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Studies on cyclohexanoneformaldehydeStyrenated CNSLcoatings.

V D A t h a w a l e a n d N J Shetty D e p a r t m e n t o f Chemistry, University o f M u m b a i , V i d y a n a g a r i (East), M u m b a i 400 098, I n d i a

Inlroduclion
In parts of the world ketonic (cyclohexanone forn~aldehyde) resins, due to their high compatibility and solubility with a wide range of film-formers, >~ play a prime role in the field of coatings (paints, inks, varnish, and lacquer) as an excellent additive. However, meagre informationr is available where ketonic (cyclohexanone formaldehyde) resin is used as a blend for the improvement of coating properties. Ketonic resin in a blend with another coating polymer may serve as a modifier for the other fihn-former, or it may be the principal f-tim-former, while the polymer may serve as a modifier to improve certain properties of the ketonic resin.

Summary
Studies on cydohexanone Iormaldehyde - Styrenated CNSLblended coatings.
Commercial blends were prepared from Ketonic (CyclohexanoneFormaldehyde) - Cashew out shell liquid (CNSL)-slwenated resin and lheir cooling properlies such as drying lime, hardness, adhesion, flexibilily, gloss, skinning tendency, impact resistanceand chemical resistancewere studied for different compositions. The scope of the work was to produce a better combination of properties lhan lhose of lhe individual comonenls. It was observed lhat lhe blend of of 50:50 percent (w/w) of ketonic (cyclohexanone formaldehyde) - slyrenated CNSLresin shows a notable improvement in cooling properlies over lhose of individual resins.

Blending with 'coating resins' provides a variety of ways to improve the performance of ketonic resins. Cashew mlt shell liquid (CNSL) containing 90% anacardic acid and 10% of a phendic compound, cardanol, is used in the preparation of resins, lacquers and varnishes. 8 The modification of CNSL with styrene, improves the water and acid resistance of the coatings Hence, to produce a cost effective, as well as a high performance coating system, a comprehensive study of the effect of blended resins on the coat, hag properties was carried out. Essentially, the present paper reports the effect of ketonic (cyclohexanone formaldehyde) - styrenated CNSL (prepared from CNSL oil, styrene, and hexamine) resin blends on the coating properties such as drying thne, adhesion, hardness, flexibility, gloss, storage stability, impact resistance and chemical resistance.

Experimenlal Materials
Ketonic (cyclohexanone formaldehyde) resin having the specification which appears in Table 1 was obtained from Hindustan Inks (IVlumbai, India). The structure of cyclohexanone formaldehyde resin as suggested by Tilichemko 1~is shown in Scheme I. CNSL refined oil as per Indian Standard (IS-840) was obtained from a local dealer of repute. Styrene and Hexamine (nRnhnum assay 99%) was purchased from Fluka, (Switzerland) and S D Fine Chem. Ltd, (Mumbai, India) respectively.

Studieu iiber Beschichlungsslofleaus Mischungenvon Cydohexanon-Formaldehyd und styrolisiertes Cashewnuss~lbarzen.

Man stellte Kommerzielle Mischungen aus Keton (Cyldohexanon-Formddehyd) Cnshewn~i~l-Slyrolen Harzen her und denen Beschichtungsei@nschaften solch als Trockeazeit, Nrte, Adhiision, FlexibiltiJt, Glanz, Haulbildung,Sschl@esligkeit und Chemikoliea bestiindigkeit wurden bei verschiedenen Zusammensetzungenstudiert. Der Neck dieser,%heit war die Schaffung eine bessere Komhination der Eigenschaftenals de@nigen individuelles Komponents. Es wurde notiert, dass die Mischung van 50:50 proceatunler Gewichlsanteil der Ketun (Cyklohexanon-Formddehyd) und slyrolisiertes CosbewnessGIharzezeigt eine hetTiichlticheVerbesserunggegenOberdenjenigen des iadividuellen Harzes.

Table 1: Specificationsof the ketonic(cydohexanoneformaldehyde)resin.

Spedficat[on Melting point (%) Gardner colour 50% in butyl acetate/ n-butanol (85/15) Density at 20 ~ C ( g/cm t) Acid value (rag KOH/g ) Hydroxyl value ( mg KOH/g ) Water content ( wt. % ) Value-Unit 92-108 <2 1.13-1.14 03 330 4 max. lesl Method DIN 4625 ASTM D1544-80 DIN 53 479 DIN 53 402 DIN 53 240 ASTM E 222-67 DIN 51 777.part 1

Etudes sur revilements fi base de m&lmjes des r~sinesde cyr el d'huile d'~cales d~ noix d'acajou stymlis~e.
On n pr~par~ des m61angescommercJellesdes r~Jnes c~tunJques(cyclohexanone-formol) et d'huile d'~cales de noix d'acaju styrolJs~eet I'on a ~tudJ~, aux dJversescompositions, leurs coroct6ristiquesen taut que rev~tements telles que temps de s~chage, duret6, adh6rence, flexiblJt6, brillant, formation de peau, r~sistanceau choc et aux produils chJmJques.Le but de ces tTavaux~taJt de r~aliser une meJlleurecombination de proprJ~t~s que celles de chaque consfituant. On a remarqu~ que la 50:50 m~lage par pourcentage pond~rol des r6sines c6toniques (cyclohexanone-formol) et d'huile d'~cdes de noix d'aeajou met en 6vJdenceune amelioration notable des caract~rJsliquesdu rev~tement en comNraison de cellos de chaque r~sJneJndJvJduelle.

Azoisobutyronitrile (AIBN) used as an hlitiator in the reaction was obtained from Fluka, (Switzerland). Solvents of minimum assay 99% (GC) were purchased from S D Fine Chem. Ltd, (Mumbai, India). All the solvents of analytical grade were used without further purification.

Synthesis
The formulation used for the preparation of the resin appears in Table 2. The requisite quantity of CNSL was placed in a reaction kettle equipped with a thermometer,

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Sr

1: Synthesisof styrenatedCNSLresinand [Is blendw[lh kelonk resin.

CH CtHsCH=CH2

Driers
OH

AIBiq

~ C15H31+ (Cardonol)

Styrene

ClsH31 O-CNSL-Slyrene product OH

CH2-CH2-C6Hs

Driers u s e d in the study were obtained from Narchem Industries (Mumbai, India). The system u s e d for the blends was of the following combination.

Driersw[lhtheft metal cenlenl

LeadNapthenate (18%) CopperNapthenate(6%) ManganeseOctoates(6%)

Perr by weighl of resinsolid

0.50 0.20 0.05

CH2~fl2-f6fls P-CNSL-Slyrene product (CH2)6N4 Hexamine 3H20 4 NH3 + 6 HCHO

OH HCHO C15H31 CNSL (r

OH

..CH2 OH 0 CH2~_ "10S

"ill2

_n

Ketonk (CyclohexanoneFormaldehyde) Resin

water condenser, stirrer and nitrogen inlet. The oil was heated to 100~ a n d one fourth of the total required quantity of the initiator (AIBN) was a d d e d to the kettle. The requisite quantity of styrene containing half the total required quantity of initiator was then a d d e d dropwise into the kettle through the Y-adapter. After the m o n o m e r addition was completed, the rest of the initiator was a d d e d and heating continued in an atmosphere of nitrogen until a reduction in the rate of reflux of the material was observed. Hexamine was a d d e d in small quantities in 10-15 minutes to the styren a t e d CNSL product, and the temperature was maintained at 135~176 after which it was raised slowly m 240~ a n d maintained at b e t w e e n 240~176 for 30 minutes. The resin formation was confirmed b y IR analysis of the product. IR specn-um of CNSL styrene resin s h o w e d a b a n d at 3000 cm -t attributed to alkene C-H stretching. The p e a k s at 1600, 1460, 920 a n d 700 cm -z are attributed to aromatic ring, vinyl group, mono, meta and symmetrical tri substitution with a ring b e n d i n g vibration respectively. The resin obtained was dissolved in a solvent system (xylene, cyclohexanone, butanol in the ratio of 50:30:20 by volume respectively) to m a k e 50% solution. The ketonic resin was also thinned to 50% solids b y using the same solvent system utilised for CNSL-styrene resin.

The p e r c e n t of driers u s e d were as p e r the resin solids. Tests carried out for the study of coating properties Drying Timer 2 Drying times for the b l e n d proportions were deternm~ed at 80% hmnidity and at 30~ temperature, The samples were a p p l i e d onto mild steel panels using a 50p Sheen bar coater a n d the time n o t e d for surface as OH well as tack-free drying. Hardness: 13 Panels coated uniformly with the sample using bar coater were allowed to dry for a w e e k before test. ing. A comparative m e a s u r e m e n t of hardness was achieved b y rating the hardness with l e a d pencils, Gloss: 14 The gloss of the film is assessed b y measuring the reflectance of the coated panel. Glass panels were coated with different samples, and their gloss characteristics were m e a s u r e d using a Sheen gloss meter at an angle Blend of 60 ~. Adhesion:13 Sample coated mild steel panels were allowed to mature for a w e e k before undergoing the test. The cross-cut adhesion method was e m p l o y e d for the above adhesion test, Flexibility:l~ Flexibility of the film was m e a s u r e d b y the conical mandrel test, o n tin plates that were allowed to dry for a w e e k before checking flexibility on a conical mandrel (1/4"). Storage Stability: The storage stability of the samples was studied b y storing them in cylindrical sample containers for four months, after w h i c h the condition of the surface was visually observed. Impact Resistance: hnpact resistance is a measure of the ability of a n~aterial or structure therefrom to withstand the application of a s u d d e n l o a d without failure. It is m e a s u r e d using a falling weight type impact tester (Komal Scientific,

Table 2: CHSL-slyreneresin formulationfor laboratory preparation. Ingredients

CNSL Slyrene Hexamine AIBN (initiator) Water Curingagents

Wl. %
50.00 35.00 04.00 03.00 07.25 00.75

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Mumbai, India). The machine is driven by gravity. In this method a hemispherical indenter of known weight is dropped down on to the panel, which is fixed at the base of the instalment, An opening opposite to the indenter in the base support on which the panel rests permits deformation of the panel, The indenter is dropped from varying heights until the film cracks (The maximum height of the instrument is 48 inches and weight of the indenter is 2.82 k~. The direct impact test is carried out with the coated side facing upwards, and downwards for reverse knpact test, Prior to the testing of the above property the films were matured on mild steel panels for ten days. resins act simultaneously to increase the oxidative crosslinking and hence the drying time. Hardness: Mild steel panels coated with different blends were tested for hardness using pencils graded from 5B to 5H. Table 3 reveals that poor hardness was shown by ketonic resin. This is attributed to the aliphatic chain of the ketonic resin (structure shown in Scheme I). Hardness remains constant for ketonic- styrenated CNSL resin blends up to 60:40 (% w/w) concentration. On increasing the percentage (w/w) of styrenated CNSL resin in the blend, a significant improvement in the hardness of the blends was observed. This is attributed to the aromatic nature of the styrenated CNSL resin. Hence, the compatible blend prepared possessed aromaticity due m which the hardness increased.

Chemical resislance
Water immersion test: Glass panels coated with samples of different proportions were allowed to dry for three days, The periphery of the glass panels was coated with wax in order to restrain the migration of water under the film from open ends. The panels were then dipped into water and were examined for the change in the appearance and disappearance after 24 hours. Acid immersion test: Coated glass panels were prepared as mentioned in the water i~m~ersion test, These panels were dipped into 3 percent (w/w) sulphuric acid sdution and the change in the appearance was monitored after 24 hours.

labia 3: Pencil hardness end slorage stability of Ihe ketonir styrenated CNSL resin blends Kelanic CNSL-styrene resin (percentage w/w)
100:0 90:10 80:20 70:30 60:40 50:50 40:60 30:70 20:80 10:90 0:100

Hardness (lead pendls)

HB HB HB HB HB H 2H 3H 5H 5H 5H

Skinning tendency (after four months) no skinning no skinning no skinning no skinning skinning skinning skinning skinning skinning skinning skinning

Resulls and Discussion

A detailed study was carried out on the coating properties of different blend ratios. When the blends were studied below 10% (w/w) concentration of the individual resin no significant changes were observed. Drying Time: It was observed from Fig-ure 1, that surface drying and tack-free drying time improved remarkably with the increase in the concentration of the styrenated CNSL resin in the blends. Drying is explained as the intake of oxygen by the film former. The blending ratio of 50:50 (% w/w) shows a notable fast drying time, Ketonic (cyclohexanone formaldehyde) resin contains carbonyl groups in the polymer backbone chain. This carbonyl group activates the methylene group in the ketonic resin, Therefore, in the presence of suitable driers, the oxygen activation of the methylene group is further accelerated and that results in faster drying. The presence of the styrenated CNSL resin adds to this property of drying to a renmrkable extent, since styrenated CNSL resin is a fast drying resin due to its high degree of unsaturation. Hence both these characteristics of the

Gloss: Gloss of the surface depends upon the amount of light reflected or absorbed by the coating material. Figure 2 shows a gradual decrease in the gloss of the blends with increase in the percentage (w/w) of the styrenated CNSL resin. Initially, the superior gloss was due to the low colour and excellent light stability of the ketonic resin. Colour does not affect gloss. Adhesion and Flexibility: All the blends showed excellent adhesion. Table 4 shows that the ketonic as well as styrenat: ed CNSL resin exhibits 100% adhesion.

labia4: Adhesion andflexibility of Ihe kelonic - slyrenaled CHSL blends Ketonic(HSL-styrene resin (percentage w/w)
100:0 90:10 80:20 70:30 60:40 50:50 40:60 30:70 20:80

Adhesion(percentage)
1O0 100 1O0 1O0 1O0 1O0 1O0

Flexibilily
pass pass pass pass pass pass

Figure 1: Graph of drying time (minutes) against r blend (wl%).

of ketonic resin

40
~ 30

Surface Drying tack free

1 O0
1O0

~ 20

10:90 0:1 O0 0 10 20 30 40 50 60 70 80 90 Concenlration of Ketonic resin in the blend, wl.% 100

100 1 O0

fail fail fail fail fail

The blends up to 50:50 percent (w/w) concentration of ketonic-styrenated CNSL resin passed the 1/4 bend test. The ketonic resin composed of an aliphatic chain was soft, while

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Figure 2: Graph of gloss at 60 ~ against concentration of ketonic resin blend (wl%).
of the styrenated CNSL resin was increased, the films showed superior acid resistance as can be seen in Table 5. However, at 50:50 percent (w/w) blend neither blushing nor blistering were observed. Therefore, 50:50 percent (w/w) concentration of ketonicstyrenated CNSL resin can be considered as the optinmm concentration at which both blushing and blistering were eliminated. Impact resistance: From Table 8, it can be seen that the blend of ketone-styrenated CNSL resin ratio 50:50 (w/w) showed the highest impact resistance. As the percentage of

Table 6: Drying lime o[ Ihe kelonic-slyrenaled CNSL resin blends 0 10 20 30 40 50 60 70 80 90 100 Concentrationof Kelonic resin in the blend,wl.%
styrenated CNSL resin due t o its aromaticity was hard and brittle. Therefore, on increasing the percentage (w/w) concentration of styrenated CNSL resin in the blends, the flexibility declined. This can be attributed also m the high crosslinking of the styrenated CNSL resin. Storage stability: Ketonic and styrenated CNSL resins stored without driers showed no skhming tendency. The blend ratio up to 70:30 percent (w/w) concentration of ketonic-styrenated CNSL resin showed no skinning tendency as shown in Table 3. However, on increasing the concentration of the styrenated CNSL resin in the blends the skinning tendency increased. The above observation revealed that on addition of driers the skinning tendency increases. This was because of the fast drying property of the styrenated CNSL resin, which was enhanced by the addition of the driers.

KetanicG',lSL-styrene resin (percentage w/w)

100:0 90:10 80:20 70:30 60:40 50:50 40:60 30:70 20:80 10:90 0:100

Surface dry (minules)

35 15 14 13 11 06 07 08 09 10 12

Tack-free (minutes)
50 30 27 25 20 09 10 11 12 15 17

Table 7: Gloss of the ketonic-slyrenaled CHSL resin blends Kelanic(BSL-slyrene resin (percentage w/w)
100:0

Gloss at 60 ~
96 95 94 92 89 86 82 75 70 64 60

Chemical resislance
Water immersion test: Water resistance of the blends increased with the increase in the percentage of the styrenated CNSL resin, From Table 5 it can be seen that the blends with the higher percentage of ketonic resin showed marked blushing but no blistering. However, above 60:40 percent (w/w) composition of the blends the blushing effect diminished. At 50:50 percent (w/w) composition of the blends both blushing and blistering were not observed. Acid immersion test: The ~ass panels coated wdth ketone-styrenated CNSL resin w h e n inm~ersed in 3% sulphuric acid showed marked blushing for blends containing up to 70% ketonic resin. Whereas, when the concentration

9o:1o
80:20
70:30

60:40
50:50 40:60 30:70

20:80
10:90 0:100

Table 8: Impacl resislance of Ihe ketonic-slyrenated r KetanicG',lSL-styrene resin (percentage w/w)

100:0 90:10 80:20 70:30 60:40 50:50 40:60

resin blends

TableS: Chemical resislance of Ihe ketonic- slyrenaled CNSL blends KelanicCHSL-slyrene resin (percentage w/w)
100:0 90:10 80:20 70:30 60:40 50:50 40:60 30:70 20:80 10:90 0:100

Impact resislance (Ibs inch*) Direct (passes) Reverse (passes)

Add resislance
Heavyblush,no blistering Heavyblush,no blistering Heavyblush,no blistering Heavyblush,no blistering Slight blush,no blistering Unaffected no blistering Unaffected blistering Unaffected blistering Unaffected blistering Unaffected blistering Unaffected blistering

Waler resislance
Heavyblush,no blistering Heavyblush,no blistering Heavyblush,no blistering Heavyblush,no blistering Heavyblush,no blistering Unaffected,no blisterin~ Slight blush, blisterin Unaffected,blisterin Unaffected,blisterin Unaffected,blisterin Unaffected,blisterin

25 25 50 25 75 50 100 75 100 100 125 125 125 100 30:70 100 100 20:80 75 75 10:90 75 50 0:1 O0 50 50 ~he valuesarearrivedet by multiplvin~weightof indenterin Ibs (6.251bs)withmaximumheight in if~hasfromwhereindenterfellswithoutanyvisibledeme~eto the film.

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the styrenated CNSL resin increased, the films exhibited poorer impact resistance. Ttds is due to the hardness and brittleness of the styrenated CNSL resin that leads to cracking of the film. On the other hand, compared to styrenated CNSL resin, ketonic resin shows better knpact resistance owing to its stlucture.

Conclusions
From the foregoing studies, it can be concluded that w h e n Ketonic (cyclohexanone formaldehyde) resin was blended with styrenated CNSL resin in the optimum ratio of 50:50 (w/w) the blend exhibited excellent coating properties such as drying time, hardness, chemical resistance, impact resistance, adhesion, flexibility and moderate gloss, This can be attributed to the synergistic effect of the resins.

References
1. Bognar J, Kovacs L and Szabo L, Hungarian Patent HP 55, 420, 1991, Chem. Abstr. 115: 210376w, 1991. 2. Bognar J, Kovacs L and Szabo L, Hungarian Patent HP 55, 421, 1991, Chem. Abstr. 115: 210377x, 1991. 3. Penc R and Cihlar J, Czech 153, 930 1974, Cheni. Abstr. 82: 45197d 4. Sailor Pen Co. Ltd, Jpn. Kokai Tokkyo Koho JP, 58 05, 381, 1983, Chem. Abstr. 99: 55184n. 5. Ttn'cu E, Bratalescu O, Filipache M and Ionita S, Romania RO 89, 433 1986, Chem. Abstr. 106: 215609y. 6. Bugrov GA, Gorin VP, Samokhvalov AI, Tikhonov VP, Levina FS, Gilyazetclinov LP, and Matishev VA, USSR SU 1,060, 662, 1983, Chem. Abstr. 100: 158359s 7. Athawale VD and Chamankar AV, JAOCS, "75, 887~89, 1998 8. Basu DS and Kar AK, Chemical Age of fndia, 24, 6, 341-344, June 1973. 9. Shirsalkar,MM and Sivasamban MA, Paint India, 25, 12, 17-20 (Eng.), Dec. 1975. 10. Tilichenko M and Zykova LV, 'Folyl~etone'EncylqOediaof Chemical Science and Technology, 11, 273-279. John Wiley and Sons, New York. 11. Gowri VS and Saxena M, tnd, J, Chem. TechnoL, 4, 145-149, 1997. 12. ASTM D, 1640~3, American Society for Testing and Materials, Philadelphia, Pa., 06.03, 1994. 13. Odell LB, Encyclopedia Of Industrial C~)emical Analysis, Enamels, Edited by Foster Dee Snell and Leslie S Ettre, Interscience Publishers a division of John Wiley & Sons, Inc. United States of America, 12, 170-192, 1971. 14. ASTM D 523~9, American Societyfor Testing and Materials, Philadelphia, Pa., 06.03, 1994. 15. ASTM D 522-93a, American Societyfor Testing and Materials, Philadelptda, Pa., 06.03, 1994. 16. ASTM D 1647-89, American Societyfor Testing and Materials, Vol. 06.03, 1994.

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