Page 9 - Handbook of Adhesion Promoters

2 Introduction

1.2 HISTORY

Various simple technological processes of binding were used as early as 10,000 years. In
the Neolithic period, a resin from birch trees was used to attach the heads of spears and
axes. Later, when Iceman was discovered on Hauslabjoch (lived around 3300 BC), tools
and pieces of clothing were found, including an ax made from yew wood whose blade was
attached with birch pitch (adhesive) and strips of leather.
Other examples of products used as adhesives include animal blood, protein, various
plant resins and asphalt that were used as adhesives in Babylon to build houses and tem-
ples. Such applications were used all over the world, even recently (Asia, Africa). It is
expected that this technology is known for at least 7,000 years.
Fish and animal glues were known to Egyptians 4,000 years ago. They were
obtained by boiling of animal hides, hooves, and connective tissues and used for rein-
forcement of papyrus scrolls and production of furniture (Tutankhamun casket was glued
using this technology). This was the first technology of adhesive production which
involved professional people having knowledge of how to make a glue. Glue produced in
this way was expensive and, therefore, used only for furniture for noble people. The tech-
nology was later transferred to the Greeks and Romans.
Greeks and Romans further developed the technology. The ancient Greeks used
adhesives in carpentry. The glues were usually made out of egg whites, blood, bones,
milk, cheese, vegetables and grains. Tar and beeswax were implemented later by the
Romans. Also, Chinese used ox and stag horns for the production of adhesives at least
3,000 years ago.
In South America, the developments came in this area later or perhaps earlier devel-
th
opments are still unknown. In the mid 14 century, the Aztecs used the adhesive proper-
ties of blood for construction work. The structures are still in an excellent condition.
th
The modern area of adhesives begins in the 19 century with the use of natural rub-
ber as adhesive in 1830. Eleven years later vulcanization of rubber was discovered by
Goodyear and used for adhesive purposes, followed by celluloid (1864) and phenolic resin
(Bakelite, 1905). The big developments came about during second world war including
polybutadiene (1935 and later developments, Buna or earlier in Russia), epoxy resin (1938
and later), cyanoacrylate (1942-1951, Eastman, superglue), and thermoplastic glue (hot
melt, Procter & Gamble, 1940).
Bookbinding illustrates how important was the development of adhesives to the
book production. Books were produced in various forms (scrolls, tablets, parchment
sheets, etc.) for millennia but “pages” could only be held together by threads, ropes, etc.
because of lack of durable glue. In 1447, Gutenberg introduced printing press which
automatized printing process, but bookbinding was still done by manual work because
there was no glue available to match the developments in printing. So book production
th
remained manual process until developments in the 20 century. Perfect binding was
invented in 1895 but it was first adapted for book production by Penguin Books (UK) in
1935 using cold glues which were quite rapidly becoming brittle with time. Hot-melt
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bookbinding was developed by DuPont in 1940 which started the modern area of publish-
ing and made books available to anyone who was interested in reading (because their price
was not any longer an issue). Polyamide having softening temperature in the range of 45-
o
155 C was the first polymer used for bookbinding by hot-melts.