SYNTHESIS REPORT FOR PUBLICATION

PROJECT N“: CR-1112-91

C O N T R A C T N “ : BRE2-CT93 0 6 3 5
STARTING DATE: 01.12.93 DULRATION: 2 YEARS

TITLE: “DEVELOPMENT OF AQUEOUS BASED VARNISHES FOR USE IN

INTERIOR WOOD” (VINTEW}

PROJECT COORDINATOR: CJDEMCO

PROPOSERS: PRODUCT(M SOLRAC R&D PERFORMERS: CIDEMCO

ALBUS S./$+. CTBA
DSM RESINS
BARBERAN S.A.
SKM ESP@OLA S.A.
BYK CHEMIE GmbH
DANONA S. COOP.
LEROA S. COOP.
CELIL1OSE PEINTURES ET VERNIS
CUISINES SCHMIDT
TINTAS 2000

FOR THE PERIOD FROM: 01.12.93 TO: 30.11.95

PROJECT FUNDED BY THE COMMISSION OF THE EUROPEAN

COMMUNITIES UNDER THE CRAFT ACTION OF THE BRITE-EURAM
PROGRAMME
 DEVELOPMENT OF AQUEOUS BASED VARNISHES
FOR USE IN mTTEl?UOR WOOD

M. Txoperena, 1. Garmendia, A. Lanchas. CIDEMCO

B 0 Landeta sh, 20730 Azpetia, (Spain)

1. ABSTRACT

A project supported by the European Community has been developed to achieve water based
varnishes for industrial use in the wood coating in furniture field.

In the project developed between December 1.993 and November 1.995 different related to wood
and furniture fields have worked together in the development of an ambitious project.

m The companies belong to several countries of the EC and consider different areas of the coating and
painting field.

The group has developed the technology for the use of waterborne coatings systems for interior
industrial coating of wood.

2. INTRODUCTION. OBJECTIVES OF THE PROJECT

The aim of this project was to reach the biggest degree of development in the technology of
waterborne varnishes possesing as adequate performance in several areas.

First stteps considered the characterization of adequate raw materials to improve positive
performances in final formulations. Taking all this information performant formulations could be
prepared.

The initially objective considered was the development of water-based varnishes with low solvent
emision, non toxic, fire proof, safe and healthy to offer an option face to the current solvent-based
materials for interior woods varnishing in furniture industries and the “do it yourself” works at
home.
 At the same time, it is necessary to develop the suitable machinery for a correct appl ication of the
new materials. Applying systems must be adequated to the characteristics of the waterborne
systems. Only the conjunction of desirable characteristics in machinery and coatings will reach the
required performances.

2.1. Different objetives were considered:

1.- Industrial obietive: The development of the products had to be enough to get at least a
varnishing process for various application fields commonly used for internal wood varnishing in
furniture industries.

The developed complete process must to be incorporated at the end of the project in the productive
process of furniture enterprises taking part in the development (from Spain and from France).

These enterprises were considered to be as a real and tangible base to promote and divulge the use
of those products all over the furniture sector, firstly in their own countries and after in the rest
of the community countries.

11. The technical obietives to reach to get the industrial ones were the following:

A.- To obtain a range of water-based produc~s for interior woods varnishing in furniture
industry, fixed to the basic necessities of furniture industries related to chosen
B manufacturing processes.

B.- To deve~ope and/or modify the application and drying industrial systems which allow to fit
the requirements of water-based products in industrial installations and to reach the optimum
final properties. These installations industrially tested in a pilot plant.

c.- To study the factor that influence the formation of a wet film over water-based products
(nettability, compatibility, contact angle, minimum temperature for film formation, etc.)
related to supports used in these industries (wood and decorative plastic surfaces).

~.- Industrial and technical objetives have a wide repercussion over generai obietives:

A.- To increase the knowledge of water-based products, with have a great future in the
industrial application, by extending its applications to specific uses (furniture).
B.- To develop new product formulations, suitable to industries and capable to comply EEC
environmental reglamentatiom concerning the emision of solvents (VOC ‘s) into the
atmosphere (ranged as dangerous and toxic substances).

c.- To improve safety and hygienic working conditions, as well as interior environmental
conditions:

.- Non risk of fire and inflammability.

.- Possibility to applicate them in places with low ventilation and by non-skilled staff,
avoiding healthy and hygienic problems because of exposure and inhalation of these
substances.

3. TECHNICAL DESCXII?TION

The development of the project is based in some points or tasks. First steep has been a waste
analysis of the raw materials involved in the formulation of the varnishes and paints. This task
provides the knowledge to select the most interesting raw materials for each case. Besides, it
brings us the way to develop new most performing raw materials.

Resin is the major part at any formulations contributing with basic characteristics. All these resins
can be taken as major formulating parts or like resins with modifying properties in total
formulations when they are added in a low percentage.

Required properties for the different resins are the following ones:

.- Right forming of the film

,- Habitual hardness in solvent-base products
.- Enough elasticity controlled by measures of elastic recovery using a Vickers pressing
method
.- Ageing resistance
.- Viscosity (High viscosity implies a low solid content to the application viscosity)
.- Minimum temperature of film formation (T.M. F. P.) less than 30-40% which allows no
more than 5 % of coalescent addition to reduce the minimum temperature of film formation
until app~ications limits (minimun 5°C)
. -. Glass transition temperature (material thermic behaviour)
.- General properties (gloss transparency)
 The most suitable resins will be chosen depending on the characterization of these and other basic
properties to follow the study, so right suggestion will be given to resin manufacturers to modify
their raw materials characteristics. Resin characteristics to be modified are defined by:

.- Monomers configuration, which influences over all kind of properties like: Viscosity,
pigment humectation, adhesion on different substrates . . .

.- Particle size, molecular mass and its distribution, which influence on particle compaction
and subsequent f~lm formation influencing cn transparency, glass transition temperature,
abrasion resistance and viscosity.

.- Plasticiser use tendering the fiIm and also operating on the hardness, glass transition
temperature...

.- Polymerization auxiliar additives. Polymerization system and kind of emulsifier infuence

on stability behaviour when put in storage and on water coating resistance.

Coalescent are added to formulations to allow a right formation using a temperature lower than
the temperature of film formation (M. F. F. T.) of the isolated resin (allowing coalescence or particle
union). The added coalescent percentage is important because it’s part of an organic solvent which
is maintained in a water-based varnish formulation being reduced at lowest rate.

For each resin it has to be found the coalescent which reduces the most the film formation
temperature using the lowest percentage.
I
The influence of a wide coalescent range will be studied (simple and combined) related to the drop
of temperature films formation of chosen resins, which promote the maximum cohesion with a
maximum evaporating velocity (properties of developing time). The reduction of final properties
to be controHed are: hardness development, adhesion, water resistance, miscibility, glass transition
temperature, abrasion resistance, scratching resistance, chemical resistance and gloss. Just like
others effects of system application to be controlled:

.- Drying time (evaporation curve)

.- Rheological properties (material viscosity)

y
.- Support s nettability and static surface tension
 The basic properties of a formulation are contributed by resins, but there are properties which can
be improved and modified by some product’s addition. All additives have to be considered in their
best use dimensions within some strict percentages because an overdose can cause problems over
bigger then the ones we are trying to avoid using additives. Also, as a rule most of additives are
water sensitive reducing washing capacity and emulsified covering duration, therefore they must
be used in a fair way.

The following raw materials have been studied:

* Drvirw agents, acting over drying velocity (cobalt, magnesium drying agents)

* Defoamers, because aqueous systems are capable of making form soft during preparation
and application. It’s very important to find a combination of nonfoaming agents which are
able to provide a right air exit, when related to spray-gun and curtain application, and
removing the mocrofoam which is produced when it’s applicated using a roller. Because
defoamer agents when they are added are very ofen silicones, their wrong dosage can cause
craters, bad extensibility and low brightness.

* Ultraviolet absorbents in emulsion have to be considered to avoid the photooxidizing

degradation of }igands and wood surfaces.

* Photoinitiatimzs and reactive monomers in the case of photopolymerizating varnishes

* Biocides. antiflotationin~ aizents and antised imentation

* Dis~ersants which have to act as pigments’ humidifying agents but also as dispersion
stabilizer during storage and drying and geological additives providing stabIe viscosity and
pH of the system during storage and application.

* Thickners. If we have a very low viscosity we must use auxiliar thickners because the
thickness given by the resin is very low having a strong influence on consistency,
application workability, leveling, drying and storage stability and secondary effects on
brightness, water sensibility, viscosity, phase separability, pigment flocculation.

For non-transparent systems it will be studied the right kind of pigment and filling substances to
a be used, as well as the pigmentation system which could be dealt with the following points of view:

.- Preparation of pigmentary pastes in water humidifying and thicknering agents

.- LJsing a willing agent (for example an acrylic and colloidal emulsion with a highh pigment
absorption}

During the elaboration of a finished lacquer it’s important not to disturb the acidity alkalinity
delicate balance of the emulsion (factor related to volubleness and stability in pigment dissolution).
For this reason it’s necessary to avoid incorporating filling substances and additives which might
rnodif y the pH value, as well as for example alkaline loading, adhes ivit y promoters, acids or
catalyzers.

The influence of fineness, type of pigment and its voiume concentration on different properties
(microhardness, adherence, impact resistance, bright resistance, specially near critical concentration
of pigment on volume) will be taken into account. The use of pigment humidifying agents deserves
a special chapter to be able to get the most beneficial bright.

With all the information about raw materials obtained in the raw materials study, manufacturers
~{ill make under their experience and knowledge formulations they consider feasible Which wi] 1 be
sent to the laboratories of two research centers for following evaluation.

Besides, the technological centers have studied and characterized the european products found in
the different countries. This is an interesting help to know which are the qualities of the products
in each market.

The studied products are water-based or solvent-based. This will be a way to test the Ievel reached
by the products developed in the project.

Because the whole products used now, for wood coatings and plastic surfaces, are solvent-based
products, these products have to mark some reference conditions to be reached by new water-based
developments. The solvent-based coating to be considered are the following ones: Varnishes or
nitrocellulose lacquers, pol yurethanes, ureas, polyesters and photopolymerizab les coatings.

Characteristics shown by products will be studied divided in different groups of properties like:

General urouerties

Control of sediment or skin generation and storage stability

Right density
Viscosity and theological properties which allow a suitable application using the different
systems known as guns, rollers, curtains, keeping on the other hand a suitable dried content
or dried weight.
 Dried weight, the highest one to get in each application the rnaximun deposited dried
substance
Right pH, which also have a great significance over the emulsion stability, higher or lower
stab ility values drive to hydrolysis of resin material and to the emulsion’s coagulation
Thermic behaviour
Minimun temperature of film formation (M. F. F. T.)

ph;rs~cal and chemical ~rouerties

Light ~esistance by artificial ageing to know the 1 ight resistance of different products and
the improvements achieved adding ultraviolet absorbents and water-based tertiarial amines.
Cold-check resistance: varnishes have to be flexible enough to bear dimensional changes of
the support neither breaking nor showing damages in dried film because of temperature
changes.
Chemical product resistance, looking for the rnaximun stain resistance (blisteres, bright
losing) by contacting home use products or solvents. This property requires a bigger
incidence related to necessary improvements to be on a level with solvent based varnishes.

‘s Mechanical mo~erties

Adherence to different used supports to be covered

Abrasion resistance, mechanical wear has to be kept at low limits which allow the material
continuity in time.
Hardness, both superficial and to penetration (vickers). Hardness has to reach some
minimun values to be acceptable tub also it has to be obtained in a period of time which
can’ t be to much long, to allow to pile and manipulate them.

A~Plication and drvimz DroDerties

II
Nettability and contact angle, constituted with surfaces (surfaces tension)
Extensibility, lifting tendency, porosity disappearance microbubbles
Theological properties
Interaction and removal of previous dyes, with possible appearance of glazing and lack of
brightening
Leveling, workability
 Drying, necessities of energetical contribution, achieving time of final physical and
mechanical properties, minimun temperature film formation and a coalescence formulation
obtained with the highest performance wil [ be the groundwork to use to get the following
taks .

Next steep has been to characterize surface properties of different supports chosen as coating
application base, which covers different kind of industrial surfaces on furniture and trading floor
industry.

The support, used as a coating base, has a basic influence over material application properties
because of its different interracial tensions. Also in the case of using water as a solvent, covering
porous substrates which can absorbe the aqueous @se, the surface hasn’ t got the necessary
percentage of cosolvents to get the suitable film formation at fitted temperature.

For each selected wood and also in the case of decorative plastic surfaces, the wet film evolution
wil 1 be followed until dry state observing the different influences of porosity size, roughness
sommothing and grain conditions. Surface quality will be guarantied by nettability radius.

It has to be taken into account in the case of wooden supports that the nettability over the support
changes as a function of humidity percentage of the support.

Water-based products can create problems with grain lifting, waving and others irregularities when
they are used with resinous woods.

Industrial machinery manufacturers have modified the material application equipment to the new
application needs with an action of changes and development of new components and systems.

The efficiency of the technical application systems is basic to reduce the quantity of material used
in it as well as the application qua] ity. The development of this task has to be directed to two faces
which are complementary:

Formulation matching, formulation will be as far as possible adjusted to be compatible with the
application systems developed to solvent-based products.

EcmiDment control and new develo~ments: Coordinating with two manufacturers of painting
application systems equipment it is expected the development of new equipments which allow to
so}ve problems related to industrial application of water-based products. It has to be taken into
account water corrosive characteristics when manufacturing materials of application systems have
to be selected.
The difference kind of systems to be checked and modified am the following ones: Roiling
machines, Curtains, and pneumatic, air mix, airless and electrostatics spray guns.

With the support of coating manufacturers and laboratories, convenient changes w i] 1 be introduced
in former machinery or will build new application prototypes related to the specific problem shown
by the. application of selected formulation.

Problems derived from the use of those water-based materials will be tested on the app! ications,
which have beenmade during the first formulating test, and the results will be delivered to
manufacturers of resins, additives and varnishes and with a joint consent to improve the quality of
Iigands, in order to obtain a final good more suitable as far as possible.

Drying evaluation have been checked to study the most beneficial mater;al drying conditions taking
into account the admissible limits in productive systems.

The type of coalescent used has a high influence on the drying of a waterborne system. The
coalescent plays an important role in the film formation and the ability and speed presented by the
coalescent to leave the formulation to get a dry film has been studied.

Last steep has been the industrial process evaluation working with the developed products in pilot
plants and comparing the results with present systems.

The idea is to verify the development of the new types of aqueous base varnishes ans shellacs
specifically designed for interior woods in industrial plants. The idea is to see which is the
performance of the new products in industrial plants. Besides, the performance of new application
machines were tested at an industrial leveI.

4. RESULTS

Industrials trials experience with waterborne varnishes and machinery from the project has been
really positive. They have been observed interesting results at the end of the project.

Many new waterborne formulations of coatings have been presented by the three manufacturers
invoived in the project. They offer good chemical characteristics and the application problems have
been exceled. The aspect offered by the products is aesthetically pleasant.
Besides, raw materials have successfully performed and new materials offer better characteristics
and qualities.

The project has helped to know better the characteristics of the products and the substrates.

5. CONCLUSIONS

Waterborne systems application over interior wood nowadays a fact. After two years of team
work, the Consortium has reached a high degree at of technical level.

Varnish companies have developed many waterborne products for interior wood. It k possible to
find varnishes or pigmented systems. They have created primers and topcoats bringing many
possibilities of gloss and colour. Besides, all those products present as well good chemical
properties as resistance and hardness. Their aspect is acceptable nice and they are able to be
competitive with some solvent products.

Although technical problems are overcome, now it is time to see how they can to be inserted in the
market. We suppose that maybe their prizes will be initially a problem to be competitive
comparing with solvent products. Anyway, there is no doubt the time will reduce their prizes and
they will be more and more present in the market. The present and the futur are waiting for them.

Their use will bear with the change of the application machinery used with solvent products.
Machinery has been modified and accommodated to the problems and characteristics presented by
the waterborne systems. A new machinery has been developed for waterborne systems.

Industrial applications have been really succesful and it has been observed a big progress in ali the
products developed by the varnish companies. They are ready to be presented in the market.

Besides, all the knolodgements adquired by the companies wiU be helgful to develop more and
more products and maybe with better properties.

Raw materials characterization and the work developed by resin companies has got to develop more
waterborne resins. The characteristics and properties of the new resins are quite superior to the
initial ones two years ago, it was difficult to find a resin with good properties. Nowdays, there
are many possibilities. This steep has been basic of course for the final results.

Taiking about additives, it has happened something similar than with the resins. There have been
developed new additives specially designed for waterborne systems really interesting.
 So, technically the project has been greatful. All the areas have ameliorated beggining from the
raw materials and ending in the application machinery.

Attheend, many waterborne products designed for interior wood have been succesfully developed
and applied.

6. ACKNOWLEDGEMENTS

All the partners and R & D performers of the project want” to acknowledge the collaboration of the
Consortium to achieve the objectives of this project.

1= The Consortium wants to acknowledge the invaluable help of Mr. Mario Mizlinconico (Project
Technical Advicer) as well as to Mm. Maria Douka @ojec& Scientific Officer) and Mrs. O.
Demuth accomplish correctly all the points, technical and burocratics, of the project. Thanks too
to the European Commission by their economical support, so needful for the execution of the
project. Without this support, the research would not have been possible.

7. REFERENCES

(1) S.z. CHOW

“Infrared spectral characteristics and surface inactivation of wood at high temperatures”
Wood Science and Technology, 5, 1971

(2) R.M. ROWELL, A.M. TILLMAN, R. SIMONSON

J.Wood Chem. Technol., 6, 1986

(3) LUCAS, PAUL; SMITH, LEONARD

“Effect of solvent choice on water-based coating/wood combinations”.
J .Coa.Technologie,v 57

(4) P Schirmann, M Dexterm Handbook of Coating Additives, Marcel Decker Inc, New
Yorkl%sle 1987,225

(5) G Berner, G Deslex, F Schoohf, Fatipec Congress, Amsterdam 1980, Volume II, 61.
 (11) M HoIt, D Bramer, Co~gressbook 13th Int. Conference on “Advance in the Stabilization
and Degradation of Polymers”, Lucerne 1991, 23

(12) F Gugumus, “Current Trends in mode of Action of Hindered Amine Light Stabilizers”, 16th
Annual Meet~ng of “Polymer Stabilization & Application; Birmingham, Sep. 1991 (to be
published 1992 in Polymer Degradation and Stability),

(13) E Denisov, Polymer Degradation and Stability 34 (1991), 325

(14) D R Baue, M J Dean, J L Gerlock, Ind. Eng. Chern. Res. 27, 1988, 65

(15) J L Gerlock, I) R BAuer, D F MieIewski, Congress book “ 1 lth Int. Conference O n

Advances in the Stabilization and Controlled Degradation of Polymers”, Lucerne 1989,25

(16) E Haring, J Reh, K Sonnenberg, Farbe + Lack, 88 [1982), 1004

(17) A Hult, Y Yuan, B Ranby, Polymer Degradation and Stability 8 (1984), 241

(18) A Hult, B Ranby, Amer. Chem. Sot. Symp. Series, 266 (1984), 457

(19} N S Allen, P J Robinson, N J White, Polymer Degradation and Stability 19 (1987), 147

(’20) K J 0’Hara, PoIymers Paint colour Journai, VOI. 175, No. 4154 (1985), 776

(21) L R Gatechair, H J Evers, “Progress in Improving the Weatherability of Radiation Cured

m Coatings”. Paper presented at the Waterborne& Higher-Solids Coatings Symposium. Feb.
(22) B Ranby, AHult, Org. Coatings(7) 1984, 137

(23) Zhao, C-L, Wang, Y., Hruska, S., and Winnik, M. A., “Molecular Aspects of Latex Film
Formation: An Energy Transfer Study, ” Macromolecules, 23, 4082 (1990)

(24) Wang, Y. Zhao, C-L., and Winnik, M. A., “Molecular Diffusion and Latex Film
Formation: An Anal ysk of Direct Nonradiative Energy Transfer Experiments, ” J. Chem,
Phys., 95, 2143 !1991)

(25) Winnik, IvI. A., Wang, Y and Zhao, C-L., “Polymer Diffusion in Latex Films, “in
Photochemical Processes in Organized Molecular Systems. Honda, K (Ed,), Ek-evier
Science Publications, p 275, 1991

O’ Connor, D .V. an Phillips, D, Time - Correlated Single Photon Counting, Academic

Press, London, 1984

(27) Ber]man, I. B., Energy Transfer Parameters of Aromatic Molecules, Academic Press, New
York, 1973

(28) Forster, T., Discuss, Faraday Sot., 7, 27 (1959)

(29) Crank, J. and Park, G.S. (Eds.), Diffusion in Polymers, Academic Press, New York, 1968

(30) Crank, G. S., The Mathematics of Diffusion, Clarendon Press, Oxford, 1975

(31) Child, W.C. Jr. and Ferry, J. D., “Dynamic Mechanical Properties of Pol y-n-Butyl
Methacrylate, ” J. CoIl. Sci, 12, 327 (1957).

(32) J. Prideaux: Surf. Coat, Int. 76 (1993) (4), pages 180-183

(33) E.J. Schaller and P.R. Sperry. Handbook of Coatings

Additives, Marcel Dekker, Inc., New York, Basel, Hong Kong Vol. 2, 1992, Chap. 4,
pages 105-163

(34) J. Ph. Kaczmarski, R.H. Fernando and J.E. Glass J. of Coat. Technol. 65 (1993) (818),
pages 39-46

(35) T. L. Mavex J. of Coat. Technol. 64 (1992) (812), pages 45-58

(36) P . R . S p e r r y , J.C. Thibeault and E.C. Kostansek: 1 Ith Proc. lnt. Cont. IRg. Coat. Sci.
Technol. New Paltz. N. Y., pages 1-11

(37) J.H. 13ie]emann, F.J.J. Riesthuis and P. M., van der VeIden Polym. Paint. Col. J. 176 June
H, 1986. No. 4169

(38) H.N. Nae and R. H. Bank: Rheology 91, October 1991, pages 170-178

(39j F.G. Schwab: ADv. Chern. Ser. 213 (Water. Soluble Polym.), pages 369-373

(40) A.J. Whit ton and R.E. van Doren. Polym. Paint. Col. J. 181, June 26, 1991, pages 372-
375

(41) A.J. Bielemarm: Polym. Paint CO]. J. 181, May 15, 1991, No. 4283

(42) P.R. Howard et al: PoIym. Mater. Sci. Eng. 61 (1989), pages 619-623

(43) J. C. Thibeault, P.R. Sperry and E. J. Schaller

Adv. Chern. Ser, 213 (WAter-Soluble Polym), pages 375-389

(44) A. Karusena and J.E. Glass. Org. Coat. Appl. Polym. Sci. Proc. 56 (1987), pages 624-628

(45) T. Muzakrni, R. 1-1. Fernando and .l.E. Glass: J. Oil Colour Chem. -4SSOC, 71 (1988)(10),
pages 315-323

(46) Brown, B .K. and Crawford, F. M., Survey of Nitrocellulose Lacquer, The Chemical Catalog
Company, Inc., New York, 1928, p 4.

(47) Imperial Chemical Industries, Ltd., French Patent 683, 728 (Oct. 22, 1929)

(48) Martin, R. C., Lacquer and Synthetic Enamel Finishes, D. Van Nostrand Company, Inc.,
New York, 1940, pp 170-171

(49) Creasy, J., “Nitrocellulose Emulsions for Leather Finish ing, ” J. Sot. Leather Trades’
Chemists, 34, 113-16 (1950).

(50) Hirt, R. P., “Preparation and Performance of Nitrocellulose Lacquer Emulsions, ” TAPPI,
(51) Zoia, J. C.. U.S. Patent 2, 591, 904 (Apr. 8, 1952)

(52) Tremain, A. and Morris, W., “Single-Coat Multicolor Finishes, ” Paint Technolo., 21, 83-7
(1957)

(53) Winchester, C. M., “Waterborne Nitrocellulose Wood Lacquers with Lower VOC, ” Proc.
18th Annual Waterborne. Higher Solids, and Powder Coatings Symposium, 367 (1991);
JOURNAL OF COATINGS TECHNOLOGY, 63. No.803.47 (1991)

(54) Murphy, C.V. and Zunker, .D.W. (to E.I. du Pent de Nemours and Company), U.S.
Patents 3, 953, 386 (Apr.27, 1976) and 4,011.388 (Mar. 8, 1977)

(55) Adams, J.W. and Vltavsky, H., “Combating Foam and Air-Entrapment in Coatings,” Pro.
17th Annual Waterborne, Higher-Solids, and Powder Coatings Symposium, 389 (1990)

{56) Ball, F. M. “Plasticization of Coatings, ” in ‘Treatise on Coatings , Volume I, part III,

Myers, R.R. and Long, J.S. (Eds.). Marcel Dekker, New York, 1972, pp 182-189

(57) Sao, K. “The Hardness of Coating Films, ” Progr. Org. Coat., 8, 1 (1980)

(58) Zunker, D-W., “Unique Aqueous NitroceiIulose/Acry lic Air-Dry Systems for Industrial
Finishing, ” JOURNAL OF COATINGS TECHNOLOGY, 48, No. 616, 37 (1976)

(59) Chainey, M., Wilkinson, M.C. and Hearn, J., “Permeation Through Homopolymer Latex
Films, ” J. Polymer Sci., Polymer Chem. Ed., 23, 2947 (1985)

(60) Patton, T. C., Paint Flow and Pigment Dispersion, Wiley -Interscience, New York, 1979

(61) Eckersley, S.T. and Rudin, A., “Mechanism of Film Formation from Polymer Latexes, ”
.TOURNAL OF COATINGS TECHNOLOGY, 62, No. 780, 89 (1990)

(62) Joanicot, M. Wong, K., Maquet, J. Chevalier, Y., Pichot, C., Graillat, C., Kindner, P.,
Rios, L., and Cabane, 13., “Ordering of Latex Particles During Film Formation, “Prog.
Coil Polymer Sci., 81, 175 (1990)

(63) Protxman. T.F. and Brown, G. L., “An Apparatud for the Determination of the Minimun
Film Temperature of Polymer Emulsions, “ .T. Appl. Polymer Sci., 4, 81 (1960)

(64) ASTM D2354-68m “Standard Test Method for Minimum FiIm Formation Temperature of
Emulsion Vehicles, ” ASTM. Philadelphia, PA
Bradford, E.B. and Vanderhoff, J. W., “Morphological Changes in Latex Films, ” J.
Macromol. Chem., 1, 335 (1966)

Voyutskii, S. S., Autohesion and Adhesion of High Polymers, Wiley .Interscience, New
York, p74, 1963

Turner, G.P. A. Introduction to Paint Chemistry, 3rd Edition, Chapman and Hall, London,
pp 144 ff, 1988

Karsa, D.R. (Ed), Additives for Organic Coatings, Royal Chemical Society. London, 1990

Ferry, J .D., Viscoelastic Properties of Pol ymers, 3rd Edition, J. Wiley, New York, Chapter
17, 1980

Yoo, J.N. Sperling. L.H. GIinka, C.J. and Klein, A.., “Characterization of Film Formation
from Polystyrene Latex Particles via SANS 2. Moderate Molecular Weight,
“Macromolecules, 23, 3962 (1990); “Part 2. High Molecular Weight, “Macromolecules,
23, 3962 (1990): “Part 2. High Molecular Weight, ” ibid, 24, 2868 (1991)