Ethoxyl Ethoxyl Ethoxyl Ethoxyl (c) Viscosity Types(b) (Viscosity on all types run at 5% concentration by weight and 25C.)

* *

in the table indicate no demand at present for the particular type. However, this does not mean that these types cannot be produced. is determined in 80:20 toluene:ethanol by weight on a sample dried 30 min at 100C. (See ASTM D 914.) (c)Viscosity is 18-35 cps. Note: Ethanol in this booklet refers to specially denatured (S.D.) ethyl alcohol, 2B, 190 proof.
(b)Viscosity

(a)Blanks

* * * * * * * * *

* * * *

Designation, cps 4 7 10 14 22 50 100 200 300

Limits, cps 3.0-5.5 5.6-8.0 8.0-11 12-16 18-24 40-52 80-105 150-250 250-350

OUTSTANDING CHARACTERISTICS
The outstanding physical and chemical properties that distinguish Aqualon ethylcellulose, together with some of its indicated uses, are described briefly in the paragraphs that follow. Color Ethylcellulose is practically colorless, and retains this condition under a wide range of uses. Neither sunlight nor ultraviolet light affects the color. Accurate color control through the use of dyes and pigments is readily attained in protective coatings, plastics, and other compositions where close color control is often important. Compatibility Ethylcellulose is compatible with an unusually wide range of resins and plasticizers, including oils and waxes. This wide range of compatibility makes it easy to develop economical formulations in the great variety of uses to which it is adaptable. Small additions of ethylcellulose to waxes toughen their texture and raise their melting point. In varnishes, its use reduces tackiness and increases drying rate. It is quite useful in printing inks. Plastics with rigid or soft properties can be readily formulated. Density The low density of ethylcellulose makes it possible to get greater coverage and greater volume per unit weight than with the other cellulose derivatives. For example, it has about 45% greater coverage than nitrocellulose and 20% greater coverage than cellulose acetate in coatings and adhesives of similar weight composition. In plastics, film, and foil, the low density of ethylcellulose gives the same corresponding advantages of greater volume for a given weight. Lacquers are generally formulated with N4, N7, and N10 types, where a minimum viscosity is desired for a maximum solids content. Higher viscosities would be used, however, for maximum toughness. Electrical Properties The excellent electrical properties of ethylcellulose, combined with its good thermal stability and outstanding flexibility and toughness, led to its early and continued use in cable lacquers, where conditions requiring these properties are encountered. It also has been used in plastics for electrical insulation for many purposes. Flexibility The great flexibility of ethylcellulose over a wide range of temperatures is one of its most marked characteristics. Its retention of flexibility at very low temperatures is especially notable, for many compositions remain flexible even at 70C. Ethylcellulose also retains a large measure of its initial flexibility, even after long exposure to temperatures approaching its softening point (156C). This flexibility is carried over into many compositions, such as protective coatings, adhesives, foil, and plastics. It is a property that is desirable, for example, in plastics for high

impact resistance at low temperatures, in furniture lacquers for prevention of cold-checking, in fabric coatings for good flexibility and cold-crack resistance at low temperatures, and in hot-melt compositions and plastics for sustained toughening action after compounding. Flammability Ethylcellulose flammability is of as low an order as that of any other cellulosic material. If it is held in an open flame, it will catch fire and burn, but its formulations can be made fire resistant by proper choice of plasticizer and other flameproofing agents. Softening Point The softening point (156C) of ethylcellulose is relatively low and, if desired, can be made even lower by proper adjustment of plasticizers. These factors permit ease of working and application, as in hot-melt application of adhesives, calendar application on cloth, and in injection and extrusion plastics. Solubility Ethylcellulose is soluble in a wide variety of solvents, thus making it easy to formulate this versatile material for any purpose where solvent application is desirable. Among the useful solvents are the esters, aromatic hydrocarbons, alcohols, ketones, and chlorinated solvents. Inexpensive solvent combinations can be used with ethylcellulose. Among the most generally useful combinations are 70-90% aromatic hydrocarbons or synthetic aromatics (dehydrogenated naphthenes and cyclicized hydrocarbons of varied kauri-butanol values, depending on grade and manufacturer) with 30-10% alcohols. Although such combinations are relatively low in cost, they can be made even more economical by the addition of petroleum distillates such as heptane or VM&P naphtha. In some cases, as much as 50% of the total solvent can be replaced with such low-priced mineral spirits. Stability to Chemicals Of all cellulose derivatives, none is more stable to chemicals than ethylcellulose. It is resistant to alkalies, both dilute and concentrated, and to salt solutions. Ethylcellulose is more sensitive to acidic materials than are cellulose esters; however, lacquer coatings satisfactorily withstand the action of dilute acids for limited exposure periods. It is resistant to oxygen under high pressures at room temperature for extended periods of time, and to an ozonized atmosphere for one to two weeks with no detectable trace of degradation. Oxygen at temperatures above the softening point of ethylcellulose has a marked degrading effect unless the compositions are stabilized with antioxidants. Stability to Water The types of ethylcellulose discussed here are not affected by water. It takes up very little water from moist air or during immersion, and that small amount evaporates readily, leaving the ethylcellulose unaltered. Dimensional stability, which is related to water absorption, is unusually good. This property can be especially valuable in many applications of ethylcellulose.

Light Transmission, %

Stability to Light Light, visible or ultraviolet, has no discoloring action on ethylcellulose. Clear films transmit practically all the visible light of the spectrum and varying amounts of ultraviolet light, depending on the stabilizers and plasticizers used in formulation. Figure 2 shows the ultraviolet absorption characteristics of ethylcellulose: (a) the effect of film thickness on absorption, and (b) the effect of certain stabilizers known to reduce the embrittling effect of ultraviolet light on ethylcellulose. (See Stabilization of Ethylcellulose, page 13.) Ethylcellulose, because of its light transmission, together with its flexibility, great toughness, and chemical resistance, is an unusual material when properly used in protective films. Such films can be applied from solution, from hot-melt, by calendering, or by lamination. Stability to Heat Application of heat up to its softening point has little effect on ethylcellulose. At higher temperatures, embrittlement and discoloration may occur unless the ethylcellulose is protected by antioxidants. Acidic materials such as high-acidnumber resins have a degrading effect on ethylcellulose, particularly at elevated temperatures, and thus should not be used in plastics, in adhesives, or in other hot-melt applications of ethylcellulose. When properly formulated and stabilized, ethylcellulose compositions have remarkably good resistance to high temperatures, so plastic compounding, molding operations, and hot-melt compounding and application can be carried out without degrading the ethylcellulose. Similarly, this resistance to heat makes ethylcellulose useful in formulations subject to heat, as in lacquers for electric cable. See page 13 for a discussion of modifiers contributing to the heat stability of ethylcellulose. Taste Ethylcellulose has no taste. It has been used as a coating for paper, film, and foil in contact with food. (See section on Food Contact and Pharmaceuticals.) Plastic uses also are possible in the food-packaging field. Thermoplasticity Ethylcellulose possesses excellent plastic flow characteristics; it is possible to process plastics completely in heated Banbury mixers or on heated two-roll mills without the aid of volatile solvents, thus making compounding more economical. This characteristic is essential for injection, extrusion, lamination, and calendering operations, as well as for hotmelt compounding and application of adhesives, paper coatings, and casting plastics. Toughness The high tensile strength of ethylcellulose is worthy of note. Combined with its excellent flexibility over a wide temperature range, this results in unusual toughness. Toughness, at high and low temperatures, is one of the most useful qualities of ethylcellulose. In this respect, it has marked advantages over synthetic resins. It is superior in this property to other cellulose derivatives. The toughening action that ethylcellulose imparts can be of fundamental importance for protective coatings, plastics, and adhesives. 6

FIGURE 2 ULTRAVIOLET ABSORPTION STUDY OF ETHYLCELLULOSE FILMS

100 80 60 40 20 0 220 Ethylcellulose, 10 mils Thick 260 300 340 380 Ethylcellulose Film, 2 mils Thick

Wavelength, m

a. Effect of ethylcellulose film thickness on light transmission.

100 Light Transmission, % 80 60 40 20 0 220 Ethylcellulose With 1% Ionol Ethylcellulose With 0.5% Each of Ionol and Uvinul 400 Ethylcellulose Film

260

300

340

380

Wavelength, m

b. Examples of how ultraviolet light stabilizers can affect light transmission of ethylcellulose film. All films were 3 mils thick.

PHYSICAL PROPERTIES (EFFECTS OF ETHOXYL CONTENT AND VISCOSITY)

As in the case of the other cellulose derivatives, there are certain properties of ethylcellulose that depend somewhat on the degree of substitution (ethoxyl content). For example, the effect of substitution on softening point, hardness, water absorption, solubility in ethanol, and solubility in 80:20 tolune:ethanol is given in Figure 3. The effect of substitution on solubility in different solvents is discussed at length later. Conversely, there are certain other properties such as tensile strength, elongation, and flexibility that are not greatly affected by the degree of substitution, but depend largely on the degree of polymerization, which can be measured by viscosity. Table III (page 8) presents data on the tensile strength, elongation, and flexibility of various viscosity grades of N-type ethylcellulose. Figure 4 shows these data in graphic form. It will be seen that there is a marked leveling off of the curves (Figure 4) for tensile strength and elongation between N50 and N100 types. This means that very little additional tensile strength or elongation can be gained by using viscosity types higher than about N100. On the other hand, there is no break in the flexibility curve within the range shown to indicate what the ultimate folding endurance of ethylcellulose might be. The softening point of unplasticized ethylcellulose is not greatly affected by the viscosity. Within the substitution range offered, N-type ethylcellulose (48.0-49.5% ethoxyl content) meets most requirements and is usually specified because it exhibits the most generally useful combination of properties. The other types are selected when special requirements must be met. For instance, K-type is usually selected for special uses requiring harder, higher melting compositions having better resistance to certain solvents and oils. K-type should be selected for injection molding because it can be injected without surfacelamination or similar mold defects, and yields plastics of better resistance to distortion under heat. K-type is used where oil- and gasoline-resistance is important. T- and X-types are useful where extreme dilution with straight-chain hydrocarbon solvents is desirable, and where maximum water resistance is important. The physical properties of N-type ethylcellulose are presented in Table IV. A study of these data will show this material to be unusual in many respects.

FIGURE 3 THE EFFECT OF SUBSTITUTION ON PHYSICAL PROPERTIES OF ETHYLCELLULOSE

180 170 160 150 140 42 Softening Point Hardness, Shore

Moisture Absorption at 19C and 70% Relative Humidity

Softening Point, C

Moisture Absorption(e)

4 105 3 100 2 95 1 90 0 85

Range of Ethanol Solubility Range of 80:20 Toluene:Ethanol Solubility

43 44 45 46 47 48 49 50 51 Ethoxyl of Ethylcellulose (50-cps Type), %

(e)

The moisture absorption of ethylcellulose decreases as the ethoxyl content increases over the 43-51% range. Within this same range, softening point and hardness are at a minimum at 48% ethoxyl content. Ethanol dissolves ethylcellulose at 45-49% ethoxyl, while a mixture of 80:20 toluene:ethanol is a solvent for the product over the 43-51% ethoxyl range.

FIGURE 4 TENSILE STRENGTH AND ELONGATION

2,400 11,000 10,000 9,000 8,000 7,000 6,000 5,000 4,000 3,000 2,000 1,000 Elongation at Rupture, % Tensile Strength, lbs/in.2 Tensile Strength 40 30 20 10 Elongation MIT Folds 2,000 1,600 1,200 800 400 Flexibility, MIT Double Folds

4 6 810 20 30 50 100 300 5 79 40 200 Viscosity(f) of N-Type Ethylcellulose (Log Scale), cps

(f)

Viscosity of ethylcellulose has a marked effect on flexibility over the entire range studied. Also, viscosity has a marked effect on tensile strength and elongation up to 50 to 100 cps, at which zone there is a noticeable leveling off in effect.

Shore Hardness, R Scale

190

5 110

TABLE IIIEFFECTS OF VISCOSITY ON PHYSICAL PROPERTIES OF N-TYPE ETHYLCELLULOSE(g)

Viscosity(h) Centipoises in 5% Solution 8 9 13 24 43 94 184
(g)Films (h)Solvent

Intrinsic (), dL/g(i) 0.73 0.79 1.04 1.40 1.70 2.16 2.53

Tensile Strength lbs/in.2 6,800 7,000 7,300 8,100 9,500 10,400 10,500

Elongation at Rupture, % 10 14 19 28 32 35 35

Flexibility, MIT Double Folds 160 200 330 595 1,000 1,480 2,020

0.003 in. thick were cast from solution in 80:20 toluene:ethanol, dried 16 hrs at 70C, conditioned 48 hrs at 70F and 65% relative humidity, and tested. was 80:20 toluene:ethanol. (All solvent values in this book are in terms of wt%.) (i)These intrinsic viscosity values are appropriate. They were obtained by measuring the relative viscosities at several concentrations, calculating the reduced viscosities, and extrapolating to zero concentration, using the Martin equation, log10sp/c=log[] + k []c, where c is concentration in g/dL in a solvent of 80:20 toluene:ethanol.

VISCOSITY-CONCENTRATION RELATIONSHIPS
Typical viscosity-concentration curves for N-type ethylcellulose are shown in Figure 5 (page 10). These curves should prove useful in the control of the viscosity of solutions since they show the viscosity concentration for the different viscosity types of N-type ethylcellulose. From this chart, one observes how the viscosity of the solution of a given type varies when the concentration of ethylcellulose is changed. It also shows how the viscosity of a given solution changes if a different viscosity type of ethylcellulose is substituted in the same concentration. This same viscosity-concentration relationship holds for other ethoxyl types of ethylcellulose. A comparison of the viscosity-concentration relationships for the low-viscosity lacquer types of N-type ethylcellulose and nitrocellulose is given in Figure 6 (page 11).

Blends can be calculated directly from this equation. However, it is more convenient to use the blending chart (Figure 7, page 12). With this chart, it is possible to determine, without calculation, the percentage of any two ethylcelluloses of different viscosities that must be blended to secure a desired intermediate viscosity. Likewise, it is possible to determine the viscosity that will result from making any blend. This chart is set up on semilogarithmic plotting paper marked off so that the divisions on the horizontal axis represent percentages from 0 to 100, while the divisions on the vertical axis represent viscosity in centipoises from 2 to 500 for standard 5% solutions of ethylcellulose as indicated in Table II (page 4). The position of each of the standard viscosity grades is shown on the chart. How to Use the Blending Chart The exact procedure can be described most easily by the use of specific examples. Suppose you wish to obtain an ethylcellulose having a viscosity of 150 cps in a 5% solution, and the materials available consist of Type 100 (80 to 105 cps with an exact viscosity of 99 cps in 5% solution) and Type 200 (150 to 250 cps with an exact viscosity of 200 cps in 5% solution). The diagonal line (corresponding to a straightedge) connects Type 100 at the 99-cp point, on the left side of the chart (V1), with Type 200, on the right (V2). The diagonal intersects the horizontal line corresponding to 150 cps at the vertical line marked 60%, point A. This means that 60% of Type 200 and 40% of Type 100 should be mixed to obtain 150-cps ethylcellulose. Similarly, other blends can be obtained. It is not necessary to draw lines; merely use a straightedge and read directly. Remember that the percentage read from the diagonal refers to the ethylcellulose type indicated on the right-hand axis (V2).

BLENDING
On occasions when the stock of a certain viscosity type of ethylcellulose is not on hand, or a use may be developed for an ethylcellulose of a viscosity differing from any standard type, it is useful to know that different viscosity types can be blended to produce a product of the desired viscosity. The principle of blending is based on the Arrhenius equation, which relates viscosity and concentration. It can be conveniently expressed as follows: Log Vs = n log V1 + (100 n)log V2 100

where Vs = viscosity sought n = % of first component of blend having a viscosity V1 V2 = viscosity of second component of blend All viscosities must be expressed in the same unit.

The chart also can be used to calculate the viscosity that will result by blending predetermined weights of two viscosity types. Suppose that equal weights of the same Type 100 and the same Type 200, used to illustrate the first example, were mixed. What would be the viscosity of the resulting blend? The vertical 50% line intersects the diagonal at point B on the horizontal viscosity line, designating 140 cps.

Limitations of Blending Certain cautions to be observed in blending should be pointed out. First, the two viscosity types selected for the blend should be as close together as possible. If widely separated viscosity types are blended, there is danger that the resulting blend may yield a lumpy or granular solution. Second, different substitution types should not be blended, because lumpy, granular or even incompatible solutions can result.

TABLE IVPHYSICAL PROPERTIES(j) OF N-TYPE ETHYLCELLULOSE

Bulking density, lbs/gal, in granular form Bulking value, gal/lb, in solution Color, Hazen, in solution, ASTM D 365 Discoloration by sunlight Electrical properties Dielectric constant at 25C, 1 Mc Dielectric constant at 25C, 1 kc Dielectric constant at 25C, 60 cyc Dielectric strength, V/mil, 10-mil film, ASTM D 149-64, step by step Power factor at 25C, 1 kc Power factor at 25C, 60 cyc Volume resistivity, ohm/cm Elongation at rupture, %, 3-mil film, conditioned at 77F and 50% RH Flexibility, folding endurance, MIT double folds, 3-mil film Hardness index, Sward, 3-mil film Light transmission, practically complete, nm Light transmission, better than 50% complete, nm Moisture absorption, by film in 24 hrs at 80% RH, % Odor, flake Refractive index, cast film Softening point, C Specific gravity Specific volume, in.3/lb in solution Taste Tensile strength, lbs/in.2, 3-mil film, dry Tensile strength, wet (% of dry strength) Water vapor transmission, g/m2/24 hrs, 3-mil film, ASTM E 96. Procedure E
(j)Values

2.6-2.8 0.099-0.104 2-5 Very slight 2.8-3.9 3.0-4.1 2.5-4.0 1,500 0.002-0.02 0.005-0.02 1012-1014 7-30 160-2,000 52-61 310-400 280-310 2 Slight 1.47 152-162 1.14 23.9 None 6,800-10,500 80-85 890

shown are not routinely determined and are not to be construed as sales specifications.

FIGURE 5 VISCOSITY-CONCENTRATION CURVES (WT%) FOR AQUALON N-TYPE ETHYLCELLULOSE (DISSOLVED IN 80:20 TOLUENE:ETHANOL AND MEASURED AT 25 0.1C)
1,000,000 500,000

N200

100,000 N100 50,000 N50

10,000 N22 5,000 N14 N10 Viscosity, cps

1,000 500

N7

100 50

10 5 4 3 2 1

10

12

14

16

18

20

22

24

26

28

Concentration of Ethylcellulose by Weight

10

FIGURE 6 VISCOSITY-CONCENTRATION COMPARISONS FOR AQUALON ETHYLCELLULOSE AND HERCULES RS NITROCELLULOSE (MEASURED AT 25C)
5,000 4,000 3,000 2,000 RS nitrocellulose, 1/2-sec 1,000 RS nitrocellulose, 1/4-sec

500

N7 ethylcellulose

N22 ethylcellulose 100 Viscosity, cps

50

10

5 4 3 2

.5 0 5 10 15 20 25 30 35

Concentration, wt%
Solvents: For ethylcellulose, 4:1 toluene:ethanol. For nitrocellulose, 3:1 butyl acetate:ethanol.

11

FIGURE 7 ETHYLCELLULOSE BLENDING CHART(k)

0 500 400 300 250 200 150

10

20

30

40

50

60

70

80

90

100 500 400

Viscosity Type 300

300 250 200 150

Viscosity Type 200 A

100 80 70 60 50 40 30 20 15 10 8 7 6 5 4 3 2 0 10 20 30

Viscosity Type 100

100 80 70 60 50 40 30

Viscosity of V1, cps

Viscosity Type 50

Viscosity Type 22

20 15 10 8 7 6 5 4 3 2 100

Viscosity Type 14 Viscosity Type 10 Viscosity Type 7

Viscosity Type 4

40

50

60

70

80

90

Ethylcellulose V2 in Blend, %

(k)Based

on 5% solutions of N-type in standard 80:20 toluene:ethanol mixed solvent, with viscosities run at 25 0.1C. (V1 and V2 represent the low- and highviscosity types, respectively, to be blended.)

12

Viscosity of V2, cps

FORMULATION

STABILIZATION OF ETHYLCELLULOSE
Ethylcellulose formulations, if not stabilized, are subject to oxidative degradation in the presence of sunlight or ultraviolet light and at elevated temperatures, especially above the softening point of ethylcellulose (156C). Ethylcellulose thus oxidized becomes brittle, and the surface can become badly crazed. Discoloration generally occurs during prolonged exposure at excessive temperatures. Investigation has shown that the harmful effects of oxidation can be inhibited for extended periods of time by the use of antioxidants and by the proper selection of resins, plasticizers, and other modifiers. The use of antioxidants is the most effective and generally the easiest method of inhibiting oxidative degradation. Ethylcellulose compositions that are subjected to high temperatures during compounding or subsequent use and that may be exposed to ultraviolet light or sunlight should always contain an antioxidant. Acid acceptors should be added to ethylcellulose formulations containing components such as chlorinated resins and plasticizers, which form acidic degradation products. Epoxy types are especially useful because of their excellent capacity to absorb free acids. Stabilizers of these types should always be incorporated when ethylcellulose is used in hot-melts, in plastics, and in clear-film applications. Additional studies show that compounds that absorb light waves in the range of 230 to 340 nm are effective stabilizers against light-catalyzed oxidation. A typical ultraviolet light absorber of this type is 2,4-dihydroxybenzophenone (Uvinul 400). Usually, the addition of one part of antioxidant or a blend with equal parts of a light absorber or epoxy stabilizer for each 100 parts of ethylcellulose is sufficient to obtain longterm ethylcellulose stability. Larger quantities of stabilizer result in very small increased benefits, and as little as 0.25 part will give marked improvement over unstabilized ethylcellulose compositions. Stabilization studies in Aqualon laboratories have shown that stabilizer activity is often dependent on the type of ethylcellulose composition. Some specific examples: Hot-Melts Diamyl phenol, 2,6-di-tert-butyl-para-cresol (BHT), and octyl phenol are suitable antioxidants for a satisfactory compromise between color and viscosity retention. Diethyl oxalate and dibutyl tartrate give good results in hot-melts when used primarily as color stabilizers during formulation and application. An acid acceptor should be used with the antioxidant to absorb acidic degradation products caused by the high processing temperature of the melt. Plastics Stabilizers effective in hot-melts, such as diamyl and octyl phenols, are also useful in plastics. Diamyl phenol demonstrates excellent stabilizing action in a heated ethylcellulose disk test with respect to color and embrittlement.

Clear Films Outdoor exposures of clear ethylcellulose films show that a combination of antioxidant, light absorber, and acid acceptor is more effective than a single stabilizer. As antioxidants, Pentaphen 67 (para-tert-amylphenol), BHT (2,6-di-tert-butylpara-cresol), and Antioxidant 2246 [2,3-methylene bis (4methyl-6-tert-butyl) phenol] are effective. An example of a light absorber is 2,4-dihydroxybenzophenone. Useful acid acceptors are epoxy compounds used either as plasticizers or solely as stabilizers. Some of the substituted phenols, such as diamyl phenol, are plasticizers as well as stabilizers, and can be used either alone or as a component of a mixed plasticizer. Likewise, some materials ordinarily considered as plasticizers have a stabilizing effect. Some single or mixed plasticizers that have been found to contribute stability to ethylcellulose compositions during outdoor exposure are listed in the order of their effectiveness: 1. 2. 3. 4. 5. 6. Tricresyl phosphate with diamyl phenol, 70:30. Tricresyl phosphate with triphenyl phosphate, 70:30. Tricresyl phosphate with diphenyl phosphate, 70:30. Diamyl phenol. Diphenyl phosphate. Phenyl diglycol carbonate.

Most pigments protect ethylcellulose against degradation during outdoor exposure. In pigmented systems where added stability is desired, antioxidants are more effective than ultraviolet light absorbers, because light is excluded by the pigment.

SOLVENTS AND SOLUBILITY

Solubility Parameters Solubility parameters provide a convenient method for determining the best solvent or solvent system for a film-former such as ethylcellulose. The solubility parameter of a polymer can be established indirectly from the solubility parameter of solvents that dissolve the polymer. Data on the solubility parameters of Aqualon ethylcellulose, for three classes of solvents, are given in Table V. Additional information can be found in CSL204, Solubility Parameter Maps of Aqualon Film-Formers. Effects of Ethoxyl Content The solubility of Aqualon ethylcellulose in organic solvents merits careful consideration in its extensive application in lacquers and coating compositions. The effect of substitution on solubility is illustrated by the data given in Table VI. It will be seen from this data that there are relatively few single solvents for the lower substitution types. Solubility in all classes of organic solvents improves with increased ethoxyl content until an optimum level is reached within the range of substitution of the N-, T-, and X-types. Above this level of substitution, solubility again becomes more restricted, being limited in the highest levels of substitution to highly nonpolar compounds such as the aromatic hydrocarbons.

13

Solvents for N-Type It was pointed out that the variety of solvents for N-type ethylcellulose is unusually wide. The solubility of this type in organic solvents is indicated in Table VII (page 17). It will be seen that the aliphatic or straight-chain hydrocarbon class is the only one having essentially no solvent power to dissolve N-type ethylcellulose. This wide range of solvents greatly simplifies the task of selecting solvents for specific applications. A comparison of the solubility of ethylcellulose, N22 type, with RS nitrocellulose, 1/2-sec, is given in Table VIII (page 18). Effects of Alcohols Although there are special uses that may require single solvents, for general use, they are inadvisable. Almost all ketone, ester, and hydrocarbon solvents for ethylcellulose can be greatly improved by mixing them with relatively small quantities of the lower aliphatic alcohols such as ethanol or butanol. Such binary mixtures are much better solvents for ethylcellulose than is either component alone, and they have several advantages. These binary solvents will completely dissolve a much wider range of substitution types of ethylcellulose than will single solvents. For example, toluene alone is a good solvent only for the range of substitution covered by the T-type. However, N-type, although soluble, does not always form a good solution in toluene alone, as evidenced by the fact that it is difficult to duplicate the viscosity in successive solutions of the same concentration, indicating incipient gel formation. Low degree of substitution types are poorly soluble in toluene alone. But a solvent combination of 80:20 toluene:ethanol will completely dissolve all substitutions from 43.4% to 50%. In general, the quantity of alcohol required with the esters, ketones, and hydrocarbons to make good binary solvents increases as the degree of substitution becomes lower. For example, 90:10 toluene:ethanol is a good solvent for the N-type, but to obtain comparable results with the K-type and its ethoxyl content of 46.1%, one would need a ratio of 70:30 toluene:ethanol. The alcohols are especially valuable in improving the solvent power of the so-called toluene substitutesproprietary products derived in many cases by catalytic dehydrogenation of naphthenes and cyclicized hydrocarbons. They are characterized by having kauri-butanol values between 40 and 70, and alone show considerably poorer solvency for ethylcellulose than do the aromatic hydrocarbons such as toluene and xylene. However, the toluene substitutes become excellent solvents for all substitution types of ethylcellulose when they are mixed in a ratio of 70:30 toluene substitute:ethanol. Some are better solvents than others; in general, the higher the kauri-butanol value, the less ethanol is required to obtain good solvency. Butanol is somewhat less effective than ethanol in these binary mixtures, which is reflected by the fact that viscosities at a given concentration are higher.

14

TABLE VSOLUBILITY PARAMETERS

Class I (Weakly Hydrogen-Bonded) Range Aqualon K100 ethylcellulose Aqualon N22 ethylcellulose Aqualon T10 ethylcellulose Midpoint Class II Class III (Moderately Hydrogen-Bonded) (Strongly Hydrogen-Bonded) Range 8.5-10.8 9.6 9.0 7.4-11.0 7.8-9.8 Midpoint 9.6 9.2 8.8 Range 9.5-11.4 9.5-14.5 9.5-11.4 Midpoint 10.4 12.0 10.4

Insoluble 8.1-11.1 8.5-9.5

TABLE VISOLUBILITY OF ETHYLCELLULOSE (EFFECTS OF ETHOXYL SUBSTITUTION(1))

Relative Solubility Solvent Used Toulene Xylene 80:20 Toluene:Alcohol Ethyl acetate Butyl acetate Acetone Methanol Ethanol Butanol Isopropanol (91% by volume) Ethylene glycol monobutyl ether Ethylene dichloride Carbon tetrachloride Methylene chloride
(1)Each

K-Type gs gi cs vhs gs i vhs hs i hs gs hs g cs

N-Type cs cs cs vhs vhs vhs hs hs hs hs cs cs cs

T-Type cs cs cs vhs vhs vhs i hs hs hs i cs cs cs

X-Type cs cs cs vhs vhs vhs i hs hs hs i cs cs cs

Key: c = clear; g = gelled mass; h = hazy; i = insoluble, although some particles might be gelled; s = solution; v = very. test was made at 15% concentration, by weight, of ethylcellulose in the solvent.

Marked reduction in solution viscosity is another advantage to be gained by using a binary solvent mixture in which one of the lower aliphatic alcohols is a constituent of the solvent mixture. This is brought out clearly by the curves in Figure 8. An evident advantage to be derived from use of a mixed solvent is the possibility of obtaining more concentrated solutions without encountering objectionable gelation or granulation. Control of viscosity in such binary solvents is much easier because the solutions are less sensitive to small changes in concentration or temperature. Other advantages to be gained by using binary solvents containing an alcohol are improved clarity of solution, freedom from the granulation or gelation encountered when poor or lean solvents are used, and improved tolerance for petroleum thinners. Dilution With Petroleum Thinners The tolerance of ethylcellulose solutions for dilution with nonsolvent petroleum thinners is unusually good; it becomes

progressively better with increased ethoxyl content. Such dilution, however, is affected not only by the potency of the active solvent being diluted but also by the degree of substitution of the ethylcellulose. A poor or lean solvent will obviously tolerate less dilution than a rich or active solvent. Table IX (page 18) shows the effect of substitution on dilution with VM&P naphtha of the 70:10 toluene:ethanol solvent mixture. Rule 422Exempt Solvents Since N-type and T-type ethylcellulose have a high tolerance for alcohols and aliphatic hydrocarbons, the formulation of exempt lacquers and inks generally presents no serious problems. Suggested approaches can be found in CSL-204, Solubility Parameter Maps for Aqualon Film-Formers. Suggested acceptable solvent blends can be found in CSL-173.

15

Economy Through Solvent Choice Many ethylcellulose solvent mixtures are relatively inexpensivefor example, mixtures of aromatic hydrocarbons with ethanol and mixtures of the toluene substitutes with ethanol. These mixtures can be made even more economical by dilution with heptane, VM&P naphtha, or some other petroleum thinner, using the appropriate boiling range. The degree to which such dilution can be practiced with true economy will vary with the concentration of the solution to be diluted. The viscosity data in Figure 9 illustrate graphically the effects of solvent composition. Curve 2 in Figure 9 shows that substituting heptane for 33.3% of the toluene in Formula 1 solvent is real economy because there has been no appreciable change in viscosity, and solvent cost is appreciably lower. On the other hand, substitution of heptane for 50% of the alcohol present in Formula 1 solvent (Curve 3, Figure 9) or for 50% of the alcohol plus 33.3% of the toluene in Formula 1 solvent (Curve 4, Figure 9), or for 66.7% of the toluene (Curve 5, Figure 9) results in a marked increase in the viscosity with a necessary lower solids content at any viscosity level, and without a probably sufficient compensating saving in cost over the Formula 2 solvent (Curve 2, Figure 9) to represent any real economy. It can be stated, therefore, that dilution with a petroleum thinner can be practiced with real economy by substituting it for a limited quantity of the aromatic hydrocarbon, but not for the alcohol, in a binary solvent.

FIGURE 9 EFFECTS OF SOLVENT COMPOSITION(m)

10,000 5

4 Viscosity (Stormer Viscometer) at 25C, poises 1,000 3 2 1

100

10 Solvent Formulas 1. 60:40 Toluene:Ethanol 2. 40:40:20 Toluene:Ethanol:Heptane 3. 60:20:20 Toluene:Ethanol:Heptane 4. 40:20:40 Toluene:Ethanol:Heptane 5. 20:40:40 Toluene:Ethanol:Heptane 1 20

FIGURE 8 ALCOHOL-TOLUENE VISCOSITY CURVES (5 G OF ETHYLCELLULOSE N-22 IN 95 G SOLVENT)

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 100 Viscosity on Horizontal Viscometer, sec

30 40 Aqualon N-7 Ethylcellulose, wt%

tert-Butyl alcohol-toluene

(m)In

solvent formulas for ethylcellulose coating compositions, part of the toluene (up to 3313%, but not as much as 6623%) can be replaced by heptane without causing any appreciable increase in viscosity; similar replacement of the alcohol by heptane causes a much greater viscosity increase (Curves 1, 4, and 5).

Methanol-toluene

80

60

40 30 Toluene, %

20

10

When ethylcellulose is dissolved in a binary solvent system composed of one of the lower alcohols in the proper amount and an aromatic hydrocarbon, viscosity of the solution is greatly lowered, allowing better viscosity control and the use of more concentrated solutions.

16

TABLE VIISOLUBILITY OF N-TYPE ETHYLCELLULOSE IN REPRESENTATIVE ORGANIC SOLVENTS (15 G ETHYLCELLULOSE IN 85 ML SOLVENT)
Solvents Alcohols Methanol Ethanol Propanol Isopropanol Butanol Amyl alcohol Cyclohexanol Benzyl alcohol Diacetone alcohol Chlorinated Hydrocarbons Methylene chloride Chloroform Carbon tetrachloride Ethylene dichloride Trichloroethylene Pentachloroethane Esters Methyl acetate Ethyl acetate Propyl acetate Isopropyl acetate Butyl acetate Amyl acetate Methyl Cellosolve acetate Cellosolve acetate Glycol diacetate Benzyl acetate Cyclohexyl acetate Methyl formate Ethyl formate Ethyl lactate Butyl lactate Ethers Ethyl ether Methyl Cellosolve Cellosolve Butyl Cellosolve Carbitol Solubility s s s sw s s ps s sw s s s s ps s s s s s s s s s ps s ps s s s s s ps s s sw Solvents Hydrocarbons Toluene Xylene Hi-Flash naphtha Cyclohexane Tetralin Dipentene No. 122 Turpentine Aromatic petroleum distillates dehydrogenated naphthenes and cyclicized hydrocarbons Petroleum ether Hexane VM&P naphtha Varsol Ketones Acetone Methyl ethyl ketone Dipropyl ketone Hexone Cyclohexanone Methyl cyclohexanone Miscellaneous Solvents Dichloroethyl ether Dioxane Pine oil Mixed Solvents 80:20 Toluene:ethanol(n) 80:20 Xylene-butanol(n) 6623:3313 Ether:ethanol 15:1 Ethanol:camphor 70:30 Turpentine:butanol 70:30 Dipentene No. 122 to butanol 70:30 Aromatic petroleum distillates (dehydrogenated naphthenes and cyclicized hydrocarbons:butanol) Nitroparaffins 1-Nitropropane 2-Nitropropane Nitroethane Nitromethane Solubility s s ps ps s ps sw ps i i i i s s ps s s s ps s s s s s s s s s s s ps i

Key: i = insoluble; ps = partly soluble, but contains gel and granulation; s = soluble (films obtained from these solutions were clear, although some might appear slightly hazy to others); sw = swollen, but granules not merged into cohesive gel.
(n)These

solvent mixtures are the most generally useful because they combine good clarity with low viscosity and are economical.

17

TABLE VIIISOLUBILITY OF AQUALON N22 ETHYLCELLULOSECOMPARISON WITH RS NITROCELLULOSE, 1/2-SEC

N22 RS Nitrocellulose, Solvents Ethylcellulose 1/2-sec Methanol s s Ethanol s i Butanol s i Cyclohexanol ps i Diacetone alcohol sw s Methylene chloride s i Ethylene dichloride s i Chloroform s i Carbon tetrachloride s i Pentachloroethane s i Methyl acetate s s Ethyl acetate s s Butyl acetate s s Ethyl lactate s s Butyl lactate s s Methyl Cellosolve acetate s s Cellosolve acetate s s N22 RS Nitrocellulose, Solvents Ethylcellulose 1/2-sec Ethyl ether s tr Dioxane s s Methyl Cellosolve s s Cellosolve s s Toluene s i Xylene s i Dipentene No. 122 ps i Turpentine sw i Hexane i i VM&P naphtha i i Acetone s s Methyl ethyl ketone s s Cyclohexanone s s 1:15 Camphor:ethanol s s 2:1 Ethyl ether:ethanol s s 80:20 Toluene:ethanol s i 70:30 Xylene:ethanol s i 90:10 Methylene chloride:ethanol s i 90:10 Ethylene dichloride:ethanol s i

Key: i = insoluble; ps = partly soluble, but contains gel and granulation; s = soluble; sw = swollen, but granules not merged into cohesive gel; tr = particles become translucent, but not swollen.

TABLE IXTOLERANCE OF LOW-VISCOSITY ETHYLCELLULOSE FOR PETROLEUM THINNERS (EFFECT OF ETHOXYL SUBSTITUTION)

Solubility Solvent Toluene:ethanol: VM&P naphtha 7:3:90 14:6:80 21:9:70 28:12:60 49:21:30 63:27:10 N-Type T-Type X-Type

swollen swollen sl. hazy sl. hazy v. sl. hazy clear

swollen v. sl. hazy v. sl. hazy v. sl. hazy clear clear

swollen partly soluble v. sl. hazy v. sl. hazy clear clear

18

Figure 10 shows that raising the temperature of application greatly reduces viscosity, thus allowing correspondingly increased solids concentration at any given viscosity level. There are many applications where this principle can be practiced with real economy. Effects of Solvent Composition on Film Properties The physical properties of ethylcellulose films depend somewhat on the composition of the solvent from which they are deposited. Care must be exercised, therefore, in proper selection of solvents to ensure the preparation of strong, flexible films. In general, flexible films of maximum tensile strength are obtained when nonpolar solvents such as toluene or xylene (which have no affinity for water) or butyl acetate or methyl isobutyl ketone (which have little affinity for water) constitute a major portion of the solvent at the moment the film sets to a gel. Brittle films with relatively poorer tensile strength usually result when polar solvents such as acetone or alcohol, which are miscible with water in all proportions, are present in major amounts at the moment of gelation.

FIGURE 10 TEMPERATURE AND VISCOSITY(o)

10,000

Solvent 60:40 Toluene:Ethanol

Viscosity (Stormer Viscometer) at 25C, poises

1,000

35C 25C

10

50C

1 20

30 Aqualon N7 Ethylcellulose, wt%

40

(o)The

viscosity of an ethylcellulose solution is lowered by an increase in its temperature. This allows the application, at the higher temperature, of a more concentrated solution at a given viscosity.

19

FIGURE 11 EFFECT OF SOLVENT SYSTEM ON FLEXIBILITY AND STRENGTH OF ETHYLCELLULOSE FILM

0 1,000 20 Butanol 40 60 80 20 Ethanol 40 60 80 20 Ethanol 40 60 80 100 1,000

800 MIT Folding Endurance

800 MIT Folding Endurance Tensile Strength

600

600

400

400

200

200

0 100

0 80 60 40 20 80 60 40 20 80 60 40 20 0 Xylene Butanol 40 60 Toluene Ethanol 40 60 Acetone Ethanol 40 60

20

80

20

80

20

80

100

8,000 Tensile Strength 7,000 6,000 5,000 4,000 100

8,000 7,000 6,000 5,000 4,000 80 60 40 20 80 60 40 20 80 60 40 20 Xylene Toluene Acetone

The charts illustrate how the flexibility and tensile strength of ethylcellulose film can be affected by the composition of the solvent system from which the film is cast. Best films are generally obtained when the major part of the solvent is nonpolar at the moment the film sets to a gel.

Figure 11 illustrates the effects on tensile strength and flexibility when highly nonpolar solvents are used. It is clearly evident from these graphs that a suitable solvent mixture should contain not more than about 30-40% of a low-boiling, water-miscible solvent such as ethanol or acetone. The remainder should consist of solvents such as xylene, toluene, toluene substitute, butyl acetate, or butanol. Water in relatively small amounts in a solvent mixture is known to have a pronounced effect on the physical properties of films. This water either may be present in the solvent initially or may be introduced into the film solution by condensation brought about by the rapid rate of cooling during the drying period.

The foregoing discussion has been based on the supposition that most applications are carried out under ordinary atmospheric conditions where no control of relative humidity is exercised. It should be pointed out that strong, flexible films can be obtained from any good solvent mixture, even though they are composed wholly of water-miscible solvents, provided care is taken to use anhydrous solvents and to control the moisture content of the air and the rate of evaporation. This requires special drying rooms or cabinets equipped with air-conditioning apparatus.

20

TABLE XGASOLINE RESISTANCE OF ETHYLCELLULOSE FILMS

Condition of Film(p) After 72-hr Immersion in Test Solvent Slight curl Softened Gelled and partly dissolved Badly curled Soft, curl Soft, curl, exudation

Types of Ethylcellulose 1. K100 (46.1-47.2% ethoxyl) 2. N100 (48.0-49.5% ethoxyl) 3. T100 (49.6-51.5% ethoxyl) 4. K100 5. K100 6. K100
(p)Film:

Plasticizer None None None Paraplex RG-2 Bakers Pale No. 16 castor oil Dimethoxyethyl phthalate

60 parts ethylcellulose to 40 parts plasticizer; tests were made in a solvent composed of 60 parts 100-octane gasoline, 5 parts benzene, 15 parts xylene, and 20 parts toluene.

Gasoline Resistance There are special uses for ethylcellulose compositions where wide solubility in solvents and great tolerance for diluents are not advantageous properties. One such use is in coatings for automotive and aviation ignition cables, where gasoline resistance is an important requisite. Aviation engines, in particular, are frequently washed with high-test gasoline containing an appreciable amount of aromatic hydrocarbons. Reference to Table X shows that resistant compositions for this use can be prepared best by resorting to the use of the lower-substitution K-type ethylcellulose (which shows the lowest solubility in aromatic hydrocarbons and tolerates the least dilution with petroleum thinners) and compounding it with gasoline-resistant plasticizers. Many situations arise where special conditions must be met. Shown here is one such situation (the need for gasoline resistance), which was handled by making use of the special properties peculiar to one type of ethylcellulose. Other situations calling for special properties can also be facilitated by becoming familiar with the properties of ethylcellulose discussed in this booklet.

Effects of Ethoxyl Content It is seen from Table XI that N-type ethylcellulose, with a substitution of 48.0-49.5% ethoxyl content, is compatible with more classes of resins than is any other substitution range. Compatibility becomes more restricted with both lower and higher substitution types. These data show that Aqualon ethylcellulose of all substitution types is compatible with rosin (which is made up largely of isomeric resin acids) and Paraplex RG-2. It is further apparent that there are compatible resin types for all ethylcellulose types, from K through X, thus simplifying the task of the formulator. Compatibility With N-Type Ethylcellulose Since N-type ethylcellulose is more generally used than are other types, compatibility data with a majority of the available lacquer resins have been obtained with this type. Table XII A. (page 23) lists resins that have been found to give clear films with this type in all proportions, up to and including 1:1 resin:ethylcellulose. Some partially compatible resins produce clear films with ethylcellulose in proportions up to and including 0.3-0.5:1 resin:ethylcellulose. In higher proportions of resin, incompatibility develops. Table XII B. (page 23) lists resins with such limited compatibility. In Table XII C. (page 23) are listed resins that failed to give clear films with ethylcellulose in any proportion tested. Table XII data show that N-type ethylcellulose is generally compatible with resin acids and the glycerol, glycol, and diethylene glycol esters of resin acids; with varnish-type pure phenolics of both the oil-soluble and oil-reactive classes; with rosin-modified phenolics; with many natural resins, several of which were compatible only after heat treatment or other special treatment such as dewaxing; and with toluenesulfonamide-formaldehyde resins.

RESINS
Resins are used as modifying agents in ethylcellulose compositions for many applications. In coating compositions, they impart hardness, gloss, adhesion, and improved water resistance. In plastics, they impart hardness, improved water resistance, and, in some cases, better dimensional stability. Conversely, ethylcellulose diminishes tack and imparts toughness to resins. Such beneficial effects, however, are obtained only when the resin is compatible with the ethylcellulose.

21

N-type ethylcellulose shows restricted compatibility with maleic-modified rosin esters; urea-formaldehyde resins; coumarone-indene resins; alkyds modified with phenolics, rosin, or oils; cycloparaffins; and zinc resinates. This restricted compatibility is usually controlled by the degree of resin modification. For instance, compatibility becomes more restricted as the percentage of maleate is increased, as the melting point of the coumarone-indene resins increases, and with increased zinc content in the zinc resinate. Compatibility with modified alkyds becomes less restricted with increased oil or fatty acid modification, or with increased phenolic or rosin modification. N-type ethylcellulose is incompatible in all proportions with all pure alkyds based on glycerol phthalate, and short oil modifications of such alkyds, acrylates and methacrylates, polystyrene, polyisobutylenes, and vinyl acetate resins. With some specific resins of borderline compatibility, there may be inconsistencies in compatibility data, depending on minor variations in the resin from lot to lot or other factors not strictly controlled. Consequently, it is possible that other investigators may find discrepancies between their results and those reported here. However, the table gives an accurate idea of the kinds of resins that are compatible or incompatible with ethylcellulose. Note that many resins normally incompatible with ethylcellulose alone can be usefully incorporated into compositions containing ethylcellulose by employing a mutually compatible third ingredient to prevent separation, with its resultant dullness or haze. Solvent plasticizers often serve in this capacity. Cellulose nitrate is also effective.

Compatibility With K-Type Ethylcellulose K-type ethylcellulose is used in both plastics and protective coatings because of such special properties as its higher melting point, special molding characteristics, and restricted solubility and compatibility. It is interesting, therefore, to consider the resins that can be used to modify this type of ethylcellulose. Table XIII (page 24) gives a list of resins that are compatible in all proportions, up to and including 1:1 resin:K-type ethylcellulose. Many urea-formaldehyde and melamine resins show a restricted compatibility with K-type ethylcellulose, but are of interest within their limited sphere of compatibility because they are colorless resins and because they possess thermosetting characteristics. The list of resins in Table XIII is incomplete because many of the resins listed in Table XII are compatible in ethylcellulose, K-type as well as N-type.

PLASTICIZERS
Ethylcellulose alone yields very tough films of excellent tensile strength, flexibility, and elongation characteristics; yet such films lack suppleness. Also, ethylcellulose alone softens and flows at too high a temperature to be practical in molding operations or in other applications requiring good thermoplasticity. Therefore, plasticizing or softening agents are added to ethylcellulose to obtain the proper degree of suppleness, to lower the softening point, and to improve thermoplasticity.

TABLE XIETHYLCELLULOSE-RESIN COMPATIBILITYEFFECTS OF ETHOXYL SUBSTITUTION

Compatibility Data for Different Types of Ethylcellulose Resin(q) Ester gum 80 Wood rosin Dewaxed dammar Aroplaz 1351 Paraplex RG-2
Key: c = compatible; i = incompatible.
(q)Each

K-Type i c c c c

N-Type c c c c c

T-Type c c c i i

X-Type c c c i i

resin listed is representative of a general class. Ratio: 1:1 ethylcellulose:resin.

22

TABLE XIICOMPATIBILITY OF RESINS WITH N-TYPE ETHYLCELLULOSE

A. Resins Compatible In All Proportions Up to 1:1 Resin:Ethylcellulose Natural Batu, run Congo, run Dammar, dewaxed Batavia Elemi Kauri Manila gum, all grades Mastic gum Pontianak, run, mixed bold Rosin, wood Sandarac Shellac, dewaxed Vinsol Alkyd Aroplaz 1271 Paraplex RG-2, RG-8 Coumarone-Indene Cumar P10, R28 Phenolic Resins Super-Beckacite 1001 B. Resins Compatible In All Proportions Up to 0.3-0.5:1 Resin:Ethylcellulose Natural White shellac Coumarone-Indene Cumar R-3, R-11
(r)

Rosin- and Terpene-Base Abalyn Abitol E Cellolyn 21, 102M Ester gum 8D Hercolyn D Lewisol 28 Pentalyn A, H, 830, 856 Pentrex 28 Poly-pale 10 ester Poly-pale resin Staybelite Staybelite 3, 10 ester Vinsol ester gum Zinar Zirex Zitro Miscellaneous Orlon Piccolastic A-5

Rosin- and Terpene-Base Uni-Rez 7200 Miscellaneous Chlorowax 70(r)

This resin is compatible at 1:10 resin:ethylcellulose.

C. Resins Incompatible Even at Ratios as Low as 1:10 Resin:Ethylcellulose Natural Accroides Congo Ester No. 10 East India Macassar, pale East India Singapore, pale Orange shellac Alkyd Beckosol 12-021 Paraplex G-20 Rosin Base Uni-Rez 7200 Metalyn Pentalyn G, K Urea- and Melamine-Formaldehyde Beckamine 21-510 Resimene Uformite MM-55 Miscellaneous Acryloid C10LV, F10, B72 Dow Corning Fluid 200 Epon 1004 Keltrol Vinylite VAGH

23

The variety of plasticizing agents for ethylcellulose is unusually large, and includes, with two exceptions, all classes of compounds that have been offered as softening or flexibilizing agents for coatings or plastics. The two exceptions comprise the heat-bodied vegetable oils and the highly unsaturated drying oils such as tung, perilla, and oiticica oils. Table XIV lists a large number of plasticizing agents compatible with ethylcellulose. Note that the fatty acids derived from incompatible oils are compatible with ethylcellulose. In general, it has been observed that air-bodying an oil improves its compatibility over that exhibited by the raw oil. Practically all of the compounds listed can be used with all substitution types of ethylcellulose, from K-type through T-type. Both vegetable and mineral oils, however, show a more marked tendency to exude from compositions based on the lower-substitution K-type; also, solid plasticizers, such as triphenyl phosphate, tend to crystallize from ethylcellulose plastics if used in an excessive proportion: they show a greater tendency to crystallize from K-type compositions than from the other ethylcellulose types. Tests for compatibility were made by preparing solutions containing both ethylcellulose and plasticizer, making flowouts of the solutions on glass plates, drying them, and examining the dry films. Strangely enough, in spite of its wide compatibility, ethylcellulose is actually insoluble at room temperature in almost all plasticizers. For example, if powdered ethylcellulose is added to a liquid plasticizer such as dioctyl phthalate, the particles do not even become swollen at room temperature; at 100C, a solution is formed and the ethylcellulose remains in solution when the composition is cooled. In commercial practice, ethylcellulose compositions are always compounded by a solvent process or by hotmilling or hot-melt procedures. This unusual property of wide compatibility, along with very limited room-temperature solubility, may explain why ethylcellulose lacquers and plastics are much more resistant to oils and greases, to plasticizer migration, and to contaminating influences generally than one would expect. Ethylcellulose is somewhat softer than nitrocellulose and cellulose acetate, and therefore requires proportionately less plasticizer than either of these to attain the desired degree of softening for any particular purpose. Both cellulose acetate and nitrocellulose plastics normally require from 30-35% plasticizer by weight for most plastics applications. Ethylcellulose plastics, on the other hand, normally require only 15-20% plasticizer to obtain comparable hardness. Nitrocellulose lacquers frequently contain as much as one part plasticizer to two parts nitrocellulose. Ethylcellulose lacquers seldom contain more than one part plasticizer to four parts ethylcellulose at comparable hardness.

TABLE XIIICOMPATIBILITY OF RESINS WITH K-TYPE ETHYLCELLULOSE

Resins compatible in all proportions, up to 1:1 resin:ethylcellulose Boea, run Cellolyn102M(s) Paraplex RG-2
(s)Completely

Wood rosin Zitro resin

compatible in all proportions, up to 0.3-0.5:1 resin:ethylcellulose.

TABLE XIVPLASTICIZERS FOUND COMPATIBLE WITH ETHYLCELLULOSE

Phosphate Esters Tricresyl phosphate Triethyl phosphate Triphenyl phosphate Phthalate Esters Benzyl methyl phthalate Cyclohexyl butyl phthalate Cyclohexyl ethyl phthalate Cyclohexyl methyl phthalate Diamyl phthalate Dibutyl phthalate Dicapryl phthalate Dicyclohexyl phthalate Diethyl phthalate Diisobutyl carbinyl phthalate Diisopropyl phthalate Dimethyl phthalate Dinonyl phthalate Dioctyl phthalate Diphenyl phthalate(t) Diethoxyethyl phthalate Dibutoxyethyl phthalate Dimethoxyethyl phthalate Miscellaneous Esters Abalyn methyl abietate Acetyl tributyl citrate Acetyl triethyl citrate Monoplex DIOA (diisooctyl adipate) Amyl oleate Flexricin P-3 (butyl ricinoleate) Benzyl benzoate Butyl and glycol esters of fatty acids Butyl diglycol carbonate Butyl oleate Butyl stearate Di(-methoxyethyl) adipate Dibutyl sebacate Dibutyl tartrate Diisobutyl adipate Dihexyl adipate Flexol 3GH [triethylene glycol di(2-ethyl butyrate)] Tegmer 804 [polyethylene glycol di(2-ethyl hexoate)] Hercoflex 600 monomeric PE ester Hercolyn D hydrogenated methyl ester of rosin Methoxyethyl oleate Butoxyethyl stearate
(t)Solid

plasticizers that exhibit a tendency to crystallize from the film when they are used as the sole plasticizing agent.

24

TABLE XIVPLASTICIZERS FOUND COMPATIBLE WITH ETHYLCELLULOSE (CONTINUED)

Miscellaneous Esters (Continued) Tributyrin (glycerol tributyrate) Triethylene glycol dipelargonate beta-(p-tert-amylphenoxy) ethanol beta-(p-tert-butylphenoxy) ethanol beta-(p-tert-butylphenoxyethyl) acetate Bis(-p-tert-butylphenoxydiethyl) ether Camphor Cumar R-3, R-14 Diamyl phthalate (Diamylphenoxyl) ethanol Diphenyl oxide Amides Bis(dibutyl) adipamide Dibutyllauramide Diethyldiphenylurea Mineral Oils Dutrex 25 Gloria white mineral oil Lubricating oil, practically all grades Mineral oils, refined Necton 45 Nujol Fatty Acids Linseed Oleic Ricinoleic Stearic Tung and many others Fatty Alcohols Cetyl Myristyl Stearyl and others Vegetable Oils Blown castor oil, Bakers No. 15 and 30, and Pale 4, 16, 1000 Castor oil, raw Corn oil, raw and air-blown Cottonseed oil, raw and air-blown Linseed oil, raw and air-blown Soybean oil, raw and air-blown Miscellaneous Types Abitol E technical hydroabietyl alcohol Beckolin Chlorinated paraffin, 40% chlorine content Piccolastic A-5 Glycerol alpha-methyl alpha-phenyl ether Halowax 1013 (chlorinated naphthalene) HB-40 Monoamylphthalate Nevillac 10 o-Nitrodiphenyl

Water-Sensitive Plasticizers Ethylcellulose has been tested and found compatible with a number of materials that were not included in Table XIV because their excessive water sensitivity detracts from their general usefulness. These materials include triethyl citrate, glyceryl triacetate, glyceryl diacetate, triethylaconitate, triethyl carballylate, and a number of partially esterified glycol, diethylene glycol, and glycerol compounds made with the higher fatty acids. Examples of the latter compounds are ethylene glycol mono-ricinoleate, -laurate, -oleate, and -stearate; and glyceryl mono- and di-ricinoleates, -laurates, -oleates, and -stearates. These are mentioned because there may be special uses where such water-sensitive softening agents could be useful. Oils as Ethylcellulose Plasticizers The oils, both mineral and vegetable, are relatively inexpensive plasticizing agents, and can play a unique and important part in the plasticization of ethylcellulose. Unlike the high-boiling solvent esters, they possess very little active solvent action for ethylcellulose unless heated to temperatures approaching the softening point of ethylcellulose. The oils possess much less softening action on the ethylcellulose than do the more active high-boiling esters, and they can be used in the development of compositions requiring a degree of toughness not possible with the high-boiling esters because of their excessive softening action. Refined mineral oil can be cited as one example. It is used extensively either as the sole plasticizer or as an important constituent of plasticizer blends in the preparation of extrusion and injection plastics where low water resistance, good dimensional stability under adverse temperature and humidity conditions, and low-temperature toughness and flexibility are important requisites. Mineral oils of refined and lubricating grades can be used in amounts up to about 20-23% by weight in an ethylcellulose composition without excessive exudation being encountered at ordinary temperatures. Castor oil is unique among the vegetable oils compatible with ethylcellulose in that it does not exude from compositions even when it is present in proportions as high as equal parts of oil and ethylcellulose. All of the other vegetable oils exude when present in such high proportions (1:1 ratio). This tendency to exude is lessened somewhat if the oil is air-blown. Oil blends containing castor oil, Hercolyn D hydrogenated ester of rosin, or one of the chemical esters as a component of the blend also have a reduced tendency to exude. However, vegetable oils, such as corn, soybean, cottonseed, and linseed, can be incorporated into ethylcellulose compositions up to 30-40% by weight before objectionable exudation is encountered. Linseed and soybean oils exude less readily than do corn and cottonseed oils. It is appropriate at this point to call attention to the toughening type of plasticizers. In addition to the vegetable oils, the sebacic acid type of alkyd resins and very long oil-extended alkyds impart suppleness to ethylcellulose plastics with a minimum effect on softening point and toughness. Various mixtures of the vegetable oils with these alkyd resins can also serve as valuable toughening plasticizers that can be used in proportions as high as 50% by weight of the plastic without exudation or stickiness. Such compositions form the basis for cable coatings and calendered coatings. 25

Table XV gives evaluation data for a number of plasticizerethylcellulose compositions. The compositions consisted of one part plasticizer to four parts ethylcellulose, with two ethoxyl types of ethylcellulose, N100 and K100, being tested. Tensile strength, elongation, and flex life were measured for 5-mil films of each composition.

TABLE XVEVALUATION OF PLASTICIZERS IN ETHYLCELLULOSE FILMS (APPROXIMATELY 5 MILS THICK 1:4 PLASTICIZER:ETHYLCELLULOSE)

N100 Ethylcellulose MIT Flex, Double Folds 2,000 1,400 1,200 980 910 880 600 600 560 520 430 400 400 360 145 110 105 Tensile Strength, lbs/in.2 5,500 5,000 6,700 6,400 5,850 6,400 7,150 6,700 6,400 7,200 6,950 6,800 6,200 7,850 2,650 8,200 2,700 Elongation, % 45 50 42 38 66 42 37 35 37 32 38 26 39 27 13 19 19

Plasticizer Dibutyl phthalate Tegmer 804 Raw castor oil Tricresyl phosphate Aroplaz 1351 Diamyl phthalate Paraplex RG-2 Bakers Pale No. 16 Diisobutyl carbinyl phthalate HB-40 beta-(p-tert-butylphenoxy) ethanol Dutrex 25 Diphenyl phthalate Pentaphen Butyl diglycol carbonate Piccolastic A-5 Butoxyethyl stearate

TABLE XVIETHYLCELLULOSE PLASTICIZERS INSOLUBLE IN PETROLEUM HYDROCARBONS AND OILS

Acetyl triethyl citrate Bakers Pale No. 16 Benzyl ether of glycerol Dimethyl phthalate Diphenyl phthalate PhosFlex CEF [tri(beta-chloroethyl) phosphate] Dimethoxyethyl phthalate Paraplex RG-2 (sebacic alkyd) Triacetin (glycerol triacetate) Triethyl citrate

With the exception of castor oil, all of the compatible vegetable oils form rigid gels with relatively minor amounts (35% by weight) of ethylcellulose. Such gels are prepared as hot-melt mixtures by dissolving the ethylcellulose in the oil at about 180 to 200C and then permitting the mixture to cool to room temperature. Gasoline- and Oil-Resistant Plasticizers Earlier in this booklet (page 21), the subject of gasoline resistance was dealt with in showing how certain problems could be met by employing special formulations. Table XVI lists a somewhat more inclusive group of plasticizers resistant to petroleum hydrocarbons and oils. The number of plasticizing agents possessing these special properties is sufficiently extensive so that the formulator has a relatively wide latitude of choice in developing suitable formulations for resistance to petroleum hydrocarbons and oils. The proper selection of ethylcellulose for such use should be made from the lower-substitution K-types.

26

SPECIFIC APPLICATIONS

Experience has shown that ethylcellulose can be used in many ways. A large and growing accumulation of data in Aqualon laboratories points the way to numerous specific uses, and those who have tested ethylcellulose are continually finding new applications. The following brief notes are intended to aid potential users in more definitely determining where and how ethylcellulose can fit their needs.

Examples of the varied uses of ethylcellulose lacquers are as follows: Hard Lacquers for Rigid Surfaces Such lacquers will give satisfactory service where a tough, crack-resistant coating is desired on a rigid surface, even when it is exposed to the extremes of outdoor temperature. For such applications, ethylcellulose is modified with hard resins and plasticizers. Tough Lacquer Many lacquer applications on nonrigid surfaces require, as basic desired properties, toughness, wear resistance, good adhesion, resistance to discoloration and alkali, and flexibility. Such properties are required in lacquers for paper, linoleum, cellophane, surgical tape, wet or dry sandpaper, and lacquers for the decoration of textiles. Properly plasticized and stabilized ethylcellulose lacquers meet these requirements. Bronzing Lacquer Many ethylcellulose compositions are substantially free from discoloration and gelation in copper and aluminum bronze lacquers. Resin choice is an important consideration; in an experimental series, dewaxed dammar developed less color in the lacquer than other resins tested. Citric acid (1% based on the ethylcellulose) is an effective stabilizer against the development of any green color. Lacquer for Polystyrene Plastic The solvent combination is an important factor in any successful coating for polystyrene plastic. In an ethylcellulose lacquer for this plastic, alcohols must constitute the major portion of the solvent, although a small amount of an active solvent for the plastic is desirable to get some bite into the molded part. A suitable active solvent would be an ester, ketone, or aromatic hydrocarbon. For further details, see CSL-61, A Report on Lacquer for Plastics. Lacquer for Rubber Whether the emphasis is on gloss, adhesion, or flexibility, coatings can be formulated to give the desired properties. Ethylcellulose lacquers have met these requirements when applied to either cured or uncured rubber, and yield a finish with outstanding adhesion and good flexibility.

LACQUERS
Satisfactory formulation of ethylcellulose lacquers and their good performance depend largely on selection of the proper kind and proportion of modifying agents to meet the requirements of each case. Ethylcellulose has been found to yield lacquers of excellent toughness and flexibility. These properties are retained over a temperature range extending from low to high. Ethylcellulose lacquers, for example, can be formulated to be unusually resistant to cold-checking. Furthermore, they can be formulated to retain their color extremely well on exposure to sunlight. Tests and experience indicate that properly formulated ethylcellulose lacquers are as durable as conventional nitrocellulose lacquers, and their specific properties make them a desirable choice for use over metal, wood, leather, and rubber. In general, the solvent system for ethylcellulose lacquers consists of 80% aromatic hydrocarbons and 20% alcohols. The hydrocarbon portion is composed of toluene and xylene or mixtures of these two materials; the remainder is composed of ethanol, isopropanol, and butanol or mixtures of these alcohols. For some coatings applications, such as those on asphalt tile and polystyrene plastics, it is necessary to use special solvent combinations instead of the cited mixtures. These special solvent compositions may give higher viscosities and somewhat hazy solutions, but the lacquers dry to clear films and can be used without difficulty if the lower solids necessary with these solvents can be tolerated.

TABLE XVIIEFFECTS OF RESINS ON SELECTED PROPERTIES OF ETHYLCELLULOSE COMPOSITIONS

Discoloration by Ultraviolet Light Formula A B Cumar R-29 (coumarone-indene) Dewaxed Batavia dammar (natural resin) Composition of Formulas Ethylcellulose Resin vb v sl vb sl Sensitivity to Water Formula A B sl blis blis r t bl v sl bl v sl r Sensitivity to 5% HCl Formula A B OK v sl t v v sl r v v sl r Sensitivity to 5% NaOH Formula A B OK vv sl r t bl vv sl r Sward Hardness Formula A B 54 82 36 84 Temperature Change, Cycles Formula A B 47 35 50 5

A 10 5

B 10 10

Key: b = bad(ly); bl = blush; blis = blistered; m = moderate; r = rust; sl = slight(ly); t = temporary; v = very.

27

Specialty Wood Finishes Ethylcellulose lacquers containing high proportions of lowcost resins and a small proportion of high-viscosity ethylcellulose are economical, air-drying coatings. Although the films may be somewhat soft, their flexibility and toughness are sufficient to make them interesting for applications such as drawer coatings or backboards for chests. Water-White Wood Finish When ethylcellulose films are exposed to ultraviolet light, they tend to bleach rather than discolor. This tendency indicates that they have a place in water-white wood finishes. K-type ethylcellulose without a plasticizer produces a waterwhite composition hard enough to stand some rubbing and polishing. An 80:20 nitrocellulose:ethylcellulose lacquer also shows reasonably good color retention. Alkali-Resistant Lacquer Because there is an increasing interest in maintenance paints that have good alkali resistance, work has been done on the use of stabilized ethylcellulose compositions in this field. It was found that the use of epoxide-type stabilizers, plus antioxidants, produces ethylcellulose coatings of very high alkali resistance. Ethylcellulose lacquers applied to steel panels were found to be unaffected after 100 days at room temperature in either a 5% caustic solution or a 1% ammonia atmosphere. A more spectacular test showed these coatings to be unaffected, even though they remained immersed in a 70% caustic solution at 76C (170F) for 19 days. Paper Lacquers Because of the varied special properties that ethylcellulose makes possible in paper lacquers, it is used widely in this field. Achievable with this material are: light initial color and good color retention under sunlight and aging exposures, heat-sealing, good gloss, resistance to blocking, resistance to heat discoloration, flexibility over a wide range of temperatures, and alkali resistance. Reconstituted cigar wrappers are flexible, yet tough, when they are formulated with ethylcellulose. Flowback High-Gloss Lacquer Other interesting ethylcellulose lacquers are flowback paper coatings. These formulations are designed to give especially high gloss when the coating is reflowed by application of heat at about 177C (350F) for a few seconds after the lacquer is applied and dried in a normal manner. Solvent-Based Strip Coatings In recent years, there has been much interest in temporary protective coatings that can later be stripped from the surface they protect. The major volume of these coverings has been deposited from hot-melts, but a growing market is developing for the solvent-based products.

EMULSIONS
Ethylcellulose emulsions can be formulated for environmental concerns and low cost. Ethylcellulose emulsions were developed for use as a permanent sizing agent for textiles to replace starch and various water-soluble gums. The method of preparation, choice of materials, stability, and sample formulations are discussed in CSL-76.

INKS
Screen-Process Inks The use of ethylcellulose in screen-process inks has grown substantially. Ethylcellulose is soluble in organic solvents that are not injurious to lacquer stencils, and it has wide compatibility with many resins and plasticizers. Compositions are usually based on one part by weight of ethylcellulose and a few parts of plasticizer and resin. A heavy loading of pigment and inert ingredients is possible. Magnetic Inks Because of the high dielectric constant of ethylcellulose, it can also be used for formulating magnetic inks. These have unique adhesion and holdout properties. Gravure and Flexographic Inks Ethylcellulose is being used in both gravure and flexographic inks. It contributes good scuff resistance, pigment dispersion, and holdout features, and controls viscosity. Compatibility with ink resinates is good. Pigments are easily incorporated by adding ethylcellulose color chips or flushed colors, or by any of the usual methods of grinding. Typically, one to three parts by weight of an N-, T-, or X-type are used. Flexographic inks are commonly formulated with shellac, or combinations of shellac and hard resins, in alcohol solutions. Ethylcellulose is added to promote adhesion and toughness and provide other features, the same as with rotogravure inks.

VARNISHES
Use of ethylcellulose in certain types of varnishes gives them the inherent toughness and quick-drying properties associated with the cellulose derivatives. Addition of ethylcellulose to some varnishes shortens drying time appreciably, increases toughness, reduces the amount of metallic drier necessary, decreases surface tack, and improves resistance to rapid temperature changes. There are two different procedures for adding ethylcellulose to varnishes. The simplest and most foolproof is the coldcut method. Ethylcellulose is first dissolved in its usual solvent combination, then added to a varnish that has been thinned with a solvent rich enough to hold the ethylcellulose in solution. If the varnish contains the usual solvent of mineral spirits or other aliphatic hydrocarbon, the ethylcellulose will precipitate on being added to the varnish.

28

The hot-melt procedure involves the addition of ethylcellulose flake to the hot varnish. Careful temperature control is necessary to avoid degradation of the ethylcellulose. The quantity of ethylcellulose added will control the properties of the coating, but 10%, based on resin and oil, is adequate for most purposes. The type of ethylcellulose can be either N or T, with the T-type having a slight advantage. The viscosity can vary from 10 to 200 cps, depending on the amount of extra bodying desired in the varnish.

TABLE XVIIITYPICAL DATA FOR ETHYLCELLULOSE HOT-MELT CASTING PLASTIC

Rockwell hardness, M scale Izod impact, ft-lbs/in. notch Softening point, ring-and-ball method, C Scratch hardness, by pencil Tensile strength, lbs/in.2 Compressive strength, lbs/in.2 Flexural strength, lbs/in.2 Modulus of elasticity, lbs/in.2 Mold shrinkage, in./in. Coefficient of expansion, in./in./C 105 Distortion under heat, C Specific gravity Water absorption, % gain after 48 hrs immersion at 21C 50-+50 0.5-5.0 130-170 4B-H 1,000-4,000 3,000-10,000 3,000-10,000 100,000-350,000 0.0025-0.015 5-15 28-50 1.08-1.33 0.15-0.75

ADHESIVES
In adhesives, ethylcellulose contributes: Low-temperature flexibility. A broadening of the critical melting range with a resultant decrease in plastic flow. Strength. An increase in melting point of the mixture. A decrease in sweating of plasticizers. Better control of tackiness in adhesive film. Hot-melt adhesives incorporating ethylcellulose have quick tack while still molten, but harden quickly on cooling. Furthermore, there is no residual solvent odor or taste. Solvent-type ethylcellulose adhesives are useful in places where ethylcellulose film or plastic must adhere to another surface.

CASTING PLASTICS
Table XVIII gives typical data obtained on formulations designed for hot-melt casting applications. Such compositions are composed of resins, plasticizers, waxes, and mineral fillers toughened with ethylcellulose. This type of plastic can be cast in bronze, brass, iron, aluminum, wood, or plaster molds. Some mold materials, such as wood and plaster, require a sealer coat. Remarkably accurate surface reproduction is possible with these hot-melt plastic castings. They are used for the preparation of dies, jigs, and tools in the aircraft industry, and hold promise of wide use in other industrial applications.

HOT-MELT APPLICATIONS
Hot-melt applications of ethylcellulose have received considerable attention. This is because ethylcellulose is a product with an unusual combination of properties, which makes it easily adaptable to this mode of application. It can be made stable to heat; it has excellent thermoplasticity; it dissolves readily in many hot resins, plasticizers, oils, and wax mixtures; and of particular interest is the fact that it imparts to such mixtures a remarkable toughness. Furthermore, all hot-melt compositions are economical to apply. No volatile solvents are involved. Application is usually a simple, oneoperation procedure. A variety of such compositions is now in use. Some of the applications are relatively well known and have been in use for years. Others are new, have interesting possibilities, and are expanding rapidly. Examples of well-known uses are shellac substitutes, potting compounds used in electrical insulation work, and decalcomania transfer compositions toughened with ethylcellulose. Numerous possibilities exist for the hot-melt coating of paper with resin and plasticizer mixes toughened with ethylcellulose. Compositions based on ethylcellulose can be tailored to specific requirements such as nonblocking, flexibility over a wide temperature range, high gloss, or pale color. Ethylcellulose hot-melt strip coatings provide protection during both shipping and storage. Detailed information is available.

PIGMENT-GRINDING BASE
Ethylcellulose has been found to be an excellent base for pigment grinding. Because of its low melting point, ethylcellulose, plasticized or unplasticized, can be colloided readily on either the two-roll or the Banbury mill. Plastic thus produced is very tough and sticky while hot, and is well adapted to pulling apart pigment agglomerates. The high temperatures at which ethylcellulose can be worked without decomposition ensure uniform grinding and dispersion of pigment particles.

FILM AND FOIL

In film form, ethylcellulose is well suited in properties and appearance as a wrapping material and as electrical insulation. Unplasticized film can be produced to have a high degree of toughness and flexibility. Unplasticized film 0.001 in. thick, for example, can be flexed over 2,000 times on the MIT fold tester before failure occurs. Even at 70C the film has a high degree of flexibility. Tensile strength is on the order of 7,000 to 11,000 lbs/in.2, while elongation runs 1035%. Moisture absorption in highly humid atmospheres runs to approximately 2%, but has no appreciable effect on the dimensional stability of the film. In fact, ethylcellulose film is not noticeably affected even after long immersion in water, followed by drying. 29

PLASTICS
Ethylcellulose plastic belongs to the group known as thermoplastic materialsthat is, those that can be shaped by pressure while hot, and that, when cool, retain the impressed form. A plastic make from ethylcellulose has the usual operating advantages of other thermoplasticsi.e., reuse of scrap; adaptability to fast, low-cost injection and extrusion processes; ready workability with hand or machine tools; and easy finishing. An outstanding characteristic of ethylcellulose plastic is its high impact resistance at low temperatures. It has the lowest specific gravity of any of the cellulosic thermoplastics now available, and, with the exception of nitrocellulose, it shows the lowest water pickup of these thermoplastics. This material has the highest alkali resistance and also has fair resistance to acid. Ethylcellulose plastic easily meets all ordinary requirements of practical strength properties at temperatures between 57C and 77C (70F and 170F). Use of ethylcellulose plastic is indicated where hardness, combined with toughness, close dimensional tolerance, ability to hold dimensions during immersion in water, and high impact strength at low temperatures, is required. Military rocket tapes and molded parts can be made from a premium grade of K-type ethylcellulose. This is a result of a low ash content, critical to the shelf life of the product.

FOOD CONTACT AND PHARMACEUTICALS

TabletsCoatings NF-grade ethylcellulose produces durable tablet coatings that offer good adhesion and function to control the rate at which the ingested medication is released. Typically, the tablet is spray-coated from a solvent system. Pharmaceutical manufacturers also treat products with an EC-based aqueous polymer dispersion that is spray-coated onto the tablets, thus avoiding solvent systems that are sometimes undesirable. In either case, the coating masks bitter tastes and improves stability. Further details on aqueous dispersions can be found in U.S. Patent 4,963,896, FMC Corporation. TabletsBinding Ethylcellulose has long been used as a binder and filler in tablets of vitamin, mineral, and prescription drugs for both humans and animals. It helps produce a stable, attractive tablet without significantly affecting the dissolution rate. Encapsulation Microencapsulation of drug particles with NF-grade ethylcellulose offers pharmaceutical manufacturers another means of controlling solubility rates. The coacervation process with a solvent is found in U.S. Patent 3,567,650, NCR Corporation.

30

APPENDIX

PRODUCT LISTING SUPPLEMENT

The following list of products, along with their chemical identity and source of supply, may be helpful to the reader who is unfamiliar with some of the products referred to in this book. Read and understand the Material Safety Data Sheets (MSDSs) before using these products.
Product Abalyn Abitol E Acryloid B72, C10LV Acryloid F10 Antioxidant 2246 Aroplaz 1351 Aroplaz 1271 Bakers castor oil No. 15, 30; Pale No. 4, 16, 1000 Beckacite, Super-, 1001 Beckamine 21-510 Beckolin Beckosol 12-021 Butyl Cellosolve Carbitol Cellolyn 21 Cellolyn 102M Cellosolve Cellosolve acetate Chlorowax 70 Cumar P10 Chemical Identity Methyl ester of rosin Hydroabietyl alcohol Flexible acrylic ester resins Mineral-thinner-soluble acrylic ester resin 2,3-methylene bis (4-methyl6-tert-butyl) phenol Nonoxidizing alkyd resin Long oil phthalic alkyd Processed castor oil Oil-soluble pure phenolic resin Urea-formaldehyde resin Synthetic oil Alkyd resin Ethylene glycol monobutyl ether-solvent Diethylene glycol monoethyl ether Rosin-derived alkyd Modified ester of rosin Ethylene glycol monoethyl ether-solvent Ethylene glycol monoethyl ether acetate-solvent Chlorinated paraffin Manufacturer Hercules Hercules Rohm & Haas Rohm & Haas Ciba Geigy Reichhold Reichhold CasChem Reichhold Reichhold Reichhold Reichhold Union Carbide Union Carbide Hercules Hercules Union Carbide Union Carbide U.S. Industrial Chemicals Neville Chemical Neville Chemical Ashland Hercules Dow Corning Shell Shell Hercules CP Hall CasChem Sonneborn Bakelite Monsanto Hercules Hercules Hercules

Product

Chemical Identity

Manufacturer Allied Signal Shell UK Reichhold Hercules Hercules Union Carbide Union Carbide CP Hall Exxon Neville Chemical Schering E. I. du Pont de Nemours CP Hall CP Hall Hercules Hercules Hercules Hercules Hercules Atochem Hercules Akzo Chemie Hercules Hercules Hercules Hercules Monsanto Hercules Hercules CP Hall

Hi-Flash naphtha Solvent hydrocarbon Ionol Oxidation inhibitor Keltrol Fatty oil-vinyl toluene copolymer Lewisol 28 Maleic-modified ester gum resin Metalyn Distilled methyl ester of tall oil Methyl Cellosolve Ethylene glycol monomethyl ether Methyl Cellosolve Ethylene glycol monomethyl acetate ether acetate Monoplex DIOA Diisooctyl adipate Necton 45 Petroleum lubricating oil base Nevillac 10 Phenol-indene-coumarone resins Nujol Liquid paraffin oil Orlon Acrylic synthetic fiber Paraplex G-20 Paraplex RG-2, RG-8 Pentalyn A Pentalyn G Pentalyn H Pentalyn K Pentalyn 830, 856 Pentaphen 67 Pentrex 28 PhosFlex CEF Piccolastic A-5 Pine oil Poly-pale 10 ester Poly-pale resin Resimene Staybelite Staybelite 3, 10 ester Tegmer 804 Tetralin Triacetin Tributyrin Uformite MM-55 Uni-Rez 7200 Uvinul 400 Varsol Vinsol Vinsol ester gum Vinylite VAGH Zinar, Zirex, Zitro Sebacic, unmodified, nonoxidizing alkyd resin Sebacic, oil-modified alkyd resins Pentaerythritol ester of rosin Modified pentaerythritol ester of rosin Pentaerythritol ester of hydrogenated rosin Pentaerythritol ester of modified rosin Hard, pale, thermoplastic resins para-tert-amylphenol Maleic-modified glycerol ester of rosin Tri(beta-chloroethyl) phosphate Styrene resin Ester of polymerized rosin Polymerized rosin Melamine resin Hydrogenated rosin Esters of hydrogenated rosin Polyethylene glycol di-2-ethylhexoate Tetrahydronaphthalene

Plastic-grade coumaroneindene resin Cumar R-3, R-11, Coumarone-indene resins R-14, R-28, R-29 BHT 2,6-di-tert-butyl-para-cresol Dipentene No. 122 Solvent, C10H16 Dow Corning Silicone dimethyl fluid Fluid 200 Dutrex 25 Petroleum-derived plasticizer Epon 1004` Polymer of bisphenol and epichlorohydrin Ester Gum 8D Glycerol ester of rosin Flexol 3GH Triethylene glycol di(2-ethyl butyrate) Flexricin P-3 Butyl ricinoleate Gloria White mineral oil Halowax 1013 Chlorinated naphthalene resin HB-40 Hydrogenated terphenyl Hercoflex 600 Monomeric PE ester Hercolyn D Hydrogenated methyl esters of rosin Hercules RS nitrocellulose

E. I. du Pont de Nemours Glycerol triacetate Bayer AG Glycerol tributyrate Eastman Chemical Melamine-formaldehyde resin Reichhold Hard maleate resin Union Camp 2,4-dihydroxybenzophenone BASF Petroleum thinner Exxon Dark, hard pine resin Hercules Glycerol ester of Vinsol Hercules Vinyl resin Union Carbide Zinc resinates Arizona

31

METHODS OF ANALYSIS
Product specifications are based on Aqualon test methods. The following standard test methods are essentially equivalent to the Aqualon test methods, except where indicated: EthylcelluloseStandard Grades ASTM D 914(2) EthylcelluloseNF Grades National Formulary (current edition) Ethylcellulose Official Monograph

(2)ViscosityThe

Aqualon test method utilizes the Hercules horizontal capillary viscometer, in accordance with ASTM D 914, for ethylcellulose types having a viscosity of 250 cps or less. For viscosities greater than 250 cps on the horizontal capillary viscometer, the following test method is used:

Apparatus Brookfield viscometer Model LVF Procedure Prepare the viscosity solution in accordance with ASTM D 914 procedure specified for Hercules horizontal capillary viscosity. After the solution is complete by visual inspection, place it in a 12-oz bottle, adjust the temperature to 25C, and measure the viscosity, using a Brookfield viscometer Model LVF (No. 2 spindle, 30 rpm). Calculation Multiply the 3-min dial reading by 10 to obtain viscosity in centipoises.

PRODUCT SAFETY
Read and understand the Material Safety Data Sheet (MSDS) before using this product.

32

Cellulose and Its Derivatives

HERCULES INCORPORATED Aqualon Division Hercules Plaza 1313 North Market Street Wilmington, DE 19894-0001 www.aqualon.com (800) 345-0447 ORDER PLACEMENT INFORMATION (800) 334-8426 PRODUCT AND TECHNICAL INFORMATION (800) 345-0447

The products and related information provided by Hercules are for manufacturing use only. Hercules makes no express, implied, or other representation, warranty, or guarantee concerning (i) the handling, use, or application of such products, whether alone, in combination with other products, or otherwise, (ii) the completeness, definitiveness, or adequacy of such information for users or other purposes, (iii) the quality of such products, except that such products are of Hercules standard quality. Users are advised to make their own tests to determine the safety and suitability of each such product or product combination for their own purposes. Read and understand the Material Safety Data Sheet (MSDS) before using this product. Hercules does not recommend any use of its products that would violate any patent or other rights.

250-42A 3-02

Supersedes all previous editions.

PRINTED IN U.S.A.