DRYER-ACTIVATED FABRIC CONDITIONING AND ANTISTATIC COMPOSITIONS WITH IMPROVED PERFUME LONGEVITY

Abstract: The present invention relates to dryer-activated fabric softening compositions comprising: (A) fabric softening compounds; and (B) an ester of an alcohol perfume wherein the ester has at least one free carboxylic acid. The ester has general formula (I), wherein R is selected from the group consisting of substituted or unsubstituted C1-C30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group; or ring containing a heteroatom, R' is a perfume alcohol with a boiling point at 760 mm Hg of less than about 300 DEG C; and m and n are independently an integer of 1 or greater.

Description: DRYER-ACTIVATED FABRIC CONDITIONING AND ANTISTATIC COMPOSITIONS WITH IMPROVED PERFUME LONGEVITY 5 TECHNICAL FIELD i i nv. pι .u.ι.1 i iVCi iυu i iαt a io oil uilμiovciiiciu m α uvcucύ, e.g., vliycl- added, softening products and compositions. These products and/or compositions are either in particulate form, compounded with other materials in solid form, e.g., tablets, pellets, agglomerates, etc., or preferably attached to a substrate. 5 BACKGROUND OF THE INVENTION Consumer acceptance of laundry products is determined not only by the performance achieved with these products but the aesthetics associated therewith. The perfume systems are therefore an important aspect ofthe successful formulation of such commercial products. 0 What perfume system to use for a given product is a matter of careful consideration by skilled perfumers. While a wide array of chemicals and ingredients are available to perfumers, considerations such as availability, cost, and compatibility with other components in the compositions limit the practical options. Thus, there continues to be a need for low-cost, compatible perfume materials useful 5 for laundry compositions. Furthermore, due to the high energy input and large air flow in the drying process used in the typical automatic laundry dryers, a large part of many perfumes would be lost from the dryer vent. Perfume can be lost even when the fabrics are line dried. It is desirable to formulate efficient, enduring fabric softener perfume 0 compositions that remain on fabric for aesthetic benefit, and are not lost, or wasted, without benefiting the laundered items. The present invention provides improved compositions using a combination of softener and efficient perfumes in dryer-activated fabric softening compositions while, surprisingly, also providing improved longevity of perfumes on the laundered 5 clothes, by utilizing enduring perfume compositions. It has been discovered that esters of perfume alcohols are particularly well suited for fabric softening compositions. In particular, it has been discovered that esters of perfume alcohols wherein the ester has at least one free carboxylate group will hydrolze on a fabric substrate to give an alcohol perfume. In addition, slowly hydrolyzable esters of perfume alcohols provide release ofthe perfume over a longer period of time than by the use ofthe perfume itself in the fabric softening compositions. Such materials therefore provide perfumers with more options for perfume ingredients and more flexibility in formulation considerations. These and other advantages ofthe present invention will be seen from the disclosures hereinafter. A UKUUNL) AK1 General ester chemistry is described in Carey et al., Advanced Organic Chemistry, Part A, 2nd Ed., pp. 421-426 (Plenum, N.Y.; 1984). Compositions of fragrance materials (having certain values for Odour Intensity Index, Malodour Reduction Value and Odour Reduction Value) said to be used as fragrance compositions in detergent compositions and fabric conditioning compositions are described in European Patent Application Publication No. 404,470, published December 27, 1990 by Unilever PLC. Example 1 describes a fabric-washing composition containing 0.2% by weight of a fragrance composition which itself contains 4.0 % geranyl phenylacetate. A process for scenting fabrics washed with lipase-containing detergents is described in PCT application No. WO 95/04809, published February 16, 1995 by Firmenich S.A. SUMMARY OF THE INVENTION The present invention relates to dryer-activated fabric softening compositions and articles having improved softness, perfume delivery from sheet substrates (lower m.p. range), and/or antistatic effects, for use in an automatic cloϋhes dryer. In accordance with a first aspect ofthe present invention, a dryer activated fabric softening composition is provided. The composition comprises from about 10% to about 99.99% by weight of a fabric softening component comprising a fabric softening compound and from about 0.01% to about 15% by weight of a perfume component having an ester of a perfume alcohol wherein the ester has at least one free carboxylate group. The ester has the formula: (I) O II HOCJ-R COV] wherein R is selected from the group consisting of substituted or unsubstituted C \ - C30 straight, branched or cyclic alkyl, alkenyl. alkynyl, alkylaryl, aryl group; or ring containing a heteroatom, R' is a perfume alcohol with a boiling point at 760 mm Hg of less than about 300 °C; and m and n are independently an integer of 1 or greater. The fabric softening component is preferably a fabric softening compound which is a quaternary ammonium compound or its precursor amine selected from the following groups Formula II: -wiiticiii c di Y is -G-(0)C-, υr -C(υ;-u-; p is 1 to 3; each v is an integer from 1 to 4; each Rl substituent is a short chain Cj-Cg alkyl group; each R^ is Cg-C3o hydrocarbyl or substituted hydrocarbyl substituent; and the counterion, X-, can be any softener-compatible anion. Formula III wherein each Q is -O-C(O)- or -C(O)-O-, each R^ is C1-C4 alkyl or hydroxy alkyl group; each R^, V, and X " are defined hereinbefore for Formula II. Formula IV: wherein R^ is a short chain C1-C4 alcohol; p is 2; R* ,R2 , v, Y, and X" are defined hereinbefore for Formula II and Formula V: wherein R^, R^, p, v, and X" are defined hereinbefore for Formula II; and and mixtures thereof, wherein at least one Y group is O O 11 NH-C or — c-NH- and mixtures thereof. Most preferably, the quaternary ammonium compound is fully saturated Formula II compound, such as dimethyl bis(tallowyl oxy ethyl) ammonium methyl sulfate, derived from hardened tallow or a dimethyl bis(acyl oxy ethyl) ammonium methyl sulfate derivatives of Cg-C3o fatty acids, such as dimethyl bis(tallowyl oxy ethyl) ammonium methyl sulfate; dimethyl bis(oleyl oxy ethyl) ammonium methyl sulfate or dimethyl bis(cocoyl oxy ethyl) ammonium methyl sulfate. The composition may comprise from about 15% to about 90% of Formula II compound. The dryer activated fabric softening compositions ofthe present invention m γ fiirther The co -softener may comprise .a. λ ;ϋι αciύ salt of a tertiary amine, tertiary amine ester, or mixtures thereof. The carboxylic acid salt forming anion moiety ofthe co-softener may be selected from the group consisting of lauric, myristic, palmitic, stearic, oleic and mixtures thereof. The amine salt ofthe co-softener may be selected from the group consisting of oleyldimethylamine stearate, dioleylmethylamine stearate, linoleyldimethylamine stearate, dilinoleylmethylamine stearate, stearyldimethylamine stearate, distearyl- methylamine myristate, stearyldimethylamine palmitate, distearylmethylamine palmitate, distearylmethylamine myristate, distearylmethylamine palmitate, distearylmethylamine laurate, dioleyldistearylmethylamine oleate, distearylmethylamine oleate, and mixtures thereof. The perfume component of the compositions of the present invention comprises from about 0.01% to about 15% by weight of said composition. The perfume component may comprises an ester of a perfume alcohol wherein the ester has at least one free carboxylate group in admixture with a fully esterified ester of a perfume alcohol. R may be selected from the group consisting of substituted or unsubstituted C\ - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group, or ring contaiing a heteroatom. R' is a perfume alcohol and may be selected from the group consisting of geraniol, nerol, phenoxanol, floralol, β- citronellol, nonadol, cyclohexyl ethanol, phenyl ethanol, isoborneol, fenchol, isocyclogeraniol, 2-phenyl-l -propanol, 3,7-dimethyl-l -octanol, and combinations thereof. The ester is selected from maleate, succinate, citrate, pyromellitate, trimellitate, phthalate or adipate esters of said alcohol perfume. Accordingly, the preferred esters include geranyl succinate, neryl succinate, (β-citronellyl) maleate, nonadol maleate, phenoxanyl maleate, (3,7-dimedιyl-l- octanyl) succinate, (cyclohexylethyl) maleate, floralyl succinate, (β-citronellyl) phthalate and (phenylethyl) adipate. The fully esterified ester of a perfume alcohol which may be included in conjunction with the perfume ester having at least one free carboxylic group may be selected from the group consisting of digeranyl succinate, dineryl succinate, geranyl neryl succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, neryl laurate, di(β-citronellyl) maleate, dinonadyl maleate, diphenoxanyl maleate, di(3.7-dimethyl-l -octanyl) succinate, di(cyclohexylethyl) maleate, difloralyl succinate, and di(phenylethyl) adipate and mixtures thereof. Additional ingredients to the compositions may include: (A) a stabilizer selected from the group consisting of ascorbic acid, ascorbic palmitate, propyl gallate, citric acid, butylated hydroxytoluene, tertiary b tylhydrcquinoric, natural toccpii roia, uuiylaicd hyuroxyanisoie and mixtures thereof; (B) a soil release polymer; and (C) mixtures thereof. In accordance with another aspect ofthe present invention, a dryer activated fabric softening composition is also provided. The composition comprises: (A) from about 30% to about 85% of dimethyl bis(tallowyl oxy ethyl) ammonium metiiyl sulfate, dimethyl bis(oleyl oxy ethyl) ammonium methyl sulfate, dimethyl bis(cocoyl oxy ethyl) ammonium methyl sulfate, N-methyl, N,N-di-(2- oleyloxyethyl) N-2-hydroxyethyl ammonium methylsulfate and mixtures thereof; (B) from about 0.01 % to about 15% by weight of the composition of a perfume component having an ester of a perfume alcohol wherein the ester has at least one free carboxylate group, said ester having the formula: wherein R is selected from the roup consisting of substituted or unsubstituted C \- C30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group; or ring containing a heteroatom, R' is a perfume alcohol with a boiling point at 760 mm Hg of less than about 300 °C; and m and n are independently an integer of 1 or greater; (C) from about 20% to about 75% of oleyldimethylamine stearate, distearylmethylamine myristate, and mixtures thereof; and (D) from about 15% to about 40% of C j ø^g acyl sorbitan monoester, diester, and mixtures thereof. In addition, the composition has a thermal softening point of from about 35 °C to about 100 °C. Component D in the composition may comprise sorbitan monooleate, and sorbitan monostearate, and mixtures thereof. Component (C) may comprises a mixture of oleyldimethylamine stearate and distearylmethylamine myristate in a weight ratio of from 1 :10 to 10: 1. The ratio of A:C:D in the composition is preferably 5:3:2. In the perfume component B, R' is a perfume alcohol which may be selected from the group consisting of geraniol, nerol, phenoxanol, floralol, β-citronellol, nonadol, cyclohexyl ethanol, phenyl ethanol, isoborneol, fenchol, isocyclogeraniol, 2-phenyl-l -propanol, 3,7-dimethyl-l -octanol, and combinations thereof. The ester is selected from maleate, succinate, citrate, pyromellitate, trimellitate, phthalate or adipate esters of alcohol perfumes. Accordingly, the ester is preferably selected I Λ from th group c nsis in of gcraayl -.uc uαit, iiuyl bucciiuue, (β-chrυneiiyi maleate, nonadol maleate, phenoxanyl maleate, (3,7-dimethyl-l -octanyl) succinate, (cyclohexylethyl) maleate, floralyl succinate, (β-citronellyl) phthalate and (phenylethyl) adipate. Accordingly, it is an object ofthe present invention to provide a dryer 15 activated fabric softening composition having a perfume component including a ester of a perfume alcohol wherein the ester has at least one free carboxylate group. It is another object ofthe present invention to provide a fabric softening composition that provides superior consumer recognizable results in the the delivery of perfume to a fabric placed in contact with the compositions ofthe present invention. These 0 and other objects, features and advantages of the present invention will be recognizable to one of ordinary skill in the art from the following description and the appended claims. All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incoφorated by 25 reference. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to fabric softening compositions and articles having improved softness, delivery from the sheet, and/or antistatic effects, for use 30 in an automatic clothes dryer. The dryer activated fabric softening compositions of the present invention include a perfume component which comprises an ester of a perfume alcohol wherein the ester has at least one free carboxylate group. The esters ofthe present invention have d e general formula: (I) 35 wherein R is selected from the group consisting of substituted or unsubstituted C j - C30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group or ring containing a heteroatom; R' is a perfume alcohol with a boiling point at 760 mm Hg of less than about 300 °C; and m and n are independently an integer of 1 or greater. Preferably, R is selected from the group consisting of substituted or unsubstituted C 1 - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group or ring containing a heteroatom. Most preferably, the esters are maleate, succinate, pyromellitate, trimellitate, citrate, phthalate or adipate esters ofthe alcohol perfume. Ai> can be seen, Fυπnuia (I) includes at least one tree carboxylate group. Preferably, the perfume component includes at least about 2% by weight, and more preferably at least about 5% by weight ofthe ester of Formula (I). R' is a perfume alcohol with a boiling point at 760 mm Hg of less than about 300 °C. While most any perfume alcohol having a boiling point of less than about 300 °C may be employed, preferred alcohols include geraniol, nerol, phenoxanol, floralol, β-citronellol, nonadol, cyclohexyl ethanol, phenyl ethanol, isoborneol, fenchol, isocyclogeraniol, 2 -phenyl- 1 -propanol, 3,7-dimethyl-l -octanol, anisyl alcohol, cinnamyl alcohol, dec-9-en-l-ol, 3-methyl-5-phenyl-l-pentanol, 7-p- methan-1-ol, 2,6-dimethylloct-7-en-2-ol, (Z)-hex-3-enl-ol, 1 -hexanol, 2-hexanol, 5- ethyl-2-nonal, nona-2,6-dien-l-ol, bomeol, oct-l-en-3-ol, 4-cyclohexyl-2-methyl-2- butanol, 2-med yl-4-phenyl-2-butanol, 2-methyl- l-phenyl-2-propanol, cyclomethylcitronellol, decanol, dihydroeugenol, 8-p-menthanol, 3,7-dimethyl-l - octanol, 2,6-dimethyl-2-heptanol, dodecanol, eucalpytol, eugenol, tetrahydro-2- isobutyl-4-methyl-4(2H)-pyranol, isoeugenol, linalool, 2-methoxy-4-propyl-l- cyclohexanol, terpineol, tetrahydromuguol, 3,7-dimethyl-3-octanol, 3- and 4-(4- hydroxy-4-methylpentyl)cyclohex-3-ene-l-carbaldehyde and combinations thereof. Thus, preferred esters ofthe present invention include geranyl succinate, neryl succinate, (β-citronellyl) maleate, nonadyl maleate, phenoxanyl maleate, (3,7- dimethyl-l -octanyl) succinate, (cyclohexylethyl) maleate, (β-citronellyl) phthalate, floralyl succinate, and (phenylethyl) adipate. Of course, one of ordinary skill in the art will recognize that other esters satisfying the general Formula (I) may also be employed in the present invention, such as monogeranyl citrate, di(β-citronellyl) pyromellitate and di(cyclohexylethyl) citrate and the isomers of all such compounds. The perfume component ofthe dryer activated fabric softening compositions ofthe present invention may include one or more additional fully esterified esters of a perfume alcohol in conjunction with the esters of Formula (I) described above. Suitable fully esterified perfume alcohol esters which may be employed in the present invention are disclosed in U.S. Patent Application 08/277,558 to Hartman et al. filed on July 19, 1994, U.S. Patent Application 08/499,158 to Severns et al. filed on July 7, 1995 and U.S. Patent Application 08/499,282 to Severns et al. filed on July 7, 1995, of which the disclosures of all three are herein incoφorated by reference. Preferably, the fully esterified esters of perfume alcohols are di-esters of perfume alcohols. Di-esters of both allylic and non-allylic alcohols may be employed. Suitable fully esterified esters of perfume alcohols which may be employed in the present invention include digeranyl succinate, dineryl succinate, geranyl neryl succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, ιιcι_yl lauiαic, ύi(υ-ciuυneiiyi) maieaie, dinonadol maleate, diphenoxanyl maleate, di(3,7-dimethyl-l -octanyl) succinate, di(cyclohexylethyl) maleate, difloralyl succinate, and di(phenylethyl) adipate and mixtures thereof. Most preferably, the additional added ester of a perfume alcohol is the di-ester which corresponds to the ester of Formula (I) according to the present invention. For example, if the ester of Formula (I) employed in the present invention is the mono-ester geranyl succinate, then the additional added fully esterified ester of a perfume alcohol is digeranyl succinate. Furthermore, it is typical that in the production of geraniol, nerol, an isomer of geraniol, is also produced. Thus, in the production of esters from geraniol, the esters of nerol are produced as well. The typical commercial use of gernaiol involves a 70:30 mixture of geraniol to nerol. Also, during the production of diesters of geraniol, the mono-esters are aslo typically present. However, they are typically present at levels of less than 10% by weight ofthe diester. Methods for manufacturing certain of these esters are known, and methods are also exemplified hereinafter. Fabric Softening Component Compositions ofthe present invention contain from about 10% to about 99.99%, preferably from about 15% to about 90%, more preferably from about 30% to about 85%, and even more preferably from about 30% to about 55%, of fabric softening component, the fabric softening component is preferably ester quaternary ammonium compounds (EQA). Preferably, the EQA ofthe present invention is selected from Formulas II, III, IV, V, and mixtures thereof. Formula II comprises: wherein each Y = -O-(O)C-, or -C(O)-O-; p = 1 to 3; each v = is an integer from 1 to 4, and mixtures thereof; each Rl substituent is a short chain Cj-Cg, preferably C1-C3, alkyl group, e.g., methyl (most preferred), ethyl, propyl, and the like, benzyl and mixtures thereof; each R2 is a long chain, saturated and/or unsaturated (Iodine Value of from about 3 to about 60), C8-C30 hydrocarbyl, or substituted hydrocarbyl substituent and mixtures thereof; and the counterion, X , can be any softener- compatibl ύiiiu.., foi example, incύiyisulfate, eihyisuirate, cnlonde, bromide, formate, sulfate, lactate, nitrate, benzoate, and the like, preferably methylsulfate. It will be understood that substituents R^ and R^ of Formula II can optionally be substituted with various groups such as alkoxy 1 or hydroxyl groups. The preferred compounds can be considered to be diester quaternary ammonium salts (DEQA), specifically variations of ditallow dimethyl ammonium methyl sulfate (DTDMAMS), which is a widely used fabric softener. At least 80% ofthe DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be EQA monoester (e.g., only one -Y-R2 group). As used herein, when the diester is specified, it will include the monoester that is normally present. For the optimal antistatic benefit the percentage of monoester should be as low as possible, preferably less than about 2.5%. The level of mono¬ ester present can be controlled in the manufacturing ofthe EQA. EQA compounds prepared with fully saturated acyl groups are excellent softeners. However, it has now been discovered that compounds prepared with at least partially unsaturated acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met. Variables that must be adjusted to obtain the benefits of using unsaturated acyl groups include the Iodine Value ofthe fatty acids, the odor of fatty acid starting material, and or the EQA. Any reference to Iodine Value values hereinafter refers to Iodine Value of fatty acyl groups and not to the resulting EQA compound. Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. As the Iodine Value is raised, there is a potential for odor problems. Some highly desirable, readily available sources of fatty acids such as tallow, possess odors that remain with the compound EQA despite the chemical and mechanical processing steps which convert the raw tallow to finished EQA. Such sources must be deodorized, e.g., by absoφtion, distillation (including stripping such as steam stripping), etc., as is well known in the art. In addition, care must be taken to minimize contact ofthe resulting fatty acyl groups to oxygen and/or bacteria by adding antioxidants, antibacterial agents, etc. The additional expense and effort associated with the unsaturated fatty acyl groups is justified by the superior performance which has not been recognized. Generally, hydrogenation of fatty acids to reduce polyunsaturation and to lower Iodine Value to insure good color and odor stability leads to a high degree of trans configuration in tlic iϊiυlcculc. Tueiefυre, diester compounds derived rrom tatty acyl groups having low Iodine Value values can be made by mixing fully hydrogenated fatty acid with touch hydrogenated fatty acid at a ratio which provides an Iodine Value of from about 3 to about 60. The polyunsaturation content of die touch hardened fatty acid should be less t .han about 5%, preferably less than about 1 %. During touch hardening the cis/trans isomer weight ratios are controlled by methods known in the art such as by optimal mixing, using specific catalysts, providing high availability, etc. It has been found that a solvent may be used to facilitate processing ofthe Formula II EQA and or ofthe fabric softening composition containing the Formula II EQA. Possible solvents include C1-C30 alcohols, with secondary and tertiary alcohols preferred, e.g., isopropanol, and C8-C30 fatty acids. It has also been found that for good chemical stability ofthe diester quaternary compound in molten storage, water levels in the raw material must be minimized to preferably less than about 1 % and more preferably less than about 0.5%. Storage temperatures should be kept as low as possible and still maintain a fluid material, ideally in the range of from about 45 °C to about 70 °C. The optimum storage temperature for stability and fluidity depends on the specific Iodine Value of the fatty acid used to make the diester quaternary and the level/type of solvent selected. Also, exposure to oxygen should be minimized to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal transportation/storage/handling ofthe material in manufacturing operations. The following are non-limiting examples of EQA Formula II (wherein all long-chain alkyl substituents are straight-chain): Saturated (C2H5)2 + N(CH2CH2OC(O)C ] 7 H35)2 (CH3SO4)- (HO-CH(CH3)CH2)(CH3) + N(CH 2 CH 2 OC(O)C j 5H3 j ) 2 Br (CH3)(C2H5) + N(CH2CH 2 OC(O)Ci3H27)2 (HCOO) " (C 3 H7)(C2H5) + N(CH2CH 2 OC(O)Cι !H 23 )2 (CH 3 SO 4 )- (CH3) 2 + N-CH2CH2θC(O)C 1 5 H3i (CH3SO4)- I CH2CH 2 OC(O)C 17 H35 (CH3)2 + N(CH2CH 2 0C(0)R2)2 (CH3SO4)- where -C(O)R 2 is derived from saturated tallow. Unsaturated (C 2 H5)2 + N(CH 2 CH2OC(O)C 1 7 H 33 ) 2 (CH 3 SO 4 )" (HO-CH(CH3)CH2)(CH 3 ) + N(CH2CH 2 OC(O)C 1 5 H 2 9)2 Br (C 2 H5)2 + N(CH 2 CH2OC(O)C 7 33 ) 2 C 1 - (CH 3 )(C2H5) + N(CH2CH2OC(O)C 13 H27)2 (C 6 H 5 COO)- (CH3)2 + N-CH2CH 2 OC(O)Ci5H29 (CH3CH2SO4)- I CH2CH 2 OC(O)C 17 H33 (CH 2 CH 2 OH)(CH3) + N(CH2CH2θC(O)R 2 )2 (CH3SO4)- (CH3) 2 + N(CH2CH 2 OC(O)R 2 )2 (CH 3 SO )' (HOCH 2 CH2)(CH3)N + (CH 2 CH2θC(O)R 2 )2(CH3Sθ4)- where -C(O)R 2 is derived from partially hydrogenated tallow or modified tallow having the characteristics set forth herein. In addition to Formula II compounds, d e compositions and articles ofthe present invention comprise EQA compounds of Formula III: wherein, for any molecule: each Q is -O-C(O)- or -C(O)-O-; each Rl is C1-C4 alkyl or hydroxy alkyl; R 2 and v are defined hereinbefore for Formula II; and wherein preferably R* is a methyl group, v is 1 , Q is -O-C(O)-, each R 2 is C14-C18, and X" is methyl sulfate. The straight or branched alkyl or alkenyl chains, R 2 , have from about 8 to about 30 carbon atoms, preferably from about 14 to about 18 carbon atoms, more preferably straight chains having from about 14 to about 18 carbon atoms. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl 5 materials. A specific example of a Formula III EQA compound suitable for use in the fabric softening compositions herein is: 1 ,2-bis(tallowyl oxy)-3 -trimethyl ammoniopropane methylsulfate (DTTMAPMS). Other examples of suitable Formula III EQA compounds of this invention are ι n obtained by, e.g., rephcing "tallov.yl" in t v. v compounds wiiii, for example, cocoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing "methyl" in the above compounds widi ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals; replacing "methylsulfate" in the above compounds with chloride, ethylsulfate, 15 bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is preferred. In addition to Formula II and Formula III compounds, the compositions and articles ofthe present invention comprise EQA compounds of Formula IV: 0 wherein R4 = a short chain C1-C4 alcohol; p is 2; Rl,R 2 , v, Y, and X" are as previously defined for Formula II. A specific example of a Formula IV compound suitable for use in the fabric 25 softening compositions herein is N-methyl-N,N-di-(2-(C 14-C j g-acyloxy) ed yl), N- 2-hydroxyethyl ammonium methylsulfate. A preferred compound is N-methyl, N,N- di-(2-oleyloxyethyl) N-2-hydroxyedιyl ammonium methylsulfate. Compositions ofthe present invention may also comprise Formula V compounds: Rl, R 2 , p, v, and X" are previously defined in Formula II; and Q* 4-p - N -« CH 2 ) V -Y-R 2) P x* and mixtures thereof, wherein at least one Y" group is 0 n ° II NH-C or — C-NH- An example of this compound is methyl bis (oleyl amidoethyl) 2-hydroxyethyl ammonium methyl sulfate. Preferably, Component (A) ofthe present invention is a quaternary ammonium compound. The compounds herein can be prepared by standard esterification and quaternization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180, incoφorated herein by reference. Optional Ingredients Well known optional components included in fabric conditioning compositions are narrated in U.S. Pat. No. 4,103,047, Zaki et al., issued July 25, 1978, for "Fabric Treatment Compositions," incoφorated herein by reference. (!) Co-Softener Fabric softening compositions employed herein contain as an optional component, at a level of from about 0% to about 95%, preferably from about 20% to about 75%, more preferably from about 20% to about 60%, a carboxylic acid salt of a tertiary amine and/or ester amine which has Uie formula: wherein R^ is a long chain aliphatic group containing from about 8 to about 30 carbon atoms; R and R^ are die same or different from each other and are selected from d e group consisting of aliphatic groups containing containing from about 1 to about 30 carbon atoms, hydroxyalkyl groups of d e Formula R^ OH wherein R^ is an alkylene group of from about 2 to about 30 carbon atoms, and alkyl ether groups ofthe formula R^O(C n H2 n O) m wherein R^ is alkyl and alkenyl of from about 1 to about 30 carbon atoms and hydrogen, v is 2 or 3, and m is from about 1 to about 30; wherein R^, R^, R \ R8, and R^ chains can be ester interrupted groups; and wherein R? is selected from d e group consisting of unsubstituted alkyl, alkenyl, aryl, alkaryl and aralkyl of about 8 to about 30 carbon atoms, and substituted alkyl, alkenyl, aryl, alkaryl, and aralkyl of from about 1 to about 30 carbon atoms wherein the substituents are selected from die group consisting of halogen, carboxyl, and hydroxyl, said composition having a thermal softening point of from about 35 °C to about 100 °C. This component provides the following benefits: superior odor, and/or improved fabric softening performance, compared to similar articles which utilize primary amine or ammonium compounds as the sole fabric conditioning agent. Either R 4 , R 5 , R 6 , R 7 , R 8 , and or R 9 chains can contain unsaturation. Preferably, R 5 is an aliphatic chain containing from about 12 to about 30 carbon atoms, R" is an aliphatic chain of from about 1 to about 30 carbon atoms, and R 4 is an aliphatic chain of from about 1 to about 30 carbon atoms. Particularly iti iicύ i.cιii i amine.. foi siaiic cυnuυi performance are those containing unsatu¬ ration; e.g., oleyldimethylamine and/or soft tallowdimetiiylamine. Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form d e tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallowdimethylamine, coconutdimethylamine, dilaurylmethylamine, distearylmethylamine, ditallowmethylamine, oleyldimediylamine, dioleylmethylamine, lauryldi(3-hydroxypropyl)amine, stearyldi(2- hydroxyethyl)amine, trilaurylamine, lauryletiiylmethylamine, and Preferred fatty acids are those wherein R? is a long chain, unsubstituted alkyl or alkenyl group of from about 8 to about 30 carbon atoms, more preferably from about 1 1 to about 17 carbon atoms. Examples of specific carboxylic acids as a starting material are: formic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid, benzoic acid, 4-hydroxy benzoic acid, 3- chloro benzoic acid, 4-nitro benzoic acid, 4-ed yl benzoic acid, 4-(2-chloroethyl)- benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4- hydroxyphenyl)acetic acid, and phd alic acid. Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and mixtures diereof. The amine salt can be formed by a simple addition reaction, well known in the art, disclosed in U.S. Pat. No. 4,237,155, ardouche, issued Dec. 2, 1980, which is incoφorated herein by reference. Excessive levels of free amines may result in odor problems, and generally free amines provide poorer softening performance than the amine salts. Preferred amine salts for use herein are those wherein the amine moiety is a g-C3ø a lkyl or alkenyl dimethyl amine or a di-Cg-C3ø alkyl or alkenyl methyl amine, and d e acid moiety is a Cg-C3o alkyl or alkenyl monocarboxylic acid. The amine and the acid, respectively, used to form the amine salt will often be of mixed chain lengths rather than single chain lengths, since ti ese materials are normally derived from natural fats and oils, or syndietic processed which produce a mixture of chain lengths. ALu, it ia υfieπ ucsήabie io utilize mixtures or diiierent chain lengths in order to modify the physical or performance characteristics ofthe softening composition. Specific preferred amine salts for use in the present invention are oleyldimethylamine stearate, stearyldimetiiylamine stearate, stearyldimethylamine myristate, stearyldimethylamine oleate, stearyldimetiiylamine palmitate, distearylmethylamine palmitate, distearylmethylamine laurate, and mixtures diereof. A particularly preferred mixture is oleyldimethylamine stearate and distearylmethylamine myristate, in a ratio of 1 : 10 to 10:1, preferably about 1 :1. (2) Optional Nonionic Softener An optional softening agent ofthe present invention is a nonionic fabric softener material. Typically, such nonionic fabric softener materials have an HLB of from about 2 to about 9, more typically from about 3 to about 7. In general, the materials selected should be relatively crystalline, higher melting, (e.g., >25 °C). The level of optional nonionic softener in d e solid composition is typically from about 10% to about 50%, preferably from about 15% to about 40%. Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides diereof, wherein die alcohol, or anhydride, contains from about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty acid moiety contains from about 8 to about 30, preferably from about 12 to about 20, carbon atoms. Typically, such softeners contain from about one to about 3, preferably about 2 fatty acid groups per molecule. The polyhydric alcohol portion of die ester can be ed ylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. The fatty acid portion ofthe ester is normally derived from fatty acids having from about 8 to about 30, preferably from about 12 to about 22, carbon atoms. Typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid. Highly preferred optional nonionic softening agents for use in the present invention are C10-C26 acyl sorbitan esters and polyglycerol monostearate. Sorbitan esters are esterified dehydration products of sorbitol. The preferred sorbitan ester comprises a member selected from the group consisting of C10-C26 acyl sorbitan monoesters and C10-C26 ac yl sorbitan diesters and ethoxylates of said esters wherein one or more ofthe unesterified hydroxyl groups in said esters contain from 1 to about 6 oxyethylene units, and mixtures thereof. For the puφose ofthe present invention, sυrbiian esiers containing unsaturation (e.g., sorbitan monooleate) can be utilized. Sorbitol, which is typically prepared by the catalytic hydrogenation of glucose, can be dehydrated in well known fashion to form mixtures of 1 ,4- and 1,5- sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No. 2,322,821, Brown, issued June 29, 1943, incoφorated herein by reference.) The foregoing types of complex mixtures of anhydrides of sorbitol are collectively referred to herein as "sorbitan." It will be recognized diat d is "sorbitan" mixture will also contain some free, uncyclized sorbitol. The preferred sorbitan softening agents ofthe type employed herein can be prepared by esterifying the "sorbitan" mixture widi a fatty acyl group in standard fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and or fatty acid. The esterification reaction can occur at any ofthe available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from such reactions, and die stoichiometric ratios of the reactants can be simply adjusted to favor the desired reaction product. For commercial production ofthe sorbitan ester materials, etherification and esterification are generally accomplished in d e same processing step by reacting sorbitol directly widi fatty acids. Such a mediod of sorbitan ester preparation is described more fully in MacDonald; "Emulsifiers:" Processing and Quality Control:, Journal ofthe American Oil Chemists' Society. Vol. 45, October 1968. Details, including formula, of the preferred sorbitan esters can be found in U.S. Pat. No. 4,128,484, incoφorated hereinbefore by reference. Certain derivatives of d e preferred sorbitan esters herein, especially the "lower" ethoxylates thereof (i.e., mono-, di-, and tri-esters wherein one or more of the unesterified -OH groups contain one to about twenty oxyethylene moieties (Tweens®) are also useful in die composition ofthe present invention. Therefore, for puφoses ofthe present invention, the term "sorbitan ester" includes such derivatives. For the puφoses ofthe present invention, it is preferred that a significant amount of di- and tri- sorbitan esters are present in the ester mixture. Ester mixtures having from 20-50% mono-ester, 25-50% di-ester and 10-35% of tri- and tetra-esters are preferred. The material which is sold commercially as sorbitan mono-ester (e.g., monostearate) does in fact contain significant amounts of di- and tri-esters and a typical analysis of sorbitan monostearate indicates that it comprises about 27% mono-, 32% dl- nd 30% iii- an leua-csters. Commercial sorbitan monostearate therefore is a preferred material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 10: 1 and 1 :10, and 1,5- sorbitan esters are useful. Both the 1,4- and 1,5-sorbitan esters are useful herein. Other useful alkyl sorbitan esters for use in the softening compositions herein include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-esters. Such mixtures are readily prepared by reacting the foregoing hydroxy-substituted sorbitans, particularly d e 1,4- and 1,5-sorbitans, with the corresponding acid, ester, or acid chloride in a simple esterification reaction. It is to be recognized, of course, that commercial materials prepared in this manner will comprise mixtures usually containing minor proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide structures, and die like. In the present invention, it is preferred d at such impurities are present at as low a level as possible. The preferred sorbitan esters employed herein can contain up to about 15% by weight of esters of die C20-C26' an ^ higher, fatty acids, as well as minor amounts of Cg, and lower, fatty esters. Glycerol and polyglycerol esters, especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and or di- esters, preferably mono-, are also preferred herein (e.g., polyglycerol monostearate with a trade name of Radiasurf 7248). Glycerol esters can be prepared from naturally occurring triglycerides by normal extraction, purification and/or interesterifϊcation processes or by esterification processes of die type set forth hereinbefore for sorbitan esters. Partial esters of glycerin can also be edioxylated to form usable derivatives that are included within the term "glycerol esters." Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric. isostearic, myristic, and or behenic acids and die diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is under¬ stood that the typical mono-ester contains some di- and tri-ester, etc. The "glycerol esters" also include the polyglycerol, e.g., diglycerol through octaglycerol esters. The polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages. The mono- and/or diesters ofthe polyglycerol polyols are preferred, die fatty acyl groups typically being those described hereinbefore for die sorbitan and glycerol esters. (3) Optional Soii Release Agent Optionally, die compositions herein contain from 0% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.1% to about 2%, of a soil release agent. Preferably, such a soil release agent is a polymer. Polymeric soil release agents useful in the present invention include copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like. U.S. Pat. No. 4,956,447, Gosselink/Hardy/Trinh, issued Sept. 11, 1990, discloses specific preferred soil release agents comprising cationic functionalities, said patent being incoφorated herein by reference. A preferred soil release agent is a copolymer having blocks of terephthalate and polyetiiylene oxide. More specifically, tiiese polymers are comprised of repeating units of ethylene and or propylene terephtiialate and polyetiiylene oxide terephtiialate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephtiialate units of from about 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 5,000 to about 55,000. U.S. Pat. No. 4,976,879, Maldonado/Trinh/Gosselink, issued Dec. 1 1, 1990, discloses specific preferred soil release agents which can also provide improved antistat benefit, said patent being incoφorated herein by reference. Anodier preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1. Examples of this polymer include the commercially available materials Zelcon® 4780 (from DuPont) and Milease® T (from ICI). A more complete disclosure of these highly preferred soil release agents is contained in European Pat. Application 185,427, Gosselink, published June 25, 1986, incoφorated herein by reference. (4) Optional Cvclodextrin/Perfume Complexes and Free Perfume The products herein can also contain from about 0.5% to about 60%, preferably from about 1% to about 50%, cyclodextrin/perfume inclusion complexes and/or free perfume, as disclosed in U.S. Pat. Nos. 5,139,687, Borcher et al., issued / mg. io, ι ^ ώ, tmu ->,.--"-t,υiu, jaiuii ci ai., to issue Aug. iυ, ιyyj, whicn are incoφorated herein by reference. Perfumes are highly desirable, can usually benefit from protection, and can be complexed with cyclodextrin. Fabric softening products typically contain perfume to provide an olfactory aesthetic benefit and/or to serve as a signal that the product is effective. The optional perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in d e art including U.S. Pat. Nos.: 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of said patents being incoφorated herein by reference. Many of the art recognized perfume compositions are relatively substantive to maximize their odor effect on substrates. However, it is a special advantage of perfume delivery via the perfume/cyclodextrin complexes that nonsubstantive perfumes are also effective. If a product contains both free and complexed perfume, the escaped perfume from the complex contributes to the overall perfume odor intensity, giving rise to a longer lasting perfume odor impression. As disclosed in U.S. Pat. No. 5,234,610, Gardlik/Trinh/Banks/Benvegnu, issued Aug. 3, 1993, said patent being incoφorated herein by reference, by adjusting the levels of free perfume and perfume/CD complex it is possible to provide a wide range of unique perfume profiles in terms of timing (release) and/or perfume identity (character). Solid, dryer-activated fabric conditioning compositions are a uniquely desirable way to apply the cyclodextrins, since they are applied at the very end of a fabric treatment regimen when the fabric is clean and when diere are almost no additional treatments that can remove the cyclodextrin. (5) Stabilizers Stabilizers can be present in the compositions ofthe present invention. The term "stabilizer," as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably from about 0.05% to about 0.1% for antioxidants and more preferably from about 0.01 % to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions for the compositions. Use of antioxidants and reductive agent stabilizers is especially advantageous for low scent products (low perfume). Examples of antioxidants diat can be added to the compositions of this invention include a mi ture of as - i iv, α».id, αscυiυic paimitate, propyi gaiiate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox S-l ; a mixture of BHT, BHA, propyl gallate, and citric acid available from Eastman Chemicals Products, Inc., under die trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane ® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-l/GT- 2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA. Examples of reductive agents include sodium borohydride, hypophosphorous acid, and mixtures thereof. (6) Other Optional Ingredients The present invention can include other optional components (minor components) conventionally used in textile treatment compositions, for example, colorants, preservatives, optical brighteners, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and die like. D. Substrate Articles In preferred embodiments, die present invention encompasses articles of manufacture. Representative articles are those that are adapted to soften fabrics in an automatic laundry dryer, ofthe types disclosed in U.S. Pat. Nos.: 3,989,631 Marsan, issued Nov. 2, 1976; 4,055,248, Marsan, issued Oct. 25, 1977; 4,073,996, Bedenk et al., issued Feb. 14, 1978; 4,022,938, Zaki et al., issued May 10, 1977; 4,764,289, Trinh, issued Aug. 16, 1988; 4,808,086, Evans et al., issued Feb. 28,1989; 4,103,047, Zaki et al., issued July 25, 1978; 3,736,668, Dillarstone, issued June 5, 1973; 3,701,202, Compa et al., issued Oct. 31,1972; 3,634,947, Furgal, issued Jan. 18, 1972; 3,633,538, Hoeflin, issued Jan. 11, 1972; and 3,435,537, Rumsey, issued Apr. 1, 1969; and 4,000,340, Muφhy et al., issued Dec. 28, 1976, all of said patents being incoφorated herein by reference. In a preferred substrate article embodiment, the fabric treatment compositions are provided as an article of manufacture in combination with a dispensing means such as a flexible substrate which effectively releases the composition in an automatic laundry (clothes) dryer. Such dispensing means can be designed for single usage or for multiple uses. The dispensing means can also be a "carrier material" that releases the fabric softener composition and dien is dispersed and/or exhausted from the dryer. The dis cuόiiig c iia will iiυimaiiy carry an effective amount ot tabπc treatment composition. Such effective amount typically provides sufficient fabric conditioning/antistatic agent and/or anionic polymeric soil release agent for at least one treatment of a minimum load in an automatic laundry dryer. Amounts of fabric treatment composition for multiple uses, e.g., up to about 30, can be used. Typical amounts for a single article can vary from about 0.25 g to about 100 g, preferably from about 0.5 g to about 20 g, most preferably from about 1 g to about 10 g. Highly preferred paper, woven or nonwoven "absorbent" substrates useful herein are fully disclosed in U.S. Pat. No. 3,686,025, Morton, issued Aug. 22, 1972, incoφorated herein by reference. It is known that most substances are able to absorb a liquid substance to some degree; however, die term "absorbent" as used herein, is intended to mean a substance widi an absorbent capacity (i.e., a parameter representing a substrate's ability to take up and retain a liquid) from 4 to 12, preferably 5 to 7, times its weight of water. Another article comprises a sponge material releasably enclosing enough fabric treatment composition to effectively impart fabric soil release, antistatic effect and/or softness benefits during several cycles of clothes. This multi-use article can be made by filling a hollow sponge with about 20 grams of the fabric treatment composition. E. Usage The substrate embodiment of d is invention can be used for imparting the above-described fabric treatment composition to fabric to provide softening and or antistatic effects to fabric in an automatic laundry dryer. Generally, die method of using d e composition ofthe present invention comprises: commingling pieces of damp fabric by tumbling said fabric under heat in an automatic clothes dryer with an effective amount ofthe fabric treatment composition. At least the continuous phase of said composition has a melting point greater than about 35°C and die composition is flowable at dryer operating temperature. This composition comprises from about 10% to about 99.99%, preferably from about 15% to about 90%, ofthe quaternary ammonium agent selected from the above-defined cationic fabric softeners and mixtures thereof, from about 0% to about 95%, preferably from about 20% to about 75%, more preferably from about 20% to about 60% ofthe above-defined co- softener. The present invention relates to improved solid dryer-activated fabric softener compositions which are either (A) incoφorated into articles of manufacture in which the compositions are, e.g., on a substrate, or are (B) in the form of particles (including, where appropriate, agglomerates, pellets, and tablets of said particles). Such compositions contain from about 30% to about 95% of normally solid, dryer- softenable material, typically fabric softening agent, containing an effective amount of unsaturation. In die specification and examples herein, all percentages, ratios and parts are by weight unless otherwise specified and all numerical limits are normal approximations. The following examples illustrate die esters and compositions of this invention, but are not intended to be limiting thereof. EXAMPLE I Mono-geranyl succinate Geraniol (70:30 geraniol/nerol mixture) in the amount of 606.50 g (3.93 mol) and succinic anhydride in die amount of 202.82 g (1.97 mol) were combined in a 2000 mL three-necked round-bottomed flask fitted wid a condenser, argon inlet, mechanical stirrer and internal thermometer. The mixture was heated to 75 °C for 18 hours during which time the mixture became homogeneous. The product mixture was cooled to room temperature, filtered, and concentrated by Kugelrohr distillation at 80 °C (0.5 mm Hg) for 6 hours. The product mixture was purified by chromatography on silica gel eluting with a 5% solution of etiiyl acetate in petroleum etiier. The monoester fractions were collected after the diester fractions to give mono-geranyl succinate as a light yellow oil. Purity ofthe product was determined by tiiin layer and gas chromatography and die structure confirmed by 1 H and 13 C NMR. EXAMPLE II Mono-(cw-3-hexenyl) maleate c/s-3-Hexenol in the amount of 30.00 g (0.299 mol) and maleic anhydride powder in the amount of 24.46 g (0.249 mol) were combined in a 250 mL three-necked round- bottomed flask fitted with a condenser, argon inlet, mechanical stirrer and intemal thermometer. The mixture was heated to 100-105 °C for 2 hours during which time 5 the mixture became homogeneous. The product mixture was cooled to room temperature, filtered, and concentrated by Kugelrohr distillation at 40 °C (0.3 mm Hg) for 4 hours. Mono-(cw-3-hexenyl) maleate was isolated as a colorless oil. Purity ofthe product was determined by thin layer and gas chromatography and the structure confirmed by *H and ^C NMR. EXAMPLE III Mono-phenoxanyl maleate Phenoxanol in the amount of 16.13 g (0.091 mol) and maleic anhydride in die 15 amount of 8.96 g (0.091 mol) were combined with 75 mL of toluene in a flask fitted with a condenser, argon inlet and magnetic stirrer. The mixture was heated to reflux for 4 hours. The product mixture was concentrated by rotary evaporation leaving a yellow oil. The oil was purified by chromatography eluting with ethyl acetate to give pure mono-phenoxanyl maleate after concentrating appropriate fractions. 0 Purity ofthe product was determined by thin layer chromatography and the structure confirmed by J H and 13 C NMR. EXAMPLE IV Mono-phenoxanyl fumarate 5 Maleic anhydride in d e amount of 9.07 g (0.092 mol) and butylbenzene (10.6 mL) were combined in a 250 mL round-bottomed flask equipped witii a magnetic stirrer, condenser, and argon inlet. A catalytic amount of iodine (90 mg) was added to die mixture followed by phenoxanol in die amount of 16.13 g (0.091 mol). The mixture 0 was heated at 60 °C for 1 hour. The cooled mixture was purified by column chromatography on silica gel eluting with a 20% solution of ethyl acetate in petroleum to provide mono-phenoxanyl fumarate as a white solid. Purity of d e product was determined by thin layer chromatography and die structure confirmed by lH and ^C NMR. 5 EXAMPLE V cis- and trαrts-Di-(β-citronellyl) pyromellitate Pyromelltic dianhydride in the amount of 50.00 g (0.229 mol) and β-citronellol 71.64 g (0.458 mol) were heated under argon in a 250 mL round-bottomed flask equipped with a mechanical stirrer, and condenser. The mixture was heated for 4 h at 155-160 °C. The cooled mixture was concentrated by Kugelrohr distillation (80 ° C, 0.5 mm Hg) and purified by column chromatography on silica gel (eluting with a 20% solution of ethyl acetate in petroleum ether) to provide cis- and trans-di-φ- citronellyl) pyromellitate. Purity of the product was determined by thin layer chromatography and the structure confirmed by ^H and ^ 3 C NMR. I U EXAMPLE VI Mono-(β-citronellyl) succinate The method of Example 1 is repeated with the substitution of β-citronellol for 15 geraniol. EXAMPLE VII Mono-phenoxyethyl succinate 0 The method of Example 1 is repeated widi die substitution of phenoxyethanol for geraniol. EXAMPLE VIII Mono-(β-citronellyl) phthalate 5 The method of Example 1 is repeated widi die substitution of β-citronellol for geraniol and phthalic anhydride for succinic anhydride. EXAMPLE IX 0 A dryer added fabric conditioner formula includes die following. K L M N O Component Wt.% Wt.% Wt.% Wt.% Wt.% DEQA (1 1) 39.16 34.79 - - - DEQA (12) - - 51.81 - - DTDMAMS (13) - - - 20.64 25.94 Co-Softener (14) 54.41 40.16 27.33 33.04 41.52 Glycosperse S-20 ( 15) - - 15.38 - - Glycerol Monostearate - - 20.87 26.23 Perfume 1.61 1.65 1.52 1.61 1.21 Perfume/Cyclodextrin - 18.88 - 19.13 - Complex Geranyl/Neryl succinate (5) 0.80 0.35 0.50 0.20 1.20 Di(Geranyl/NeryI) succinate - 0.15 - 0.20 - (6) Cyclohexylethy maleate (7) - - 0.20 0.10 - Phenoxanyl maleate (8) - - - 0.20 - cis-3-hexenyl maleate (9) - - 0.10 0.10 - Clay (16) 4.02 4.02 3.16 3.91 3.90 (5) 1 ,4-Butandioic acid, 3,7-dimetiιyl-2,6-octadienyl ester (6) 1 ,4-Butandioic acid, 3,7-dimethyl-2,6-octadienyl diester (7) cis-Butendioic acid, cyclohexylethyl ester (8) cis-Butendioic acid, 3-methyl-5-phenyl-pentanyl ester (9) cis-Butendioic acid, cis-3-hexenyl ester (11) Di-(oleyloxyethyl) dimetiiyl ammonium methylsulfate (12) Di-(soft-tallowyloxyethyl) hydroxyethyl methyl ammonium methylsulfate (13) Ditallow dimetiiyl ammonium methylsulfate (14) 1 :2 Ratio of stearyldimemyl amine:triple-pressed stearic acid (15) Polyethoxylated sorbitan monostearate , available from Lonza (16) Calcium Bentonite Clay, Bentonite L, sold by Southern Clay Products Preparation of Coating Mix (Formula A) A batch of approximately 200 g is prepared as follows: Approximately 109 g of co- softener and about 78 g DEQA(l) are melted separately at about 80° C. They are combined witii high shear mixing in a vessel immersed in a hot water batii to maintain the temperature between 70-80°C. Calcium bentonite clay (8 g) is mixed in to achieve die desired viscosity. Geranyl/Neryl succinate (1.6 g) and perfume (3.2g) are added to die formula and mixed until homogeneous. Coating mixes for Formulas B - F are made in a like manner, using d e materials indicated in die table above. Preparation of Fabric Conditioning Sheets The coating mixture is applied to preweighed substrate sheets of about 6.75 inches x 12 inches (approximately 17 cm x 30 cm) dimensions. The substrate sheets are comprised of about 4-denier spun bonded polyester. A small amount ofthe formula is placed on a heated metal plate with a spatula and dien is spread evenly with a wire metal rod. A substrate sheet is placed on the metal plate to absorb the coating mixture. The sheet is then removed from the heated metal plate and allowed io cυυi tυ rυυm temperature so uiat the coating mix can solidity. Ihe sheet is weighed to determine the amount of coating mixture on the sheet. The target sheet weight is 3.49g. If the weight is in excess ofthe target weight, the sheet is placed back on the heated metal plate to remelt the coating mixture and remove some of die excess. If die weight is under the target weight, the sheet is also placed on die heated metal plate and more coating mixture is added. WHAT IS CLAIMED IS:

Claims: Claims. 1. A dryer activated fabric softening composition comprising: from 10% to 99.99% of by weight ofthe composition of a fabric softening component comprising a fabric softening compound; and from 0.01% to 15% by weight ofthe composition of a perfume component having an ester of a perfume alcohol wherein the ester has at least one free carboxylate group, said ester having the formula: wherein R is selected from the group consisting of substituted or unsubstituted C j - C30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group; or ring containing a heteroatom, R' is a perfume alcohol with a boiling point at 760 mm Hg of less than 300 °C; and and n are independently an integer of 1 or greater. 2. A dryer activated fabric softening composition comprising: (A) from 30% to 85% of dimethyl bis(tallowyl oxy ethyl) ammonium methyl sulfate, dimethyl bis(oleyl oxy ethyl) ammonium methyl sulfate, dimethyl bis(cocoyl oxy ethyl) ammonium methyl sulfate, N-methyl, N,N-di-(2-oleyloxyethyl) N-2- hydroxyethyl ammonium methylsulfate and mixtures thereof, (B) from 0.01 to 15% by weight ofthe composition of a perfume component having an ester of a perfume alcohol wherein the ester has at least one free carboxylate group, said ester having the formula: wherein R is selected from the group consisting of substituted or unsubstituted Cj- C30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group; or ring containing a heteroatom, R' is a perfume alcohol with a boiling point at 760 mm Hg of less than 300 °C; and m and n are independently an integer of 1 or greater. (C) from 20% to 75% of oleyldimethylamine stearate, distearylmethylamine myristate, and mixtures thereof, and (D) from 15% to 40% of C10- 26 ac Y' sorbitan monoester, diester, and mixtures thereof; wherein the composition has a thermal softening point of from 35 °C to 100 °C 3. A dryer activated softening product comprising: a substrate in the form of a sheet; and a dryer activated fabric softening composition disposed on said sheet, said composition comprising: (a) from 0.01% to 15% by weight of said composition of a perfume component, said perfume component comprising: (i) a succinate mono-ester of a perfume alcohol wherein the ester has at least one free carboxylate group, said mono-ester being selected from the group consisting of geranyl succinate, a ! uic aic, and mixtures thereof; and (ii) a fully esterified succinate di-ester selected grom the group consisting of digernyl succinate, dineryl succinate, gemyl/neryl succinate, and mixtures thereof; and (b) from 10% to 99.99% by weight of said composition of a fabric softening component. 4. The dryer-activated fabric conditioning composition as claimed in claims 1 or 3 wherein said fabric softening compound is a quaternary ammonium compound selected from the group consisting of: Formula π wherein each Y is -O-(O)C-, or -C(O)-O-; p is 1 to 3; each v is an integer from 1 to 4; each R 1 substituent is a short chain C\-C alkyl group; each R^ is Cg-C o hydrocarbyl or substituted hydrocarbyl substituent; and the counterion, X", can be any softener-compatible anion; and Formula UI wherein each Q is -O-C(O)- or -C(O)-O-, each R 3 is C1-C4 alkyl or hydroxy alkyl group; each R^, V, and X " are defined hereinbefore for Formula II; Formula IV: wherein R 4 is a short chain C1-C4 alcohol; p is 2; R*,R 2 , v, Y", and X- are defined hereinbefore for Formula II; Formula V: wherein Rl, R2, p, v, and X" are defined hereinbefore for Formula II; and and mixtures thereof, wherein at least one Y ' group is: 11 II NH-C or — C-NH- and mixtures thereof. 5. The dryer activated fabric softening composition as claimed in any of claims 1-3 wherein the composition further includes a co-softener comprising a carboxylic acid salt of a tertiary amine, tertiary amine ester, or mixtures thereof. 6. The dryer activated fabric softening composition as claimed in any of claims 1-3, wherein said perfume component comprises an ester of a perfume alcohol wherein the ester has at least one free carboxylate group in admixture with a fully esterified ester of a perfume alcohol. 7. The dryer activated fabric softening composition as claimed in any of claims 1-3 wherein R is selected from the group consisting of substituted or unsubstituted C\ - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group or ring containing a heteroatom. 8. The dryer activated fabric softening composition as claimed in any of claims 1-3 wherein R' is a perfume alcohol selected from the group consisting of geraniol, nerol, phenoxanol, floralol, β-citronellol, nonadol, cyclohexyl ethanol, phenyl ethanol, isoborneol, fenchol, isocyclogeraniol, 2-phenyl-l -propanol, 3,7-dimethyl-l -octanol, and combinations thereof. 9. The dryer activated fabric softening composition as claimed in claim 8, wherein said ester is selected from maleate, succinate, citrate, pyromellitate, trimellitate, μliiiioύc c i adiμάim caieis of said aicohoi perfume. 10. The dryer activated fabric softening composition as claimed in claim 9 wherein said ester is selected from the group consisting of geranyl succinate, neryl succinate, (β-citronellyl) maleate, nonadol maleate, phenoxanyi maleate, (3,7-dimethyl-l- octanyl) succinate, (cyclohexylethyl) maleate, floralyl succinate, (β-citronellyl) phthalate and (phenylethyl) adipate, and mixtures thereof 11. The dryer activated fabric softening composition as claimed in claim 10 wherein said perfume component further includes a fully esterified ester of a perfume alcohol selected from the group consisting of digeranyl succinate, dineryl succinate, geranyl neryl succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, neryl laurate, di(β-citronellyl) maleate, dinonadyl maleate, diphenoxanyl maleate, di(3,7- dimethyl-1 -octanyl) succinate, di(cyclohexylethyl) maleate, difloralyl succinate, and di(phenylethyl) adipate and mixtures thereof 12. The dryer activated fabric softening composition as claimed in any of claims 1-11 wherein the composition additionally comprises: (A) a stabilizer selected from the group consisting of ascorbic acid, ascorbic palmitate, propyl gallate, citric acid, butylated hydroxytoluene, tertiary butylhydroquinone, natural tocopherols, butylated hydroxyanisole and mixtures thereof; (B) a soil release polymer, and (C) mixtures thereof.

Inventors: HARTMAN FREDERICK ANTHONY, SEVERNS JOHN CORT, SIVIK MARK ROBERT, WAITE SCOTT WILLIAM, HARTMAN, FREDERICK, ANTHONY, SEVERNS, JOHN, CORT, SIVIK, MARK, ROBERT, WAITE, SCOTT, WILLIAM
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 1996
Main classification: C11D3
IPC codes: C11B9, C11D1, C11D3, C11D17