Nitrocellulose Lacquers

Nitrocellulose (cellulose nitrate) lacquers are a mixture of binders (nitrocellulose and resins), plasticizers, and (optionally) pigments dissolved/dispersed in organic solvents. The nonvolatile components are: 1 ) Nitrocellulose 2) Resin 3) Plasticizer 4) Pigment (extender, dye) optional

The volatile components are 1) solvents 2) Non solvents (diluents such as benzene, toluene, or xylene) Physical evaporation of the solvents results in formation of the desired solid film on the substrate surface. Films may also be obtained from aqueous, low-solvent, or solvent-free nitrocellulose emulsions or dispersions.

Raw Materials The compositions of cellulose nitrate lacquers are summarized in Table. Nitrocellulose is an outstanding film-forming substance which displays rapid solvent evaporation (short drying time). It is compatible with most coating raw materials. Nitrocellulose is characterized by its nitrogen content and solubility. The nitrogen contents are: High-viscosity, medium-viscosity, and low-viscosity formulations of each type are available. Films formed from high-viscosity nitrocellulose have good flexibility combined with a high crack resistance. They are therefore employed where high mechanical stress is to be expected (e.g., in leather coatings, putty, adhesives). Only lacquers with low solids contents can be obtained from highviscosity nitrocellulose.

Low-viscosity nitrocellulose is used to prepare high-solids lacquers. Since low-viscosity nitrocellulose produces hard to brittle coating films, plasticizers and plastifying resins must be added to the lacquer formulation. They are used in putty, dipping paints, and printing inks. The medium-viscosity nitrocelluloses have the broadest application range, a major field being furniture lacquers. They are also employed in paper and metal coatings as well as in reaction lacquers (e.g., acid-catalyzed lacquers and polyurethane paints).
Ester-soluble nitrocelluloses are mainly used in the lacquers described above. Alcohol-soluble nitrocellulose (which is also soluble in esters and ketones) is used for odorless lacquers, particularly for printing inks and sealing waxes.

Plasticizers. Plasticizers that are compatible with nitrocellulose and resins are used in coatings for the following purposes: 1) To improve adhesive strength and gloss 2) To improve mechanical properties such as elongation, pliability, crease resistance. 3 ) To increase resistance to light, heat. cold, and sudden temperature changes . Plasticizers may be solvents or nonsolvents for nitrocellulose. The type used depends on the application. Nitrocellulose is for example soluble in dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, tricresyl phosphate, and triphenyl phosphate. Plasticizers in which nitrocellulose is insoluble include vegetable oils, stearates, and oleates.

Resins. A large number of synthetic coating resins (e.g., alkyd, ketone, urea, malamine, and acrylic resins) are available for formulating nitrocellulose combination lacquers. Selection criteria include price, color, influence on solvent release, gloss, hardness, yellowing, and durability of the final coating.
Nitrocellulose (generally in the form of chips) is used in polyurethane coatings to improve drying behavior, to increase body, and to obtain good flow.

Solvents. The solvent mixture has a large influence on the quality of the coated film. The solvent that evaporates last should be a solvent for all raw materials in the lacquer formulation. The most important active (true) solvents are acetate esters ( e g , ethyl, butyl, or propyl acetate) and ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone). Latent solvents, which become effective only in the presence of active or true solvents, include alcohols ( e g , methanol, ethanol, and propanol). Like the nonsolvents these are used to reduce costs. The lower alcohols (e.g., methanol or ethanol) are, of course, true solvents for alcohol-soluble nitrocellulose.

Application and Uses The preparation of nitrocellulose lacquers is simple and involves dissolution and mixing procedures. The viscosity should be compatible with the equipment used. Nitrocellulose lacquers can be sprayed efficiently with compressed air or by an airless technique. An important use of nitrocellulose lacquers is in printing inks employed in flexographic, gravure, or silk-screen printing. The most important areas of use of nitrocellulose lacquers are for coating wood, metal (e.g., automotive repair), paper, foil (cellophane, aluminum), leather, and textiles and in nail polish. Aqueous nitrocellulose lacquers that contain small amounts of solvent are used in the form of emulsions or dispersions to coat leather, and decorative foils. Solvent-free dispersions are cured by UV radiation after evaporation of the water and are used to coat furniture, profiled boards, and paper.

PAINT FILM FORMATION

Drying and Film Formation

As the paint dries on the substrate, a firmly bonded film is formed. The properties of this film are determined both by the substrate and its pretreatment (cleaning, degreasing) and by the composition of the coating and the application method used. Drying of the paint on the substrate takes place physically (1 - 3 ) or chemically (4): 1) Evaporation of the organic solvents from solvent-containing paints 2) Evaporation of water from waterborne paints 3 ) Cooling of the polymer melts (powder coatings) 4) Reaction of low molecular mass products with other low or medium molecular mass binder components (polymerization or cross-linking) to form macromolecules

Physical Drying.
Physical drying takes place mainly for paints with high molecular mass polymer binders such as cellulose nitrate, cellulose esters, chlorinated rubber, vinyl resins, polyacrylates, styrene copolymers, thermoplastic polyesters and polyamide and polyolefin copolymers. These materials give good flexibility and stability because of their high molecular mass. Their glass transition temperature should be above room temperature to ensure adequate hardness and scratch resistance. With these polymers, film formation can also take place from solutions or dispersions in organic solvents or water, from which the solvent or water evaporates, leaving behind the chemically unchanged polymer film.

Film formation can be accelerated by drying at elevated temperatures (forced drying). Physically drying solvent-containing paints have a low solids content because the molecular mass of the binder is relatively high. Higher solids contents are obtained by dispersing the binder in water (dispersions, emulsions) or in organic solvents (nonaqueous dispersion or NAD systems). Films formed from physically drying paints, especially those formed from solutions, are sensitive to solvents (dissolution or swelling). The physically drying coatings also include many powder coatings that contain thermoplastic binders. Film formation takes place by heating the powder that has been applied to the substrate above its melting point. This ensures that a sealed film of polymer is formed.

Plastisols and organosols are a special case of physically drying coatings systems in which the binders consist of finely dispersed poly(viny1 chloride) or thermoplastic poly(meth)acrylates suspended in plasticizers. Organosols also contain some solvent. On drying at elevated temperatures, the polymer particles are swollen by the plasticizer, a process known as gelation.

Chemical Drying Chemically drying paints contain binder components that react together on drying to form cross-linked macromolecules. These binder components have a relatively low molecular mass, so that their solutions can have a high solids content and a low viscosity. In some cases, solvent-free liquid paints are possible. Chemical drying can occur by polymerization, polyaddition, or polycondensation.
When polymerization is used as the hardening principle, reactive components combine to form the binder, e.g., unsaturated polyesters with styrene or acrylate monomers. Here, one component often behaves as a reactive solvent for the other, and low-emission coating systems are the result. Cross-linking can be carried out at room temperature (cold curing) or by radiation curing.

In drying by polyaddition, low molecular mass reactive polymers such as alkyd resins, saturated polyesters, or polyacrylates react with polyisocyanates or epoxy resins to form cross-linked macromolecules. Because this reaction can take place at room temperature, the binder components must be mixed shortly before application. The period of time during which a coating of this type remains usable after mixing of the components is known as the pot life. These are known as two-pack coatings, differing from the onepack systems, which can be stored for months or even years. Chemically blocking one of the polyaddition binder components (e.g., the polyisocyanate) gives a coating system stable at room temperature. Heat is required to deblock the component and enable cross-linking to occur. Stoving paints of this type are used in industry and in powder coatings.

Polycondensarion drying requires the addition of catalysts or the use of higher temperatures. Acid-catalyzed coatings are well-known cold-curing paint systems used in the furniture industry, while heat-curing and stoving paints are used as industrial and automotive coatings. The binding agents used are functional alkyd resins, saturated polyesters, or polyacrylates in combination with urea resins, melamine resins, or phenolic resins. On cross-linking, water, low molecular mass alcohols, aldehydes, acetals, and other volatile compounds are released.

Note: In practice drying of coatings and paints does not take place by one method alone. With solvent-containing and waterborne heat-curing coatings, physical drying by solvent evaporation always precedes chemical drying. Depending on the composition of the binder system, physical and chemical drying can take place simultaneously, and the various mechanisms of chemical drying can proceed concurrently or consecutively, depending on the nature of the binder. A knowledge of binder composition is important in order to assess the drying of a coating and able to accelerate it by heat, radiation, and addition of catalysts.

CROSS LINKING FILM FORMATION EVAPORATION BASED FILM FORMATION COALESCENCE BASED FILM FORMATION

CROSS LINKING FILM FORMATION

Some of the highest-performance coatings films are based totally on the reacting of polymer precursors to build up a threedimensionally cross-linked network. . This is at once both a very old and a very new technology. During the middle Ages drying oils were used without solvent to formulate a paint that formed films totally by oxidative cross-linking .

When they react with oxygen in the air, these oils cross-link to form network polymers that have decorative and protective properties. Drying oils modified with soluble natural resins such as tree gum and rosin and naturally derived solvents such as turpentine are known as varnishes. When cast and allowed to dry (more accurately, harden) on various substrates, varnishes form films by evaporation of the solvent and by the cross-linking reactions of the unsaturated fatty acids in the oils. The cross-linking reactions are quite complex, but they essentially involve the addition of atmospheric oxygen to the fatty acids, leading to the formation of hydro peroxide derivatives of the fatty acids. These hydro peroxides decompose, especially in the presence of driers such as white lead or cobalt naphthenate, to form free radicals , which then cross-link with the remaining unsaturated fatty acid.

New cross-linking technologies are based on two-component 100-percent-solids reactive systems that are mixed just prior to or during application and form the final polymer coating by rapid cross-linking. An example is the reaction of isocyanatecontaining compounds with alcohols to form polyurethane. In many cases, solvents are used to control viscosity, which can increase considerably as rapid polymerization proceeds. Furthermore, a catalyst is often required to help the reaction reach completion within the time and temperature requirements of the specific application.

EVAPORATION-BASED FILM FORMATION

In this mode of film formation, the molecular weight and the properties of the polymer to be used in a coating are fully developed before being dissolved in a solvent; pigments and additives are then added to develop the fully formulated coating. The liquid coating is applied to a substrate and the film forms solely by solvent evaporation, which leaves behind a solid coating.

Evaporation-based film formation is based on low solids content and large amounts of organic solvents. It is one of the fastest and simplest methods of film formation and was the basis of the nitrocellulose lacquers used in automotive production lines from the 1920s to the 1950s; it is still the mode of film formation of many spray paints. But it is a mode of film formation that, by itself, releases large quantities of solvent into the atmosphere. For this reason the use of lacquers (as coatings that form films solely by solvent evaporation are often called) has become severely limited by environmental legislation.

COALESCENCE-BASED FILM FORMATION

If small polymer particles of 0.05 to 1.0 micrometre in size are formed as dispersion in water or organic solvent and if the polymer is above its glass transition temperature (Tg) and is rubbery in nature, then a clear polymer film may form after the dispersion is applied to a substrate. The polymer particles suspended in the water flow together, or coalesce, to form a film because of surface-mediated forces. If the polymer is below its Tg and is therefore in a rigid, glassy state, a small amount of coalescent (a solvent that will plasticize the polymer and lower its effective Tg) is added to the system to assist film formation. This coalescent later evaporates, leaving the solid polymer film .

Coalescence-based film formation takes place mainly with latex polymers, but it also occurs with systems in which the polymer particles are dispersed in an organic solvent. However, limitations on the use of organic solvents have made water the predominant carrier solvent. Another mode of film formation closely related to water-based coalescence is the melting and fusing of solid paint particles such as occurs in what is known as powder coating, a process in which an object is coated by a spray or fluidized bed of pigmented polymer particles and the particles are fused by heating to form a continuous film. Other reactions may occur during the melting and fusing processes, but the predominant film-formation reaction is the fusing, or coalescence, of the particles.