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Background

Water repellents are topical finishes or coatings applied to fabrics to


provide protection against water, oil and soil. Water repellent coatings add value
to textile products. In addition to providing protection against water, oil and soil,
these coating product also extend the life of products and keep them looking
newer longer. Water repellent technology has historically been achieved with
textile coating that contain a polymer to which long-chain perfluoroalkyl groups
have been attached.
Water repellent coatings are formulates to be vapor permeable, or
breathable. They do not seal the surface completely to water vapor so it can
enter the fabric as well as leave the fabric. So, water repellent coatings are needed
by people who want to keep their fabric dry, one of which is shoe as their
footwear. The foot is arguably the most important limb of a human being. It
supports the entire humans weight, and what makes mobility possible. It has the
most bones than any other limbs. It has 26 bones, 37 joints, 107 ligaments and 19
muscles and tendons. It is also the part of the human body with the most direct
contact with the environment. It is therefore only natural that humans take
extraordinary measures to protect their feet. Good feet protection improves
mobility, enhances health by reducing risks to injury, and ultimately improves life
quality by making life more comfortable for the human being.
When it rains, many people are worried about his shoes will be wet.
Although the people are using an umbrella or raincoat, their shoes will be wet
because of rain splash or step on the rain puddles due to holes in the road.
Moreover, Indonesia has a high rainfall and the quality of road
infrastructure in Indonesia is still low. So there is still a lot of potholes and can be
rain puddles if the rain comes. The seasonal to interannual variabilities of
Indonesian rainfall are characterized mainly by the monsoon (Ramage, 1971) and
the El Nino-Southern Oscillation.
The amount and season of maximum rainfall vary with the different
exposure of the islands to these monsoon systems. Jakarta, on the northern side of
the island of Java, has average annual rainfall of 1650 mm, most of which comes
from the north monsoon between November and March. Ambon, on the southern
Figure XX : Average Monthly Temperature and Rainfall in Indonesia from 1900-2012
Source : The Climatic Research Unit (CRU) of University of East Anglia (UEA).

side of the Moluccas to the east, is much wetter with an annual average rainfall of
3640 mm, and is most affected by the south monsoon from May to September.
Medan, in north Sumatra, has rain throughout the year totalling 2260 mm on
average. Similarly, Balikpapan on Borneo has little seasonal variation in rainfall
with an average annual amount of 2230 mm.
CHAPTER 2
BASIC THEORY

2.6.3 Turpentine Oil


Turpentine is one of the volatile oils that can be extracted from
pine wood. It is initially extracted at Kinlieth as crude sulphate
turpentine, CST, (with it being in the sulphate form due to the kraft
processing of the wood), and then refined by fractional distillation.
The refining and further processing used to be carried out in Japan
and the final products reimported, but in 1983 a new company called
Pine Chemicals Ltd. started to process CST and crude tall oil in New
Zealand. The company is currently owned by the Dutch group Akzo
Nobel, and operates under the name Eka Chemicals (NZ) Ltd. The
products are sold in New Zealand and exported to Australia, Japan, the
United Kingdom and South East Asia.
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CST is a volatile amber liquid, with a density of 0.85g cm . It is
a mixture of - and - pinene (30 and 60% respectively) and other
monoterpenes of the general formula C10H16 and various impurities
such as small quantities of unpleasant-smelling sulphurous
compounds (e.g. methyl mercaptan and dimethyl sulphide) and
inorganics. There are safety risks associated with handling CST and
refined turpentine, both because of its volatility and because it has a
low flash point.
Refined turpentine is used as a solvent for resins, varnishes and
oil-based paints, and in the manufacture of p-cymene, isoprene,
terpene polymers and perfumes for soaps and cosmetics. Lubricating
oil has even been manufactured by polymerisation from sulphate
turpentine.

Figure 1. -pinene and -pinene


(Source : )
In addition, turpentine can be separated into its major
constituents: - and -pinene. The former is converted into -terpene
and then into pine oil and dipentene. Pine oil is used in a wide variety
of applications including use as a flavour and perfume in
pharmaceuticals, as a solvent, disinfectant and deodorant, for the
flotation of lead ores and in textile scouring. Dipentene is used as a
wetting and dispersing agent, as a solvent for lacquers and inks, as a
degreasing agent and in the manufacture of air fresheners. -pinene is
used for the production of camphor and some insecticides.
2.6.3.1 Extraction And Processing Of Turpentine
Initially, CST is extracted from wood chips. This crude
product is then sent off for further processing, during which
time the turpentine is distilled to separate the - and -pinenes.
The -pinene is sold as is, and the -pinene converted to pine
oil in two further process steps.
1. Extraction of turpentine from the wood chips
Wood chips are either 'cooked' in a batch or a
continuous process (see article), and the method of
turpentine extraction differs depending on the method
used. In the batch process turpentine is obtained by
venting the digester and then separating the fibres and
black liquor from the water and turpentine in a cyclone
separator. In the continuous process less turpentine is
obtained, although the process is still economically viable,
and this time water and turpentine vapour is obtained by
flashing the black liquor twice.
The vapour mixture is piped to a condenser and
thence to a separation tank, where the aqueous and
turpentine phases separate due to their density difference.
The aqueous underflow is piped off, and the CST overflow
is also piped off to storage tanks. Because of the corrosive
effects of CST, piping and storage tanks are made of mild
steel, and all other components of stainless steel. The
various non-condensibles (i.e. unable to be condensed
under the operating conditions used) are passed to a
scrubbing column where they are cleansed of undesirable
compounds by caustic solution (to form non-volatile salts).
2. CST distillation

The CST plant is a batch operation. A kettle


connected to a distillation column is filled with crude
turpentine and a vacuum drawn whilst the charge is heated
up to the point where the lightest compounds begin to boil
off. These "heads" are of no use as they contain mostly
water and light sulphurous compounds, and they are sent
to an incinerator. Once these heads have been driven off,
temperature can be increased and vacuum intensified. As
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the pinenes begin to boil off the reflux ratio can be
increased to improve the degree of separation achieved in
the column. The difference in volatility between the alpha
and beta forms is sufficient to permit quite good separation
by distillation, but to assure product quality in minimum
distillation time a small intermediate cut of mixed alpha
and beta pinenes is taken. These intermediate cuts are
stored until sufficient is held to make up a batch for
redistillation.
Following the collection of the pinenes, the residues
can be removed from the kettle and a fresh charge of
turpentine admitted. Overall time for a batch distillation is
about 20 to 24 hours. The alpha and beta pinenes
recovered from the distillation are held in stock tanks. The
beta pinene is exported in bulk ship loads whilst the alpha
pinene is used in the next stage of the process.
3. Crude pine oil production
The alpha pinene recovered from the CST distillation
is 96% -pinene, 3% -pinene and 1% camphene. To
make crude pine oil, the -pinene is converted to a mixture
of alpha terpineol (the pine oil ingredient), dipentene (an
isomer of pinene), unreacted pinene and some minor
quantities of other by-product and impurities.
The conversion of -pinene to pine oil, of which the
major component is the tertiary alcohol -terpineol,
involves hydration of the carbenium ion. Further
hydration of -terpineol will yield terpin, or alternatively
the -terpineol can be dehydrated to dipentene. The terpin
may undergo partial dehydration to an -terpineol and
other terpineols.
Alternatively the -pinene may also undergo
isomerisation to camphene or thermal isomerisation to
dipentene. As the two pinenes are eaily interconverted
using certain acids, bases and hydrogenation catalysts, the
-pinene in the distillation fraction can be converted to the
same end products. The reactions concerned are
summarised on the next page. The pinene hydrolysis
reaction yield is dependent on both time and temperature.
An increase of either will cause a higher conversion of
alpha pinene, but would also increase the proportion of
pinene converted to dipentene.
As pine oil is the preferred product, the reaction
conditions are controlled to minimise loss of pinene to
dipentene. In the PCNZ process the pinene is hydrolysed
using aqueous phosphoric acid at temperatures of up to
o
70 C for 3 hours. The immiscible fluids are agitated
vigorously in a batch reactor and small amounts of
surfactant can be added to promote good interphase
contact. Under these conditions the reaction yield is
expected to be :
Unreacted pinenes and camphene 55%
Dipentene 10%
Pine Oil 30%
Residue (terpin and hydrate) 5%
After reaction the reaction mass is washed free of acid and
then washed with caustic to neutralise any remaining free
acid, prior to distillation.
4. Crude pine oil distillation
The distillation of crude pine oil is again a batch
process under vacuum and produces three cuts and a
residue. The first cut is the unreacted pinene, plus any
camphenes and similar isomers, which is recycled to the
pine oil reaction. The second cut is dipenetene and a 90%
pine oil is the third cut. Terpin and other hydrates form a
residue which is periodically discharged from the kettle.
Due to the recycling of -pinene, over time
"impurities" such as camphene and *-3-carene build up in
the feed stock. To prevent them from causing problems
they are periodically destroyed by hydrolysing a batch of
feed at higher than normal temperatures and for a longer
time. This causes a complete conversion to dipentene
which can then be directly drummed off for sale as a
solvent without the need for further distillation.
2.6.3.2 Uses of Turpentine Oil
Turpentine was formerly the most widely used paint and
varnish thinner and is still used in some paints and coatings.
The use of less expensive petroleum-based products has
replaced the use of turpentine in paints. When turpentine is
used today, it is most likely in specialty applications such as
spray painting, pottery and ceramic coatings, artists paints,
and naval paints. Turpentine is sometimes present in shoe and
furniture polishes, and is used as a metal cleaner. Currently, the
major use of turpentine is as a raw material for the chemical
industry.
Terpenes and other compounds extracted from turpentine
can be used for such products as tires, plastics, adhesives,
flavors and fragrances, cosmetics, paints, and pharmaceuticals.
The value of turpentine represents about 25% of the value of
all aroma chemicals produced for both sale and for internal use
each year. Past uses for turpentine include printing processes,
hairdressing formulations, and as medicinals.

CHAPTER 3.
NEEDS IDENTIFICATIONS

3.1 Needs Identifications Methods


Water repellent is a coating added to fabrics at the factory to make them
water resistant or hydrophobic. Most factory-applied treatments
are fluoropolymer based. Durable water repellents are commonly used in
conjunction with waterproof breathable fabrics to prevent the outer layer of
fabric from becoming saturated with water. This saturation, called 'wetting
out,' can reduce the garment's breathability (moisture transport through the
breathable membrane) and let water through.
We thougt many people who need water repellent for their shoes when
it rains. They want to keep their shoes dry, so that it always feels comfortable
to wear. Shoe is one of the human basic needs, many people who wear it
every day in their activities, both indoor and outdoor. So we conduct some
method of needs analysis about the water repellent for shoes that we can
produce.
We will expose and analyze the consumer needs for the product. Then,
we will formulate the products spesification by analyzing the consumer
requirements. Consumer requirement is consumer voices that have been
surveyed, analyzed, and examined where those consumer voices are affecting
the sustainability of product design and development. In consumer
requirement, to know the market demand for the product, market analysis will
be executed with direct interview method and also spread the questionnaires
to the respondents.
Interviews conducted directly to our target market or consumers. The
results of the survey are considered to represent the consumer needs of water
repellent product for shoes. Consumer requirement will give the product
specifications which are made not only to provide what is needed by
consumer, but also to be able to meet consumer satisfaction. In order to meet
the consumer satisfaction, in the step of development of the water repellent
product, the authors performed a simple concept first from the results of the
review of existing literature, both patent and benchmarking. We do some
direct interview and also spread the questionnaire to 222 respondents. We
choose 222 respondent as a sample group because the more respondents who
participate, the better represent the needs of consumers who want water
repellent product.
The respondent who participated in completing the questionnaire has a
variety of ages, occupations, and income. The diversity of respondents helped
us to get many insights and point of views to develop the water repellent
product. From this method we also got many information about the needed
and some expected performance from the our potential consumers.
Doing interview helped us to explore more from the answer of the
consumer and we get so many chances to ask open ended questions.
Distributing questionnaire help us easily make a mapping of our consumer
and their needed digitally and technically it could reach more consumer to fill
the questionnaire.

3.2 List of Needs


After distributing questionnaire and conducting interview, we make a
list of some needs that was expressed by the target consumers. We combine
some needs expressed by the consumer and the result is summarized below.

1 Water repellent that can be waterproof


2 Water repellent that is safe for all the shoe materials
3 Water repellent that can be applied easily
4 Water repellent that contains anti-bacterial
5 Water repellent which can quickly dry
6 Water repellent which keeps color shoes
7 Water repellent that has unsticky content
8 Water repellent that is easy to clean
9 Water repellent which has a refreshing aroma
10 Water repellent that is transparent
11 Water repellent that can be used for all colored shoes
12 Water repellent that has attractive packaging
13 Water repellent that is easy to carry
14 Water repellent with an affordable price
15 Water repellent that is safe for the skin
16 Water repellent that contains neutral content
17 Water repellent that contains non-toxic content

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