Document wgD0qx29VNer4yOMzbmmqZJB3

"FOR DU FONT USE ONLY" Report Number: Indexed File: 1865 ESR-69-55 Distribution on last page E. I. du Pont de Nemours & Company F & F, Research & Development Division Experimental Station Laboratory Research Report PIGMENT DISPERSION COMMERCIAL POTENTIAL OF A-B DISPERSANTS Date Issued: Period Covered: Project Number: Previous Reports Notebook Number: DEC 31 1969 June 15, 1969 ~ December 15, 211449 ESR-69-26, ERM-69-3 424E t 1969 PREPARED BY; T. P. Concannon APPROVED BY Jp. b. (Jot R. D. Vest When this report is no longer needed, please return it to the File Room, F & F Department, Experimental Station. TABLE OF CONTENTS Page INTRODUCTION................. ............................................... ........................ 1 OBJECTIVES...................... ,....................................................................... 1 SUMMARY AND CONCLUSIONS....................................... ....................... 2 ACTION TAKEN OR PROPOSED..................................................... 3 PATENT STATUS. . ................... 4 PUBLICATION STATUS.......................................................... .. ............ 4 ACKNOWLEDGMENTS.................................. 4 DISCUSSION................. 5 I. L.B.A. Urethane Product System................... 5 II. Automotive Acrylic Organosol Product System. .......................................................................... 6 BIBLIOGRAPHY FIGURES Sample 424E-163A Sample 424E-163B Sample 424E-163C APPENDIX GLOSSARY ' ABSTRACT DISTRIBUTION LIST DUP03001 3557 INTRODUCTION A program to utilize the concepts of Entropic repulsion,in developing deflocculated pigment dispersions, has been in progress at this laboratory for several years (1, 2, 3, 4, 5, 6, 7). Until recently, the flocculation stability of pigmented dispersion made using A-B* type polymeric disper sants was very sensitive to highly polar solvents and to polymers present in most major film forming systems. Recently developed A-B dispersants have provided deflocculated pigment dispersions which function satisfactorily in several commer cial film forming systems. The current program is designed to establish the commercial potential of selected A-B dispersants by defining their performance in selected new product developments. OBJECTIVES The overall program objective is to provide a simplified high quality mill base system based on A-B type polymeric dispersants. The immediate program objective is to define the commercial potential of specific A-B dispersants in selected new product systems; namely, acrylic organosol automotive lacquers and LBA urethane enamels. The acrylic organosol program is our top priority product system at this time. The program work is designed to show the advantages of deflocculated mill bases in the product system and to establish that the A-B dispersants do not adversely effect other film or product properties. *A-B polymeric dispersants are specifically designed to pro vide flocculation stability for dispersed pigment particles in an organic medium. The "A" segment of the molecule is designed for strong adsorption on pigment while the "B" segment of the molecule is designed to provide a solvated polymeric environment around the pigment particle. DUP030013558 2 SUMMARY AND CONCLUSIONS Recently developed A-B type polymeric dispersants are capable of providing deflocculated pigment dispersions which remain deflocculated whe,n let down into commercial film forming systems. Deflocculated films of dispersions made with A-B dispersants have been made in: A. Alkyd and modified alkyd products B. Acrylic (solution and organosol form) products C. Acrylic modified urethane products I. The L.B.A. Urethane Enamel Product System Deflocculated mill bases were formulated for -74 (Ti02), W-686 (Chrome Yellow), -819 (Quinacrdone red), -765 (Monastral green), -577 (Monastralblue), -608 (Yellow Ni-TiOg Complex), and -362 (Red Iron Oxide). The disper sions for -74, -686, and W-819 were scaled-up to the l/2 gallon continuous feed "47PH unit and two gallons of each dispersion was sent to the Marshall Laboratory for more extensive comparative evaluation of their performance in the L.B.A. urethane product system. These dispersions used a silane type A-B dispersant which has the following structure: (mma')33 2EHA-U NH(CHa)3Si(OEt)3 NH(CH2)3Si(OEt)3 II. Automative Acrylic Organosol Product System A formulating technique is being established for compounding organosol products so that effective evaluation of A-B dispersant mill bases can be obtained. Initial results show that deflocculated dispersions can be made with A-B dispersants for use in the acrylic organosol product. These dispersions can be made with and without solution form organo sol polymer. The use of the solution form organosol polymer is primarily, to control mill base viscosity, if it is needed to permit efficient mill base manufacture and processing. DUP030013559 3 Mild flocculation of the dispersed pigment is encountered during the let down into finished product formulation and also during film formation. The floccula tion is believed due to the solubility and compatibility of the A-B dispersant with solvent system during let down and to the compatability of the A-B dispersant with the polymer phases during film formation. However, the quality of the final film is still quite good, showing good color development and transparency. Prototype formulations for both product compounding and mill bases are being sent to Flint for further evaluation. Initial results with product compounding indicate a revised solvent system and specific order of addition may provide a high solids product (26-30# vol. solids) with the required stability. III. Acrylic Modified PVT? Coil Coating Product System Work begun in this product system early in the report period has been discontinued. Initial results indi cated that the acrylic nB,r segment of the silane type A-B dispersant [ (MMA33 |2EHAX1|-------< silane ^ ^ needed to be modified to improve the compatability of the dispersant with the product vehicle and solvent system. Further work has been postponed. IV. During this report period the acrylic organosol product system and the acrylic modified polyurethane product system were selected as the two top priority areas for this program effort. ACTION TAKEN OR PROPOSED Efforts will continue to establish commercial potential of A-B dispersants in the acrylic organosol product system. Development of mill base formulations that are compatible with the overall production of an organosol automotive finish will be continued in coopera tion with Flint and Marshall Lab personnel. Data will be obtained to determine what measurable effects A-B disper sants have on major film and product properties such as durability, cold crack resistance, Cleveland Humidity whitening, etc. DUP030013560 -k- Additional work on dispersions for the L.B.A. urethane system has been postponed until we have some data back on the effect of A-B dispersants on durability and other properties. PATENT STATUS The patent situation concerning the A-B disper sants is covered in ESR-69-52. No patent action is contem plated on the contents of this report. PUBLICATION STATUS Publication of this work is not anticipated. ACKNOWLEDGMENTS The writer wishes to acknowledge helpful discus sions with F. N. Jones and I. C. Chu concerning A-B disper sants and their performance, to W. S. Bullock, Flint Lab, and to L. A. Becton, Marshall Lab for valuable assistance on the acrylic organosol product system, and to G. G. Sun and D. R. Strehlau, Marshall Lab, for assistance on the L.B.A. urethane system. Also, to acknowledge the diligence and conscientious effort of R. A. Lambert in executing most of the laboratory work. DUP030013561 5 DISCUSSION Early in this report period, after evaluating the many possible routes to commercialize A-B dispersants and discussing possible routes with production, sales, and research personnel, the L.B.A. urethane enamel and the acrylic organosol product systems were selected. The two product systems selected represent both new technology and new product developments of large potential in both enamel and lacquer product systems. I. L.B.A. Urethane Product System The L.B.A. product system has two major film forming components, RC-66047 which is a Styrene/MMA/HEA/-Phthal. Anh./Cordura E 29.5 /15/16.5/ 14 / 25 (containing hydroxyl and some acid functionality) and Desmodur "N" a tri-functional isocyanate. The RC-66047 is a good dispersing polymer for some pigments such as Ti02 and iron oxide. The RC-66o47 is not as efficient or effec tive as several A-B type dispersants in dispersing and deflocculating pigments. From several satisfactory A-B type polymeric dispersants, the MMA33 | 2EHAn t" silane dispersant ( silane dispersant was chosen because it worked with a wide range of pigments, was available in large quantities, and is being used In the acrylic organosol program. The MMA| 2EHA "BM segment is used with the following "A" groups: 1. Acid "A" group CHaCOOH -[SCHCOOH] 2. Silane "A" group [NH(CH2)3Si(OEt)3]2/3 3. Mixed-Silane-Amine "A" group 1----- [NH(CHS)Si(OEt)33a/3 2/3 to 1/3 respectively ---[NH(CH2)2N(ME)3J1/3 These dispersants should provide the capability of a complete pigment gamut with excellent deflocculation of the pigment. Well deflocculated dispersions were made using A-B dispersants for Ti02, Chrome yellow. Monastral Red, Red Iron Oxide, Ehthalo Blue and Green. (Formulations for each of the dispersions are DUP03001 3562 6- - contained m the Appendix, Section I.) Evaluation of each of the above dispersions in the L.B.A. product showed superior color development and excellent gloss and appear ance when compared with control dispersions dispersed in RC-66047. Dispersions of TiOa (W-74), Chrome yellow (W-686), and Monastral Red (W-819) were scaled up to a 1/2 gallon continuous "47P" unit. Each of the dispersions processed satisfactorily. The TiOg dispersion was slightly thixotropic which was not indicated in the "47 P" beaker grinds. A slight modification in the level of A-B dispersant (0.1 to 0.25# increase) is expected to eliminate the problem. The disper sion for the -819 (monastral red) was also thixotropic at 20# pigment. Reduction to 15# pigment with additional solvent eliminated the thixotropy. Samples of each of the scaled up dispersions were supplied to the Marshall Laboratory for evaluation to determine the effects of these dispersions on film and product properties. Each of the dispersions were also evaluated in other vehicle systems. The dispersions provided excellent deflocculation of the pigment in Alkyd, melamine, and some acrylic polymer and vehicle systems. This data indicates possible use of this type of dispersion in other product systems such as 93 Line, 195 Line, 180 Line, 780 Line, 752 Line, etc. However, the solvent system used in the disper sions (H-735-iaoisture free cellosolve acetate) was chosen for the L.B.A. system only. A compromise in the mill base solvent would be possible if sufficient Justification was shown for reformulating existing product systems. IX. Automotive Acrylic Organosol Product System F. N. Jones has selected 3 A-B type dispersants for use in developing pigmented dispersions for the acrylic organosol product system. Each of the dispersants uses the same "B" segment, i.e. MMA33 I 2EHAaa.J. The three (3) "A" segments are silane, acid, and s/3 sllane-x/3 amine in functionality.. The silane type A-B dispersant has been used to prepare pigmented dispersions of TiOa (W-74), Monastral Red DUP030013563 -7 - (W-819 and W-839), Chrome yellow (W-686). Dispersions of other pigments have been made by F. N. Jones and I. C. Chu and are reported separately. Most of the work in this report period on the acrylic organosol phase of the program has been with W-839 (Monastral Red). This work has been pursued in three related but separate phases: Mill base formulation using A-B disper sants, product compounding for effective evaluation of mill base quality, and product compounding in terms of viscosity and rheological stability at high product solids. Two mill base formulations have been developed for W-839 (see Appendix, Section II). Each formulation contains a solvent blend, the silane A-B dispersant and pigment. One of the formulations also contains a solution form of the organosol polymer (9470-5). The solution form polymer 9470-5 is an older self-stabilized polymer form which showed moder ately good wetting properties for some pigments (Ti02, Phthalo Green). It is expected that other solution form polymers would function as well. The solution form polymer Is used to increase the mill base viscosity, to improve milling effi ciency in the ,,47P<I unit, and to provide improved processing and handling capability in plant equipment. Microscopic examination of the two dispersions does show improved grind ing efficiency with the solution form polymer in the mill base. Each of the above dispersions are well deflocculated. When let down into the product system, some mild flocculation of the dispersion does take place. The degree of floccula tion can be effected by orders of addition in product com pounding. (See Appendix, Section II, for recommended formu lation. ) The flocculation encountered on let down and during film formation is not severe and is expected to provide more than adequate product quality. The flocculation encountered is believed due to 1. the multiphase nature of the polymer in the dry film and 2. the mutually antagonistic requirements for the dispersant in this vehicle system i.e. tolerance to aliphatic solvents and oompatability with the organosol polymer. DUP030013564 8- A tentative procedure for let down of the mill base into a product is to add the two plasticizers to the organosol polymer with some xylene and mix 1/2 hour. At this point, the plasticizers and the xylene will solvate some additional organosol polymer. The viscosity increase is slight and well within production equipment capability. The added polymer in solution aids in coating the pigment particles and tends to protect them against flocculation when the non-solvent, Isopar-E, is added slowly as the last ingredient. (See Appendix, Section II for formula details.) It should be noted that additional data are required with several pigments and pigment to binder ratios to finalize the above procedure. A tentative formulation technique is also presented as a possible route to a high solids product make-up. Sufficient data are not yet available to insure capability but initial viscosity stability at ambient and elevated (l4oF) temperatures is promising (see Appendix, Section It, for formulation details and viscosity data). DUP030013565 BIBLIOGRAPHY 1. Huntsberger, J. R. 2. Heino, W. L. 5. Thompson, D. R. 4. Thompson, D, R. 5. Thompson, D. R. 6. Thompson, D. R. 7. Ashe, T. A. ESR-63-52 ESR-64-36 ESR-65-6 ESR-66-25 ESR-66-54 ESR-67-51 ESR-68-26 TFC/ayk 12/12/69 DUP030013566 SAMPLE 42.4E-I63A VOLUME SOLIDS * 26.5% LEGA MO --..-............. -- `|N|T|iaViSCOSITy |40*F VIS COS IT y AFTER 4" DAY'S m m x& lj * SHEAR STRESS DVN/c m*- DUP030013567 SAMPLE 424E-I6S 6 yOLonc s o l id s = 27.5 % UC&AND WTlAi. vise os ny Ko%F viscostVy AFTSii A DAys Wo f --o--o--o vise os fry Am 7 DAys V)fN/ C M ^ DUP030013568 iooocp ................L. i.. SAMPLE 424E-J63C VOLUME SOLIDS r 30.5% l eg and x h Xt XAl v is c o s Ty l4oF -------------------- vtscosiVy a f t e r 4 Oay s |40*F -- 0--O----- 0 viscosity AFTER 7 DAys \40*f -- X--.x------ x viscosTy Af t e r 7 Myi ( +. t OAy AML8M&X. 7MP) JOG CPs micos iiy I.O<f --4- *~4- .. .4-- i- ....... .... i- SHEAR STRESS Dy n /c m* too DUP030013569 APPENDIX, SECTION I L.B.A. URETHANE PRODUCT - MILL BASE FORMULATION Code H-735 448E-104 W-74 % 34.0 1.0 ^0 100.0 Remark: (Cellosolve acetate) (Silane Dispersant) > (Ti02 R-96O) Add in order with mixing Mix 1/2 hour after all TiOa is in Grind n47P'' 50/50 sand/base 6 min. stay time H-735 448-E-104 W-686 33.75 1.25 65.00 100.00 (Chrome * yellow) Instructions above. same as The level of A-B dispersant was chosen to minimize settling via beaker type formulations some modification of dispersant level may be required on scale-up to retain desired properties. If the use of RC-66o47 is desired in the mill base, new levels (lower) of A-B dispersant will be required to minimize settling. H-735 448E-104 W-819 77.0 8.0 15.0 (Monastral 100.0 Mill base formulations for other pigments mentioned in this report can be supplied on request. DUP030013570 APPENDIX, SECTION II AUTOMOTIVE ACRYLIC ORGANOSOL PRODUCT - MILL BASE FORMULATIONS Code H-47 H-79 H-13009 W-839 Isopar "E" % 15.0 15-0 20.0 20.0 20.0 Toluene 1 Add in order with Cellosolve Acetate? mixing,mix 10 min. Silane dispersant J Monastral Red } Add slowly with mixing. Aliphatic solvent-^ Mix 30 min. Add slowly with mixing, mix 10 min. Grind H47P" 50/50 sand/base 20 min. staytime H-47 H-79 9^70-5 H-13009 W-839 Isopar "E" 10.0 20.0 20.0 20.0 20.0 10.0 (Solution form'* organosol polymer) Instructions same as above except first por tion mix 1/2 hr. to insure solution of poly mer DUP030013571 APPENDIX. SECTION II (part two) AUTOMOTIVE ACRYLIC ORGANOSOL - ORDER OF ADDITION 424E-163B Code H-11947 RL-G-32345 RL-3340 H-583 % 66.25 4.17 4.51 8.83 Organosol Polymer 1 Plasticizer > Plasticizer ^ ' 1 Xylene J Add in order with mixing, mix 1/2 hr 424-E-151-C 424-E-134-B Isopar mE" 1.66 2.65 W-839 Mill base.*[Add in order with Aluminum base ' ' J mixing, mix 1/2 hr 11.93 100.00 Non-solvent (III)^ Add slowly with mixing, mix 1/4 hr. Some modification to this formula may be required to insure optimum results with different formulations. It is expected that the ratio of H-583 to Isopar "E" will be the only variables to adjust. DUP03001 3572 ^a cr oo 04 st =* O OMA in o 204 in in o N- n * in H pH UN c- UN ao i St vo o m ON o o VO 3- S UN on cu 4J c <v *> ea ft *H O a- > O TJ -rH -ah acr >o --4< poH f*N pH mao pH CO vO in 41 CQ 8 T3 a h H i--4 oo > CO 43-*> pH CD C3 rH Hte <0 T5 Hfc *4 pH o CO o in On to a ao 43 CO <0 x> MpaH -porHi 43 0 04 pH CQ CO1^ t- ON 00 mvocfc*-4voo<ut^ t^-ONinb-vOONONt-- to a J* *H paH poH 43 W co cx> in CU N- CM ON ON vO VHO * 1 in ocu CpOH >R rH coo 4) 4* as =*fc TJ c; eb ac 0a +j c M >* oooom o o o cu 4~ ON om 6 in co o d o d o o O UN d cu tf-t s cu o CU UN pH -=* in pH 0- pH UN CU UN sr co cu st fOcO H ON UN m 0- UN ao tv st pH o 6 UN O pH ON o GO O RHfc pH CU -SI * O VO * O *in % o =*- s* cu m in o ON in =r -cau- imn ^t o OJ VO ON o * a(0 M -H pH rH aO NO o 43 0) O NO VO *N t*- On cu in in o~ mco oo od in 8 8o in do CU oo in u n UN in itn- o o oo cu cu cu CU pH n 44 t*p>4 pH pH 4a3 oM m CmU vpoH CcOu CO n to- in cm 0o0S CU {V ON ON ON ON o n in m o cu mm 5 m St On VO vaq* o o m UN o si in OJ o ao ON man vo cu O CO u n o- % % CU vo co % cu in OJ UN Volume S o lid s * 27,5 W eight S o lid s * 36.5 +J d 4} <H 0) 'O XJ 4) O UO c H PC 0T> VC fi I &2 OJ -=t c o TT3J < in pH , cu pH UN vd st sf u 0. & HW aO. s s- n st m pH fQ -si ft ON oo -oan mu n cmui i i oO pH HE K IC pH 0I tf> X u Mas o -S' (i N mmi a*4s +f>t CU m co vino ON CO o o is- 4-> u s* 1 i 1* 0o ON 44 Cu pH x 0 p o 0 0 Ou c O c 0 1 0 (0 0 m < o 0 pH c H 0 pH H e 0c 0 m ao U1N 0 W 403 pH in pH 1 w -sr 0 a pH O 6H a n i < 1 +* 0 X pH a to pH pH 0 oo o pH >1 X pH rH XX On me CO w 1r 3c 14 c sa 0O aa rH 0k 0 0 CQ 5 cq -=1r m -=t e pH pH ai pH CX I w ictu as pH | < n o -cmau msf m w mo i a a Ih Q. O 0 M UN VO DUP030013573 GLOSSARY Silane dispersant MMA J2EHA T3 I TT NH(CH2)3Si(OEt)3 -NH(CHs)3Si(OEt)3 Acid function dispersant . MMA 2EHA m IT ' CHaCOOH j --SGHGOOH SCHCOOH CHaCOOH Mixed Silane-Amine functionality MMA |2EHA TS| TT NH(CHg)3Si(OEt)a - a/3 NH(CHa)aN(ME)a = 1 /3 MMA Methyl Methacrylate 2EHA 2 Ethyl Hexyl Methacrylate HEH Hydroxy Ethyl Methacrylate Phthal. Anh. Phthalic Anhydride Cordura E /KGlycidyl ester of versatic acid * fl R-(J-C-0-CH2CH-CHa R Desmodur MN" = Trifunctional isocyanate W-74 = TiOa W->62 - Iron oxide (coarse pigment) w-608 -686 * Nickle - Ti02 complex - yellow pigment = Pb-Chromate yellow pigment W-577 Phthalo cyanine blue pigment -819 Quinaeradone Red pigment W-839 Quinacradone Red pigment DU P030013574 ABSTRACT The ability of A-B dispersants to deflocculate pigment dispersions is established. The effect of A-B dispersants on film and product properties will be deter mined. Dispersions containing A-B type dispersants were supplied to the Marshall Laboratory for evaluation of film and product properties in the L.B.A. urethane enamel prod uct system. Formulation of dispersions using A-B disper sants for use in the acrylic organosol product continues. Initial results are good and work indicates the possibility of stable high solids product system. DUP030013575 RESEARCH REPORT DISTRIBUTION PIGMENT DISPERSION REPORTS ESR REPORTS FULL REPORT FIRST PART W. D. Lawson, Wilm. -1 R. S. Prengle, Wilm. 1- C. K. Ikeda, Wilm. P. I. Poindexter, Wilm. 11-- J. A. Klacsmann, Wilm.) J. C. Richards, Wilm. ) In turn " 1 S. R. Miller, Wilm. ) D. L. Herndon, Wilm. ) In turn K. F. Browning, Wilm.) - 1 A. J. Wells, Wilm. -1 C. W. Stahl, Wilm. -1 W. S. Woods, Wilm. -1 P. J. Graham, Wilm. R. W. Laurrell, Wilm. 1*1 M. M. Coburn, Wilm. -1 T. R. Matthews, MRL -1 C. E. De Boer, MRL -1 D. M. Glenn, MRL -1 S. Hochberg, MRL 1 - W. S. Zimmt, MRL 1- C. Victorius, MRL 1- G. E. Lewis, MRL 1 J. R. Sanderson, MRL 1-- R. H. Churi, MRL 1- Information Services, MRL 1-- C. H. Knop, MRL - 16 Library, MRL 3- C. R. Swinehart, Phila. Plant -1 H. P. Wood, Fairfield -1 G. I. Mulholland, Flint 26 L. W. Crissey, Flint 1- F. M. Gavin, Flint 1- A. F. Nugent, Flint 1- C. W. Bullock, Flint 1- G. W. Or vis, Flint ` : 1- Library, PRL N. G. Fisher, CRD, ESL 31- R. D. Vest, ESL 1- I. C. Chu, ESL 1-- T. P. Concannon, ESL 1- F. N. Jones, ESL 1- File 3- DUP03001 3576