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The Modern Paint Manufacturing Era

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The Modern Paint Manufacturing Era

The Modern Paint Manufacturing Era

Outline of some Historical Dates (by Stuart Croll NDSU 2009)

Paint in 1844

Charles Goodyear discovers that heating sulphur containing natural rubber produces a

very elastic solid. This is "vulcanization" and the first crosslinked polymer.

Paint in 1846

"Gun cotton" (cellulose trinitrate) was patented by Schonbein, although one can probably

trace nitrated cellulose back to Henri Braconnot (France) in 1832.

Paint in 1865

Alexander Parks (England) treats cellulose nitrate with other materials (that we now

know were plasticizers) to make (and patent) 'Parkesine', with which he could make

some simple articles for display for the Royal Society of Arts. Later (1869) patented by J.

W. and H. Hyatt in USA (the bounders!) when they improved Parkesine as Celluloid,

being the first commercial plastic that modern users would recognize.

Paint in 1905

Paint and coatings research starts at North Dakota Agricultural College, now North

Dakota State University.

Phenol-formaldehyde resins ("Novolac" resin) made by Leo Hendrik Baekeland, patented

in 1907: "Method of Making Insoluble Products of Phenol and Formaldehyde". These

are better known as Bakelite.

A. H. Munsell, a painter and art teacher, publishes his colour notation system; the first

useful description of a colour space.

Paint in 1912

Dispersion polymerization of isoprene patented in Germany by Kurt Gottlob (German

patents 254 & 255). Used egg albumin or starch as emulsifier.

Acrylic resins patented.

Paint in 1913

Rosin-modified phenolic resins

Paint in 1914

Polyvinyl acetate patented by Klatte and Rollet.

Paint in 1914-18

First synthetic detergents developed in Germany during World War I. They were shortchain

alkyl naphthalene sulphonates. Similar materials are still used.

Paint in 1916

Joel H. Hildebrand makes strides in solubility theory for non-electrolytes.

Paint in 1917

Staudinger presents the macromolecular concept at a meeting of the Swiss Chemical

Society. He received the Nobel prize for this discovery in 1953.

Paint in 1920

Staudinger publishes macromolecular concept: Staudinger, H. Ber. Deut. Chem. Ges.

Paint in 1920, 53, 1073

DuPont scientists make a fast-drying lacquer from nitrocellulose. Dupont had a

background with nitrocellulose since it had been making it for explosives since the 1890s.

Patent applied for use of Aluminium and Zinc Stearates as pigment stabilizers in oil

paints (US 1,421,625 in 1922). Metal soaps had been known to help stabilize pigments

for some time before this.

Paint in 1922

DuPont patents nitrocellulose lacquers.

Paint in 1923

Cellulose nitrate lacquers first used on cars ("Duco" from DuPont). The use came

because a low viscosity resin (sprayable at useful solids) was discovered by DuPont in

1920 (see above), as opposed to the very high molecular weight resins that been

investigated prior to that. This was taken up by many of the companies that later became

General Motors, Chrysler and Ford. Ford most famously used it as one of the enablers

for assembly line production. Previously, the oil paints had needed 3 - 6- weeks to cure

and be dry to the touch on the vehicle.

Paint in 1925

BASF (Glasurit-Werke) introduce nitrocellulose car paints in Europe.

"Tamol" name first used for compounds in dying, tanning and textile industries (see


Paint in 1921 - 1925

Alkyd resins introduced but they were slow drying, even when baked. Note: one can

trace polyesters back to Berzelius who condensed glycerol tartrate in 1847.

Maleated rosin varnish gums introduced.

Paint in 1920s

Spray guns developed.

R. H. Kienle of GE develops unsaturated alkyds.

Paint in 1926

Paint Research Station founded in UK.

GE introduce Glyptal® resins (glycerol phthalate)

DuPont introduce alkyd resin (glycerol/phthalic anhydride/linseed oil). Alkyd modified

oil paints and then alkyd paints were eventually used on cars and household appliances.

Paint in 1927

R. Kienle et al. of G.E. patents alkyds, but the patent is ruled invalid in 1935 due to prior

art, which enables other companies to make and sell alkyds (after 1935). Kienle was

probably responsible for the combination of the word alkyd - from the condensation of

alcohols and acids.

Paint in 1928

R. H. Kienle and C. S. Ferguson present a paper at an ACS meeting in September,

entitled "Alkyd Resins as Film-Forming Materials. This was published in 1929 in Ind.

Eng. Chem.

Paint in 1929

W. H. Carothers (DuPont) publishes on linear polyesters, J. Am Chem Soc, 51, 2560

(1929). He is generally credited with formalizing the concept of functionality, although

Kienle had almost certainly been thinking along the same lines.

Paint in 1930

Paul Flory starts work on molecular weight distributions (experimentally and

theoretically) and shows that step-growth polymerizations follow the Gaussian

distribution for molecular weight.

Rehbinder, Lagutkina, Wenstrom, gain first insights into steric stabilization of colloidal

particles, Z. Physik. Chem. (1930).

Paint in 1931

Commission Internationale de l" Eclairage, CIE, meets in Cambridge and defines the

primary stimuli for colour vision to be red (700 nm), green (546.1 nm) and blue (435.8

nm). The meeting also defines several illumination standard spectra and the first standard


DuPont makes TiO2 pigment by sulphate process, having purchased the Commercial

Pigments Corporation that held the patents. These pigments were sold by the Krebs

Pigment and Colour Corporation (a DuPont subsidiary) as TiPure® but it continued to

make a TiO2 enhanced lithopone as Duolith®.

Paint in 1931-32

DuPont introduce "Dulux" as a brand name for alkyd paint. However, DuPont and Nobel

collaborated in the early 1920s on explosives, as much as anything else, and Nobel used

the name in Europe. DuPont and ICI (UK) started a technical collaboration in October

1929 but dissolved the association in 1952. Clearly, the name "Dulux" stayed with ICI


Luther and Huck patent a method for making a SBR latex material (working for I. G.

Farbenindustrie in Germany), US patent 1,864,078 (June 21, 1932)

Paint in 1930s

Wallace Carothers at DuPont synthesizes aliphatic polyesters, polychloroprene and

polyamide 6,6 (Nylon, patented 1937). Work supported the macromolecular concept and

his definition of a polymer is one that fits modern usage better than Staudinger"s.

Herman Mark, Werner Kuhn, Eugene Guth find that polymers in solution are flexible and

that viscosity is related to molecular weight of the polymer.

P. Castan (Switzerland) and S. Greenlee (USA) patent epoxy resins.

Triton surfactants invented by Herman Bruson (for Rohm and Haas?).

Paint in 1933

National Grid for supplying electricity was established in the United Kingdom by

interconnecting regional grids and was more fully integrated in 1938. Electrical power

was becoming much more available during the 30s". Plenty of coal was available in the

UK and elsewhere for fuel.

Paint in 1934

Mark, Kuhn and Guth generate first statistical mechanical theory for rubber elasticity.

Paint in 1930 - 1935

Urea formaldehyde resins combined with alkyd resins; vinyl chloride was made useful

for coatings (soluble) by copolymerizing with vinyl acetate.

Ford and Chrysler use alkyd enamel topcoats.

Paint in 1933

Schlak patents the first epoxy resins: diglycidyl ethers made from epichlorhydrin and

bisphenol A: German Patent 676,117. Styrene-Butadiene rubber made in Germany

Paint in 1935

Polyvinyl butyral made for use in wash primers.

Paint in 1936

Joel H. Hildebrand identifies the square root of the cohesive energy density as a

quantification of solvency.

Paint in 1937

Urethane resins produced by Bayer for elastomers and foams (urea reaction produces

CO2 naturally).

First commercial production of pentaerythritol - important for alkyd chemistry.

Paint in 1937

Patent 2,071,250 (filed in 1931) Linear Condensation Polymers granted for the work that

leads to Nylon W. H. Carothers (DuPont)

Paint in 1939

Thermosetting acrylics developed by D. E. Strain (U.S. Patent 2173005 to DuPont,1939).

Paint in 1940

Melamine formaldehyde resins.

The paint roller was invented by Norman Breakey of Toronto.

Paint in 1940s

Styrene-Butadiene synthetic rubber latex developed as the "Mutual Recipe" in the USA

(75% butadiene, 25% styrene with a rosin soap and a little mercaptan) since isoprene did

not give a useful material. Production started in 1943. This project involved a number of

universities and large chemical companies in the US at the time and it is claimed that the

project rivaled the Manhattan Project in size and importance

( ).

Flory develops his version of rubber elasticity theory to model the properties of

crosslinked polymers (with Rehner for solvent swelling).

For some historians the "2

nd Chemical Revolution" starts in this period (1

st chemical

revolution took place with the work of Lavoisier and Berzelius, 1780 etc)

Paint in 1941 - 1945

German warplanes use urethane paints (and baffle Allies initially).

Paint in 1941

Derjaguin and L. Landau, publish their version of the DLVO theory [Acta Physicochim.

(URSS) 14 (1941) 633-662.].

First widely sold commercial water based paint: Sherwin-Williams sell "Kemtone®."

The binder used casein, corn protein, rosin and a small amount of linseed oil in an

emulsion with TiO2, chalk, clay and mica.

Paint in 1942

Flory and Huggins in 1942 independently [P. J. Flory, J. Chem. Phys., Vol. 10, 51

(1942); M. L. Huggins, J. Am. Chem. Soc, 64, 1712 (1942)] developed a theory of

solubility and interactions to improve regular solution theory to include better the

connected nature of polymer molecules. Originated "theta" solvent concept.

Paint in 1944

Germans use waterborne paint similar to PVA, for Tiger tanks. Linseed oil was in very

short supply in Germany and it was known their railway rolling-stock was also being

painted with a waterborne finish. [Keith Hammond series in PPCJ, Polymers Paint

Colour Journal Feb-July 2003]

Paint in 1945

GE and Dow Corning announce silicone rubbers for gaskets etc. Silicone polymers are

used in high temperature and weather resistant applications since the silicon is fully

oxidized and cannot oxidize more. They have been used in a wide variety of chemical

resistant applications, coil coatings etc.

UV curing patent to DuPont US patent 2367670, R. E. Christ

Pentarythritol used in alkyds instead of glycerol.

Styrenated alkyds appear.

Paint in 1946

Ciba commercialises an epoxy resin.

Styrene-butadiene latex commercialized for paper coatings

UV curing ink, Inmont, US patent 2406878

Paint in 1947

Dupont introduces the pentarythritol type alkyd paint, which is introduced two years later

in UK [Standeven].

Paint in 1948

First use of styrene-butadiene latexes in architectural paints - Glidden"s "Spred Satin®".

Verwey and Overbeek publish their contribution to what became DLVO theory [E. J. W.

Verwey and J. Th. G. Overbeek, Theory of Stability of Lyophobic Colloids, Elsevier,

Amsterdam, 1948]

Paint in 1947 - 1950

Epoxy resins commercialized [1].

Paint in 1949

Kienle publishes on alkyd resins that dry much faster [R. H. Kienle, Ind. Eng. Chem. 41,

p.726 (1949) ].

Paint in 1950

Hildebrand, in the third edition of his book coins the term "solubility parameter"

[Hildebrand, J. H., and Scott, R. L., "The Solubility of Nonelectrolytes," Chap. XI

(Reinhold Publ. Corp., New York, N.Y., 1950)]

M. Van der Waarden begins to understand steric stabilization of colloids in "Stabilization

of carbon black dispersions in hydrocarbons", Journal of Colloid Science, 5 317-25

Paint in (1950)

Unsaturated polyester resins appear [1], probably following Carothers" work.

Natrosol® registered as trademark for alkali soluble cellulose ethers, and enters the

market for thickeners.

Research into epoxy coatings at Devoe and Raynolds Inc.

Paint in 1951 - 1955.

Epoxy-polyamide resin systems are introduced[1].

Paint in 1951

Acrylic polymers for emulsion paints under development.

DuPont introduces the chloride process for refining TiO2 at its Edgemoor plant.

Paint in 1952

Powder coatings invented in Germany for fluidized bed use.

Thixotropic alkyds (in some ways the forerunner for hydrocarbon environments of

associative thickeners for aqueous systems).

Paint in 1953

First all-acrylic latex introduced commercially: Rhoplex® AC-33 in USA, (= PrimalTM

AC-33 in Europe).

Paint in 1954

Thixotropic alkyd resins introduced [1].

Paint in 1955

Water soluble/dispersible thermosetting resins introduced, e.g. alkyds and acrylics [1].

Paint in 1956

G. L. Brown"s research into latex film formation ["Formation of Films from Polymer

Dispersions," J. Polym. Sci., Vol. 22, pp. 423 - 434 (1956).

Commercial production of isophthalic acid [Alkyd Resins by C. R. Martens, Reinhold

Publishing Corporation NY 1961. (Chapman and Hall Ltd. London)].

Shell introduces amine and polyamide cured epoxy resins.

Paint in 1956 - 1960

General Motors uses acrylics and acrylic-melamine resins in place of some of the

cellulose nitrate and alkyd coatings for automotive finishes.

Urethane Oils and alkyds, thermoplastic acrylics for lacquers, thermosetting acrylics for

enamels, silicone copolymers [1].

Crosslinking latexes are introduced [17].

Paint in 1957

George Brewer develops anodic electrophoretic coatings at Ford Motor Company. See

introduction in 1964.

Paint in 1960

US patent 2930775, composition of a dispersing aid for pigments etc., maleic aciddiisobutylene

copolymer ~ 1:1, corresponds to Tamol 731.

Paint in 1961 - 1965

Fluoropolymers first introduced [look up Teflon].

Paint in 1962

Texanol® registered as trademark by Eastman Chemicals and found use as a coalescing

aid for latex paints by Eastman together with several customers and other resin suppliers

[Del Rector, Eastman Chemical Company, private communication]. The discovery of the

compound was somewhat accidental.

Paint in 1960s- early 1970

First polyurethane dispersions (in water) were patented [D. Dieterich, "Aqueous

Emulsions, Dispersions And Solutions Of Polyurethanes; Synthesis And Properties,"

Progress in Organic Coatings, 9 p. 281 - 340, (1981); Dr. R. Roesler, Bayer Chemicals,

private Communication]

Paint in 1964

Epoxy, acrylic and other resins used for anodic electrophoretic primers - pioneered by

Ford Motor Company (Brewer, 1964). First electrophoretic (otherwise known as

electrodeposition) paint tank filled at Ford Wixom works by PPG.

Eastman built the first plant producing Texanol as a commercial chemical. This

coalescing additive made the application of latex paints possible over a much broader

range of environmental conditions.[Del Rector, Eastman Chemical Company, private


Paint in 1966 - 1970

Ultraviolet and electron-beam cured polymer coatings appear for very fast cure

requirements with low solvent emissions.

Non-aqueous dispersions of acrylics are developed.

Paint in 1967

Los Angeles County invoked EPA Rule 66(5) that regulated the use of potentially

harmful solvents in industrial coatings. This was to restrict photochemically (helped by

UV) reactive solvents that combine with nitric oxide from automobiles and industrial

processes to produce the well-known "smog". Calculations quickly showed that "high

solids" coatings would be necessary. The world changed for coatings in the US. High

Solids means ~ 60% solids by weight or higher.

UV wood coatings (Bayer) (see 1946).

Paint in 1969

Commercialization of UV curing printing ink.

Paint in 1970s

Start of serious work on thermoplastic and thermosetting polyester powder coatings and

rapid development of UV curing compounds.

Paint in 1970

Clean Air Act passed in US.

Paint in 1971

Cathodic electrophoretic paints for automotive use introduced by PPG.

First non-mercurial mildewcide introduced: Skane M-8.

Acrylic polyelectrolyte thickeners introduced.

Paint in 1973-75

Arab oil embargo, shortages of petrochemical feedstock puts more impetus behind

chemistries that avoid use of lots of organic solvents and so attention turned to waterborne

or high solids types.

Paint in 1976

Cathodic electrocoat primer released by PPG.

Acrylic, polyester and urethane oligomers developed for high solids coatings.

Paint in 1980s

The modern "High Solids" age starts here. One might compare it to the Iron Age.

Paint in 1981

Modified polyelectrolyte thickeners introduced, HASE (hydrophobically modified alkaliswellable

emulsions) and HEUR (hydrophobically modified urethane block copolymers).

Paint in 1982

Epoxy water borne dispersions introduced.

Hard latex with hollow core introduced as opacifier.

Paint in 1983

Group transfer polymerization [U.S. Patent, 4417034, November 22, 1983, DuPont Co.;

S. N. Lewis., Letter to the Editor, Chem.. Eng. News, 61, No. 48, 3 (1983)]. New method

of tailoring very specific designs of polymers.

Paint in 1983 - 86

Acceptance of powder coatings in several niche markets, based on polyesters combined

with epoxies, triglycidyl isocyanurate etc.

Paint in 1987

ISO 9000 is born from BS 5750. ISO 9000 is essentially a standard for organizations to

create their own standards; requires strict adherence, follow-up and improvement.

Analytical Instrumentation

Methods such as IR, FTIR, UV, NMR, XRD, Raman, TGA, DTA, DSC, ESCA-XPS,

Auger, SEM, TEM, DMTA (torsional braid analysis), Rheometers, MS, Chromatography,

are all techniques that have made a major contribution to the science and technology of

polymers and coatings. This section is very incomplete, and additions are welcome since

it represents major enablers in the 2nd chemical revolution. A good starting reference to

the history of instrumentation is "The History and Preservation of Chemical

Instrumentation," Eds John T. Stock and Mary Virginia Orna, D. Reidel Publishing Co.

(Springer), 2008

Mass Spec history is available at

and see also S. Borman, H. Russell, G. Siuzdak, " Mass Spec Timeline" TODAY"S

CHEMIST AT WORK, September, 47-49. (2003)

Crystallography and X-ray diffraction started with von Laue and Bragg in 1912 and a

useful history can be found in J.-L. Hodeau, R. Guinebretiere, "Crystallography: past and

present," Appl. Phys. A 89, 819 -823 (2007).

Paint in 1881

Infrared absorption first studied in by Abney and Festing.

Paint in 1903

Russian botanist Mikhail Semenovich Tswett, coined "chromatography" from Latin for

colour writing, reports column adsorption chromatography. He passed extracts of plant

tissue through a chalk column to separate pigments by differential adsorption. [M. S.

Lesney, "Chromatography, A brief history of "colour writing", Today's Chemist at Work,

1998, 7 (8), 67-68, 71-72].

Paint in 1931

Richard Kuhn and others use chromatography to separate isomers of polyene pigments,

showing that this was a more widely useful technique [M. S. Lesney, "Chromatography,

A brief history of "colour writing", Today's Chemist at Work, 1998, 7 (8), 67-68, 71-72]..

Paint in 1920-1930s

Further research done in universities on infrared spectroscopy.

Paint in 1934

Don Brookfield sells the first dial viscometer.

Paint in 1941

Beckman makes the first commercial infrared spectrometer.

Vitamin A is discovered to absorb in ultraviolet part of spectrum which is then used in

US to check that military rations had vitamins.

Paint in 1946

Purcell, Torrey, and Pound at Harvard (Purcell et al., 1946) and Bloch, Hansen, and

Packard at Stanford (Bloch et al., 1946) independently found that they could detect

characteristic magnetic moments of spinning atomic nuclei, i.e. nuclear magnetic

resonance, NMR.

Paint in 1953

First NMR spectrometer made by Varian Associates, HR-30.

Synthetic Pigments

N.B. At present, most of the entries for TiO2 are above.

Egyptian Antiquity (4

th Dynasty ~ 2500)

Egyptian blue, a glass really, (Cuprorivaite) CaO.CuO.4SiO2

Cobalt used to colour materials, such as glass (and ground to make a pigment in medieval

times, "smalt"), and pottery glazes - probably occurred around whole of Middle East.

Chinese Antiquity (~ 800 B.C.)

Chinese Blue and Purple, similar compositions to Eqyptian blue but with barium instead

of calcium. Mayan Antiquity, the- 8th (?) Century A.D.

Maya Blue, indigo intercalated into palygorskite clay [G. Chiari et al.]. This is an

example of what has become a very modern approach to nanocomposites!

Paint in 1704 (approx)

Prussian blue introduced, i.e. Fe4[Fe(CN)6]3.14 - 16 H2O. First synthetic pigment of the

modern(?) era.

Paint in 1828 (approx)

Ultramarine blue.

Paint in 1905

Red -naphthol ["Industrial Organic Pigments," W. Herbst, K. Hunger, 2nd. Ed. 1997,


Paint in 1907

Toluidine red (PR 3) ["Industrial Organic Pigments," W. Herbst, K. Hunger, 2nd. Ed.

Paint in 1997, VCH-Wiley]


Hansa yellow (PY 1) first made in Germany - monoazo pigment that is usefully light

stable ["Industrial Organic Pigments," W. Herbst, K. Hunger, 2nd. Ed. 1997, VCH-Wiley]

Paint in 1916

First type of titanium dioxide pigment made. Farup and Jebsen in Norway invent the

sulphate process for industrial production.

Paint in 1919

First production of TiO2 pigment (anatase mixed with barium sulphate) Frederikstad by

the Titan Company.

Paint in 1920

First synthesis of diffraction effect pigments materials using HgCl2 platelets (Note use of

material from fish scales dates back to 17th. Century).

Paint in 1923

Anatase pigments were introduced in France [Napier et al.], but rutile pigments did not

appear until the early 1940s

Paint in 1930 approx

Interference pigments made with other heavy metals, lead, arsenic and bismuth salts as

platelets. Note that in 1959 Merck makes basic lead carbonate (white lead) as an

interference (platelet shaped particles) pigment.

Fluorescent paints made from anthracene dyes in shellac, by Robert and Joseph Switzer

of Berkeley, California [Pinchin and Tsang].

Paint in 1932

ICI in England introduce alkyd paint, based on technology from DuPont in USA.

Paint in 1935

Commercialization of diarylide yellows (patented in 1911)

Phthaloblue appeared, a synthetic, organic pigment that is very light stable.

Paint in 1938

Phthalogreen is commercialised ["Industrial Organic Pigments," W. Herbst, K. Hunger,

2nd. Ed. 1997, VCH-Wiley].

Paint in 1948

DuPont commercialise the chloride process for making rutile TiO2 pigments.

Paint in 1954

Disazo condensation pigments ["Industrial Organic Pigments," W. Herbst, K. Hunger, 2nd

Ed. 1997, VCH-Wiley]

Paint in 1955

Quinacridones - intense, stable organic red pigments ["Industrial Organic Pigments," W.

Herbst, K. Hunger, 2nd. Ed. 1997, VCH-Wiley]

Paint in 1956

Perylene chemistry pigments, versatile chemistry that produces cheaper, but less stable

red pigments than quinacridones.

Paint in 1960

Benzimidazoline series of pigments appear ["Industrial Organic Pigments," W. Herbst, K.

Hunger, 2nd. Ed. 1997, VCH-Wiley]

Paint in 1963

DuPont patents metal oxide (TiO2) coated mica flakes as interference effect pigments,

closely followed by patents from Mearl in 1964.

Paint in 1971

Use of aluminium flake pigments in metallic effect coatings for Lincolns. The flake

pigments were made by Avery [G. P. Bierwagen, NDSU, private communication].

Paint in 1972

Dupont, then others, supply titanium dioxide pigments in slurry form to the US paint


Paint in 1978

White lead pigments banned in US.

Paint in 1984

Use of interference effect pigments in automotive use [VCH Interference Pigment book].


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