Organoclay compositions containing two or more cations and one or more organic anions, their preparation and use in non-aqueous systems

A novel organophilic clay gellant comprising the reaction product of: PA1 (a) a smectite clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of natural clay without impurities; PA1 (b) a first organic cation in an amount of from about 75% to about 150% of the cation exchange capacity of the smectite clay; PA1 (c) a second organic cation provided by a polyalkoxylated quaternary ammonium salt; and PA1 (d) one or more organic anion(s) that is capable of reacting with said first and second organic cations, to form an organic cation-organic anion complex with said smectite clay. The organophilic clay gellant is used in a non-aqueous fluid system such as paints, inks, and coatings to provide improved theological properties.

BACKGROUND OF THE INVENTION 
1. Brief Description of the Field of the Invention 
The present invention relates to novel organophilic clays which are 
dispersible in non-aqueous fluids to provide rheological properties to 
such fluids. The invention also pertains to a process for preparing these 
organophilic clays using multiple cations such as quaternary ammonium 
compounds, and one or more organic anions. The invention includes 
non-aqueous fluid compositions including such organophilic clays as 
rheological additives. 
2. Description of the Prior Art 
It has long been known that organophilic clays can be used to thicken a 
variety of organic compositions. Such organophilic clays are prepared by 
the reaction of an organic cation with a clay in various methods known in 
the art. If the organic cation contains at least one alkyl group 
containing at least 8 to 10 carbon atoms, then such organoclays have the 
property of increasing viscosity in organic liquids and thus providing 
rheological properties to a wide variety of such liquids including paints, 
coatings, adhesives and similar products. 
It is also well known that such organoclays may function to thicken polar 
or non-polar solvents, depending on the substituents on the organic salt. 
J. W. Jordan, in "Proceedings of the 10th National Conference on Clays and 
Clay Minerals" (1963), discusses a wide range of applications of 
organoclays from high polarity liquids to low polarity liquids. 
The efficiency of organophilic clays in non-aqueous systems can be further 
improved by adding a low molecular weight polar organic material to the 
composition. Such polar organic materials have been called dispersants, 
dispersion aids, solvating agents and the like. See, for example, U.S. 
Pat. Nos. 2,677,661; 2,704,276; 2,833,720; 2,879,229; and 3,294,683. The 
most efficient polar materials for use as such have been found to be low 
molecular weight alcohols and ketones, particularly methanol and acetone. 
Furthermore, U.S. Pat. Nos. 3,977,894; 4,382,868; 4,464,274; and 4,664,820 
describe the preparation of preactivated organophilic clay gellants that 
are used to thicken organic compositions wherein the activators are 
admixed with the organophilic clay. 
More recently, organophilic clay gellants have been developed which are the 
reaction products of smectite-type clays having a cation exchange capacity 
with certain organic cations or organic cations and organic anion 
combinations. These gellants have the advantage of being effectively 
dispersible in particular organic compositions without the need for a 
dispersion aid under normal shear conditions. Illustrative patents which 
describe such improved organophilic clay gellants are U.S. Patent Nos. 
4,105,578; 4,208,218; 4,287,086; 4,391,637, 4,410,364; 4,412,018; 
4,434,075; 4,434,076; 4,450,095; and 4,517,112. 
One way to enhance the gelling and dispersing efficiency of an organophilic 
clay is to replace some of the hydrophobic side groups attached to the 
organic cation with hydroxyalkyl groups. In these groups, the hydroxyl 
group is attached to any carbon atom on an aliphatic radical, except for 
the carbon atom adjacent to the positively charged atom as disclosed in 
U.S. Pat. No. 4,434,076. 
To further impart improved gelling properties, the groups attached to the 
organic salt may be replaced by a mono- or polyhydroxylated group. 
Modified organophilic clays containing these compounds swell and gel in 
organic liquids without the need for polar dispersion additives. For 
example, European Patent Application 0,133,071 describes modified 
organophilic clays resulting from the combination of a smectite clay, a 
quaternary ammonium salt having a long hydrocarbon chain, and a mono- or 
polyhydroxylated nitrogeneous surfactant. The mono- and polyhydroxylated 
nitrogeneous organic surfactants used in the disclosed formulations are 
ethoxylated amines and alkoxylated quaternary ammonium salts having long 
hydrocarbon chains, such as (tallow alkyl)- or di(tallow alkyl)-(methyl or 
benzyl) ammonium salts. 
Further increases in the amount of alkoxylated groups, however, result in 
clay compositions that impart gelling properties to aqueous systems rather 
than to non-aqueous systems. For example, U.S. Pat. No. 4,677,158 
describes a reaction product of a smectite clay and a quaternary ammonium 
compound that is used as a thickener for aqueous suspensions, particularly 
water based latex paints and caulks. The disclosed quaternary ammonium 
compound is said to consist of a nitrogen atom bonded to separate carbon 
chains where one chain can be a methyl group or alkyl group containing 10 
to 20 carbon atoms, and the second chain is an alkyl group containing from 
10 to 22 carbon atoms or a polyoxyethylene chain, The third and fourth 
chains are polyoxyethylene chains such that the total number of ethylene 
oxide units is from 5 to 200 moles, 
The disadvantages of most existing organoclay compositions for non-aqueous 
systems are that (a) relatively large amounts of the organoclay 
compositions are needed to impart the required viscosity; (b) polar 
activators are required in many cases to enhance their gelling properties; 
and (c) the organoclays are limited to either polar or non-polar systems 
depending upon their organic content. 
SUMMARY OF THE INVENTION 
A new type of organophilic clay gellant has been discovered in which the 
synergistic action of two or more types of organic cations derived from 
organic salt compounds in addition to the presence of an organic anion 
provides improved gelling properties in organic solvents, the first 
organic cation employed in the formulations of the invention contains 
hydrophobic groups whereas the second organic cation contains hydrophilic 
groups, It has been unexpectedly discovered that the combination of these 
hydrophobic and hydrophilic organic salts and the organic anion provides 
an organophilic clay gellant which exhibits improved gelling properties in 
non-aqueous systems, 
The present invention provides an improved, more efficient organophilic 
clay gellant for gelling or thickening non-aqueous solvent-based 
compositions. 
Thus, according to one aspect of the invention, an organophilic clay 
gellant is provided which comprises the reaction product of: 
(a) a smectite-type clay having a cation exchange capacity of at least 75 
milliequivalents per 100 grams of clay; 
(b) a first organic cation in an amount of from about 75% to about 150% of 
the cation exchange capacity of the smectite-type clay; 
(c) a second organic cation provided by a polyalkoxylated quaternary 
ammonium salt from about 0.01% to 20% by weight of the total organic 
cation content; and 
(d) one or more organic anion(s) that is capable of reacting with the first 
and the second organic cations to form a complex. 
The present invention also contemplates a process for preparing an 
organophilic clay gellant which comprises: 
(a) preparing an aqueous slurry of a smectite-type clay having a cation 
exchange capacity of at least 75 milliequivalents per 100 grams of clay; 
(b) heating the slurry to a temperature between about 20.degree. C. and 
100.degree. C.; 
(c) adding to the slurry: 
(i) a first organic cation in an amount of from about 75% to about 150% of 
the cation exchange capacity of the smectite-type clay; 
(ii) a second organic cation provided by a polyalkoxylated quaternary 
ammonium salt from about 0.01% to 20% by weight of the total organic 
cation content; and 
(iii) one or more organic anion(s) that is capable of reacting with the 
first and/or second organic cations; 
(d) reacting the resulting mixture for a sufficient time to form an 
organophilic clay gellant; and 
(e) recovering the organophilic clay gellant. 
The first and second organic cations and the organic anion may be added to 
the clay slurry separately in any order or simultaneously. 
The invention also provides non-aqueous solvent compositions thickened with 
the above-indicated organophilic clay gellant. A third aspect of the 
invention therefore relates to a non-aqueous fluid system which comprises: 
(a) a non-aqueous composition; and 
(b) an organophilic clay gellant comprising the reaction product of: 
(i) a smectite-type clay having a cation exchange capacity of at least 75 
milliequivalents per 100 grams of clay; 
(ii) a first organic cation in an amount of from about 75% to about 150% of 
the cation exchange capacity of the smectite-type clay; 
(iii) a second organic cation provided by a polyalkoxylated quaternary 
ammonium salt from about 0.01% to 20% by weight of the total organic 
cation content; and 
(iv) one or more organic anions that is capable of reacting with the first 
and the second organic cations to form a complex. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
As stated above, one aspect of the present invention relates to an 
improved, more efficient organophilic clay gellant. The organophilic clay 
is prepared by reacting a smectite-type clay with a first hydrophobic 
organic cation, a second hydrophilic organic cation provided by a 
polyalkoxylated quaternary ammonium salt, and an organic anion. 
According to a first aspect of the invention, an organophilic clay gellant 
is provided which comprises the reaction product of: 
(a) a smectite-type clay having a cation exchange capacity of at least 75 
milliequivalents per 100 grams of clay; 
(b) a first organic cation in an amount of from about 75% to about 150% of 
the cation exchange capacity of the smectite-type clay; 
(c) a second organic cation provided by a polyalkoxylated quaternary 
ammonium salt from about 0.01% to 20% by weight of the total organic 
cation content; and 
(d) one or more organic anion(s) that is capable of reacting with the first 
and the second organic cations to form a complex. 
The clay which is used in the present invention is a smectite-type clay 
having a cationic exchange capacity of at least 75 milliequivalents per 
100 grams of clay as determined by the well-known ammonium acetate method. 
Smectite-type clays are well known in the art and are commercially 
available from a variety of sources. Prior to use in the formulations of 
the instant invention, the clays are preferably converted to the sodium 
form if they are not already in this form. This may be conveniently 
carried out by preparing an aqueous clay slurry and passing the slurry 
through a bed of cation exchange resin in the sodium form. Alternatively, 
the clay can be mixed with water and a soluble sodium compound, such as 
sodium carbonate, sodium hydroxide, etc., and the mixture sheared, such as 
with a pugmill or extruder. Conversion of the clay to the sodium form can 
be undertaken at any point before reaction with the reagents of the 
invention. 
Smectite-type clays prepared synthetically by either a pneumatolytic or, 
preferably, a hydrothermal synthesis process may also be used to prepare 
the novel organic clay complexes of the invention. 
Representative of smectite-type clays useful in accordance with the present 
invention are the following: 
Montmorillonite 
EQU [Al.sub.4-x Mg.sub.x)Si.sub.8 O.sub.20 (OH).sub.4-f F.sub.f ]xR.sup.+ 
where 0.55.ltoreq.x.ltoreq.1.10, f.ltoreq.4 and R is selected from the 
group consisting of Na, Li, NH.sub.4, and mixtures thereof; 
Bentonite 
EQU [Al.sub.4-x Mg.sub.x (Si.sub.8-y Al.sub.y)O.sub.20 (OH).sub.4-f F.sub.f 
](x+y)R.sup.+ 
where 0&lt;x&lt;1.10, 0&lt;y&lt;1.10, 0.55.ltoreq.(x+y)&lt;1.10, f&lt;4 and R is selected 
from the group consisting of Na, Li, NH.sub.4 and mixtures thereof; 
Beidellire 
EQU [Al.sub.4+y (Si.sub.8-x-y Al.sub.x+y)O.sub.20 (OH).sub.4-f F.sub.f 
]xR.sup.+ 
where 0.55.ltoreq.x.ltoreq.1.10, 0.ltoreq.y.ltoreq.0.44, f.ltoreq.4 and R 
is selected from the group consisting of Na, Li, NH.sub.4 and mixtures 
thereof; 
Hectorite 
EQU [Mg.sub.6-x Li.sub.x Si.sub.8 O.sub.20 (OH).sub.4-f F.sub.f ](x+y)xR.sup.+ 
where 0.57.ltoreq.x.ltoreq.1.15, f.ltoreq.4 and R is selected from the 
group consisting of Na, Li, NH.sub.4, and mixtures thereof; 
Saponite 
EQU [Mg.sub.6-y Al.sub.y Si.sub.8-x-y Al.sub.x+y O.sub.20 (OH).sub.4-f F.sub.f 
]xR.sup.+ 
where 0.58.ltoreq.x.ltoreq.1.18, 0.ltoreq.y.ltoreq.0.66, f.ltoreq.4 and R 
is selected from the group consisting of Na, Li, NH.sub.4, and mixtures 
thereof; and 
Stevensite 
EQU [Mg.sub.6-x Si.sub.8 O.sub.20 (OH).sub.4-f F.sub.f ]2xR.sup.+ 
where 0.28.ltoreq.x.ltoreq.0.57, f=4 and R is selected from the group 
consisting of Na, Li, NH.sub.4, and mixtures thereof. 
The preferred clays used in the present invention are bentonite and 
hectorite. In addition, it will be understood that the above listed 
smectite-type clays which have been subjected to the application of shear 
may also be used. 
To achieve shearing of the smectite-type clay, the clay is typically 
dispersed in water at a concentration of from about 0.5 to about 80% by 
weight. The slurry may optionally be first centrifuged to remove non-clay 
impurities which constitute about 10% to about 50% of the starting clay 
composition. Of course, if the clay has previously been treated, such as 
by the clay vendor, to remove the impurities, the treated clay can be 
formed into a slurry and subjected to shear conditions. Shear can be 
imparted to the smectite-type clay slurry by means of commercially 
available equipment that is known to impart high shear to the material. 
Illustrative of such equipment are a Manton-Gaul in Homogenizer available 
form Manton-Gaul in Company, a Tekmar SD-45 Homogenizer available from 
Tekmar Company, a Sharples Super Centrifuge available from Sharples 
Division of Pennwalt Corporation, an Oakes mill available from Oakes 
Machinery, a Waring Blendor available from Waring Products, a 
Microfluidizer available from Microfluidics Corporation, a division of 
Biotechnology Corporation, and similar devices which can impart high 
laminar and turbulent shear to the clay slurry. Exemplary conditions using 
a Manton-Gaul in homogenizer are a pressure in the range from about 500 to 
about 8,000 psi with one or more passes of the clay slurry through the 
homogenizer. Representative processes for shearing clay slurries are 
described in U.S. Patents No. 4,695,402 and 4,743,098, both of which are 
herein incorporated by reference. 
The smectite-type clays may be synthesized hydrothermally by forming an 
aqueous reaction mixture in the form of a slurry containing mixed hydrous 
oxides or hydroxides of the desired metals with or without, sodium (or 
alternate exchangeable cation or mixture thereof) fluoride in the 
proportions defined by the above formulas and the preselected values of x, 
y and f for the particular synthetic smectite desired. The slurry is then 
placed in an autoclave and heated under autogenous pressure to a 
temperature within the range of approximately 100.degree. to 325.degree. 
C., preferably 275.degree. to 300.degree. C., for a sufficient period of 
time to form the desired product. Formulation times of 3 to 48 hours are 
typical at 300.degree. C. depending upon the particular smectite-type clay 
being synthesized. The optimum time can be readily determined by pilot 
trials. 
Representative hydrothermal processes for preparing synthetic smectite 
clays are described in U.S. Pat. Nos. 3,252,757; 3,586,478; 3,666,407; 
3,671,190; 3,844,978; 3,844,979; 3,852,405 and 3,855,147, all of which are 
herein incorporated by reference. 
The cationic organic salts which are useful in this invention may be 
selected from a variety of materials that are capable of forming an 
organoclay by exchange of cations with the smectite-type clay. The organic 
cations which are reacted with the smectite-type clay must have a positive 
charge localized on a single atom or on a small group of atoms within the 
compound. For example, the cation may be provided by a compound selected 
from the group consisting of quaternary ammonium salts, phosphonium salts, 
sulfonium salts and mixtures thereof. The first organic cation is 
preferably a cation which contains at least one linear or branched, 
saturated or unsaturated alkyl groups having 12 to 22 carbon atoms. The 
remaining groups of the cation may be selected from the group consisting 
of (a) linear or branched aliphatic, alicyclic or aromatic groups having 1 
to 22 carbon atoms; (b) aralkyl groups which are benzyl and substituted 
benzyl moieties including fused ring moieties having linear or branches 1 
to 22 carbon atoms in the alkyl portion of the structure; (c) aryl groups 
such as phenyl and substituted phenyl including fused ring aromatic 
substituents; (d) beta, gamma-unsaturated groups having six or less carbon 
atoms or hydroxyalkyl groups having 2 to 6 carbon atoms; and (e) hydrogen. 
The long chain alkyl radicals may be derived from naturally occurring oils 
including various vegetable oils, such as corn oil, coconut oil, soybean 
oil, cottonseed oil, castor oil and the like, as well as various animal 
oils or fats such as tallow oil. The alkyl radicals may likewise be 
petrochemically derived from, for example, alpha olefins. 
Representative examples of useful branched, saturated radical s include 
12-methyl stearyl and 12-ethyl stearyl. Representative examples of useful 
branched, unsaturated radical s include 12-methyloleyl and 12-ethyloleyl. 
Representative examples of unbranched saturated radicals include lauryl; 
stearyl; tridecyl; myristyl (tetradecyl); pentadecyl; hexadecyl; 
hydrogenated tallow, docosanyl. Representative examples of unbranched, 
unsaturated and unsubstituted radicals include oleyl, linoleyl, linolenyl, 
soya and tallow. 
Additional examples of aralkyl, that is benzyl and substituted benzyl 
moieties, include those materials derived from, e.g., benzyl halides, 
benzhydryl halides, trityl halides, alpha-halo-alpha-phenylalkanes wherein 
the alkyl chain has from 1 to 22 carbon atoms, such as 
1-halo-1-phenylethane, 1-halo-1-phenypropane, and 
1-halo-1-phenyloctadecane; substituted benzyl moieties, such as those 
derived from ortho-, meta- para-chlorobenzyl halides, para-methoxy- benzyl 
halides, ortho-, meta- and para-nitrilobenzyl halides, and ortho-, meta- 
and para-alkylbenzyl halides wherein the alkyl chain contains from 1 to 22 
carbon atoms; and fused ring benzyl-type moieties, such as those derived 
from 2-halomethylnaphthalene, 9-halomethylanthracene and 
9-halomethylphenathrene, wherein the halo group comprises chloro, bromo, 
iodo, or any other such group which serves as a leaving group in the 
nucleophilic attack of the benzyl type moiety such that the nucleophile 
replaces the leaving group on the benzyl type moiety. 
Examples of aryl groups that are useful in the first organic cation include 
phenyl and substituted phenyl, N-alkyl and N,N-dialkyl anilines, wherein 
the alkyl groups contain between 1 and 22 carbon atoms; ortho-, meta- and 
para-nitrophenyl, ortho-, meta- and para-alkyl phenyl, wherein the alkyl 
group contains between 1 and 22 carbon atoms, 2-, 3-, and 4-halophenyl 
wherein the halo group is defined as chloro, bromo, or iodo, and 2-, 3-, 
and 4-carboxyphenyl and esters thereof, where the alcohol of the ester is 
derived from an alkyl alcohol, wherein the alkyl group contains between 1 
and 22 carbon atoms, aryl such as a phenol, or aralkyl such as benzyl 
alcohols; fused ring aryl moieties such as naphthalene, anthracene, and 
phenanthrene. 
The beta, gamma unsaturated alkyl group which may be included in the first 
organic cation component of the organophilic clay gellants of the 
invention may be selected from a wide range of materials well known in the 
art. These compounds may be cyclic or acyclic, unsubstituted or 
substituted with aliphatic radicals containing up to 3 carbon atoms such 
that the total number of aliphatic carbons on the beta, gamma unsaturated 
radical is 6 or less. The beta, gamma unsaturated alkyl radical may be 
substituted with an aromatic ring that likewise is conjugated with the 
unsaturation of the beta, gamma moiety or the beta, gamma radical may be 
substituted with both aliphatic radicals and aromatic rings. 
Representative examples of cyclic beta, gamma unsaturated alkyl groups 
include 2-cyclohexenyl and 2-cyclopentenyl. Representative examples of 
acyclic beta, gamma unsaturated alkyl groups containing 6 or less carbon 
atoms include propargyl; allyl(2-propenyl); crotyl(2-butenyl); 2-pentenyl; 
2-hexenyl; 3-methyl-2- butenyl; 3-methyl -2-pentenyl; 
2,3-dimethyl-2-butenyl; 1,1-dimethyl -2-propenyl; 1,2-dimethyl propenyl; 
2,4-pentadienyl; and 2,4-hexadienyl. Representative examples of 
acyclic-aromatic substituted compounds include cinnamyl(3-phenyl-2 
propenyl): 2-phenyl-2-propenyl; and 3-(4-methoxyphenyl)-2-propenyl. 
Representative examples of aromatic and aliphatic substituted materials 
include 3-phenyl-2-cyclohexenyl; 3-phenyl-2-cyclopentenyl; 
1,1-dimethyl-3-phenylpropenyl; 1,1,2-trimethyl -3-phenyl-2-propenyl; 
2,3-dimethyl-3-phenyl-2-propenyl; 3,3-dimethyl - 2-phenyl-2propenyl; and 
3-phenyl-2-butenyl. 
The hydroxyalkyl group may be selected from a hydroxyl substituted 
aliphatic radical wherein the hydroxyl is not substituted at the carbon 
atom adjacent to the positively charged atom; the group has from 2 to 6 
aliphatic carbon atoms. The alkyl group may be substituted with an 
aromatic ring independently from the 2 to 6 aliphatic carbons. 
Representative examples include 2-hydroxyethyl; 3-hydroxypropyl; 
4-hydroxypentyl; 6-hydroxyhexyl; 2-hydroxypropyl; 2-hydroxybutyl; 
2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxycyclohexyl; 3-hydroxycyclohexyl; 
4-hydroxycyclohexyl; 2-hydroxycyclopentyl; 3-hydroxycyclopentyl; 2-methyl 
-2-hydroxypropyl; 1,1,2-trimethyl-2-hydroxypropyl; 2-phenyl 
-2-hydroxyethyl; 3-methyl-2-hydroxybutyl; and 5-hydroxy-2pentenyl. 
The first organic cation can therefore be provided by a compound selected 
from the group consisting of at least one of the following formulae: 
##STR1## 
wherein X is nitrogen or phosphorous, Y is sulfur, R.sub.1 is a linear or 
branched, saturated or unsaturated alkyl group having 12 to 22 carbon 
atoms and R.sub.2, R.sub.3 and R.sub.4 are independently selected from the 
group consisting of (a) linear or branched alkyl groups having 1 to 22 
carbon atoms; (b) aralkyl groups which are benzyl and substituted benzyl 
moieties including fused ring moieties having linear chains or branches of 
1 to 22 carbon atoms in the alkyl portion of the structure; (c) aryl 
groups such as phenyl and substituted phenyl including fused ring aromatic 
substituents; (d) beta, gamma unsaturated groups having six or less carbon 
atoms or hydroxyalkyl groups having 2 to 6 carbon atoms; and (e) hydrogen. 
The anion which will normally accompany the organic cation is typically one 
that will not adversely affect the reaction product or the recovery of the 
same. Such anions include, for example, chloride, bromide, iodide, 
hydroxyl, nitrite and acetate, used in amounts sufficient to neutralize 
the organic cation. 
The preparation of the organic salt can be achieved by techniques 
well-known in the art. For example, when preparing a quaternary ammonium 
salt, one skilled in the art may prepare a dialkyl secondary amine, for 
example, by the hydrogenation of nitriles, see U.S. Pat. No. 2,355,356, 
and then form the methyl dialkyl tertiary amine by reductive alkylations 
using formaldehyde as a source of the methyl radical. According to 
procedures set forth in U.S. Pat. Nos. 3,136,819 and 2,775,617, a 
quaternary amine halide may then be formed by adding benzyl chloride or 
benzyl bromide to the tertiary amine. The disclosure of the above three 
patents are incorporated herein by reference. 
As is well known in the art, the reaction of the tertiary amine with benzyl 
chloride or benzyl bromide may be completed by adding a minor amount of 
methylene chloride to the reaction mixture so that a blend of products 
which are predominantly benzyl substituted is obtained. This blend may 
then be used without further separation of components to prepare the 
organophilic clay. Illustrative of the numerous patents which describe 
organic cationic salts, their manner of preparation and their use in the 
preparation of organophilic clays are commonly assigned U.S. Pat. Nos. 
2,966,506; 4,081,496; 4,105,578; 4,116,866; 4,208,218; 4,391,637; 
4,410,364; 4,412,018; 4,434,075; 4,434,076; 4,450,095 and 4,517,112; the 
contents of which are incorporated herein by reference. 
The instant invention is based on the unexpected discovery that the 
combination of hydrophobic and hydrophilic organic cations and one or more 
organic anion(s) provides a synergistic effect in which the organoclay 
complex containing the organic salts imparts improved viscosity to 
non-aqueous systems containing the organoclay complex. [he organophilic 
clay gellant provided by the invention imparts a higher viscosity to 
non-aqueous systems (at a given concentration) than is achieved by 
separately adding an organophilic clay gellant containing only the first 
organic cation and organic anion(s) of the invention and a second 
organophilic clay gellant containing only the second organic cation of the 
invention and mixtures thereof. 
The second organic cation utilized in the products of the invention 
comprises a quaternary ammonium salt which contains alkoxy moieties. The 
second organic cation contains at least one linear or branched alkoxylated 
group containing at least two carbon atoms and one oxygen atom. 
The compound is preferably a hydrophilic agent having the following general 
formula: 
##STR2## 
wherein R.sub.1, R.sub.2 are independently selected from the group 
consisting of (a) linear or branched alkyl groups having 1 to 22 carbon 
atoms; (b) aralkyl groups which are benzyl and substituted benzyl moieties 
including fused ring moieties having linear chains or branches of 1 to 22 
carbon atoms in the alkyl portion of the structure; (c) aryl groups such 
as phenyl and substituted phenyl including fused ring aromatic 
substituents; (d) beta, gamma unsaturated groups having six or less carbon 
atoms; and (e) hydroxyalkyl groups having 2 to 6 carbon atoms; x and y 
represent the number of repeating alkyl oxide groups and are integers and 
the total x+y may be 1 to 200. The alkyl oxide (AO, DO) groups may include 
independently, two to eight carbon atoms such as ethyl, propyl, butyl, 
pentyl, etc. 
The salt anion may be selected from the group consisting of halogen anions, 
preferably chloride and bromide, hydroxide, acetate, nitrite, and the like 
and mixtures thereof. These anions are required to have such charge that 
they neutralize the alkoxylated quaternary ammonium salt. 
Illustrative examples of suitable alkoxylated quaternary ammonium chloride 
compounds include those available under the tradename Ethoquad from Akzo 
Chemie America, namely, methyl bis(2-hydroxyethyl)cocoalkyl ammonium 
chloride, methyl bis(polyoxyethylene (15)) cocoalkyl quaternary ammonium 
chloride, methyl bis(2-hydroxyethyl) oleyl ammonium chloride, methyl 
bis(polyoxyethylene (15)) oleyl quaternary ammonium chloride, methyl 
bis(2-hydroxyethyl) octadecyl ammonium chloride, and methyl 
bis(polyoxyethylene (15)) octadecyl quaternary ammonium chloride. 
The organic anion(s) employed in the products of the invention may be 
selected from a wide range of materials that are capable of reacting with 
the first and second organic cations in order to form an organic 
cation/organic anion complex. The molecular weight of the organic anion is 
preferably 3,000 or less, and more preferably 1,000 or less, and contains 
at least one anionic moiety per molecule so as to permit the formation of 
the organic cation/organic anion complex. 
Preferred organic anions are derived from carboxylic acids, such as stearic 
acid, oleic acid, palmitic acid, succinic acid, tartaric acid, etc.; 
sulfonic acids; and alkyl sulfates, such as the lauryl half ester of 
sulfuric acid. 
The organic anion, which may include mixtures of organic anions, is reacted 
with the organic cations and smectite-type clay to form the desired 
organophilic clay gellant. The organic anion may be added to the reaction 
mixture in acid or salt form. Exemplary of the latter form are alkali 
metal salts, alkaline earth salts, ammonium and organic amines. 
Representative salts of the organic anion are those formed with hydrogen, 
lithium, sodium, potassium, magnesium, calcium, barium, ammonium and 
organic amines such as ethanolamine, diethanolamine, triethanolamine, 
methyldiethanolamine, butyldiethanolaine, diethylamine, dimethylamine, 
triethylamine, dibutylamine, and so forth, and mixtures thereof. The most 
preferred salt form is with sodium. 
The amount of organic anion reacted with the smectite-type clay and the 
organic cations must be sufficient to obtain a milliequivalent ratio of 
organic cations to organic anion in the range of from about 1.70:1.0 to 
about 50:1.0, preferably from about 3.0:1.0 to about 15:1.0. The most 
preferred ranges depend on the particular organic cations and organic 
anion utilized and the intended environment of use and can be determined 
by experimentation guided by the information set forth above. Illustrative 
patents which describe suitable organic anions that may be co-reacted with 
the organic cations and the smectite-type clay in order to form the 
organophilic clay include commonly assigned U.S. Pat. Nos. 4,412,018; 
4,434,075, and 4,517,112. 
The present invention also contemplates a process for preparing an 
organophilic clay gellant which comprises: 
(a) preparing an aqueous slurry of a smectite-type clay having a cation 
exchange capacity of at least 75 milliequivalents per 100 grams of clay; 
(b) heating said slurry to a temperature between about 20.degree. C. and 
100.degree. C.; 
(c) adding to said slurry: 
(i) a first organic cation in an amount of from about 75% to about 150% of 
the cation exchange capacity of the smectite-type clay; 
(ii) a second organic cation provided by a polyalkoxylated quaternary 
ammonium salt in an amount from about 0.01% to 20% by weight of the total 
organic cation content; and 
(iii) one or more organic anion(s) that is capable of reacting with the 
first and the second organic cations to form a complex. 
(d) reacting the resulting mixture for a sufficient time to form an 
organophilic clay gellant; and 
(e) recovering said organophilic clay gellant. 
The organoclays of this invention may be prepared by admixing the clay, 
organic salts and water together, preferably at temperatures within the 
range from 20.degree. C. to 100.degree. C., and most preferably from 
35.degree. C. to 80.degree. C. for a period of time sufficient for the 
organic compounds to react with the clay. The reaction is followed by 
filtering, washing, drying and grinding. The organic salts may be added 
simultaneously or at separate intervals in any order. 
The clay is preferably dispersed in water at a concentration from about 1 
to 80%, most preferably, from 2 to 8%. Optionally, the slurry may be 
centrifuged to remove non-clay impurities which may constitute about 10% 
to 50% of the starting clay composition. 
The amount of organic salts added to the clay for purposes of this 
invention must be sufficient to impart to the clay the improved gelling 
and dispersion characteristics. This amount is defined as the 
milliequivalent ratio, which is the amount of milliequivalents (m.e.) of 
the organic salt in the organoclay per 100 grams of natural clay, without 
impurities. The organic salts of this invention must have a combined 
milliequivalent ratio of 1 to 150, preferably 75 to 125 m.e. The amount of 
the hydrophobic organic cation should be from about 1 to 149.99 m.e., 
preferably from 75 to 149.99. The amount of the hydrophilic organic cation 
employed should be from about 0.01 to about 30 m.e., preferably from 1 to 
15 m.e. The organic anion may be present in amounts of from about 1 to 66 
milliequivalents, preferably from about 6 to about 35 milliequivalents of 
anion for example, oleate, palmitate, tartrate, succinate, stearate and 
the like and mixtures thereof. 
The organophilic clay gellants prepared according to the this invention may 
be used as rheological additives in non-aqueous compositions such as 
paints, varnishes, enamels, waxes, paint-varnish lacquer remover, oil base 
drilling fluids, lubricating grease, inks, polyester resins, epoxy resins, 
mastices, adhesives, sealants, cosmetics, detergents, and the like. These 
fluids are prepared by any conventional method as described in U.S. Pat. 
No. 4,208,218, including colloid mills, roller mills, ball mills and high 
speed dispersers. Consequently, the invention also provides non-aqueous 
solvent compositions thickened with the above-indicated organophilic cay 
gellant. Thus, a third aspect of the invention relates to a non-aqueous 
fluid system which comprises: 
(a) a non-aqueous composition; and 
(b) an organophilic clay gellant comprising the reaction product of: 
(i) a smectite-type clay having a cation exchange capacity of at least 75 
milliequivalents per 100 grams of cay; 
(ii) a first organic cation in an amount of from about 75% to about 150% of 
the cation exchange capacity of the smectite-type clay; 
(iii) a second organic cation provided by a polyalkoxylated quaternary 
ammonium salt in an amount of 0.01% to about 20% by weight of the total 
organic cation content; and 
(iv) one or more organic anion(s) that is capable of reacting with the 
first and/or the second organic cations to form a complex. 
The organophilic clay complexes of the invention are added to the 
non-aqueous compositions in amounts sufficient to obtain the desired 
rheological properties. Amounts of the organophilic clay complexes in the 
non-aqueous compositions are from about 0.01% to 15%, preferably from 
about 0.3% to 5%, based on the total weight of the non-aqueous fluid 
system.

The following examples are given to illustrate the invention, but are not 
deemed to be limiting thereof. All percentages given throughout the 
specification are based upon weight unless otherwise indicated. It should 
be noted that Organic Salts A and B referred to in the following examples 
provide the first and second organic cations, respectively, of these 
inventive formulations. 
EXAMPLE 1 
This example illustrates the preparation of an organophilic clay gellant 
according to the present invention. 
45.00 grams of dried bentonite clay, which has been previously treated in 
water by centrifugation to remove non-clay impurities and ion-exchanged to 
provide the clay in sodium form, is mixed with water to form a 3% by 
weight slurry of clay in water. The slurry is heated to 70.degree. C. in a 
reaction flask of suitable size equipped with a stirrer, thermometer and 
addition funnel. 2.08 grams of methyl bis(polyoxyethylene (15)) cocoalkyl 
quaternary ammonium chloride (5 milliequivalents per 100 grams of clay 
solids) dissolved in 10 grams of isopropyl alcohol is added to the clay 
slurry. The mixture is stirred at 70.degree. C. for 1 hour. 27.20 grams of 
dimethyl dihydrogenated tallow quaternary ammonium chloride (107 
milliequivalents per 100 grams of clay solids) dissolved in 100 grams of 
isopropanol at about 60.degree. C. is added to the mixture. 2.88 grams of 
palmitic acid is then added to the reaction flask. The mixture is stirred 
for another hour at 70.degree. C. The product is filtered through a 
Buchner funnel to collect the solids. The wet solids are reslurried in 
1500 grams of water at 70.degree. C. for 20 minutes and then re-collected 
on a Buchner funnel. The filtercake is dried in a 60.degree. C. oven for 
16 hours. 
Comparative Example A 
For comparative purposes, the procedure of Example 1 is repeated, except 
that the hydrophilic quaternary ammonium chloride and the organic anion 
component of the gellant are omitted. 
EXAMPLE 2 
This Example illustrates the preparation of an organophilic clay gellant 
according to the invention, wherein the first and second organic cations 
and the organic anion are added simultaneously to the smectite-type clay 
slurry. 
45.00 grams of dried bentonite clay, which has been previously treated in 
water by centrifugation to remove non-clay impurities and ion-exchanged to 
provide the clay in sodium form, is mixed with water to make a 3% by 
weight slurry of clay in water. The slurry is heated to 70.degree. C. in a 
reaction flask of suitable size equipped with a stirrer, thermometer and 
addition funnel. 2.08 grams of methyl bis(polyoxyethylene (15)) cocoalkyl 
quaternary ammonium chloride (5 meq/100 grams), 27.20 grams of 
commercially available dimethyl dihydrogenated tallow quaternary ammonium 
chloride (107 meq/100 grams) and 2.88 grams of palmitic acid are dissolved 
in 110 grams of isopropyl alcohol at 60.degree. C. and added to the 
reaction flask. The reaction mixture is stirred for one hour at 70.degree. 
C. and then filtered through a Buchner funnel to collect the solids. The 
wet solids are reslurried in 1500 grams on a Buchner funnel. The 
filtercake is dried at 60.degree. C. in an oven for 16 hours. 
EXAMPLE 3 
This Example illustrates the preparation of an organophilic clay gellant 
according to the invention using a sheared smectite-type clay. 
About 2.5 gallons of a 3.0% solids slurry of bentonite clay in water, which 
has been previously treated by centrifugation to remove non-clay 
impurities and ion-exchanged to provide the clay in the sodium form, is 
passed through a Manton-Gaul in homogenizer at 5,000 psi pressure. 1500 
grams of this slurry is placed in a reaction vessel of suitable size 
equipped with a stirrer, thermometer, and addition funnel. The clay slurry 
is heated to 70.degree. C. 2.08 grams of methyl bis(polyoxyethylene (15)) 
cocoalkyl quaternary ammonium chloride (5 meq/100 grams) dissolved in 10 
grams of isopropyl alcohol is added to the clay slurry. The mixture is 
stirred at 70.degree. C. for one hour. 27.20 grams of dimethyl 
dihydrogenated tallow quaternary ammonium chloride (107 meq/100 grams) 
which has been dissolved in 100 grams of isopropyl alcohol at about 
60.degree. C. is added to the mixture. 2.88 grams of palmitic acid is then 
added to the reaction flask. The reaction mixture is stirred for one 
additional hour at 70.degree. C. and then filtered through a Buchner 
funnel to collect the solids. The wet solids are reslurried in 1500 grams 
of water at 70.degree. C. for 20 minutes and then recollected on a Buchner 
funnel. The filtercake is dried at 60.degree. C. in an oven for 16 hours. 
EXAMPLES 4-12 
The compositions are prepared according to the procedure set forth in 
Example 1 (or Example 3 for sheared clay) except that different amounts of 
the methyl bis(polyoxyethylene (15)) cocoalkyl quaternary ammonium 
chloride (commercially available form Akzo Chemie as Ethoquad C/25) 
(Organic Salt B) and commercially available dimethyl dihydrogenated tallow 
quaternary ammonium chloride (Organic Salt A) are used as shown in Table 
1. The amount of palmitic acid is maintained constant in the formulations 
of Examples 4-12. 
TABLE 1 
__________________________________________________________________________ 
Organic Salt A* 
Organic Salt B 
Organic Anion* 
Example 
meg/100 grams** 
meg/100 grams** 
meg/100 grams** 
Clay 
__________________________________________________________________________ 
4 111 1 25 Bentonite 
1 107 5 25 Bentonite 
5 102 10 25 Bentonite 
6 87 25 25 Bentonite 
7 62 50 25 Bentonite 
8 111 1 25 Bentonite (sheared) 
9 107 5 25 Bentonite (sheared) 
10 102 10 25 Bentonite (sheared) 
11 87 25 25 Bentonite (sheared) 
12 62 50 25 Bentonite (sheared) 
__________________________________________________________________________ 
*Organic Salt A is dimethyl dihydrogenated tallow quaternary ammonium 
chloride. Organic Salt B is methyl bis(polyoxyethylene (15)) cocoalkyl 
quaternary amonium chloride (Ethoquad C/25). The organic anion is 
palmitate. 
**meq/100 grams is milliequivalents per 100 grams of clay solids. 
EXAMPLES 13-22 
The compositions are prepared according to the procedure set forth in 
Example 1 (or Example 3 for sheared clay) except that methyl 
bis(polyoxyethylene (15)) oleyl quaternary ammonium chloride (commercially 
available from Akzo Chemie as Ethoquad 0/25) (Organic Salt B) is 
substituted for methyl bis(polyoxyethylene (15)) cocoalkyl quaternary 
ammonium chloride. The amounts of methyl bis(polyoxyethylene (15)) 
quaternary ammonium chloride, dimethyl dihydrogenated tallow quaternary 
ammonium chloride and palmitate anion are used as shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Organic Salt A* 
Organic Salt B 
Organic Anion* 
Example 
meg/100 grams** 
meg/100 grams** 
meg/100 grams** 
Clay 
__________________________________________________________________________ 
13 111 1 25 Bentonite 
14 107 5 25 Bentonite 
15 102 10 25 Bentonite 
16 87 25 25 Bentonite 
17 62 50 25 Bentonite 
18 111 1 25 Bentonite (sheared) 
19 107 5 25 Bentonite (sheared) 
20 102 10 25 Bentonite (sheared) 
21 87 25 25 Bentonite (sheared) 
22 62 50 25 Bentonite (sheared) 
__________________________________________________________________________ 
*Organic Salt A is dimethyl dihydrogenated tallow quaternary ammonium 
chloride. Organic Salt B is methyl bis(polyoxyethylene (15)) oleyl 
quaternary amonium chloride (Ethoquad 0/25). The organic anion is 
palmitate. 
**meq/100 grams is milliequivalents per 100 grams of clay solids. 
EXAMPLES 23-26 
The preparative procedure set forth in Example 1 is followed except for the 
substitution of various types and amounts of organic salts as indicated in 
Table 3. 
TABLE 3 
__________________________________________________________________________ 
Organic Salt A* 
Organic Salt B* 
Organic Anion* 
Example 
meq/100 grams 
meq/100 grams 
meq/100 grams 
Clay 
__________________________________________________________________________ 
23 107 5 25 Bentonite 
24 107 5 25 Bentonite 
25 107 5 25 Bentonite 
26 107 5 25 Bentonite 
__________________________________________________________________________ 
*Organic Salt A is dimethyl dihydrogenated tallow quaternary ammonium 
chloride. Organic Salt B is: Ex. 23 methyl bis(2hydroxyethyl) oleyl 
ammonium chloride (Ethoquad 0/12); Ex. 24 methyl bis(2hydroxyethyl) 
octadecyl aninonium chloride (Ethoquad 18/12); Ex. 25 methyl 
bis(2hydroxy-ethyl) cocoalkyl ammonium chloride (Ethoquad C/12); Ex. 26 
methyl bis(polyoxy ethylene (15)) octadecyl quaternary ammonium chloride 
(Ethoquad 18/25). The organic anion source is palmitic acid. 
EXAMPLES 27-35 
These examples illustrate the formation of organophilic clay gellants 
according to the invention using various organic anions. The preparative 
procedure set forth in Example I is followed. The types and amounts of 
organic salts and organic anion sources are indicated in Table 4. 
TABLE 4 
______________________________________ 
Ex- 
am- Organic Salt A* 
Organic Salt B* 
ple meq/100 grams 
meq/100 grams 
Organic Anion* 
______________________________________ 
27 107 5 Tartaric acid 
28 107 5 Stearic acid 
29 107 5 Succinic acid 
30 107 5 Oleic Acid 
31 107 5 Sodium Tartrate 
32 107 5 Disodium tartrate 
33 107 5 Sodium stearate 
34 107 5 Disodium succinate 
35 107 5 Sodium palmitate 
______________________________________ 
*Organic Salt A is dimethyl dihydrogenated tallow quaternary ammonium 
chloride. Organic Salt B is methyl bis(polyoxyethylene (15)) cocoalkyl 
quaternary ammonium chloride (commercially available from Akzo Chemie 
under the tradename Ethoquad C/25). Organic anion is 25 meq/100 grams. Th 
clay is bentonite. 
EXAMPLES 36-44 
The preparative procedure set forth in Example 3 is used. The types and 
amounts of organic salts and organic anion sources are indicated in Table 
5. 
TABLE 5 
______________________________________ 
Ex- 
am- Organic Salt A* 
Organic Salt B* 
ple meq/100 grams 
meq/100 grams 
Organic Anion* 
______________________________________ 
36 107 5 Tartaric acid 
37 107 5 Stearic acid 
38 107 5 Succinic acid 
39 107 5 Oleic Acid 
40 107 5 Sodium Tartrate 
41 107 5 Disodium tartrate 
42 107 5 Sodium stearate 
43 107 5 Disodium succinate 
44 107 5 Sodium palmitate 
______________________________________ 
*Organic Salt A is dimethyl dihydrogenated tallow quaternary ammonium 
chloride. Organic Salt B is methyl bis(polyoxyethylene (15)) cocoalkyl 
quaternary ammonium chloride (comercially available from Akzo Chemie unde 
the tradename Ethoquad C/25). Organic anion is 25 meq/100 grams. The clay 
is sheared bentonite. 
EXAMPLES 45-52 
The preparative procedure set forth in Example 3 is used. The types and 
amounts of organic salts and organic anion sources are indicated in Table 
6. 
TABLE 6 
______________________________________ 
Ex- 
am- Organic Salt A* 
Organic Salt B* 
ple meq/100 grams 
meq/100 grams 
Organic Anion* 
______________________________________ 
45 107 5(a) Tartaric acid 
46 107 5(a) Succinic acid 
47 107 5(a) Palmitic acid 
48 107 5(a) Oleic acid 
49 107 5(b) Tartaric acid 
50 107 5(b) Succinic acid 
51 107 5(b) Palmitic acid 
52 107 5(b) Oleic acid 
______________________________________ 
*Organic Salt A is dimethyl dihydrogenated tallow quaternary ammonium 
chloride. Organic Salt B is: (a) methyl bis(polyoxyethylene (15)) oleyl 
quaternary ammonium chloride; (b) methyl bis(2hydroxyethyl) oleyl 
ammonium chloride. Organic anion is 25 meq/100 grams. The clay is sheared 
bentonite. 
EXAMPLES 53-62 
These examples demonstrate the dispersion and viscosity-build properties 
provided when the organic modified clay complexes of the invention are 
used in a mineral oil ink formulation. A mineral oil based news red ink is 
prepared according to Formulation 1. 
__________________________________________________________________________ 
Formulation I 
News Red Ink Formula 
Fomulation 
Ingredient Generic Name 
Manufacturer 
(parts by wt.) 
__________________________________________________________________________ 
Part I: Base Red 
Multi-mix Red Flush 
Red Flush Color 
BASF 26.0 
45MM2247 
Sunprint HP 750 
Naphthenic Mineral Oil 
Sun Refining 
35.0 
Mineral Oil 
SUS 750 Viscosity 
Nevchem 140 in 
Hydrocarbon Resin 
Neville Chemical 
29.0 
EXX-Print 705 
Solution, 52% Solids 
90.0 
Mix the base at 6000 rpm for 2-3 minutes or until uniform, then add: 
Part II: Rheological Additive 
Rheological Additive 3.0 
Water 0.2 
Disperse the rheological additive in the base at 6000 rpm for 15 minutes, 
then add: 
Part III: Letdown 
EXX-Print Naphthenic Solvent 
Exxon 7.0 
Total 100.2 
__________________________________________________________________________ 
A red ink is prepared according to Formulation 1. The ink is allowed to 
equilibrate at room temperature for 24 hours. Tack and misting are 
measured with a Thwing-Albert Inkometer operating at 1200 rpm and 
90.degree. F. Tack is measured according to ASTM Method D 4361-84 entitled 
"Apparent Tack of Printing Inks by the Inkometer. 
NPIRI (National Printing Ink Research Institute) grind values are measured 
to evaluate dispersion according to ASTM Method D 1316-68 entitled 
"Fineness of grind of Printing Inks by the Production Grindometer." 
Dispersion ratings are presented in Table 7. The ink is rated for overall 
scratches and background haze. A dispersion rating of medium heavy 
indicates poor dispersion resulting in many scratches and a medium to 
heavy background haze. A rating of light indicates better dispersion 
properties although some background haze is evident. 
Viscosity for the ink formulations are determined using a Brookfield RVT 
viscometer with a No 15 spindle. Dispersion measurements, Brookfield 
viscosities, tack, and misting are presented in Table 7. 
TABLE 7 
__________________________________________________________________________ 
Brookfield 
Prep. Viscosity (cP) 
Example 
Ex. Organic Anion 
G-3 Grind 
Tack 
Misting 
2.5 rpm 
20 rpm 
__________________________________________________________________________ 
53 27 Tartaric acid 
0/17 M 
4.8 
F 17000 
6500 
54 30 Sodium tartrate 
0/10 LM 
4.7 
F 24000 
8250 
55 31 Disodium tartrate 
0/20 MH 
4.7 
F 23000 
9000 
56 28 Stearic acid 
0/8 LM-M 
4.7 
F 17000 
6000 
57 32 Sodium stearate 
0/18 MH 
4.5 
F 18000 
7125 
58 29 Succinic acid 
0/13 LM 
5.1 
F 19000 
6500 
59 33 Disodium succinate 
0/14 MH 
4.4 
F 19000 
7250 
60 1 Palmitic acid 
0/8 LM 
4.7 
F 15000 
4500 
61 35 Sodium palmitate 
0/22 MH 
4.4 
F 7000 4000 
62 Comp. A 
None 0/20 MH 
5.5 
F-P 4000 3250 
__________________________________________________________________________ 
where F = Fair; P = Poor; M = Medium; H = Heavy; L = Light. 
EXAMPLES 63-65 
These Examples demonstrate the dispersion and viscosity-build properties 
provided when the organic-modified clay complexes are used in a mineral 
oil ink formulation described in Formulation 1. This set of Examples 
compares organic-modified clay complexes prepared with sheared bentonite 
clay to organic-modified clay complexes prepared with non-sheared 
bentonite clay. 
Dispersion measurements, Brookfield viscosities, tack and misting are 
presented in Table 8. 
TABLE 8 
__________________________________________________________________________ 
Brookfield 
Prep. Viscosity (cP) 
Ex. 
Ex. Organic Anion 
Clay G-3 Grind 
Tack 
Misting 
2.5 rpm 
20 rpm 
__________________________________________________________________________ 
53 27 Tartaric acid 
non-sheared 
0/17 M 
4.8 
F 17000 
6500 
63 36 Tartaric acid 
sheared 
0/22 M 
5.0 
F 27000 
8250 
58 29 Succinic acid 
non-sheared 
0/13 LM 
5.1 
F 19000 
6500 
64 38 Succinic acid 
sheared 
0/19 M 
5.1 
F 26000 
8125 
60 1 Palmitic acid 
non-sheared 
0/8 LM 
4.7 
F 15000 
4500 
65 3 Palmitic acid 
sheared 
0/22 M 
4.9 
F 24000 
6875 
__________________________________________________________________________ 
Where F = Fair; M = Medium = L = Light. 
EXAMPLES 66-78 
These Examples demonstrate the dispersion and viscosity-build properties 
provided when the organic-modified clay complexes are used in a soya bean 
oil based ink formulation. A red soya news ink formulation is prepared 
according to Formulation 2. 
__________________________________________________________________________ 
Formulation 2 
Soya News Red Ink Formula 
Fomulation 
Ingredient Generic Name 
Manufacturer 
(parts by wt.) 
__________________________________________________________________________ 
LR 6247 SB Flushed Color 
Magruder Color 
26.4 
Lithol Rubine 
Special T Oxidized Soya Bean 
Spencer-Kellogg Div. 
40.5 
Blown Soya Oil 
Oil Z.sub.2 -Z.sub.4 
Reichhold Chemicals 
Mix at 8000 rpm until uniform, then add: 
Rheological Additive 3.8 
Disperse at 8000 rpm for 20 minutes, then add as letdown: 
Superior Soya Oil 
Highly Refined 
Spencer-Kellogg Div. 
29.1 
Soybean Oil A 
Reichhold Chemicals 
Total 99.8 
__________________________________________________________________________ 
NPIRI (National Printing Ink Research Institute grind values are measured 
to evaluate dispersion. G-3 grind (dispersion) ratings are presented in 
Table 9. 
Viscosity data for the ink formulations are determined using a Brookfield 
RVT Viscometer with a No. 15 spindle. Dispersion measurements, Brookfield 
viscosities, tack, and misting are presented in Table 9. 
TABLE 9 
__________________________________________________________________________ 
Brookfield 
Viscosity (cP) 
Example 
Prep. Ex. 
Organic Salt B* 
Organic Anion 
Grind Tack 
Misting 
20 RPM 
2.5 RPM 
__________________________________________________________________________ 
66 36 a Tartaric acid 
0/19 MH 
5.5 
F 3250 4000 
67 38 a Succinic acid 
0/18 M 
5.5 
F 3750 6000 
68 3 a Palmitic acid 
0/11 LM 
5.3 
F 4700 8000 
69 39 a Oleic acid 
0/30 MH 
5.5 
F 3000 4000 
70 45 b Tartaric acid 
0/28 H 
5.3 
F 4500 7000 
71 46 b Succinic acid 
0/22 MH 
5.2 
F 4500 7000 
72 47 b Palmitic acid 
0/22 MH 
5.2 
F 4500 9000 
73 48 b Oleic acid 
0/18 MH 
5.1 
F 3875 7000 
74 49 c Tartaric acid 
0/15 MH 
5.8 
F 3625 5000 
75 50 c Succinic acid 
0/12 LMM 
5.4 
F 5250 10000 
76 51 c Palmitic acid 
0/13 MH 
5.2 
F 3875 6000 
77 52 c Oleic acid 
0/16 MH 
5.2 
F 3625 6000 
78 Comp. A 
-- None 0/22 MH 
5.7 
F 3187 4000 
__________________________________________________________________________ 
where F = Fair; M = Medium; H = Heavy; L = Light. 
*Organic Salt B is that of the preparation example, namely: 
a -- methyl bis(polyoxyethylene (15)) cocoalkyl quaternary ammonium 
chloride (Ethoquad C/25); 
b -- methyl bis(polyoxyethylene (15)) oleyl quaternary ammonium chloride 
(Ethoquad 0/25); 
c -- methyl bis(2hydroxyethyl) oleyl quaternary ammonium chloride 
(Ethoquad 0/12). 
Organic Salt A for each of these examples is dimethyl dihydrogenated 
tallow quaternary ammonium chloride. 
EXAMPLES 79-91 
The ink formulations described in Table g were passed through a three roll 
mill and their properties are presented in Table 10: 
TABLE 10 
______________________________________ 
Ex- Brookfield 
am- Ink Viscosity (cP) 
ple Ex. Organic Salt B* 
Organic Anion 
20 rpm 2.5 rpm 
______________________________________ 
79 66 a Tartaric acid 
10375 36000 
80 67 a Succinic acid 
9875 30000 
81 68 a Palmitic acid 
8250 24000 
82 69 a Oleic acid 
7500 29000 
83 70 b Tartaric acid 
7750 21000 
84 71 b Succinic acid 
10000 36000 
85 72 b Palmitic acid 
7125 21000 
86 73 b Oleic acid 
11250 40000 
87 74 c Tartaric acid 
9125 30000 
88 75 c Succinic acid 
11625 44000 
89 76 c Palmitic acid 
9000 32000 
90 77 c Oleic acid 
9125 30000 
91 78 -- None 6750 18000 
______________________________________ 
*Organic Salt B is that of the preparation example, namely: 
a -- methyl bis(polyoxyethylene (15)) cocoalkyl quaternary ammonium 
chloride (Ethoquad C/25); 
b -- methyl bis(polyoxyethylene (15)) oleyl quaternary amonium chloride 
(Ethoquad 0/25); 
c -- methyl bis(2hydroxyethyl) oleyl quaternary ammonium chloride 
(Ethoquad 0/12). 
Based on the foregoing results, it is apparent that the organophilic clay 
gellants provided by the invention are highly effective in improving the 
rheological properties of non-aqueous systems. Without wishing to be bound 
by any particular theory, it is believed that the action of the 
polyalkoxylated quaternary ammonium cation is required in order to impart 
the desired hydrophobic/hydrophilic balance to the non-aqueous system, 
while the organic anion is essential in separating the clay platelets so 
that they form smaller aggregates with higher surface area. In this 
regard, reaction products containing the anion appear to be more "open" in 
structure than those containing no anion. It is believed that these 
compositions expose more surface area, thus improving the efficacy of the 
gellant. 
The invention thus being described, it will be obvious that the same may be 
varied in many ways. Such variations are not to be regarded as a departure 
from the spirit and scope of the invention and all such modifications are 
intended to be included within the scope of the claims.