FORM 2
THE PATENT ACT 197 0 (39 of 1970)
&
The Patents Rules, 2003 COMPLETE SPECIFICATION
(See Section 10, and rule 13)
1. TITLE OF INVENTION
MODIFIED RESIN FROM CASHEW NUT SHELL LIQUID AND METHOD OF MANUFACTURING THE SAME

APPLICANT(S)
a) Name
b) Nationality
c) Address

GOODLASS NEROLAC PAINTS LIMITED
INDIAN Company
NEROLAC HOUSE, GANPATRAO KADAM MARG,
LOWER PAREL,
MUMBAI - 400 013

PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed : -

MODIFIED RESIN FROM CASHEW NUT SHELL LIQUID AND METHOD OF MANUFACTURING THE SAME.
INTRODUCTION:
This invention relates to a novel method of synthesizing a resin by modification of Cashew Nut Shell Liquid i.e. CNSL with aldehyde / aldehyde releaser and phenol /
substituted phenol. The resultant resin is a reaction product of CNSL, phenol and aldehyde with or without other materials. Better properties like water resistance, adhesion and corrosion resistance of this resin over normal CNSL resin, make it suitable for use in formulating anticorrosive primer, enamels & waterproof coatings. This invention also relates to coating compositions based on the developed novel resin, utilizing the superior physico-chemical properties of the resin.
BACKGROUND OF THE INVENTION:
1. Field of invention:
This invention is in the field of surface coatings and parent resin based on phenol & aldehyde chemistry.
2. Description of The Background Art
Cashew Nut Shell Liquid i.e. CNSL is a fairly abundant naturally occurring low cost renewable substance consisting of alkyl-substituted phenols.
CNSL primarily consists of Anacardic Acid (3-n-pentadecylsalicylic acid) (70 %) as shown in figure 1, Cardnol (3-n-pentadecylphenol) (18 %) as shown in figure 2 & Cardol (5-tt-pentadecylresorcinol) (5 %) as shown in figure 3.
CNSL is a naturally occurring material in which a benzene ring bears one or two hydroxyl groups, a carboxyl group, and in the meta position relative to the hydroxyl
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group or groups, an unsaturated 15 carbon atom hydro-carbylene group. The hydrocarbylene radical may contain one, two or three double bonds in un-conjugated relationship; on an average, the chain contains about two double bonds. It is presently
believed that the 15-carbon side chain may contain a single double bond at the 8-9
position & two or three bonds at the 8-9 and 11-12, or 8-9,11-12 and 14-15 positions. The carboxyl group is normally lost during recovery of oil from the shell and early processing.
CNSL undergoes all reactions of phenol. The Anacardic acid, which is de-carboxylated when heated in presence of acid & alkali, gives meta substituted phenol, cardanol.
Its phenolic nature makes it suitable for polymerization into resins by condensation with aldehyde under both acid & alkaline conditions, no further cross-linking agent would be needed as both the functionalities would be inherent in every molecule. The remaining alkyl aldehyde groups would increase the reactivity of the system towards crosslinking & impart high degree of hydrophobicity. Hence it gives water resistance.
The existing technology describes modification of Cashew nut shell Liquid with aldehyde & oils to obtain resins used in various coating compositions. However these coatings have limitations when used in surface coating industries due to,
• It's brittleness / hardness characteristics.
• Limited adhesion on metals.
• Problem of excessive foaming during the processing.
The existing CNSL resin manufacturing process involves solvent charging after resin formation, which results in a resin having broad molecular weight distribution.

BRIEF DESCRIPTION OF THE DRAWINGS:
OH # # str (
Y^1~~C00H
. V/ J C15H25 – 29 )# #
FIGURE 1


C15H25 - 29


C15H25 - 29
OH FIGURE 3
FIGURE 1 is a chemical structure of Anacardic Acid (3-n-pentadecylsalicylic acid). FIGURE 2 is a chemical structure of Cardanol (3-n-pentadecylphenol). FIGURE 3 is a chemical structure of Cardol (5-n-pentadecylresorcinol).

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SUMMARY OF INVENTION:
The novelty of the disclosed invention lies in use of phenol / substituted phenols as a reactant to produce CNSL resins for coatings to overcome above limitations.
The subject innovative process involves polymerization of CNSL with phenol / substituted phenols & aldehyde / aldehyde releasers in presence of solvent, instead of charging solvent after resin formation, so as get resin of narrow molecular weight distribution.
The novel compound disclosed here is produced by condensation of CNSL with phenols / substituted phenols like m-cresol, p-cresol, o-cresol, p-nonylphenol, p-phenyl phenol, bisphenol A, p-tert. -butyl phenol & aldehydes / aldehyde releasers like paraformaldehyde, glyoxal, furfuraldehyde, hexamine, acetaldehyde, aldol, crotonaldehyde, acrolein, benzaldehyde with or without catalyst.
The initial stage of preparation of this novel composition includes reacting CNSL with phenol/ substituted phenols & aldehyde / aldehyde releasers in presence / absence of catalyst to form an intermediate. This condensation intermediate has a chromone ring structure.
In the second stage of preparation i.e. reaction with CNSL this chromone group gets added across the un-saturation in CNSL. Thus the resin composition formed by this process shows excellent corrosion resistance, excellent adhesion on metal, concrete, & better water resistance than the normal resin composition formed by CNSL aldehyde modification.

DETAILED DESCRIPTION OF INVENTION:
This disclosed compound is derived from CNSL, which contains anacardic acid, cardanol, cardol as basic ingredients.
The CNSL, phenol / substituted phenols & aldehyde / aldehyde releasers are reacted in solvent vehicles such as benzol, gasoline, kerosene, naphtha, white spirit & the like. The reaction proceeds through condensation of phenol - aldehyde.
This reaction may be carried out in presence of alkaline catalysts such as sodium hydroxide, ammonia, triethylamine, imidazole etc.
The amount of catalyst required for the desired rate of reaction may vary from 0% to 10% based on total reactant weight depending on the specific reaction system.
The phenols/ substituted phenols used in this product are phenol, m-cresol, p-cresol, o-cresol, p-nonylphenol, p-phenyl phenol, bisphenol A & p-tert-butyl phenol singly or in combination.
Aldehydes/ aldehyde releasers used are from the group comprising paraformaldehyde (paraform), glyoxal, furfuraldehyde, hexamine, acetaldehyde, aldol, crotonaldehyde, acrolein & benzaldehyde, singly or in combination.
Conventionally the reaction temperature must be controlled between 40° C to 200° C; according to this invention the preferred temperature for this reaction is 90° C to 160° C.
Higher reaction temperature may lead to gelation of product.
The reaction may often be finished in 2 hrs to 8 hrs after all the reactants are mixed together. Thickening of resinous material i.e. rise in the viscosity is a sign of being close to the end of the reaction. The reaction can be converted to desired viscosity & %NVM
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(non-volatile matter) depending on end applications. The required viscosity of the end product is 150 ± 25 seconds on Ford cup B4 @ 30° C. Prolonged reaction may cause gelation of the product. According to this invention, the molar ratio of CNSL, phenol, aldehyde may vary from 1:0.1:0.5 to 2:1:3.
The final product is recovered by filtration.
EXAMPLES -
The following examples constitute some resin formulation based on the experimental work. This is not an exhaustive list of the compositions tested, comparative composition 8 is an example of the prior state of art resin formulation.
Abbreviations:
NV : Non Volatile Content
Sec : seconds
Hrs : hours
gms: grams
IV : Iodine value
Example 1
Charge 71.42 gms (0.76 moles) of phenol & 47.82 gms of paraform (1.53 moles) in glass flask & heat the reaction mixture to 40° C for 10 minutes. Then charge 4.62 gms of ammonia (25%). Heat the flask to 100° C & then charge 352.81 gms (1.18 mole) of CNSL to the flask with continuous stirring. Continue heating to 110° C, then add 523.33 gms of white spirit in 40 minutes maintaining 110° C. Process the batch at 160° C as shown in Block Diagram 1 till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 <@ 30° C is attained. This process is completed in 3 - 4 hrs. The reaction product is then filtered.
Results: Final NV = 45 %, Viscosity at 30° C on Ford Cup B4 = 135 sec, Color = dark brown, I.V. = 274
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Example 2
Charge 66.4 gms (0.70 moles) of phenol & 57.5 gms of paraform (1.84 moles) in a glass
flask & stir the mixture for 10 minutes. Then charge 4.3 gms of ammonia to this mixture.
Heat the flask to 100° C within 40 - 45 minutes. Then charge 333.7 gms (1.09 mole) of CNSL to the flask with continuous stirring. Continue heating to 110° C, then add 538.10 gms of white spirit in 40 minutes maintaining 110° C. Raise the temperature up to 180° C in 3 hrs. Process the batch as shown in the block diagram 1 till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 @ 30° C is attained. The reaction product is then filtered.
Results: Final NV = 44 %, Viscosity at 30° C on Ford Cup B4 = 157 sec, Color = dark brown, I.V. = 272
Example 3
Charge 379.9 gms (1.24 mole) of CNSL & 69.75 gms (0.31moles) of nonyl phenol in a glass flask & heat it to 40° C. To this add 30.90 gms (0.22 moles) of hexamine & mix it for 20 min. Add 4.59 gms of ammonia under stirring to the mixture. Then heat the contents in the flask to 100 ° C slowly in 35 - 40 minutes & maintain 100 ° C for 1 hr. Continue heating up to 110 ° C, then add 514.86 gms of white spirit in 40 minutes maintaining 110 ° C. Then raise the temperature to 150 ° C slowly in 2hrs. Process the batch as shown in the Block diagram 2 till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 @ 30° C is attained. The reaction product is then filtered.
Results: final NV = 45 %, viscosity at 30 ° C on Ford Cup B4 = 127 sec, Color = dark brown, I.V. = 270
Example 4
Charge 343.60 gms (1.12 mole) of CNSL & 73.65gms (0.784 moles) of phenol crystals in a glass flask. To this add 64.31 gms (2.058 moles) of paraform & mix it for 20 min. Add 5 gms (0.036 moles) of hexamine under stirring to the mixture. Then heat the contents in
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the flask to 100° C slowly in 35 - 40 minutes & maintain 100° C for 1 hr. Continue heating to 110 ° C, then add 513.44 gms of white spirit in 40 minutes maintaining 110°
C. Then raise the temperature to 150° C slowly in 2hrs. Process the reaction as shown in the block diagram 4 till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 @ 30° C is
attained. The reaction product is then filtered.
Results: Final NV = 45 %, Viscosity at 30° C on Ford Cup B4 = 175 sec, Color = dark brown, I.V. =274
Example 5
Charge 387.24 gms (1.27 mole) of CNSL & 79.2 gms (0.84 moles) of phenol crystals in a glass flask. To this add 48.23 gms (1.54 moles) of paraform. Mix it for 20 min. Add 5.1 gms of ammonia under stirring to the mixture. Then heat the contents in the flask to 100° C slowly in 35 - 40 minutes & maintain 100° C for 1 hr. Continue heating to 110° C, then add 480.23 gms of white spirit in 40 minutes maintaining 110° C Then raise the temperature to 150° C slowly in 2hrs. Process the reaction as shown in block diagram 4 till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 @ 30° C is attained. The reaction product is then filtered.
Results: Final NV 45 %, Viscosity at 30° C on Ford Cup B4 = 140 sec, Color = dark brown, I.V. = 270
Example 6
Charge 74.45 gms (0.32 moles) of bis-phenol in glass flask then heat it to 40 ° C. To this add 362.53 gms (1.184 mole) of CNSL & stir the mixture for 10 min. Add 4.55 gms of ammonia to this mixture. Charge 28.33 gms (0.91 moles) of paraform to this mixture. Continue heating to 110° C, then add 530.14 gms of white spirit in 40 minutes maintaining 110° C Raise the temperature up to 150 ° C in 3 hrs. Process the reaction till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 @ 30° C is attained. This process
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takes 3 to 4 hrs. The reaction product is then filtered. The process is as per block diagram 3.
Results: Final NV 45 %, Viscosity at 30 ° C on Ford Cup B4 = 126 sec, Color = dark
brown, I.V. = 271
Example 7
Charge 331.35 gms (1.08 mole) of CNSL & 68.05 gms (0.30 moles) of bisphenol A in a glass flask. To this add 58.23 gms (1.87 moles) of paraform. Mix it for 20 min. Add 4.4 gms of ammonia under stirring to the mixture. Reaction goes to exotherm. Then heat the contents in the flask to 100° C slowly in 35 - 40 minutes & maintain 100° C for 1 hr. Continue heating to 110° C, then add 537.97 gms of white spirit in 40 minutes maintaining 110° C. Then raise the temperature to 150° C slowly in 2hrs. Process the reaction till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 @ 30° C is attained. The reaction product is then filtered. The process is as per block diagram 4.
Results: Final NV 44 %, Viscosity at 30° C on Ford Cup B4 = 128 sec, Color = dark brown, I.V.= 272.
Example 8:
Charge 432.19 gms (1.41 mole) of CNSL in a glass flask. To this add 30.89 gms (1.029 moles) of paraform. Hold it for 80° C for 20 minutes. Add 4.66 gms of ammonia under stirring to the mixture. Then heat the contents in the flask to 100° C slowly in 35 - 40 minutes & maintain 100° C for 1 hr. Then raise the temperature to 150° C slowly in 2 hrs. Process the reaction till final viscosity of 150 ± 25 sec (@ 45% NVM) on FCB4 @ 30° C is attained. The resin is thinned with 532.26 gms of white spirit. The reaction product is then filtered. The process is as per block diagram 5.
Results: Final NV 45 %, Viscosity at 30° C on Ford Cup B4 = 180 sec, Color = dark brown, I.V. = 317.
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OBSERVATIONS:
Iodine values (I.V) of first seven examples were observed in the range of 270-275, while
that of example number 8 was observed to be within ranges of 310-320.
This decrease in I.V. of first seven examples compared to example number 8, reveals the possibility of the reaction given below (Figures 1 to 6), resulting in improvement of all the physico - chemical properties of the resultant CNSL resin.
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TESTING OF THE PHISICO-CHEMICAL PROPERTIES OF THE NOVEL RESIN:
To evaluate the phisico-chemical properties of the resin, a lab scale redoxide primer was
prepared. The redoxide primer of following composition was processed with each individual resin obtained from all above examples, using a ball mill, in laboratory and their physico -chemical properties were determined.

Ingredients wt%
CNSL resin (45% NVM)) 35%
Calcite (400 mesh) 18%
China clay (400 mesh) 18%
Natural Red oxide 18%
Zn- chrome 0.5%
Driers 05%
White spirit 10%
OUTLINE OF TESTING METHODS:
1) DETERMINATION OF VISCOSITY ON FLOW CUP B4: (ASTM - D -1200)
2) NON - VOLATILE CONTENT: (IS -197-1969)
3) DETERMINATION OF IODINE VALUE (WIJ'S METHOD)
4) WHITE SPIRIT TOLERENCE:
Take 5-10 gms of the material in 100 ml round flask with flat bottom, placed on a printed paper Add white spirit slowly to the flask and check the clarity of the contents. Continue white spirit dilution till the solution obliterates the printed matter. Note that quantity of white spirit consumed.
wt. of white spirit used
WHITE SPIRIT TOLERENCE % = X 100
wt. of the sample
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5) DETERMINATION OF DRYING TIME: (IS -197)
6) CROSSCUT ADHESION OF FILM: (ASTM - D - 3363)
7) CORROSION RESISTANCE: Salt Spray test (ASTM-B-117)
8) WATER RESISTANCE: (IS 101)
9) PENCIL HARDNESS: (ASTM - D - 3363)

10) STABILITY: (IS 101)
11) IODINE VALUE: IS -24 -1979
APPLICATION METHOD:
1) The final paint is thinned with white spirit up to 60 sec viscosity on Ford cup B4
@ 30° C & applied by brushing on MS panel.
Or
2) The paint is thinned with white spirit up to 20 sec viscosity on Ford cup B4 @ 30°
C & applied by spraying on MS panel.
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TEST RESULTS:

Sr TEST Example1 Example 2 Example 3 Example4Darkbrown Example5 Example 6 Example7 Example 8
A Physical propertiesDark ~brown
1 Color Darkbrown DarkBrown DarkBrown Darkbrown DarkBrown DarkBrown Darkbrown Darkbrown
2 Non volatile matter 45% 44% 45% 45% 45% 45% 44% 45%
3 Viscosity on ford cup B4 @ 30 °C 135 sec 157 sec 127 sec 175 sec 140 sec 126 sec 128 sec 180 sec
4 White spirit tolerance Infinite Infinite Infinite Infinite Infinite Infinite Infinite Infinite
5 Stability Stable Stable Stable Stable Stable Stable Stable Stable
6 Iodine value 274 272 270 274 270 271 272 317
B Dry film properties of paintNt
Surface dry Lhr lhr lhr 15" lhr lhr 30" Thr lhr
1 Hard dry 2hrs 2hrsl5" 3hrs30" 2hrs 2hrs 2hrs 2hrsl5 4hrs
Tack free 6hrs30" 6hrs 6hrs 6hrs 3hrs 6hrs 6hrs 10-12 hrs
2 Adhesion on metal Passes Passes Passes Passes Passes Passes Failure
3 Corrosion resistance (IS-197) Water resistance (IS-101) R=6 R=6 R=8 R=7 R=9 R=9 R=8 R=4i
4 Water resistance(IS-101) R=6 R=7 R=8 R=9 R=9 R=9 R=6 R=4
5 Pencil Hardness (After 7 days) F F F F F F F HB
6 Finish Sheen Sheen Sheen Sheen Sheen Sheen Sheen Matt 1
CONCLUSIONS:
Phenol / substituted phenol modified CNSL resin formed by this invention when compared with other similar resin (example 8) shows:
1) Better Gloss & surface finish with optimum level of toughness & elasticity.
2) Better water & corrosion resistance.
3) Faster drying film characteristics.
4) Good stability.
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BLOCK DIAGRAM OF PROCESS:
PROCESS 1 PROCESS 2 PROCESS 3 PROCESS 4 PROCESS 5


ENOL

FINISHED RESIN

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We Claim:
1. A method of manufacturing a modified resin from Cashew Nut Shell Liquid
comprising:
a) reacting CNSL phenols, aldehydes in the molar ratio 1:0.1:0.5 to 2:1:3 with or
without catalyst in presence of solvent;
b) heating the reactants at 40* C to 200* C for 2 to 8 hours to achieve required viscosity of the end product 150 ± 25 seconds on ford cup B4 @ 30* C;
c) separating the reaction product by filtration.

2. A method as claimed in claim 1 wherein the phenols are selected from alkylated/ arylated phenols like m-cresol, p-cresol, o-cresol, p-nonylphenol, p-phenyl phenol, bisphenol A, p-tert-butyl phenol or mixture thereof.
3. A method as claimed in claim 1 wherein the aldehydes / aldehyde releasers are selected from glyoxal, fufuraldehyde, formaldehyde, acetaldehyde, aldol, hexamine, crotonaldehyde, acrolein, benzaldehyde singly or in combination.
4. A method as claimed in claim 1 where the reaction proceeds with or without aid of alkaline catalyst.
5. A method as claimed in claim 1 wherein catalyst used like sodium hydroxide, imidazole, ammonia, triethylamine.
6. A method as claimed in claim 1 in which catalyst is included in the reactants in an amount from 0% to 10%.
7. A method as claimed in claim 1 in which reaction temperature varies from 40° C to 180* C
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A method as claimed in claim 1 in which reaction time varies from 2 hr to 8 hrs. A method as claimed in claim 1 in which the molar ratio of CNSL: phenols:
aldehyde is from 1:0.1:0.5 to 2:1:3.
A method as claimed in claim 1 in which reaction product is separated by filtration.
A modified resin from CNSL made by the process as claimed in claim 1 to 10.
A condensation product of CNSL obtained from the reaction of claim 1 showing following properties:
1) Better gloss & surface finish with optimum level of toughness & elasticity.
2) Better water & corrosion resistance.
3) Fast drying film characteristics.
4) Good stability.
Dated this 17th day of May 2005.

HARISHCHANDRA MEGHRAJ BHARUKA
MANAGING DIRECTOR
GOODLASS NEROLAC PAINTS LIMITED
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ABSTRACT:
The present invention comprises a novel process for the manufacture of Cashew Nut
Shell liquid (CNSL) based resin modified with phenol / substituted phenols. The novel resin composition is produced by a controlled reaction of CNSL (25 - 50 wt. %), aldehyde / aldehyde releasers (5 - 15 wt %) and phenol (5 - 15 wt %) in presence of alkaline catalyst (0-10 wt.%) at temperatures between 40° C and 180° C. The water resistance, adhesion and corrosion resistance of the resultant resin makes it suitable for use in formulating anticorrosive primer, enamels, waterproof coatings and other paints.
To,
The Controller Of Patents,
Patent Office,
Mumbai.