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63-1

63
ÞIfroceIIuIose
63.1 Piepaiation ........................................................................1
63.2 Solubility............................................................................2
63.3 Film Piopeities ..................................................................3
Appendix: Typical Piopeities of RS Nitiocellulose...................5
When most people think of nitiocellulose, they think of guncotton, a mateiial that was developed foi
explosives oi gum piopellant. But they aie only paitially coiiect. Nitiocellulose is one of the oldest and
most widely used flm foimeis adaptable to a numbei of uses. It is deiived fiom cellulose, a mateiial
fiom plants, and theiefoie a ienewable souice. Soluble nitiocellulose possesses a unique combination of
piopeities such as toughness, duiability, solubility, gloss, and iapid solvent ielease. As the flm foimei
in lacquei systems, it affoids piotective and decoiative coatings foi wood and metal. In addition, it fnds
use in ßexible coatings foi papei, foil and plastic flm, piinting inks, and adhesives. This chaptei biießy
coveis the piopeities, uses, and handling pioceduies foi nitiocellulose and the foimulations made fiom it.
63.1 Preparatiun
Nitiocellulose is the common name foi the nitiation pioduct of cellulose. Othei names include cellulose
(tii)nitiate and guncotton. The commeicial pioduct is made by ieacting cellulose with nitiic acid.
Cellulose is composed of a laige numbei of -anhydioglucose units, which aie jointed togethei into a
chain. The anhydioglucose units aie six-membeied iings having thiee hydioxyl (-OH) gioups attached
to them. The numbei of anhydioglucose units in the typical cellulose chain ianges fiom 500 to 2500 in
chemically puiifed cellulose.
63.1.1 Degree ul Substitutiun
Nitiic acid can ieact with these thiee hydioxyl gioups of the anhydioglucose units to foim the nitiate
estei. Fully nitiated cellulose would then be a tiinitiate - that is, a nitiate having a degiee of substitution
of 3. The calculated nitiogen content of such a fully nitiated cellulose is 14.14%.
In piactice, howevei, the maximum nitiogen level that can be achieved is 13.8%. This coiiesponds to
a degiee of substitution of 2.9. At this level, nitiocellulose does not piocess piopeities that aie useful foi
coatings use. Film foiming piopeities aie bettei at degiees of substitution between 1.8 and 2.3.
IanIeI N. ZavIsza
Hercu|e· Incor¡orored
© 2006 by Taylor & Erancis Group, LLC
Solvents and Diluents · Viscosity Effects · Blushing · Solution
Giades
Piepaiation
Degiee of Substitution · Degiee of Polymeiization · Types and
Plasticizeis · Resins · Cioss-Linkable Coating Systems · Safety
Consideiations
63-2 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
63.1.2 Degree ul Pu!ymerizatiun
The degiee of polymeiization of nitiocellulose is the numbei of anhydioglucose units that aie linked
togethei to foim one molecule. The moie units aie linked, the highei the viscosity of the nitiocellulose
in solution at a given concentiation. Commeicial nitiocellulose is categoiized into giade by the viscosity
of a 12.2% solids solution at 25C in teims of centipoise oi the time it takes, in seconds, foi a metal ball
of a specifed size to fall a measuied distance thiough the solution. The solvent system used is usually
55 paits by weight toluene, 25 paits denatuied ethanol, and 20 paits ethyl acetate.
63.1.3 Types and Grades
Nitiocellulose is divided into types accoiding to the nitiogen content of the pioduct, which ießects highei
oi lowei degiees of substitution. The lowest commeicially useful nitiogen content is 11% (10.0 to 11.2%).
This coiiesponds to a degiee of substitution of 1.8 to 2.1. This type is fuithei classifed into viscosity
giades ianging fiom 30 to 35 cp¯ to 40 to 60 sec. These giades aie useful in lacqueis foi papei and foil,
low odoi lacqueis, sealeis, flleis, piinting inks, and plastics. At this level of nitiogen, nitiocellulose is
moie toleiant of alcohol than highei nitiogen types.
A second type has an aveiage nitiogen content of 11.5% (11.3 to 11.7%). Viscosity giades of 0.5 and
5 to 6 sec aie available foi use in lacqueis foi coating cellophane, papei, and textiles.
The next type contains an aveiage of 12% nitiogen (11.8 to 12.2%) and is available in a laige numbei
of viscosity giades, fiom 18 to 25 cp to 2000 sec. This type is moie toleiant of aiomatic hydiocaibon
solvents, such as toluene, and less toleiant of aliphatic hydiocaibons. This giade is compatible with many
iesins and has many uses. It is used in coatings foi wood, metal, papei, textiles, and foil; foi lacquei
emulsions foi wood and metal; and foi aichitectuial fnishes, adhesives, cements, and inks. Highei
nitiogen levels (>13%) fnd use in the manufactuie of gun piopellants and explosives.
Solubility and viscosity in solution and compatibility of nitiocellulose with a vaiiety of modifeis, such
as plasticizeis, iesins, and pigments, deteimine its usefulness in piepaiing lacqueis and coatings. The
most commonly used foi lacqueis and coatings.
63.2 Su!ubi!ity
63.2.1 Su!vents and Di!uents
The geneially used method of foimulating nitiocellulose coating systems featuies volatile solvents that
dissolve the nitiocellulose and its modifeis to foim a homogeneous system (with the exception of
pigments and flleis).
The iesulting foimulation can then be applied to the substiate by one of a numbei of methods such
as biushing, spiaying, oi cuitain coating. The solvent evapoiates to leave a solid flm on the substiate.
Tiue solvents aie liquids that will dissolve nitiocellulose completely. Foi 12% nitiogen nitiocellulose,
these aie ketones, esteis, amides, and nitiopaiaffns. Some solvents, such as ethyl oi isopiopyl alcohol,
will not dissolve nitiocellulose on theii own. They may be added to tiue solvents without piecipitating
the nitiocellulose. These aie teimed °cosolvents." Aliphatic and aiomatic hydiocaibons aie nonsolvents.
Teimed °diluents," they may be added to nitiocellulose solutions in limited amounts without piecipitation
to lowei cost and impiove solubility of iesin modifeis. Aiomatics may usually be added to a gieatei
extent than aliphatics. At the lowei nitiogen level of 11%, moie hydiocaibon can be added to the
nitiocellulose solution without piecipitation.
¯The viscosity of veiy low moleculai weight nitiocellulose is measuied and desciibed in centipoise. The falling
ball method is used foi times of a quaitei-second and highei. This iesults in a change of units used to desciibe the
viscosity giades.
© 2006 by Taylor & Erancis Group, LLC
chaptei appendix is a table of the typical piopeities of nitiocellulose containing 12% nitiogen, the type
Nírroce||u|o·e 63-3
Dilution iatio is the iatio of the volume of diluent that can be added to a given volume of nitiocellulose
solution in a tiue solvent befoie sepaiation of the nitiocellulose takes place. Foi example, staiting with
8 g of nitiocellulose in 100 m of solvent, butyl acetate, the dilution iatio foi toluene is 2.75 compaied
with 1.5 foi MV&P naphtha (an aliphatic hydiocaibon mixtuie). Diffeient solvent-diluent combinations
will have diffeient dilution iatios and must be measuied sepaiately. When ethanol, a cosolvent, is
combined with a tiue solvent, the dilution iatio foi a given diluent is highei than with the tiue solvent
alone. Raising the tempeiatuie will usually lowei the dilution iatio foi a diluent-solvent mixtuie.
63.2.2 Yiscusity Ellects
The viscosity of a polymei solution will noimally inciease with the solvating powei of the solvent at a
given concentiation, because this allows the polymei to stietch out fuithei and to become entangled
with othei polymei molecules moie easily. A pooiei solvent foices the polymei to become moie compact
and to occupy a smallei volume, iesulting in a lowei solution viscosity.
Toluene is a pooiei solvent foi nitiocellulose than esteis oi ketones. Up to a point, howevei, it may be
added to solutions of nitiocellulose in tiue solvents, such as esteis on ketones, without piecipitating the
nitiocellulose. The effect is that the viscosity of the iesulting solution is lowei foi solutions containing
toluene than without it at the same solids level. This technique allows a foimulatoi to maximize the solids
level foi a given application viscosity. The most common diluents used in this way aie toluene and xylene.
Solutions piepaied of nitiocellulose exhibit a viscosity diop on standing. A solution of half-second
giade at 20 wt% solids in an ethanol-toluene-ethyl acetate solvent blend exhibits, foi example, a viscosity
of 3.8 sec by a falling ball method 1 h aftei addition of the solvent but 3.5 sec aftei 24 h. This viscosity
loss will stop aftei a fnite time.
63.2.3 B!ushing
Foimulating lacqueis that contain too gieat a peicentage of iapidly evapoiating solvents may iesult in a
white chalky appeaiance upon diying. The cause of this is cooling of the flm suiface below the atmo-
spheiic dew point by the evapoiating solvent, condensing watei onto the flm. If suffcient moistuie is
condensed, the nitiocellulose can piecipitate. This blushing pioblem is woisened duiing humid weathei.
The iemedy foi blushing is to add a slowly evapoiating solvent to the solvent blend. This has the effect
of ietaiding the evapoiation iate and loweiing the cooling effect. Examples of such solvents aie diisobutyl
ketone, methyl amyl acetate, amyl acetate, methyl amyl ketone, and 2-butoxyethanol.
Blushing oi haze foimation can also occui when a pooi solvent, which has a slow evapoiation iate,
is used with a fast, good solvent. The good solvent will evapoiate fist, causing piecipitation of the
nitiocellulose by the pooi solvent. Too much high boiling hydiocaibon diluent will do this.
63.2.4 Su!utiun Preparatiun
The type of mixing appaiatus is usually the piepaiei`s choice. A veitical tank with piopellei oi disc
agitatois woiks well. Laboiatoiy samples aie easily dissolved by tumbling oi iolling jais containing the
nitiocellulose and solvent. If a solvent blend is to be used, it is best to dispeise oi wet the nitiocellulose
with the cosolvent oi diluent fist, then add the active solvent poition. This pioceduie will ieduce the
time iequiied to effect solution. Solvent blends containing highei iatios of diluent to active solvent will
take longei to dissolve the nitiocellulose than those with lowei diluent iatios.
63.3 Fi!m Pruperties
Film piopeities of nitiocellulose aie affected by the solvents used, the casting technique, the diying
conditions, as well as othei paiameteis. Diffeient types of modifei aie also used to altei nitiocellulose
diy flm piopeities. Nitiocellulose is only one ingiedient in lacqueis and coatings. The following desciip-
tion of modifeis is intended to give a ßavoi of how nitiocellulose systems may be modifed.
© 2006 by Taylor & Erancis Group, LLC
63-4 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
63.3.1 P!asticizers
Plasticizeis aie nonvolatile mateiials added to contiol ßexibility and elongation of a flm. Plasticizeis
should be nonvolatile, coloiless, odoiless, and tasteless. They should be nontoxic and should piovide
maximum ßexibility with minimum loss in flm stiength and toughness. They should not destabilize the
flm chemically.
Plasticizeis fall into two types: solvent and nonsolvent. Solvent-type plasticizeis aie those that exhibit
complete miscibility with nitiocellulose in all piopoitions. Examples aie dibutyl phthalate and diisononyl
phthalate.
Nonsolvent-type plasticizeis neithei dissolve noi cause foimation of colloidal nitiocellulose at ioom
tempeiatuie. Howevei, they aie compatible with nitiocellulose in solution and in the diy flm. Examples
of nonsolvent-type plasticizeis aie castoi oil and polymeiic oi polyestei-type plasticizeis. The polymeiic
plasticizeis impiove ßexibility and have veiy low volatility, aie nonmigiating and nonspewing, and do
not leave the flm at elevated tempeiatuies.
63.3.2 Resins
Resins aie used in nitiocellulose coating compositions to impiove the degiee of flm build by incieasing
the solids content at a given viscosity (i.e., spiay viscosity). Depth, gloss, and adhesion can also be
piomoted by added iesin.
Natuial iesins, such as shellac, dammai, elemi, and mastic, weie some of the fist iesins used to modify
nitiocellulose. Most of these iesins aie not flm foimeis in themselves and do not impiove tensile stiength,
ßexibility, oi elasticity. The use of natuial iesins is limited.
Some synthetic iesins now available aie designed to have specifc piopeities that make them geneially
moie adaptable foi use in lacqueis than natuial iesins. Alkyd iesins aie widely used. They aie piepaied
by ieacting a polyhydiic alcohol, such as pentaeiythiitol, with a polybasic acid, such as phthalic acid.
Alkyd iesins modifed with diying oils oi unsatuiated fatty acids aie good flm foimeis. Addition of
nitiocellulose to these iesins acceleiates the diying time and often eliminates the need foi baking.
Phenol-foimaldehyde iesins have excellent iesistance to alcohols, acids, and alkalies. When used with
nitiocellulose, howevei, theie may be compatibility pioblems and pooiei coloi stability. Othei useful
iesins aie aciylic iesins, vinyl iesins such as polyvinyl butyial and polyvinyl acetate, ceitain polyamides,
epoxies, and low moleculai weight polyestei.
Pigments aie added foi pioducing opaque, coloied fnishes. Because nitiocellulose tends to be degiaded
in sunlight, some pigments extend the seivice life of flms exposed to sunlight. Ceitain pigments should
be avoided because they show alkaline ieactions, which cause nitiocellulose degiadation.
63.3.3 Cruss-Linkab!e Cuating Systems
Soluble nitiocellulose contains iesidual hydioxyl gioups that may be utilized to piepaie coatings that aie
cioss-linked to othei vehicle mateiials thiough these hydioxyls. Some gioups that ieact with these
hydioxyls aie methylolamino and alkylated methylolamino gioups, isocyanates, and epoxides.
Catalyzed nitiocellulose-alkyd-aminoplast systems aie systems that will cuie by acid catalysis. The
nitiocellulose and the alkyd piovide the hydioxyl gioups. The aminoplast can be an alkylated uiea- oi
melamine-foimaldehyde iesin. These systems aie catalyzed to cioss-link with a stiong acid, such as p-
toluenesulfonic acid oi phenyl acid phosphate. The coatings pioduced aie tough and solvent iesistant
and fnd application on kitchen cabinets. Once catalyzed, the system must be used piomptly because the
solution will gel with time.
Nitiocellulose-uiethane systems aie piepaied fiom the ieaction of a polyisocyanate with nitiocellulose.
The coatings may be toughened by the addition of a polyol such as a polyestei, aciylic, vinyl, oi alkyd
polyol. Each of these polyols will give diffeient piopeities. Conventional uiethane catalysts, such as zinc
octoate, may be used to speed up the cioss-linking.
© 2006 by Taylor & Erancis Group, LLC
Nírroce||u|o·e 63-5
Epoxy-containing iesins may be used; but since the available hydioxyls in nitiocellulose aie less ieactive
than he usual polyols in epoxy systems, they aie not used extensively foi coatings systems.
63.3.4 Salety Cunsideratiuns
Some basic safety piecautions must be obseived because nitiocellulose is a veiy ßammable mateiial. It
is sold wetted with some mateiial such as ethanol oi isopiopanol, which loweis its ßammability. It should
nevei be allowed to diy, because then it is extiemely ßammable. No spaik-pioducing souices, ßames, oi
heat oi static electiicity souices should come into pioximity of nitiocellulose. Nitiocellulose containeis
should be kept tightly closed. Smoking must be piohibited when handling nitiocellulose oi its solvents,
diluents, oi solutions. Safety pioceduies aie contained in National Fiie Piotection Association (NFPA)
Standaid 35, Manufactuiing Chemists Association Chemical Safety Data Sheet SD-96, the Hazaidous
Mateiials Regulations of the U.S. Depaitment of Tianspoitation (009) and the U.S. Occupational Safety
and Health Standaids, Pait 1910.
Appendix: Typica! Pruperties ul RS Nitruce!!u!use
Geneial Piopeities
Odoi of mateiial None
Taste of mateiial None
Coloi of flm Watei-white
Claiity of flm Excellent
Physical Piopeities of Solid oi Film
Bulking value in solution 0.0704 gal/lb
Specifc volume in solution 16.26 in.
3
/lb
Specifc giavity of cast flm 1.58-1.65
Refiactive index, piincipal 1.51
Light tiansmission, lowei limit of substantially complete 3130
Electiical Piopeities of Unplasticized Film
Dielectiic constant at 25-30C
60 Hz 7-7.5
1 kHz 7
1 MHz 6
Powei factoi at 25-30C
60 Hz 3-5%
1 kHz 3-6%
Electiic chaige on iubbing with silk Negative
Mechanical Piopeities of Unplasticized Film
Tensile stiength at 23C, 50% ielative humidity 9000-16,000 psi
Elongation at 23C and 50% ielative humidity 13-14
Flexibility of 3- to 4-mil flm, MIT double folds undei 200-g
tension
30-500
Haidness, Swaid, of glass 90%
Softening point iange (Paii) 155-200C
Solubility and Compatibility Chaiacteiistics
Solvents, piincipal types Estei, ketones, ethei-alcohol
Resins, compatible types Almost all
Plasticizeis, compatible types Almost all including many vegetable oils
Waxes and tais, compatible types None
Compatible cellulose deiivatives Ethyl cellulose, cellulose acetate, ethylhydioxyethyl cellulose
© 2006 by Taylor & Erancis Group, LLC
63-6 Cooríng· Tec|no|ogy Hondboo|, T|írd ídíríon
Chemical and Physical Piopeities of Unplasticized Cleai Film
Moistuie absoiption at 21C in 24 h in 80% ielative
humidity
1.0%
Watei vapoi peimeability at 21C 2.8 g/cm
2
/cm/h 10
6
Sunlight effect on discoloiation Modeiate
Sunlight effect on embiittlement Modeiate
Aging Slight
Effect of cold watei Nil
Effect of hot watei Nil
Geneial iesistance:
Acids, weak Faii
Acids, stiong Pooi
Alkalies, weak Pooi
Alkalies, stiong Pooi
Alcohols Paitly soluble
Ketones Soluble
Esteis Soluble
Hydiocaibons
Aiomatic Good
Aliphatic Excellent
Oils
Mineial Excellent
Animal Good
Vegetable Faii to good
Scurce. Nitrccellulcse (technical biochuie), Heicules Incoipoiated, Wilmington, DE.
© 2006 by Taylor & Erancis Group, LLC