WO2000075426A1 - Paper softner/debonders compositions - Google Patents

Abstract

A composition comprising: (a) compounds of general formulas (I) and (II), wherein R is -H, -CH3, -C2H5, or benzyl; R?1, R2, and R3¿ are each independently a linear, branched, saturated, or unsaturated fatty acid radical having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups; and A- is an inorganic or organic anion; and (b) a papermaking additive.

Description

PAPER SOFTNER/DEBONDERS COMPOSITIONS

The present invention relates to quaternary ammonium compounds and other nitrogen-containing compounds and formulations thereof useful as, for instance, paper softeners and debonders, and the like.

Heretofore quaternary ammonium compounds and a very few dialkyl ammonium compounds ("conventional quats") have found widespread use in many applications. In general, such compounds exhibit properties which present some difficulty in the manufacture, formulation use, aesthetic properties, biodegradability, and environmental compatibility of these compositions. For example, many of the conventional compositions used for these functions, even if completely biodegradable with time, do not biodegrade as rapidly as could be desired and are thus not considered readily biodegradable. In addition, several of the commercial readily biodegradable paper debonders do not function as effectively as the conventional products that are less biodegradable. Thus, to maintain effective levels of performance, increased amounts of such less effective, more readily biodegradable products must be employed and, as will be readily apparent, this factor decreases the cost-effectiveness of the product. The relatively poor solubility of conventional quats also contributes to certain difficulties that will vary, depending on the application. Thus, there remains a need for identification of new amine and ammonium derivatives, and particular quaternary derivatives, which are useful as paper debonders and which are also biodegradable, highly effective in softening, debonding, and the like, and yet avoid these problems upon manufacture, formulation, and use. It is also desirable for the active agents used in such paper softeners and debonders to be readily biodegradable and to exhibit a satisfactorily high activity. Conventional products have to date not been able to exhibit both properties to a high degree, thus necessitating acceptance of reduced biodegradability or reduced activity. There is thus still a need for compounds exhibiting levels of activity as paper debonders, and so on, as the case may be, which are comparable or superior to conventionally employed actives, such as conventional quats, while also exhibiting ready biodegradability.

SUMMARY OF THE INVENTION

The present invention achieves these objectives and also exhibits the properties and advantages described herein. The present invention relates to quaternary ammonium compounds and formulations thereof useful as, for instance, paper debonders and softeners. An object of the present invention was to overcome the abovementioned disadvantages of traditional paper softener and debonder formulations or paper treatment compositions and to provide paper softener and debonder compositions or paper treatment formulations which, in addition to good biodegradability, have a significantly improved level of simultaneously good debonder and softener performance. This object was achieved using quaternary fatty acid amino alcohol esters of methylethanolisopropanolamine (MEIPA) with fatty acids in the ratio of from 1 J.5 to 1 :2 with use of monofunctional alcohols or bifunctional alcohols.

The instant invention provides paper treatment formulations containing compounds of the general formula (I)

and of the general formula (II)

wherein R is -H, -CH3, -C2H5, or benzyl;

Rl, R2, and R^ are each independently of one another linear, branched, saturated or unsaturated fatty acid radicals having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups; and A- is an inorganic or organic anion. In general, A-, whether shown or understood, may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Preferred examples of the anions are chloride, bromide, methyl sulfate, ethyl sulfate, and salicylate.

The invention also provides a method of treating paper using compositions comprising compounds of the general formula (I) and/or (II) or compositions comprising compounds of the general formula (I) and/or (II). In preferred embodiments of such paper treatment compositions, the amount of the compounds of the general formula (I) and/or (II) generally ranges from about 5 wt.% to about 95 wt.%, preferably 20 wt.% to 90 wt.%, and more preferably 28 wt.% to 85 wt.%, of the total composition. In other preferred embodiments of such paper treatment compositions including water or other solvent, the amount of the compounds of the general formula (I) and/or (II) generally ranges from about 5 wt.% to about 95 wt.%, preferably 20 wt.% to 90 wt.%, and more preferably 28 wt.% to 85 wt.%, of the total composition, excluding any water or solvent present. The invention additionally provides compositions comprising compounds of the general formula (I) and/or (II) in combination with conventional quaternary ammonium compounds that comprise from about 5% to about 95%, preferably from about 10% to 90%, more preferably from about 20%) to about 80% and most preferably from about 25% to 75% by weight of the total amount of quaternary ammonium compounds, which is the compounds of the general formula (I) and/or (II) (whether in quatemized or protonated form) and the conventional quaternary ammonium compounds, in the composition. Other preferred embodiment of the instant invention comprises compounds of the general formula (I) and/or (II) in combination with water.

The invention further provides paper softening and debonding formulations comprising compounds of the general formulas (I) and (II) which can be prepared by esterification of MEIPA with fatty acids in the molar ratio of from 1 : 1.5 to 1 :2 and subsequent quaternization carried out under conditions well known in this field for quaternization of amines, by reaction of the esterified a ine with a suitable quaternizing agent.

The invention further provides aqueous paper treating compositions comprising at least one of the compounds of the general formula (I) and/or (II).

In all of such paper treating applications, the paper treating composition of the present invention is contemplated to be applied in any of the many conventional ways paper treatments are applied to paper and paper fibers. For example, the paper treating compositions of the instant invention may be applied or used at any time in the papermaking process or before or after the papermaking process. For example, the paper treating compositions of the instant invention may be added at the wet end by addition to the water bath or at the dry end by spraying or printing directly on the paper web. The paper treating compositions of the present invention may include compounds of the general formulas (I) and/or (II), in combination with other surfactants, silicone compounds, antistatic agents, or other additives, such as wet strength additives, that are conventionally used in the paper industry, in which case, the paper treating compositions of the present invention may additionally impart the qualities that such additives provide; for example, excellent antistatic properties, wet strength, and hydrophilicity.

The invention also provides a paper web comprising (a) papermaking fibers; and (b) compounds of the general formulas (I) and/or (II). The invention also provides a paper web comprising the reaction product of (a) papermaking fibers; and (b) compounds of the general formulas (I) and/or (II). In preferred embodiments of the invention, the compounds of the general formulas (I) and/or (II) comprise from about 0.005% to 5.0% by weight of the papermaking fibers; more preferably from about 0.01% to about 3.0% by weight of the papermaking fibers; even more preferably from about 0.05% to about 2.5% by weight of the papermaking fibers; and most preferably from about 0.1% to about 2.0% by weight of the papermaking fibers. As used herein, the terms "paper", "paper web", "web", "paper sheet",

"tissue", or "tissue paper" is intended to designate an of the nonwoven materials commonly used as paper products, including tissue paper, from which at least a portion thereof comprises papermaking fibers, which may be selected, without limitation, from the group consisting of: hardwood fibers, softwood fibers, recycled fibers, baggasse fibers, fluff pulp, and natural papermaking fibers, synthetic papermaking fibers, cellulosic fibers, and blends thereof.

Ranges in amounts given for each ingredient or component of a composition or formulation set forth herein in certain circumstances may be theoretically capable of adding up to a sum of greater than 100%. As would be appreciated by those of skill in the art, it is understood that such impossible formulations (that is, those formulations whose component amounts add to a sum greater than 100%) are excluded from the claims and disclosure. For example, a formulation having components A and B, where the amount of A is said to range from 25% to 75% and the amount of B is said to range from 25% to 55%, if containing 65% of A, is understood to have 35% or less of B in that formulation, so that the sum of A and B does not exceed 100%. Thus, all formulations or compositions presented herein whose component amounts add to a sum less than or equal to 100% are understood as being part of the claims and disclosure.

As noted above, the compounds of the general formulas (I) and/or (II) can be used alone or in mixtures, used in combination with other compounds or additives, or used as a formulation with other compounds or additives, depending on the intended use in paper treatment and the advantages and disadvantages attendant with each alternative application method. Some examples of compounds or additives that may be used in conjunction with compounds of the general formulas (I) and/or (II) or made into formulations with compounds of the general formulas (I) and/or (II) include surfactants, especially other quaternary ammonium compounds, perfumes, preservatives, insect and moth repelling agents, antistatic agents, dyes and colorants, viscosity control agents, antioxidants, silicones, mineral oils and petrolatums, synthetic lubricants, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, and mixtures thereof. Many examples of these additives are set forth in detail and are intended to demonstrate the scope of the invention. Other compounds or additives familiar to those of skill in the art and appropriate to a particular use, however, may also be used with or formulated with compounds of the general formulas (I) and/or (II).

The compounds of the general formula (I) and (II) which are used according to the invention are prepared by the processes generally known in this field by esterification of methylethanolisopropanolamine

CH₂-CH₂-OH CH₃-N

CH₂— CH— OH CH₃ with fatty acid and subsequent quaternization.

Fatty acids used for the esterification or transesterification are the monobasic fatty acids based on natural vegetable and animal oils having 6-22 carbon atoms, in particular having 14-18 carbon atoms, which are customary and known in this field, such as, in particular, rapeseed oil fa ty acids, palm, tallow, castor fatty acids in the form of their glycerides, methyl or ethyl esters or as free acids. Thus, the fatty acids may be any linear, branched, saturated, or unsaturated fatty acid having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups.

The extent of unsaturation in these fatty acids or fatty acid esters is, as far as desired, adjusted to a desired iodine value by known catalytic hydrogenation processes, or achieved by mixing fatty components which are completely hydrogenated with fatty components which are not completely hydrogenated.

The iodine value (IN.), a measure of the mean degree of saturation of a fatty acid, is the amount of iodine which is absorbed by 100 grams of the compound to saturate the double bonds.

Preferred according to the present invention are tallow fatty acids and palm fatty acids with iodine values between 15 and 50. These are commercially available products and can be obtained from various firms under the respective trade names for these products.

According to the invention, preference is given to tallow fatty acids and palm fatty acids having iodine values between 1-50 and rapeseed oil fatty acids having iodine values between 80-120. They are commercially available products and are supplied by various companies under their respective tradenames.

The esterification or transesterification is carried out using known processes.

The methylethanolisopropanolamine is reacted with the amount of fatty acid or fatty acid ester corresponding to the desired degree of esterification, optionally in the presence of a catalyst, for example, methanesulfonic acid, under nitrogen at 160-240°C, and the water of reaction which forms and the alcohol is continuously distilled off, it being possible to bring the reaction to completion by, if necessary, reducing the pressure.

The subsequent quaternization is also carried out by known processes. According to the invention, this involves adding equimolar amounts of the quaternizing agent, with stirring and optionally under pressure, to the ester, optionally with use of a solvent, preferably isopropanol, ethanol, 1 ,2-propylene glycol and/or dipropylene glycol, at 60-90°C, and monitoring completion of the reaction by checking the overall amine value.

Examples of quaternizing agents which can be used in combination with the compounds of general formula (I) and/or (II), are organic or inorganic acids, but preferably short-chain dialkyl phosphates and sulfates, such as, in particular, dimethyl sulfate (DMS), diethyl sulfate (DES), dimethyl phosphate, diethyl phosphate, short-chain halogenated hydrocarbons, in particular methyl chloride or dimethyl sulfate.

For the preparation of the quaternary ammonium compounds, methylethanolisopropanolamine (MEIPA) and fatty acids were reacted and quaternized by the processes generally known to those of skill in the art and discussed above. Preferred fatty acids are as follows (in the following tables ' indicates mono-unsaturation, " indicates di-unsaturation). In all of these cases, the compounds were quaternized with dimethylsulfate so that, referring to formulas (I) and (II), R is -CH3 and A^~ is CH3SO4-).

A. Tallow fatty acids with an acid number of 202-208, an iodine value of 36-44, and a carbon chain distribution as follows.

B. Palm fatty acids with an acid number of 205-212, an iodine value of 30-40, and a carbon chain distribution as follows.

C. Palm fatty acids with an acid number of 205-215, an iodine value of 15-25 and a carbon chain distribution as follows.

D. Rapeseed oil fatty acid (RFA) with an acid value of 190-210 and an iodine value of 85-

1 10 and a carbon chain distribution as follows.

In the following description, Components A-G are produced by reacting MEIPA with fatty acid mixtures FA-I, FA-II, FA-III, or FA-IV as indicated in the table, in the molar ratio of MEIPA to acid mixtures indicated.

Component A: [MEIPA : FA I = 1 : 1.6]+ A"

Component B: [MEIPA : FA I = 1 : 2]+ A^~

Component C: [MEIPA : FA II = 1 : 1.6]+ A^"

Component D: [MEIPA : FA II = 1 : 2]⁺ A^~

Component E: [MEIPA : FA III = 1 1.6]⁺ A- Component F: [MEIPA : FA III = 1 2]⁺ A- Component G: [MEIPA : FA IV = 1 2]+ A-

DETAILED DESCRIPTION OF THE INVENTION

The products as described herein exhibit a number of desirable properties making them particularly suitable for formulation into commercial paper treating formulations, as mentioned above.

I. ADDITIVES

Among the more common additives that may be used in conjunction with or formulated with the compounds of the general formula (I) and (II) are the following. A. Papermaking and Tissuemaking Additives Paper and tissue softening or debonding compositions of the present invention would typically contain other chemicals that are commonly used in papermaking or tissuemaking or are added to the paper or tissue furnish (which may hereinafter be referred to as "papermaking additives"). Many such papermaking additives are well known to those of skill in the art and are described, for example, in G.A. Smook, Handbook for Pulp & Paper Technologists (2nd Edition) (Angus Wilde Pub. Inc., 1992), which should be consulted to appreciate the state of the art. Such papermaking additives are selected and used in amounts such that they do not significantly and adversely affect the softening, absorbency of the fibrous material, and other actions of the compounds of the present invention. 1. Wetting Agents

The present invention may contain as an optional ingredient from about 0.005% to about 3.0%, more preferably from about 0.03% to 1.0% by weight, on a dry fiber basis of a wetting agent. Such wetting agents may be selected from polyhydroxy compounds, nonionic surfactants such as alkoxylated compounds and linear alkoxylated alcohols, and anionic wetting agents such as diisooctylsulfosuccinate (DOSS), available from Witco Corporation under the tradename EMCOL® 4500 or REWOPOL® SB DO 75 PG. Additional examples include diols, triols, and glycols, whether alkoxylated or nor, particularly those having 2 to 6 carbon atoms and 13 or more carbon atoms, for example 13 to 100 carbon atoms, 14 to 60 carbon atoms, and 15 to 40 carbon atoms. Examples of water soluble polyhydroxy compounds that can be used as wetting agents in the present invention include glycerol. polyglycerols having a weight-average molecular weight of from about 150 to about 800, and polyoxyethylene glycols and polyoxypropylene glycols having a weight-average molecular weight of from about 200 to about 4000, preferably from about 200 to about 1000, most preferably from about 200 to about 600. Polyoxyethylene glycols having an weight-average molecular weight of from about 200 to about 600 are especially preferred. Mixtures of the above-described polyhydroxy compounds may also be used. A particularly preferred polyhydroxy compound is polyoxyethylene glycol having an weight average molecular weight of about 400, available from Union Carbide Corporation under the tradename PEG-400. Suitable nonionic surfactants can be used as wetting agents in the present invention. These include addition products of alkoxylating agents such as ethylene oxide (EO), propylene oxide (PO), or butylene oxide (BO), or a mixture thereof, with fatty alcohols, fatty acids, fatty amines, etc. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant. Suitable compounds are substantially water- soluble surfactants of the general formula: RlO-Y- C2H4θ)_z-C2H4θH wherein RJQ for both solid and liquid compositions is selected from the group consisting of primary, secondary and branched chain alkyl and or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a hydrocarbyl chain length of from about 8 to about 20, preferably from about 10 to about 18 carbon atoms. More preferably the hydrocarbyl chain length for liquid compositions is from about 16 to about 18 carbon atoms and for solid compositions from about 10 to about 14 carbon atoms. In the general formula for the ethoxylated nonionic surfactants herein, Y is typically -0-, -C(0)0-, -C(0)N(Rι ] , or -C(0)N(R] ι)Rι \- wherein R\ \ is hydrogen, a primary, secondary, or branched chain alkyl and/or acyl hydrocarbyl group; a primary, secondary, or branched chain alkenyl hydrocarbyl group; or a primary, secondary, or branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl group, wherein the hydrocarbyl groups have a hydrocarbyl chain length of from about 8 to about 20; and z is 3 to 40, more preferably 6 to 20, most preferably 8 to 16. Performance and, usually, stability of the softener composition decrease when fewer ethoxylate groups are present.

Examples of nonionic surfactants according to the above formula follow, wherein the integer in parenthesis identifies the number of EO groups in the molecule. In particular, the deca-, undeca-, dodeca-, tetradeca-, and pentadecaethoxylates of n-hexadecanol and rt-octadecanol are useful wetting agents in the context of this invention. Exemplary ethoxylated primary alcohols useful herein as the viscosity/dispersibility modifiers of the compositions are rø-octadecanol EO(10); and H-decanol EO(l l). The ethoxylates of mixed natural or synthetic alcohols in the "oleyl" chain length range are also useful herein. Specific examples of such materials include oleyl alcohol EO(l l), oleyl alcohol EO(18), and oleyl alcohol EO(25). In addition, the deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, and nonadecaethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol can be used as wetting agents in the present invention.

As in the case of the alcohol alkoxylates, the hexa- through octadecaethoxylates of alkylated phenols, particularly monohydric alkylphenols, are useful as the viscosity/dispersibility modifiers of the instant compositions. In particular, the hexa- through octadeca-ethoxylates ofp-tridecylphenol, m-pentadecylphenol, and the like, are useful herein. Exemplary ethoxylated alkylphenols useful as the wetting agents of the mixtures herein are: >-tridecylphenol EO(l 1) andp-pentadecylphenol EO(18). As used herein and as generally recognized in the art, a phenylene group in the nonionic formula is the equivalent of an alkylene group containing from 2 to 4 carbon atoms. It should also be noted that the alkenyl alcohols, both primary and secondary, and alkenyl phenols corresponding to those disclosed immediately hereinabove can be ethoxylated and used as wetting agents in the present invention. Furthermore, branched-chain primary and secondary alcohols, usually synthesized using the well-known Oxo Process, can be ethoxylated and can be used as wetting agents in the present invention.

The above ethoxylated nonionic surfactants are useful in the present compositions alone or in combination, and the term "nonionic surfactant" encompasses mixed nonionic surface active agents. The level of surfactant, if used, is preferably from about 0.01% to about 2.0% by weight, based on the dry fiber weight of the tissue paper. The surfactants preferably have alkyl chains with eight or more carbon atoms. Exemplary anionic surfactants are linear alkyl sulfonates, and alkylbenzene sulfonates. Exemplary nonionic surfactants are alkylglycosides including alkylglycoside esters such as that available from Croda, Inc. under the tradename CRODESTA™ SL-40; alkylglycoside ethers as described in U.S. Patent No.

4,01 1,389, which patent is herein incorporated by reference in its entirety; and alkylpolyethoxylated esters such as those available from Lonza Inc. under the tradename

PEGOSPERSE® 200 ML and available from Rhόne-Poulenc Corporation under the tradename IGEPAL® RC-520.

2. Strength Additives

Other types of chemicals which may be added, include the strength additives to increase the dry tensile strength and the wet burst of the tissue webs. The present invention may contain as an optional component from about 0.01 wt.% to about 3.0 wt.%, more preferably from about 03 wt.% to about 1.5 wt.%, on a dry fiber weight basis, of a water- soluble strength additive resin. Such water-soluble strength additive resins may include dry strength additives, permanent wet strength resins, temporary wet strength resins, or a compatible mixture thereof.

Examples of suitable dry strength additives include carboxymethyl cellulose and cationic polymers from the ACCO chemical family such as ACCO 71 1 and ACCO 514, with ACCO chemical family being preferred. These materials are available commercially from the American Cyanamid Company. As used herein, the term "permanent wet strength resin" refers to a resin which allows the paper sheet, when placed in an aqueous medium, to keep a majority of its initial wet strength for a period of time greater than at least two minutes. Permanent wet strength resins useful herein can be of several types. Generally, those resins which have previously found and which will hereafter find utility in the papermaking art are useful herein. Numerous examples are described by Westfelt in Cellulose Chemistry and Technology, Volume 13, at pages 813- 825 (1979), which is herein incorporated by reference in its entirety. Usually, the wet strength resins are water-soluble, cationic materials. That is to say, the resins are water-soluble at the time they are added to the papermaking furnish. It is quite possible, and even to be expected, that subsequent events such as cross-linking will render the resins insoluble in water. Further, some resins are soluble only under specific conditions, such as over a limited pH range. Wet strength resins are generally believed to undergo a cross-linking or other curing reactions after they have been deposited on, within, or among the papermaking fibers. However, such cross- linking or curing does not normally occur so long as substantial amounts of water are present. Of particular utility are the various polyamide-epichlorohydrin resins. These materials are low molecular weight polymers provided with reactive functional groups such as amino, epoxy, and azetidinium groups. The patent literature is replete with descriptions of processes for making such materials, for example, U.S. Patent Nos. 3,700.623 and 3,772,076, both herein incorporated by reference in their entireties. Such polyamide-epichlorohydrin resins available from Hercules Inc. under the trademarks KYMENE® 557H and KYMENE® 2064 are particularly useful in this invention. In addition, base-activated polyamide- epichlorohydrin resins are generally described in U.S. Patent Nos. 3,855,158; 3,899,388; 4,129,528; 4,147,586; and 4,222,921 , which patents are herein incorporated by reference in their entireties. These materials are available from the Monsanto Company under the tradename SANTO-RES™, such as SANTO-RES™ 31. Other water-soluble cationic resins useful herein are the polyacrylamide resins, such as those generally described in U.S. Patent Nos. 3,556,932 and 3,556,933, which are both herein incorporated by reference in their entireties. Such materials are available from the American Cyanamid Company under the tradename PAREZ®, such as PAREZ® 63 INC. Other types of water-soluble resins useful in the present invention include acrylic emulsions and anionic styrene-butadiene latexes, numerous examples of which are provided in U.S. Patent No. 3,844,880, which is herein incorporated by reference in its entirety. Still other water-soluble cationic resins finding utility in this invention are the urea formaldehyde and melamine formaldehyde resins. These polyfunctional, reactive polymers have molecular weights on the order of a few thousand. The more common functional groups include nitrogen containing groups such as amino groups and methylol groups attached to nitrogen. Although less preferred, polyethylenimine-type resins find utility in the present invention. More complete descriptions of the aforementioned water-soluble resins, including their manufacture, can be found in TAPPI Monograph Series No. 29, Wet Strength In Paper and Paperboard, Technical Association of the Pulp and Paper Industry (New York: 1965), which is herein incorporated by reference in its entirety. The above-mentioned permanent wet strength additives are those that produce paper products with permanent wet strength, that is, paper which when placed in an aqueous medium retains a substantial portion of its initial wet strength over time. However, permanent wet strength in some types of paper products can be an unnecessary and undesirable property. Paper products such as toilet tissues, etc., are generally disposed of after brief periods of use into septic systems and the like. Clogging of these systems can result if the paper product permanently retains its hydrolysis-resistant strength properties. Thus, manufacturers use temporary wet strength additives to paper products for which wet strength is sufficient for the intended use, but which then decays upon soaking in water. Decay of the wet strength facilitates flow of the paper product through septic systems.

Examples of suitable temporary wet strength resins include modified starch temporary wet strength agents, such as that available from the National Starch and Chemical Corporation under the tradename NATIONAL STARCH™ 78-0080. This type of wet strength agent can be made by reacting dimethoxyethyl-/V-methyl-chloroacetamide with cationic starch polymers. Modified starch temporary wet strength agents are also described in U.S. Patent Nos. 4,675,394 and 4,981,557, both of which are herein incorporated by reference in their entireties.

3. Other Additives

Other suitable additives may be used in paper and tissuemaking applications, depending on the application. For example, glycerin may also be used in the composition and formulations thereof. If used, the amount of glycerin in the aqueous softening composition can be from about 0.1 wt.% to about 98 wt.%, more preferably from about 60 to about 80 wt.%, and still more preferably from about 40 to about 60 wt.%, of the composition. In addition, the compositions and formulations of the instant invention can contain glycols, such as propylene glycol or polyethylene glycol, or mineral oils instead of or in addition to glycerin in such formulations. Silicones and other additives set forth below may also be used in combination with the compounds of formulas (I) and/or (II), either together or sequentially in the papermaking or tissuemaking process, for example, when the compounds of formulas (I) or (II) are applied to the wet end and a silicone is topically applied by print or spray or, alternatively, the compounds of formulas (I) and/or (II) and silicone are both used in the wet end or are both sprayed topically on the furnish. B. Conventional Quaternary Ammonium Compounds

Additional conventional quaternary ammonium compounds or salts may be present with the compound or compounds of formulas (I) and/or (II) in accordance with the present invention. The compounds presented below are only examples of conventional quaternary compounds that are suitable for use in the formulations of the present invention. As with the compounds of formulas (I) and/or (II), these conventional quaternary ammonium compounds (quats or salts) may have an anion to provide electrical neutrality and, in general, such anion may be any anion which is not deleterious to the properties of the overall compound. Thus, in the structural formulas (i) to (xxiii) below, the counteranion, whether designated as A- or not shown but understood, may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like. Preferred examples of the anions are chloride, bromide, methyl sulfate, ethyl sulfate, and salicylate. If the anion is monovalent (has a charge of -1), A- represents the anion group, if the anion is divalent (has a charge of -2), A- represents half of the anion group, if the anion is trivalent (has a charge of -3), A- represents a third of the anion group, and so on.

The conventional quats that may be formulated with the compounds of formulas (I) and/or (II) in accordance with the present invention include, but are not limited to, nitrogenous compounds selected from the group consisting of quaternized or acid salt derivatives of: (i) alkylenediamines, including compounds of the formula:

wherein each R\ is an acyclic alkyl or alkylene C 12-C21 hydrocarbon group, each Z is -(R2θ)θ-4H, or -R2H, and R2 and R3 are divalent Cj-Cg alkylene groups; (ii) substituted imidazoline compounds having the formula:

(iii) reaction products of higher fatty acids with alkylenetriamines in, for example, a molecular ratio of about 2:1, the reaction products containing compounds of the formula: V V V

RI Ri wherein R\, R2 and R3 are defined as above; and

(iv) substituted imidazoline compounds having the formula:

wherein G is -O- or -NH- and R] and R2 are defined as above; and mixtures thereof.

Preferred examples of compounds of structural formula (i) are those derived from hydrogenated tallow fatty acids and the hydroxyalkylalkylenediamine is N-2- hydroxyethylethylenediamine, such that R\ is an aliphatic C15-C21 hydrocarbon group, and R2 and R3 are divalent ethylene groups. A preferred example of a compound of structural formula (iii) is stearic hydroxyethyl imidazoline, wherein R\ is an aliphatic C21 hydrocarbon group and R2 is a divalent ethylene group.

A preferred example of compounds of structural formula (iii) is N . '- ditallowalkanoyldiethylenetriamine where R\ is an aliphatic C15-C21 hydrocarbon group and R2 and R3 are divalent ethylene groups.

A preferred example of compounds of structural formula (iv) is 1- tallowamidoethyl-2-tallowimidazoline wherein R\ is an aliphatic C15-C21 hydrocarbon group and R2 is a divalent ethylene group.

Both NN"-ditallowalkanoyldiethylenetriamine and l-tallowethylamido-2- tallowimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of methyl- l-tallowarnidoethyl-2-tallowimidazolinium methylsulfate. NN"- ditallowalkanoyldiethylenetriamine and l-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Corporation. Methyl- l-tallowamidoethyl-2-tallowimidazolinium methylsulfate is available from Witco Corporation under the tradename VARISOFT® 475 and REWOQUAT® W 75.

Other suitable quats are those containing one long chain acyclic aliphatic C$- C22 hydrocarbon group, selected from the group consisting of: (v) acyclic quaternary ammonium salts having the formula:

wherein R4 is an acyclic aliphatic Cg-C22 hydrocarbon group, alkyl, benzyl or (C4- C18 alkyl)-(OCH2CH2)2-3- R5 and R are C1-C4 saturated alkyl or hydroxyalkyl groups, and A- is an anion as defined above; for example, behenyltrimethylammonium chloride available from Witco Corporation under the tradename VARISOFT® BT 85. (vi) substituted imidazolinium salts having the formula:

wherein R\ is an acyclic alkyl or alkylene C 12-C21 hydrocarbon group, R7 is hydrogen or a C 1-C4 saturated alkyl or hydroxyalkyl group, and A- is an anion as defined above;

(vii) substituted imidazolinium salts having the formula:

wherein R\, R2, R5, and A- are as defined above; (viii) alkylpyridinium salts having the formula:

.θ

wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon group and A- is an anion as defined above; and (ix) alkanamide alkylene pyridinium salts having the formula:

A^θ

wherein Rj is an acyclic aliphatic C12-C21 hydrocarbon group, R2 is a divalent Cj-Cό alkylene group, and A- is an anion as defined above; and mixtures thereof.

Examples of compounds of structural formula (v) are the monoalkyltrimethylammonium salts including monotallowtrimethylammonium chloride, mono(hydrogenated tallow)-trimethylammonium chloride, palmityltrimethylammonium chloride and soyatrimethylammonium chloride, available from Witco Corporation under the tradenames ADOGEN® 471, ADOGEN® 441, ADOGEN® 444, and ADOGEN® 415, respectively. In these compounds, R4 is an acyclic aliphatic C\β-C\$ hydrocarbon group, and

R5 and Rg are methyl groups. In this application, mono(hydrogenated tallow)trimethylammonium chloride and monotallowtrimethylammonium chloride are preferred. Other examples of compounds of structural formula (v) are behenyltrimethylammonium chloride wherein R4 is a C22 hydrocarbon group, which is available from the Humko Chemical Division of Witco Corporation under the tradename

KEMAMINE® Q2803-C; soyadimethylethylammonium ethylsulfate wherein R4 is a C \ β-C\ $ hydrocarbon group, R5 is a methyl group, Rg is an ethyl group, and A- is an ethylsulfate anion; and methyl bis(2-hydroxyethyl)octadecylammonium chloride wherein R4 is a Cj8 hydrocarbon group, R5 is a 2-hydroxyethyl group and R is a methyl group.

An example of a compound of structural formula (vii) is 1 -ethyl- 1 -(2- hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfate wherein R\ is a C \η hydrocarbon group, R2 is an ethylene group, R5 is an ethyl group, and A- is an ethylsulfate anion.

Other quats useful in the present invention include cationic nitrogenous salts having two or more long chain acyclic aliphatic Cg-C22 hydrocarbon groups or one long chain acyclic aliphatic C8-C22 hydrocarbon group and an arylalkyl group. Examples include: (x) acyclic quaternary ammonium salts having the formula:

wherein each R4 is an acyclic aliphatic C8-C22 hydrocarbon group, R5 is a C 1-C4 saturated alkyl or hydroxyalkyl group, Rg is selected from the group consisting of R4 and R5 groups, and A- is an anion as defined above; (xi) diamido quaternary ammonium salts having the formula:

wherein each R\ is an acyclic alkyl or alkylene C12-C2I hydrocarbon group, each R2 is a divalent alkylene group having 1 to 3 carbon atoms, R5 and Ro are C1-C4 saturated alkyl or hydroxyalkyl groups, and A^~ is an anion as defined above; (xii) alkoxylated diamido quaternary ammonium salts having the formula:

wherein n is equal to 1 to about 5, and R\, R2, R5, and A- are as defined above; (xiii) quaternary ammonium compounds having the formula:

wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon carbon group, each R5 is a C\-

C4 saturated alkyl or hydroxyalkyl group, and A- is an anion as defined above; (xiv) amide-substituted imidazolinium salts having the formula:

wherein each R\ is an acyclic aliphatic C12-C2I hydrocarbon group, R2 is a divalent alkylene group having 1 to 3 carbon atoms, and R5 and A- are as defined above, or R5 is -H; and (xv) ester-substituted imidazolinium salts having the formula:

wherein R\ , R2, R5, and A- are as defined above; and mixtures thereof.

Examples of compounds of structural formula (x) are the well-known dialkyldimethylammonium salts including ditallowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, distearyldimethylammonium chloride, di(hydrogenated tallow)dimethylammonium chloride, dibehenyldimethylammonium chloride.

Di(hydrogenated tallow)dimethylammonium chloride and ditallowdimethylammonium chloride are preferred. Examples of commercially available dialkyldimethylammonium salts usable in the present invention are di(hydrogenated tallow)dimethylammonium chloride (available from Witco Corporation under the tradename ADOGEN® 442); ditallowdimethylammonium chloride (available from Witco Corporation under the tradename ADOGEN® 470); distearyldimethylammonium chloride (available from Witco Corporation under the tradename

AROSURF® TA-100); dicocodimethyl ammonium chloride (available from Witco Corporation under the tradename ADOGEN® 462), and dibehenyldimethylammonium chloride, wherein R4 is an acyclic aliphatic C22 hydrocarbon group (available from the Humko Chemical

Division of Witco Corporation under the tradename KEMAMINE® Q-2802C).

Examples of compounds of structural formula (xi) are methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate, wherein R] is an acyclic aliphatic C 15-C17 hydrocarbon group, R2 is an ethylene group, R5 is a methyl group, Rα is a hydroxyalkyl group and A- is a methylsulfate anion; both of these materials are available from Witco Corporation under the tradenames VARISOFT® 222 and VARISOFT® 1 10, respectively.

An example of a compound of structural formula (xiii) is dimethylstearylbenzylammonium chloride, wherein R4 is an acyclic aliphatic Cj8 hydrocarbon group, R5 is a methyl group and A- is chloride, which is available from Witco Corporation under the tradename VARISOFT® SDC.

Examples of compounds of structural formula (xiv) are 1 -methyl- 1- tallowamidoethyl-2-tallowimidazolinium methylsulfate and 1 -methyl- 1 -(hydrogenated tallowamidoethyl)-2-(hydrogenated tallow)imidazolinium methylsulfate wherein R\ is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, R5 is a methyl group and A- is a chloride anion; available from Witco Corporation under the tradenames VARISOFT® 475 and VARISOFT® 445, respectively.

Additional examples of quaternary ammonium compounds useful in the present invention include: (xvi) compounds having the formula:

A^θ

wherein R\ \ is selected from the group consisting of: (a) -CH3, -CH2CH3, - CH2CH2OH, or straight chain aliphatic hydrocarbon groups each of which contains from 12 through 24 carbon atoms, (b) ether groups each of which has the structure: Ri3θ(CH2θ)y-, (c) amide groups each of which has the structure:

and (d) ester groups each of which has the structure:

R12 is a straight chain aliphatic hydrocarbon group containing from 8 to 32 carbon atoms,

Rl3 is a straight chain aliphatic hydrocarbon group containing from 8 to 21 carbon atoms,

Rl4 is a straight chain aliphatic hydrocarbon group containing from 7 to 17 carbon atoms,

Z is an alkoxy group containing one oxygen atom and either two or three carbon atoms, A- is an anion as defined above, m is an integer from 1 through 12, and y is an integer which is either 2 or 3. Yet additional examples of conventional quaternary ammonium compounds useful in the present invention include: (xvii) compounds having the formula: O

Rl5 Rl6- N (CH₂)n- Rl7 (Rl7)y H wherein R15 is hydrogen or C1-C4 alkyl,

Rl5

each R_{] 6} is C1-C4 alkyl or (^R18)y each Ri 7 is a C -C28 alkyl or alkenyl group, R j 8 is hydrogen or C 1 -C4 alkyl, each y is 0 or 1, x is 0 or 1, and each n is from 1 to 6; (xviii) amides represented by the structural formula:

wherein R19 and R20 are selected independently from the group consisting of C]_22 alk(en)yl aryl or alkyl aryl groups, R21 is hydrogen or a C]_22 alk(en)yl, aryl or alkyl-aryl group or is O-R22, wherein R22 is a Cj-22 alk(en)yl, aryl or alkyl-aryl group, and R21 and

R22 optionally contain 1 to 10 alkylene oxide units or functional groups selected from hydroxy, amine, amide, ester, and ether groups; the aryl groups being possibly derived from heterocyclic compounds; at least one of the R19 and R20 groups contains 10 or more carbon atoms; and where the sum of carbon atoms in Rl9⁺R20⁺^21 '^s equal to or greater than 14.

Preferably, the sum of carbon atoms in R19+R20 is equal to or greater than 16. Examples of compounds of structural formula (xviii) include NN-ditallow acetamide, NN-dicoconut acetamide, N,N-dioctadecyl propanamide, N-dodecyl-N-octadecyl acetamide, N-hexadecyl-N- dodecyl butanamide, NN-ditallow benzamide, N,N-dicoconut benzamide, and N,N-ditallow 2- phenyl acetamide.

Additional quaternary ammonium compounds useful in the present invention include all ester quaternaries, including but not limited to: (xix) compounds of the following structural formulas: , θ

wherein each R21 is independently a saturated or unsaturated alkyl or alkylene radical containing 12 to 22 carbon atoms; each Q21 is independently an alkyl group containing 1 to 4 carbon atoms, benzyl, - CH2CH2OH, -CH CH(OH)CH3, or R₂ ι-C(0)-(0-(Alk21))₁.4-; each Alk^l is independently C2H4, C3H6 or C4H8; and

A- is an anion as defined above; (xx) compounds of the formula:

wherein each A^2 is the same or different and each is alkyl containing up to 3 carbon atoms, benzyl, or H-(Alk22-θ)ι _3-Alk - wherein each Alk22 signifies -CH2CH2-, -CH(CH3)CH2- or -CH₂CH(CH >-, provided further that one of the A22 can be hydrogen;

D is methyl, ethyl, propyl, -(CH2)i -3COO-, benzyl or hydrogen; i is 0 or 1 and j is 0 or 1 , provided that the sum of (i + j) is 1 or 2; each χ22 is a straight or branched saturated or unsaturated aliphatic group containing up to 3 carbon-carbon double bonds and containing 1 1 to 23 carbon atoms; n is two minus the number of- CH2)i.3COO- substituents present; and

A- is an anion as defined above; (xxi) compounds of the formula:

R23-[C(O)O(CH2)l-5]0-l-C(O)NH(CH₂)2-5-N(R23a)(R23bHCH2)2-5-OC(O)R23A- wherein each R23 is independently straight or branched alkyl or alkenyl containing 8 to 22 carbon atoms;

R23a i straight or branched alkyl or hydroxyalkyl containing 1 to 3 carbon atoms, benzyl, or -C2F-4θC(0)R26, wherein R26 is straight or branched alkyl or alkenyl containing 8 to 22 carbon atoms;

R23b i -H, -CH3, -C2H5 or benzyl; and A- is an anion as defined above; and

(xxii) compounds of the following structural formulas:

«Θ

A^Θ

YR25

© I

(R₂₄)₃- N-CH₂-CH

CH₂YR₂₅ wherein each R24 is independently straight or branched alkyl or alkenyl containing 1 to 8 carbon atoms and 0 to 3 hydroxyl groups; each R25 is straight or branched alkyl or alkenyl containing 10 to 22 carbon atoms and 0 to 3 hydroxyl groups; each Y is -O-C(O)- or -C(0>-0-; each m is 1 to 3; each n is from 1 to 8; and

A- is an anion as defined above.

Preferred examples of compounds of structural formulas (xxii) include methyl diethanolamine (MDEA) ester quats, triethanolamine (TEA) ester quats, for example, di- (tallow carboxyethyl) hydroxyethyl methylammonium methosulfate, available from Witco

Corporation under the tradename REWOQUAT® WE 16, or epichlorohydrin-based ester quats.

Additional conventional quaternary ammonium compounds useful in the present invention include polyester polyquaternary compounds, including but not limited to: (xxiii) compounds of the following structural formula:

wherein each of R* and R** is independently a linear, branched or cyclic alkylene group containing 2 to 12 carbon atoms, wherein no two nitrogen atoms are separated by fewer than 2 carbon atoms; each of A', A , A-*, A^, and A 5 is independently a straight or branched alkylene containing 2 to 4 carbon atoms; each of R¹, R², R3, R4_{? anc}j R5 J_S independently -H or R^AC(0)- wherein R^A is straight or branched alkyl or alkenyl containing 7 to 21 carbon atoms and 0 to 4 carbon-carbon double bonds; provided that at least one of R¹ , R², R3, R.4, _or R5 j_s RA O)-; each of Q¹, Q² and Q³ is independently -H, -CH3, -C2H5, -C3H7, -C4H5, benzyl, -

CH2COOH, or -CH2COOA-; or, if R* is a -CH2CH2- group, Q¹ and Q³ together or Q¹ and

Q2 together may be a -CH2CH2- group to form a six-membered piperazine ring; or, if R** is a -CH2CH2- group, Q³ and Q³ together may be a -CH2CH2- group to form a six-membered piperazine ring; m is 0 to 4; r is 0 to 2; each of v, w, x, y, and z is independently 1 to 8; i is 0 to 1, j is 0 to 1, and each k is 0 to 1, and the sum of (i+j+k) is 0 to 4; each A- is independently an anion as defined below; and n is the number of moles of A- needed to give the compound of structural formula (xiii) a zero net charge. Compounds of structural formula (xxiii), formulations thereof, and uses thereof, form the subject matter of pending U.S. application No. 09/170,623, filed on October 13, 1998. C. Additional Surfactants

Other suitable non-quaternary compound surfactants, whether anionic, cationic, zwitterionic, nonionic, or amphoteric, may be used in combination with the compounds and formulations of the invention, depending on the application. D. Other Additives Other additives and adjuvants can be optionally added to the compounds and formulations of the present invention for their known purposes. Such additives and adjuvants include, but are not limited to, perfumes, preservatives including bactericides and fungicides, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, especially bluing agents, viscosity control agents, antioxidants, silicones, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, aloe, humectants, skin protectants, feel modifiers, waxes, glycerin, vitamins and extracts, and mixtures thereof. The identity and amounts of the additives and adjuvants used would depend on the application of the formulation and its desired properties. The additives and adjuvants are well-known to those of skill in the art and the additives and adjuvants listed below are not meant to be an exhaustive list but merely a guide to the types of additives that would typically be used. J. Preservatives

Optionally, solubilized, water-soluble preservatives can be added to the present invention. Preservatives are especially preferred when organic compounds that are subject to microorganisms are added to the compositions of the present invention, especially when they are used in aqueous compositions. When such compounds are present, long term and even short term storage stability of the compositions and formulations becomes an important issue since contamination by certain microorganisms with subsequent microbial growth often results in an unsightly and/or malodorous solution. Therefore, because microbial growth in these compositions and formulations is highly objectionable when it occurs, it is preferable to include a solubilized water-soluble, antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear and often aqueous compositions and formulations of the present invention. In general, the preservative can be any organic preservative material which is appropriate for the paper treating application, for example, such preservative will preferably not cause damage to paper appearance, for example, discoloration or coloration of the paper. If the antimicrobial preservative is included in the compositions and formulations of the present invention, it is preferably present in an effective amount, wherein an "effective amount" means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time. Preferred levels of preservative are from about 0.0001% to about 0.5%, more preferably from about 0.0002% to about 0.2%, most preferably from about 0.0003% to about 0.1%, by weight of the composition. Bacteriostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, for example, less than about pH 4, preferably less than about pH 3. Low pH for microbial control is not a preferred approach in the present invention because the low pH can cause chemical degradation of the cyclodextrins. Therefore, aqueous compositions of the present invention should have a pH greater than about 3.0, preferably greater than about 4.0, more preferably greater than about 4.5. As stated above, it is preferable to use the preservative at an effective amount, as defined hereinabove. Optionally, however, the preservative can be used at a level which provides an antimicrobial effect on the treated paper. 2. Antistatic Agents

The composition of the present invention can optionally contain an effective amount of antistatic agent to provide the treated paper with static protection. Preferred antistatic agents are those that are water soluble in at least an effective amount. Examples of these antistatic agents include monoalkyl cationic quaternary ammonium compounds, for example,

alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammonium chloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride (available from Henkel Corporation under the tradename DEHYQUART® E), and ethyl bis(polyethoxyethanol) alkylammonium ethylsulfate (available from Witco Corporation under the tradename VARIQUAT® 66, or methyl bis(polyethoxyethanol) alkylammonium methosulfate (available from Witco Corporation under the tradename REWOQUAT® CPEM), or polyethylene glycols, polymeric quaternary ammonium salts (such as those available from Rhόne-Poulenc Corporation under the MIRAPOL® tradename), quaternized polyethyleneimines, vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer (available from GAF Corporation under the tradename GAFQUAT® HS-100), triethonium hydrolyzed collagen ethosulfate (available from Maybrook Inc. under the tradename QUAT-PRO™ E), and mixtures thereof. It is preferred that a no foaming, or low foaming, agent is used, to avoid foam formation during paper treatment. When an antistatic agent is used it is typically present at a level of from about 0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 03% to about 3%, by weight of the composition.

3. Viscosity Control Agents

Viscosity control agents can be organic or inorganic in nature and may either lower or raise the viscosity of the formulation. Examples of organic viscosity modifiers (lowering) are aryl carboxylates and sulfonates (for example, benzoate, 2-hydroxybenzoate, 2- aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.), fatty acids and esters, fatty alcohols, and water-miscible solvents such as short chain alcohols. Examples of inorganic viscosity control agents are water-soluble ionizable salts. A wide variety of ionizable salts can be used. Examples of suitable salts are the halides and acetates of ammonium ion and the group IA and IIA metals of the Periodic Table of the Elements, for example, calcium chloride, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, ammonium iodide, sodium acetate, potassium acetate, or mixtures thereof. Calcium chloride is preferred. The ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity. The amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desire of the formulator. Typical levels of salts used to control the composition viscosity are from 0 to about 10 wt.%, preferably from about 0.01 wt.% to about 6 wt.%, and most preferably from about 0.02 wt.% to about 3 wt.% of the composition.

Viscosity modifiers (raising) or thickening agents can be added to increase the ability of the compositions to stably suspend water-insoluble articles, for example, perfume microcapsules. Such materials include hydroxypropyl substituted guar gum (such as that available from Rhόne-Poulenc Corporation under the tradename JAGUAR® HP200), polyethylene glycol (such as that available from Union Carbide Corporation under the tradename CARBOWAX® 20M), hydrophobic modified hydroxyethylcellulose (such as that available from the Aqualon Company under the tradename NATROSOL® Plus), and/or organophilic clays (for example, hectorite and/or bentonite clays such as those available from the Rheox Company under the tradename BENTONE™ 27, 34 and 38 or from Southern Clay Products under the tradename BENTOLITE™ L; and those described in U.S. Patent No. 4,103,047, which is herein incorporated by reference in its entirety). These viscosity raisers (thickeners) are typically used at levels from about 0.5 wt.% to about 30 wt.%, preferably from about 1 wt.% to about 5 wt.%, more preferably from about 1.5 wt.% to about 3.5 wt.%, and most preferably from about 2 wt.% to about 3 wt.%, of the composition. 4. Silicones

The present compositions can contain silicones to provide additional benefits. As used herein, the term "silicones" comprises cationic and amphoteric silicones, polysiloxanes, and polysiloxanes having hydrogen-bonding functional groups consisting of amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups. Such polysiloxanes include, but are not limited to, polyether-modified polysiloxanes, amino- modified polysiloxanes, epoxy-modified polysiloxanes, polyhydrido-modified polysiloxanes, phenol-derivative-modified polysiloxanes, ABA-type polysiloxanes, [AB]]\[-type polysiloxanes, amino [AB]jv[-type polysiloxanes, including those available from OSi Specialties, Inc. (a division of Witco Corporation), under the SILWET®, NUWET®, NUDRY™, NUSOFT™, MAGNASOFT® tradenames.

Suitable silicones may include polydimethylsiloxanes of viscosity of from about 100 centistokes (cs) to about 100,000 cs, preferably from about 200 cs to about 60,000 cs and/or silicone gums. These silicones can be used in emulsified form, which can be conveniently obtained directly from the suppliers. Examples of these preemulsified silicones are the 60% emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning Corporation under the tradename DOW CORNING® 1 157 Fluid and the 50% emulsion of polydimethylsiloxane (10,000 cs) sold by General Electric Company under the tradename GENERAL ELECTRIC® SM 2140 silicones. The optional silicone component can be used in an amount of from about 0.1 wt.% to about 6 wt.% of the composition.

Silicone foam suppressants can also be used. These are usually not emulsified and typically have viscosities of from about 100 cs to about 10,000 cs, preferably from about

200 cs to about 5,000 cs. Very low levels are used, typically from about 0.01% to about 1%, preferably from about 0.02% to about 0.5%. Another preferred foam suppressant is a silicone/silicate mixture, for example, Dow Coming's ANTIFOAM™ A.

The pH (10% solution) of the compositions of this invention is generally adjusted to be in the range of from about 2 to about 7, preferably from about 2J to about 6.5, more preferably from about 2.6 to about 4. Adjustment of pH is normally carried out by including a small quantity of free acid in the formulation. Because no strong pH buffers are present, only small amounts of acid are required. Any acidic material can be used; its selection can be made by anyone skilled in the softener arts on the basis of cost, availability, safety, etc. Among the acids that can be used are methyl sulfonic, hydrochloric, sulfuric, phosphoric, citric, maleic, and succinic. For the purposes of this invention, pH is measured by a glass electrode in a 10% solution in water of the softening composition in comparison with a standard calomel reference electrode.

5. Lubrication and Slip Additives

Compositions and formulations of the present invention can contain additives such as water, insoluble organics such as fatty acids, fatty esters, triglycerides, oils, alcohols, fatty alcohols, fatty amines and derivatives, amides, hydrocarbons, mineral oils, waxes, and the like, and mixtures thereof, as lubrication and slip agents.

II. APPLICATIONS

The compositions of the present invention have many advantages over the prior art compounds. Such compositions and formulations according to the present invention are water soluble/dispersible, even cold water dispersible; readily formulate with other classes of quaternary amine softener/debonders; and are hydrolytically stable and color stable on storage. In addition, as shown below, the compositions of the present invention are extremely effective debonders as measured by tensile reduction and are hydrophilic, affording very absorbent tissue and towels. Although the compositions of the present invention exhibit a wide range of tissue softening, they do impart softness and certain compounds exhibit effective softening, which may be comparable to commercial softeners.

In one aspect, the present invention provides compounds and formulations that have the ability to impart to paper and paper products bulk enhancement, softness, lubricity, and antistatic properties, and improve ease of handling of the substrate and surface appearance; in the papermaking process, such compounds of the present invention are termed debonders. Debonders are usually added to the aqueous slurry of paper fibers in the head tank or headbox of a papermaking machine just prior to feeding the resulting slurry onto the papermaking or dewatering screen. These debonders condition the fibers to give improved softness feeling to the paper fibers that is valuable for their use in tissue and towelmaking. The compositions and formulations of the present invention can also be incorporated into the paper or tissue by any suitable means such as spraying or printing onto the surface of the paper or tissue. If the quaternary compounds of the general formula (I) and (II) are applied without the presence of water or other solvent, no evaporation need occur and the possibility of wrinkling is avoided. The present disclosure shows that the compounds and formulations of the present invention may be used for many purposes and suitable additives may be incorporated therein based on the ultimate application. Such ingredients, for example, may contribute significantly to the ease of formulation, stability, dispersibility, fluidity, and the performance properties of the compositions. As noted above, the compositions and formulations of the present invention can also optionally contain other components, depending on the additional properties one may wish to provide in the finished composition. Such additional components include, but are not limited to, additional coupling agents and solvents, additional quaternary ammonium compounds, additional surfactants, hydrocarbon actives, perfumes, preservatives including bactericides and fungicides, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, especially bluing agents, viscosity control agents, antioxidants, silicones, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, aloe, humectants, skin protectants, feel modifiers, and mixtures thereof. Each of the foregoing reactions can be carried out in solvent or in solvent- free conditions, in each case employing conditions well established for the respective reactions in this field.

III. PAPER SOFTENING/DEBONDING FORMULATIONS AND EXAMPLES

Many of the compounds of formulas (I) or (II) have been synthesized and tested in various applications and formulations and the results set forth below. In order to identify such compounds of formulas (I) or (II) and certain other commercial compounds and formulations discussed herein, a unique designation has been applied to each, as set forth as a legend in Table 1 , which serves to identify the compound being discussed, whether a quaternary ammonium compounds of the general formula (I) and/or (II), other formulations, or a commercial product, such as that sold by Witco Corporation under the tradename VARISOFT® 3690.

The following examples are but a few examples of more particular formulations embodying the compositions of the present invention. The following examples are provided for purposes of further description of the present invention and are not intended to limit the scope of that which is regarded as the invention.

These examples illustrate formulations of compounds of the general formula (I) and/or (II) for use as softener/debonding agents, for example, in tissue or paper products. Application methods, papermaking and tissuemaking additives, and other additives are well known to those of skill in the art and are described, for example, in G.A. Smook, Handbook for Pulp & Paper Technologists (2nd Edition) (Angus Wilde Pub. Inc., 1992), which is hereby incorporated by reference in its entirety to better describe the state of the art. Examples 1 to 3 are specific examples, while Example 4 presents a general softener/debonder formulation according to the present invention. Examples 1 to 3 are particularly easy to disperse in water.

In general, the softener/debonder formulation of the present invention would include the components set forth in Example 4 in the amounts shown.

In the following tests, the performance of certain quaternary ammonium compounds of the general formula (I) and/or (II) of the present invention were compared to the performance of commercial products, for example, those available from Witco Coφoration under the tradenames VARISOFT® 3690, AROSURF® PA-801, AROSURF® 8-

190/REWOPOL® EO 70, at dosages corresponding to 1, 3, 5, and 8 lbs. (#) debonder/ton of fiber using various fiber furnish. The designations for each compound or formulation used and tested below and their respective identity or description are set forth as a legend in Table 1. Table 2 similarly identifies the various furnishes used in the testing below.

Standard preparation and test methods were employed to prepare handsheets and to conduct the comparative tests against AROSURF® 8-190, AROSURF® PA-801 , and VARISOFT® 3690; they are as follows: handsheet preparation (TAPPI test method T-205); dry tensile (TAPPI test method T-492); soφtive rate and capacity (TAPPI test method T-561 ); paper conditioning (TAPPI test method T-402); and grammage and thickness (TAPPI test method T-220). Softness was evaluated using paired comparison softness panels.

In each case, a dispersion of the appropriate formulation was prepared in water at 20-25°C. An aqueous slurry of selected fibers was treated with the dispersion of the respective formulation at dosages corresponding to 1, 3, 5, and 8 lbs. (#) debonder/ton of fiber. Tissue weight handsheets, approximately 60 g/π.2, were prepared according TAPPI test method T-205. The handsheets were equilibrated under conditions specified in TAPPI test method T-402. The handsheets were tested for tensile and soφtive rate and capacity according to TAPPI test methods T-492 and T-561, respectively. The handsheets were tested for and grammage and thickness according to TAPPI test method T-220. The results presented in the following Tables demonstrate the performance of many debonders according to the present invention in comparison with commercial products on a variety of furnishes.

The results show that the compounds of the general formula (I) and (II) are effective debonders and compare favorably in performance to industry standards. Indeed, the compounds of the general formula (I) and/or (II) afford debonded tissue products with good absorbency rates and capacities and hand panels confirm that the formulations of the instant invention give better softness than AROSURF® PA-801 debonder. As with all of the Examples given, these examples are only exemplary and, although applied here to various fibers and fiber blends, they may be used with hardwood fiber, softwood fiber, recycled fiber, baggasse fibers, fluff pulp, and all natural papermaking fibers, or cellulosic fibers and blends thereof.

From the results presented in Table 4, it can be seen that the compounds of the general formula (I) and (II) (GS 60136 and GS 60137) are effective debonders and are comparable to the commercial product AROSURF® PA-801 at 8#/ton in tensile reduction. Furthermore, the canola-based compounds of the general formula (I) and (II) (GS 60136), exhibits the same absorbency on this fiber as AROSURF® PA-801, which contains a wetting aide (AROSURF® 8-190), and was more absorbent than the partially hydrogenated tallow- based compound of the general formula (I) and (II) (GS 60136). Lastly, the density of the handsheets decreases with increasing debonder dosage, a reflection of bulk enhancement through fiber debonding.

From the results presented in Table 7, it can be seen that the compounds of the general formula (I) and (II) (GS 60136 and GS 60137) are effective debonders, comparable in tensile reduction to the commercial product AROSURF® PA-801 at 8#/ton dosage. Furthermore, the canola-based compounds of the general formula (I) and (II) (GS 60136), exhibits the same absorbency on this fiber as AROSURF® PA-801, which contains a wetting aide (AROSURF® 8-190), and was more absorbent than the partially hydrogenated tallow- based compound of the general formula (I) and (II) (GS 60136). Lastly, the density of the handsheets decreases with increasing debonder dosage, a reflection of bulk enhancement through fiber debonding (tensile reduction).

For use as overspray softeners, the formulations containing the compounds of general formula (I) and (II) were also prepared as aqueous dispersions (5 wt.% in water) and the resulting dispersions were sprayed on handsheets prepared from furnish SW/HW. After treatment with the dispersions, the handsheets were dried under standard humidity conditions. Achieved softness was evaluated by an internal panel test performed by six experienced persons. For the softness ranking, the untreated handsheets and the handsheets treated with different formulations (as dispersions) were compared, every handsheet being given a certain number of points (the softest handsheets receive the lowest number of points). The number of points given to every handsheet by the internal panel was summed: the lower the sum, the better the softness. According to the achieved sums, the following ranking criteria was applied as follows: 1 is very good; 2 is good; 3 is satisfactory; and 4 is less satisfactory. The results are presented in Table 8.

As noted above, the examples provided are intended to further describe the aspects of the present invention. The examples are illustrative only and are not to be construed as limiting the scope of that which is regarded as the invention. Therefore, the scope of the present invention is only to be limited by the following claims and the equivalents thereto. In the specification and claims, the terms "comprise", "comprising", or "comprises" are intended to convey that the composition or formulation has or includes the recited components, but does not exclude other non-recited components.

Claims

WE CLAIM:

1. A composition comprising:

(a) compounds of the general formulas (I) and (II)

wherein R is -H, -CH3, -C2H5, ^or benzyl; Rl, R2, and R3 are each independently a linear, branched, saturated, or unsaturated fatty acid radical having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups; and A- is an inorganic or organic anion; and

(b) a papermaking additive.

2. The composition according to claim 1, wherein the amount of the compounds of the general formula (I) and (II) ranges from about 5 wt.% to about 95 wt.% of the total composition.

3. The composition according to claim 1, wherein the amount of the compounds of the general formula (I) and (II) ranges 20 wt.% to 90 wt.% of the total composition.

4. The composition according to claim 1, further comprising a solvent.

5. The composition according to claim 4, wherein the solvent is water.

6. The composition according to claim 1, wherein the papermaking additive is selected from the group consisting of wetting agents, strength additives, glycerins, diols, silicones, and oils.

7. The composition according to claim 6, wherein the papermaking additive is a wetting agent selected from the group consisting of polyhydroxy compounds, nonionic surfactants, and anionic wetting agents.

8. The composition according to claim 7, wherein the papermaking additive is a polyhydroxy compound selected from the group consisting of glycerol, polyglycerols having a weight-average molecular weight of from about 150 to about 800, and polyoxyethylene glycols and polyoxypropylene glycols having a weight-average molecular weight of from about 200 to about 4000

9. The composition according to claim 7, wherein the papermaking additive is a nonionic surfactant of the general formula:

RlO-Y-(C2H4θ)_z-C2H4θH wherein:

RlO is a primary, secondary, or branched chain alkyl and/or acyl hydrocarbyl group; a primary, secondary, or branched chain alkenyl hydrocarbyl group; or a primary, secondary, or branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl group, wherein the hydrocarbyl groups have a hydrocarbyl chain length of from about 8 to about 20; Y is -0-, -C(0)0-, -C(0)N(Rπ)-, or -C(O)N(Rπ)Rπ- where Rπ is hydrogen, a primary, secondary, or branched chain alkyl and/or acyl hydrocarbyl group; a primary, secondary, or branched chain alkenyl hydrocarbyl group; or a primary, secondary, or branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl group, wherein the hydrocarbyl groups have a hydrocarbyl chain length of from about 8 to about 20; and z is 3 to 40.

10. The composition according to claim 7, wherein the papermaking additive is an anionic surfactant selected from the group consisting of linear alkyl sulfonates and alkylbenzene sulfonates.

1 1. The composition according to claim 6, wherein the papermaking additive is a strength additive selected from the group consisting of a dry strength additive, a permanent wet strength resin, a temporary wet strength resin, or a compatible mixture thereof.

12. The composition according to claim 6, wherein the papermaking additive is glycerin.

13. The composition according to claim 6, wherein the papermaking additive is a diol or glycol.

14. The composition according to claim 1, wherein A- is selected from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate.

15. A paper web comprising:

(a) papermaking fibers; and (b) a compound of the general formulas (I) and (II)

wherein R is -H, -CH3, -C2H5, or benzyl; R', R2, and R are each independently a linear, branched, saturated, or unsaturated fatty acid radical having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups; and A- is an inorganic or organic anion.

16. A paper web comprising the reaction product of:

(a) papermaking fibers; and

(b) a compound of the general formulas (I) and (II)

wherein R is -H, -CH3, -C2FI5, or benzyl; Rl, R2, and R are each independently a linear, branched, saturated, or unsaturated fatty acid radical having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups; and A- is an inorganic or organic anion.

17. A method of treating papermaking fibers comprising: (a) adding papermaking fibers to an aqueous solution;

(b) adding a compound of the general formulas (I) and (II)

wherein R is -H, -CH3, -02^5, or benzyl; R¹, R , and R3 are each independently a linear, branched, saturated, or unsaturated fatty acid radical having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups; and A- is an inorganic or organic anion, to the aqueous solution before, during, or after the point at which the papermaking fibers are added to the aqueous solution;

(c) allowing the compound of the general formulas (I) and (II) to debond the papermaking fibers to a selected degree;

(d) removing the papermaking fibers from the aqueous solution.

18. A method of treating a paper web, comprising applying to the paper web a compound of the general formulas (I) and (II)

CHs CH2-CH₂-OR¹ CHs _CH2__CH2__OR ³

A° N A° N ^XCH₂— CH-OR^{2 X}CH₂— CH-OH

^CH3 (I) and ^CH3 (II) wherein R is -H, -CH3, -C2H5, or benzyl; R], R2, and R3 are each independently a linear, branched, saturated, or unsaturated fatty acid radical having 6 to 22 carbon atoms and 0 to 3 hydroxyl groups; and A- is an inorganic or organic anion.

19. The method of treating a paper web according to claim 18, wherein the compound of the general formulas (I) and (II) is applied to the paper web by spraying a composition comprising wherein the compound of the general formulas (I) and (II) onto the surface of the paper web.

20. The method of treating a paper web according to claim 18, wherein the compound of the general formulas (I) and (II) is applied to the paper web by printing a composition comprising wherein the compound of the general formulas (I) and (II) onto the surface of the paper web.