Document B5q7mRGawDkJ7ypRQr8o89N9w

: '! 'llI***1 k' ^ V-i:" 0e20'54 mmm m m m mmimm Indexed cc: W. . Lawson, Lab. Hi B, Davis9 Lab, 0* B* Bullitt, mim.p Exp, Sts ,, Patent; Section, Lab, Library, Lab* (5) C. Shay, Lab, Files 1810 Ktarshall Laboratory December 10, 1954 MGMHDim REPORT HO, M-746 PREPARED BY C. W, Seeker, B. R Heikel BMIVERSAL TIHTBJG BASES Objective t To develop a line of tinting colors which will be compatible with both orthodox oil-type finishes and emulsion finishes of the o/w type. Background t During the development of the Custom Color System, a decision was made by Sales to include a latex emulsion to the throe alkyd whites already formulated. Minting of all whites was to be done with a single.line of colorants. However, the alkyd colorants which had been formulated for the alkyd whites were not compatible with 391-012 "Flow Koto" White. It was recognised that this dial compatibility could be accomplished either one of two ways? 1. by reformulating the line of alkyd colorants, which was considered the soundest, but the most time consuming and, 2 by formulating a new type of "Flow Kote", doped with the proper ingredients to make it compatible with the existing alkyd colorants, Because of the close time table, along with the urgent need for a latex finish to be included, the second approach was followed, and a Custom Color Flow Kote was developed which could provide 320 of the total 572 Custom Colors involved. Its initial cure, however, was inferior to 393>022 and to date all eleven batches of the deep tone Custom Color Flow Koto have fallen off for color development after from .3 to 6 months aging, possibly due to an inactivation of the surface active agents by adsorption on the pigment surfaces. N35502 Advantages; By replacing the "632-Line" Custom Color Minting Bases with the proposed Universal Tinting Bases, we will eliminate the need for the special Custom Color "Flow Kofce" Whites and allow the use of a standard type o"Flow Kote", similar to 391-012 (only an adjustment In the hiding level should he necessary} , In addition, we should be able to provide more of the 572 colors available. Simplification of existing tinting lines and simpli fication of plant tinting practices could be a long range advan tage of this project. Theory ? In developing a Universal Tinting Base, the following three components are important; 1. Vehicle 2. Pigment 3. Surface Active Agent Vehicles The most Important requirement for a vehicle in a universlTl?rnting Base is that it should be one, which it self has the characteristics of surface activity, that Is, one portion of the molecule should be hydrophilic (water-loving) and the other portion hydrophobic (oil-loving). The balance of these two portions of the molecule along with the degree of its surface activity determine Its usefulness. However, vehicles which do not have surface active characteristics can be used if some surface active agent Is Incorporated with It. Other requirements, as good grinding characteristics, proper viscosity for optimum dis persion with the paint vehicles, cure,color retention, shelf stability and effect on brushing must be considered. Pigment t From a universal standpoint pigments fall into two dlstlnc^claises: nature and. 1, Inorganic pigments, which are hydrophilic by 2. Organic pigments, which are hydrophobic by nature The mechanism for tinting with each pigment type appears to be quite similar5 the pigment particle is wetted with vehicle in the grinding process which forms an envelope around the surface of the particle. When this vehicle-coated particle is introduced Into an emulsion, one of two things probably happens.; 1. The oil on the surface of the pigment particle, for all practical purposes & emulsified, leaving the pigment particle now uncoated. If the unseated particle is hydrophilic, as in the ease"of Inorganic pigments. It tends to migrate to the external or water phase, where it tints. If the unbodied pigment particle- is Hydrophobic, as Is the case with organic pigments. It tends to migrate to the Internal or latox-oil phase, This causes pote* color development, since the pigment must be in the* external or water phase to tint. If a hydrophilic surface active agent is DUP030003728 -3- present either la the white or the color base* the mechanism is probably modified, in that the uncoated pigment particle adsorbs some of this wetting 'agent on Its surface. 'Hits action would leave the inorganic pigment more hydrophilic and the hydro*phobic/organic pigment now hydrophilic, depending upon the amount of surface active agent present. 2. The vehicle-coated pigment, on being Introduced into the emulsion or beforehand in the grinding process, is itself coated with the proper surface active agent to make it hydrophilic. This differs from the first case, in that the vehicle is not emul sified. The particle is not uncoated but has an envelope of wet ting agent around both the pigment particle and the vehicle. This wetting agent must be hydrophilic in order to carry the vehiclecoated particle into the sternal or water phase to tint. There fore in this case it makes no difference whether the pigment is organic or inorganic. This second consideration appears to be possible only if there Is a difference between migration into the latex phase and the added vehicle phase from the standpoint of color development* Surface Active Agent: These are compounds in which one portion of~'Me^iolecuIe",is''Hydrophilic and the other portion is hydrophobic, thereby forming a bridge between oil-type materials and water-type materials. The balance of the two portions of the molecule determines Its relative affinity for either hydrophilic or hydrophobic materials. Basically these compound fall Into three general classes. If the molecule tends to ionise, the sur face active agent is said to be cationic or anionic. It is cationic when the oil-soluble portion of the molecule is the positive ion and anionic when the oil-soluble portion is negative. When the surface active.agent does not incise the agent is non-ionic. From our work thus far a non-ionic type of wetting agent gave the best resultg. Cationic and anionic surface active '.agents' appear to be interfefred with by the ions already present in $ emulsions. In addition to being non-ionic, the surface .active agent must be hydrophilic.to carry the pigment or vehicle-coated pigment particle into the external phase. Summary of Completed Work? In order to be considered universal, the bases which were formulated had to be compatible in the following products: 639-776 ; ; ' - 639-780 639-778 ' 389-00? 391-012 389-001 P-38g~UW25 Custom Color does Deep " n Semi-GlossDeep * " - Flat Deep 51 n "Flow Bote" Deep t5Plow Eote" White PVA Sealer Coster Rhoplex Sealer Coater These whites were tinted tottie 28/1 deep tone color level and brushed out on pearl board* The brfrshout was .subjected to a rub-up test to determine if crocking developed and a flow-out was mad indicating color development in the can.. In order to be considered good for' DUP030003729 ~4. compatibility, maximum col02? had to develop in the cap* If color development In the can was good, brushouts and rub-ups were usually good. The panels were also recoated overnight. By taking into consideration these four factors* brushoui, in itial and overnight, rub-up and flow-out, the overall appearance of the panels was rated as follows; 5 ~ excellent (flow-out matches brushouti no rub-up) 4 k good (flow-out matches brushout* only slight rub-up) 3 fair (Flow-out light to bmshoutj also slight rub-up) 2 m poor (flow-out indicates incompatibility, however, brushout develops some color) 0 no good (Completely Incompatible). Since the proposed universal tinting bases eventually are to be used as replacements for the present ,!39~LlneM Custom Color Bases, it was necessary that the pigment concentrations should remain the same for corresponding bases in both lines, in order to elim inate variations in tinting strength. Following is a list of . the pigments used and their corresponding concentrations; Inorganic Pigments; W-679 W-.630 W-622 W-895 W-303 Chrome Yellow Lt. Ferrite Yellow Molybdate Orange Red Iron Oxide . Red Iron Oxide ~JL 74.2 63.7 63.4 4?.4 7O.2 / Organic Pigments; ^ ) M-j527 Monastral Blue W-300 B.Q.K. Red. Ik. W-765 Monastral Green W-205 lampblack ,*. 20.1 30.8 26,3 22.4 e began by grinding these pigments on formulas similar to the 39"*Line" formulas, the only difference being that the RC-601, Soya P *.S. resin was replaced on a weight basis with KH-5186, Kelsol (Spemeer~Kello@g{s Aasaonlated linseed Oil), which is both a drying and,-water dispersible oil. While these bases were compatible with the aIkycl and t3Flow Kote" whites, they were not compatible with either the PVA or Bhoplex Sealer Costers. For this reason we decided to incor porate some surface active agent.; which when used in conjunction with he1sol would improve compatibility in the Sealer Coat&r for mulations. The following surface active agents were examined with this end in mind.; 1. E-609,Triton X-100, an alkylated aryl polyether alcohol, which Is aon-lonlc. 2. KH-5185,Triton 770, a sodium salt of alkylated polyether sulfonate, which is anionic. DUP030003730 -5- ' t 3* DS-23858,Nacconol IESF, alkyl aryl m1fonate, which is anionic. 4. G-414, Duponol ME., sodium Xauryl sulfate, which is anionic 5* BS-26332, Ethomeen 0-20, a tertiary amine having on fatty alkyl group aad two poly- . oxycthylene groups substituted on the nitrogen, mis agent is. cationic 6. Ethofats - mono-fatty or resin acid esters of polyethylene glycols* These agents are non-ionic. (a) B.S.~2?693 Ethofat 142/60 (ethylene 03ri.de portion equals 50 moles). (b) BS-26115 Ethofat 142/15 (ethylene oxide portion equals 5 moles). 7. Taiaol 731 (35$ soln) - believed to be the sodium salt of dicarboxylic acid with a long alkyl chain. This agent is anionic. These agents were incorporated into the grinds at approxi mately 5$ by weight on the total base and of the above series 1-609* Triton X-100 showed the best results, giving us compatibility in the Sealer Coater formulations to souse extent. However, in order to improve the compatibility still further, we decided that an in vestigation of other vehicles besides Kelsol would be of value. Below is a list of other materials we looked at as possible vehicles for our Universal Tinting basess ^ 3. KH-5187 Glyceryl Mono Hiccinoleate ^ 4. -JS-156. .Dehydrated Castor Oil 5. K-154and H-534 Oleic Acid and Triethanolamine 6. .H-22 Castor O1! ^7. B:48i Tween 81 8, DS-27716 loa-Break safflower Oil 9 . a:-253 Haw linseed oil 10. H-59 Soya Varnish Oil 11. A.B.M.% ir.T, Oil #4 Grinds in these vehicles were spot-cheeked In our tinting whites for compatibility both with and without the use of Triton X-100 and of the above list we selected the following matrials' as'showing the most promise as a universal vehicles 1* KH-5186, Kelsol (Spencer Kellogg5s Ammoniated Lin seed Oil, a water-soluble drying oil. 2. KH-5187* Glyceryl Mono Hiccinoleate, .a non-drying, non-ionic, hydrophobic wetting agent. DUP030003731 3. H~356, dehydrated Castor Oil, a semi-drying oil, having some surface active characteristics* 4. H~48l * Tween $1, Atlas* Polyoxyethylene sorbitaa $ono Qleate, a non^drying, non-ionic, hydrophilic wetting agent. In order to evaluate these four materials more properly# a complete series of grinds was prepared, in which all the pig ments of interest to ns were dispersed in each of the four vehicles on formulas similar to the present M39~Llne'' bases. In addition, another series of grinds was1: prepared using these vehicles, however in this- case, an arbitrarily set amount of 5$ Triton X-100 was added. -Inorganic pigmented bases were given 2 passes on a 5 roll mill with organic pigmented bases being ground 24 hours conventional S.U.W. at a 40/80 ratio. Fineness of grind of these bases was approximately 1.0 mils. All white bases were tinted with these series of color bases to the 28/1 fl. os. level, checked for compatibility and overall appearance' and given a numerical rating. A summary of the results obtained for each vehicle and vehicle/wetting agent combination for both the inorganic and organic grinds is shown in the following tables? k* DUP030003732 lA fl> & e? &, m oJ foO -as-* ?> s CO*-& & ? H 5 I* br^OOCDinGNOGi} O ChWfiW OS-sbOlj m rtHHririHH I r*f Ma3 I I S 5 o\ S3 fA ONO ! COW-tr-ie>~e.sJ- 5 % H WWW CU PIrl IA W sSos s O W lAaS- COOOCO Hri CM HHCJ tofi\ 0o0n tn 9 t b~ 9 cofointom^md m I H W 03 0101 01 03 01 w fOO* r-- O IA 01 CVi 03 H<aS- b~| ON m 00 0103 01 01 3 01 Oi Hi oi m | ON<OOJCOJ^,Js3'-aJ->sS*J lA PAON H 01 Ol H 01 W 01 03} 01 VO \0 w W W 03 WWW W So w ON co VO 8 43 I 53 O I 43 43 d # 0> 0 O <$r-1 Hurl'" o 3 a rS & HW H$3 ggOO 00 0 P s ssllssgg Z o S fe Oi sumsssei *V!*i cornoocsi rorocoi ssssmsi g b-com^ b~Hwr-ii!l mH w 01 b- 03 W ONW W| (A OrtCOM3M3v0NpOiHOHrllj H(A rormrurvoim^f-^j in H rt HrirtHI H uvt oomnfunj m rlrl rlriH r!| ri in-as*oo^nmtni m rt H HrlHHl rt 483 I i 4> I 4 aoH3 a 0 *8 H rlH * * o rl fGfi 0OKK ? riHggOO aSffloHHS* DUP030003733 O $ s i I 5e8imas| 5 .<nn cu 1 HI $ Mtwfasisa s HHrlr!HH<l)ril <M JA s A o o v o ia ^u y o of o a OlOOOSCVi 05 00001 at p. co "s^^saj 00 01 r-i or0-1o\ <noooow^5^tnto! *SSS?S CtSSMSMBId OIMfSHO <3H ' I I I O T IOIMVDHQMI $on at5 E*"CV100 OWO OVOVJ O o\ 00 0OG1 (-5 00000000I at v0o0 vOoO\ JP>O-PVOOOOI OCOOAOOUOO.*OtaOt|i aOt 4I3 It -P l 4 r*,OG.-{ 43 jB,| pj OO 03 It m 43 O_ O_OK3dS3i P sS sS s ^ E B K DUP030003734 * * Explanation of the Above fables (See Table I.): (1) Total of the brushout ratings la each white base for the number of pigments involved in this particular vehicle or vehicle/wetting agent combination, (2) Maximum rating If all brushouts were rated excellent for the number of pigments involved* (3) Total of the brushout ratings for the number of pigments involved in all 6 whites tested, for the particular ve hicle or vehicle/wetting agent combination. (k) Arrived at by dividing the total described in #3 by the number of whites times the number of pigments involved. (Ex, In Table I. the average is obtained by dividing the total by 30.) (5) letter ratings for the average by our rating system. Comments on the Above Tables: 1. In all oases, compatibility in the sealer Coater formulations was improved by the addition of Triton X-X0O to the vehicle. This was especially true in the ease of 389-001, FVA Sealer-Coater. The exception was Tween 81, which showed good compatibility even without the addition of Triton X-100. 2. It should he kept In mind that the Triton X-100 level used In preparing the color bases was arbitrarily set at 5% on the total base, Compatibility in some cases could be fur ther improved by raising the Triton level above 5$, This is es pecially true with the [DCO & Triton) bases. 3. Although the Inorganic pigmented bases with GMR and (OB & Triton) were compatible with the alkyds, the organic pigmented bases in these vehicles were not compatible, W-300 and W-785 dispersions in these vehicles were' very poor, probably due to exceeding the OMR tolerance of the alkyds. k, 391-012 "Flow Kote" is only slightly better for com patibility over 389-OO7 Custom Color "Flow Kote" Deep, however, the latter contains approximately 0,4#/gal, of added wetting agent. 3* A marked improvement was noted using Rhoplex SealerCsater over FVA Sealer"Coater with respect to compatibility, i 6. Use of straight Tween 81 as the grinding vehicle gave the best results for compatibility for both the inorganic and organic pigmented bases. Running a very close second was the combination of (Tween 81 and Triton). About equal for third and fourth was {Kelso! & Triton) and (DCO & Triton), (BOO & Triton) organic pig mented grinds appeared to be low in tinting strength in the alkyds. However, later work indicated that this tinting strength problem was due to the method of dispersion (5Bi vs, SOT) rather than to the nature of the dispersing vehicle. DUP030003735 ' ~10 Scrubability and Met Adhesion: . To check the effect' on scrubability and wet adhesion of the color bases dispersed in these'vehicles or vehiele/wetting agent combinations, tints were made with the W-527 pigmented bases at the 8/4 fl. os. deep tone level in 389-007 and 391-012, (the maximum- tinting level in our present Custom Color System). Brushouts were aaflebn waliboarcl panels that bad previously been coated with primer Sealer and Flat Wall Paint. These panels were aged for one week and subjected to the standard Marshall Laboratory scrub test, using a 5$ soln. of T.S.P. All panels except those tinted with the (DCO & Triton) grind of W-527, showed complete failure after only 200.cycles. Those tinted with the (DCO & Triton) grind showed almost no failure after 2000 cycles, at which the testing is said to be complete. Untinted 389-007 end 391-012, used as controls, were also intact after com pletion of 2000 cycles. Failure, where noted, appeared to be due to lifting of the film and in some cases due to the solubilizing of the film in the T.S.P. Soln. Failure of the films which con tained (DCO & Triton) appeared to be due to erosion at a point where the film was defective initially. In addition, a series of stains, which included ink, #2 soft lead pencil, Mongol Fed pencil #966, .China-Marker Red 169-T, were made on the panels and cleaned with both Ivory soap and scourv" ing powder. Most of the stains could be removed with soap, the ink and China-Marker Red stains being removed by mild rubbing with scouring powder. In most cases the film was not appreciably damaged by this action. Drying, gag Resistance and gloss: Because of the far superior results obtained with the (DCO & Triton) combination in our scrub tests and the knowledge that the compatibility of the bases dispersed in this vehicle/ wetting agent combination could be improved by raising the Triton level, we decided to adopt this combination as the dispersion medium for our Universal Tinting Bases. To determine the effect on drying, sag resistance and gloss with this combination, we added to the three alkyd whites amounts of these ingredients approximately equal to what they would contain if tinted to the 28/4 fl. os, deep tone color level, The doping was done fox' color bases which would pos sibly contain up to 15$ Triton on the total base. Also included were similar dopings with RC-601, soya/P.E. alkyl resin to.simulate 32-Line tintlngs, The untinted whites were used as controls. Results of these teats are shown in the following table: DUP030003736 TABLE IV Tack Free Dry Thru sag 60 Gloss 639-776 639-776 -f BO-601 639-776 + H-156 639-776 -5- H-136 v 150 H-609 639-760 639-780 + RC-601 639-780 + H-156 639-780 + H-156 + 15* H-609 639-778 639-778 + EC-601 639-778 + H-156 639-778 + H-156 + 150 H-609 8 hrs. 9 ** 10 " 14 " 8 11 14 " 14 " <6 " 14 " 14 " 22 B 10 hrs. 10 " 12 " 18 8" 11 ls 11 " 22 ,4 14 " 14 " 22 " 24 " 18 mm 20 " 21 " 23 " 18 " 19 " 20 " 33 ; 17 " 19 l 21 B 20 " 90 91 88 89 22 56 64 74 3 5 24 23 This increase in drying time of the alkyd whites, when doped with the ingredients comprising our universal vehicle, is most evident with the Triton X-100 addition, which of itself, has no drying potential. .DCO, which slows the dry to some ex tent, is a semi-drying oil. To bring these drying times more in line, we feel that a drier combination should be incorporated into the color bases since the drier level in the white bases cannot be increased because of the skinning risk. These dopings also gave us higher sag readings, in most eases from 2-3 mm., which in this range becomes significant. Where DCO and Triton were added to the Semi-Gloss, a reading of 33 mm. was noted, ibis is considered excessive. It should be kept In mind that the addition of any wetting agent to the alkyd whites will tend to defloceulate the system, causing an increase in sag. Al though the above sag readings are indicative, actual tintings should be checked for more accurate results. Finally, we checked the effect of the above dopings on the gloss of these products and a considerable increase for both the Semi-Gloss and Flat, when read initially against the controls, was evident. This initial increase in gloss, however, is not considered unusual and is noted whenever any of our standard shelf goods are tinted. Although the increase noted for Custom Color products is analogous to that found in our standard shelf goods, its magnitude could possibly result in flashing complaints, par ticularly with the Semi-Gloss and Flat. Since it Is anticipated that for some time, the existing s,632'-LineH colorants and the proposed Universal colorants will be used simultaneously in the field, some adjiistmsnt should be made to reduce the gloss differences noted. Effect on Emulsion Viscosity s In order to determine the effect on viscosity when 383-OQ7 and 391-0X2-are tinted with our universal Tinting Bases, tints were made at the 28/4 and 28/1 f,l, os, level with a W-527 DUP030003737 V --12-- and a W-895 gz'ind in BCG at the 5$ Triton level. Ho significant viscosity increase on tinting was noted either initially or on standing overnight with either 389-007 Pff 391-012. The maximum viscosity increase in these products was approximately 5-7 Krebs Units. Stability'; A two month oven stability check of all pigments involved, dispersed in (DCO h Triton) were rated excellent for separation and settling resistance. Also, to date, there has been no indication that the ability of these bases to develop color has been impaired by either shelf or oven storage a r39 LinetlDopings: To determine if our present t,39LineH RC-601, soya/p.E., alkyd based colorants could be made compatible in the emulsion products, the following five ingredients were added to these bases both singly and in combination; 1.H-609, Triton X-100 at the 5$ level 2. KH-5186, Kelsol at the 10$ level 3. KH-5187, OMR at the 10$ level 4. B-I56? DCO at the 10$ level 5# H-481, Tween 81 at the 10$ level These dopings were compatible to some extent in 389-007 and 391-012, the Kelsol doping giving the best results with in organic pigmented bases and GMR giving the best results with or ganic pigmented bases. However, compatibility in the Sealer-Ceater formulations was poor. A comparison of the,, relative compatibility of. the doped f,39-l>ine11 bases vs. the (DCO +. Triton) Universal Bases shows the latter to he far superior. Competitive Universal Tinting Systems vs. Du Pont; An evaluation of competitive universal tinting systems compared with Du Pont (DCO + Triton bases} is shown in the follow ing table. It.should be noted that no competitive system includes organic pigmented colorants. P-398' 639-776 639-778 398-007 391-012 389-001 U~ 9**25 Sherwin-Williams I E E GG E Pittsburgh plate Glass P F E EG E Areher-Danlels-Midland F % G 1 KG IfG Sears Key Tint KG MG F F F F E IS E G P G Du Pont* E E G GF F ^Ratings for both organic and inorganic pigmented color bases with DCO and 5$ Triton X-100 on the total base.- DUP030003738 The compatibility rating of Key Tint in 389-001, PA Sealer Coater floes not correlate with the results obtained when examined previously# Compatibility at that time was rated ex cellent in 389-001. Suggested Future Work; 1. Determine optimism Triton X-100 level for maximum compatibility. 2. Determine if H-632, Odorless mineral Spirits , can be eliminated from our dispersions without Impairing their uni versal tinting ability. 3. Develop a suitable grind of W&205, Lampblack* in Cisco + Triton} Develop the composite pigmented bases, similar to the 632-Linen Custom Color Bases, 5. Develop extended color bases 6. Spot check blending of the color bases on an inter mix basis. 7. Prepare cost data on final color base formulations. 8. Put out exposure study of Universal Tinting Bases in Two Purpose Outside White and Cement and Stucco White. DUP030003739 4 04 Pk G> o % Cm 04 CM Pk <0 o o 04 & & PS " fb Pk m m m mm W m m H P3 M .M in CM ro so o cvi t*- * .* V O o H rl o ash * bJ" O *53 " to rt to H t i < os =S.*r iS- rt OS <0 V' O Oi CM .* 41 4 mOJ 0C0i o4 O4 o4 o + to in (A m ITS *** tn tn \o rt* CM* fv . VC- so* CJ\ rt 00 VCOO oCVJ o SO, in to OS CO tvb * *! * cu rt CO CO sCoO StoO -t=sr* ot>- O01 oto sCoM soCISo:O sCCoiMM 22 tons co| & t>to*3ooi5 Jv iCn5J & Oeo 3t ciEnol> Se sp EO Sv" JSi00 OS cu oISs* OS o o 0O3S CCOO cs so rt CO OS .sj4 CM cOos DUP030003740 -15Improvement 3h the compatibility ratings for these bases can be made, especially in the Sealer-Coater formulations,if the Triton X-100 level is Increased. notebooks: C... 5*95* 5828*) SALES DEVELOP!HT C. W. SECKER HRH:CnS:pc 12/T/5* * DUP030003741