WO2000075426A1 - Compositions de plastifiants/deliants pour papier - Google Patents

Compositions de plastifiants/deliants pour papier Download PDF

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Publication number
WO2000075426A1
WO2000075426A1 PCT/US1999/012314 US9912314W WO0075426A1 WO 2000075426 A1 WO2000075426 A1 WO 2000075426A1 US 9912314 W US9912314 W US 9912314W WO 0075426 A1 WO0075426 A1 WO 0075426A1
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compounds
group
composition according
papermaking
compound
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PCT/US1999/012314
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English (en)
Inventor
Yvonne Deac
Craig Poffenberger
Floyd Friedli
Hans-Jurgen Kohle
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Witco Corporation
Witco Surfactants Gmbh
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Priority to PCT/US1999/012314 priority Critical patent/WO2000075426A1/fr
Publication of WO2000075426A1 publication Critical patent/WO2000075426A1/fr

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds

Definitions

  • 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.
  • 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.
  • MEIPA methylethanolisopropanolamine
  • the instant invention provides paper treatment formulations containing compounds of the general formula (I)
  • 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.
  • A- 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • 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).
  • 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.
  • tissue or tissue paper
  • 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%.
  • such impossible formulations that is, those formulations whose component amounts add to a sum greater than 100%
  • 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%.
  • 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.
  • 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.
  • 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 synthetic lubricants
  • defoaming agents antif
  • 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.
  • 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 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.
  • tallow fatty acids and palm fatty acids having iodine values between 1-50 and rapeseed oil fatty acids having iodine values between 80-120 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.
  • a catalyst for example, methanesulfonic acid
  • 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.
  • a solvent preferably isopropanol, ethanol, 1 ,2-propylene glycol and/or dipropylene glycol
  • 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.
  • DMS dimethyl sulfate
  • DES diethyl sulfate
  • hydrocarbons in particular methyl chloride or dimethyl sulfate
  • 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-).
  • Palm fatty acids with an acid number of 205-212, an iodine value of 30-40, and a carbon chain distribution as follows.
  • Palm fatty acids with an acid number of 205-215, an iodine value of 15-25 and a carbon chain distribution as follows.
  • Rapeseed oil fatty acid with an acid value of 190-210 and an iodine value of 85-
  • 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.
  • 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.
  • 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.
  • a wetting agent 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.
  • DOSS diisooctylsulfosuccinate
  • 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.
  • 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- C2H4 ⁇ ) z -C2H4 ⁇ H 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.
  • 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.
  • Y is typically -0-, -C(0)0-, -C(0)N(R ⁇ ] , or -C(0)N(R] ⁇ )R ⁇ ⁇ - 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
  • nonionic surfactants according to the above formula follow, wherein the integer in parenthesis identifies the number of EO groups in the molecule.
  • 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 r ⁇ -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).
  • oleyl alcohol EO(l l) oleyl alcohol EO(18), and oleyl alcohol EO(25).
  • 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.
  • the hexa- through octadecaethoxylates of alkylated phenols, particularly monohydric alkylphenols are useful as the viscosity/dispersibility modifiers of the instant compositions.
  • 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).
  • a phenylene group in the nonionic formula is the equivalent of an alkylene group containing from 2 to 4 carbon atoms.
  • 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.
  • 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.
  • 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 CRODESTATM SL-40; alkylglycoside ethers as described in U.S. Patent No.
  • 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.
  • water-soluble strength additive resins may include dry strength additives, permanent wet strength resins, temporary wet strength resins, or a compatible mixture thereof.
  • 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.
  • 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.
  • 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.
  • polyamide-epichlorohydrin resins 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.
  • 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-RESTM, such as SANTO-RESTM 31.
  • SANTO-RESTM such as SANTO-RESTM 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.
  • 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.
  • 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 STARCHTM 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.
  • glycerin may also be used in the composition and formulations thereof.
  • 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.
  • 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.
  • 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.
  • these conventional quaternary ammonium compounds 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.
  • the counteranion 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.
  • A- represents the anion group
  • A- represents the anion group
  • A- represents half of the anion group
  • A- represents a third of the anion group
  • 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:
  • each R ⁇ is an acyclic alkyl or alkylene C 12-C21 hydrocarbon group, each Z is -(R2 ⁇ ) ⁇ -4H, or -R2H, and R2 and R3 are divalent Cj-Cg alkylene groups; (ii) substituted imidazoline compounds having the formula:
  • 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
  • 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.
  • 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:
  • 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
  • A- is an anion as defined above
  • 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:
  • Rj is an acyclic aliphatic C12-C21 hydrocarbon group
  • R2 is a divalent Cj-C ⁇ alkylene group
  • 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.
  • R4 is an acyclic aliphatic C ⁇ -C ⁇ $ hydrocarbon group
  • R5 and Rg are methyl groups.
  • 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 ⁇ ⁇ -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 ⁇ hydrocarbon group, R2 is an ethylene group, R5 is an ethyl group, and A- is an ethylsulfate anion.
  • 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.
  • 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:
  • 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
  • A- is an anion as defined above
  • 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
  • n 1 to about 5, and R ⁇ , R2, R5, and A- are as defined above; (xiii) quaternary ammonium compounds having the formula:
  • R4 is an acyclic aliphatic C8-C22 hydrocarbon carbon group
  • each R5 is a C ⁇ -
  • each R ⁇ is an acyclic aliphatic C12-C2I hydrocarbon group
  • R2 is a divalent alkylene group having 1 to 3 carbon atoms
  • R5 and A- are as defined above, or R5 is -H
  • 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
  • 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, R ⁇ 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.
  • 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: Ri3 ⁇ (CH2 ⁇ )y-, (c) amide 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
  • y is an integer which is either 2 or 3.
  • Conventional examples of conventional quaternary ammonium compounds useful in the present invention include: (xvii) compounds having the formula: O
  • each R ] 6 is C1-C4 alkyl or ( R 18)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:
  • 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.
  • the sum of carbon atoms in R19+R20 is equal to or greater than 16.
  • 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: , ⁇
  • 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 R 2 ⁇ -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:
  • each A ⁇ 2 is the same or different and each is alkyl containing up to 3 carbon atoms, benzyl, or H-(Alk22- ⁇ ) ⁇ _3-Alk - wherein each Alk22 signifies -CH2CH2-, -CH(CH3)CH2- or -CH 2 CH(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 ⁇ 22 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:
  • R23a i straight or branched alkyl or hydroxyalkyl containing 1 to 3 carbon atoms, benzyl, or -C2F-4 ⁇ C(0)R26, wherein R26 is straight or branched alkyl or alkenyl containing 8 to 22 carbon atoms;
  • 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
  • polyester polyquaternary compounds including but not limited to: (xxiii) compounds of the following structural formula:
  • 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 R 1 , R 2 , R3, R4 ?
  • 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 R 1 , R 2 , R3, R.4, or R5 j s RA O)-; each of Q 1 , Q 2 and Q 3 is independently -H, -CH3, -C2H5, -C3H7, -C4H5, benzyl, -
  • Q2 together may be a -CH2CH2- group to form a six-membered piperazine ring; or, if R** is a -CH2CH2- group, Q 3 and Q 3 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the preservative can be used at a level which provides an antimicrobial effect on the treated paper.
  • 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.
  • 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 Rh ⁇
  • QUAT-PROTM E under the tradename QUAT-PROTM E
  • QUAT-PROTM E QUAT-PROTM E
  • a no foaming, or low foaming, agent is used, to avoid foam formation during paper treatment.
  • an antistatic agent 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.
  • Viscosity control agents can be organic or inorganic in nature and may either lower or raise the viscosity of the formulation.
  • organic viscosity modifiers lowering
  • aryl carboxylates and sulfonates for example, benzoate, 2-hydroxybenzoate, 2- aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.
  • fatty acids and esters for example, benzoate, 2-hydroxybenzoate, 2- aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.
  • fatty acids and esters for example, benzoate, 2-hydroxybenzoate, 2- aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.
  • fatty acids and esters for example, benzoate, 2-
  • 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 Rh ⁇ ne-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 BENTONETM 27, 34 and 38 or from Southern Clay Products under the tradename BENTOLITETM L; and those described in U.S.
  • compositions can contain silicones to provide additional benefits.
  • 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®, NUDRYTM, NUSOFTTM, 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
  • foam suppressant is a silicone/silicate mixture, for example, Dow Coming's ANTIFOAMTM 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • compositions and formulations of the present invention may be used for many purposes and suitable additives may be incorporated therein based on the ultimate application.
  • suitable additives may contribute significantly to the ease of formulation, stability, dispersibility, fluidity, and the performance properties of the compositions.
  • 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.
  • 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.
  • the softener/debonder formulation of the present invention would include the components set forth in Example 4 in the amounts shown.
  • 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); so ⁇ tive 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.
  • 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/ ⁇ .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 so ⁇ tive 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 compounds of the general formula (I) and (II) are effective debonders and compare favorably in performance to industry standards.
  • 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.
  • 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.
  • the compounds of the general formula (I) and (II) are effective debonders and are comparable to the commercial product AROSURF® PA-801 at 8#/ton in tensile reduction.
  • the canola-based compounds of the general formula (I) and (II) 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).
  • the density of the handsheets decreases with increasing debonder dosage, a reflection of bulk enhancement through fiber debonding.
  • the compounds of the general formula (I) and (II) are effective debonders, comparable in tensile reduction to the commercial product AROSURF® PA-801 at 8#/ton dosage.
  • the canola-based compounds of the general formula (I) and (II) 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).
  • the density of the handsheets decreases with increasing debonder dosage, a reflection of bulk enhancement through fiber debonding (tensile reduction).
  • 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).

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Abstract

L'invention concerne une composition contenant: (a) des composés des formules générales (I) et (II) dans lesquelles R représente -H, -CH3, -C2H5 ou benzyle; R?1, R2 et R3¿ représentent chacun indépendamment un radical d'acide gras linéaire, ramifié, saturé ou insaturé ayant 6 à 22 atomes de carbone et 0 à 3 groupes hydroxyle; A- représente un anion inorganique ou organique; et (b) représente un additif de fabrication de papier.
PCT/US1999/012314 1999-06-03 1999-06-03 Compositions de plastifiants/deliants pour papier WO2000075426A1 (fr)

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WO2007058609A2 (fr) * 2005-11-17 2007-05-24 Akzo Nobel N.V. Procede de fabrication de papier
US7604715B2 (en) 2005-11-17 2009-10-20 Akzo Nobel N.V. Papermaking process
WO2017151084A1 (fr) * 2016-02-29 2017-09-08 Kemira, Oyj Composition d'adoucissant

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US5279767A (en) * 1992-10-27 1994-01-18 The Procter & Gamble Company Chemical softening composition useful in fibrous cellulosic materials
WO1996019616A1 (fr) * 1994-12-19 1996-06-27 The Procter & Gamble Company Produit de papier pour mouchoirs jetables et produits analogues comprenant un compose d'ammonium quaternaire, un compose de polysiloxane et des materiaux liants
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US5753079A (en) * 1995-04-27 1998-05-19 Witco Corporation Obtaining enhanced paper production using cationic compositions containing diol and/or diol alkoxylate

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US5240562A (en) * 1992-10-27 1993-08-31 Procter & Gamble Company Paper products containing a chemical softening composition
US5279767A (en) * 1992-10-27 1994-01-18 The Procter & Gamble Company Chemical softening composition useful in fibrous cellulosic materials
US5679218A (en) * 1994-07-29 1997-10-21 The Procter & Gamble Company Tissue paper containing chemically softened coarse cellulose fibers
WO1996019616A1 (fr) * 1994-12-19 1996-06-27 The Procter & Gamble Company Produit de papier pour mouchoirs jetables et produits analogues comprenant un compose d'ammonium quaternaire, un compose de polysiloxane et des materiaux liants
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007058609A2 (fr) * 2005-11-17 2007-05-24 Akzo Nobel N.V. Procede de fabrication de papier
WO2007058609A3 (fr) * 2005-11-17 2007-07-26 Akzo Nobel Nv Procede de fabrication de papier
US7604715B2 (en) 2005-11-17 2009-10-20 Akzo Nobel N.V. Papermaking process
WO2017151084A1 (fr) * 2016-02-29 2017-09-08 Kemira, Oyj Composition d'adoucissant
KR20180119634A (ko) * 2016-02-29 2018-11-02 케미라 오와이제이 연화제 조성물
CN109072565A (zh) * 2016-02-29 2018-12-21 凯米罗总公司 软化剂组合物
RU2700056C1 (ru) * 2016-02-29 2019-09-12 Кемира Ойй Композиция умягчителя
US10570567B2 (en) 2016-02-29 2020-02-25 Kemira Oyj Softener composition
AU2016395426B2 (en) * 2016-02-29 2020-10-08 Kemira Oyj A softener composition
AU2016395426C1 (en) * 2016-02-29 2021-01-21 Kemira Oyj A softener composition
CN109072565B (zh) * 2016-02-29 2021-07-30 凯米拉公司 软化剂组合物
US11492760B2 (en) 2016-02-29 2022-11-08 Kemira Oyj Softener composition
KR102582518B1 (ko) 2016-02-29 2023-09-26 케미라 오와이제이 연화제 조성물

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