SURFACE MODIFICATION OF POLYESTR

MOHAMMAD MAHBUBUL ALAM

Textile fibers are treated with enzymes in the absence of surfactants, with the effect of increasing the wettability and
absorbency of the fibers. The enzymes are pectinases, cellulases, proteases, lipases or combinations thereof. The effects
of enzymes on improving the hydrophilicity of several polyester fabrics. The lipases improve the water wetting and
absorbent properties of the regular polyester fabrics more than alkaline hydrolysis under optimal conditions. Compared
to aqueous hydrolysis, the enzyme reactions are effective under more moderate conditions, including a relatively low
concentration, a shorter reaction time, at an ambient temperature. Lipase has also to be effective in improving the
wetting and absorbent properties of sulfonated polyester and microdenier polyester fabrics.

Polyesters are manufactured synthetic compositions comprising any long chain synthetic polymer composed of at least
85% by weight of an ester of a substituted aromatic carboxylic acid, including but not restricted to substituted
terephthalic units and para substituted hydroxybenzoate units. The polyester may take the form of a fiber, yarn, fabric,
film, resin or powder. Many chemical derivatives have been developed, for example, polyethylene terephthalate (PET),
polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT) and polyethtlene naphthalate (PEN). However,
PET is the most common linear polymer produced and accounts for a majority of the polyester applied in industry
today.

Because of its strength, polyester fabrics and/or garments are subject to pill formation, and possibly the most important
of the cloth-finishing processes applied to polyester staple fibre materials are those designed for control of pilling. All
staple-fibre materials tend to form small balls or "pills" of entangled fibres at the cloth surface, when subjected to mild
abrasion during wash and wear. If the fabric contains a substantial proportion of fibres having high resistance to
flexural abrasion, the pills may be retained on the surface of the cloth in sufficient numbers to produce an unpleasant
handle and appearance.

In the textile industry, polyester has certain key advantages including high strength, soft hand, stretch resistance, stain
resistance, machine wash ability, wrinkle resistance and abrasion resistance. However, polyester is not so optimal in
terms of its hydrophobicity, pilling, static, dyeability, inactive surface as a medium for adhering, i.e., softening or
wettability enhancing compounds, and lack of breathability. Moreover, in the 1960's and 1970's, polyester textiles
suffered from poor consumer perception and was synonymous with the phrase "cheaply made" and derided for the
horrendous colors with which polyester was associated. This latter problem is due in large part to the unavailability of a
large selection of dyes which are compatible with polyester. To combat this perception, the industry has made strong
efforts to improve the characteristics of polyester.

One of the problem areas that the industry has sought to improve involves the characteristic that polyester is very
resistant to uptake of polar or charged compositions, i.e., fabric softeners, finishes and dyes. In the past, many synthetic
fibers such as those of cellulose acetate, cellulose triacetate, acrylonitrile, polyesters, polyamides and polyhydrocarbon
polymers were thought not to be satisfactorily dyed with basic dyes nor with cotton dyes. Dyeing of polyester include
replacing chemical substitution of terephthalate with compounds such as isophthalate and sulfo-isophthalate which
improve the uptake of the dye, improving chemical penetration of the dyes by using high temperature, emulsified
aromatic and/or chlorinated aromatic solvents, adding colorant to the molten polyester, and the use of cross-linking
polymers to glue the pigment to the fabric.

The mechanism of pilling is as follows : i) Mechanical action causes fibers to migrate out of the fabric body to the
surface, ii) Further action causes the surface fibers to rotate around other protruding fibers forming pills, iii) Additional
action may continue to form more pills or to sever fibers anchoring pills. The pilling propensity of the fabric depends
on the surface fuzz formation, the rate of fuzz entanglement, and finally the rate of pills breaking off. The rate of the
pills breaking off is directly related to the tenacity of the anchor fibers.

Bio-polishing is a finishing process where a textile fiber or yarn is treated with an enzyme to impart properties such as
anti-pilling, softness and smoothness. This concept was initially developed in Japan where the first experiments were
performed on cotton woven fabrics using cellulases.

Pilling prevention is an ongoing challenge for manufacturers of cotton, polyester and blended fabrics. There is no
simple solution to the problem of pilling. In the textile industry, polyester fibers are produced as medium-and high-
tenacity filament yarns and as staple fibers of various lengths and fiber color to suit the kind of spinning machinery
found in the textile trade. Staple fibers are usually drawn to give medium tenacities, but may be spun from polymers of
lower average molecular weight to give improved "pilling" performance at the expense of some loss in abrasion
resistance. Also, the finisher may reduce the pilling propensity of a fabric by the removal of protruding hairs from the
surface of the cloth and by heat treatment to reduce the tendency of the fibres to migrate within the yarns. Another
problem with polyester relates to the difficulty of removing oily and/or hydrophobic stains. These stains often adhere
strongly to the fabric or fiber and cause a permanent stain.

Improving the surface characteristics of polyester have been developed in an attempt to improve the dyeing, stain
resistance and other properties associated with the strongly hydrophobic nature of the polyester. For example, chemical
methods such as nucleophilic substitution via nucleophile attack at the ester carbonyl or hydrolysis; surface
polymerization by crosslinking a topical finish to either the fiber or the fabric; chemical penetration of the polyester
polymer with aromatic compounds; and topical application of a surface coating from an aqueous solution which has
affinity for the polyester. Nonetheless, these processes often have inherent deficiencies such as cost of chemicals,
energy and capital equipment, the use of environmentally unsafe solvents, limited flexibility and negative effects on
strength of the material and other aesthetic properties of the fabrics.

Synthetic fibers such as polyester have high water contact angles, low wettability and minimal water retention. In
contrast to cellulose-based fibers, these effects are not caused by the presence of impurities, but are rather an inherent
characteristic of the polyester surface. If it is desired to dye the polyester fabric, the situation is further complicated as
standard polyester fibers, and fabrics made from these fibers, have no reactive dye sites. Polyester fibers are typically
dyed by diffusing dyes into the amorphous regions of the fibers.

The modification of the surface of polyester fibers by physical or chemical means is known. For example, anionic sites
have been added to polyester fibers using 5-sulfoisophthalate as a method to make polyester fibers reactive towards
cationic dyestuffs. The surface of polyester fibers can be modified by alkaline treatment of freshly extruded fiber to
improve comfort and increase water sorption. Alkali treatment of polyesters, however, often results in a weakening of
the fiber strength.

The enzymes commonly used include amylases, cellulases, pectinases and lipases. In typical applications, amylases are
used to remove sizing agents (e.g., starch), cellulases are used to alter the surface finish of, or remove impurities from,
cotton fibers and lipases are used to remove fats and oils from the surface of natural fibers (e.g., cotton, silk, etc.).

Enzymes have also been used for denim garment finishing, to achieve soft hand and the fashionable worn look
traditionally obtained by stone-washing and acid washing.

The use of lipases to remove oily stains from garments is known in the detergent. Lipases have also been used in textile
finishing. For example, when treating natural fibers with lipases to remove residual triglycerides and other fatty
materials. The process is also useful for removing oil or ester coatings that have been added during processing. No
mention is made in Petersen of using lipases to alter the properties of a polyester fiber by cleaving structural ester
bonds at the surface of the fiber. The lipases are used to form esters between the carboxylic acids and fibers which have
reactive hydroxyl groups at their surfaces.

Lipases dramatically improve the wettability and water retention of aromatic polyester fibers while, causing a minimal
loss of fiber weight and strength. Therefore, in yet another invention that altering the physical properties of polyester
fibers, comprising treating the polyester fibers with an aqueous solution of a lipase to produce polar groups on the fiber.
The polar groups on the fiber can modify physical properties of the fiber including its wettability and absorbency.
Surfactants used as a component of the reaction medium. Lipases are obtainable from milk, yeasts, bacteria, wheat
germ, animal sources (e.g. pancreas) and various fungi. Suitable lipases are bacterial or fungal origin. Chemically or
genetically modified mutants are included.

The alkali processing of fibers using NaOH has several inherent disadvantages. The use of large quantities of boiling
aqueous sodium hydroxide is undesirable for reasons of safety, convenience and also for the volume of waste salt
which is produced neutralization of the alkali bath. The use of hot alkali to treat fibers also results in damage to the
fibers which lessens their strength and durability. Thus, a means for treating fabrics to increase their wettability and
absorbency which avoided the use of an alkali bath would constitute a considerable advance in the field of textile
processing.

When polyester is treated with organic acids so as to further increase the hydrophilicity and/or charge of the surface and
thereby improve the uptake of cationic compounds and/or the stain resistance of the fabric. The polyester is capable of
reacting and forming bonds to a greater extent with chemicals which will react and form bonds with alcohols and
carboxylic acids.

Modifying the surface of a polyester fabric comprising treating polyester with an enzyme having polyesterase activity
for a time and under conditions such that the chemical properties of the surface are modified to produce a surface
modified polyester. Preferably, the surface modified polyester fabric obtained is subjected to further treatment, the
benefit of which treatment has been improved by the enzymatic surface modification. The enzymatically surface
modified polyester fabric is reacted with a chemical reagent to form a non-covalent interaction between the surface of
the polyester and the reagent and is reacted with a chemical reagent to form a covalent bond between the polyester and
the reagent or another compound.

A preferred covalent interaction between the chemical reagent and the surface modified polyester comprises treating
the polyester with a chemical resulting in a further increase in hydrophilic groups on the surface of the composition.
Whereas covalent interaction comprises further derivating chemically or enzymatically the surface of a polyester with a
reagent which carries a desired functionality, for example, color or dye, antimicrobial, antiperspirant, deodorant, anti-
stain or fabric finishing activity. An especially preferred covalent interaction comprises treating the surface modified
polyester with a dye to form a dye-polyester covalent bond. A preferred non-covalent interaction between the chemical
reagent and the surface modified polyester comprises treating the polyester with a dye which forms a non-covalent
bond with the polyester.

For improving the uptake of a cationic compound onto a polyester fabric starting material is provided comprising the
steps of obtaining a polyesterase enzyme; contacting polyesterase enzyme with the polyester fabric starting material
under conditions and for a time suitable for the polyesterase to produce surface modification of the polyester fabric
starting material and produce a surface modified polyester; and contacting the modified polyester fabric, subsequently
or simultaneously with the enzymatic treatment step, with a cationic compound whereby adherence of the cationic
compound to the modified polyester is increased compared to the polyester starting material. Preferably, the
polyesterase is contacted with the polyester fabric in conjunction with a surfactant.

The fiber, fabric or yarn is incubated with the enzyme solution under conditions effective to allow the enzymatic action
to confer the desired effect to the fabric. The example, during enzyme treatment, the pH, liquor ration, temperature and
reaction time may be adjusted to optimize the conditions under which the enzyme acts. "Effective conditions"
necessarily refers to the pH, liquor ratio, and temperature which allow enzyme to react efficiently with the substrate.
The reaction conditions for any particular enzyme are easily ascertained using well known methods.