Present invention provides plastic container that are stable for storage of strong agrochemicals.
Present invention further provides a process for producing fluorinated plastic container used for long term storing of agrochemicals such as emulsifiable concentrate (EC) of isoprothiolane 28% and fipronil 5%w/w EC, or suspoemulsion (SE) of Pyriproxyfen 8% + Diafenthiuron 30% SE.
BACKGROUND OF THE INVENTION
High density polyethylene single layered packaging made up of one material (HDPE) only, has been used as containers, especially bottles for storing of agrochemical products. As they are made up of single polymer, hence are 100% recyclable however they suffer from major drawback of deformation. These single layered or mono-layered packaging are not stable and due to the interaction with strong chemicals/solvents contained in pesticides or insecticides, they get deformed and hence are not suitable for long term storage of agrochemical products.
Multi-layered COEX containers were introduced as improvement over single layered containers as a response to the need of solution for deformation. The packaging known as COEX multilayer combines several layers of different plastics materials, one of them with barrier properties. Therefore, this type of container is ideal to preserve plant protection products inside without suffering from deterioration. This packaging is resistant to contact with chemicals, to solvents and to high temperatures. However, they are not 100% recyclable & are very costly.
Hence, there is always a need to develop a 100% recyclable plastic container which are stable enough for storage of strong chemicals such as agrochemicals. Present

invention is focussed to develop a plastic container which is easy to manufacture and is environmentally non-toxic and serve the purpose of the need of agroindustry.
OBJECT OF THE INVENTION
Main object of the present invention is to provide recyclable plastic container that are stable for storage of strong agrochemicals.
Another object of the present invention is to provide a process for the preparation of plastic container that is stable against strong agrochemicals such as emulsifiable concentrate (EC) of isoprothiolane 28% and fipronil 5%w/w EC, or suspoemulsion (SE) of Pyriproxyfen 8% +" Diafenthiuron 30% SE.
Another object of the present invention is to provide a process for the preparation of plastic container wherein said plastic material is mono-layered plastic material and wherein said plastic container is a fluorinated plastic container.
SUMMARY OF THE INVENTION
Present invention provides plastic container for long term storage of strong agrochemicals.
Accordingly, in one aspect, the present invention provides fluorinated plastic container used for storage of agrochemicals containing organic solvent.
In another aspect, the present invention provides fluorinated plastic container used for storage of agrochemicals such as emulsifiable concentrate (EC) of isoprothiolane 28% and fipronil 5%w/w EC, or suspoemulsion (SE) of Pyriproxyfen 8% + Diafenthiuron 30% SE.

In another aspect, the present invention provides a process in which a surface of a plastics material is fluorinated using a source of fluorine to produce a plastics material having at least one fluorinated surface, said surface(s) having fluorine adsorbed thereon.
In another aspect, the present invention provides a process in which a surface of a plastics material is fluorinated using a source of fluorine wherein the fluorine molecules replace the hydrogen molecules of polyethylene and make a barrier wall between the agrochemical liquid and the plastic container.
In another aspect, the present invention provides a process for producing surface-fluorinated plastics container for agrochemical products, said process comprising: surface-fluorinating a plastics material with a source of fluorine to produce a plastics material having at least one fluorinated surface; and contacting the fluorinated surface with inert gas.
In another aspect, the present invention provides a process for fluorinating a plastic material while moulding it into a hollow body container for agrochemical products, wherein plastic material is brought into contact with a mixture of fluorine and inert blowing gas; characterized in that
a) the introduction of the mixture of fluorine and inert blowing gas takes place in a temperature range between 40 to 80°C, and
b) level of fluorination is > 3 wherein the percent transmission ratio of fluorine is > 6.0 %.
In another aspect, the present invention provides a process for moulding and fluorinating a hollow body container made of plastic material wherein a preform is brought into contact with the inner wall of the blow mould by blowing in a mixture of fluorine and inert blowing gas; characterized in that

a) the introduction of the mixture of fluorine and inert blowing gas takes place in a temperature range between 40 to 80°C, and
b) level of fluorination is > 3 wherein the percent transmission ratio of fluorine is > 6.0 %.
In another aspect, the present invention provides fluorinated plastic container, wherein the fluorination is done in a single layer plastic container.
In another aspect, the present invention provides fluorinated plastic container for long term storage of organic solvent containing agrochemicals. The organic solvent used in such agrochemicals are generally capable of dissolving or interacting with polyethylene polymer and hence deform the plastic of the container during long term storage. Present invention provides a plastic container that are resistant and stable to such solvents and hence helps in improving longevity & shelf life of agrochemical product.
In another aspect, the present invention provides fluorinated plastic container for long term storage of agrochemicals wherein said agrochemicals have petroleum as an organic solvent.
DETAILED DESCRIPTION
In one embodiment, the present invention provides fluorinated plastic container used for storage of agrochemicals containing organic solvent.
In another embodiment, the present invention provides fluorinated plastic container for long term storage of agrochemicals wherein said agrochemicals have petroleum as an organic solvent.
In another embodiment, the present invention provides fluorinated plastic container used for storage of agrochemicals such as emulsifiable concentrate (EC) of

isoprothiolane 28% and fipronil 5%w/w EC, or suspoemulsion (SE) of Pyriproxyfen 8% + Diafenthiuron 30% SE.
In another embodiment, the present invention provides a process in which a surface of a plastic material is fluorinated using a source of fluorine to produce a plastics material having at least one fluorinated surface, said surface(s) having fluorine adsorbed thereon.
In another embodiment, the present invention provides a process in which a surface of a plastic material is fluorinated using a source of fluorine wherein the fluorine molecules replace the hydrogen molecules of polyethylene and make a barrier wall between the agrochemical liquid and the plastic container.
In another embodiment, the present invention provides a process for producing
surface-fluorinated plastic container for agrochemical products, said process
comprising:
surface-fluorinating a plastic material with a source of fluorine to produce a plastic
material having at least one fluorinated surface; and
contacting the fluorinated surface with inert gas.
In another embodiment, the present invention provides a thick-walled storage container for agrochemicals having a wall thickness at least 1.0 mm, fabricated from a high-density polyethylene, or a blend of the high density polyethylenes or the high density copolymer with a low density polyethylene, and having at least one surface of the container fluorinated wherein the percent transmission ratio of fluorine is more than equal to 6.0%.
Fluorinated surface or a fluorinated surface derived therefrom is contacted with inert gas. Fluorination process generally results into formation of some by products that can get adsorbed on the surface of the container. Inert gas neutralizes said adsorbed by-product. Said by-products are known to corrode components in

fluorinated plastics container and to degrade polymeric material comprising acid sensitive bonds. Advantages of preferred embodiments of the present invention include reducing such corrosion and/or degradation by contacting the container with mixture of fluorine and inert gas, wherein fluorine gas treat the plastic container to fluorinate the surface and inert gas helps in neutralizing the by-products thus formed.
The containers of the present invention exhibit properties which cannot be achieved by using polyethylene alone, since polyethylene cannot withstand "strong agrochemicals". However, it is observed that high density polyethylene (HDPE), when fluorinated, was found to provide good barrier properties. Surprisingly, when high density polyethylene layer is flushed with mixture of fluorine gas and inert gas, during moulding and .preparation of the container, the interior polyethylene layer does not deform or delaminate from the overall polyethylene layer, even when subjected to strong agrochemicals such as insecticides, pesticides and the like.
In another embodiment, the fluorinated container of the present invention can be prepared by use of various moulding techniques selected from extrusion moulding, compression moulding, blow moulding, injection moulding, rotational moulding or mixture thereof.
The fluorinated container may be prepared by use of extrusion moulding wherein the coextruded container having both improved thermal resistance and improved chemical barrier properties comprising: a polyethylene inner layer which forms the interior surface of the container, and a polyethylene outer layer which forms the exterior surface of the container, wherein said polyethylene layer in together having a thickness of atleast 1.0 mm or more, and wherein said polyethylene layer which forms the interior surface of the container has been treated with a reactive source of fluorine.

The fluorinated container may be prepared by use of blow moulding wherein the process comprises of fluorinating a plastic material while moulding it into a hollow body container, wherein plastic material is brought into contact with a mixture of fluorine and inert blowing gas; characterized in that
a) the introduction of the mixture of fluorine and inert blowing gas takes place in a temperature range between 40 to 80°C, and
b) level of fluorination is > 3 wherein the percent transmission ratio of fluorine is > 6.0 %.
In another embodiment, the present invention provides a process for moulding and fluorinating a hollow body container made of plastic material wherein a preform is brought into contact with the inner wall of the blow mould by blowing in a mixture of fluorine and inert blowing gas; characterized in that
a) the introduction of the mixture of fluorine and inert blowing gas takes place in a temperature range between 40 to 80°C, and
b) level of fluorination is > 3 wherein the percent transmission ratio of fluorine is > 6.0 %.
In another embodiment, the fluorination process is carried out by blowing a mixture of fluorine and inert blowing gas at a temperature range between 40-80°C, preferably between 50-60°C, for time period of 2-5h and preferably for 3h.
In another embodiment, the present invention uses plastic material made up of polymer selected from, but not limited to, medium density polyethylene (MDPE) and high-density polyethylene (HDPE)). MDPE and HDPE resins offer greater stiffness, tensile strength and heat resistance. However, other polymer such as low density polyethylene, linear low density polyethylene (LLDPE) and single-site LLDPE can also be used. The Thermoplastic polymers such as polyolefins including polyethylene (PE) and polypropylene (PP), polystyrene (PS), polyvinyl

chloride (PVC), polylactic acid (PLA) or polyethylene terephthalate (PET) can also be used for preparing the containers. Preferably the plastic material is made of high density polyethylene (HDPE).
In another embodiment, the inert gas substantially do not react with molecular fluorine at ambient temperature. Suitable inert gases are selected from helium, neon, argon, xenon, nitrogen and NF3. Preferably, the inert gas is selected from argon, nitrogen and mixtures thereof. In one particularly preferred embodiment, the inert gas is nitrogen.
In another embodiment, the containers can be produced by combination of blow moulding and rotational moulding processes. Generally, blow moulding processes is used for the containers made of polymers at the lower end of the melt index range and for those in the higher end of the range, rotational moulding processes are used.
The containers of the present invention are particularly suitable for the storage of agrochemicals such as emulsifiable concentrate (EC) of isoprothiolane 28% and fipronil 5%w/w EC, or suspoemulsion (SE) of Pyriproxyfen 8% + Diafenthiuron 30% SE because of their reduced absorption of or permeability to petroleum.
In another embodiment, the present invention provides a stable and recyclable surface fluorinated container for storing agrochemical i.e. emulsifiable concentrate (EC) of isoprothiolane 28% and fipronil 5%w/w EC, wherein said agrochemical comprising of:
a) 28.00% w/w of isoprothiolane a.i,
b) 5.00% w/w of fibronil,
c) 5.00% w/w of dimethyl formamide,
d) 8.0% w/w of combination of calcium alkyl aryl sulfonate and phenol, ethylene oxide condensate blend non-ionic, and
e) light aromatic naphtha solvent.

In another embodiment, the present invention provides a stable and recyclable surface fluorinated container for storing agrochemical i.e. suspoemulsion (SE) of Pyriproxyfen 8% + Diafenthiuron 30% SE, wherein said agrochemical comprising of:
8.0% w/w of pyriproxyfen a.i, 30% w/w of daifenthiuron a.i, 20% w/w of dimethyldecanamide, 12% w/w of ethyoxylated fatty acid, 8% w/w of propylene glycol, 2% w/w of Agnique CP 72L fattyalcohol alcoxylate, 0.50% w/w of polydimethyl silioxane, 0.50% w/w of silica, 0.04% w/w of Xanthum gum powder, 0.01% w/w of benisothiazolin and De-mineralized water.
In another embodiment, the container prepared by the process of the present invention comprises of fluorine treated high density polyethylene and wherein the master batch is coated/embedded with pearl white colour material made up of LLDPE, pigment, minerals and T1O2.
In another embodiment, the present invention provides fluorinated plastic container for long term storage of agrochemicals wherein said agrochemicals have organic solvent selected from petroleum, petroleum ether, naphtha, naptha 76, ligroin, shellsol, special naphtholite, dearomatized white spirit, hydrosol, indusol, terpentine tetrasol, solvarex, gasoline, kerosene, diesel, fuel oil, road oil, dimethyl formamide, dimethyldecanamide or mixture thereof.
In another embodiment, the container of the present invention has a shelf life of more than two years.
In another embodiment, the present invention provides fluorinated plastic container for long term storage of agrochemicals wherein said agrochemicals are selected from insecticides, pesticides such as miticides, nematicides, herbicides, fungicides, bactericides, and the like or plant growth regulators, fertilizers and the like.

EXAMPLES
EXAMPLE 1: Fluorination of container:
The container was prepared by purging fluorine and nitrogen gas at 50°C to 60°C for 3 h to high density polyethylene polymer during moulding. The container further contains pearl white colour material made up of LLDPE, pigment, minerals and Ti02.
Experiment 2: Method of testing level of fluorination in the container:
The level of fluorination was tested using Double beam high resolution FTIR spectrometer capable of recording a spectrum over at least the 1900-600 cm'1 and complying with the requirement of resolution of 4 cm"1, maximum.
Procedure:
Took the background graph without the test sample by giving appropriate command on the computer. Took a piece of sample (5 mm to 1 cm) from the fluorinated HDPE Bottle with the help of a knife. Cleaned the FTIR crystal with the help of tissue paper. Kept the sample piece on the crystal for scanning. Applied the pressure of 1-2kg on sample with the help of pressure adjusting knob and then performed the scanning in the range of 600 to 1900 cm-1.
Similar procedure was repeated for obtaining graph for HDPE bottles without fluorination.
Following method was used for calculations:
Firstly, checked for the C-H and C-F heights from the graph. Calculated the ratio
by dividing the C-F height by C-H height.
The Transmittance ratio is calculated as C-F Peak height/C-H peak height.

RESULTS Table 1: The level of Fluorination is as given below;

Transmission Ratio (Percent T) Level of Fluorination
>12 5
>8 & <12 4
>6.5 & <8 3
The results above demonstrate that, the fluorination occurred at level 5 with percent transmission ratio of more than 12%.
TABLE 2: Stability of container under the impact of emulsifiable concentrate (EC) of isoprothiolane 28% and fipronil 5%w/w EC, is as follows:

Container Condition
HDPE Severely deformed
Fluorinated HDPE No deformation
Coextruded HDPE No deformation
The results above demonstrate that, while HDPE container severely deform under the impact of agrochemicals containing solvent such as petroleum, the fluorinated HDPE containers and coextruded containers with HDPE inner and outer layers sustained agrochemicals.
Table 3: Stability of container under the impact of suspoemulsion (SE) of Pvriproxvfen 8% + Diafenthiuron 30% SE is as follows:

Container Condition
HDPE Severely deformed
Fluorinated HDPE No deformation
Coextruded HDPE No deformation

The results above demonstrate that, while HDPE container severely deform under the impact of agrochemicals containing solvent such as petroleum, the fluorinated HDPE containers and coextruded containers with HDPE inner and outer layers sustained agrochemicals.

We Claim

1. A surface fluorinated plastic container for storage of agrochemicals containing organic solvent, wherein said organic solvent are selected from petroleum, petroleum ether, naphtha, naptha 76, ligroin, shellsol, special naphtholite, dearomatized white spirit, hydrosol, indusol, terpentina, tetrasol, solvarex, gasoline, kerosene, diesel, fuel oil, road oil, dimethyl formamide, dimethyldecanamide or mixture thereof.
2. The container as claimed in claim 1, wherein said plastic is made of polymer selected from medium density polyethylene (MDPE), high-density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), single-site LLDPE, polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polylactic acid (PLA) and polyethylene terephthalate (PET).
3. The container as claimed in claim 1, wherein said agrochemical is selected from emulsifiable concentrate (EC) of isoprothiolane 28% and fipronil 5%w/w EC, or suspoemulsion (SE) of Pyriproxyfen 8% + Diafenthiuron 30% SE.
4. The container as claimed in claim 1, wherein said containers are prepared by moulding technique selected from extrusion moulding, compression moulding, blow moulding, injection moulding, rotational moulding or mixture thereof.
5. A process for the production of surface fluorinated plastic container for
agrochemical products, said process comprising:
surface-fluorinating a plastic material while moulding it into a hollow body
container, wherein plastic material is brought into contact with a mixture of fluorine
and inert blowing gas;
characterized in that
a) the introduction of the mixture of fluorine and inert blowing gas takes place in a
temperature range between 40 to 80°C, and

b) level of fluorination is > 3 wherein the percent transmission ratio of fluorine is > 6.0 %.
6. A process for the production of surface fluorinated plastic container for
agrochemical products, said process comprising:
surface-fluorinating a plastic material wherein a preform is brought into contact with the inner wall of the blow mould by blowing in a mixture of fluorine and inert blowing gas; characterized in that
a) the introduction of the mixture of fluorine and inert blowing gas takes place in a temperature range between 40 to 80°C, and
b) level of fluorination is > 3 wherein the percent transmission ratio of fluorine is > 6.0 %.

7. The process as claimed in claims 5 and 6, wherein said inert gas is selected from helium, neon, argon, xenon, nitrogen and NF3.
8. The container as claimed in any of the preceding claims, wherein said container has a wall thickness of at least 1.0 mm.
9. The container as claimed in any of the preceding claims, wherein said container has at least one surface fluorinated.
10. The container as claimed in any of the preceding claims, wherein said container
has a shelf life of more than two years.