CA2261954A1 - Hydrophobically modified resin compositions and uses thereof - Google Patents

Abstract

Resin compositions that are the reaction product of epihalohydrin and hydrophobically modified aminoamide obtained by the reaction of: (a) aminoamide containing at least one primary amine group and at least one secondary and/or tertiary amine groups, the aminoamide being obtained by reaction of polyamine containing at least two primary amine groups and at least one secondary and/or tertiary amine group, with dicarboxylic acid or derivatives thereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivative thereof, is greater than about 1.4:1, and, (b) hydrophobizing agent having from about 12 to about 40 carbon atoms, wherein the amount of hydrophobizing agent employed is sufficient to react with at least a portion of the primary amine groups, but insufficient to react with more than about 60 % of the secondary and/or tertiary amine groups of the aminoamide. Also disclosed are uses of the compositions in the treatment of paper, particularly the sizing of paper.

Description

W O 98/39376 PCT/U~.3~ 3'.58 HYDROPHOBICALLY MODIFIED RESIN
COMPO,~ITIONS Al~D U~E~ T~F.~F,OF
~ield of the Invention This invention relates to hydrophobically modified epihalohydrin-5 aminoarnide resins and ~eir uses.

I'~ack~round of the Invention A variety of materials has been used in the paper m~king art for surface sizing paper. These include alkyl ketene dimers, styrene-maleic anhydride (SMA) polymers, and epichlorohydrin-modified bis-stearamides. Each of these 10 has serious deficiencies in use. For example, both the alkyl ketene dimers and the bis-stearamides significantly lower the coefficient of friction of paper when applied to the surface. This adversely affects the performance of the paper in high speed converting operations. Moreover, the bis-stearamides have a negative effect on the tensile properties of the paper. SMA solution polymers 15 are foamy, can be supplied only at low solids, and give only limited sizing in some grades. Moreover, SMA polyrners are inef~ective when applied over paper that does not have intemal sizing~
The materials of the present invention do not cause deterioration of the tensile ~JI opc. lies of the papcr to which they are applied, nor do they causc a 20 si~nificant reduction in coef~lcient of friction. Thcy also do not foa n excessively and are hi~hly effective sizing agents, even when applied over paper that does not have internal sizing.
U.S. Patent No. 3,922,243 to Aldrich et al. discloses water-insoluble, water-dispersible thermosetting cationic resins derived by reaction of a water-25 soluble aminopolyamide, a hydrophobizing compound and an epihalohydrin.The aminopolyan~ide contains secondary amine groups and is prepared using a mole ratio of polyaLkylene polyamine to dicarboxylic acid from about 0.9 to W O 98/3g376 PCT~US98/033S8 about 1.2. The amount of hydrophobizing agent is in~llffiçient to react wi~
more than about 50% of the secondary amine groups of the aminopolyamide.
U.S. Patents 3,923,745, 3,968,317 and 3,992,345 to Dumas disclose water-insoluble, water-dispersible thermosetting cationic resins derived by S reaction of a diallylamine polymer, a hydrophobizing compound and epihalohydrin.

~ummary of the lnvention A resin composition comprises the reaction product of epihalohydrin and hydrophobically modified aminoamide obtained by the reaction of:
(a) aminoarnide containin~ at least one primary amine group and at least one non-primary amine group selected from the group consisting of secondary and tertiary amine groups, the arninoamide being obtained by reaction of an .
amlne composltlon comprlsmg polyamme contamlng at least two pnmary an~ine groups and at least one amine group selected from the group consisbng lS of secondary and terhary amine groups, with dicarboxylic acid or derivatives thereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivabve thereof, is greater than about 1.4:1, and, (b) hydrophobizing agent having from about l2 to about 40 carbon atoms, wherein the amount of hydrophobizing agent employed is sufficient to 20 react with at least a portion of the primaly amine groups, but insufficient to react with more than about 60% of the non-primary a,mine groups.
A method for making the resin composition comprises: a) reacbng an .
amme composlbon compnsln~ polyamlne contalnlng at least two pnmary amine groups and at least one amine group selected from the group consisting 25 of secondary and tertiary amine groups with dicarboxylic acid, or derivativesthereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivativethereof is greater than about 1.4:1, to form aminoamide cont~inin~ at least one primary amine group and at least one non-prirnary amine group selected from ~e group consisting of secondary and ter~ary amine groups;

W O 98139376 PCTrUS98/03358 b) reacting ~e aminoamide with hydrophobizing agent having from about 12 to about 40 carbon atoms to form hydrophobically modified aminoamide, wherein the arnount of hydrophobizing agent employed is sufficient to S react with at least a portion of the primary amine groups, but incllfficient to react with more than about 60% of the non-primary amine groups of the Pminosmide; and c) reacting the hydrophobically modifled aminoamide with epihalohydrin.
A method for sizin~ paper comprises adding to the surface of paper sheet an aqueous suspension of the resin composition. Another method for sizing paper comprises the steps of (a) providing an aqueous pulp suspension;
(b) adding to the aqueous pulp suspension an aqueous suspension of the resin composltlon;
15 (c) forming the pulp into a sheet; and (d) drying the sheet to obtain sized paper.

netailed nescriDtion of the lnvention The aminoamides used in prepanng the resin compositions are derived by reaction of dicarboxylic acid or derivatives thereof, and polyamine containin~ at least two primary amine ~roups and one or more secondary or 20 tertiary amine groups. Dicarboxylic acid derivatives suitable for preparing the ~ntinos~ides include esters, anhydrides and acid halides.
Dicarboxylic acids for use in preparing the arninoarnides include gliphstiC, alicyclic or aromatic dicarboxylic acids, or their derivatives, contsinin~e from 2 to about 44 carbon atoms. Preferably the dicarboxylic acids 25 are selected from the group consisting of oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid, diglycolic acid, C36-C44 dimer acids, aLkenyl succinic acids and alkyl succinic acids. More p.cr~lably, ~e dicarboxylic acids are adipic acid and aL~cenyl succinic acids.

W 098/39376 PCT~US98/03358 ~1_ C36-C44 dimer acids are derived by dimerizing or polymerizing naturally occurring lm.c~tllrated fatty acids and are available as EMPOL~9 dimer acid, from Henkel-Emery, Cincinnati, Ohio. Alkenyl succinic acids, or anhydrides, are available by reaction of maleic anhydride with straight chain or br~n 5 olefins, and have the following general structures I and Il ~0 _~COOH
R ~O R COOH

(I) (Il) wherein R' is a straight chain or branched, llnc~tllrated alkyl radical hav ng from about 8 to about 22 carbon atoms, preferably from about 16 to about 22 10 carbon atoms. Alkyl succinic acids or anhydrides may be prepared by hydrogenation of the corresponding alkenyl succinic acid or anhydride.
Specific examples of anhydrides of formula I are isooctadecenyl succinic anhydride, n-oct~decenyl succinic anhydride, n-hex~-lecenyl succinic anhydride, n-dodecyl succinic anhydride, i-dodecenyl succinic anhydride, n-15 decenyl s~ccinic anhydride,n-octenyl succinic anhydride, and isobutylene oligomers succinic anhydride.
The corresponding acids of formula ll are derivable from ~e anhydrides by hydrolysis.
Preferably, at least 50 mole % of the amine composition used for 20 reaction with the dicarboxylic acid will be polyamine containing at least twoprimary amine groups and one or more secondary or tertiary amine groups.
P~efelled polyamines are N-alkyl bis(3-aminopropylamine), wherein the N-alkyl group is an alkyl group cont~ining from 1 to about 12 carbon atoms, and polyaLkylene polyamines c~ two primary amine groups and at least one W O 98/39376 PCTrUS98/03358 secondary arnine group where the nitrogen atoms are linked together by groups of the formula -CnH2n-, where n is from 2 to 6.
Preferred polyalkylene polyamines include polyethylenepolyamines, polypropylenepolyamines and polybutylenepolyA~ .es.
5 Polyethylenepoly~mines are more preferred. The most preferred polyethylenepoly~mines for use in this invention are diethylenetri~mine7 triethylenete~ e or tetraethylenepent~mine. The most preferred is diethylenetriamine.
The preferred N-alkyl bis(3-aminopropylamine) is N-methyl bis(3-1 0 aminopropylamine).
ln addition to the polyamine contAinin~ at least two primary an~inegroups and one or more secondary or tertiary amine groups, the amine composition used for reaction with the dicarboxylic acid may contain other diamines, preferably those having the forrnulas III, IV and V.
H2N-(CH2)x-NHz~
(III) H2N-CH-CH2[0-CH2CH]y~NH2 C~13 CH3 (IV) CH3 CH3 CH, H2N-cH-cH2-[ocHcH2-].-[ocH2cH2-]b-[ocH2cH-]c-NH2 (V) wherein x is an integer f~om 2 to about 10, y is an integer firom 2 to about 100, b is an integer ~om 2 to about 100, and a and c, which can be the same or e~ are integers firom 0 to about 5.

.

Exemplary ~i~mines of formula III are ethylene ~ mine propylene min~, and hexarnethylene ~ mine. Materials corresponding to formulas IV
are available as Jel~ e~)D-230, D-400, D-2000 and D-4000 from H-~ntcm~n Corporation, Houston, Texas. Materials corresponding to formula V are available as Jel~-.. ;.. Pq~)ED-600, ED-900 and ED-2001 from H~
Corporation.
ep~illg the ~mino~mides the arnine composition is used in substantial molar excess over dicarboxylic acid. The aminoamides that result contain substantial quantities of primary amine groups, and are oligomeric, i.e., 10 contain from about I to about 6 repeating units. ln order to achieve these properties, the molar ratio of polyamine to dicarboxylic acid is greater than sbout 1.4 to l. Preferably, the molar ratios is from about 1.5 to I to about 3 to 1, more preferably from about 1.55 to I to about 2.5 to l, and most preferably from about 1.6 to I to about 2 to l.
Temperatures employed for carrying out the reaction between dicarboxylic acid and amine can vary from about 110~C to about 250~C or higher, at atmospheric pressure. Temperatures between about 160~C and 210~C
are preferred. Where re~uce-l pressures are employed, lower tempe.~lu,es can l)tili7PA. as is well known in the art. Reaction time will usually vary from 20 about 1/2 to about 2 hours, although shorter or longer reaction times can be u~li7~1 depending on reaction conditions. Reaction times vary inversely with tC.ll~)C~ at~lre.
In preparing the novel resin compositions of this invention, the ~mino~mide is reacted with at least one compound, referred to hereinafter as a 2S "hydrophobizing agent", to form a hydrophobically modified, substantially water-insoluble aminoamide. Hydrophobizing agents are compounds having from about 12 to about 40 carbon atoms that will react with the prirnary and secondary amine groups of the alminoamide to form subct~n~i~lly water-insoluble compounds. Suitable hydrophobizing agents include, e.g., acids, 30 anhydrides, acid halides, esters and isocyanates.

W 0 98139376 PCT/U~&~'~3358 The amount of hydrophobizing agent will be that amount sufflcient to react with at least a portion of the prirnary amine groups, but insufficient to react with more than about 60% of the non-primary amine groups of the ~rninoqlnide. Preferably the amount of hydrophobizing agent will be sufficient 5 to react with at least about 20% of the primary amine groups, but insufficient to react with more about 30% of the non-primary a~une groups. More preferably the amount of hydrophobizing agent will be sufficient to react with at least 20%of the primary amine groups, but insufficient to react with more than about 10% of the non-primary amine groups.
Examples of ~,efe.,ed hydrophobizing agents are: a) monocarboxylic acids or derivatives thereof, of the formula RCOOH, where the R group is alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl; b) substituted succinic anhydrides of formula I
o ~0 R' S
o 1 5 (I) where R' is alkyl, alkenyl, cycloalkenyl, aralkyl or aralkenyl groups containingfrom about 8 to about 22 carbon atoms; and c) ketene dimer or multimer of structure Vl R~R'~R"

(VI) where n is an integer of 0 to about 20, R and R", which may be the same or di~elent, are saturated or lln~tllrated straight chain or branched aLkyl groups W O 98/39376 PCT~US98/03358 having 8 to 24 carbon atoms, and R' is a satu,~led or lm.c~tllrated straight chain or branched alkyl group having from about 5 to about 40 carbon atoms.
Suitable derivatives of the carboxylic acids RCOOH include esters, anhydrides, acyl halides and isocyanates. With respect to the group of ketene dimers and 5 mlllhmers of formula VI, ketene dimers are preferred. The most preferred hydrophobizing agents are subsht~te~ succinic anhydrides of formula I.
Specific examples of the monocarboxylic acids or derivatives thereof, of the formula RCOOH that can be used are rosin acid, myristic acid, palmitic acid, oleic acid and stearic acid.
Specific examples of the anhydrides of formula I are isooct~-lPcenyl succinic anhydride, n-oct~-lecenyl succinic anhydride, n-hex~d~cenyl succinic anhydride, n-dodecyl succinic anhydride, i-dodecenyl succinic anhydride, n-decenyl succinic anhydride and n-octenyl succinic anhydride.
Ketene dimers for use in the process of this invention have the structure 15 of formula Vl where n=0 and the R and R" groups, which can be the same or different, are hydrocarbon radicals. Preferably the R and R" groups are aIkyl oralkenyl groups having at least 6 carbon atoms, cycloalkyl groups having at least6 carbon atoms, aryl having at least 6 carbon atoms, aralkyl having at least 8 carbon atoms, alkaryl having at least 10 carbon atoms, and mixtures thereof.
20 More preferably ketene dimer is selected from the group consicting of (a) octyl, decyl, dodecyl, tetradecyl, hex~decyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, p-naphthyl, and cyclohexyl ketene dimers. and (b) ketene dimers prepared from organic acids selected from the group consisting of montanic acid, naphthenic acid, 9,10-decylenic acid, 9,10-dodecylenic acid, 25 p~lmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, eleostearic acid, naturally occurring mixtures of fatty acids found in coconut oil, babassu oil, palrn kernel oil, palm oil, olive oil, peanut oil, rape oil, beef tallow, lard, whale blubber, and mixture of any of the above named fatty acids with each other.
Most ~refelably ketene dimer is selected from the group conci.ctin~ of octyl, CA 022619F,4 1999-01-29 decyl, dodecyl, tetladecyl, h~(lecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, ~-naphthyl, and cyclohexyl ketene dimers.
Suitable ketene dimers are disclosed in U.S. Patent No. 4,279,794, in United Kingdom Patent Nos. 903,416; 1,373,788 and 1,533,434, and in European Patent Application Publication No. 0666368 A3.
Ketene dimers are commercially available, as Aquapel~ and Precis~9 sizing agents from Hercules Incorporated, Wilmin~ton, Delaware. Preferred are Aquapel~)364 and Precis 787~) sizing agents.
Ketene multimers for use in the process of this invention have the formula Vl where n is an integer of at least 1, R and R", which may be the same or different, are saturated or llnc~ rated straight chain or branched alkylgroups having 8 to 24 carbon atoms, preferably 14 or 16 carbon atoms; and R' is a saturated or Imc~h~rated straight chain or branched alkyl group having fromabout 5 to about 40 carbon atoms, preferably 5 to about 20 carbon atoms.
Ketene multimers are described in: European Patent Application Publication No. 0629741AI, European Patent Application Publication No.
0666368A3 and U.S. Patent No. 5,685,815 The reaction of aminoamide and hydrophobizing agent can be carried out neat or in solvent. Il is carricd out under relatively mild conditions such that essentially the only reaction taking place is the reaction of the hydrophobizin~g a~ent with the primaly and secondary (if present) an~ine, whereby the amines arc convertcd in~o ~mi~eS. ureas, p-ketoamides, imirl~7~1ines, or ~-amidoacids, depending on the specific hydrophobizing agent and reaction conditions utilized. Thus the aminoarnide and hydrophobizin~
agent are reacted under atmospheric or higher pressure at a reaction temperature of from about 0~C to about 250~C to produce a reaction product that is es~çnti~lly water-insoluble. When the hydrophobizing agent is a sul)sliluled succinic anhydride of formula I, it is panticularly convenient to carry out the reaction in the absence of solvent, and it has been found that therelatively mild temperature conditions of 100~-150~C are suitable. Reaction of W O 98/39376 PCTrUS98/03358 substituted succinic anhydrides with primary amine may lead to the formation of cyclic imide under sufficiently high temperalu,es.
The reaction of epihalohydrin, preferably epichlorohydrin, with the water-insoluble reaction product of aminoamide and hydrophobizing agent yields a cationic, hydrophobically modified resin. The reaction with epihalohydrin occurs at the amine groups of the hydrophobically modified q-nino~mide. It is believed that tertizry anunes react with epihalohydrin by initial opening, then reclosure of the epoxide ring with expulsion of the halideion, to form a glycidyl (2,3-epoxypropyl) ammonium salt; secondary ~minPs react with epihalohydrin to form tertiary aminohalohydrins, which cyclize to form reactive 3-hydroxy-azetidinium salts; and primary amine groups react to form a halohydroxypropyl-substituted secol ~ry amine, which can then react with a second mole of epihalohydrin as described above for secondary amines.
The reaction with epihalohydrin may be canied out in aqueous medium or in solvent. Suitable solvents include: alcohols, e.~., methanol, ethanol, propanol, isopropanol and butanol; benzene; toluene, and the like. Mixtures of two or more solvents can be used if desired. It is to be understood that the solvent employed is non-reactive with the reactants or the reaction product under the reaction conditions.
The reaction with epihalohydrin is carried out at a temperature of from about 0~C to about 100~C, prefcrably from about 20~C to about 40~C, for a period of time of from about 1/2 hour to about 3 hours (time varies inversely with temperature). The arnount of epihalohydrin used will be that amount sufficient to react with at least 40%, preferably at least 70%, and most preferably at least 90% of the arnine groups present in the hydrophobically modified aminoamide. The epihalohydrin-reacted composition may be crosslinked by further heating at a temperature of from about 40~C to about 90~C. The solids level of t~e hydrophobized aminoamide is preferably from about 5% to about 50%.

W O 98/39376 PcTlu'',J~l~w358 If the reaction with epihalohydrin is carried out in aqueous medium, the hydrophobized aminoamide may be provided to the reaction as an aqueous dispersion. When the reaction of hydrophobizing agent with ~mino~mide is carried out molten, such dispersions are readily ~Jrel~a(ed by adding water to the molten reaction product under agitation. Further dispersion may be accomplished by homogeni7~tion.
If reaction with epihalohydrin is to be carried out in solvent, the neat hydrophobized ~mino?mide can be dissolved in the a~)p~ol.liate solvent prior to the reaction with epihalohydrin. Alternatively, if the hydrophobized aminoamide is prepared in solvent, the product solution may be used for the epihalohydrin reaction directly. Water may be added to the reaction rnixture before, during, or after addition of the epihalohydrin.
When water is employed as the reaction medium for carrying out the epihalohydrin reaction, the reaction product (which is a thermosettable cationicresin) in its aqueous reaction medium can be homogenized if necess~ry to reduce the particle size of the solids. Subsequently, the pH of the dispersion may be adjusted to pH of from about 2.5 to about 8 to provide for optimum stability of the dispersion. In this way stable dispersions having a solids content of from about 5% to about 50% can be ~ie~,~ed.
When the reaction with epihalohydrin is carried out in a solvent other than water, aqueous dispersions of the product can be prepared by the followinL~, procedure. The solution of the reaction product is dispersed in water with vigorous agitation such as, for example, by homogeni7~tion at pressures of from about 1,000 to 5,000 p.s.i., to provide an aqueous emulsion that is essenti~lly stable. Subsequently, the organic solvent is removed by distillation, either under atmospheric pressure or under vacuum, to provide a stable aqueous dispersion of the reaction product.
The resin compositions of this invention, generally as aqueous dispersions, may be used in ~e m~m-facture of paper and other fibrous substrates. Preferably, they are used in the m~m~f~cture of surface treated ~ . , . . . , ~ ... .. .. .

W O 98/39376 PCT/u'~8~33s8 paper, particularly surface sized paper by applicqtion to the surface of the paper after sheet formation, generally at a size press. They may also be incorporated into a pulp sluny at the wet end of a paper machine to provide sizing or other plope.lies such as, for example, improved pitch dispersion, deposit control, 5 sheet bulk, sheet softness, and size promotion. The amount of resin employed for the sizing of paper will usually be from about 0.05% to about 2% based on the weight of the dly pulp fibers.
After incorporation of the resin compositions of this invention into the paper, either by incorporation into the pulp slurry or by addition to the surface, 10 the resins are cured to a thermoset state by application of heat. Generally the hPvhn~ will take place during drying of the paper sheet at tempe.atules of from about 85~C to about 125~C for periods of from about 5 seconds to about 60 seCor~c ln actual practice, the conventional dmm drying of the treated paper sheet will provide for sufficient curing of the resin.
This invention is illustrated by the following examples, which are exemplary only and not intended to be limiting. All pelc~ a~es, parts, etc., areby weight, based on the weight of the dry pulp, unless otherwise indicated.

F.s~mDle I
This exarnple illustrates the ~-ep~ation of an qminoqmide from adipic 20 scid and diethylenetriamine and its rcaction with the hydrophobizin~ a~ent hexq-~ecenylsuccinic anhydride.
Adipic acid, 131.5 g (0.9 moles) was added to diethylenetrian~ine, IS4.
g (1.5 moles) in a stirred reaction vessel. The mixture was brought to 170~C
and held for 3 hours while the water of con~enstqtion was removed by 25 ~i~tillqtion. The molten arnino~mide was then cooled to 120~C . Using the assum~,tion that all of the carboxyl groups reacted with primary amine, it is calc~ l~te~l that the product contained 1.5 equivalents of secondary amine and 1.2 equivalents of plima~y amine in 254 g.
-W O 98/39376 PCT~US98/03358 To the entire amount of the aminoamide at 120~C was added 195.6 g (0.6 moles) of predQmin~tely hex~-lecenylsuccinic anhydride (ASA 100, obtained from Dixie Chemical Comp~ny, Houston, Texas), cont~inin~ 95-98%
C~6 succinic anhydride, the remainder be;ng a mixture of higher alkenyl succinic anhydrides . The temp_rature was m~int~ined at 124~C for 2 hours.
The product after cooling had an acid number of 25 mg KOH/g and an amine number of 4.05 meq/g (equating to an amine equivalent weight of 247).

FxamDle 2 This example describes the preparation of a crosslin'ked hydrophobically modified cationic resin composition by reaction of epichlorohydrin with the hydrophobically modified aminoamide ~re~,ared in Example 1.
The aminoamide of Example 1 (98.5 g, 0.40 equivalents of amine) was crushed and dispersed in 281 g of water. Epichlorohydrin (43.2 ~, 0.47 moles) was then slowly added to the dispersion while the temperature was maintained at below about 40~C. The resultin~ reaction mixture was then stirred for 30 minllteS at 40~C and then crosslinlced by he~in~ at 85~C for 2 hows. The crosstinlrecl resin was homo~enized hot usin,g a laboratory homo~enizer, and then cooled to room te."pelature. The product cont~ined 19.1% total solids~
had pH 5.02 and particle size of 0.50 microns. lt conî~ined 0.70% 1,3-dichloro~)ropan-2-ol, 0.19% 2,3-ChlOrO~)lOpanediOI~ and less than 0.01%
residual epichlorohydrin.

~.xample 3 This example describes the plepa~tion of a crosslinked, hydrophobically modifled cationic resin composition by reaction of epichlorohydrin with the hydrophobically modified aminoamide prepared in Example 1 in an orgarlic solvent.

....

The hydrophobically modified aminoamide of Example 1 (97.6 g, 0.39 equivalents of amine) was crushed and dissolved in a llliA~ of toluene (440 g) and ethanol (496 g). Deionized water (468 g) was added to the solution of aminoamide to form a dispersion.. Epichlorohydrin (43.4 g, 0.47 moles) was 5 then slowly added to the dispersion while the tempe~alu~e was m~int~ined at below about 40~C. The resulting reaction mixture was then stirred for 2 hours at 40~C and then crosslinke-l by he~tin~ to reflux at 75~C for 2 hours. The crosslinked resin was cooled to 20~C, further dilu~ed with water (1180 g), blended and homo~eni7ed using a laboratory homo~eni7~r. The solvent was removed by distillation. The product cont~ine~l 10.8% total solids, had pH 6.6 and particle size 0.047 microns. It contained 0.48% 1,3-dichlorol)lopa"-2-ol, 0.12% 2,3-chloro~rol)anediol, and less than 0.01% residual epichlorohydrin.

Fxample 4 This example illustrates preparation of an aminoamide from adipic acid and diethylenetriamine modified by reaction with the hydrophobizing agent hexadecenylsuccinic anhydride.
Adipic acid (65.77 g, 0.45 mo!es) was added to diethylenetriamine (77.35 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to 170~C and held at this temperature for 3 hours while the water of conclenc~tion w8s removed by distillation. The molten product was cooled to 123~C, and then there was added 97.8 g (0.3 moles) of hex~decenylr~ccinic anhydride (Accosize~)18, from Cytek lndustries, West Patterson, New Jersey), The resl-l~-n~ mixture was held at 125~C for 1 hour, at 146~C for 1 hour, and then quenched by addition of water. The product arninoamide had an amine number of 4.51 meq/g (amine equivalent weight, 222) and acid number of 38. The molecular weight determined by SEC was 756 number average and 1468 weight average. The product was diluted with enough water to produce a dispersion with 23.3% solids as me~cl~red in a 150~C oven. The dispersion had a pH of 10.2.

CA 0226l954 l999-0l-29 W O 98/39376 PCT~US98/03358 ~,Y~nQ~le 5 A crosslinl~e~l hydrophobically modified cationic resin composition was l.~pal ed from the hydrophobically modified arninoamide of F.x~mple 4. The dispersed hydrophobically modified aminoamide (12S.4 g, 29.2 g solids, 0.13 S amine equivalents) was blended with 65.1 g of water. Epichlorohydrin ( 11.1 g,0.12 moles) was slowly added while keeping the ~e.~ e'ature below 40~C. The resulting reaction rnixture was stirred for 30 minl~tes at 40~C and then crosslinked by heating at 65~C for 2 hours, after which it was quenched and diluted by adding enough water to bring the mixture to about 15% solids.
10The product was divided into two portions. The first was homo~eni7Pd using a laboratory homogenizer at room temperature. The second had no further treatment. The product from the first part had 15.1% solids, pH 5.4 and particle size 0.13 microns. The product of the second part had 15.1% solids, pH 5.4, particle size 0.15 microns and contained 0.16% 1,3-dichlorG~Iopan-2-15ol, 0.07% Z,3-chloropropanediol and less than 0.01% residual epichlorohydrin.
Potassium sorbate (0.1%) was added to both portions as a biocide.

F.xam~le 6 This example demonstrates the surface sizin~ efficiency of products of Exarnples 2 and 3 of this invention compared to conventional commercial 20 sizing a~ents.
Waterleaf paper was prepared on a trial paper In~chine at a basis wei~ht of 64.9 k~~ tl.000 m2 from a 50:S0 blend of bleached krafl hardwood and softwood pulps. The paper was prepared at a paperm~king pH of 8.0 and contained 0.5% alum (based on dly pulp). The paper was unfilled and was not 25 surface treated.
The paper was treated with an aqueous dispersion of resin using a laboratory size press operating at room temperature. The resin level required inthe aqueous dispersion to achieve the desired sizing agent level in the paper was detç. .,.il~e(l by first ~et~ -ing the amount of absorbed water picked up .. ....... .

CA 0226l954 l999-0l-29 W O 98/39376 PcT/u~ 3358 when the paper was treated with water only in the size press. The level of the resin in the dispersion was then adjusted according}y to give the desired level of addition to the paper. The paper was drum dried at 104~C inunediately following tre~tmen~
S Sizing was mP~cllred after storing the paper for I week, using the Hercules Size Tester (Hercules Incorporated., Wilmin~on, DE) at 80%
reflectance with an ink con~ining 1% formic acid and a green dye.
(Reference: The Sizing of Paper, Second Edition, W. F. Reynolds editor, TAPPI Press, 1989). Higher values correspond to higher sizing. The commercial sizing agents used for comparison were Scripset~)740 styrene maleic anhydride copolymer from Monsanto Corp., St. Louis, MO and Hercon~)70 alkylketene dimer based sizing agent from Hercules lncorporated, Wilmin~on, DE). Alkylketene dimers are known to impart slip related problems to paper when applied to the surface of the sheet in sufficient quantities.

TABLF. I
H.~T .Siz;"g (seconds to 80% reflectance) .~i7in~ A~ent l evel (Dry B~is) .~i7i~A~ent 0.05% Q~ 0.2%
Product of Exarnple 2 6 9l 218 Product of Example 3 2.5 83 298 Scripset~9740 1 9 62 Hercon~70 308 494 590 The data in Table 1 show that the resins of this invention give sizing at levels between the two common commercial sizing agents, Scripset~740 and Hercon~70 .

W O 98/39376 PCT~US98/03358 F.s~n~le 7 This example illustrates ~ ~alion of an aminoamide from adipic acid and diethylenetriarnine modified by reaction with he~-lecenylsuccinic anhydride hydrophobizing agent. Adipic acid (66.0 g, 0.45 moles) was added S to diethylenetriamine (77.4 g, 0.75 moles) in a stirred reaction vessel. The was brought to 170~C and held at this tempe.~lure for 3 hours while the water of condenc~hon was removed by distillation. The molten product was cooled to 122~C, and then there was added 97.8 g (0.3 moles) of hex~lecenylsuccinic anhydride (ASA 100). The resulting mixture was held at 123~C for 2 hours and then ql~Pnched with water. The product aminoamide had an amine number of 4.44 meq/g (amine equivaJent weight, 225) and acid number of 44. The product was diluted with enou~h water to produce a dispersion with a measured solids of 20.6%. The dispersion had a pH of 10.6.

F.xample 8 A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Exarnple 7. The dispersed hydrophobically modified aminoamide (142.0 g, 29.4 g solids, 0.13 amine equivalents) was blended with 48.6 g of water. Epichlorohydrin (11.1 ~, 0.12 moles) was slowly added while keeping the temperature below 40~C. The 20 resulting reaction mixture was stirred for 30 minutes at 40~C and then crosslinked by he~tin~ at 65~C for 2 hours. Thc hot product ~ as homogenizcd usin~ a laboratory homogenizer. The product had 20.2% solids, pH 6.2 and particle size 0.074 rnicrons. It cont~ined 0.17% 1,3-dichloropropan-2-ol, 0.06% 2,3-chloropropanediol and less than 0.02% residual epichlorohydrin.
Example 9 This example illustrates the re~ ced tendency to foam of the crosslinked hydrophobically modified cationic resin composition of Example 8 colnpaled to common commercial surface sizing agents.

W O 98/39376 PCT/U~ 3358 The modified laboratory foam cell consisted of a pump and air introduction device to allow air percolation through a starch solution cont~ining the cros~linked hydrophobically modified cationic resin composition. Time for the foarn to reach a designated height in a gr~dl~te-l cylinder was recorded.
The test solution (700 g) con~ine~l 0.25% resin (based on dry starch), 0.6%
so~ m chloride (based on dry starch) added to a 6% solution of Stayco M (A.
E. Staley l~nl-frctllring Co"~al~y, Decatur, IL) ~re~,aled by cooking at 95~C
for 30 rninutes. The cornmercial sizing agents used for comparison are Scripset~720 and Scripset 740 styrene maleic anhydride copolymers from Monsanto Corp., St. Louis, MO. The results, presented in Table 2 are the tirne for the foarn to reach a volume of 1800 rnl. Higher values indicate a lower fo~ming tendency.

TABI F. 2 Time (seconds) to J 800 ml of Foam 15Sizin~Agent Time. sec.
Scripset 720 75 Scripset 740 60 Product of Example 8 255 F.~ ple 10 This example illustrates ~)re~)a,ation of an ~mino~mide from adipic acid and diethylenetriamine modified by reaction with hex~decenylsuccinic anhydride hydrophobizing agent. Adipic acid (54.80 g, 0.375 moles) was added to diethylenetriamine (77.35 g, 0.75 moles) in a stirred reaction vessel.
The mixture was brought to 1 70~C and held at this temperature for 3 hours while the water of condensation was removed by distillation. The molten product was cooled to 125~C, and then there was added 91.28 g (0.28 moles) of hex~(lecenylsuccinic anhydride (ASA 100). The resulting n~ e was held at 125~C for 1 hour, at 140~C for 1 hour, and then quenched by addition of water.

W O 98/39376 PCT/U~8t~33~8 The product had an amine number of 5.60 meq/g (amine equivalent weight, 178) and acid number of 42 (acid equivalent weight, 1,336). It was diluted with enou~h water to produce a dispersion with 23.4% solids. The dispersion had a pH of lO.4.

F~mple 11 A crosslink~l hydrophobically modified cationic resin composition was l,.e~ ed from the hydrophobically modified aminoamide of Example 10. The dispersed hydrophobically modified aminoamide (123.3 g, 28.9 g solids, 0.16 amine equivalents) was blended with 65.4 g of water. Epichlorohydrin ( 11.1 g, 0.12 moles) was slowly added while keeping the temperature below 40~C. The res!-lting reaction mixture was stirred for 30 minntes at 40~C and then crosslinked by heating at 65~C for 2 hours, after which it was quenched and diluted by adding enou~h water to bring the mixture to about 15% solids.
The product had 15.7% solids, pH 6.0 and particle size 0.070 microns and contained 0.23% 1 ,3-dichloropropan-2-ol, O. l 6% 2,3-chloropropanediol and less than 0.01% residual epichlorohydrin.

F.Y~nlPIe 12 This exarnple illustrates another preparation of aminoamide from adipic acid and diethylenctriamine followed by reaction with hexadecenylsuccinic anhydride.
Adipic acid (54.80 g, 0.375 moles) was added to diethylene~iamine (77.38 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to 1 70~C and held at this temperature for 3 hours while the water of condensation was removed by llist~ tion. The molten product was cooled to 125~C, and then there was added 146.7 g (0.45 moles) of hexadecenylsuccinic anhydride (ASA 100). The resulting mixt~re was held at 125~C for 1 hour, at 140~C for 1 hour, and then quenched by addition of water. The product had an amine number of 3.69 meqtg (an~ine equivalent weight, 271) and acid number of 57.5 W O 98/39376 PCT/U~Z~ 58 (acid equivalent weight, 975). The product was diluted with enough water to produce a dispersion with 23.3% solids. The dispersion had a pH of 10.1.

Example 13 A crosslin~e~l hydrophobically modified cationic resin composition was 5 prepared from the hydrophobically modified arninoarnide of Example 12. The dispersed hydrophobically modified ~mino~mide (152.0 g, 35.4 g solids, 0.13 amine equivalents) was blended with 69.3 g of water. Epichlorohydrin ( I 1.1 g, 0.12 moles) was slowly added while keeping the temp~ e below 40~C. The resulting reaction rnixture was stirred for 30 minutes at 40~C and then 10 crosslinked by he~tin~ at 65~C for 2 hours, after which it was q~lenchPd and diluted by addin~ enough water to bring the mixture to about 15% solids.
The product had 15.3% solids, pH 5.8 and particle size 2.18 microns and contained 0.084% 1,3-dichloropropan-2-ol, 0.075% 2,3-chloropropanediol and less than 0.01% residual epichlorohydrin.

F.xam~le 14 This example illustrates another l)lc~ ation of aminoamide from adipic acid and diethylenetriamine hydrophobically modified by reaction with hexPdecenylsuccinic anhydride.
Adipic acid (58.40 L~. 0.40 moles) was added to diethylenetriamine (68.78 g. 0.66 moles) in a stirred reaction vessel. The mixture was brou~,ht to 170~C and held at this te..l~)c.~ture for 3 hours while the water of condens~honwas removed by distillation. The molten product was cooled to 128~C, and then there was added 173.7 g (0.53 moles) of hçx~tl.ocenylsuccinic anhydride (ASA 100). The resul~ing mixture was held at 125~C for ] hour, at 140~C for 1 25 hour, and then quenched by addition of water. The product had an amine number of 2.35 meq/g (amine equivalent weight, 425) and acid number of 54 (acid equivalent weight, 1042). The product was diluted with enough water to produce a dispersion with 24.1% solids. The dispersion had a pH of 9Ø

F,s~mple 15 A crosslink~d hydrophobically modified cationic resin composition was ~re~d from the hydrophobically modified aminoamide of Example 14. The dispersed hydrophobically modified aminoamide (178.65g, 43.0 g solids, 0.10 amine equivalents) was blended with 80.75 g of water. Epichlorohydrin (7.4 g, 0.08 moles) was slowly added while keeping ~e temperature below 40~C. The res~l~in~ reaction rnixture was stirred for 30 minutes at 40~C and then crosslin~ed by h~hn~ at 65~C for 2 hours, after which it was quenchecl and diluted by adding enough water to bring the mixture to about 15% solids.
The product had 14.8% solids, pH 5.8 and particle size 1.14 microns. It contained 0.12 % 1,3-dichloro~,lopan-2-ol, 0.18 % 2,3-chloropropanediol and less than 0.01 % residual epichlorohydrin.

Comp~r~tive F.~m~le A
This is a comparative example illustrating preparation of an aminoamide from adipic acid and diethylenetriamine hydrophobically modified with he~r~decellylsuccinic anhydride usin~g polyamine to dicarboxylic acid ratios described in U.S. Patent No. 3,922,243, but using water as a dispersing medium.
Adipic acid (109.61 ~, 0.75 moles) was added to diethylenetriamine (77.38 B~ 0.75 moles) in a stirrcd reaction vessel. The mixture was brou~ht to 160~C and held at this temperature for 5 hours whilc the water of condens~ion was removed by distillation. The molten product was cooled to 128~C, and then there was added 97.8 g (0.30 moles) of hexadecenylsuccinic anhydride (ASA 100). The resulting mixture was held at 160~C for I hour and then quenched by addition of water to give a nominal 25% solids. The product was in two layers and was not useable for resin preparation.

. .

W O 98/39376 PCTIU~J~3S8 Co~p~rative FY~nIPIe R
Colnp~ e FY~mrle A was repeated, except that in this case milder reaction conditions, i.e., reaction of the hydrophobizing agent at temperatures less than 150~C were applied.
Adipic acid (109.61 g, 0.75 moles) was added to diethylenetriamine (77.38 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to 160~C and held at ~is temperature until 1/3 of the theoretical water of conden~hon was removed by distillation. The molten product was cooled to 128~C, and then there was added 97.8 g (0.30 moles) of he~decenylsuccinic anhydride (ASA 100). The resulting mixture was held at 125~C for I hour and 140~C for I hour and then quenched by addition of water to give a nominal 25% solids. The product had an amine number of 3.26 meq/g (amine equivalent wei~,ht, 307) and acid number of 33 (acid equivalent weight, 1696).
The product had a measured solids of 22.1% and a pH of 8.11.

Ccm~ar~tive ~xample C
A crosslinke~l hydrophobically modified cationic resin composition was prepared from the hydrophobically r! odified aminoamide of Comparative Example B. The dispersed aminoamide (155.52g, 34.37 g solids, 0.11 amine equivalents) was blended with 60.73 ~ of water. Epichlorohydrin (11.10 g, 0.12 moles) was slowly added while keeping the temperature below 40~C. The resultinL~ reaction mixture was stirred for 30 minl~tes at 40~C and thcn crosslinked by he~tin~ at 65~C for 2 hours, after which it was quPnche~ and diluted by adding enough water to bring t}le mixture to about 15% solids.
The product had 12.5% solids, pH 5.8, p~rticle size 0.32 microns, and contained 0.42% 1,~-dichlolup:-opan-2-oL 0.45% 2,3-chloropropanediol and less than 0.02~/~ residual epichlorohydrin.

W O 98/39376 PCT/U'3~ 3~58 Comparative F,Y~rn~PIe D
This is a comparative example illustrating preparation of aminoarnide from adipic acid and diethylenetriarnine hydrophobically modified by reaction with hex~lecenylsuccinic anhydride using polyamine to dicarboxylic acid ratios as described in U.S. Patent No. 3,922,243. The milder reaction conditions of this patent were applied.
Adipic acid (73.07 g, 0.50 moles) was added to diethylenetriamine (51.59 g, 0.50 moles) in a stirred reaction vessel. The mixture was brou~ght to 160~C and held at this temperature until 1/3 of the theoretical water of condenc~tion was removed by distillation. The molten product was cooled to 128~C, and then there was added 130.40 g (0.4 moles) of hex~lecenylsuccinic anhydride (ASA 100). The resulting rruxture was held at 1''5~C for I hour and 140~C for 1 hour and then ql~enchçd by addition of water to give a norrunal 25% solids. The product had an amine number of 1.53 meq/~, (an~ine lS equivalent weight, 652) and acid nurnber of 76 (acid equivalent weight, 740).
The product had a measured solids of 24.0% and a pH of 5.7.

(~omparative F~x~mple F, A crosslinked hydrophobically modified cationic resin composition was ~ d from the hydrophobically modified an~inoarnide of Comparative Example D. The dispersed hydropnobically modified ~mino~n~ide (197.71g, 47.41 6 solids, 0.07 amine equivalents) w3s blended with 84.34 g of water.
Epichlorohydrin (1 1.10 g, 0.12 moles) was slowly added while keeping the temperature below 40~C. The resulting reaction mixture was stirred for 30 mim-tes at 40~C and then crosslinked by heating at 65~C for 2 hours, after which it was quenched and diluted by adding enough water to bring the rnixture to about 15% solids.
The product had 14.4% solids, pH 6.0, and particle size 0.28 rnicrons. It cont~ined 0.21 % 1,3-dichloroplol,an-2-ol, 0.64 % 2,3-chlorop1o~ ediol and 0. l9 % residual epichlorohydrin.

.. ... . . . ... ......

W 098/39376 PCT/U~J& W358 Co~parative F~ ple F
This is a coll~parali-~e example illustrating plep~lion of aminoamide from adipic acid and diethylenetriamine hydrophobically modified by reaction with hexadecenylsuccinic anhydride using polyamine to dicarboxylic acid ratios as described in U.S. Patent No. 3,922,243, but higher than those used in the previous col"y~ e examples. The milder reaction conditions of the patent were applied.
Adipic acid (81.84 g, O.SS mo!es) was added to diethylenetriamine (77.38 g, 0.75 moles) in a stirred reaction vessel. The mi~lule was brought to 170~C and held for 3 hours while the water of con~çnc~tion was removed by distillation. The molten product was cooled to 129~C, and then there was added 122.25 g (0.375 moles) of hex~decerlylsuccinic anhydride (ASA 100).
The resulting mixture was held at 125~C for 1 hour and 140~C for 1 hour and then quenched by addition of water to give a nominal 25% solids. The product had an amine number of 2.78 meq/g (amine equivalent weight, 360) and acid number of 49 (acid equivalent weight, 1156). The product had a measured solids of 25.2% and a pH of 9Ø

(~om~r~tive F.~mple (.
A crosslinked hydrophobically modified cationic resin composition was ~,-el)a,cd from the hydrophobically modificd aminoamide of CGI-lp~ative Example F. The dispersed hydrophobically modified arninoamide (138.46~, 34.88 g solids, 0.10 amine equivalènts) was blended with 80.34 g of water.
Epichlorohydrin (11.10 g, 0.12 moles) was slowly added while keeping the ~e..,~trature below 40~C. The resulting reaction mixture was stirred for 30 minllteS at 40~C and then crosslinked by he~ting at 65~C for 2 hours, after which it was quenched and diluted by adding enough water to bring the m-ixture to about 15% solids.

W O 98/39376 PCT~US98/03358 The product had 14.2% solids, pH 5.4, and particle size 0.30 microns. It contained 0.04 % 1,3-dichloro~ro~an-2-ol, 0.15 % 2,3-chlorol)rol,al~ediol and less than 0.01 % res~ l epichlorohydrin.

Example 16 This ex~mple demonstrates the sizing efficiency of resins of ~is invention co~ ed to materials described in U.S. Patent No. 3,922,243.
Waterleaf paper was prepared on a trial paper m~c~ine. The paper was prepared at a basis weight of 64.9 kg /1,000 m2 from a 50:50 blend of bleached kraft hardwood and softwood pulps. The paper was prepared at a paperm~kin~
pH of 8.0 and contained 0.5% alum and 12% Albacar 5970TM precipitated calcium carbonate (Speciality Minerals lr.c., Bethlehem, Pa.). The paper wa~s not surface treated. All additive amounts are on a dry basis based on the dry weight of pulp.
The paper was treated witl1 an 8% solution of an GPC D-150 oxidized starch (from Grain Proc~ssing Coml)al~y, Ml-sc~ine, IA), also cont~ining the resin of this invention in dispersed form, using a laboratory size press operating at 65~ C. The level of resin needed in the starch solution was determined by f~rst deterrnining the amount of adsorbed starch solution when the paper was treated with starch solution only in thc sizc prcss. The levcl of resin in the starch solution was then adjusted accordin~lly to ~,ive thc desired level of addition to the psper (0.25 %). The sizing solu ions ~ ere prepared both with (at a level of0.2% based on paper) and without optical bri~,htener (Phorwite P, Mobay Corp., Pittsburgh, PA). Optical brig,htening agents are con~nonly used in the size press to increase the brightness of paper. The paper was drum dried at 96~C immediately following treatment.
Sizing results are shown in Table 3. Sizing was measured on the paper after storage for 2 weeks, using the Hercules Size Tester (Hercules, Inc., Wilmin~on, DE) at 80% reflect~ce with an ink conl~ 1% formic acid W O 98/39376 PCT/U~58t~3358 and a green dye. A duplicate of Example 2 was used as the control. The molar ratios of polyamine to dicarboxylic acid and hydrophobizing agent to polyamine used to ~le~ e the hydrophobically modified ~mino~mide are shown for comparison.

Table 3 -rface si7in~ Comparison~HST ~izinP l.seconds to 80% reflect~lnce) HST
Molcs Hy~ophobe/ withoul HST
Amine/Diacid Equivalentsof Optical withOptical Si7inr Ae~ntMolc R~ S~ Aminrn~ l.".~. . Rr~fn~r Product of Example 2 1.66 0.4 64 56 Product of Example 151.66 0.8 36 60 Product of Comp. Example E1.0 0.8 2 24 The results in Table 3 demonstrate substantially improved surface sizing when the polyamine to dicarboxylic acid ratios in the arninoamide is ~reater than about 1.4.

F.~tPmple 17 This example demonstrates the sizin~ efflciency of the products of this invention compared to ma~erials described in U.S. Patent No. 3,922,243.
A waterleaf paper was prepared on a trial papermachine. The paper was prepared at a basis weight of 64.9 kg /1,000 m2 from a 50:50 blend of bleached kraft hardwood and softwood pulps. The paper was prepared at a paperm~kin~
pH of 8.0 and contained 0.5% alum. The paper was not filled and not surface treated. All additive amounts are on a dly basis based on the dry weight of pulp.
The paper was treated with an aque~us dispersion of the resin using a laboratory size press operating at room temperature. The paper was drum W O 98/39376 PCT~US98/03358 dlyed immediately following treatment at 104~ C. The level of sizing agent neerlecl in the aqueous dispersion was detellluned by first dele. ..~ -p the amount of absorbed water picked up when the paper was treated with water only in the size press. The level of resin in the dispersion was then adjusted 5 accordingly to give the desired level of addition to the paper (0.2%).
Sizing results are shown below in Table 4. Sizing was m~cllred after storing the paper for 1 week, using the Hercules Si~ Tester at 80% reflectance with an ink cont~inin~ 1% formic acid and a green dye. A duplicate of Example 2 was used as the control. The molar ratios of polyamine to 10 dicarboxylic acid and hydrophobizing agent to polyamine used to ~,lc~,are the hydrophobically modified aminoamide are shown for comparison.

TA~ 4 Surface Size Comp~ri~on HST Sizin~ (seconds to 80% reflectance) Moles Hydrophobe/
Arnine/Diacid ~QL Equivalents of ~iQ Secondary~mirle HST. seconds Product of Example 2 1.66 0.4 >1200 Product of Exarnple 11 2.00 0.4 1107 Product of FY~nlrle 13 2.00 0.8 652 Product of Comp. Example C1.00 0.4 12 Product of Comp. Example G1.33 0.5 513 The data in Table 4 indicate the higher levels of sizing that are obtained wi~ the resins of this invention when compared to resins prepared by the methods of U.S. Patent No. 3,922,243.

W O 98/39376 PCT/U~ 3358 Compar~tive Fs~mple ~
This example describes plcpalation of a bis-~lea~u"ide.
Stearic acid (Emersolg)152, from Henkel Corporation, Cincinnati, Ohio), 512.1 g (1.8 moles), was melted in a stirred reaction vessel and heated to 106~C. To this was slowly added diethylenetriamine (103.2 g, 1.0 moles). Theu, e was brought to 1 70~C and held at this tel,~er~l lre for 3 hours while water of conden~tion was removed by ~listill~tion. The molten product was cooled. The product had a mel~ing pOillt of 105~C and an amine number of 2.02 meq/g (amine equivalent weigh., 495).

Com~rative F.xample J
This example describes preparation of a crosslinked cationic resin composition from the bis-stearanide of Comparative Example H.
The molten bis-stearamide (97.0 g, 0.20 amine equivalents) of Comparative Example H was slowly blended into hot water (1200 ml) to form a dispersion. The temperature of the dispersion was set at 85~ C and epichlorohydrin (18.5 B, 0.20 moles) was rapidly added. The mixture was stirred for 2 hours, aRer which it was homo~enized and then cooled to room temperature.
The product had 8.2% solids, pH 4.0, and panicle size 0.40 microns.

F.~Pmple 18 This example demonstrates the sizing ef~lciency and impact on sheet properties of products of this invention compared to a sizing agent based on bis-stearamide and to conventional conunercial sizing agents.
Paper was prepared on a trial papermachine with sizing agents added both int~rn~lly and to the surface of the sheet at the size press. The paper waspre~ared at a basis weight of 64.9 kg /1,000 m2 from a 75:25 blend of bleached kraft hardwood and softwood pulps ref:ned to 425 CSF. The paper was W O 98/39376 PCT/U'~U~358 prepared at a papçrm~kin~ pH of 8.0, contained 0.25% alum (based on pulp), was filled with Albacar 5970 precipitated calcium carbonate at 10%, and was surface treated with a size press solution CO~ i.,g 4~/O Stayco M oxidized starch and 0.05% so~ m chloride at 55~C. For surface application, the solids 5 level of resin and sodium chloride needed to apply the desired amount of m~tcri~l was determined by first determinin~ the amount of absorbed starch solution piclced up when the paper was treated with starch solution only in the si~ press. The level of resin and sodium chloride in the starch solution was then adjusted accordingly to give the desired level of addition to the paper. The 10 paper was dried to give 4-6% moisture at the reel.
Sizing agent was applied either internally or in the size press solution.
The base sheet had at least 0.05% of Hercon~)70 alkylketene dimer sizing agent in all sheets to aid in size press operation. Sizing and coefficient-of-friction(COF) results are shown in Table 5. All results were measured after storing the 15 paper for 1 week. Sizing was measured using the Hercules Size Tester (Hercules, lnc., Wilmington, DE) at 80% reflectance with an ink containing 1%
formic acid and a green dye. COF was measured using a Thwing-Albert (Thwing-Albert lnstrument Company, Philadelphia, PA) in the machine direction, felt-to-wire, using a 200 ~ sled. The static COF is shown. A sizing 20 agent equivalent to that in Exarnple 3 was used as the control. Alkylketene dimcrs and bis-stearamides are known to cause slip related problems in paper whcn applied to the surface of the sheet, or intemally, in sufficient quantities.

CA 022619~4 1999-01-29 W O 98/39376 PCTrUSs8/03358 TABI.F, 5 Iml~act on Sizin~ Emci~ncy and Sheet Properties' Size Addition Size Addition Sizin~Agent Lev~l (%) ~ HST, sec. COF, Static Hercon 70 0.05 internal 2 0.482 " 0.075 intern~ 166 0.510 O. 10 intenn~ 272 0.500 Ex~nple 3 0.025 surface 41 0.575 0.10 su~ace 152 0.502 " 0.10 intennal 43 0.~25 " 0.20 i~tennal 83 0.532 Ccmp.
Ex~nple J 0.025 surface 9 0.542 0.10 surface 229 0.315 " 0.10 in~ern~ 172 0.478 " 0.20 intennal 236 0.395 I.Hercon70isinallsh~ atO.05~/Ou~esso~,c.~is~ in~

The data in Table 5 show that resins as described herein impart a si~nificant level of sizing to paper when used in combination with a low level of internal size, without ne~atively inlr~cting the coefficient-of-friction of 20 paper. The bis-stearamide size, Comparative Example J, imparts sizing but also has a large negative impact on the coef~lcient-of-friction of paper.
Commercial experience shows that high levels of alkylketene dimer based sizing agents also can negatively irnpact the coefficient-of-friction of paper and the perforrnance of paper in high speed converting,' as discussed by C.L.
25 Brungardt and J.C. Gast, Proceedings of the TAPPI 1996 Papermakers Conference, p. 297.

W O 98/39376 PCT/U~J5~ 58 F~ .ple 19 This example illustrates the ~-el)alalion of an aminoamide from adipic acld and diethylenetliamine hydrophobically modified by reaction with stearic acld.
Adipic acid, 65.7 g (0.45 moles) was added to diethylenetriamiine, 77.4 g (0.75 moles) in a stirred reaction vessel. The mixture was brought to 170~C
and held for 3 hours while the water of con~l~nc~tion was removed by distillation. The molten aminoamide was then cooled to 125~C .
To the entire amount of the aminoamide at 125~C was added 85.3 g (0.3 moles) of 95% stearic acid (Aldrich Chemical Co., Milwaukee, Wl). The temperature was raised to 170DC for 2 hours. The product was diluted with hot water to give a nominal total solids of 23.0%. The product had a measured total solids of 21.9%, pH 10.4, an acid number of 13 mg KOH/~n and an amine number of 5.39 meq/g (equating to an amine equivalent weight of 185).
The number average molecular wei~ht by SEC was 790.

FY~ml~le 20 This example describes the preparation of a crosslinked hydrophobically modified cationic resin composition by reaction of epichlorohydrin with the hydrophobically modified aminoamide prepared in FY~mple 19.
The dispersed hydrophobically modified ~mino~nide of Example 19 (674.4 g, 147. 7 g solids, 0.8 equivalents of an~ine) was blended with 308.7 ~ of water. Epichlorohydrin (61.1 g, 0.66 moles) was then slowly added to the dispersion while the temperature was maintained at below about 40"C. The resulting reaction mixture was then stirred for 30 minutes at 40~C and then crosslinked by heating at 65~C for 2 hours, after which it was quenched and diluted by adding enough wa.er to bring the nlixlule to about 10.5% solids.

W O 98~9376 PCT/U~J'~3~58 The product contained 10.7% total solids, had pH 5.91, and particle size of z1.00 rnicrons. It contained 0.076% 1,3-dichloroplo~ 2-ol, 0.04% 2,3-chlo-o~ro~anediol, and less than 0.01% residual epichlorohydrin.
Surface sizing with the product resin was evaluated using the same 5 procedures as described in F.~mple 18 except that the paper was prepared at 75.0 kg/1000 m2 and internal addition of Hercon 70 was at 0.075% based on dIy pulp. Under these conditions the sizing agent (0.2%, based on paper) of this example gave 217 seconds HST sizing when added to the size press starch co.l-paled to 1 second HST sizing with the internal size and size press starch 10 alone.
It is not inten~e~l that the examples presented here should be construed to limit the invention, but rather they are submitted to illustrate some of the specific embo~lim~ont~ of the invention. Various modifications and variations ofthe present invention can be made without departing from the scope of the 15 appended claims.

Claims (50)

What is claimed is:

1. A resin composition comprising the reaction product of epihalohydrin and hydrophobically modified aminoamide obtained by the reaction of:
(a) aminoamide containing at least one primary amine group and at least one non-primary amine group selected from the group consisting of secondary and tertiary amine groups, the aminoamide being obtained by reaction of an amine composition comprising polyamine containing at least two primary amine groups and at least one amine group selected from the group consisting of secondary and tertiary amine groups, with dicarboxylic acid or derivatives thereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivative thereof, is from about 1.5:1 to about 3:1, and (b) hydrophobizing agent having from about 12 to about 40 carbon atoms, wherein the amount of hydrophobizing agent employed is sufficient to react with at least a portion of the primary amine groups, but insufficient to react with more than about 60% of the non-primary amine groups of the aminoamide.

2. The resin composition of claim 1 wherein the hydrophobizing agent comprises at least one member of the group consisting of: i) monocarboxylic acids, or derivatives thereof, ii) dicarboxylic acid anhydrides having the formula wherein R' is a straight chain or branched, saturated or unsaturated alkyl radical having from about 8 to about 22 carbon atoms; iii) ketene dimers or multimers; and iv) mixtures thereof.

3. The resin composition of claim 1 wherein the molar ratio of polyamine to dicarboxylic acid, or derivatives thereof, is from 1.55:1 to 2.5:1.

4. The resin composition of claim 1 wherein the molar ratio of polyamine to dicarboxylic acid, or derivatives thereof, is from 1.6:1 to 2:1.

5. The resin composition of claim 1 wherein at least 50 mole percent of the amine composition comprises polyamine containing at least two primary amine groups and at least one amine group selected from the group consisting of secondary and tertiary amine groups.

6. The resin composition of claim 1 wherein the polyamine comprises at least one member selected from the group consisting of N-alkyl bis(3-aminopropylamine) wherein the N-alkyl group contains from 1 to about 12 carbon atoms, and polyalkylene polyamines containing two primary amine groups and at least one secondary amine group, the nitrogen atoms being linked together by groups of the formula -CnH2n- where n is from 2 to 6.

7. The resin composition of claim 6 wherein the polyamine is polyalkylene polyamine containing two primary amine groups and at least one secondary amine group where the nitrogen atoms are linked together by groups of the formula -CnH2n- where n is from 2 to 6.

8. The resin composition of claim 7 wherein the polyalkylene polyamine is at least one member selected from the group consisting of polyethylenepolyamines, polypropylenepolyamines and polybutylenepolyamines.

9. The resin composition of claim 7 wherein the polyalkylene polyamine is at least one member selected from the group consisting of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

10. The resin composition of claim 6 wherein the N-alkyl bis(3-aminopropylamine) is methyl bis(3-aminopropylamine).

11. The resin composition of claim 5 wherein the amine composition further comprises diamine selected from the group consisting of wherein x is an integer from 2 to about 10, y is an integer from 2 to about 100,b is an integer from 2 to about 100, and a and c, which can be the same or different, are integers from 0 to about 5.

12. The resin composition of claim 1 wherein the dicarboxylic acid derivatives are selected from the group consisting of esters, anhydrides and acid halides.

13. The resin composition of claim 1 wherein the dicarboxylic acid comprises an aliphatic, alicyclic or aromatic dicarboxylic acid containing from 2 to about 44 carbon atoms, or a derivative thereof.

14. The resin composition of claim 13 wherein the dicarboxylic acid is at least one member selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid,diglycolic acid, C36 dimer acid, and dicarboxylic acid having the formula or derivatives thereof, wherein R' is a straight chain or branched, saturated orunsaturated alkyl radical having from about 8 to about 22 carbon atoms.

15. The resin composition of claim 14 wherein the dicarboxylic acid is at least one member selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid. adipic acid, pimelic acid, suberic acid and azelaic acid.

16. The resin composition of claim 14 wherein the derivative of dicarboxylic acid of formula (II) is the cyclic anhydride.

17. The resin composition of claim 13 wherein the dicarboxylic acid is adipic acid, or a derivative thereof.

18. The resin composition of claim 17 wherein the dicarboxylic acid is adipic acid.

19. The resin composition of claim 1 wherein the polyamine comprises diethylenetriamine and the dicarboxylic acid comprises adipic acid, or a derivative thereof.

20. The resin composition of claim 2 wherein the hydrophobizing agent is monocarboxylic acid, or a derivative thereof, of the formula RCOOH
where the R group is selected from the group consisting of alkyl, alkenyl, aryl,cycloalkyl and cycloalkenyl.

21. The resin composition of claim 20 wherein the monocarboxylic acid derivatives are selected from the group consisting of esters, anhydrides, acid halides and isocyanates.

22. The resin composition of claim 2 wherein the hydrophobizing agent is a substituted succinic anhydride of the formula:

where R' is selected from the group consisting of branched or straight chain alkyl, branched or straight chain alkenyl, cycloalkyl, aralkyl and aralkenyl hydrocarbons containing from about 8 to about 22 carbon atoms.

23. The resin composition of claim 2 wherein the hydrophobizing agent is the reaction product of maleic anhydride with C16-C18 olefins.

24. The resin composition of claim 2 wherein the hydrophobizing agent is ketene dimer or multimer of structure:

wherein n is an integer of 0 to about 20, R and R", which may be the same or different, are saturated or unsaturated straight chain or branched alkyl groups having 8 to 24 carbon atoms; and R' is a saturated or unsaturated straight chainor branched alkyl group having from about 5 to about 40 carbon atoms.

25. The resin composition of claim 1 wherein the amount of hydrophobizing agent employed is insufficient to react with more than about 30% of the non-primary amine groups of the aminoamide, when the polyaminoamide contains secondary amine groups.

26. The resin composition of claim 25 wherein the amount of hydrophobizing agent employed is insufficient to react with more than about 10% of the non-primary amine groups of the aminoamide.

27. The resin composition of claim 1 wherein the amount of hydrophobizing agent employed is sufficient to react with at least 20% of the primary amine groups.

28. The resin composition of claim 1 wherein the epihalohydrin comprises epichlorohydrin.

29. The resin composition of claim 1 which has been crosslinked.

30. The resin composition of claim 1 wherein at least 40% of the amine groups of the hydrophobically modified aminoamide have been reacted with epihalohydrin.

31. The resin composition of claim 30 wherein at least 70% of the amine groups of the hydrophobically modified aminoamide have been reacted with epihalohydrin.

32. The resin composition of claim 31 wherein at least 90% of the amine groups of the hydrophobically modified aminoamide have been reacted with epihalohydrin.

33. The resin composition of claim 1 wherein the polyamine comprises diethylenetriamine; the dicarboxylic acid comprises adipic acid, or a derivative thereof; the epihalohydrin is epichlorohydrin; the hydrophobizing agent comprises a substituted succinic anhydride having the formula where R' is a branched or straight chain alkenyl group containing from 8 to about 22 carbon atoms, the amount of hydrophobizing agent being sufficient to react with at least 20% of the primary amine groups; and wherein at least 70%
of the secondary amine groups have been reacted with epichlorohydrin.

34. A method for preparing a resin composition comprising:
a) reacting an amine composition comprising polyamine containing at least two primary amine groups and at least one amine group selected from the group consisting of secondary and tertiary amine groups with dicarboxylic acid, or derivatives thereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivative thereof is greater than 1.4:1, to form aminoamide containing at least one primary amine group and at least one non-primary amine group selected from the group consisting of secondary and tertiary amine groups;
b) reacting the aminoamide with hydrophobizing agent having from about 12 to about 40 carbon atoms to form hydrophobically modified aminoamide, wherein the amount of hydrophobizing agent employed is sufficient to react with at least a portion of the primary amine groups, but insufficient to react with more than about 60% of the non-primary amine groups of the aminoamide; and c) reacting the hydrophobically modified aminoamide with epihalohydrin.

35. The method of claim 34 wherein the epihalohydrin comprises epichlorohydrin.

36. The method of claim 34 wherein the hydrophobizing agent comprises at least one member selected from the group consisting of: i) monocarboxylic acids, or derivatives thereof; ii) dicarboxylic acid anhydrides having the formula:

wherein R' is a straight chain or branched, saturated or unsaturated alkyl radical having from about 8 to about 22 carbon atoms; iii) ketene dimers; iv) ketene multimers; and v) mixtures thereof.

37. The method of claim 34 wherein steps (a) and (b) are carried out neat.

38. The method of claim 34 wherein steps (a) and (b) are carried out in solvent.

39. The method of claim 34 wherein step (c) is carried out in aqueous medium.

40. The method of claim 36 wherein the hydrophobizing agent has the structure of formula I and the temperature during reaction of the aminoamide with hydrophobizing agent is from about 100°C to about 150°C.

41. The method of claim 34 further comprising (d) crosslinking the resin composition by heating it at a temperature of from about 40°C to about 90°C.

42. A resin composition prepared by the method of claim 34.

43. A method for sizing paper comprising adding to the surface of a paper sheet an aqueous suspension of the resin composition of claim 1.

44. A method for sizing paper comprising adding to the surface of a paper sheet an aqueous suspension of the resin composition of claim 29.

45. Sized paper made by the process of claim 43.

46. Sized paper made by the process of claim 44.

47. A method for preparing sized paper comprising the steps of (a) providing an aqueous pulp suspension; (b) adding to the aqueous pulp suspension an aqueous suspension of the resin composition of claim 1; (c) forming the pulp into a sheet; and (d) drying the sheet to obtain sized paper.

48. A method for preparing sized paper comprising the steps of (a) providing an aqueous pulp suspension; (b) adding to the aqueous pulp suspension an aqueous suspension of the crosslinked resin composition of claim 29; (c) forming the pulp into a sheet; and (d) drying the sheet to obtain sized paper.

49. Paper prepared by the method of claim 47.

50. Paper prepared by the method of claim 48.