Stable dispersions of fortified rosin

Disclosed are novel aqueous dispersions which consist essentially of finely-divided fortified rosin particles; a water-soluble or water-dispersible cationized starch dispersing agent for the finely-divided fortified rosin particles; an anionic surface-active agent; and water. The novel aqueous dispersions are used to size paper.

This invention relates to novel aqueous dispersions of fortified rosin. 
Particularly, this invention relates to aqueous dispersions which consist 
essentially of finely-divided fortified rosin particles, a water-soluble 
or water-dispersible cationized starch dispersing agent for the 
finely-divided fortified rosin particles, an anionic surface-active agent, 
and water. The cationized starch dispersing agent will be detailed more 
fully hereinafter. The novel fortified rosin dispersions of this invention 
are used to size paper. 
U.S. Pat. No. 3,966,654 discloses aqueous fortified rosin dispersions 
consisting essentially of, by weight, (A) from about 5% to about 50% 
fortified rosin, (B) from about 0.5% to about 10% of water-soluble 
cationic resin dispersing agent, and (C) water to 100%. Dispersing agent 
(B) is selected from the group consisting of (i) a water-soluble 
aminopolyamideepichlorohydrin resin, (ii) a water-soluble 
alkylenepolyamineepichlorohydrin resin and (iii) a water-soluble 
poly(diallylamine)-epichlorohydrin resin. The fortified rosin is the 
adduct reaction product of rosin and an acidic compound containing the 
##STR1## 
Also disclosed are methods of preparing the dispersions. 
U.S. Pat. No. 3,966,654 also discloses prior art relating to aqueous 
fortified rosin dispersions. The disclosure of this patent, U.S. Pat. No. 
3,966,654, is incorporated herein by reference. 
U.S. Pat. Nos. 4,199,396 and 4,203,776 also disclose aqueous fortified 
rosin dispersions prepared by an inversion process. Prior art dispersions 
and methods of making the same are also disclosed. The disclosures of U.S. 
Pat. Nos. 4,199,396 and 4,203,776 are incorporated herein by reference. 
U.S. Pat. Nos. 3,070,542 and 3,130,118 disclose the use of certain cationic 
starches in the preparation of aqueous ketene dimer emulsions. The 
emulsions are used to size paper. 
Commerically available aqueous dispersions of fortified rosin particles for 
use in sizing paper cannot be stored for long periods of time because the 
fortified rosin particles tend to settle out on long standing and also 
have a tendency to agglomerate under conditions of agitation and shear 
such as that encountered in pumping the dispersions from their place of 
storage to their place of use. 
The aqueous dispersions of this invention have excellent storage stability 
and are more resistant to particle agglomeration due to agitation and 
shear as encountered in pumping, for example. 
In accordance with this invention there are provided aqueous dispersions of 
fortified rosin, adapted for use in the sizing of paper, which consist 
essentially of, by weight, (A) from about 5% to about 50% fortified rosin; 
(B) from about 0.5% to about 10% of at least one water-soluble or 
water-dispersible cationized starch dispersing agent; (C) from about 0.1% 
to 4% of at least one anionic surface active agent; and (D) water to 100%, 
component (B) being selected from 
(I) an anionic starch modified by reaction with a cationizing resin 
selected from the group consisting of (a) a water-soluble 
aminopolyamideepihalohydrin resin containing no epoxy groups, (b) a 
water-soluble alkylenepolyamineepihalohydrin resin, (c) a water-soluble 
poly(diallyamine)-epihalohydrin resin containing no epoxy groups, (d) a 
water-soluble poly(diallyamine) resin, (e) a water-soluble 
poly(alkylenimine) resin, and (f) a water-soluble 
poly(alkylenimine)-epihalohydrin resin, and 
(II) starch modified by reaction with a water-soluble cationizing resin 
containing epoxy groups selected from the group consisting of (a) a 
water-soluble poly(N-alkyldiallylamine)-epihalohydrin resin containing 
epoxy groups, and (b) a water-soluble aminopolyamide-epihalohydrin resin 
containing epoxy groups, the aminopolyamide moiety of which contains 
tertiary amines, said fortified rosin (A) being the adduct reaction 
product of rosin and an acidic compound containing the 
##STR2## 
In its preferred embodiment, the composition described above will consist 
essentially of from about 10% to about 40% component (A); from about 1% to 
about 8% component (B); from about 0.2% to about 2% component (C); and (D) 
water to 100%. 
The fortified rosin can be extended if desired by known extenders therefor 
such as waxes (particularly paraffin wax and microcrystalline wax); 
hydrocarbon resins including those derived from petroleum hydrocarbons and 
terpenes; and the like. This is accomplished by melt blending or solution 
blending with the fortified rosin from about 10% to about 100% by weight, 
based on the weight of fortified rosin, of the fortified rosin extender. 
Also blends of fortified rosin and rosin; and blends of fortified rosin, 
rosin and rosin extender can be used. 
Fortified rosin-rosin blends will comprise about 25% to 95% fortified rosin 
and about 75% to 5% rosin. Blends of fortified rosin, rosin, and rosin 
extender will comprise about 25% to 45% fortified rosin, about 5% to 50% 
rosin, and about 5% to 50% rosin extender. 
The aqueous fortified rosin dispersions of this invention can be prepared 
by homogenizing a solution or a melt of the fortified rosin or by the 
so-called inversion process. 
In preparing the aqueous fortified rosin dispersions of this invention by 
the solution process, the fortified rosin (including the extender or rosin 
or both if either or both are employed) is first dissolved in a 
water-immiscible organic solvent therefor such, for example, as benzene, 
xylene, methylene chloride, chloroform, or 1,2-dichloropropane. Mixtures 
of two or more solvents can be used if desired. The selected solvent will 
also be non-reactive with the components of the aqueous dispersion to be 
subsequently prepared. 
An emulsion is prepared which is comprised of the organic solvent-fortified 
rosin solution as the dispersed phase and, as the continuous phase, an 
aqueous solution or dispersion of cationized starch dispersing agent and 
anionic surface active agent. The essentially unstable aqueous emulsion is 
then subjected to extreme shear to provide an essentially stable emulsion. 
Extreme shear is conveniently accomplished by means of an homogenizer. 
Thus, passing, at least once, the unstable aqueous emulsion through an 
homogenizer under a pressure on the order of from about 1000 p.s.i.g. to 
about 8000 p.s.i.g., will provide an essentially stable emulsion. 
Subsequently, the organic solvent component of the emulsion is removed 
from the emulsion, as by vacuum distillation, and there is provided an 
essentially stable aqueous dispersion of fortified rosin particles. These 
procedural steps are described in U.S. Pat. No. 3,565,755, the disclosure 
of which is hereby incorporated by reference. 
In preparing dispersions of this invention by the melt process, the 
fortified rosin is heated, under pressure if required, in admixture with 
an aqueous solution of cationized starch dispersing agent and anionic 
surface active agent. The unstable aqueous dispersion is heated to a 
temperature of from about 80.degree. C. to about 195.degree. C. Agitation 
thereof during the time required to reach the necessary temperature is 
recommended. The heated dispersion is then subjected to extreme shear, 
whereby there is provided an essentially stable aqueous dispersion. 
Extreme shear is conveniently accomplished by means of an homogenizer. 
Thus, passing, at least once, the heated mixture through an homogenizer 
under a pressure on the order of about 2000 p.s.i.g. to about 8000 
p.s.i.g. will provide an essentially stable dispersion. The pressure 
selected is within the skill of the art. 
The aqueous fortified rosin dispersions of this invention can also be 
prepared by an inversion process. The fortified rosin is admixed with an 
aqueous solution of cationized starch dispersing agent and anionic surface 
active agent in an amount to provide a water-in-oil emulsion which is 
subsequently inverted to a oil-in-water emulsion by the rapid addition of 
water with vigorous stirring. 
ROSIN 
The rosin used to prepare the fortified rosin employed in this invention 
can be any of the commerically available types of rosin, such as wood 
rosin, gum rosin, tall oil rosin, and mixtures of any two or more, in 
their crude or refined state. Partially or substantially completely 
hydrogenated rosins and polymerized rosins, as well as rosins that have 
been treated to inhibit crystallization such as by heat treatment or 
reaction with formaldehyde, can be employed. 
The fortified rosin employed is the adduct reaction product of rosin and an 
acidic compound containing the 
##STR3## 
group and is derived by reacting rosin and the acidic compound at elevated 
temperatures of from about 150.degree. C. to about 210.degree. C. 
The amount of acidic compound employed will be that amount which will 
provide fortified rosin containing from about 1% to about 12% by weight of 
adducted acidic compound based on the weight of the fortified rosin. 
Methods of preparing fortified rosin are disclosed and described in U.S. 
Pat. Nos. 2,628,918 and 2,684,300, reference to which is hereby made. 
Examples of acidic compounds containing the 
##STR4## 
group that can be used to prepare the fortified rosin include the 
alpha-beta-unsaturated organic acids and their available anhydrides, 
specific examples of which include fumaric acid, maleic acid, acrylic 
acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid 
and citraconic anhydride. Mixtures of acids can be used to prepare the 
fortified rosin if desired. Thus, for example, a mixture of the acrylic 
acid adduct of rosin and the fumaric acid adduct can be used to prepare 
the novel dispersions of this invention. Also, fortified rosin that has 
been substantially completely hydrogenated after adduct formation can be 
used. 
If rosin (that is, unfortified rosin) is used in combination with fortified 
rosin, it can be any of the commercially available types of rosin, such as 
wood rosin, gum rosin, tall oil rosin, and mixtures of any two or more, in 
their crude or refined state. Partially or substantially completely 
hydrogenated rosins and polymerized rosins, as well as rosin that have 
been treated to inhibit crystallization such as by heat treatment or 
reaction with formaldehyde, can be employed. 
CATIONIZED STARCH DISPERSING AGENTS 
The dispersing agents used in this invention are water-soluble or 
water-dispersible cationized starches selected from (I) anionic starches 
modified by reaction with a cationizing resin selected from the group 
consisting of (a) a water-soluble aminopolyamide-epihalohydrin resin 
containing no epoxy groups, (b) a water-soluble 
alkylenepolyamine-epihalohydrin resin, (c) a water-soluble 
poly(diallylamine)-epihalohydrin resin containing no epoxy groups, (d) a 
water-soluble poly(diallylamine) resin, (e) a water-soluble 
poly(alkylenimine) resin, or (f) a water-soluble 
poly(alkylenimine)-epihalohydrin resin; and (II) starch modified by 
reaction with a water-soluble polyamine resin containing epoxy groups. 
Examples of such resins are water-soluble 
poly(N-alkyldiallylamine)-epihalohydrin resins containing epoxy groups; 
and water-soluble aminopolyamide-epihalohydrin resins containing epoxy 
groups, the aminopolyamide moiety of which contains tertiary amines. 
DISPERSING AGENTS (I) 
As above set forth, dispersing agents (I) are anionic starches modified by 
reaction or combination with a cationizing resin as described. The precise 
nature of the reaction, or the combining of the anionic starch with the 
cationizing resin is not fully understood and it is not the intention of 
applicant to be bound to any particular theory. However, it is believed 
that the anionic starch and the cationizing resin are tied by ionic 
bonding. 
Anionic Starches 
The anionic starch employed can be (1) any of the natural starches 
containing phosphate groups such, for example, as potato starch, or (2) 
starches into which carboxyl groups have been introduced by oxidation 
such, for example, as by reaction with with sodium hypochlorite, or (3) 
starches that have been modified by carboxymethylation, or (4) starches 
into which phosphate groups have been introduced as by reaction with a 
sodium acid phosphate. 
Starches containing carboxyl groups are prepared by means well known in the 
art and are available commerically. For the purposes of this invention, it 
is preferred to use carboxylated starches containing at least one 
milliequivalent of carboxyl per 100 grams starch, the upper practical 
limit being about 15 millieqivalents of carboxyl per 100 grams starch. 
Starches into which carboxyl groups can be introduced via oxidation include 
those derived from a plant source such as corn, potato, wheat, rice, sago, 
tapioca, waxy maize, sorghum, and high amylose corn. 
One common method of oxidizing starches to introduce carboxyl groups 
entails the addition of a predetermined quantity of sodium hypochlorite to 
an aqueous starch slurry. Alkali is added to maintain the pH at 8-10 
throughout the reaction and cooling is used to maintain the temperature in 
the range 21.degree.-38.degree. C. The amount of hypochlorite added is 
usually equivalent to between 0.5 and 6.0% available chlorine, based on 
starch. Since the viscosity of the starch is inversely related to the 
degree of oxidation, the amount of hypochlorite is often chosen based on 
the desired viscosity of the starch to be made. Following a reaction 
period of 5-24 hours, the slurry is neutralized and free chlorine is 
destroyed with sodium bisulfite. Soluble by-products are then removed and 
the starch is collected on vacuum filters and dried. 
As to starches containing phosphate groups, it is preferred to use those 
containing at least one milliequivalent of phosphate per 100 grams starch, 
the upper practical limit being about 15 milliequivalents of phosphate per 
100 grams starch. Starches into which phosphate groups have been 
introduced are well known in the art as are their methods of preparation. 
Starches that have been modified by carboxymethylation are known in the art 
as are their methods of preparation. 
Cationizing Resin (a) 
As cationizing resin (a) there can be employed the water-soluble 
aminopolyamide-epihalohydrin resins disclosed in U.S. Pat. Nos. 2,926,116 
and 2,926,154 and 3,966,654. The disclosures of these patents are 
incorporated herein by reference. 
In preparing resin (a) there is first prepared a water-soluble 
aminopolyamide resin which is derived by reaction of a dicarboxylic acid 
and a polyalkylene polyamine in a mole ratio of polyalkylene polyamine to 
dicarboxylic acid of from about 0.8:1 to about 1.4:1. 
Particularly suitable dicarboxylic acids are diglycolic acid and saturated 
aliphatic dicarboxylic acids containing from 4 through 10 carbon atoms 
such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic 
acid, azelaic acid, and sebacic acid. 
Other suitable dicarboxylic acids include terephthalic acid, isophthalic 
acid, phthalic acid, maleic acid, fumaric acid, itaconic acid, glutaconic 
acid, citraconic acid, and mesaconic acid. 
The available anhydrides of the above acids can be used in preparing the 
water-soluble aminopolyamide as well as the esters of the acids. Mixtures 
of two or more dicarboxylic acids, their anhydrides, and their esters can 
be used to prepare the water-soluble aminopolyamide, if desired. 
The polyalkylene polyamine employed in preparing the aminopolyamide is 
represented by the formula 
##STR5## 
where R is hydrogen or C.sub.1 -C.sub.4 alkyl; n is an integer 2 through 6 
and x is a integer 1 through 4. Examples of C.sub.1 -C.sub.4 alkyl are 
methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and t-butyl. 
Specific examples of polyalkylene polyamines of the above formula include 
diethylenetriamine; triethylenetetramine; tetraethylenepentamine; 
dipropylenetriamine; dihexamethylenetriamine; pentaethylenehexamine; 
methyl bis(3-aminopropyl)amine; methyl bis(2-aminoethyl)amine; and 
4,7-dimethyltriethylenetetramine. Mixtures of polyalkylene polyamines can 
be used, if desired. 
The spacing of amino groups on the aminopolyamide can be increased if 
desired. This can be accomplished by substituting a diamine such as 
ethylenediamine, propylenediamine, hexamethylenediamine and the like for a 
portion of the polyalkylene polyamine. For this purpose, up to about 80% 
of the polyalkylene polyamine can be replaced by a molecularly equivalent 
amount of diamine. Usually, a replacement of about 50% or less will be 
adequate. 
Temperatures employed for carrying out reaction between the dicarboxylic 
acid and the polyalkylene polyamine can vary from about 110.degree. C. to 
about 250.degree. C. or higher at atmospheric pressure. For most purposes, 
temperatures between about 160.degree. C. and 210.degree. C. are 
preferred. The time of reaction will usually vary from about 1/2 hour to 2 
hours. Reaction time varies inversely with reaction temperatures employed. 
In carrying out the reaction, it is preferred to use an amount of 
dicarboxylic acid sufficient to react substantially completely with the 
primary amine groups of the polyalkylene polyamine but insufficient to 
react with the secondary amine groups and/or tertiary amine groups to any 
substantial extent. This will usually require a mole ratio of polyalkylene 
polyamine to dicarboxylic acid of from about 0.9:1 to about 1.2:1. 
However, mole ratios of from about 0.8:1 to about 1.4:1 can be used. 
Aminopolyamides containing secondary amine groups can be alkylated so as to 
replace the secondary amine groups by tertiary amine groups. This is 
accomplished by means of a monofunctional alkylating agent such as lower 
alkyl esters of mineral acids such as the halides, sulfates and 
phosphates, substituted alkylhalides. Illustrative of the compounds which 
can be used are dimethyl, diethyl and dipropyl sulfate; methyl chloride; 
methyl iodide; ethyl iodie; methyl bromide; propyl bromide; and the mono-, 
di- or tri-methyl, ethyl and propyl phosphates. Certain aromatic compounds 
such as benzyl chloride and methyl p-toluene sulfonate can be used. From 
about 0.1 mole to about 0.9 mole of monofunctional alkylating agent for 
each amine group can be used. Alkylation conditions are well known in the 
art and form no part of this invention. 
Cationizing resin (a) is derived by reacting a water-soluble 
aminopolyamide, as above described, with an epihalohydrin, such as 
epichlorohydrin, at a temperature of from about 45.degree. C. to about 
100.degree. C., and preferably between about 45.degree. C. and 70.degree. 
C., until the viscosity of a 20% solids solution in water at 25.degree. C. 
has reached about C or higher on the Gadner-Holdt scale. This reaction is 
preferably carried out in aqueous solution. pH adjustment is usually not 
necessary. However, since the pH decreases during the polymerization phase 
of the reaction, it may be desirable, in some cases, to add alkali to 
combine with at least some of the acid formed. When the desired viscosity 
is reached, water can be added to adjust the solids content of the resin 
solution to a desired amount, usually from about 2% to about 50%. 
In the aminopolyamide-epichlorohydrin reaction, satisfactory results can be 
obtained utilizing from about 1.0 mole to about 5 moles of epichlorohydrin 
for each secondary or tertiary amine group of the aminopolyamide, and 
preferably from about 1 mole to about 1.5 moles of epichlorohydrin. 
Aminopolyamide-epihalohydrin resins where the aminopolyamide moiety 
contains tertiary amine nitrogens can contain halohydrin groups of epoxy 
groups depending on solution pH. For the purposes of preparing dispersing 
agent (I), it is important that this resin contain halohydrin groups and 
no epoxy groups. This is accomplished by acid-stabilization of the resin 
in accordance with the teachings of U.S. Pat. No. 3,311,594, the 
disclosure of which is incorporated by reference. 
In all the examples herein, all parts and percentages are by weight unless 
otherwise specified.

The following example is illustrative of a method for the preparation of a 
resin of the cationizing resin (a) type. 
EXAMPLE A 
an aminopolyamide is formed by adding 219.3 parts of adipic acid slowly, 
with stirring, to 151.3 parts of diethylenetriamine in a flask fitted with 
a stirrer and a condenser for collecting water distillate. The reaction 
mixture is stirred and heated at 170.degree.-180.degree. C. under a 
nitrogen blanket until amide formation is complete. After air cooling to 
approximately 140.degree. C., hot water is added with stirring to provide 
a 50% solids aqueous solution of aminopolyamide resin with an intrinsic 
viscosity of 0.140 measured by using a 2% solution in 1 N NH.sub.4 Cl. An 
epichlorohydrin derivative of the aminopolyamide is prepared by adding 
about 110 parts of water to about 50 parts of the 50% solids solution and 
then adding 14.0 parts (0.157 mole) of epichlorohydrin. The reaction 
mixture is heated at 70.degree. C. with stirring under a reflux condenser 
until the Gardner-Holdt viscosity attains a value of E to F. The reaction 
mixture is diluted with water to a solids content to about 12.5%. A 12.5% 
aqueous solution of a resin prepared substantially in accordance with the 
method of this example is available commercially under the trademark 
Kymene and grade designation 557H. 
Cationizing Resin (b) 
Cationizing resin (b) is the water-soluble alkylene polyamine-epihalohydrin 
resin derived by reaction of an epihalohydrin, epichlorohydrin being 
preferred, and an alkylene polyamine. Water-soluble 
alkylenepolyamine-epihalohydrin resins and their method of preparation are 
well known in the art. 
Alkylene polyamines which can be reacted with epichlorohydrin are 
polyalkylene polyamines having the formula (I) above and monoalkylene 
polyamines such as ethylenediamine, propylenediamine, and 
hexamethylenediamine. 
The relative proportions of alkylene polyamine and epichlorohydrin employed 
can be varied depending upon the particular polyalkylene polyamine used. 
In general, it is preferred that the molar ratio of epichlorohydrin to 
alkylene polyamine be in excess of 1:1 and less than 2:1. In the 
preparation of a water-soluble resin from epichlorohydrin and 
tetraethylenepentamine, good results are obtained at molar ratios of from 
about 1.4:1 to 1.94:1. Reaction temperature is preferably in the range of 
from about 40.degree. C. to about 60.degree. C. 
The following example is illustrative of a method for the preparation of a 
resin of the cationizing resin (b) type. 
EXAMPLE B 
To a mixture of 29.2 parts triethylenetetramine and 70 parts water is added 
44.4 parts epichlorohydrin over a period of about 12 minutes with periodic 
cooling. After the epichlorohydrin addition is complete, the reaction 
mixture is heated to 75.degree. C. and maintained at a temperature of from 
about 70.degree. C. to about 77.degree. C. for about 33 minutes, at which 
point the Gardner-Holdt viscosity reaches about I. The resulting reaction 
mass is diluted with 592 parts water to provide an aqueous solution that 
has a solids content of about 11.7% and a pH of about 6.3. 
Cationizing Resins (c) and (d) 
Cationizing resin (c) is a water-soluble poly(diallylamine)-epihalohydrin 
resin. Resins of this type and their method of preparation are described 
in U.S. Pat. No. 3,700,623. The disclosure of this patent is incorporated 
herein by reference. Resins of this type are also disclosed in Canadian 
Pat. No. 999,300. 
A poly(diallylamine)-epihalohydrin resin is the reinous reaction product of 
(i) a water-soluble linear polymer produced by polymerizing the 
hydrohalide salt of a diallylamine of the formula 
##STR6## 
where R is hydrogen or lower alkyl and R' is hydrogen or alkyl, either 
alone or as a mixture with other copolymerizable ingredients, in the 
presence of a free radical catalyst followed by neutralization of the salt 
to give the polymer free base and (ii) an epihalohydrin, epichlorohydrin 
being preferred. 
The water-soluble linear polymer (unreacted with epihalohydrin) is used as 
cationizing resin (d). 
In the above formula, each R can be the same or different and the alkyl 
groups contain from 1 to 3 carbons and are preferably methyl, ethyl or 
isopropyl. R' of the formula represents hydrogen or alkyl groups. The R' 
alkyl groups will contain from 1 to 6 carbon atoms such as methyl, ethyl, 
propyl, isopropyl, butyl, tert-butyl and hexyl. 
Diallyamines and N-alkyldiallylamines are well known in the art, as are 
their methods of preparation. 
Specific hydrohalide salts which can be polymerized to provide the 
water-soluble polymer include diallylamine hydrochloride and 
N-methyldiallylamine hydrochloride. Other salts are disclosed in U.S. Pat. 
No. 3,700,623. 
For the purpose of this invention homopolymers of diallylamines such, for 
example, as poly(N-methyldiallylamine) are preferred as they are readily 
available. However, copolymers of two or more different diallylamines or 
copolymers containing at least one other copolymerizable monomer which is 
not a diallylamine can be used. Typically, the comonomer is a different 
diallylamine; a monoethylenically unsaturated compound containing a single 
vinyl or vinylidene group; or sulfur dioxide. Specific comonomers and 
specific copolymers are disclosed in U.S. Pat. No. 3,700,623. 
The epihalohydrin, preferably epichlorohydrin, is used in an amount ranging 
from about 0.5 mole to about 1.5 moles and preferably about 1 mole to 
about 1.5 moles per mole of secondary plus tertiary amine present in the 
polymer. 
Resin (c) can be prepared by reacting a homopolymer or copolymer of a 
diallylamine with epichlorohydrin at a temperature of from about 
30.degree. C. to about 80.degree. C. and preferably from about 40.degree. 
C. to about 60.degree. C. until the viscosity measured on a solution 
containing 20% to 30% solids at 25.degree. C. has reached a range of A to 
E and preferably about C to D on the Gardner-Holdt scale. The reaction is 
desirably carried out in aqueous solution to moderate the reaction, and at 
a pH of from about 7 to about 9.5. When the desired viscosity is reached, 
sufficient water is added to adjust the solids content of the resin 
solution to about 15% or less and the product cooled to room temperature 
(about 23.degree. C.). 
As prepared, aqueous solutions of poly(N-alkyldiallylamine)-epihalohydrin 
resins, such as poly(N-methyldiallylamine)-epichlorohydrin resin, contain 
epoxy groups which are reactive and thus the resins in solution have a 
tendency toward gelation. Stabilization against gelation is accomplished 
by adding to the aqueous resin solution sufficient water-soluble acid 
(such as hydrochloric acid and sulfuric acid) to obtain and maintain a 
solution pH of about 2. This acid treatment results in conversion of 
substantially all the reactive epoxy groups to unreactive halohydrin 
groups. 
The unreactive halohydrin groups are converted to reactive epoxy groups by 
the addition of a base, such as sodium hydroxide, in an amount sufficient 
to accomplish this conversion. This is within the skill of the art. See 
the teachings in U.S. Pat. No. 3,700,623. 
Methods of preparing water-soluble poly(diallylamine) polymers and 
water-soluble poly(diallylamine)-epihalohydrin resins are well known in 
the art. See U.S. Pat. No. 3,700,623 and Canadian Pat. No. 999,300. 
The following example illustrates the preparation of a water-soluble 
poly(diallylamine) polymer and a water-soluble 
poly(diallylamine)-epichlorohydrin resin which can be reacted with anionic 
starch to form a dispersing agent for use in this invention. 
EXAMPLE C 
1. An aqueous solution of poly(N-methyldiallylamine), a homopolymer, is 
prepared as follows. A solution of 69.1 parts of N-methyldiallylamine and 
197 parts of 20.degree. Be hydrochloric acid in 111.7 parts of 
demineralized water is sparged with nitrogen to remove air, then treated 
with 0.55 part of tertiary butyl hydroperoxide and a solution of 0.0036 
part of ferrous sulfate in 0.5 part of water. The resulting solution is 
allowed to polymerize at 60.degree.-69.degree. C. for 24 hours to give a 
polymer solution containing about 52.1% solids with an RSV of 0.22. The 
polymer, in aqueous solution, can be used as cationizing resin (d). 
2. A solution of poly(N-methyldiallylamine)-epichlorohydrin resin that can 
be used as cationizing resin (c) is prepared as follows. 122 parts of the 
above solution is adjusted to pH 8.5 by the addition of 95 parts of 3.8% 
aqueous sodium hydroxide and then diluted with 211 parts of water and 
combined with 60 parts of epichlorohydrin. The mixture is heated at 
45.degree.-55.degree. C. for 1.35 hours until the Gardner-Holdt viscosity 
of a sample cooled to 25.degree. C. reaches B+. The resulting solution is 
stabilized against gelation by adding 25 parts of 20.degree. Be 
hydrochloric acid and heating at 60.degree. C. until the pH of the 
solution remains constant at 2.0. The resulting resin solution has a 
solids content of 20.8% and a Brookfield viscosity of 77 cp. (measured 
using a Brookfield Model LVF Viscometer, No. 1 spindle at 60 r.p.m. with 
guard). 
Cationizing Resins (e) and (f) 
Cationizing resin (f) is a water-soluble poly(alkylenimine)-epihalohydrin 
resin derived by reacting an epihalohydrin, such as epichlorohydrin, with 
a water-soluble poly(alkylenimine) cationizing resin (e) such, for 
example, as poly(ethylenimine). Reaction with epihalohydrin is carried out 
in a manner similar to that employed in the preparation of water-soluble 
aminopolyamide-epichlorohydrin resin used as cationizing resin (a). 
In general, any poly(alkylenimine) having a molecular weight of at least 
about 1500 is operable for use in the present invention. The upper limit 
of the molecular weight is limited only by the solubility of the resin in 
water. Thus, resins having a molecular weight of 1,000,000 and higher may 
be used. 
The polymerization of alklenimines has been reviewed in Jones, "The 
Polymerization of Olefin Imines", in P. H. Plesch, ed., The Chemistry of 
Cationic Polymerization, New York, Macmillan (1963), pages 521-534. 
Suitable resins for the purpose of this invention are disclosed by Jones 
and include the polymers of ethylenimine, 2-methylethylenimine, 
2-ethylethylenimine, cis-2,3-dimethylethylenimine, 
trans-2,3-dimethylethylenimine, and 2,2-dimethylethylenimine. 
EXAMPLE D 
This example illustrates the preparation of fumaric acid fortified rosin. 
Fumaric acid, 8.5 parts, is adducted, at a temperature of about 
205.degree. C. with formaldehyde treated tall oil rosin, 91.5 parts. The 
fumaric acid dissolves in the fused tall oil rosin and reacts therewith to 
provide fumaric acid fortified tall oil rosin. After substantially all the 
fumaric acid has reacted with the tall oil rosin, the fortified rosin is 
cooled to room temperature (about 23.degree. C.). Substantially all the 
fumaric acid is in the combined or adducted form; that is, very little, if 
any, of the fumaric acid is present in the reaction mass in its free form. 
EXAMPLE E 
This example illustrates the preparation of fumaric acid fortified rosin. 
Fumaric acid, 14 parts, is adducted at a temperature of about 205.degree. 
C. with formaldehyde treated tall oil rosin, 86 parts. The fumaric acid 
dissolves in the fused tall oil rosin and reacts therewith to provide 
fumaric acid fortified tall oil rosin. After substantially all the fumaric 
acid has reacted with the tall oil rosin, the fortified rosin is cooled to 
room temperature (about 23.degree. C.). Substantially all the fumaric acid 
is in the combined or adducted form. 
EXAMPLE F 
This example illustrates the preparation of maleic anhydride fortified 
rosin. Formaldehyde treated tall oil rosin (3000 parts) was heated to 
150.degree. C. at which time 2.98 parts concentrated sulfuric acid was 
added followed by 261 parts maleic anhydride. Twenty minutes after the 
maleic anhydride was added, additional concentrated sulfuric acid (0.75 
part) was added, and 30 minutes after that, an additional 0.75 part 
sulfuric acid was added. Thirty minutes after that addition, the product 
was cooled to room temperature. Substantially all the maleic anhydride was 
in the combined or adducted form. 
Anionic Surface Active Agents 
As above set forth, one of the essential components of the composition of 
this invention is an anionic surface active agent. Anionic surface active 
agents are well known in the art. In carrying out this invention the 
preferred anionic surface active agent is a soap, such as the sodium soap, 
of a rosin-base material of which the dispersion is comprised. Other 
suitable anionic dispersing agents include salts of alkylaryl sulfonic 
acids, salts of condensed naphthalene sulfonic acids, salts of dialkyl 
esters of sulfosuccinic acid, salts of alkyl half esters of sulfuric acid, 
and salts of alkylphenoxy-(polyethyleneoxy)ethanol half esters of sulfuric 
acid. 
The rosin soap can be prepared separately and added to the composition or 
it can be formed in situ by addition of a base, such as sodium hydroxide, 
potassium hydroxide or ammonium hydroxide to the composition of which the 
fortified rosin is comprised. Sodium soap of fortified rosin is the 
preferred anionic surface active agent and it is preferred that it be 
formed in situ by addition of sodium hydroxide. This is exemplified in the 
working examples. 
In the case of the alkyl aryl sulfonates, the alkyl group may be linear or 
branched with ten to eighteen carbon atoms. Various mixtures of these 
alkylaryl sulfonates can be used. The preferred aryl group is phenyl. 
Sodium alkylbenzene sulfonates are available commercially. One 
commercially available product is Ultrawet DS. Ultrawet is a trademark of 
Arco Chemical Company. Condensed naphthalene sulfonic acid salts are 
products prepared by condensing formaldehyde with naphthylene followed by 
sulfonation with sulfuric acid and are available commercially. 
Commercially available products are Tamol SN and Stepantan A. Tamol is a 
trademark of Rohm & Haas Company and Stepantan is a trademark of Stepan 
Chemical Co. 
In the case of the salts of dialkyl esters of sulfosuccinic acids, the 
alkyl groups will include cyclohexyl, hexyl, isobutyl, octyl, pentyl and 
tridecyl. In the case of the salts of half alkyl esters of sulfuric acid, 
the alkyl group may have ten to eighteen carbon atoms. In the case of the 
salts of alkylphenoxy(polyethyleneoxy)ethanol half esters of sulfuric 
acid, the preferred alkyl group is the nonyl group obtained in propylene 
trimerization. The polyoxyethylene content can average from one to twenty 
moles per mole, but an average of four to twelve is preferred. 
The anionic starch is cooked prior to its use. Cooking may be by methods 
well known in the art. Cationization of the starch with the cationizing 
resin is accomplished either during the cooking of the starch or after the 
starch has been cooked. 
Thus, the starch can be cationized with the cationizing resin by adding the 
resin to the water in which the starch is to be cooked. The pH of the 
starch slurry in the thus formed aqueous solution, prior to cooking, 
should be between about 3 and about 10, preferably between about 5 and 
about 9. The starch-cationizing resin solution is then cooked or heated at 
a temperature of about 95.degree. C. to about 100.degree. C. for a period 
of about 10 minutes to about 30 minutes. 
As above set forth, the starch can be cooked first and the cationizing 
resin, in aqueous solution, added to the cooked starch solution, while hot 
or after cooling to room temperature, followed by pH adjustment as 
described above. To hasten reaction, the mixture can then be cooked if 
desired for about 10 minutes at about 95.degree. C. to 100.degree. C. 
Before addition of the cationizing resin to the starch solution, it may be 
desirable to subject the starch solution to high shear, as with an 
homogenizer, to break down any starch granules remaining after cooking or 
to reduce the viscosity of the starch solution or both. 
Applicable proportions for preparation of the cationized starches used in 
this invention are, by weight, about 99.5 parts starch (dry basis) and 
about 0.5 part cationizing resin (dry basis) to 90 parts starch and 10 
parts cationizing resin. Thus the range of proportions of starch to 
cationizing resin will be, by weight, about 99.5:0.5 to 90:10. 
EXAMPLE 1 
This example illustrates the preparation of a cationized starch dispersing 
agent and dispersions prepared therefrom. In this example, the anionic 
starch employed is available commercially as Amiogum 688 from American 
Maize Products Company. As sold, Amiogum 688 contains about 88% oxidized 
waxy maize starch and about 12% water. A 28% aqueous solution of the 
oxidized starch has a viscosity of about 4000 centipoises at 20.degree. C. 
after cooking or heating for 30 minutes at 95.degree.-100.degree. C. The 
oxidized waxy maize starch contains about 6.4 milliequivalents of carboxyl 
per 100 grams of starch. 
400 grams of Amiogum 688 (about 88% total solids) was blended with 3,500 
milliliters distilled water. The aqueous blend is adjusted to pH 7.0 with 
an aqueous solution of NaOH and subsequently cooked with stirring at 
95.degree. C.-100.degree. C. for 20 minutes. This solution was cooled to 
room temperature, adjusted to 4,000 grams total weight with distilled 
water and then homogenized two times at 3,000 p.s.i.g. in a 15 gal/hr. 
laboratory Manton-Gaulin homogenizer. The final solution has pH 5.8 and 
8.9% total solids. 
A second batch was prepared as above, except 600 grams starch was used 
which yields a product having a final total solids of 12.3% and pH 5.8. 
A blend of 1555 grams of the first solution and 2961 grams of the second 
solution was made to give a solution with 11.5% total solids. 2000 grams 
of this blend was mixed with 62 grams of Kymene 557H (12.5% total solids) 
and the mixture pH adjusted to 7.0 with aqueous sodium hydroxide. The 
blend was stirred and heated at 95.degree. C.-100.degree. C. for 10 
minutes. After cooling the blend was diluted to 3235 grams total with 
distilled water to give a final solution with 7.2% total solids and pH 
5.6. 
975 grams of fortified rosin was dissolved in 675 grams methylene chloride. 
The fortified rosin used was an 8.5% fumaric acid adduct of formaldehyde 
treated tall oil rosin. The solution was blended with a mixture of 870 
grams of the above prepared starch-cationic resin reaction product 
solution, 870 grams water, and 27 grams of a 4% aqueous sodium hydroxide. 
This blend was homogenized two times at 3000 p.s.i.g. and the homogenizate 
distilled to remove methylene chloride. The final emulsion had 35.7% total 
solids. Examination with a Coulter Counter apparatus for measuring 
particle size showed about 38% of the adducted rosin particles to be over 
0.4 micron in diameter. About 27% were between 0.4 and 1.0 micron. Thus, 
about 89% of the fortified rosin particles are 1 micron or smaller in 
diameter. 
EXAMPLE 2 
Using the method of Example 1, 2000 grams of the blend of the prepared 
starch solutions was mixed with 41 grams Kymene 557H (12.5% total solids) 
to give a solution with 7.3% total solids and pH 5.6. 
Again using the method of Example 1, 975 grams of fortified rosin, 
dissolved in 675 grams methylene chloride, was emulsified in 1305 grams of 
the above prepared cationized starch solution mixed with 435 grams 
distilled water and 36 grams 4% aqueous sodium hydroxide. The solvent 
stripped emulsion has 38.5% total solids. Examination with a Coulter 
Counter apparatus shows about 48% of the adducted rosin particles to be 
over 0.4 micron in diameter. About 29 are between 0.4 and 1 micron. Thus, 
about 81% of the adducted rosin particles are 1 micron and smaller. 
EXAMPLE 3 
The dispersions of Examples 1 and 2 were diluted to about 3% solids with 
demineralized water and used for sizing a 120 lb./3000 ft..sup.2 sheet of 
100% bleached kraft hardwood pulp refined to 500 CSF. Sizing was carried 
out with 0.3% size solids at tray pH 4.4-4.5 using 2.5% alum (percentage 
based on dry pulp). The finished sheets were tested for sizing using the 
Hercules size tester with 20% formic acid test solution. The following are 
the test values. The values are the average of five separate tests on the 
same sized sheet. These results show good sizing of the paper sheets. 
______________________________________ 
Example Hercules Size Test, Seconds 
______________________________________ 
1 132 
2 139 
______________________________________ 
EXAMPLE 4 
This example illustrates the preparation of cationized starch, cationized 
with aminopolyamide-epichlorohydrin cationizing resin. 331 grams Amiogum 
688 (about 88% solids, about 12% water) and 1600 grams water were placed 
in a vessel and stirred. During stirring, 72 grams of Kymene 557H (12.5% 
solids) was added to the contents of the vessel to provide an aqueous 
composition and the pH thereof was adjusted to 7.0 by addition of a 4% 
aqueous solution of NaOH. The aqueous composition was heated to 
95.degree.-100.degree. C. and maintained at this temperature for 30 
minutes. The resulting aqueous cationized starch composition was cooled to 
room temperature (about 23.degree. C.) and diluted with water to a solids 
content of 5.9%. 
EXAMPLE 5 
This example illustrates the preparation of a fortified rosin dispersion 
using as dispersing agent the cationized starch of Example 4. 975 grams of 
a fumaric acid fortified formaldehyde treated tall oil rosin (about 7.5% 
fumaric acid) was dissolved in 675 grams methylene chloride with stirring. 
1305 grams of the Example 4 aqueous cationized starch composition was 
further diluted with 435 grams of water followed by the addition of 36 
grams of a 4% aqueous solution of NaOH. This was added to the fortified 
rosin solution to provide a mixture which was stirred for 2 minutes and 
then homogenized 2 times at 3000 p.s.i.g. The resulting emulsion was 
stripped, under vacuum, to remove methylene chloride and to provide an 
aqueous dispersion of fortified rosin containing cationized starch 
dispersing agent, and the sodium soap of the fortified rosin (anionic 
surface active agent), which was formed in situ. 
The amount of material that precipitated during stripping was 9.6 grams. 
The resulting dispersion (2106 grams) had a solids content of 38.4% and a 
Brookfield viscosity of 84 centipoises. 
EXAMPLE 6 
Example 5 was repeated with the exception that the fortified rosin employed 
was a maleic anhydride adducted rosin prepared in accordance with Example 
F. 
The amount of material that precipitated during stripping was 1.1 grams. 
The resulting dispersion (2361 grams) had a solids content of 38.5% and a 
Brookfield viscosity of 78 centipoises. 
EXAMPLE 7 
This example illustrates the preparation of cationized potato starch, 
cationized with aminopolyamide-epichlorohydrin cationizing resin. 331 
grams potato starch (unmodified) and 2000 grams water were placed in a 
vessel and stirred. Potato starch contains phosphate groups and thus is 
anionic. Potato starch contains about 3 milliequivalents of phosphate per 
100 gram starch. During stirring, 72 grams of Kymene 557H (12.5% solids) 
was added to the contents of the vessel to provide an aqueous composition 
and the pH thereof was adjusted to 7.0 by addition of a 4% aqueous NaOH. 
The aqueous composition was heated to 95.degree.-100.degree. C. and 
maintained at this temperature for 30 minutes. The resulting aqueous 
cationized starch composition was cooled to room temperature and diluted 
with water to a solids content of 6.9%. 
EXAMPLE 8 
This example illustrates the preparation of a fortified rosin dispersion 
using as dispersing agent the cationized starch of Example 7. 975 grams of 
fumaric acid fortified formaldehyde treated tall oil rosin (about 7.5% 
fumaric acid) was dissolved in 675 grams methylene chloride with 
agitation. 1305 grams of the Example 7 aqueous cationized starch 
composition was further diluted with 435 grams of water followed by the 
addition of 36 grams of 4% aqueous NaOH. This was added to the fortified 
rosin solution to provide a mixture which was stirred for 2 minutes and 
then homogenized 2 times at 3000 p.s.i.g. The resulting emulsion was 
stripped, under vacuum, to remove methylene chloride and to provide an 
aqueous dispersion of fortified rosin containing cationized starch 
dispersing agent and anionic surface active agent (the sodium soap of the 
fortified rosin), which was formed in situ. 
The amount of material that precipitated during stripping was 3.7 grams. 
The resulting dispersion (2348 grams) had a solids content of 38.2%. 
EXAMPLE 9 
Example 7 was repeated with the exception that there was employed 344 grams 
oxidized corn starch in place of the 331 grams potato starch. The oxidized 
corn starch employed was Amaizo 540 available from American Maize Products 
and has about 8 milliequivalents of carboxyl per 100 grams starch. 
EXAMPLE 10 
This example illustrates the preparation of a fortified rosin dispersion 
using as dispersing agent the cationized starch of Example 9. 975 grams of 
fumaric acid fortified formaldehyde treated tall oil rosin (about 7.5% 
fumaric acid) was dissolved in 675 grams methylene chloride with 
agitation. 1305 grams of the Example 9 aqueous cationized starch 
composition was further diluted with 435 grams of water followed by the 
addition of 36 grams of 4% aqueous NaOH. This was added to the fortified 
rosin solution to provide a mixture which was stirred for 2 minutes and 
then homogenized 2 times at 3000 p.s.i.g. The resulting emulsion was 
stripped, under vacuum, to remove methylene chloride and to provide an 
aqueous dispersion of fortified rosin containing cationized starch 
dispersing agent and anionic surface active agent (the sodium soap of the 
fortified rosin), which was formed in situ. 
The amount of material that precipitated during stripping was not measured, 
but visual determination indicated a very small amount. The resulting 
dispersion (2274 grams) had a solids content of 38.2% and a Brookfield 
viscosity of 200 centipoises. 
EXAMPLE 11 
This example illustrates the preparation of cationized starch. 330 grams 
Amiogum 688 (about 88% solids, about 12% water) and 1800 grams water were 
placed in a vessel and stirred. During stirring, 24 grams of Kymene 557H 
(12.5% solids) was added to the contents of the vessel to provide an 
aqueous composition and the pH thereof was adjusted to 7.0 by addition of 
4% aqueous NaOH. The aqueous composition was heated to 
95.degree.-100.degree. C. and maintained at this temperature for 30 
minutes. The resulting aqueous cationized starch composition was cooled to 
room temperature and diluted with water to a solids content of 6.5%. 
EXAMPLE 12 
This example illustrates the preparation of a fortified rosin dispersion 
using the cationized starch of Example 11. 975 grams of fumaric acid 
fortified formaldehyde treated tall oil rosin (about 7.5% fumaric acid) 
was dissolved in 600 grams methylene chloride with agitation. 1468 grams 
of the Example 11 aqueous cationized starch composition was added to the 
fortified rosin solution to provide a mixture which was stirred for 2 
minutes and then homogenized 2 times at 3000 p.s.i.g. The resulting 
emulsion was stripped, under vacuum, to remove methylene chloride whereby 
there was provided an aqueous dispersion of fortified rosin. 
The amount of material that precipitated during stripping was 1.3 grams. 
The resulting dispersion (2045 grams) had a solids content of 42.9% and a 
Brookfield viscosity of 43 centipoises. 
EXAMPLE 13 
Each of the dispersions of Examples 5, 6, 8 and 10 was diluted to about 3% 
solids with demineralized water and used for sizing paper. Size (0.35% 
size solids on dry pulp) was added to 50:50 bleached kraft 
hardwood-bleached kraft softwood pulp containing 0.75% alum. Right after 
size addition, pH was 5.2-5.3 and total acidity was 44-50 parts per 
million. Paper sheets (120 lbs./3000 sq. ft.) were prepared from each 
size-pulp mixture on an experimental paper machine. Size properties were 
determined on five samples of each sheet using Hercules sizing tester 
employing 20% formic acid test solution. The following are the test 
results which are the average of the five separate tests. The size tests 
show good sizing. 
______________________________________ 
Hercules Size Test, 
Seconds (average of 
Example 5 separate tests) 
______________________________________ 
5 85 
6 92 
8 129 
10 121 
______________________________________ 
EXAMPLE 14 
The dispersion of Example 12 was diluted to about 3% solids with 
demineralized water and used to size paper. Size (0.35% size solids on dry 
pulp) was added to 100% bleached kraft hardwood pulp containing 0.7% alum. 
Right after size addition, pH was 5.3 and total acidity was 40-45 parts 
per million. A paper sheet (120 lbs./3000 sq. ft.) was prepared and size 
properties determined on five separate samples of the sheet as in Example 
13. The following tests results are the average of the five separate 
tests. The test shows good sizing. 
______________________________________ 
Hercules Size Test, 
Seconds (average of 
Example 5 separate tests) 
______________________________________ 
12 138 
______________________________________ 
EXAMPLE 15 
This example illustrates the preparation of a cationized starch using 
poly(N-methyldiallylamine)-epichlorohydrin which contains no epoxy groups 
as the cationizing resin. 185.1 grams Amiogum 688 (about 88% solids, about 
12% water) and 1105 grams water were placed in a vessel and stirred. 
During stirring, 25 grams of a 20.8% solution of 
poly(N-methyldiallylamine)-epichlorohydrin cationizing resin prepared as 
in Example C and stabilized against gelation as in Example C was added to 
the contents of the vessel. Sufficient 4% aqueous sodium hydroxide 
solution was added to provide a pH of 7. The aqueous composition was 
heated to 95.degree.-100.degree. C. and maintained at this temperature for 
30 minutes. The resulting aqueous cationized starch composition was cooled 
to room temperature and diluted with water to a solids content of 7.2%. 
The solution had a pH of 5.8. 
EXAMPLE 16 
This example illustrates the preparation of an aqueous fortified rosin 
dispersion using the cationized starch of Example 15. 487.5 grams of 
fumaric acid fortified formaldehyde treated tall oil rosin (about 7.5% 
fumaric acid) was dissolved in 300 grams methylene chloride with stirring. 
653 grams of the Example 15 aqueous cationized starch composition was 
further diluted with 217.5 grams of water followed by the addition of 6.8 
grams of 4% aqueous NaOH. This was then added to the fortified rosin 
solution to provide a mixture which was stirred for one minute and then 
homogenized 2 times at 3000 p.s.i.g. The resulting emulsion was stripped, 
under vacuum, to remove methylene chloride whereby there was provided an 
aqueous dispersion of fortified rosin containing cationized starch 
dispersing agent, and the sodium soap of the fortified rosin (anionic 
surface active agent) which was formed in situ. 
The amount of material that precipitated during stripping was 0.3 gram. The 
resulting dispersion had a solids content of 38.1% and a Brookfield 
viscosity of 67 centipoises. The average particle size of the dispersed 
particles, as determined by the Nano-Sizer apparatus for determining 
particle size, was 2.5 microns. 
EXAMPLE 17 
This example illustrates the preparation of cationized starch. 331 grams 
Amiogum 688 (about 88% solids, about 12% water) and 1800 grams water were 
placed in a vessel and stirred. During stirring, 72 grams of Kymene 557H 
(12.5% solids) was added to the contents of the vessel to provide an 
aqueous composition and the pH thereof was adjusted to 7.0 by addition of 
4% aqueous NaOH. The aqueous composition was heated to 
95.degree.-100.degree. C. and maintained at this temperature for 30 
minutes. The resulting aqueous cationized starch composition was cooled to 
room temperature (about 23.degree. C.) and diluted with water to a solids 
content of 5.9%. 
EXAMPLE 18 
This example illustrates the use of the cationized starch of Example 17 to 
prepare a fortified rosin dispersion. 325 grams of fumaric acid fortified 
formaldehyde treated tall oil rosin (about 7.5% fumaric acid) was 
dissolved in 225 grams methylene chloride with stirring. 435 grams of the 
Example 17 aqueous cationized starch composition was added to the 
fortified rosin solution followed by addition of 4.37 grams of 23% aqueous 
solution of Siponate DS4 anionic surface active agent to provide a mixture 
which was stirred for 1 minute and then homogenized 2 times at 3000 
p.s.i.g. The resulting emulsion was stripped, under vacuum, to remove 
methylene chloride whereby there was provided an aqueous dispersion of 
fortified rosin. Siponate DS4 is sodium dodecylbenzene sulfonate. Siponate 
is a trademark of Alcolac, Inc. 
The amount of material that precipitated during stripping was 0.5 gram. The 
resulting dispersion had a solids content of 43.5% and a Brookfield 
viscosity of 374 centipoises. Average particle size of the dispersed 
particles was about 1.3 microns as determined by the Nano-Sizer apparatus. 
EXAMPLE 19 
This example is similar to that of Example 18 using a different anionic 
surface active agent. 650 grams of fumaric acid fortified formaldehyde 
treated tall oil rosin (about 7.5% fumaric acid) was dissolved in 450 
grams methylene chloride with stirring. 861 grams of the Example 17 
aqueous cationized starch composition was added to the fortified rosin 
solution followed by addition of 23 grams of 30% aqueous solution of 
Duponol (SLS) anionic surface active agent to provide a mixture which was 
stirred for 2 minutes and then homogenized 2 times at 3000 p.s.i.g. The 
resulting emulsion was stripped, under vacuum, to remove methylene 
chloride whereby there was provided an aqueous dispersion of fortified 
rosin. Duponol (SLS) is sodium lauryl sulfate. Duponol is a trademark of 
E. I. duPont de Nemours & Co. 
The amount of material that precipitated during stripping was 13.1 grams. 
The resulting dispersion had a solids content of 46.0% and a Brookfield 
viscosity of 5400 centipoises. Average particle size determined, using the 
Nano-Sizer apparatus, was 0.75 micron. 
EXAMPLE 20 
Example 19 was repeated with the exception that 20.4 grams 58% aqueous 
solution of Alipal CO436 anionic surface active agent was used instead of 
23 grams of 30% Duponol (SLS) anionic surface active agent. Alipal CO436 
is the ammonium salt of sulfate ester of four mole ethylene oxide adduct 
of nonylphenol. Alipal is a trademark of GAF Corporation. 
The amount of material that precipitated during stripping was 0.3 gram. The 
resulting fortified rosin dispersion had a solids content of 45.2% and a 
Brookfield viscosity of 2640 centipoises. Average particle size was 0.6 
micron, determined using the Nano-Sizer apparatus. 
EXAMPLE 21 
This example illustrates the preparation of cationized starch, cationized 
with poly(ethylenimine) cationizing resin. 168 grams Amiogum 688 (about 
88% solids, about 12% water) and 1158 grams water were placed in a vessel, 
heated for 30 minutes at 95.degree.-100.degree. C. and then cooled to room 
temperature. 1.7 grams of poly(ethylenimine) having a molecular weight of 
about 50,000 (5.1 grams of a 33% aqueous solution) was added to the cooked 
starch and the pH of the resulting composition adjusted to 5.7 with 
sulfuric acid. The resulting aqueous cationized starch composition was 
diluted with water to a solids content of 7.3%. 
EXAMPLE 22 
This example illustrates the preparation of a fortified rosin dispersion 
using as dispersing agent the cationized starch of Example 21. 488 grams 
of a fumaric acid fortified formaldehyde treated tall oil rosin (about 
7.5% fumaric acid) was dissolved in 300 grams methylene chloride with 
stirring. 653 grams of the Example 21 aqueous cationized starch 
composition was further diluted with 218 grams of water followed by the 
addition of 7 grams of a 4% aqueous solution of NaOH. This was added to 
the fortified rosin solution to provide a mixture which was stirred for 1 
minute and then homogenized 2 times at 3000 p.s.i.g. The emulsion was 
stripped and the amount of material that precipitated during stripping was 
0.2 gram. The total solids of the emulsion was 38.7%, the Brookfield 
viscosity was 51 centipoises and the particle size as determined by the 
Nano-Sizer apparatus was about 2.1 microns. 
EXAMPLE 23 
This example illustrates the preparation of cationized starch, cationized 
with poly(ethylenimine) cationizing resin. 167 grams Amiogum 688 (about 
88% solids, about 12% water) and 1146 grams water were placed in a vessel, 
heated for 30 minutes at 95.degree.-100.degree. C. and then cooled to room 
temperature. 3.4 grams of poly(ethylenimine) having a molecular weight of 
about 50,000 (10.2 grams of a 33% aqueous solution) was added to the the 
cooked starch and the pH of the resulting composition adjusted to 5.8 with 
sulfuric acid. The resulting aqueous cationized starch composition was 
diluted with water to a solids content of 7.4%. 
EXAMPLE 24 
This example illustrates the preparation of a fortified rosin dispersion 
using as dispersing agent the cationized starch of Example 23. 488 grams 
of a fumaric acid fortified formaldehyde treated tall oil rosin (about 
7.5% fumaric acid) was dissolved in 300 grams methylene chloride with 
stirring. 653 grams of the Example 23 aqueous cationized starch 
composition was further diluted with 218 grams of water followed by the 
addition of 7 grams of a 4% aqueous solution of NaOH. This was added to 
the fortified rosin solution to provide a mixture which was stirred for 1 
minute and then homogenized 2 times at 3000 p.s.i.g. The emulsion was 
stripped to remove methylene chloride and the amount of material that 
precipitated during stripping was 0.3 gram. The total solids of the 
emulsion was 38.1%, the Brookfield viscosity was 37 centipoises and the 
particle size as determined by the Nano-Sizer apparatus was about 2 
microns. 
EXAMPLE 25 
This example illustrates the preparation of cationized starch, cationized 
with low molecular weight poly(ethylenimine) cationizing resin. 192 grams 
Amiogum 688 (about 88% solids, about 12% water) and 1160 grams water were 
placed in a vessel, heated for 30 minutes at 95.degree.-100.degree. C. and 
then diluted with water to give 2329 grams of 7.3% solution. To 1160 grams 
of this solution was added 0.8 gram of neat poly(ethylenimine) having a 
molecular weight of about 1800 and the pH was adjusted to 5.7 with 10% 
sulfuric Acid. 
EXAMPLE 26 
This example illustrates the preparation of a fortified rosin dispersion 
using as dispersing agent the cationized starch of Example 25. 437 grams 
of a fumaric acid fortified formaldehyde treated tall oil rosin (about 
7.5% fumaric acid) was dissolved in 300 grams methylene chloride with 
stirring. 652 grams of the Example 25 aqueous cationized starch 
composition was further diluted with 217 grams of water followed by the 
addition of 6.8 grams of a 4% aqueous solution of NaOH. This was added to 
the fortified rosin solution to provide a mixture which was stirred for 1 
minute and then homogenized 2 times at 3000 p.s.i.g. The emulsion was 
stripped to remove the methylene chloride and the amount of material that 
precipitated during stripping was 1.6 grams. The total solids of the 
emulsion was 37.1%, the Brookfield viscosity was 31.8 centipoises and the 
particle size as determined by the Nano-Sizer apparatus was about 2.2 
microns. 
Dispersing Agents (II) 
As above set forth, dispersing agent (II) is a starch, or modified starch, 
modified by reaction with a cationizing resin, the cationizing resin being 
a water-soluble polyamine resin containing epoxy groups. While the precise 
nature of the reaction of starch with the epoxy groups of the polyamine is 
not fully understood and the invention is not intended to be bound to any 
particular theory, it is believed to be one of covalent bonding resulting 
in formation of ether and ester linkages. In addition, there is the 
likelihood of some ionic bonding. 
Examples of cationizing resins are water-soluble 
poly(diallylamine)-epihalohydrin resins containing epoxy groups, which 
have been described hereinabove in connection with cationizing resin (c), 
and water-soluble aminopolyamide-epihalohydrin resins containing epoxy 
groups. 
Water-soluble aminopolyamide-epihalohydrin cationizing resins containing 
epoxy groups are well-known in the art as are their methods of 
preparation. The aminopolyamide moiety of the resin is prepared in the 
same manner as disclosed hereinabove with respect to cationizing resin 
(a). It is essential, however, that the aminopolyamide moiety contain 
tertiary amine groups in its chain. This can be accomplished by using as a 
starting alkylenepolyamine one that contains tertiary amines. Thus, in 
formula (I) above, R is alkyl. A specific example of such an amine is 
methyl bis(3-aminopropyl)amine. 
Also, the aminopolyamide moiety can be prepared from secondary amines and 
prior to reaction with an epihalohydrin, such as epichlorohydrin, reacted 
with an alkylating agent such as methyl chloride whereby the secondary 
amine nitrogens of the aminopolyamide are alkylated to tertiary amines. 
This is fully described above with reference to cationizing resin (a). 
The aminopolyamide-epihalohydrin resin (wherein the aminopolyamide moiety 
contains tertiary amine nitrogens) in aqueous solutions will contain 
halohydrin groups or epoxy groups, depending on solution pH. 
Adjustment of solution pH to provide epoxy groups is within the skill of 
the art and is fully described in U.S. Pat. No. 3,311,594, the disclosure 
of which is incorporated herein by reference. 
Unmodified or modified starch can be used to prepare dispersing agent (II). 
Unmodified starches include those described above and those modified as by 
oxidation, acetylation, chlorination, acid hydrolysis, ethylene oxide 
condensation, and enzymatic action. 
The following examples illustrate dispersing agents (II) and their use in 
preparing fortified rosin dispersions of this invention. 
EXAMPLE 27 
This example illustrates the preparation of cationized starch. 170 grams of 
a 3% aqueous solution of poly(N-methyldiallylamine)-epichlorohydrin resin 
containing epoxy groups (prepared as described in Example C and 
subsequently activated by addition of aqueous sodium hydroxide whereby the 
halohydrin groups are converted to epoxy groups) and 1004 grams water were 
placed in a reaction vessel. While stirring, 185.6 grams Ethylex 3030 
starch was added to the vessel to provide an aqueous composition and the 
pH thereof was adjusted to 7 with 10% HCl. The aqueous composition was 
heated to 95.degree.-100.degree. C. and maintained at this temperature for 
30 minutes. The resulting aqueous cationized starch composition was cooled 
to room temperature and diluted with water to a solids content of 7.2%. 
Ethylex 3030 starch, used in Example 27, as sold, contains about 88.9% 
ethoxylated corn starch and about 11.1% water. 
EXAMPLE 28 
This example illustrates the preparation of a fortified rosin dispersion 
using the cationized starch of Example 27. 487.5 grams of fumaric acid 
fortified formaldehyde treated tall oil rosin (about 7.5% fumaric acid) 
was dissolved in 300 grams methylene chloride with stirring. 652.5 grams 
of the aqueous cationized starch composition of Example 27 was further 
diluted with 217.5 grams water, followed by addition of 13.5 grams of 4% 
aqueous NaOH. This was added to the fortified rosin solution to provide a 
mixture which was stirred for 1 minute and homogenized 2 times at 3000 
p.s.i.g. The resulting emulsion was stripped, under vacuum, to remove 
methylene chloride and to provide an aqueous dispersion of fortified rosin 
containing the cationized starch as dispersing agent and as anionic 
surface active agent the sodium soap of the fortified rosin (formed in 
situ). 
The amount of material that precipitated during stripping was 11.9 grams. 
The dispersion had a solids content of 38.0% and a Brookfield viscosity of 
391 centipoises. Average particle size was 1.7 microns (Coulter Counter 
apparatus). 
EXAMPLE 29 
This example illustrates the preparation of cationized starch. 170 grams of 
a 3% aqueous solution of poly(N-methyldiallylamine)-epichlorohydrin resin 
containing epoxy groups, as used in Example 27, and 1005 grams water were 
placed in a reaction vessel. While stirring, 185.1 grams Amiogum 688 
starch was added to the vessel to provide an aqueous composition. The pH 
thereof was 9.4. The aqueous composition was heated to 
95.degree.-100.degree. C. and maintained at this temperature for 30 
minutes. The resulting aqueous cationized starch composition was cooled to 
room temperature and diluted with water to a solids content of 7.2%. and a 
pH of 7.3. 
EXAMPLE 30 
This example illustrates the preparation of a fortified rosin dispersion 
using the cationized starch of Example 29. 487.5 grams of fumaric acid 
fortified formaldehyde treated tall oil rosin (about 7.5% fumaric acid) 
was dissolved in 300 grams methylene chloride with stirring. 652.5 grams 
of the aqueous cationized starch composition of Example 29 was further 
diluted with 217.5 grams water, followed by addition of 13.5 grams of 4% 
aqueous NaOH. This was added to the fortified rosin solution to provide a 
mixture which was stirred for 1 minute and homogenized 2 times at 3000 
p.s.i.g. The resulting emulsion was stripped, under vacuum, to remove 
methylene chloride and to provide an aqueous dispersion of fortified 
rosin. The anion surface active agent in the dispersion is the sodium soap 
of the fortified rosin, formed in situ. 
The amount of material that precipitated during stripping was 0.5 gram. The 
dispersion had a solids content of 38.3% and a Brookfield viscosity of 140 
centipoises. Average particle size was 0.8 micron as determined by the 
Coulter Counter apparatus. 
EXAMPLE 31 
This example illustrates the preparation of cationized starch. 170 grams of 
a 3% aqueous solution of poly(N-methyldiallylamine)-epichlorohydrin resin 
containing epoxy groups, as used in Example 27, and 1004 grams water were 
placed in a reaction vessel. While stirring, 330 grams Amiogum 688 starch 
was added to the vessel to provide an aqueous composition and the pH 
thereof was adjusted to 7.5. The aqueous composition was heated to 
95.degree.-100.degree. C. and maintained at this temperature for 30 
minutes. The resulting aqueous cationized starch composition was cooled to 
room temperature and diluted with water to a solids content of 7.3%. 
EXAMPLE 32 
This example illustrates the preparation of a fortified rosin dispersion 
using the cationized starch of Example 31. 975 grams of fumaric acid 
fortified formaldehyde treated tall oil rosin (about 7.5% fumaric acid) 
was dissolved in 600 grams methylene chloride with stirring. 1305 grams of 
the aqueous cationized starch composition of Example 31 was mixed with 435 
grams water and 5 grams of 4% aqueous NaOH. This was added to the 
fortified rosin solution to provide a mixture which was stirred for 2 
minutes and homogenized 2 times at 3000 p.s.i.g. The resulting emulsion 
was stripped, under vacuum, to remove methylene chloride and to provide an 
aqueous dispersion of fortified rosin. The anionic aurface active agent in 
this dispersion is the sodium soap of the fortified rosin, formed in situ. 
The amount of material that precipitated during stripping was 0.6 gram. The 
dispersion (1833 grams) had a solids content of 36.3% and a Brookfield 
viscosity of 391 centipoises. 
The fortified rosin dispersions of this invention have outstanding 
stability. When commercially available high free fortified rosin 
dispersions are allowed to stand undisturbed in a container, there is a 
tendency for the fortified rosin particles to agglomerate and settle to 
the bottom where further agglomeration can cause a hard layer of fortified 
rosin particles to form. This problem can be particularly severe if 
storage is at elevated temperature (35.degree.-40.degree. C.) such as can 
be found in some paper mills. There is very little agglomeration and 
settling in the dispersions of this invention. When settling does occur 
because some of the particles are too large to remain suspended by 
Brownian motion, the particles are easily redispersed with gentle 
agitation. 
The dispersions of this invention also have high shear stability. When 
commercially available high free fortified rosin dispersions are pumped 
through screens to remove particles formed by surface drying or other 
agglomeration, there is a tendency for the screens to fill, not so much 
with these large particles, but by buildup of fortified rosin particles 
due to the shear forces on the screen wires. This problem can be very 
severe at 35.degree. C. to 40.degree. C. The dispersions of this invention 
resist this kind of shear degradation. 
Dried spills of the dispersions of this invention are usually easy to clean 
up. Warm water and mild abrasion, as with a brush, will clean dried 
spills. Cleanup of dried spills of commercially available high free 
fortified rosin dispersions requires strong caustic or an organic solvent 
such as methanol or xylene for removal of the fortified rosin. This is an 
indication of less agglomeration on drying.