1.

INTRODUCTION

1.1. HLL LIFECARE LIMITED

HLL Lifecare Limited is a Government of India Enterprises, under the ministry of Health
and Welfare. HLL was set up in the natural rubber rich state of Kerala, for the production of
male contraceptive sheaths for the National Family Planning Program. The company commenced
its commercial operations on 1969 at Peroorkada in Thiruvananthapuram. The plant was
established in technical collaboration with Okamoto Industries Inc. Japan. Later HLL acquired
the RRT technology (German) also for the manufacture of condoms.

The revolution, called HLL, swept through the length and breadth of the country. It
reigned in the alarming population growth and enhanced the quality of life of families in India. A
revolution that eventually sparked off many a movement and idea, it brought quality healthcare
and prosperity to the doorstep of millions. The revolution resulted in creating a healthier India,
with a record of 189 million couple year protections (CYPs) during the past four decades. The
revolution is called Pink Revolution.

Today, with nine manufacturing units, HLL has grown into a multi-product, multi-unit
organization addressing various public health challenges facing humanity. In 2003, when HLL
had a turnover of a mere INR 163 cores, it had set its sights on becoming a INR 1000 core
company by 2010. HLL not only surpassed this figure by 2010 but also drew a clear road map to
achieve ten-fold growth by 2020.

HLL today is a multi – product, multiunit organization addressing various public health
challenges facing humanity. The company is manufacturing and marketing a wide range of
products which includes a range of Male Condoms, Female Condoms, Oral Contraceptive Pills,
Emergency Contraceptive Pills, Cu-T, Blood Collection Bags, Surgical Sutures, Tissue
Expander, Hydrocephalus shunt, Auto Disable Syringe, Surgical gloves, Examination Gloves,
Blood Transfusion Sets, Intravenous Sets and Blood Banking equipments, Iron Folic acid tablets,
ORS, Pregnancy test Kits, Sanitary Napkin, Disposable Delivery kit, Surgical Kits, Chyavanules,
Hair oil, Joint Pain Relief Ointment.
 In collaboration with the female health company (FHC), of US, HLL is manufacturing
female condom in India. The female condom is the only female controlled prevention technology
approved by the US FDA and the WHO. HLL launched the Nitrile female condom – velvet on
December 2007 in India. Targeted at contemporary Indian women and new age couples, Nitrile
condoms empower women providing dual protection against unwanted pregnancy and STDs,
HIV/AIDS.

The research and development department of HLL , is now dealing with researches about
ultrathin products. An accelerator free peroxide based system can be used economically and
effectively to cure thin films. Products produced via this new curing method can effectively be
manufactured without sulfur, accelerators, activators, and boosters. Dip molded rubber films
manufactured via this system are generally highly biocompatible, and free of the common
allergenic agents responsible for Type IV latex allergies.

While currently used vulcanization technology appears to be adequate for many dip
molding applications, this new method should be strongly considered when the highest possible
levels of biocompatibility are required. Such applications include implantable and indwelling
medical devices, non-embryotoxic gloves for embryo transfer, catheter balloons, sheaths, etc. In
addition, traditional dip molded products such as condoms and medical gloves can be improved
with the incorporation of this system.
2. RAWMATERIALS AND PROCESS DISCRIPTION

2.1. NATURAL RUBBER LATEX

Natural rubber is the nature’s most versatile product, which was discovered in Brazil, in
South America 420 years ago, has an exudates mass caused due to drying of milky liquid oozing
out of certain trees. This material has multifarious uses and there is hardly any segments of life
does not use of rubber-based materials. Guayule Shrub was probably the first known source of
rubber, which was discovered in North America. Charles–de–la-Condamine, a French man first
discovered Hevea Brasiliensis tree. Now Hevea Braseliensis is the most important source of
natural rubber and more than 97 % of natural rubber is produced from this tree. It obtained from
the bark of the rubber tree by a process called tapping.

Natural rubber latex is colloidal dispersion of 1, 4 Cis Polyisoprene in an aqueous

medium. The rubber content of field latex varies from 30-40%, with a specific gravity of 0.96 –
0.98 and a pH in the range of 6.5 – 7. The size of the rubber particle varies from 0.025 to 0.3
microns. In addition to rubber and water, latex contains small quintiles of proteins, resins, fatty
acids, other lipids and, carbohydrates and mineral matter. Lipids in fresh latex consist of fats,
waxes, sterols, sterol esters & Phospholipids. Lipids associated with the rubber and non – rubber
particles on latex play a key role in stability and colloid behavior of latex.

2.1.1. COMPOSITION OF NR LATEX

The following is a general composition of NRL. The composition of Heava latex varies
with climatic condition, season, age of the tree etc.
 Sl.No INGREDIENTS PERCENTAGE

1 Rubber Hydrocarbon 30-40

2 Water 55-60

3 Proteins 1.9-2.5

4 Fats and related compounds 0.9-1.0

5 Carbohydrates 1-1.5

6 Ash 0.40-0.60

Table:1. Composition of natural rubber latex

2.1.2. NON RUBBER SUBSTANCES IN NATURAL LATEX

The main non rubber substance in Natural Rubber is proteins. The major proteins are

 A-globulin – a surface active protein, isoelectric point pH 4.8, present on surface of

rubber particles.

 Hevein – a sulphur containing protein, soluble in the aqueous phase of latex, isoelectric
point pH 4.5.

 Rubber Elongation factor (REF) – found in the rubber phase mol wt.( It is responsible for
molecular build up)

 A number of other proteins and amino acids have been identified in the rubber phase,
aqueous phase and rubber-serum inter phase.

Another non-rubber constituent is Phospholipid. Major phospholipids are lecithin’s.

2.1.3. COLLOIDAL STABILITY OF LATEX

The rubber hydrocarbon itself is changeless. The ‘R’ group of phospholipids attach to the
rubber particle. The other end of the phospholipids particle having a +ve charge project outwards
(rubber particles with phospholipids have +ve charge.) This positively charged entity absorbs –
vely charged proteins. Thus rubber particle surrounded by proteins have –ve charge.

Proteins at the particle surface carry negative charge. Columbic repulsion between these
negative charges is responsible for the colloidal stability of natural latex.

Moreover the hydrolysis of phospholipids produces glycerol, higher fatty acid anions,
phosphate anions and organic bases. The higher fatty acid anions are absorbed on the surface of
rubber particle and thus increase the MST. Higher fatty acid anions identified in natural latex are
oleic, palmetic, stearic and arachidic.

2.1.4. PRESERVATION OF LATEX

Natural rubber latex is contained in a specialized type of cell in the Hevea Brasiliensis tree.
It is virgin inside the bark but when it comes out of the tree, it get contaminated with bacteria
(from cup, knife etc). The multiplication of the bacteria occurs very rapidly and microbial
activity in latex is an important factor in colloidal destabilization of latex. A number of chemical
changes occur shortly after the latex leaves the tree, the micro organism fed on the carbohydrate
& convert them to volatile fatty acids (formic acid & acetic acid). At the same time proteins are
decomposed to simple product. As a result, in a few hours after tapping, field latex initially
thickens; first a cream is formed on the surface and finally coagulates. This is called spontaneous
coagulation. Time required for spontaneous coagulation depends on ambient temperature and
upon the colloidal stability of the latex. Within a day or two coagulated latex putrefies producing
malodor (due to sulphur containing material). Preservation of latex is necessary to prevent both
these processes occurring. For this short term and long term preservatives are used. Short term
preservatives are commonly known as anti – coagulants.

The Characteristics of an Ideal Preservative

 Shall function as bactericide.

 Shall enhance the colloidal stability
  Increasing the bound electrical charges on rubber particle surface.
 Increasing the ability of the surface bound hydrophilic macro molecules and confer
stearic stabilization.
 Increasing the degree of hydration of the particle surface.
 Deactivating multivalent metal ions.

2.1.5. PRESERVATIVES USED FOR NR LATEX

The following is brief description of the common preservatives used in NRL.

2.1.5.1. Ammonia as a preservative

NR latex contains proteins and fatty acids in it. The ammonia added to the latex react with
fatty acid present in the latex to form an anionic soap. Therefore, colloidal stability increases.
Moreover ammonia is a bactericide and has all the characteristics of an ideal preservative.

Generally the preservation system used in NRL can classified into two- HIGH
AMMONIA PRESERVATION SYSTEM AND LOW AMMONIA PRESERVATION
SYSTEM.

i. High ammonia preservation system

This is the most commonly used system in India. Here ammonia at a concentration of
0.7% by weight is added to the centrifuged latex. This system will maintain its stability for long
periods. For field latex the non – rubber constituents are more and hence ammonia concentration
of 1% is used to preserve field latex. The quality of the preserved field latex depends on the time
of ammunition and the quantity of ammonia added to the latex.

Advantage of ammonia preservation

 Ammonia act as a bactericide.

 Ammonia as an alkali and hence enhances the –ve charge of the rubber particle.

 Ammonia and multivalent metal ions

 Ammonia is effective at low concentration like 0.35%

Disadvantage of ammonia preservation

 Ammonia has a pungent smell.

  Handling is somewhat difficult.

 Marked and progressive when compounded with ZnO.

 To be de- ammoniated to low levels before compounding.

 Consumption of more coagulant in latex dipping and extrusion process.

 Lead to thickening of latex when ZnO is added to latex.

ii. Low ammonia preservation system

The most common low ammonia system is the LATZ (Low Ammonia + Lauric Acid +
ZnO + TMTD) system. Here ammonia is used at a concentration of 0.2% by weight along with
chemicals, like 0.025% of TMTD and 0.025% ZnO.

Advantage of latz system

 Since NH3 percentage is less than 0.29% deammoniation process is not needed.

 No effluents – No atmospheric pollution.

 No toxicity – used for surgical goods.

Drawbacks of latz system

 Higher viscosity compared to HA Latex of same solid content.

 Enhanced tendency for surface skin formation in dipping time.

 Higher chances nitrosamine formation in latex articles.

2.1.5.2. Potassium hydroxide as a preservative

The only practically important alternative ammonia as a sole preservative of NR latex is

KOH. This is used for the preservation of 75% m/m evaporated NR Latex concentrate. It is an
effective bactericide by virtue of its high alkalinity. For the same reason, it gives latex which is
colloidally very stable. But it is non volatile and its removal from latex is not easy.

2.2. PROCESSING OF LATEX

About 3 to 4 hours after tapping, the latex collected from the tree is treated with
preservatives to prevent premature coagulation, and brought to factory for further processing.
About 82 to 85% of latex extruded by the tree is collected in this way as field latex.
 On arrival at the factory the latex is sieved and blended. The latex is then de-sludged by
adding calculated quantity of DAHP. Field latex is either concentrated by removing part of the
water to give latex concentrate or it is deliberately coagulated processed in to dry rubber.

2.2.1. CONCENTRATION OF NATURAL RUBBER LATEX

The process of latex concentration involves the removal of a substantial quantity of the
serum from field latex thus making the latex richer in rubber content. Concentration of the latex
is necessary for the following four reasons.

 Economy in transportation.

 Preference for high DRC by the consuming industry.

 Better uniformity in quality

 Higher degree of purity

Latex may be concentrated to 60 % DRC usually by creaming, centrifuging, evaporation

or electro decantation or alternatively coagulated and dried. Centrifuging is the most widely used
method for the commercial production of latex concentrate. Creaming and evaporation are still
used by some manufacturers.

2.2.1.1. Centrifuged latex

Centrifuged latex concentrate accounts for more than 90 % of total latex concentrate. In
centrifuging, latex is subjected to centrifugal force, several thousand times the gravitational
force, in a bowl rotating at high speeds whereby individual rubber particles tend to separate into
a layer surrounding the axes of rotation leaving an outer serum layer having comparatively low
rubber content. Each layer is removed through annular spacing around the axis of rotation. By
controlling the time to which latex is subjected to such forces and by controlling the conditions
of operations, latex having an original DRC of 30-38% can be concentrated to DRC of 60 or
more.
2.2.1.2. Creamed latex

Creamed latex is produced by adding a creaming agent, usually ammonium alginate to the
field latex preserved with a higher concentration of ammonia together with secondary
preservatives. But in this process the recovery of rubber is lower than that obtained in
centrifuging.

2.2.1.3. Evaporated latex

Evaporated latex is produced by passing field latex, preserved with KOH, through heated
film evaporators at reduced pressure repeatedly until the desired rubber concentration is
obtained. Higher DRC than that obtained in centrifuging can be obtained in this process.

2.2.1.4. Electro decantation process

This process is carried out in a special rectangular tank containing 1 cm apart many groves
in which cellophane sheets are fixed. The two electrodes are fixed at each end of the tank and
electric current is applied. The particles flout to the top as a cream, which is removed from time
to time. Latex with a solid content of 60-62% is obtained.

2.3. LATEX QUALITY PARAMETERS

The most important parameters that are used to estimate the quality of the latex
concentrate are

 Total solid content

 Dry rubber content
 Non rubber content
 Mechanical stability time
 VFA number
 KOH number
 Viscosity at 60%TS
 PH value at 250C
 Total alkalinity
 Apart from this some users of cenex test parameters mentioned below to ensure the
quality of latex.

 Zinc oxide thickening tests like

 ZOV60( Viscosity after the addition of specified quantity of ZnO)
 ZST after 60 minutes( MST after the addition of specified quantity of ZnO)
 ZHST after 60 minutes (HST after the addition of specified quantity of ZnO

2.4. COMPOUNDING OF NATURAL RUBBER LATEX

Compounding is done to make the latex suitable for further processing and for making the
final product confirming to requirements of the end user. This is achieved by incorporating
various ingredients into the latex. The process of mixing various compounding ingredients with
latex is known as compounding. All ingredients added to the latex should be brought into a
physical state that is comparable to the latex before they are added ingredients like water soluble
organic acids, salts of the polyvalent metal, acidic materials etc should not be added to the latex
as they lead to coagulation. Compounding ingredients added to latex may be water-soluble or
water-insoluble ingredients can be added to latex as solutions in water. But water-insoluble
ingredients must be added as dispersions or emulsion.

Solid ingredients are converted into dispersion before adding to latex. This can be
achieved by using equipments like ball-mill/Attritor. Dispersion agents, wetting agents,
protective colloids also added during the preparation of dispersion to get stable dispersions. The
pH of all additives is adjusted to alkaline pH (8-9) before adding to the latex. The commonly
used compounding ingredients are stabilizers (to prevent the destabilization of the latex during
the addition of chemicals), sulphur (cross linking or vulcanizing agent), Accelerators (accelerate
the reaction and reduce the cure time), ZnO (activator- activate the action of accelerator and
reduce the vulcanization time), Anti oxidants (Prevent the oxidative degradation).
2.4.1. COMPOUNDING INGREDIENTS

Sl. No. Name of the chemical Functions

1. Sulphur Vulcanizing Agent

2. Zinc Oxide Vulcanizing Activator

Setsit S5 / Pilcure S 5 / Noc celer TP / SDBC

3. Vulcanizing Accelerators
(Activated dithiocarbamates)

4. Lowinox CPL / Wingstay-L (Phenolic derivatives) Antioxidants

5. Ammonium caseinate / Pot. Oleate / Pot. Laurate / KOH Stabilizing agents

6. 1% Ammonia Solution Stabilizing agent

7. Tamol / Darvan 1 / Darvan 2 Dispersion agents

8. Color pigments To impart color to condoms

Table:2. Compounding ingredients

2.4.1.1. Stabilisers

Addition of certain chemicals to latex, generally decreases the colloidal stability. For
example, by the addition of zinc oxide, latex thickens to some extent and the chemical stability
of latex is very much affected. Hence latex has to be properly stabilized prior to the addition of
chemicals. Stabilizers generally fall under three groups, viz. fixed alkali, surface active materials
and protective colloids. Potassium hydroxide is widely used as the fixed alkali. By adding KOH
the pH of the latex is enhanced to about 12. The chemical stability of the latex is also enhanced.
Higher fatty acid soaps and synthetic organic sulphates and sulphonates, containing long
hydrocarbon chains are used as anionic stabilizers. Protective colloids include casein, glue,
gelatin etc. Non-ionic stabilizers like polyethylene oxide condensates (condensation product of
ethylene oxide with higher fatty acids, alcohols or phenols) are superior to natural products like
casein due to less variability in product quality and non-putrefying nature.

2.4.1.2. Surface active materials

Surface active substances, also known as surfactants, are substances which bring about a
marked modification in the surface properties of aqueous media of latices, even when present in
very small concentrations. Depending on the function they perform, they may be classified as
wetting agents, dispersing agents, dispersion stabilizers, emulsifiers, foam promoters, foam
stabilizers etc. Thus some of the latex stabilizers also function as surface active substances. For
the majority of the surface active materials, the principal effect is lowering of the surface free
energy against air and the inter-facial free energy against organic liquids. Depending on the
chemical nature, surface active substances can be classified as anionic, cationic, amphoteric and
non-ionogenic types. The most commonly used are anionic surface active materials.

2.4.1.3. Vulcanising agents

Elemental sulphur is the most commonly used vulcanizing agent for natural rubber latex
and is used along with some accelerators. However, to achieve some specific properties for the
vulcanized films, like heat resistance and to avoid staining of metal parts by sulphur, sulphur
donors like thiuram polysulphides (eg. TMTD) are used in latex. But vulcanization with thiuram
polysulphides and zinc oxide alone, in the absence of added sulphur proceeds at a useful rate,
only at relatively high temperatures (say 140°C) whereas with latex products, vulcanization at
about 100°C is the common practice. However, Philpott has shown that certain sulphur
containing compounds, notably thiourea, are able to activate vulcanization by thiuram
polysulphides, so that well cured latex products could be produced rapidly at 100°C and the
optimum mole ratio of thiourea to thiuram is 1:1. Dunn has reported that butyl xanthogen
disulphide in conjunction with a dithiocarbamate can be used to vulcanize natural rubber latex
films; however, the level of each chemical to be used is appreciably high and hence this method
is not adopted commercially.

Among the non~sulphur vulcanizing agents organic peroxides and hydroperoxides are the
more important. During the 1990’s peroxide vulcanization has gained some importance because
of the possible liberation of nitrosamines and nitrosatable amines, derived from accelerators for
sulpher vulcanization. t-Butyl hydroperoxide is the most important among the hydroperoxides. In
the actual process, the organic hydroperoxide is added to latex in presence of a reducing agent
like fructose. Peroxide prevulcanized latex would be particularly useful in the production of
teats, soothers and catheters where the nitrosamine problem is most significant. A new method of
prevulcanizing natural latex, by the use of gamma radiation is dealt with later.

2.4.1.4. Accelerators

Vulcanization of natural rubber with sulphur alone is a very slow process and physical
properties of the vulcanizates are very poor. The group of chemicals known as vulcanization
accelerators, when used along with sulphur imparts high state and rate of cure. The most
important class are dialkyl dithiocarbamates and the most widely used member is zinc diethyl
dithiocarbamate (ZDC). Another member zinc dibutyldithiocarbamate is used when vulcanized
films of higher clarity are needed and also when a higher level of prevulcanization is needed
even during storage at ambient temperatures, during the maturation process. Dithiocarbamates
are active even in the absence of zinc oxide. Thiazoles and to a lesser extent thiurams and
guanidines are employed as secondary accelerators in conjunction with dithio-carbamates.
Thiazoles are insufficiently active to be used on their own. The most widely used thiazole is zinc
mercaptobenzthiazole (ZMBT). Replacement of one quarter to one half of ZDC by ZMBT
results in much higher modulus being attained without any significant extension of the
vulcanization time. ZMBT is activated by thiurams and dithiocarbamatesm.

Thiurams, as a class, are insufficiently active to accelerate satisfactorily sulphur

vulcanization of diene rubbers in latex form. They are used as secondary accelerators along with
dithiocarbamates. Most commonly used thiuram is TMTD.

2.4.1.5. Activators

Activators assist in vulcanization by enhancing the reactivity of accelerator/accelerator-

sulphur complex. The most commonly used activator in latex technology is zinc oxide. It is
believed that zinc oxide reacts with the accelerator to produce an active accelerator complex
which can react with sulphur to form the effective sulphurating agent. In the sulphur
prevulcanization of natural latex, the state of cure is enhanced by addition of zinc oxide and the
tendency for reversion is reduced. In a latex compound zinc oxide addition increases tensile
strength and modulus of dry latex films.

2.4.1.6. Antioxidants

Heat and oxygen, either separately or in combination can bring about the degradation of
rubber molecules, resulting in deterioration of physical properties. The inherent ageing behaviour
of rubber molecules in latex is good, as the molecules have not undergone any mechanical
degradation, as brought about by mastication in dry rubber. However, antioxidants are
commonly used in latex compounding, especially in products like dipped goods where the
surface area to mass ratio is high. The commonly used antioxidants fall into two groups, viz.

 amine based antioxidants - they are powerful antioxidants, but can cause discoloration of
the film.

 phenol based antioxidants - they are less active than amine antioxidants, but are non-
discoloring and hence widely used in latex application. Styrenated phenol is a typical
member.

A rather recent addition to the group of non-staining antioxidants is alkyl phosphites.

Trisnonylated phenyl phosphite (TNPP) is very successfully used in radiation vulcanized natural
rubber latex (RVNRL). Alkyl phosphites do not cause the liberation of volatile nitrosamines.

2.4.1.7. Fillers

Fillers are generally added to latex compound to modify its properties and to reduce cost.
Fine particle carbon blacks and silicas, which are generally reinforcing fillers in dry rubber
compounding do not reinforce the latex film by increasing tensile and tear strengths. It is
believed that mastication of dry rubber generates rubber free radicals, which interact with the
surface of filler particles and so unites the rubber particle to filler surface. In latex compounding
this type of rubber-filler interaction is absent. Precipitated silica, china clay, whiting and
precipitated calcium carbonate are the important mineral fillers used in latex compounding.
Organic fillers (resins) can also be used as fillers in latex compounding.
2.4.1.8. Special additives

Several types of substances fall in this group. Mineral oils and non-volatile esters find
considerable application as polymer softeners and plasticizers. Certain petroleum gellies are used
as cell wall lubricants and sodium silicofluoride as delayed action gelling agent for latex foam
rubber. A number of viscous and resinous substances are used as tackifying resins in the
formulation of latex adhesives. Other substances generally used are foaming agents, flame
retardants, colours etc.

2.5. CONDOM PRODUCTION

The process of condom production includes a series of processes like

 Compounding

 Moulding

 Vulcanizing

 Quality checking

 Electronic testing

 Packing

 Final product testing/checking

2.5.1. COMPOUNDING AND PREVULCANIZATION

It involves addition of fixed quantity of chemicals to raw latex in mixers. The solid
ingredients likes S, ZnO and antioxidants are first converted into a combined dispersion. The
dispersion of compounding chemicals is being prepared by ball milling/pearl milling /sand
grinding/ attractor mill grinding. After grinding the particles size of the dispersion is checked
before adding it into the raw latex. First stabilizers are added to the latex followed by the
addition of other ingredients. The compounded latex is then stirred for few hours for the uniform
distribution of the ingredients. Then the compound latex is prevulcanized by passing steam/hot
water into jacketed mixer. The cure of the latex is checked at fixed interval and the heating is
stopped when the required cure is achieved. The latex is then cooled to low temperature to arrest
any further prevulcanization.

The compounded latex is then allowed for sufficient natural ageing (for few days) before
supplying to the dipping tanks to molding operation. The compounded latex parameters like TS,
viscosity and HST are tested and brought to the required specified level before feeding it to the
dipping tank.

Solid Raw Latex Ammonia

Compounding Solution

Attritor Mill / Sand Grinder

Pearl Mill (Optional)

Supply Tank
Mixing Tank

Steam Agitator

Chilled Heating
Water
Dipping Tank
Cooling

Fig:1. The compounding process flow chart

2.5.2. MOULDING

Moulding process consists of the following operations.

Glass formers of required dimensions are vertically arranged in an endless conveyer chain.
The cleaned moulds enter the dipping tank at a certain angle and leave with a uniform latex film
adhering to it. This is dried and again comes for second dipping. The open end of the film is
rolled up using edge rolling brush and dried again in heating chamber / bottom oven and main
ovens. For both of the below mentioned technologies the dipping process is more or less the
same.
2.5.2.1. Okamoto technology

The film sticking to moulds are passed through an alkaline batch where it get swelled (for
easy removal from the mould). Moreover leachable chemical residues and proteins are removed
form the product while passing through the batch. The former with the product then passes
through a cationic surfactant (prevent the adhesion of the film during the stripping) before being
stripped by means of silica slurry jets. The stripped product along with silica slurry moves to the
vulcanizing section by gravity flow.

2.5.2.2. Richter technology

The film sticking on to the moulds are swelled in the leaching tank (the leaching solution
contains a diluted hot water solution of Tri sodium phosphate) and are stripped off by means of
TSP solution. The stripped products are manually transferred to the powder finishing area where
the product is treated with powder and silicone emulsion. The product is then vulcanized.

Dipping Tank Unit

Drying & Pre vulcanizing

Beading Edge Roller

Pre vulcanizing & Drying Unit

Swelling Bath Unit

Anti Sticking Bath

Vulcanizing Section. Stripping dried condom unit

HP- QA Mould Washing Unit

Fig:2. Process flow in moulding

2.5.3. VULCANIZING SECTION

The stripped condom along with the slurry is passed through a dehydrator where excess
water is removed from the product. The partially dried condom is then transferred to
vulcanization barrel through pneumatic pipeline. The condoms collected in the barrel are
vulcanized by hot air and the vulcanization temperature is maintained at 80degree centigrade for
a time of 40-45 minutes. After that the vulcanized material is transferred to quenching barrel
where it is cooled to ambient temperature. It is then collected in plastic create and send to HP
section for inspection purpose. This operation is monitoring and controlling through the SCADA.

2.5.4. QUALITY CHECKING AT HALF PRODUCT STAGE

The product obtained after vulcanization can be called as half product .In order to ensure
the quality the following parameters can be checked at half product stage (moulded
product).These tests used as internal quality control standard. The quality check can include.

 Visual defect.
 Water leak.
 Burst properties.
 Dimensions.
The common visual defects are Wrinkle, Lip Cut, Inside Sticking, foam, twisted edge roll,
bad edge roll, latex deposit, nipple hole. All these tests are conducted on random sample .These
tests are done for each lot and based on the observation necessary corrective measures can be
taken in the moulding line. The lots passing the QC check are transferred to ETD section for
further processing. The molded condoms are kept for 3 days maturation before subjecting to
electronic testing.
2.5.5. ELECTRONIC TESTING OF NAKED CONDOMS

2.5.5.1. Principle of electronic testing

The electrical resistance of natural rubber latex film is utilized in pinhole testing of the
condoms. Normally the condoms (NR film) exhibit certain amount of electrical resistance and if
pinhole or weak spot are present then the resistance in that area decreases and the current passing
through it increase. For sorting the product into good & bad the threshold current (determined
after validation) is set in the PLC. Those condoms through which the passage of current is below
the set value are identified as good condoms and the other as bad. Low current at high voltage is
used for testing the condoms.

Apart from testing and segregation the condoms are also rolled up in the mandrel before
being stripped.

2.5.5.2. Testing process

The condoms are covered on stainless steel mandrels which are fixed to a conveyor chain.
There is testing station where the high voltage (900 to 1600 v) low current is applied through
conductive rubber flap. During operation the moulds having condom pass through this station.
The amount of current helps to segregate the good and the bad condoms is set in the PLC. When
the condoms pass through the conductive rubber flap ,where the high voltage is applied ,the
circuit will complete only if the steel mandrels are exposed .The exposure occurs when the
mandrels are not covered or there is a hole in the condom .when the conducting current is
greater than the set value ,the particular condom/mandrel will be rejected and the same is
segregated at the stripping separately .If the conducting current is less or equal to the set value,
the particular condom goes to the good category .

The tested condoms are then rolled by using inclined brush rolls. The rolled condoms are
pneumatically stripped of into the good and bad collection trays .The speed of the machine is
90+/-2 moulds per minute.

After electronic testing also in process quality checks is carried out as a process control
measure as well for ensuring the quality of the product .The various parameters checked are.

 Visual inspection
 Water leak test
 Burst volume & Burst pressure test

Receiving Lots From the HP

Maturation of Condoms
under controlled Condition

Electronic testing and

Rolling

Controlling of Lots by ETD Visual Inspection Bad

Handling over the lots to

Los with Leak
HPQC

Good Condoms

Fig:3. Process flow diagram of ETD

2.5.6. PACKAGING

The primary function of packing is to protect the product so that it shall retain its
properties till end of the product shelf life. Due to statutory requirements condoms should have
long shelf life of 3 to 5 years and it is impossible for natural rubber latex condoms to retain its
physical properties for long period unless it is packed properly. Packing of condoms provide two
types of protection- physical protection which is primarily contributed by secondary packing
materials (wallet/carton etc) and barrier protection (against oxygen, ozone etc) which is provided
by foils. The secondary function of packing is to market the product.

The primary packing of the condoms is done in multilayer laminate consisting of 9 micron
Al. This operation is carried out in packing machine where heated jaws are used to seal the foil.
The lubrication of the condoms are also done during the packing operation The lubricated foiled
condoms are called strips which are further packed into consumer pack( wallet),display pack(
display carton) and finally bulk packed in master carton. This is called secondary packing
operation and it is being done manually.

Generally silicone oil is used as the lubricant and the quantity of lubricant varies
depending upon customer requirement. But the lubricant quantity is above 250mg which is the
minimum limit as per schedule R of the drugs and cosmetic act.

In order to ensure the quality, various in process checks like lubricant quantity, visual
defects, package seal integrity etc are checked at random samples

2.5.7. FINAL PRODUCT TESTING

This is done after the completion of the entire manufacturing operation. The various
testing parameter depends upon the standard/customer requirement. The following are the
common final product testing parameter.

 Dimension(length ,nominal width, single wall thickness)

 Freedom from hole

 Visual defects

 Burst properties
  Package seal integrity

 Lubricant quantity

 Packaging marking and conditions

 Product bioburden

 Colour fastness

The number of samples to be tested and the acceptance/ rejection criteria are given in the
respective standards. Generally the products are tested against schedule R standard or an ISO
4074.Only batch that passes in the final product testing are dispatched to the customer.

Fig:4. Flow chart showing the overall process in condom production

3. VULCANIZATION

Vulcanization or curing is an essential step in the manufacture of almost all rubber

products. it is the process of crosslinking rubber molecules to transform them from a mainly
viscous state to an elastic state by forming a three dimensional network. In terms of conventional
physical properties this transformation enhances the modulus of the material and its resistance to
rupture and tear.

Sulphur is being used as the most popular vulcanizing agent since its discovery by
Goodyear, about 160 years ago. Although rubber can be cured by sulphur alone, the process is
very slow and the properties obtained are not ideal. Today sulphur is used in conjunction with
one or more accelerators. Accelerated sulphur vulcanization remains the crosslinking process for
the overwhelming majority of rubber products both from dry rubber and latex. The three
dimensional structure produced by crosslink fonnation during vulcanization restricts the free
mobility of the long polymeric molecules. The crosslinks have the effect of preventing the
polymer chains moving bodily past each other when an external force is applied to the matrix.
This is schematically represented in Figure 5.

Fig:5. Crosslink formation

 Sulphur vulcanization is an exceedingly complex chemical process, which is summarised
in Figure 6.

Fig:6. Vulcanization reaction

 Crosslinks formed may be through a chain of sulphur atoms, or by a single sulphur atom or
directly between carbon atoms. The vulcanizate properties are not functions of crosslink density
alone. They are affected by the type of crosslink, nature of the polymer type, amount of filler etc.
It is observed that modulus of latex films increases through a maximum and then decreases as
vulcanizing time progresses. A similar effect has been reported for dry rubber vulcanizates also.

The mechanism of accelerated sulphur vulcanization has been extensively studied. It is

believed that the mechanism of both pre-and post-vulcanization of latex will be the same, at least
in outline. The first step is the combination of the accelerator with one or more activators, which
has the effect of solubilising the accelerator in rubber. ln latex compounds the most common
activators are carboxylates, or naturally occurring amino compounds which are added as
stabilizers. The active accelerator reacts with sulphur to produce active sulphurating agent,
which, in tum, reacts with rubber hydrocarbon to give a pendant group consisting of a chain of
sulphur atoms, terminated by the accelerator derivative. The pendant group can form a crosslink
either by direct reaction with another polymer molecule or by disproportionation with another
pendant group. In either case the initial crosslinks are polysulphidic. These crosslinks are
chemically reactive and on continued heating undergo three parallel sets of reactions.

 desulphuration or crosslink shortening to disulphides and monosulphides, with the

recycling of sulphur into additional crosslinks.

 decomposition or crosslink destruction, with the formation of non-crosslinking

modifications along the polymer chain and

 exchange of sulphur-sulphur bonds, allowing rearrangement of chains and relaxation of

stress within the net work.

3.1. VULCANIZATION METHODS FOR LATEX PRODUCTS

For the sulphur vulcanization of products made from latex, two alternatives exist

(Figure 7).
 Fig:7. Methods of vulcanization

In the first method the chemicals required for vulcanization are mixed into the latex, then
the mixture is formed into the required shape and dried. The dried rubber mix containing the
chemicals is then heated to effect vulcanization. This is known as post-vulcanization since
crosslinking occurs essentially after the product has been fomred. The other altemative involves
heating the latex at a suitable temperature with the vulcanization ingredients dispersed in it, until
the required level of vulcanization has been achieved. This is called prevulcanization. The
resulting prevulcanized latex can be fonned into latex products in the normal way. Only drying is
required to obtain the vulcanized rubber product.

Prevulcanization and post-vulcanization can be considered as two extreme cases. A latex

compound prepared for post-vulcanization will generally undergo some degree of
prevulcanization between the time it is compounded and the point at which it is used. On the
other hand fully prevulcanized latex will generally contain some excess vulcanizing ingredients
which can cause some post-vulcanization during and after drying of the product.

ln post-vulcanized latex systems crosslink destruction is minimum because of the

relatively low vulcanization temperatures; crosslink shortening and exchange of sulphur-sulphur
bonds allowing rearrangement predominates, leading to a stable network containing some mono-
and disulphidic crosslinks as well as polysulphidic ones. The relative proportions of the three
types of crosslinks depend on the ratio of sulphur to accelerator in the original recipe and on the
curing time and temperature, but in most latex systems di- and polysulphidic crosslinks
predominate.

Zinc oxide is widely used in latex vulcanization systems, although zinc dialkyl
dithiocarbamate accelerated vulcanization can successfully occur without it. Zinc Oxide prevents
vulcanization to come to a premature halt due to depletion of accelerator and leads to a higher
modulus.
4. PREVULCANIZATION OF NATURAL RUBBER LATEX

lt is a special property of natural rubber latex, and also of some other types of diene latex,
that it is possible to vulcanize the individual particles in latex without destroying its colloidal
character. The product, prevulcanized latex, is colloidally stable, the dispersed polymer of which
is crosslinked into networks of indefinite extent. In appearance, prevulcanized natural rubber
latex is very similar to unvulcanized latex. The original fluidity of the latex is retained. The
particles in prevulcanized natural rubber latex have essentially the same shape, size and size
distribution as did those in the initial unvulcanized latex.

There are three principal ways in which natural rubber latex can be prevulcanized. They
are:

 by reaction with sulphur and organic vulcanization accelerator(s),

 by heating latex with organic peroxides and hydroperoxides,

 by exposing latex to high energy gamma radiation or electron beam in the presence of
sensitizers.

The possibility of vulcanizing the disperse phase of natural rubber latex without any
concomitant colloidal destabilization was first investigated by Schidrowitz. Relatively high
temperatures (about 140-145°C) were used, as very active organic accelerators were not
available then. But now it is possible to prevulcanize latex to a high state of cure in about one
hour at about 6O—7O°C.

Sulphur prevulcanized natural rubber latex is invariably prepared by allowing the rubber
molecules in the latex particles to react with sulphur under the influence of one or more organic
accelerators and possibly of an inorganic vulcanization activator as well. Compared to dry rubber
vulcanization, prevulcanization of latex proceeds much more rapidly at the same temperature
with the same vulcanizing ingredients. The speed of prevulcanization seems to be primarily
associated with the presence of water. Recent investigations into sulphur prevulcanization of
natural rubber latex have been summarized by Blackley. There are several features of the
prevulcanization process which are subject to variation. These include:
  level of sulphur

 whether the vulcanization accelerators are water soluble or water insoluble, or a

combination

 nature and levels of accelerators

 the particle size of the sulphur dispersion

 the particle size of dispersions of water-insoluble accelerators used

 whether or not an inorganic activator is used, if so the type and quantity

 the temperature-time profile which is imposed for the reaction

 the extent to which the reaction is allowed to continue

For a given level/type of accelerator, the modulus of the vulcanized films increases with an
increase in sulphur content. Hamphreys and Wake reported that no matter how much sulphur is
included in the latex compound it is not possible to attain more than 1.8% combined sulphur with
the rubber hydrocarbon. Dialkyl dithiocarbamates are the most commonly used accelerator.
Water-insoluble accelerators, unless made into fine dispersions, may sediment during storage
and the desired state of cure will not be attained. For equimolecular concentrations of sodium
and zinc dialkyl dithio-carbamate the zinc derivatives give higher modulus. For equimolar levels
of various dithiocarbamate accelerators, the state of cure attained during prevulcanization is
affected by the alkyl chain length of dialkyl dithiocarbamate. The state of cure as well as
modulus increase as the number of carbon atoms on the alkyl group increases up to 4 (ie, butyl)
and then again decreases. This is based on a balance between solubility in aqueous phase of latex
and adsorption at rubber-serum interface.

A minimum of about O.5phr accelerator is needed for reasonable level of vulcanization. lt

is seen that there is no appreciable change in tensile properties during the initial hours of
prevulcanization as the concentration of the accelerator is increased. However, on prolonged
heating, increase in modulus is observed at higher levels of accelerator concentration. For 1:1
ratio of sulphur to accelerator, tensile strength and modulus increases upto lphr each of sulphur
and zinc diethyl dithiocarbamate and further increase beyond this level has no appreciable effect.
At higher times of prevulcanization a fall in tensile properties are however observed at higher
concentrations of vulcanizing chemicals.
 The particle size of sulphur and accelerator appeared to have no significant effect upon the
tensile properties of films obtained from the latex. lt indicates that the amount of vulcanizing
ingredients which become available for reaction with rubber under these conditions is not
significantly affected by the area of interface between sulphur or accelerator particles and the
aqueous phase. Fine dispersions are essential to prevent sedimentation of ingredients during
processing and thus to guarantee homogeneity of dispersion during the manufacturing process,
but reaction can proceed from quite coarse dispersion if precautions are taken to prevent
sedimentation. The rate of prevulcanization increases as the latex particle size decreases.

The effect of temperature on prevulcanization of natural latex has been studied by several
authors. Increase in the temperature of prevulcanization was accompanied by an initial sharp
increase in tensile strength and modulus. Claramma and Mathew showed that the volume
fraction of rubber in the dry film, which is a measure of crosslink density, exhibited a maximum
when prevulcanization was conducted at 80°C for 2h or at 90°C for 1h. At each temperature,
tensile strength and elongation at break decreased when prevulcanization time was increased,
whereas modulus increased to a maximum and thereafter decreased.

The single most important factor in determining the tensile strength of film is the degree of
chemical crosslinking. The degree of crosslinking in a vulcanizate film can be varied either by
controlling the prevulcanization time, temperature or by changing the level of curatives.
Irrespective of cure time and level of curative, the optimum tensile strength occurred when the
degree of chemical crosslinking attained 1.O—2.2x1O-5 gram mole of crosslink per gram of
rubber hydrocarbon.

In the case of NR vulcanizates prepared by dry rubber compounding, it has been reported
that the optimum tensile strength occurred when the crosslink density was in the range 4-7x1O-5
gram mole per gram of rubber hydrocarbon. This range is significantly higher than that observed
for the prevulcanized latex films. This difference suggests that a mechanism other than the
degree of chemical crosslinking is operative in affecting the tensile strength of latex films.

It was believed that the presence of non-rubber constituents in natural rubber latex,
especially proteins is essential for the occurrence of sulphur prevulcanization of natural latex.
Ghazaly has shown that it is possible to sulphur prevulcanize natural rubber latex from which
most of the non-rubber materials have been removed; however the overall rate of crosslink
insertion was found to be reduced.

4.1. MECHANISM OF SULPHUR PREVULCANIZATION

There are different schools of thought regarding the mechanism of sulphur prevulcanization
of natural latex. Some authors have postulated that the reaction takes place as a result of direct
contact between particles of reactants and rubber. Some other authors believe that the reactants
must dissolve in the aqueous phase before diffusing into the rubber pa1ticles. van Gils
demonstrated that sulphur is appreciably soluble in the aqueous phase of ammonia preserved
natural rubber latex where as it is not significantly soluble in dilute aqueous ammonia solution.
Loh found that zinc di-n-butyl dithio- carbamate is appreciably soluble in the aqueous phase of
ammonia preserved natural rubber latex than in water or aqueous ammonia solution of pH 10.2.
Enhanced solubility of sulphur and accelerator in the aqueous phase of latex, presumably
facilitates sulphur prevulcanization. Recently it has been demonstrated that sulphur and zinc
dialkyl dithiocarbamate accelerators are independently able to dissolve in ammonia preserved
natural rubber latex which subsequently effect prevulcanization of latex when the other
ingredient is even added as a solid phase.

It has been reported from qualitative observations that sulphur can transfer from sulphur
particles originally present in the aqueous phase to the rubber particles remarkably rapidly. The
zinc dialkyl dithiocarbamate accelerator by itself does not transfer from its particles to any
significant extent. ln the presence of sulphur, the accelerator can transfer, although more slowly
than sulpher. It therefore, appears that the first major step of the reaction is the formation of a
sulphur-accelerator species in the aqueous phase of the latex and that this species can get
transferred to the rubber phase. lf this species were surface active, then the most obvious mode of
transfer would be adsorption from the aqueous phase onto the surface of the rubber particle.
However, this sulphur-accelerator species has to be soluble in an aqueous medium. This is
rendered soluble in water to a sufficient extent by interaction with some of the hydrophilic non-
rubber substances, which are present in ammonia preserved natural rubber latex concentrate. The
sulphur- accelerator species after adsorption loses by dissociation some or all of the hydrophilic
moieties which have rendered it sufficiently water soluble for transfer to the surface of the rubber
particles. The lost moieties would then return to the aqueous phase and be available for
interaction with other molecules of the sulphur-accelerator species in due course whereas the
residual sulphur- accelerator species at the particle surface would now be sufficiently
hydrophobic in nature to migrate into the interior of the rubber particle. The sulphureting species
that has thus entered the rubber particles bring about crosslinking reaction. When the active
sulphurating species reach the surface two simultaneous processes can occur: diffusion of the
active species and the crosslinking reaction. If the crosslinking reaction is faster than diffusion
the particles are crosslinked preferentially near their surface and the reduced mobility of the
rubber chains at the surface makes the effective fusion of the particles more difficult and the final
properties will not be optimum.

Several authors have reported on different aspects of sulphur prevulcanization of natural

latex. Porter has compared the properties of pre-and post vulcanized latex films. He has also
reported the effect of leaching and has examined the dependence of tensile strength on degree of
crosslinking for pre- and post vulcanized films. Natural latex can be prevulcanized even at room
temperature using zinc di-n-butyl dithiocarbamate. The effect of preservation system and quality
of latex on prevulcanization characteristics have been studied by Low. According to Gazeley the
rate of extraction of water soluble materials is faster from prevulcanized films than from post-
vulcanized films and increases with the degree of vulcanization. The easier extraction of water
soluble materials from prevulcanized latex films is attributed to their higher porosity. Chong and
Porter have reported that the crosslinks formed in rubber particles during prevulcanization are
predominantly polysulphidic. The proportion of mono- and disulphidic crosslinks was found to
be less than 28% of the total crosslink concentration. A similar conclusion has been arrived at by
Loh and Peethambaran and George also. Micro changes in the rubber particles during sulphur
prevulcanization of natural latex have been studied. Also vulcanization was found to be
continuing during storage.

4.1.1. ADVANTAGES

Prevulcanized latex is a convenient fonn of material for the latex goods manufacturing
industry especially the dipped goods industry. The latex does not require compounding and
vulcanization by the product manufacturer. It is especially suitable for products made by dipping
because of the convenience of vulcanizing latex in bulk in relation to the trouble and expense of
curing the equivalent amount of rubber in the form of thin deposits over innumerable formers. It
also finds application in adhesives, textile combining, carpet backing and cast rubber products."
Better quality control can be achieved by the use of prevulcanized latex in product manufacture.
Other advantages are shorter drying time and products of high clarity, particularly if
prevulcanized latex is clarified before use.

4.1.2. DISADVANTAGES

Prevulcanized latex does not find application in latex foam manufacture mainly on account
of its poor wet gel strength. Films prepared from prevulcanized latex exhibit lower tensile
strength, modulus and elongation at break as compared with postvulcanized films. Tear strength
of prevulcanized latex films tend to be inferior to those of postvulcanized films, which restricts
the application of prevulcanized latex to products of fairly thick wall section. When immersed in
solvents such as benzene or carbon tetrachloride, deposits from prevulcanized latex swell
considerably to give gels which are mechanically rather weak. Prevulcanized latex films exhibit
also inferior resistance to oils and greases. Thus a prevulcanized film is readily ruptured if a drop
of solvent is placed on it whilst it is held in an extended condition. Latex gloves which have been
produced from prevulcanized latex are more readily damaged by oil and grease than are those
which are produced by postvulcanization.
5. POSTVULCANIZATION

Postvulcanization with the use of radiation has not been commercialized for dipped latex
articles, presumably due to the complexity of adding a radiation source directly next to a dip
molding line. Peroxide postvulcanization has not been successfully done in the past because
peroxide-containing films at elevated temperatures, exposed to an oxygen atmosphere, rapidly
degrade. Many antioxidants are also rendered ineffective under these conditions.

The postvulcanization step is presumed to provide for covalent bonds between individual
coalesced rubber particles, not just within the individual particles as is the case in prevulcanized
films. In both of these processes, the latex particles are not necessarily uniformly vulcanized,
since the outer surfaces of the particles are more directly exposed to the vulcanizing agents, in
contrast to the interior of the particles. If the outer surfaces of the particles are more crosslinked
than the interior of the particles, then a pseudo case hardening effect may have occurred. Some
manufacturers allow latex to Amature in an effort to allow the crosslinks to become more evenly
distributed throughout the film.
6. PEROXIDE VULCANIZATION

6.1. PREVULCANIZATION WITH PEROXIDES

Prevulcanization of natural rubber latex, by heating in the presence of an organic peroxide

has been known for many years. Peroxides can be used for vulcanizing dry rubber also. Organic
peroxides are used in conjunction with activators, to facilitate decomposition. Even though
peroxide vulcanization of latex was a simple process, there was little industrial interest, due to
the relatively poor ageing behaviour of peroxide vulcanizates. Recently peroxide
prevulcanization was reinvestigated because of concern about the possible presence of
carcinogenic nitrosamines in products made by conventional sulphur- accelerator reaction. It has
been shown that hydro-peroxide prevulcanized lattices can produce films with physical
properties similar to those of sulphur vulcanized latex films. Also the possibility of allergic skin
reactions due to accelerators can be avoided.

The basic mechanism of peroxide prevulcanization involves O — O cleavage of the

peroxide producing alkoxy radicals. These radicals abstract hydrogen from polymer molecules
principally from the or-methylene groups adjacent to the olefinic bonds to form polymer radicals
which then crosslink together.

For fructose-activated t-butyl hydro-peroxide system crosslink density of 5-6x10-6 gram

mole per gram of rubber hydrocarbon is required for optimum tensile strength. t-Butyl
hydroperoxide concentration of about 9 milli mole/100 gram rubber and fructose/t-BHP mole
ratio of 0.6 at 60°Cgives crosslink density of about 4-5 x 10-6.

The ageing behaviour of films from peroxide prevulcanized natural rubber latex is
generally poor. It has been recently reported that phenolic antioxidants like 2, 4 dioctyl phenyl
sulphide-6-methyl phenol and 2, 2’ methylene bis- [4 methyl-6-t- butyl] phenol are very effective
anti-oxidants for peroxide prevulcanized latex films. The microstmcture of peroxide
prevulcanized latex films made from peroxide-water soluble activator combination is different
from that made using a more rubber soluble thermally activated peroxide.
6.2. WHY WE USE PEROXIDE VULCANIZATION TECHNIQUE?

As a general rule, sulfur is used as the primary vulcanizing agent for dip molded latex
rubber components. Various accelerators, activators, sulfur donors, and boosters are necessary to
properly compound these latices for use in traditional dip molding vulcanization processes. The
prevulcanization of latex rubber without the use of these types of chemicals, or with no
chemicals at all, by means of free radical crosslinking is well known.

Prevulcanizing latex by free radical crosslinking involves the use of organic peroxides
and/or hydroperoxides. These types of latices are referred to as Peroxide Vulcanized Natural
Rubber Latex (PVNRL).A typical process superheats natural rubber latex in the presence of
organic peroxide(s). After cooling, films are cast and dried, yielding vulcanized rubber films
with a tensile strength as high as 251 kg/cm2 (3739 psi). In preparing the films, the films are
only dried, and not subjected to any sort of post-drying vulcanization procedure. While this
procedure reportedly works, to be commercially viable, large and expensive heated pressure
vessels are required to prepare the latex. As with RVNRL, PVNRL also relies exclusively on the
prevulcanization of the dispersed rubber particles. There appears to be no chemical pathway
available to allow for covalent bonding of the former individual latex particles to form a truly
integrated, pore-free latex rubber film. To avoid the use of pressure vessels, some PVNRLs are
made with the use of catalysts at lower temperatures5. Such methods generally produce lower
tensile strength films, and leave chemical residuals in the films. Again, there is no means of
integrating particles together via covalent bonds.

Previous attempts at incorporating some postvulcanization characteristics into RVNRL

and PVNRL have required the use of additional vulcanization chemicals, including accelerators,
activators, etc. Postvulcanization with the use of radiation has not been commercialized for
dipped latex articles, presumably due to the complexity of adding a radiation source directly next
to a dip molding line. Peroxide postvulcanization has not been successfully done in the past
because peroxide-containing films at elevated temperatures, exposed to an oxygen atmosphere,
rapidly degrade. Many antioxidants are also rendered ineffective under these conditions.
6.3. PROCESS DESCRIPTION

To overcome the above-mentioned problems associated with the all of the previously
developed free radical curing systems, a new method was developed6 to allow for the free
radical postvulcanization of various latices via postvulcanization methods. The initial
groundwork for this technology was conducted at Apex Medical Technologies, Inc. and was
aimed at trying to improve the tensile properties of synthetic IR latex films. Even with the use of
traditional compounding agents, it was our observation that it was very difficult to obtain
suitable physical properties needed for the production of medical gloves unless large quantities
and multiples types of accelerators and/or boosters were added. Traditional free radical curing
methods were evaluated and found to be lacking, especially with respect to tensile strength.

Our development program led to the successful development of a free radical

vulcanization process, which relies exclusively on a postvulcanization process. As mentioned
previously, the main issue with postvulcanization of organic peroxide-containing films involves
the degradation of the films during curing when exposed to atmospheric oxygen. By eliminating
exposure of peroxide-containing latex films to atmospheric oxygen, it became practical to make
excellent films via a postvulcanization process.

The elimination of oxygen is accomplished by using an elevated temperature oxygen-free

environment, which can be created by several different methods. One particularly effective
method is being recommended to licensees of this technology. Elevated Temperature for
Peroxide Homolytic Cleavage and Particle Integration

By excluding oxygen, and using high temperatures, it is possible to effectively utilize

organic peroxides as latex rubber curing agents. For years, the use of organic peroxides has been
widely used in solid rubber molding applications, and now it is possible to use similar
formulations for latex dipped goods. While certain organic peroxides are especially preferred to
create free radicals for crosslinking, it is possible to use other free radical generation methods to
accomplish the same thing.

The temperature conditions used for curing are sufficiently high to thermally decompose
the organic peroxide(s), and to simultaneously fuse the latex particles together. When dip
molding latex articles, it is very advantageous to obtain good integration and bonding between
the individual rubber particles. This helps to produce pore-free films, which are necessary to
prevent the passage of pathogens, or other unwanted substances, through the wall of the dipped
part.A simplified flow diagram of this process is as follows:

Note that it is not necessary to age or mature the compounded latex. The compounded latex is
exceptionally stable with no measurable crosslinking occurring during storage.

Fig:8. Flow diagram of accelerator-free peroxide curing method

6.4. CHEMISTRY

6.4.1. VERY WELL UNDERSTOOD CHEMISTRY

Organic peroxides undergo homolytic cleavage at elevated temperature. The resulting free
radicals induce hydrogen abstraction of hydrogen atoms from the polymer backbone. These in
turn create free radicals on the polymer backbone, which allow the chains to form carbon-carbon
crosslinks with one another. These carbon-carbon bonds are stronger and more stable than those
formed by sulfur crosslinking. Also, the bond is a very predictable one, unlike the many
different types of carbon-sulfur bonds. The chemical character of the main polymer chain,
however, is not changed, so it is still necessary to add anti-degradation agents to the compounds.
It is also possible to add coagents during compounding to add a slightly different characteristic to
some of the carbon-to-carbon bonds. The addition of certain coagents help to provide for the
enhancement of certain specific physical properties, such are tear strength.
6.4.3. PEROXIDE RESIDUALS AND BREAKDOWN PRODUCTS

With the use of enough half-lives, very little organic peroxide remains in the cured film,
however, there are some decomposition products. Therefore, it is important to choose a suitable
peroxide to avoid any issues associated with unwanted breakdown products. One such organic
peroxide, 2,5-Dimethyl-2, 5- di (t-butyl-peroxy) hexane, is especially well suited for biomedical
applications due to its innocuous breakdown products. These breakdown products include
methane, t-butyl alcohol, and acetone, which are volatile and tend not to stay in the cured films.

6.4.4. TYPES OF LATICES

Many, but not all latices can be cured with the novel curing system. To date, the following
latex materials are known to be compatible with the novel curing system: natural rubber,
enzymatically deproteinized natural rubber, guayule natural rubber, polychloroprene rubber,
synthetic polyisoprene rubber, polyurethane, and nitrile rubber. One material known to be
incompatible is butyl rubber. While traditional dip molding vulcanization methods are generally
limited to partially unsaturated polymers only, it is now possible to cross-link fully saturated
elastomers such as polyurethanes.

6.4.5. TENSILE-SET PROPERTIES

The stability of the carbon-carbon bonds allows the vulcanized rubber materials to have
better tensile set properties. This is especially true for synthetic polyisoprene latex and NR latex.
For products such as catheter balloons, this is a very useful improvement compared to traditional
curing techniques.

6.4.6. CLARITY AND COLOR

Synthetic IR latex can be made essentially water-clear. The color of cured NR latex films
can also be improved, as there are few residual chemical compounds left in the rubber after
curing. CR latex films develop amber to light brown coloration.

6.4.7. HIGH TEMPERATURE HEAT STABILITY

The carbon-carbon bonds are very thermally stable, unlike carbon-sulfur bonds. The
normal polymer chain bonds are not changed with respect to their stability. This is important if
the final dipped article is to be subjected to elevated temperatures during use. The use of
coagents can also influence the exact high temperature behavior.

6.4.8. COMPOUNDED LATEX STABILITY

It is possible to compound various latices with all of the necessary curative agent(s) in
place without being concerned about the stability of the latex compound over time. With
traditionally compounded latex, some crosslinking continues to occur over time. With the novel
curing system, it is very practical to have the compounded latex to remain essentially unchanged
with respect to degree of cure over a long period of time, since there is essentially no pre-curing
taking place when stored until ambient conditions. Films made from compounded latex produce
films with essentially the same state of cure in a manner, regardless of the age of the compound.

To prove this point, a short study was conducted which measured the state of cure as a
function of storage time of the compound. Since solvent swelling is inversely correlated with
degree of cure, it was used to demonstrate the degree of cure in this study. For this test, synthetic
polyisoprene latex was utilized. Films were dip molded and cured at intervals ranging from one
hour to 12 days. Small circular disks were cut from the cured films and were immersed in
toluene for 30 minutes. They were then measured to determine the percent swell. The state of
cure remains very steady without regard to the time frame studied.