1. Monomeric Vs. Polymeric Vinyl Films Cast Vs. Calendering vinyl films Monomeric Vs. Polymeric Vinyl Films Cast Vs. Calendering vinyl films

2. The Presentation can give some clues for the following queries 1.Why monomeric vinyl films are lower durability than polymeric ? 2.Why cast films are providing greater advantages than calendering film? (such as Durability, conformability etc.) 3.How to get the optimum properties in calendering vinyl films? The Presentation can give some clues for the following queries 1.Why monomeric vinyl films are lower durability than polymeric ? 2.Why cast films are providing greater advantages than calendering film? (such as Durability, conformability etc.) 3.How to get the optimum properties in calendering vinyl films? Confidential—For Internal Use Only If we understand the chemistry involved in vinyl compounding, we will success in new graphic films business

3. How Monomeric and polymeric plasticizers effect on PVC film properties There are two ester functional groups in monomeric plasticizers(MP) but in polymeric plasticizer (PP) there may be a more than twenty ester functional groups. When we add MP/PP to PVC resin, the ester groups of plasticizer are attracted to chlorine atom of PVC (inter molecular bond) it can create hinge like structure between PVC and plasticizer and create flexibility for PVC film. If we observe the Monomeric Vinyl film, every plasticizer molecule connected with PVC through 2 inter molecular bonds where as in Polymeric vinyl film, plasticizer may bonded with more than 20 inter molecular bonds. (see in next slide)(see in next slide) When you apply high pressure or temperature on monomeric vinyl films, the plasticizer will migrate very easily due to less inter molecule bonds between PVC and plasticizer (2 bonds only) whereas in polymeric vinyl film the inter molecular bond density is very high (more than 20) so that migration of polymeric plasticizers in Polymeric vinly films are difficult. How Monomeric and polymeric plasticizers effect on PVC film properties There are two ester functional groups in monomeric plasticizers(MP) but in polymeric plasticizer (PP) there may be a more than twenty ester functional groups. When we add MP/PP to PVC resin, the ester groups of plasticizer are attracted to chlorine atom of PVC (inter molecular bond) it can create hinge like structure between PVC and plasticizer and create flexibility for PVC film. If we observe the Monomeric Vinyl film, every plasticizer molecule connected with PVC through 2 inter molecular bonds where as in Polymeric vinyl film, plasticizer may bonded with more than 20 inter molecular bonds. (see in next slide)(see in next slide) When you apply high pressure or temperature on monomeric vinyl films, the plasticizer will migrate very easily due to less inter molecule bonds between PVC and plasticizer (2 bonds only) whereas in polymeric vinyl film the inter molecular bond density is very high (more than 20) so that migration of polymeric plasticizers in Polymeric vinly films are difficult. PropertiesMonomeric filmPolymeric filmReason FlexibilityHighLowLow inter molecular bonds in Monomeric films DurabilityLowHighLow migration in polymeric films due to high bond density MigrationHighLowLow inter molecular bonds in Monomeric films AdhesionPoorGoodDue to easy migration of monomeric plasticizers Tensile & Tear StrengthLowHighHigh electrically attracted bond strength in Polymeric PVC ElongationHighLow Confidential—For Internal Use Only

4. Monomeric Vinyl film structure Polymeric Vinyl film structure How PVC and plasticizer molecules are electrically attracted Confidential—For Internal Use Only Back to slide

5. Compounding Techniques for Cast and calendering vinyl film Preparation Compounding process for Cast filmCompounding process for calender film M Plasti cizer/ solve nts resin Motor resin Plasti cizer For cast vinyl films, PVC plastisols or organosols are prepared. 1.Non porous or semi porous resin used such as micro- suspension or emulsion resin used for the plastisol preparation. 2. all resin particles are wetted with plasticizer molecule and become as a PVC suspended liquid For cast vinyl films, PVC plastisols or organosols are prepared. 1.Non porous or semi porous resin used such as micro- suspension or emulsion resin used for the plastisol preparation. 2. all resin particles are wetted with plasticizer molecule and become as a PVC suspended liquid For calender vinyl films, Pre flowing PVC powder will be used 1.High porous suspension resin used for calendering process 2. Due to high porous all plasticizer penetrate into PVC molecule and become a free flowing white powder For calender vinyl films, Pre flowing PVC powder will be used 1.High porous suspension resin used for calendering process 2. Due to high porous all plasticizer penetrate into PVC molecule and become a free flowing white powder Confidential—For Internal Use Only

6. Cast and calendering vinyl films preparation process Vinyl Film through CastingVinyl Film through calendering For making cast vinyl films Plastisols/ organosols are coated on polyester/ heat resistant web then cured in the oven to get PVC film Plastisol ----  pre-gelation ---  gelatiion ---  fusion Liquid plastisols converted into pre-gelation 135 F, complete gel at 180 F and fusion at 280 F. For making cast vinyl films Plastisols/ organosols are coated on polyester/ heat resistant web then cured in the oven to get PVC film Plastisol ----  pre-gelation ---  gelatiion ---  fusion Liquid plastisols converted into pre-gelation 135 F, complete gel at 180 F and fusion at 280 F. There are two ways For making calendering vinyl films. 1.Free flowing PVC compound is fed into extruder to get melt-polymer, feeding the said polymer melt thru the nip of calender having a 3 -4 roll. 2. free flowing PVC powder compound is fed into banbury mixture to get polymer lumps. Then the hot lumps are transpered in to two roll mill followed by three roll calendering process Confidential—For Internal Use Only

7. Why cast vinyl films are showing greater performance over Calendering films cont.. Confidential—For Internal Use Only

8. Why cast vinyl film are showing greater performance over Calendering film cont.. Thermal Stability and Flexibility. Cast film is more flexible than callendering film due to the following reason… Cast films are made with non-porous and low particle size (3 micron) micro-suspension/emulsion resin. But in calendering films high porous and higher particle size (180 micron) suspension PVC resin is used Plastisols/organsols (liquid suspensions of PVC resin) are used in cast film process. In plastisol every PVC particle coated with the plasticizer and/or liquid stabilizer so that all plasticizer spread uniformly throughout the film to provide greater flexibility and stability. In calendering film, free flowing S-PVC formulations used. If you add plasticizer to suspension PVC resin we can not sure that all polymer particles absorbed plasticizer uniformly. Some particle absorbed higher plasticizer and some are not. It is the main reason calendering films provide the poor properties than cast film Thermal Stability and Flexibility. Cast film is more flexible than callendering film due to the following reason… Cast films are made with non-porous and low particle size (3 micron) micro-suspension/emulsion resin. But in calendering films high porous and higher particle size (180 micron) suspension PVC resin is used Plastisols/organsols (liquid suspensions of PVC resin) are used in cast film process. In plastisol every PVC particle coated with the plasticizer and/or liquid stabilizer so that all plasticizer spread uniformly throughout the film to provide greater flexibility and stability. In calendering film, free flowing S-PVC formulations used. If you add plasticizer to suspension PVC resin we can not sure that all polymer particles absorbed plasticizer uniformly. Some particle absorbed higher plasticizer and some are not. It is the main reason calendering films provide the poor properties than cast film Confidential—For Internal Use Only Note: we have to add plasticizers very slowly at 65 0 C to PVC resin in high speed mixing process for better results.

9. Dimensional stability/ shrinkage/thickness In cast film: vinyl is cast on the casting sheet (paper web) in a relaxed state, this material offers very good dimensional stability. Cast process allows the film to be very thin (most cast films are 50 microns), which helps with the conformability of the product Advantages of cast films are numerous like shrinkage is the lowest of all vinyl films because the “casting sheet,” not the film itself, is pulled through the machine. Since the film has not had any stress applied during the manufacturing process, it does not try to resume or shrink back to its original form. In calendering process polymer molecule will stressed in machine direction so that polymer can undergo dimensional change ( called as shrinkage) Dimensional stability/ shrinkage/thickness In cast film: vinyl is cast on the casting sheet (paper web) in a relaxed state, this material offers very good dimensional stability. Cast process allows the film to be very thin (most cast films are 50 microns), which helps with the conformability of the product Advantages of cast films are numerous like shrinkage is the lowest of all vinyl films because the “casting sheet,” not the film itself, is pulled through the machine. Since the film has not had any stress applied during the manufacturing process, it does not try to resume or shrink back to its original form. In calendering process polymer molecule will stressed in machine direction so that polymer can undergo dimensional change ( called as shrinkage) Why cast vinyl film are showing greater performance over Calendering film cont.. Confidential—For Internal Use Only

11. Option -1 Films with Monomeric plasticizers: Better flexibility but poor durability due to higher migration Films with polymeric plasticizers: Good migration resistance but high cost and low flexibility due to High molecular weight. Why don't we try with branched polyester’s oligomers for better properties? For example: adipic acid/Isophthalic acid modified polyethylene terephthalate oligomers. These oligomer contains acid and hydroxyl end functional groups for better adhesion, flexibility and printable properties…. Option -1 Films with Monomeric plasticizers: Better flexibility but poor durability due to higher migration Films with polymeric plasticizers: Good migration resistance but high cost and low flexibility due to High molecular weight. Why don't we try with branched polyester’s oligomers for better properties? For example: adipic acid/Isophthalic acid modified polyethylene terephthalate oligomers. These oligomer contains acid and hydroxyl end functional groups for better adhesion, flexibility and printable properties…. Confidential—For Internal Use Only

12. Option -2 How to retain flexibility at low level addition of plasticizers. Better flexibility and durability can be achieved by using NBR powder in PVC compounding…. NBR will provide the good adhesion, oil resistance and flexibility to PVC even at lower level of plasticizer. Option -2 How to retain flexibility at low level addition of plasticizers. Better flexibility and durability can be achieved by using NBR powder in PVC compounding…. NBR will provide the good adhesion, oil resistance and flexibility to PVC even at lower level of plasticizer. Confidential—For Internal Use Only

13. Option -3 Generally polyesters are compatible with PVC. High melting point polyesters can not blend with PVC ( because PVC start degradation at 200 0 C) Polyesters also have poor melt strength we cannot caledering as such like PVC. But we can use the modified polyesters with PVC as a plasticizers which having Low meting point around 170 0 C. (so process with PVC at 190 0 C) Melting point can be reduced by adding azealic acid and isophthalic acid to PET. Melt-strength can be improved by adding branching agent to above CoPET. Option -3 Generally polyesters are compatible with PVC. High melting point polyesters can not blend with PVC ( because PVC start degradation at 200 0 C) Polyesters also have poor melt strength we cannot caledering as such like PVC. But we can use the modified polyesters with PVC as a plasticizers which having Low meting point around 170 0 C. (so process with PVC at 190 0 C) Melting point can be reduced by adding azealic acid and isophthalic acid to PET. Melt-strength can be improved by adding branching agent to above CoPET. Confidential—For Internal Use Only

14. Option -4 (Non –PVC graphic film) Some customers are looking for Non-PVC graphic films due to sustainability issues.  Recently Avery dennison has filed patent on Non PVC multi-layer graphic films by using polyurethane-acrylic copolymer and Acrylic copolymers (patent No: US20140017433 by CHACKO; Sujith inventor)US20140017433  In 2003 3M also patent on non –PVC graphic film by using Blend of PP and terpene hydrocarbon resin (patent No: US6531214B2 by Carter; Brandt K)US6531214B2  See the latest published 3M patent, The inventor are papered face film by using Polyurethane and cellulose ester (patent No: US2014158278 published on 12.06.2014).US2014158278 We have to develop non-PVC face film by using the following polymer’s combination. 1.Polyolefin 2. Acrylic co-polymers 3.Amorphous saturated polyesters 4. Amorphous sulfonated polyesters 5. Polyurethanes etc… Option -4 (Non –PVC graphic film) Some customers are looking for Non-PVC graphic films due to sustainability issues.  Recently Avery dennison has filed patent on Non PVC multi-layer graphic films by using polyurethane-acrylic copolymer and Acrylic copolymers (patent No: US20140017433 by CHACKO; Sujith inventor)US20140017433  In 2003 3M also patent on non –PVC graphic film by using Blend of PP and terpene hydrocarbon resin (patent No: US6531214B2 by Carter; Brandt K)US6531214B2  See the latest published 3M patent, The inventor are papered face film by using Polyurethane and cellulose ester (patent No: US2014158278 published on 12.06.2014).US2014158278 We have to develop non-PVC face film by using the following polymer’s combination. 1.Polyolefin 2. Acrylic co-polymers 3.Amorphous saturated polyesters 4. Amorphous sulfonated polyesters 5. Polyurethanes etc… Confidential—For Internal Use Only

15. Thanks Need your doubts/questions/problems/suggestions for new innovations ? Thanks Need your doubts/questions/problems/suggestions for new innovations ?