WO1994016007A1

WO1994016007A1 - Wet strength resin composition and method of making same

Info

Publication number: WO1994016007A1
Application number: PCT/US1994/000127
Authority: WO
Inventors: Nancy S. Clungeon; Stephen A. Fischer
Original assignee: Henkel Corporation
Priority date: 1993-01-15
Filing date: 1994-01-07
Publication date: 1994-07-21
Also published as: JPH08505653A; KR960700301A

Abstract

A composition is comprised of an aminopolyamide-epichlorohydrin acid salt resin having a total organically bound clorine of up to 0.7 % by weight of the resin is useful as a wet strength agent for paper. The composition further comprised of a polyol, a monoalkyl ether of a polyol, and/or a polyalkylene glycol is useful as an additive in coating formulations. The amount of total organically bound chlorine present is controlled by the manufacturing process parameters.

Description

WET STRENGTH RESIN COMPOSITION AND METHOD OF MAKING SAME

CROSS-REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part application of application serial number 07/740,369, filed on August 5, 1991, the entire contents of which are incorporated herein by reference, which is a continuation-in-part of application serial number 07/712,327, filed on June 7, 1991 which is a continuation-in-part of application serial number 07/652,346, filed on February 7, 1991 which is a continuation-in-part of application serial number 07/573,600, filed on August 24, 1990.

BACKGROUND OF THE INVENTION 1. Field of the Invention

This invention relates to wet strength resin compositions for paper and coating applications and a method for making them. 5 2. Description of the Related Art

Aminopolyamide-epichlorohydrin resins were the first commercially significant neutral-to-alkaline curing wet strength resins for paper. In addition to the health and safety benefits that result from the resins being

10 formaldehyde-free, their use also affords such benefits as reduced paper-machine corrosion and improved softness a absorbency in treated webs compared to urea-formaldehyd treated webs.

One of the drawbacks associated with the use aminopolyamide-epichlorohydrin wet strength resins is t emission of harmful chlorinated compounds into the wat systems of pulp and paper mills. These chlorinat compounds, which are the by-products of the manufacture the aminopolyamide-epichlorohydrin resins, have be identified as epichlorohydrin, l,3-dichloro-2-propanol, a 3-chloro-l,2-propanediol. These chlorinated organics a usually discharged into effluent waste water systems fr pulp and paper mills because they are only partial substantive to cellulose pulp fibers. Since permissib amounts of halogenated organics in waste waters is ev decreasing, considerable effort has been expended to redu the amount of these materials in aminopolyamid epichlorohydrin wet strength resins.

The wet strength resin compositions according to t invention contain organic chlorine compounds in amoun which are at least 99% lower than commerci aminopolyamide-epichlorohydrin resins.

The related art does not teach wet strength resi compositions comprised of an aminopolyamide-epichlorohydr acid salt resin and up to 0.7% by weight total organical bound chlorine based on the weight of said resin. T related art also does not teach a relationship between t temperature at which alcohol is removed in t aminopolyamide resin-making process and the w strengthening ability of the aminopolyamide-epichlorohydr resin made from the aminopolyamide resin. The related a also does not teach a relationship between t epichlorohydrin-aminopolyamide reaction time and very l total organically bound chlorine content in processes make wet strength resins compositions comprised of aminopolyamide-epichlorohydrin acid salt resins. SUMMARY OF THE INVENTION

The present invention provides a wet strength resi composition comprising water, and from about 1% to abou

60% by weight of an aminopolyamide-epichlorohydrin aci salt resin, up to 0.7% by weight total organically boun chlorine based on the weight of said resin.

The wet strength resin compositions according to th invention can be made by a process whose first step is th aminolysis of an ester. A C_1-3 dialkyl ester of a saturate aliphatic dicarboxylic acid having from 3 to 6 carbon atom is heated with a polyalkylenepolyaraine having two primar a ine groups and at least one secondary amine group in th absence of water. The ester to polyalkylenepolyaroine mola ratio has a value of up to 1:1. During the heating step the reaction temperature first reaches a maximum of abou 150°C-160°C at which point the alcohol formed as a resul of the reaction between the diester and th polyalkylenepolyamine begins to boil. The alcohol i retained in the reaction by refluxing it which also lower the reaction temperature. After the temperature drops t about 110°C-115°C, the alcohol is removed from the reactio at a temperature of from about 110°C to about 160°C. Th alcohol removal is continued until the viscosity of a 50 aqueous solution of resulting polyamidopolyamine at 25° reaches at least 700 cps. At this point, epichlorohydri is added to an aqueous solution of th polyalkylenepolyamine at such a rate that the reactio temperature is maintained in the range of from about 5°C t about 30°C. After all the epichlorohydrin has been added the resulting reaction mixture has an E/N ratio of from 0. to 1.08. Then the temperature of the reaction mixture i maintained in a range of from about 15°C to about 35° until all of the epichlorohydrin has reacted as indicat by analysis of the reaction mixture. The pH of t reaction mixture is then adjusted to a value of up to abo 7.0. The process produces a wet strength resin compositi comprised of an aqueous solution of an aminopolyamid epichlorohydrin acid salt resin which has a tota organically bound chlorine of up to 0.7% by weight of sai resin. The wet strength resin compositions according t the invention can also be modified for use in coatin formulations. Such modified compositions contain one o more solvents as disclosed herein in addition to th aminopolyamide-epichlorohydrin acid salt resin.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Other than in the operating examples, or wher otherwise indicated, all numbers expressing quantities o ingredients or reaction conditions used herein are to b understood as modified in all instances by the ter "about".

Polyalkylenepolya ines which can be used according t the invention are those which have two primary amine group and at least one secondary amine group such a diethylenetriamine, triethylenetetramine tetraethylenepentamine, and bis-hexamethylenetriamine an the like. The dicarboxylic acid esters which can be use in the process according to the invention are those whic are C_1-3 diesters of C₃_₆ dicarboxylic acids. Such diester can be made for example, by direct esterification of dicarboxylic acid having from 3 to 6 carbon atoms with a alcohol having from 1 to 3 carbon atoms. Examples of suc esters include but are not limited to dimethyl malonate dimethyl succinate, dimethyl adipate, and dimethy glutarate. Mixtures of any or all of such esters can als be used in the process according to the inventio Preferably, the esters are mixtures of dimethyl adipate an dimethyl glutarate which are sold as DBE-2™, a product the DuPont Corporation.

The molar ratio of ester to polyalkylenepolyamine i the aminolysis step should not exceed 1:1. Values great than 1:1 will result in gelation of the reaction produc Preferably, the ester- polyalkylenepolyamine reacti mixture is heated at atmospheric pressure in a reacti vessel equipped with a reflux condenser until t temperature first reaches a value of about 150^βC-160^β during which time the alcohol formed in the reaction begin to reflux. The refluxing alcohol removes heat from th reaction mixture and the temperature continuously falls a more and more alcohol is produced. When the reactio temperature drops to about 110^βC, the alcohol is removed a a temperature in the range of from about 110°C to abou 160°C. The alcohol removal can be accomplished by changin the condenser configuration from reflux to take-off Alcohol is continuously removed until the viscosity of 50% aqueous solution of resulting polyamidopolyamine a 25°C reaches at least 700 cps. and preferably 1000 cps. I the alcohol removal is accomplished at a temperature lowe than 110°C, the viscosity of a 50% aqueous solution of th polyamidopolyamine at 25°C will not reach at least 700 cp and the resulting wet strength resin will not increase th wet tensile of a treated sheet to an acceptable level Table II shows the effect of the viscosity of a 50% aqueou solution of the polyamidopolyamine (PAA) resin on the we tensile development of a treated sheet. The higher th viscosity of a 50% aqueous PAA solution the higher the we tensile ratio and the more closely the particular low TOC resin behaves like a commercial resin which is at least on order of magnitude higher in TOCl. Since it has been foun that product gelation results if the molar ratio of este to polyalkylenepolyamine exceeds 1:1, it is important t insure that substantially all of polyalkylenepolyamin reacts before the alcohol formed in the reaction i removed. Premature alcohol removal can result in th simultaneous removal of some of the polyalkylenepolyamin thereby altering the ester/polyalkylenepolya ine mola ratio sufficient to result in product gelation. Retentio of the alcohol in the reaction mixture for example b refluxing, insures that no polyalkylenepolyamine is los before it reacts with the ester.

The polyamidopolyamine formed in the aminolysi reaction is then reacted with epichlorohydrin in aqueou solution to form an aminopolyamide-epichlorohydrin resin The concentration of the aminopolyamide in the water is no critical as long as the combined reaction solids content o aminopolyamide and epichlorohydrin present after step (c are in the range of from about 5% to about 60% by weight The preferred % aminopolyamide solids in step (b) of th process is from about 29% to about 39% by weight. Th relative amounts of aminopolyamide-epichlorohydrin resi are expressed as the E/N ratio. The E/N ratio is defined b Equation I as moles epichlorohydrin „ . amine equivalents

where the amine equivalents is defined by Equation II as

wt. of aminopolyamide sol _'n_ x % solids as decimal x TΛ t _q, ..

and TA, which is total alkalinity, is defined by Equatio III as volume (m ) x normality of stnd. acid x 56.11 _ ... wt. of aminpolyamide sol'n x % solids as decimal

The total alkalinity of a typical aminopolyamide is in th range of from about 270 to about 380 mg/g of KOH on solids basis. The amount of epichlorohydrin to be added i step (c) of the process is calculated by substituting th numerical value for the amine equivalents as calculated b Equation II into Equation I, setting the E/N value equal t about 0.9, and solving the equation for moles o epichlorohydrin. The epichlorohydrin is added to th aminopolyamide solution neat at a rate sufficient t maintain the temperature of the reaction mixture in th range of from about 5^βC to about 30°C, preferably fro about 10°C to about 15^βC. In step (d) the temperature o the reaction mixture is then maintained in a range of fro about 15^βC to about 35^βC until all of the epichlorohydri has reacted. The epichlorohydrin reaction time referred t in Table I is the time required for step (d) and can b determined by analysis of the reaction mixture for tota organically bound chlorine as described in Example 19. Al of the epichlorohydrin has reacted when the tota organically bound chlorine is less than about 7000 pp (0.7% by weight) based on reaction solids. Th epichlorohydrin reaction time can also be determined fro viscosity measurements of the reaction mixture by means o a Brookfield viscometer using a ≠2 spindle at 30 r.p.m. a 25°C. When step (d) of the process is carried out at preferred total solids content of about 45%, th epichlorohydrin reaction temperature is maintained unti the Brookfield viscosity of the reaction mixture fall within the range of from about 500 to about 1500 cps. I another preferred embodiment, when the total solids conten of step (d) is 40%, the epichlorohydrin reactio temperature is maintained until the Brookfield viscosity o the reaction mixture falls within the range of from abou 350 to about 800 cps. In yet another preferred embodiment, when the total solids content of step (d) is 35%, th epichlorohydrin reaction temperature is maintained unti the Brookfield viscosity of the reaction mixture fall within the range of from about 200 to about 500 cps. Th product formed in step (d) is an epichlorohydrin aminopolyamide resin. After the temperature has been hel in the range disclosed above, the reaction is stopped b adjusting the pH of the reaction mixture to a value of les than about 7. The addition of an amount of water to reac a desired final % solids level followed by pH adjustmen can also stop the reaction. The preferred final solid content is from about 35% to about 45% by weight o solution. The pH of the reaction mixture is alway adjusted by acidification regardless of whether water is o is not added to stop the reaction. The acidification ca be accomplished by any means known to those of ordinar skill in the art. For example, a gaseous acid such a anhydrous hydrogen chloride can be introduced into th aqueous reaction mixture or an aqueous acid solution can b added. Preferably an aqueous acid solution is used t adjust the pH to a value of less than about 7.0 such a hydrochloric acid, sulfuric acid, phosphoric acid, aceti acid, propionic acid, or benzoic acid. The preferre aqueous acid solution is hydrochloric acid. While any p value of less than about 7.0 can be achieved, the preferre value is in the range of from about 2 to about 4. Th process according to the invention produces a wet strengt resin composition comprising an aminopolyamide epichlorohydrin acid salt resin and a total organicall bound chlorine of less than 0.7% by weight of th aminopolyamide-epichlorohydrin acid salt resin. The tota organically bound chlorine is determined by the metho described in Example 19.

The process according to the invention produce unexpectedly low levels of total organically bound chlorin in a wet strength resin which performs at least as well a resins which have one to two orders of magnitude more tota organically bound chlorine because during the synthesis o the aminopolyamide the a inolysis of the esters is carrie out until the viscosity of a 50% aqueous solution resulting polyamidopolyamine at 25°C reaches at least 70 cps and the epichlorohydrin reaction is carried out relatively low temperatures and at the relatively low E/ ratio from 0.6 to 1.08. A resin prepared by the proce according to the invention but having an E/N ratio greater than 1.08 will have an unacceptably high TO content when used as an additive in the manufacture paper such as wet strength resin applications, retenti aids, and the like. An unacceptably high TOCl content f such applications, is one which is greater than 0.7% weight of the aminopolyamide-epichlorohydrin acid sa resin. However, when the compositions according to t invention are used in coatings applications, the E/N rati can have a value as great as 2.0. Such a value of the E/ ratio will cause the TOCl content of the resin to b greater than 0.7%. based on total resin weight. Example 2-11 are resins prepared by the process according to th invention which produces the combined effects of low tota Organically bound chlorine and wet tensile developmen equal to resins containing up to about 2 orders o magnitude more total organically bound chlorine. Example 12-17 are resins prepared by the methods according to th prior art and show the effects of elevated epichlorohydri reaction temperatures at equal or greater E/N ratios fo resins prepared according to the process of the invention Conventional wisdom dictates that optimum wet strengt performance and minimum total organically bound chlorin levels are favored by optimizing the epichlorohydri reaction which is in turn favored by reaction temperature greater than room temperature and E/N ratios of from 0.6 t 1.08. When the compositions according to the invention ar used in coatings applications, the compositions wil contain one or more water- iscible solvents selected fro the group consisting of: (a) a monoalkyl ether of a polyo such as methyl carbitol(diethylene glycol monomethyl ether butyl carbitol (diethylene glycol monobutyl ether, and th like) ; (b) a polyol which is any aliphatic compound havin 2 or more hydroxyl functionalities that is miscible wit water or combinations thereof. Examples of such polyol include but are not limited to ethylene glycol, 1,2 propylene glycol, 1,3-propylene glycol, diethylene glycol dipropylene glycol, triethylene glycol, 1,6-hexyle glycol, glycerol, onosaccharides such as glucose fructose, disaccharides such as sucrose, and polyvin alcohol. Also included in this group are compounds of t formula I X

I H- C 0 C H ₂ C H_{β y} - 0H c i )

wherein X is H, CH₃, C₂H₅; a is 1 or 2; and y is less th 10. The preferred solvents are 1,2-propylene glyco methyl carbitol, polyethylene glycol 200 (PEG 200) , and mixture comprised of 10% by weight of 1,6-hexanediol a 90% by weight of butyl carbitol. When the compositions according to the inventi contain one or more solvents as disclosed herein, they c be used for coatings applications such as components in i formulations or as epoxy resin curing agents. When t compositions according to the invention are used coatings applications, they will typically contain from to 60% by weight of aminopolyamide-epichlorohydrin ac salt resin, from 5% to 95% solvent, and from 0 to 8 water. The preferred values are 30-35% PAE resin, 20-3 solvent, and 30-50% water. When the composition according to the invention a used in coatings applications, the solvent or solvents c be added during the manufacture of the aminopolyamid epichlorohydrin acid salt resin before the addition of t epichlorohydrin or the solvent or solvents can be add after the resin manufacture is complete.

The present invention also provides cellulosic fibro webs comprising a wet strengthening effective amount of aminopolyamide-epichlorohydrin acid salt resin and le than 0.7% of total organically bound chlorine by weight said aminopolyamide-epichlorohydrin acid salt resin. A w strengthening effective amount of an aminopolyamid epichlorohydrin acid salt resin is any amount required reach a desired wet strength as determined by wet tensi measurements. Different applications will require differe amounts of wet tensile and hence different amounts of w strength resin composition containing an aminopolyamid epichlorohydrin acid salt resin. The relationship betwe the amount of wet strength resin composition added to cellulosic fibrous web and the wet tensile produce therefrom is dependent upon a number of factors such as th nature of the pulp fibers and the method of application an is readily determinable by one of ordinary skill in th art. The wet strength resin compositions according to th invention are normally applied to cellulosic pulp fibers a dosage level of from about 1 to about 30 pounds of dry we strength resin per ton of fiber to produce wet strengthene webs. The wet strength resin compositions according to th invention can be applied to cellulosic pulp fibers by an method known to those of ordinary skill in the art such a by spraying, dipping or coating a pre-formed sheet or i the wet end of a paper machine since the aminopolyamide epichlorohydrin acid salt resins in the wet strength resi compositions are substantive to cellulose pulp fibers. Th preferred amount of dry wet strength resin per ton of fibe is in the range of from about 4 to about 12 lbs pounds pe ton. The following examples will serve to illustrate bu not limit the invention.

Example l Preparation of an Aminopolyamide Resin To a resin reactor was charged one mole of a dibasi acid ester mixture comprised of 65% dimethyl glutarate an 35% dimethyl adipate and one mole of diethylene triamine Stirring and nitrogen sparge were started and the content of the reactor were heated to 150°C-160^βC. Methanol bega to reflux at about 157°C. The reflux was allowed t continue until the reaction temperature reached 125°C a which time the methanol was distilled off. The reactio temperature was maintained in the 140°C-160°C range durin the approx. 3 hours required for distillation of about 85 of the theoretical amount of methanol. The Brookfiel viscosity (spindle 3 § 12 rpm) of a 48.4% aqueous solutio of the resin thus obtained was 2850 cps. A 33.5% solid resin solution had a total alkalinity of 376 mg KOH/g on solids basis and a Brookfield viscosity (spindle /2 § 6 rp ) of 280 cps.

Examples 2-17 Examples 2-11 describe the preparation of wet strengt resin compositions according to the invention and prepare according to the process of according to the invention Examples 12-17 describe the preparation of resi compositions using reaction parameters outside the scope o the process according to the invention. The entries i Table I list the various reaction parameters, wet strengt performance, and total organically bound chlorine compositions corresponding to examples 2-17. Examples 3-1 were prepared exactly like the procedure of Example 2 Comparisons of resins in Examples 2-11 to those in Example 12-17 should be made only for those resins having the sam E/N values. For example, the properties of the resin o Example 5 should be compared with those of Example 1 because both resins have an E/N ratio equal to 0.7.

Example 2 Preparation of Wet Strength Resins Compositions To a round bottom flask were charged 171 grams of

48.0% solids aminopolyamide resin solution having a tot alkalinity based on solids content (TA) of 274.8 mg KOH/ and 38 grams of water. Gentle stirring was applied and th contents of the flask were cooled to about 15°C (E addition temperature) at which time about 26 grams epichlorohydrin were added over 3 hours. After completi of the epichlorohydrin addition, the contents of t reactor were allowed to exotherm to a temperature of abo 20°C. The reaction mass was held at this temperature f 12.5 hours (ECH reaction temperature & time). The viscosi at this point (Final Vise.) was 602 cps. The reaction w stopped by adjusting the pH of the solution to 2.0 with 37 hydrochloric acid. The resin solution contained 45. solids and 0.044% total organic chlorides based on t resin solids (% total Cl) as determined by extraction-G. method. (Example 19) Example 18 Performance Testing of Wet Strength Resin Composition

1. Stock Preparation

Kraft softwood lapboard (Bowater) was beaten in large capacity Waring Blender at 4.1% consistency for minutes at 15,500 r.p.m. and then further diluted to 0.2 consistency. The drainage of the diluted stock was measur at 110-120 ml by "30 Second Britt Drainage" method using 4" circular 70 mesh screen with the Mark IV Dyna Handsheet Mold/Paper Chemistry Jar Assembly.

2. Handsheet Preparation

Blank handsheets were prepared according to t handsheet preparation method outlined in the Mark Dynamic Handsheet Mold/Paper Chemistry Jar Assem operating manual. Treated handsheets were prepared by t same method except a dosage of 8 dry pounds wet stren resin per ton of dry pulp was manually added to t dispersed stock slurry and the furnish was mixed at 7 r.p.m. for 55 seconds. Handsheets were blotted dry betwe felt sheets and pressed with a rolling pin in back forth and diagonal directions. Pressed sheets were pla between drying rings and conditioned overnight at humidity and 70°C as per instructions in the Mark Dynamic Handsheet Mold/Paper Chemistry Jar Assem operating manual. The dosage level for all sheets used generate the data given in Tables I and II was 8 lbs re /ton pulp.

3. Wet Tensile Determination

Tensile strips measuring 1" by 4" were cut f treated handsheets and soaked for 1 hour in water at 25 Tensile strengths were determined on an Instron Tens Tester using a 10 lb load cell. The wet tensile ratio, of Tables I and II is defined as the ratio of the tensile of a sheet treated with a wet strength re composition according to the invention to the ratio of wet tensile of commercial product B which is Fibrabond 33 a product of Henkel Corporation, Ambler, PA. Product A Table I is Kymene 557H™, a product of Hercules, Wilmingto DE.

Table I

1- p c oro y r n a on me n ours.

2- Temperature maintained during epichlorohydrin additi

3- Epichlorohydrin reaction time in hours.

4- Temperature maintained during epichlorohydrin reacti

5- Final viscosity in centipoise.

6- Wet tensile ratio as defined in Example 18. Table II Effect of PAA Base Viscosity on PAE Resin Performance

2. Brookfield (Spindle #2, § 12 RPM) viscosity of a 50% aqueous solution in cps

3. Wet tensile of sheet treated with PAE resin

4. Wet tensile/dry tensile x 100%

5. Wet tensile ratio defined in Example 18.

Example 19 Total Organically Bound Chlorine Analysis

Extraction-G.C. Method

1. Sample Preparation

Approximately 5.000 g of the wet strength resin composition according to the invention comprised of an aminopolyamide-epichlorohydrin acid salt resin was added into a 40ml screw-top centrifuge tube. About 25 ml of ethyl acetate was added and the contents of the centrifuge tube were shaken thoroughly until the resin solution was dispersed. The contents of the tube were allowed to stand for 5 min. and then shaken again. The contents of the tube were centrifuged at high speed for 10 min. or until the upper solvent layer was clear. A portion of the supernatant solution was taken for G.C. injection.

2. Preparation of Standards Stock solutions of approximately 1000 ppm of epichlorohydrin, l,3-dichloro-2-propanol, and 3-chloro-l,2- propanediol were prepared in ethyl acetate on a weight to weight basis. These were further diluted volumetrically to lower levels prior to use. The second dilution depended upon the anticipated concentrations of the level of organic chlorides in the aminopolyamide-epichlorohydrin res solutions.

3. Gas Chromatographic Conditions Detector: electron capture Column: 0.54 mm capillary column, polyethyle glycol stationary phase, 2.5 micron film thicknes Septum purge: 0.5 minute Carrier gas: He, 10 psi head pressure Makeup gas: Nitrogen at 40 psi

Because of the differences between the retention times epichlorohydrin and chloropropanediol, optimum integrati of all peaks was achieved when the analysis was done in t steps. The best values for 1,3-dichloro-2-propanol, and chloro-1,2-propanediol resulted from an isothermal run 190°C and for epichlorohydrin, a ramped program from 120° 190°C was used.

4. Calculations

The concentration of organically bound chlorine in t extract was calculated from the formula :

Cone, of Extract = — — X Response of Extract

Response of Stnd.

The resulting concentration in the extract was multipli by the ratio of ethyl acetate to aminopolyamid epichlorohydrin samples used in the extraction to give t concentration of organically bound chlorine in the origin sample.

Example 20.

Preparation of A Composition Containing

1,2-propylene glycol. To a round bottom flask were charged 115 grams of

45.2% solids aminopolyamide resin solution having a tot alkalinity based on solids content (TA) of 292.9 mg KOH/

78.6 grams of 1,2-propylene glycol, and 3.3 grams of wate

Gentle stirring was applied and the contents of the fla were cooled to about 10^βC (ECH addition temperature) which time about 25.2 grams of epichlorohydrin were add over 25 minutes. After completion of the epichlorohydr addition, the contents of the reactor were allowed exotherm to a temperature of about 30^βC. The reaction ma was held at this temperature for 13 hours (ECH reacti temperature & time) . The viscosity at this point (Fin Vise.) was 1400 cps. The reaction was stopped by adjusti the pH of the solution to 2.0 with 37% hydrochloric aci The resulting resin composition contained 31% 1,2-propyle glycol, 34% aminopolyamide-epichlorohydrin acid salt res and 35% water. The viscosity was 763 cps.

Example 21. Preparation of A Composition Containing Methyl Carbitol.

To a round bottom flask were charged 113 grams of 45.2% solids aminopolyamide resin solution having a tot alkalinity based on solids content (TA) of 292.9 mg KOH/ 78.6 grams of 1,2-propylene glycol, and 3.3 grams of wate Gentle stirring was applied and the contents of the fla were cooled to about 8°C (ECH addition temperature) which time about 24.7 grams of epichlorohydrin were add over 10 minutes. After completion of the epichlorohydr addition, the contents of the reactor were allowed exotherm to a temperature of about 31°C. The reaction ma was held at this temperature for 9 hours (ECH reacti temperature & time) . The viscosity at this point (Fin Vise.) was 1325 cps. The reaction was stopped by adjusti the pH of the solution to 2.0 with 37% hydrochloric aci The resulting resin composition contained 28% meth carbitol, 32% aminopolyamide-epichlorohydrin acid sa resin and 40% water. The viscosity was 485 cps.

Claims

What is claimed is:

1. A composition comprising from about 10% to about 6 by weight of an aminopolyamide-epichlorohydrin acid sa resin; from about 5% to about 90% by weight of a solve selected from the group consisting of a polyol wherein sa polyol is an aliphatic compound having two or more hydrox groups and which is miscible with water; methyl or but carbitol; and a compound of the formula I

X I

H-C0CH₂CH_a-)_y-0H C l )

wherein X is H, CH₃, C₂H₅; a is 1 or 2; and y is less th 10; and up to about 85% by weight water.

2. The composition of claim 1 wherein the amount of sa aminopolyamide-epichlorohydrin acid salt resin in sa composition is about 10% by weight.

3. The composition of claim 1 wherein the amount of sai aminopolyamide-epichlorohydrin acid salt resin in sa composition is about 35% by weight.

4. The composition of claim 1 wherein the amount of sa aminopolyamide-epichlorohydrin acid salt resin in sa composition is about 45%.

5. The composition of claim 1 wherein the amount aminopolyamide-epichlorohydrin acid salt resin in sa composition is from about 30% to about 35% by weight, t amount of solvent in said composition is from about 20% about 35% by weight, and the amount of water in sa composition is from about 30% to about 50%.

6. The composition of claim 1 wherein sa aminopolyamide-epichlorohydrin acid salt resin is compris of less than about 0.7% by weight of total organical bound chlorine.

7. The composition of claim 1 wherein said polyol is PE 200.

8. The composition of claim 1 wherein said polyol is 1,2 propylene glycol.

9. The composition of claim 1 wherein said solvent is mixture comprised of 10% by weight of 1,6-hexanediol an

90% by weight of butyl carbitol.

10. The composition of claim 1 wherein sai aminopolyamide-epichlorohydrin acid salt resin is comprise of less than about 0.7% by weight of total organicall bound chlorine.