USRE21427E - Colored titanium dioxide pigments - Google Patents

Description

D April 16, 1940- R. M. M KINNEY ET AL.

COLORED TITANIUM DIOXIDE PIGMENTS 2 Sheets-Sheet 1 Original Filed Jan. 11. 1955 WHITE w V 3 D E L p R u D.

BLACK INVENTORS. CAQL ro/v E. 501/ 77/ e5 EOBEQT M. M /f/ N/ EY. BY/flf4 2 F.

ATTORNEY.

April 16, 1940. R. M. M KINNEYLH AL 21,427

COLORED TITANIUM DIOXIDE PIGMENTS 2 Sheets-Sheet 2 Original Filed Jan. 11, 1935 VALUES ACK . INVENTORS.

CARLTON E. SM/TH f ROBERT M M /f/NNE Y. BY

M ATT RNEY.

Reismed-Apn'm 1940 UNITED sTATEs -.PATENT ,OFFICE 21.427 cononsn TITANIUM moxmn mama's Robert M. McKinney, Roselle, Del., and Carlton E. Smith, Catonsville, Md., assignors, by mesne assignments, to E. I. du Pont de-Nemonrs and Company, a corporation of Delaware according to our invention by combining an uncalcined titanium oxygencompound with a compound of a heavy metal which, on calcination with a titanium oxygen compound, forms a colored compound, and then calcining the product. The heavy metal compounds suitable in our invention are those which on heating to elevated temperatures form colored-compounds, for instance colored oxides or titanates. The presence of a titanium oxide during calcination may modify the tint or color of the oxide.

7 Other common properties which distinguish the metals useful in our invention are that their oxides are colored and that they form black sulfldes.

Commercially available for our purpose are mainly compounds of vanadium/chromium, iron, cobalt, nickel, manganese and copper which have atomic weights between about 50 and 64 inclusive.

Among the various metals of the above types which we can use, we found chromium and-vanadium particularly useful for the main reason that their power of imparting color to the 30 titanium pigment is exceedingly strong, only very small amounts of chromium and vanadium being I required ,to produce a distinct color in the pigment. .The type of compound to be used with each m w- 8' rather immaterial. We can use water insoluble 1 compounds such as the oxide or hydroxlde of the metal to be incorporated with the 'uncalcined titanium oxide, as wellas water solu-' =ble compounds such as metalsalts: chloride, sula fate, nitrate, oxalate, jor suchsalts in which the metal is in the anion, such as chromates and vanadates, provided such soluble'compounds de-x compose or are otherwise transformed on'calcination into water isoiuble compounds.

The "products of our invention comprise par- I tlcles of titanium dioxide containing a. small amount of a heavy metal compound physically or'chemically associated with the titanium ox-'- .ideQsa ld particles having a distinctivecolor or tint other than white. It will be understood that the expressions, color, tint, colored, tinted, etc. as used herein exclude white but include various shades of gray. By the expressioncol- 'ored compound of a heavy metal contained in a-tinted titanium pigment of our invention as No. 2,002,137, dated November 24, 1938, No. 1,284, January 11, 1935. Application November 15, 1988, Serial -No.

used herein we intend to designate only such compounds which represent the reaction products of a heavy metal compoundwhen calcined in the presence of a titanium compound.

The 'tinted titanium oxide of our invention produces, when mixed with paint vehicles with or without extenders, valuable tinted paints or enamels which are particularly characterized .by

non-chalking and non-fading characteristics.

Impure titanium oxide pigments have been produced in the infancy of this art but they were of the nature of discolored templated in the present invention, the amount of impurities contained in the products'was less than the amounts of colored oxides we, intentionally associate with the T101. Dark colored pigments containing minor amounts of titanium oxides have also been produced-from sludges obtained in the manufacture of white titanium products; in both above instances, however, it was impossible to control and duplicate the shade ortint or such pigments and what was obtained was entirely outside the range of tinted pigments contemplated in the present invention.

While perfectly white titanium oxide pigments can now be produced which are entirely satisfactory for the paint industries,- there is a' white pigments rather than pigments of distinctive tints as con- Tick pigments, and are in chemical properties and constitution distinguished from tits-hates which are salts' of titanic acid with bases. Ilmenite, the usual, raw material for the obtention of titanium oxide is generally considered to be an iron tltanate. 'Such known titanates are white as well as of distinctive colors depending upon the metal base combined with the titanic 'acid. Alkali, alkaline earth metal, magnesium, antimony titanates are, for instance, white,

whereas titanates of most heavy metals are deeply colored. up to black.

Such titanates are also in pigmenting propers ties clearly distinguished from straight T102 1 8- ments, and from our novel pigments which are prepondcrately composed of straight TiOa.

The small amounts-of colored compounds cantained in our novel pigments do not adversely affeet the properties of the straight 110: which form the basis of the pigments.

The tints in which titanium pigments have be-' come available through 'our invention are best identified in reference to the Munsell color scale. described in an understandable form by F. G. Cooper in Munsell Manual 01 Color, published 1929 by mmsell Color Co.. Inc., in Baltimore, Md., and isbasedon the Atlas of the Munsell Color System and the Munsell Book of Color. unabridged edition for which has been published in 1929.

According to this system'every color, shade or tint can be expressed by 3 "dimensions" namely hue; value and chroma. Hue isthename oithe color, namely red, yellow, green. blue and purple -.and listed by initialsyR 101' .red, Y for yellow, etc. Intermediate hues are designated as YR: yellow red, etc. with(sec ondary intermediate hues as YRY: yellow-red-yellow, the intermediate hues being divided into 10 graduations. '9 YR. represents, for instance, a shade of reddish yellow close to the yellow-red-yellow. Value is the amountoilightinacolorandchromaisthe degree of strength in a color. The values in this system are graduated from 0, which represents perfect black; to 10 which stands for perfect white. The chromas are likewise indicated by. numerals with the low numerals l, 2, etc. indicating chromas close to the neutral grays and figures up to 8 and more indicate increasing chromas or strengths. A given color is then represented by'a set 01 figures H V/C: first the hue initial, then comes the figure for value followed byadiagonallineandthenthefigureior chroma. R 6/3 is, for instance, ared at the sixth level of value and three steps out in chroma; it is red midway between white and black. The

V color commonly known as rose" is a grayish red,

' representingthe neutral grays, the colors of very high chromas extending outside the sphere. The

sphere is divided in horizontal zones from i to 9, each tor a diflerent value, the distances at right angle from the vertical axis represent the chromas and on the equator are plotted the hues.

The field of colors embraced in our invention forms in this system a central cylindrical portion spreading out into a part oi a spherical wedge.

Expressed in numerical figures according to the Munsell system, this field covers the grays andallhuesofvaluesfi'om4to8andchromas from 0 to 1; on chromas above 1 it embraces the huestromgreenthroughyellowtoredatvalues o! 4 to 8 at the chroma oil, up to values of 5to9forachromaoi3 andvalueso1'5to9 for chromas of 3 to 8.

Fig. 1 represents the imaginary solid circumscribing the colors represented by the above fig.-. ures for the Munsell formula H V/C. This figure is a perspective 45 view 01 this solid which' clearly shows the cylindrical portion surrounding the grays, the wedgelike zone oi the colors green through yellow to red with its inner zone of low cined white TiOs in which the values remain constant with incrsasingchromas. Thisfigurealsosbowsindotted lines the outline of the imaginary Mu'nseli sphere with its equator on which the location 01' the prin- -cipalhuesisindicated Thisfigureismainlyim.

very dark and very light shades of all colors, it

also excludes all colors which can he considered to contain dominant amounts 01' blue and purple.

The determination of the position 0! a given pigment in the Munsell color system is done by comparingalinseedoilniboutoithepigment with the colors reproduced in the Mimsell Color Atlas, whereby the values for H. Yand C in the formula EV/C are directly obtained. The values oiVandCcanthenbe plotted onadiagramofco-ordinates which can be established for hue. l'igzissuchadiagramotco-ordinateashowing the limits of the field oi colors which can be obtained according to our invention. This diagram is identical for all colors between green through yellowtored. Thesolid 0! Fig. 1 is obtained by rotation of the plane area 01 Pig. 2 through 144". We have plotted on this diagram the colors of several pigments obtained according to the examples given below. We have also shown thereon the position or the color :"rose" mentioned above. 1 I

There is within this field a second preferred field of colors which can most easily be produced by-our novel process which colors. are. the ones most desirableior commercial application 01 our invention. This preferred field covers them.

bufis, tans. yellow browns, etc. and canbe described inthe Munsell Color Scale as embracing thegraysatvalues oi'fito'Lchromasoi'Otol and the hues oi yellow-green-yellow through yellow to yellow-red at values 01.5.25 to 7.25 for chromasot1increasingtovaluesoi55to9at chromas upto4,increasingtovalues of6 to9 up to chromas of'a. In the field 0! colors of .chromas above the jgrays, namely tor chromas above 1 the pigments are most conveniently produced by the use of chromium compounds, where asthegraylareproducedbytheadditionolvanadium compoimds.

The distinguishing characteristic of our novel tinted pigments is their remarkableresistance to fading and chalking on outside exposure.

Another valuable property oi our novel pigment is that they do not separate'on standing or in paint compositions into a white and a colored component, such as is frequently the case with mixtures black, etc.

Coating compositions pigments have the, serious drawback that they iade on outside exposure. Thisfading isnot due to-Iight sensitiveness of the colored admixtures contained in the paints. Thefollowing explanation has been advanced for this-fading. The fihn with iron oxide or carbonmade from such 'oLoil or other vehiclawhich pig- 1 I power of the I 31,? ment particles proper in the coat gradually oxi- The tints desired and useful for the preparadises and is' removed on outside exposure leaving on the surface a layer pigment'particles surrounded by air. This phenomenon is known ..'as chalking of the paint. Air 'hasamuch lower index of refraction than the paint vehicle and according to ite pigment particles will in such -a layer in which the particles are surrounded by air considerably increase over that of colored particles contained in the layer and the surface of the paint will appear nearly white; this is known .as fading of tinted paints on exposure.

the chalking of the paint is suppressed.

This phenomenon of fading is greatly decreased or avoided by either or both of the following changes: if thepaintcontains pigment particles which are all of substantially the same tint or if The pigments of our invention show both fea ,tures; their chalking. is minimized and if they chalk on excessive exposure, the chalk is colored.

pigment in controlled amounts; the resulting pigposed of particles which, when observed under ments and paints retain satisfactory ncn-chalking and non-fading characteristics.

The tinted products of our invention are comthe microscope, show substantially the same tint l knowniaws of optics the hiding' of the coloring metal compound which will be present in the finished pigment and within this range the depth. of the tint increases to a certain extent with increasing amounts. with less than 0.3 mol per cent the products are of the nature of discolored white pigments and are of no utility whatsoever; with amounts above 7 mol per cent the colors are too dark and are I tures tend to increase the depth of the tint (deor color; the product appears homogeneous and is easily distinguished from a mechanical mixture of calcined TiOr and av colored pigment.-

' The uniformity oi the pigment particles as shown under the microscope is attributed to'the fact that the titanium is calcined in intimate admixture with the coloring element. To distinguish such co-calcined pigments from mere mechanical mixtures and from mere adsorption compounds we call our uniform pigments coalesced."

- In the following table a number oitinted titanium oxide pigments .are listed which were made according to our invention by calcining for.

crease the value in the Munsell system).

It is in many instances beneficial to eflect calcination in the presence of water vapor and sometimes in an oxidizing atmosphere. Water vapor or steam being desired in the presence of the pigment during calcination, it is unnecessary to dry the crude pi ment; the wet cake can be' charged directly into the calcination furnace. The oxidizing. atmowhere, when desired, is'conveni ently produced by passing a stream of air over the product during calcination;

In the following we are giving specific examplgs oi how we prepared tinted titanium oxide pigments according to our invention.

Example I.-l00cc. of 77.64 g/l KaCO: solution and 50 cc. of 122.40 g/l VsOs (Tech.)-dispound obtained by hydrolysis of a titanium sulfate solution. The colors given are those of linsolved in HCl were separately added 'to 3 l. of 300 g/1.raw T10: slurry. This corresponded to theaddition to the T10: of 1.0 mol percent-potassium and 0.5 mol per cent vanadium, or'the addition of 0.86 per cent K200: and 0.57 percent V205 by weight. The treated slurry was stirred and set aside 16 hours in.order to allow the'salts to become intimatelymixcd with the Tlcrzparticles.. The slurry was then filtered and'1200 cc. of filtrate removed. The resultant wet' 'cake was placed in a rotating ,calciner at 050 C.,

heated up to 950 C. in one hour and held at' that, temperature for 30 minutes while a stream of air plus steam was passed over the. charge. The resultant product was ground to form a pigment of desired texture. Products thus piepared were of light gray color of a rating Nil/0. By varying the calcinatio'n conditions we have.

for instance, obtained with the same amoimt oi 5 B. 7.1/0.03 and 5 Y 6.6/0.01 which arelike wlse'classed as light grays.

Increasing the amount of vanadium to 150 cc. instead of the cc..used above and calcining- .at 950 C. has given-us a pigment of medium Color in Munsell Bait added Color of rub-out system Chromic nltrate- Y Cr (N01): .9 H10 Light gray tan. Y 7.2/4 Chrome uni-'- v Co(N 01):.0 Hi0 Gray ivory. Y 8.2/2 CIHIIG nl u (NO|),.3 Hi0; Light green with 10 Y 8.5/2

very slight yellow cast. Icrrie sullen-- P "M80059 H:0;.... Cream 3 Y 8/2 KMnO. Pink fawn. YR 8.2/2 Nickel nitrate- Ni(NQ'),.0 B10 Ivory with slight a Y 9/4 green cast. I

a 0K0. P.) dimolved in Gray. Y 6.5/1.5

VpOdTeeh.) dluolved in .do Y 6.8/1,

"The exact s... obtained with the individual coloring compounds depend upon various factors.

inthepreparationofthetintedpigment.

gray color with a rating or N 5.5/0.

lt will be understood that similar pi'gments will be, obtained by the incorporation oi other compounds into the uncalcined titanium oxide or varying the amounts of compounds added and changing the calcination conditions.

Elcdmple Ilacc. of- 77.84 g/l KzCOs so- 00 vanadium pigments of the following ratings: '1'

or compound of a heavy metal and then calcine anew whereby the heavy metal compound associates itself with the titanium oxide and produces pigments entirely similar to those obtained by the above described procedures.

The following have been found to be limits for metal compound content of finished T101, the figures are given as parts of metal in lparts by weight of T102.

0.01 to 2.5 parts of Cr per 100 parts TiO: can

easily be incorporated into T102 and the resulting pigment will range from. gray to yellow to red, the best commercial products within our preferred field of colors being produced with amounts from 0.03 to 0.75. A light bufl. was. for instance, obtained with 0.064,.a medium buff with 0.225 and a dark buff with 0.73 part Cr per 100 parts T102.

In the case of vanadium, tinted pigments were obtained within the range of 0.05 to 5.0 parts V per 100 parts T: and most desirable productswith 0.2 to 2.0; 0.38 having, for instance, produced a light gray, 1.15 a medium gray and 1.75

-when the pigments contained the following amounts:

Iron 0.7 to 5.0 Cobalt 0.7 to 5.0 Copper 0.3 to 5.0 Manganese 0.3 to 5.0 Nickel 0.3 to 5.0

parts by weight of the metal per 100 parts of T102.

We have in the foregoing particularly described, explained and illustrated our invention in connection with tinted products in which straight T102 forms thewhite,base pigment. Our invention is, however, also applicable to complex pigments in which the titanium oxide is coalesced with white extenders. such as barium or calcium sulfate. g i For the production of tinted, coalesced titanium pigments we proceed in a manner entirely similar to that of producing tinted pigments from straight titanium oxide. We again add a heat decomposable compound of a heavy metal which, on calcinationin the presence of TiOz, forms a. colored compound, to the medium in which we produce the coalesced uncalcined pigment; for

instance, we add a vanadium or chromium compound, such as a salt, oxide, hydroxid, etc., to a titanium sulfate solution to which we also add calcium or barium chloride and heat the-solution to eflect hydrolysis of the titanium salt. We then separate the precipitate which-retains the vanadium, chromium, etc., compound and calcine it under the desired conditions. The amounts of heavy metal to be used in this case are substane tially the same per unit weight of white pigmentsulfate.

, When our novel products are mixed with a vehiclev to.,form a coating composition such as a paint. lacquen'enamel, etc., we have found that such a composition is exceedingly resistant to sue? main; and that it retains substantially its omnnal tint even on prolonged exposure.

It is desirable in the formulation of paints, particularly. for outside exposure, to add to the pigments proper substances of little covering power, so-called extenders, such as blanc iixe,

fibrous talc, silica, ground barytes, whiting, etc.,

for their bulking value and thickening 'eflect on position.

Besides the above white extenders we can also add leaded zinc oxide to. our tinted titanium oxide pigments 'to increase the durability of the paint films. Similarly, as is the case with the white extenders, the resistance to fading and chalking is maintained if such leaded zinc oxide is added to the tinted TiO2 paints which may therefore contain only either one or both these.

types oi added components without losing their desirable non-chalking and non-fading characteristics.

We have also found that the non-fading characteristics of the coating compositions made from our tinted TiO: pigments are maintained if we mix tinted T102 pigments of dilierent composition and color, for instance, a gray with a but! colored T101 to produce a drab, or we can associate uncalcined titanium oxygen compounds with more than one metal compound which combination on calcination produces a tinted pigment.

and we are thereby enabled to extend obtainable.- I

As a further improvement we have found that the non-fading characteristics of coating .compositions made with our novel tinted titanium oxide pigmentsis also preserved if we use only such extenders which have a tint or color approaching that .of the pigment itself. Extenders of this type are available from naturally occurring, impure, colored barytes, ochres, clays. fibrous talc, talc, also phosphate plasters, etc. When finely ground, such substances are well adapted to be used as extenders with our tinted pigments. The choice of the particular extender for use with a given tinted titanium oxide pigment is made by blending the two in the dry state. The blend is then' mixed with oil and the color in oil compared with the color in the dry state. A minimum difference between the two indicates that the fading, due to chalking, will be at a minimum. Gray, buff and off colored barytes give, due to their good durability, good chalk resistance and a range of available tints particularly adapted to serve as colored extenders for our tinted pigments.

The non-fading and chalking resistance imparted to paints, enamels or other coating compositions by our tinted titanium oxide pigments when they also contain other white or colored components is of the utmost practical importance as in few instances the paints, etc., will be made from the tinted titanium pigment and the paint vehicle only.

The formulation of coating compositions for which our novel pigments are adapted calls commonly for the addition of various solid ingredithe tints rated upon before, our. pigments arecompatible with white extenders, colored extenders or other solid ingredients such as zinc oxide, leaded ainc oxide, lead compounds and such components can be added singly or any number of them can be incorporated into the paints, etc., without detrimentally affecting the basic properties to the tions by the tinted titanium oxide.

On the contrary the various ingredients'co'operate to fully develop such properties as consistency, resistance to weathering, non-livering or the paints which are essential to the practical useiulness of the paints, etc.

as a convenience to the paint m'akers our novel tinted pigments are optionally blended in either the.wet or dry state with the particular:

extenders-and other solid ingredients desired'in the coating, composition; and the complete mixture of the solid ingredients is then marketed.

Thisinsuresthepaintmakerofauniformblend and avoids the-necessity and cost cf separately selecting and the materials for each In followingwe are giving a number of coating compositions of novel pigments. 9

1. Oil type lum The following illustrate various pigment-extendercombinations:

g v Parts by weight- (A) Tinted Tioepigment 35 Blanc iixe 10,5.

36% leadedainc oxide-.. 45 Basic carbonate white lead. CBlTlnted Ti0 a-. 00 Blane 'flxe..... 180 a 35% leaded flilc oxide-- 40 (C) 'lintede'lloe muhns fl-Blanc iixe..'..- '15 -.-Basic carbonate white lead Zinc oxide .20 CD) Tinted TlOs. p. 25 36% leaded zinc oxide 50 Fibrous talc plus silica. 2b

m fine in formula 1: insteadof the serou talc plus silica.

(l'llarytesin formulasA', a, c and a "insteadof meme. Fibrous talc informulasA, a, 5. and l insteadofblanc axe.

were-madein each case with 92% with standard mineral thinner paint having excellent ex tenor-durability is illustrated by the followin -mamm on formula was by addltion'of zinc oxide -for instance as fol- Iowatheriartsbeingbywight:

. Tinted m pigment--. 22.5 Zinc oxide 7.5 Heat bodied limo oil. 43.0 Lead ese drier 1.3

spdrits 27.7

varioustypes using our sired.

acid oil; 8% kettle bodied oil at a-28.5% znlsllintvolume .anda-drier. A long out?! of For an excellent metal protective paint the following'composition was prepared.-the parts beins'br w a i "Parts Tinted Tl2 Y Y 15.0 35% leaded zinc oxide"... 30.0 Magnesium silicate extenders 25.0 Linseed 011 37.2 head manganese drier 2.8

when the paints madefrom tinted T10: are intended for metal protective purposes. we prefer in general to incorporate into their formulation a considerable amount o'f-a basic pigment such as the leaded zinc oxide shown in theabove formula, whereby satisfactory rust resistance is obtained.

Numerous variations in the. formulation of such paints can be effected.

They can. be made for interior'iinishes where our novel tinted TiOa' pigments are characteriaed by freedom fromflooding, i. e., separation of pigments oi diiferent color. value, which is a serious drawback in such type of paints when made up from a white and a colored pigment.

Among such paints-we might further mention fiat paints of low binder content in which the pigment binder ratio is up to 1.0:0.5'and the chief vehicle is a bodied oil. such as heat in which the pigment-binder ratio ranges for instance between 1:0.5 and 1:03.

J In egg-shell finishes we still increase the amount of binder to a ratio of about 1 pigment:l.2 binder.

mgloss finishes 'within the above as... we

j'adda smallamount ofgloss oil (from 2 to5%).

The total pigment in our novel paints can range from 55% (by weight) down depending on hid-- ing power and other properties desired. At the higher'pigment contents, properly chosen extenders could be used in combination with the tinted T103, unless excemve hiding power is de- Driers useful in meee paints are cobaltdriers for a quick top set up in combination with a lead manganese drier for under dry and hardening.

The thinners in our paints canbe any desired combination of mineral spirits, turps, kerosene, etc. to obtaindesired brushing. leveling of brush marks, lap time, gloss, etc.

Various drying oils can be incorporated in our novel paints in addition or substitution of linseed oil vehicles, such as'chinawoodoil, soya 28831-011, etc. with varying .percentages'of gum The paints were made in various shades of grays and bulls and compared with paints made from a similar formulation in which the tinted titanium oxide was replaced by thesame amount of white titanium oxide and any amount of carbon black, iron oxide. etc. mixed into the paint to give it the same shade. In every instance the paints made with white T10: with leaded zinc oxide and extender and shaded by mechanical mixing with a colored pigment showed considerable chalking and fading on outside ex- (5 s ear whereas the paints'made from tinted Tiosstoodupperfectlyunderthesameexpon. snamezi containing a resin Quick drying enamels were made with the foilowing pigment mixtures:

. Part: Part:

TintedTi 1s 2s Tinted Ti 65.5

- In each instance enamels were prepared with tinted Ti| pigments of different shades and con .taining different heavy metal compounds asso-' ciated with the TiOr.

For each composition a similar enamel was pre- I pared in which the tinted T: was replaced by a mechanical mixture of white T10: and a colored pigment, such as carbon black, iron oxide. etc., of equivalent shade and both types submitted to outside exposure tests.

Here, again. it was found that the enamels made from tinted'TlOs showed hardly any fading or chalking whereas the paints madefrom mixed pigments chalked badly and faded in relatively short time. I

An orthodox enamel type of product is illustrated in the following example:

- Per cent Tinted 1102---.- f. 25.0 50 gal. ester gumyarnish 60.0 Mineral spirits 15.0

The ester gum varnish used in this composition is of the type commonin thisart and carries about 50% mineral spirits as a solvent.

The usual resins used in thepreparation of enamels can be used for the preparation of coat.

ing compositions based on our novel pigments,

enamels of'excellent characteristics, particularly non-chalking have been prepared with our tinted titanium pigments with natural resins and synthetic resins, such as glycerol-'phthalic, anhydrid resins, phenol-formaldehyde resins, etc.

As an example of such coating composition we might mention the following intended as a floor and deck paint: I

- J Per cent Tinted TiO- 22.5 silica 22.5

Glycerol-phthalic anhydrid resin dissolved in 50% mineral spirits 53.8

Drier. 1.2

Enamels containing phenol oi-mnl dehyiie res-v ins are sometimes distinguished by easy chalking and our novel tinted TiO: pigments are therefore particularly adapted for this type of coatingcompositions as the properties of our pigments allow oftheproductionof enamelsproducing aselfcleaning. fade-resistant finish. The following-is 1 a formulation of such a non fading chalk resist I Percent Tinted T10: 26.5 Phenol-formaldehyde resin ntaining China-wood oil 60.2 Mineral spirits '..v.--.. 4.3 Drier 3.0

flLcootiagcompositionsoontoiningan resin 1 Alkyd resins are oil modified condensation products. glycerol and phthalic anhydrld'as disclosed in-U. 8. Patent cfOct. 25. illttolattsnoneliewemalkyd thesealkydresinsenamels of great resistanceto chalking A fewexamples of such composition enamels are given below:

we folmd that our novel tinted titanium oxide pigments are particularly adapted to form with Per cent (a) Tinted 'IlOs; A Alkyd resin 29.4 Solvent naphtha 5.8

Mineral spirits 18.0 Lead manganese drier 2.4

(b) In this formula part of the titanium pig -ment of strong-hiding power is replaced by barytes, the parts being by weight:

Parts Tinted TiO: 1 2.2 Barytes- 36.6 Alkyd resin 6 32.6 Solvent naphtha 5.6 Mineral spirits 20.0 Lead manganese drier 3.0

(c) This example illustrates the use of antimony oxide with tinted titanium pigments. It is shown in U. 8. Patent 1,885,025 of Oct. 25, 1932,

to Patterson that antimony oxide improves the gloss of various enamels and we have found that (a) This exemplifies a: "short 011 type or enamel:

' Per cent Tinted T101 20.9 Alkyd resin 26.2 Mineral spirits- 35.0 Solvent naphtha 16.7 Cobalt drier IV. Tinted T10: in puma-vim lacquers Our novel tinted'titanium. oxide pigments, are also well adapted for 'pigmenting pyroxylin lacquers and plastics.

The following is an example of such a coating composition:

' Parts Low viscosity pyroxyiin 1-1.0

Dibutyl phthalate I Castoroil 3.5 Tinted T101 9.0 Damar gum 4.5

Theremaining 80 parts which go tomake up the lacquer are composed of the ordinary solvents used in these types of coating compositions. Such are, for instance, ethyl acetate. butyl acetate. ethyl alcohol, toluol, etc. which are usedin proportions well known in this art.

After a representative outdoor exposure of articles painted with the above pyronlin enamel it was found that the enamel films produced from this composition showed only very little chalking. Thecolorofthischaikwasaisosimilartothe color ofthefllmsothat chalkingwasevenstilllsssnoticeable.

' Films from straight T10: pigments blended with a colored pigment exposed under the same conditions are in direct contrast to the results above. The films from straight T10: showed a definite chalking which was white and, therefore, very noticeable in'contrast with the normal color of the original film.

'Ihe pyroxylin'enamel finishes from tinted T102 are'readily polished to a high luster. A similar polishing treatment applied to enamels from straight 'liO: blended with a colored pigment does not afford luster of the order of that produced on finishes obtained withtinted T102.

A very large number of coating compositions embodying our novel tinted titanium pigments have been exemplified above and it will be understood that our invention is not limited to these particular formulations. As exemplified in more detail under the oil type paints wide variations [n.the pigment content of the coating compositlons is permissible and this applies to the resin type of coating compositions as well as to pyroxylin or other enamels and plastics containing cellulose nitrate, cellulose acetate, regenerated cellulose or other cellulose derivatives.

Similarly, other solvents, resins, driers and other components useful in coating compositions can be used jointly with our novel pigments in such compositions. v

The novel non-chalking, non-fading and hemogeneity characteristics of our novel tinted T102 pigments make them very valuable for numerous other uses besides coating compositions. We might mentioned the following as typical, it being understood that these uses do not exhaust the arts in which our novel pigments can find useful applications: compounding rubber, come pounding linoleum, nitrocellulose plastics, cellulose acetate plastics, plastics derived from othercellulosc compounds, delustering artificial silk threads, pigmentlng, casein and lactic acid plastics, incorporation into paper pulp pigmenting waxed papers, opaciflers for vitrified enamels and glasses, pigmenting insoluble phenol-formaldehyde resins, pigmenting glycerol-phthalic anhydrid resins, pigmenting resins derived -from urea, etc.

We claim as our invention:

1. The process of making a tinted titanium oxide pigment which comprises incorporating into a compound selected from the group consisting of titanium dioxide and hydrated titanium dioxide a nickel compound and calcining said mixture at a temperature of at least 800 C., said nickel compound being present in said mixture in an amount corresponding to'from .3 to 5 parts by weight of nickel per '100 pa'rtsof T102.

2. The process of making a tinted titanium oxide pigment which comprises incorporating into a compound selected from the group consisting of titanium dioxide and hydrated titanium dioxide a vanadium compound and calcining at a temperature of at least 800 C. said mixture, said vanadium compound being present in said mixture in an amount corresponding to from 0.05 to 5.0 parts by weight of V for parts of T109. 5. The process of making a. tinted titanium oxide pigment which, comprises incorporating into a compound selected from the group cons'isting of titanium dioxide and hydrated titanium dioxide a' chromium compound and calcining. at a temperature of at least 800 C. said mixture, said chromium compound being present insaidmixture in an amount corresponding to from 0.03 to 0.7.5 part by weight of Cr per' 100 parts of dioxide.

4. A tinted pigment comprising as its main opacifying titanium compound titanium dioxide coalesced with a colored vanadium compound, said vanadium compound being present in an amount corresponding to from 0.05 to 5.0 parts by weight of vanadium per 100 parts of said pigment.-

5. A tinted pigment comprising as its main coalesced with a colored nickel compound, said nickel compound being present in an amount corresponding to from .3 to 5 parts by weight of nickel per 100 parts of said pigment.

6. A tinted pigment comprising as its main lopacifying titanium compound particles of titaniumdioxide coalesced with a colored vanadium compound, said vanadium compound being present in an amount corresponding to from 0.05 to 5.0 parts by weight of vanadium per 100 parts oi.

. opacifying titanium compound titanium dioxide coalesced'with a colored chromium compound, said chromiumcompound being present'in an amount corresponding to 0.01 to 2.5 parts by weight of chromium-per 100 parts of said pigment.

g 9. A tinted pigment comprising as its opa'cii'ying titanium compound particles of titanium dioxide coalesced with a colored chromium compound, said chromium compound beopacii'ying titanium compound titanium dioxide ing present in an amount corresponding to 0.01

to 2.5 parts by weight of chromium per-100 parts of titanium-dioxide.

10. A tinted pigment comprising as its main opacifying titanium compound titanium dioxide coalesced with a colored chromium compound, said chromium compound being present in an amount corresponding to 0.03 to 0.75 part by weight of chromium per 100 parts of titanium 11. A tinted pigment comprising as its main opacifying titanium compound titanium dioxide coalesced with a minor amount of a colored chromium compound, said titanium compound having a color, or tint, expressed in the Mumsell color system within the following limits: values of 5 to! for chromasoi 0 to l, at the hues of yellow-green-yellow through yellow to yellow-- red values of 5.25 to 7.25 for chromas of 1. increasing to values of 5.5 to 9 at chromas of 1 to 4 and increasing to values of 6 to 9 at chromas of 4 to 8. 12. 'As a new product titanium .dioxide coalesced with a minor amount of a colored chronadium compound, said titanium compound having a color, or tint, expressed in the Munsell color 14, As a new product titanium dioxide 00-.

alesced with a minor amount or 'a colored vanadium compound, said product having a color. or tint, expressed in the'Munsell color system, of

BatachromaoiOto 1.

15. The process of making a tinted titanium dioxide pigment having a color or tint expressed yellow to in the Munsellcolor system within the ranges: values from 4 to 8 and chromas from c, to. 1-; on chromas above 1, the hues from green through yellow to red at values of 4 to 8iat the chroma of 1, up to values oi 5 to 9 for a chroma of 3,

and values of 5 to 9-ior chromas 01 3 to 8, which comprises calcining at ,a temperature of at least 800 C. an intimate mixture oi a compound seadded, predetermined minor amount of a compound of a metal 0! the group consisting of chromium, vanadium,- nickel and copper lected from the group consisting of titanium dioxide and hydrated titanium dioxide with an.

16. The process oi 'making a tinted titaniumdioxide pigment having a color ortint expressed in the Munsell color system within the ranges:

values'irom 4 to 8 and chromas from 0 to 1;

on chromas above l, the hues from green through red at values or 4 to 8 at the chroma of 1, up to values of 5 to 9 ior-a chroma oi 8 and .values of 5m 9 ior chromas 0!. 8 to 8, which comprises calcining at a temperature of at least 800 C. an intimate mixture of a compound selected.

iron: the consisting oi titanium dioxide 9. hummus-a sess. minoramountotavansdium and hydrated predetermined compound.

1'1. The process of making a tinted titanium dioxide pigment having a color or tint in the Munsell color system within the ranges:

values from 4 to'8 and chromas from 0 to 1;

on chromas above 1, the hues from green through yellowtoredatvalues'oi4to8atthechroma of 1', up to values 02-5 to 9 for a chroma oi 3,-and values of 5 m8 for chromas 0! 3 to 8, which comprises calcining at a temperature oi'at least 800 C. an intimate mixture of a compound selected from the group consisting oi titanium dioxideand hydrated titanium dioxide with an added, predetermined minor amount of a chromium compound.

18. The process of making a tinted titanium dioxide pigment having a color or tint expressed in the Munsell color system within the ranges; values from 4' to 8 and chromaa from 0 to l; on chromas above 1, the hues from green through yellow to'red at values of 4 to 8 at the chroma oi 1,'uptovaluesoi5to8iorachromaof8, and values of 5 to 9 for chromas o! 8 to 8, which comprises calcining at a temperature of 'at least 800' C. an intimate mixture of a compolmd selected from the group consisting of titanium dioxide and hydrated titanium. dioxide with an i added, predetermined minor amount of a nickel

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