TISSUE CONTAINING SILICONE QUATERNARIES

Abstract: The invention relates to tissue products having improved softness properties and methods of making them. Specifically, improved softness is achieved by incorporating a silicone quaternary and, optionally, one or more softeners/debonders into the fiber furnish at the wet end of the tissue machine prior to formation, followed by an optional topical treatment with a silicone quaternary and/or one or more softeners/debonders after the tissue web is formed. The result is a tissue product with added bulk and a smooth surface feel, both properties contributing to improved softness characteristics.

Description: TISSUE CONTAINING SILICONE QUATERNARIES Background of the Invention Improving the softness of tissues is a continuing objective in tissue manufacture. In general, prior efforts have been directed at reducing the inter-fiber bonding within the tissue structure or coating the tissue surface with chemicals which improve the surface feel. Softness, however, is a perceived property of tissues comprising many factors including bulk softness and surface smoothness. To date, efforts have tended to focus on one or the other. Hence, there is a need for a method which improves both bulk softness and surface softness. Summary of the Invention It has now been discovered that the softness of tissues can be improved by the addition of a silicone quaternary (hereinafter defined) either to the tissue-making furnish at the wet end of the tissue machine and/or to the formed web by topical addition. Optionally, one or more softener/debonders (hereinafter defined) can be added to the tissue making furnish and/or to the surface of the web. Hence in one aspect, the invention resides in a method for making soft tissue comprising: (a) forming an aqueous suspension of papermaking fibers containing a silicone quaternary, with or without one or more softener/debonders; (b) forming a tissue web by depositing the aqueous suspension of papermaking fibers onto a forming fabric; and (c) dewatering and drying the web. In another aspect, the invention resides in a method for making soft tissue comprising: (a) forming an aqueous suspension of papermaking fibers; (b) forming a tissue web by depositing the aqueous suspension of papermaking fibers onto a forming fabric; (c) dewatering and drying the web; and (d) topically applying a silicone quaternary to the web. In another aspect, the invention resides in a method for making soft tissue comprising (a) forming an aqueous suspension of papermaking fibers containing a silicone quaternary; (b) forming a tissue web by depositing the aqueous suspension of papermaking fibers onto a forming fabric; (c) dewatering and drying the web; and (d) topically applying a silicone quaternary to the web. In all of the foregoing aspects, the amount of the silicone quaternary in the aqueous suspension or added to the web can be from about 0.01 to about 10 weight percent, based on dry fiber, more specifically from about 0.1 percent to about 3 percent. In addition, one or more softener/debonders can be optionally added, either to the aqueous suspension of papermaking fibers or by topical addition to the wet or dry web. The softener/debonder applied to the web can be the same softener/debonder added to the furnish, or it can be different, if a softener/debonder is introduced at both locations. In a further aspect, the invention resides in a soft tissue containing from about 0.01 to about 10 weight percent, based on dry fiber, more specifically from about 0.1 percent to about 3 percent, of a silicone quaternary. Optionally the tissue can further contain from about 0.1 to about 3 weight percent, based on dry fiber, of one or more softener/debonders described below. As used herein, a silicone quaternary is a compound having the following structural formulas: (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d I OCH 2 CHOHCH 2 I R wherein x = 0 -1000; y, z = 1 - 1000; RL R 2 can be the same or different, are alkyl or hydroxyalkyl, Ci - C 20 or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate or other compatible counterion; and R can be selected from among the following four numbered groups: I (1) Rs— N + — R 5 I R 4 where R 3 , R 4 , R 5 can be the same or different, are selected from hydroxyalkyi or alkyl group, Ci - C 4 , or aliphatic group, C 8 - C 24 , normal or branched, saturated or unsaturated; H O I (2) Re— + — (CH 2 ) n — N- I R 7 where Re, 7, Re can be the same or different, are selected from aliphatic group, Cβ - C 24 , normal or branched, saturated or unsaturated; and n = 1 - 6; or where R 6 , R 7 can be the same or different, are alkyl or hydroxyalkyi, C 1 - C 6 ; R 8 = aliphatic, C 8 - C 24 , normal or branched, saturated or unsaturated; and n = 1 - 6; or where R 6 = hydroxyalkyi or alkyl, C 1 - C 6 ; n = 1 - 6; m = 1 - 6; and R 9 , R 8 = aliphatic, C 8 - C 24 , normal or branched, saturated or unsaturated; or where R 6 = hydroxyalkyi or alkyl, C 1 - C 6 ; R 7 = -(CH 2 ) m — C-O— R 9 O m' = 1 - 6; and R 8 , R^ can be the same or different, are aliphatic, C 8 - C 24 , normal or branched, saturated or unsaturated; (3) | N + \ N where R 10 , Rn can be the same or different, are aliphatic C 8 - C 24 , normal or branched, saturated or unsaturated, or Rn = -(CH 2 ) 0 - O - C - R 12 where o = 1-6; and Rι 2 = aliphatic, C 8 -C 2 , normal or branched, saturated or unsaturated; (4) | R 12 -N + — R 14 I R 13 where R 12 , R 13 = Ci - C 6 , alkyl or hydroxyalkyi; p = 1 - 6; and R15 = aliphatic, C 8 - C 24 , normal or branched, saturated or unsaturated; or R 12 = Ci - C 6 alkyl or hydroxyalkyi; R 13 , R14 can be the same or different, are — (CH 2 )p— C— O— R 15 O p = 1 - 6; and Ri5 = aliphatic, C 8 - C 24 , normal or branched, saturated or unsaturated; or R 12 , R 13 can be the same or different, are d - C 6 alkyl or hydroxyalkyi; O II (CH 2 )r— O— C— R 16 / (CH 2 ) s -O-C-R 17 II o q = 1 - 6; r, s = 0 - 6; and Ri6, Rι can be the same or different, are C 8 - C 24 aliphatic, normal or branched, saturated or unsaturated. As used herein, a "softener/debonder" is a chemical compound selected from the group consisting of quaternary ammonium compounds, bis-imidazolinium compounds, di- quaternary ammonium compounds, polyammonium compounds, quaternized protein compounds, phospholipids, silicone debonders, silicone betaines, organoreactive polysiloxanes, and silicone glycols. Suitable quaternary ammonium compounds have the following structures: CH 3 I CH 3 -N-R X " I R' wherein X = chloride, methyl sulfate, or other compatible counterion; and R, R' = can be the same or different, are aliphatic, saturated or unsaturated C 8 - C 24 ; or wherein X = chloride, methyl sulfate, or other compatible counterion; R, R' can be the same or different, are aliphatic, saturated or unsaturated C 8 - C 2 ; and benzyl or epoxy group; or wherein X = chloride, methyl sulfate, or other compatible counterion; and R, R' = can be the same or different, are aliphatic, saturated or unsaturated C 8 -C 24 ; or wherein X = chloride, methyl sulfate or other compatible counterion; R f = aliphatic, saturated or unsaturated, branched or normal, C 8 - C 24 ; O II R 2 = - (CH 2 ) m — O— C— R 3 m = 1 - 6; and R 3 = aliphatic, saturated or unsaturated, branched, or normal, C 8 - C 24 ; or II I R 4 —C— NH— (CH 2 ) n — N— R 2 X " I R 3 wherein R 1 = hydrogen or Ci - C 4 alkyl; R 2 , R 3 can be the same or different, are Ci - β alkyl, hydroxyalkyi; or R 2 = — <CH 2 ) m — NH— C— R 4 II O m = 2 - 6; n = 2 - 6; R 4 = aliphatic, saturated or unsaturated, C 8 - C 24 ; and X = methyl sulfate, chloride, or other compatible counterion. or wherein R = aliphatic Cι 2 -C 24 , saturated or unsaturated; n = 2-6; and X = halide, methyl sulfate, ethyl sulfate or other compatible counterion; or CH 3 I R'n-N-R'n X " I R wherein R = aliphatic, normal or branched, saturated or unsaturated, Cβ - C 24 ; X = chloride, methyl sulfate, ethyl sulfate, or other compatible counterion; R'= 2-hydroxyethyl or polyethoxyethanol; and n = 1 to 50; or wherein Ri, R 2 , R 3 are Ci - C 6 alkyl or hydroxyalkyi, can be the same or different; O (CH 2 ) m -O— C— R 5 / R 4 CH 2 ) n \ n = 2 - 6; m = 0 - 6; p = 1 - 6; R 5 and R 6 are C 8 - C 24 aliphatic, normal or branched, saturated or unsaturated, (same or different); and X = halide, methylsulfate, ethylsulfate or other compatible counterions. or wherein Ri and R 2 are Ci - C 6 alkyl or hydroxyalkyi (can be the same or different); O II R 3 = R 4 = - (CH 2 ) m — C— O— Rs m = 1 - 6; R 5 = aliphatic, saturated or unsaturated, normal or branched C 8 - C 2 ; and X = halide, methylsulfate, ethylsulfate or other compatible counterions; or R I CH 3 — N— R' X " I R" wherein R, R', R" can be the same or different, are aliphatic alkyl, normal or branched, saturated or unsaturated, C 8 - C 24 ; and X = chloride, methyl sulfate or other compatible counterion; or CH 3 CH 3 -N-R X " I CH 3 wherein R = aliphatic, saturated or unsaturated, C 8 - C 24 ; or allyl-, or R'_θ-(CH 2 ) m — R' = normal or branched, C 4 - Cι 8 ; m = 1 - 4; and X = chloride, sulfate or any other compatible counterion. Suitable silicone betaines include the following structure: CH 3 CH 3 CH 3 CH 3 I I I CH 3 Si — O - - Si — O - Si - O- Si — CH 3 I I CH 3 CH 3 (CH 2 ) 3 CH 3 O I CH 2 I CH - OH I CH 2 I CH 3 — N + -CH 3 I CH 2 I COO- m wherein m = 1-100; and n = 1-1000. Suitable quaternized protein compounds include the following structures: CH 3 OH I Rι-C-NH-(CH 2 ) m -N-CH 2 -CH-CH 2 -R 2 X " I CH 3 wherein m = 1-6; Ri = fatty acid radical, saturated or unsaturated, branched or unbranched Cι 2 - C 24 ; R 2 = hydrolyzed soy protein, hydrolyzed silk protein, collagen, keratin moiety or hydrolyzed wheat protein; and X = chloride, lactate or other compatible counterion; or CH 3 I R N-CH 2 -CH-CH 2 -R 2 X " I I CH 3 OH wherein Ri = fatty acid radical, saturated or unsaturated, C 1 2 - C 24 ; R 2 = hydrolyzed collagen or keratin moiety; and X = chloride, lactate or other compatible counterion. Suitable phospholipids include, without limitation, those having the following structures: R- (B) y + xA + aM wherein x = 1 to 3; x + y = 3; a = 0 to 2; B = O " or OM; A = an anion; M = a cation; and R, Ri & R 2 can be the same or different, are alkyl, substituted alkyl, alkylaryl or alkenyl groups of up to 16 carbon atoms and the total carbon atoms of R + Ri + R 2 = 10 to 24; or wherein x = 1 to 3; x + y = 3; a = 0 to 2; B = O " or OM; A = an anion; M = a cation; R 5 , R 6 may be the same or different, are alkyl, hydroxyalkyi, carboxyalkyi of up to C 6 , or polyoxyalkylene of up to Cι 0 ; or R 5 , R 6 and the nitrogen they are attached to may represent an N-heterocycle; R = an amidoamine moiety of the formula: O R 3 II I R 4 -C-N-(CH 2 ) n - where n = 2 to 6; R 3 = hydrogen or alkyl, hydroxyalkyi or alkenyl of up to 6 carbons; or cycloalkyl of up to 6 carbon atoms, or polyoxyalkylene of up to 10 carbon atoms; and R 4 = alkyl, alkenyl, alkoxy or hydroxyalkyi, C 5 -C 2 ι, or aryl or alkaryl of up to C 2ϋ ; or R- 2A " wherein A = an anion; M = a cation; R, Ri & R 2 can be the same or different, are alkyl, substituted alkyl, alkyl aryl or altkenyl groups of up to 16 carbon atoms, and the total carbon atoms of R R is an amidoamine moiety of the structure: O R 3 II I R 8 -C-N-(CH 2 ) n - where n = 2 to 6; R 3 = hydrogen or alkyl, hydroxyalkyi or alkenyl of up to 6 carbons; or cycloalkyl of up to 6 carbon atoms, or polyoxyalkylene of up to 10 carbon atoms; and R 8 has the following structure: CH 3 CH 3 CH 3 CH 3 I I I I CH 3 -Si-O-(Si-O) p -(Si-O) q -Si-CH 3 CH 3 CH 3 (CH 2 ) n CH 3 where n = 3 or greater; p = 1 to 1000; q = 1 to 25. Suitable silicone debonders include the following structure: CH 3 CH 3 CH 3 CH 3 ++ I I I I R-N-Z-(Si-O)„-Si-Z-N-R 2X " I I I I CH 3 CH 3 CH 3 CH 3 wherein R = alkyl group, Cι 2 - C 24 ; Z = -CH 2 -CH 2 -CH 2 -O-(CH 2 ) 3 -; X = alkoxy, chloride or other compatible counterion; and n = 1 to 50. Suitable organoreactive polysiloxanes include the following structures: CH 3 CH 3 CH 3 CH 3 I I I I CH 3 -Si-O-(Si-O) x -(Si-O) y -Si-CH 3 I I I I CH 3 CH 3 CHCH 3 CH 3 I CH 2 R or CH 3 CH 3 CH 3 I I I R-(CH 2 ) n -Si-O-(Si-O)χ-Si-(CH 2 ) n - R I I I CH 3 CH 3 CH 3 or CH 3 CH 3 CH 3 I I I R-(CH 2 ) n -Si-O-(Si-O)χ-Si-CH 3 I I I CH 3 CH 3 CH 3 wherein R = amine, carboxy, hydroxy, or epoxy; n = 3 or greater; x = 1 to 1000; and y = 1 to 25. Suitable silicone glycols include the following structure: CH 3 CH 3 CH 3 CH 3 I I I I I I CH 3 -Si-O-(Si-O) x -(Si-O) y -Si-CH 3 I I I I I I CH 3 CH 3 R CH 3 O (CH 2 -CH 2 -O) m I (CH 2 -CH 2 -O) n -R 1 I CH 3 wherein R = alkyl group, Ci - C 6 ; Ri = acetate or hydroxy group; x = 1 to 1000; y = 1 to 50; m = 1 to 30; and n = 1 to 30. Suitable bis-imidazolinium compounds include the following structure: wherein X = halide, methylsulfate, ethylsulfate or other compatible counterions; m = 2 - 8; and Ri, R 2 may be the same or different, are aliphatic, Cι 2 - C 2 , normal or branched, saturated or unsaturated. Suitable diquatemary ammonium compounds include the following structures: R 2 - 2X " wherein X = halide, methylsulfate, ethylsulfate or other compatible counterion; n = 2 - 8; Ri, R 4 may be the same or different, are H, CH 3 , or (CH 2 ) m OH; m = 1-4; R 2 , R3, Rs, e may be the same or different, are from the following groups: (CH 2 ) P OH, where p = 1 - 6; or O II (C 2 H 4 O) q -C-R, where q = 1 - 10, R = aliphatic, Cι 2 - C 24 , saturated or unsaturated, normal or branched; or H O I II (CH 2 ) r -N-C-R\ where r = 1 - 10, R' = aliphatic, Cι 2 - C 24 , saturated or unsaturated, normal or branched; or OH I (CH 2 ) S - CH-(CH 2 ),-OR", where s = 1 - 10, t = 1 - 4, R" = aliphatic, C 12 - C 24 , saturated or unsaturated, normal or branched. Suitable poly ammonium compounds include the following structures: R 2 - χ(m+1)- wherein n = 2 - 6; m > 1 ; X = halide, methyl sulfate, ethyl sulfate or other compatible counterion; Ri, R 4 , R3, Re may be the same or different, are H, CH 3 , or (CH 2 ) P OH where p = 2 - 6, or aliphatic, C 12 - C 24 , normal or branched, saturated or unsaturated; R 2 , R 5 may be the same or different, are aliphatic, C 12 - C 24 , normal or branched, saturated or unsaturated, or (CH 2 ) q -CHOH-R' where R' = Cι 2 - C 2 , normal or branched, saturated or unsaturated, and q = 1 - 6; or (CH 2 ) r - O - R" where r = 1 - 6, R" = Cι 2 - C 24 , normal or branched, saturated or unsaturated. When a combination of a silicone quaternary and a softener/debonder is desired, the combination can be added to the thick stock simultaneously or separately. The combinations can contain one or more compounds from the above groups and added to the slurry, either in a premixed form or individually metered. The final tissue sheet comprises from about 0.01 to about 10 percent (by weight of the fiber) of the silicone quaternary either added to the wet end of the tissue making process or topically applied to the web, individually or in combination with other silicone quaternary compounds or softener/debonders. More preferably, the final tissue sheet comprises from about 0.1 to about 3 percent of the silicone quaternary added at the wet end, based on the weight of the fiber. Silicone quaternaries and softener/debonders used for the topical treatment can be delivered in an aqueous solution or be dissolved in a suitable solvent such as propylene glycol, hexylene glycol, ethylene glycol, polyethylene glycol, isopropyl alcohol, methanol, ethanol or other organic solvents. They can be applied to the surface of the basesheet individually or in combination with others. It is preferred that the composition for topical treatment comprises from about 1 to about 100 weight percent of the silicone quaternary and/or softener/debonder (individually or in combination), more preferably from about 35 to about 80 weight percent. It is also preferred that the silicone quaternary and/or the softener/debonder be topically added to the tissue sheet at an add-on ratio of from about 0.01 to about 10 weight percent of the fiber, and more preferably from about 0.1 to about 3 weight percent of the fiber. Suitable methods for the topical treatment include, but are not limited to spraying, rotogravure printing, trailing blade coating, flexographic printing, and the like. Examples Example 1 A 1-ply, blended, uncreped, through-air-dried basesheet was made. The furnish contained 50 weight percent of bleached eucalpytus hardwood kraft pulp and 50 weight percent of bleached northern softwood kraft pulp. The thick stock was diluted to approximately 0.1 percent consistency prior to forming, dewatering and drying of the tissue web. Fan pump was set at about 21 psi, while wet draw was set at about -25%. The total basis weight of the sheet was 16 lb per 2880 square feet with a target MD stretch of 20%. Pecosil 14PS (silicone quaternary, Phoenix Chemical, Inc.) was added to the thick stock at 2, 4 and 6 (0.2, 0.4 and 0.6 weight percent) kilograms of active ingredient per metric ton of fiber. In all cases the resulting tissue product was softer than the untreated control with improved surface smoothness. Example 2 Siliquat AD (silicone quartemary, Phoenix Chemical, Inc.) was added to the thick stock with the same furnish as Example 1 at the same levels. The resulting tissue product was softer than the untreated control with improved surface smoothness. Example 3 Siliquat AM (silicone quaternary, Phoenix Chemical, Inc.) was added to the thick stock (same furnish as in Example 1) at the same levels. The resulting tissue product was softer than the untreated control with improved surface smoothness. Example 4 A 2-ply, wet-pressed, creped tissue was made using a layered headbox. The first stock layer (the layer which ultimately contacts the Yankee dryer surface) contained eucalpytus hardwood fiber and provided about 60 dry weight percent of the tissue sheet. The remaining 40 percent of the tissue sheet was provided via a second stock layer consisting of northern softwood kraft pulp. The total basis weight of the sheet was about 7.3 pounds per 2880 square feet of air dried tissue. Two strength agents were added to the fiber stock layers prior to the headbox. Parez 631 NC (a glyoxalated polyacrylamide from Cytec Industries, Inc.) was metered into the softwood thick stock at 0.08 to 0.1 percent of the total fiber weight. Another strength agent, Kymene 557 LX (commercially available from Hercules, Inc.) was metered into both the hardwood and the softwood thick stock at 0.05 and 0.1 percent of the total fiber weight respectively. After drying and creping, the tissue sheet was plied together with a like sheet to form a two-ply, crimped tissue so that the eucalyptus fibers faced the outside. Silquat AC (silicone quaternary, Phoenix Chemical, Inc. 40% active) was rotogravure-printed onto both plies of the hardwood layer at an add-on amount of approximately 1 percent per ply based on the weight of fiber. The resulting tissue product had improved surface smoothness. It will be appreciated that the foregoing examples, given for purposes of illustration, are not to be construed as limiting the scope of this invention, which is defined by the following claims and all equivalents thereto.

Claims: We claim: A soft tissue comprising from about 0.1 to about 10 weight percent, based on fiber, of a silicone quaternary compound. 2. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: zY " (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d I OCH 2 CHOHCH 2 R 3 - N + - Rs I R 4 wherein x = 0 - 1000; y, z = 1 - 1000; Ri, R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; and R 3 , R 4 and R 5 are selected from the group consisting of C C 4 alkyl or hydroxyalkyi, or C 8 -C 2 aliphatic, normal or branched, saturated or unsaturated. 3. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: I (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) 0 I (OC 2 H 4 ) d R 7 wherein x = 0 - 1000; y, z = 1 - 1000; R , R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; and R 6 , R and R 8 are C 8 -C 24 aliphatic. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: CH 3 CH 3 CH 3 CH 3 CH 3 I I I I I CH3— Si— [- -M-O-S y-i- -] z --o— sμ-CH 3 zY " (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d I OCH 2 CHOHCH 2 O II Re-N + -(CH 2 ) n -NH-C-R 8 R 7 wherein x = 0-1000; y, z= 1 - 1000; Ri, R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a= 1 -4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; R 6 , R are C Ce alkyl or hydroxyalkyi; R 8 is C 8 -C 2 aliphatic; and n = 1-6. 5. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: CH 3 CH 3 CH 3 CH 3 CH 3 I I I I I CH zY " H 3 I (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d I OCH 2 CHOHCH 2 O I II Re— N + — (CH 2 ) n — N H— C- -Re wherein x = 0 - 1000; y, z = 1 - 1000; Ri, R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 20 , or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; R 6 = Cι-C 6 hydroxyalkyi; R 7 = -(CH 2 ) m - NH - C - R 9 II O n = 1-6; m = 1-6; and R 8 ; Rg= C 8 -C 24 aliphatic. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: CH 3 CH 3 CH 3 CH 3 CH 3 I I I I I CH H 3 zY " I (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d wherein x = 0 - 1000; y, z = 1 - 1000; Ri, R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; Re = Ci - Cβ alkyl or hydroxyalkyi; n = 1=6; O II m = 1-6; and Rs, R 9 = C 8 - C 2 aliphatic. 7. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: (CH 2 ) a I (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d I OCH 2 CHOHCH 2 wherein x = 0 - 1000; y, z = 1 - 1000; R L R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; and Rio, R11 = Cs - C 24 aliphatic. 8. The tissue of Claim 1 wherein the silicone quaternary compound has the following structure: CH 3 CH 3 CH 3 CH 3 CH 3 (CH 2 ) a I (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d I OCH 2 CHOHCH 2 I N + \ // C MO ■ / N / wherein x = 0 - 1000; y, z = 1 - 1000; Ri, R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; Rio = Cs - C 2 aliphatic; O II R 11 = -(CH 2 )o - 0 - C - Rι 2 where o = 1-6; and ι 2 = Cs - C 24 aliphatic. 9. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: CH 3 CH 3 CH 3 CH 3 CH 3 zY " (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d I OCH2CHOHCH2 Rι 2 - N + - R 14 I wherein x = 0 - 1000; y, z = 1 - 1000; Ri, R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 20 , or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; Rι 2 , Rι 3 = Cι-C 6 alkyl or hydroxyalkyi; O p = 1-6; and R 1 5 = Cs - C 24 aliphatic. 10. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: CH 3 CH 3 CH 3 CH 3 CH 3 I CH H 3 zY " I (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d wherein x = 0 - 1000; y, z = 1 - 1000; R , R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; R 12 = Ci - C 6 alkyl or hydroxyalkyi; R13, R = -(CH 2 )p - C - O - R15 II O p = 1-6; and R 1 5 = Cβ - C 24 aliphatic. 11. The tissue of claim 1 wherein the silicone quaternary compound has the following structure: CH 3 CH 3 CH 3 CH 3 CH 3 I I CHs— Si— -]*— O— Si-CH 3 zY " (CH 2 ) a I (OC 2 H 4 ) b I (OCHCH 3 CH 2 ) c I (OC 2 H 4 ) d wherein x = 0 - 1000; y, z = 1 - 1000; Ri, R 2 can be the same or different, are alkyl or hydroxyalkyi, Ci - C 2 o, or phenyl; a = 1 - 4; b, c, d = 0 - 20; Y = halide, methyl sulfate, ethyl sulfate, or other compatible counterion; Rι 2 , R13 = Cι-C 6 alkyl or hydroxyalkyi; O II (CH 2 ) r - O - C - R 16 / (CH 2 ) S - O - C - R 17 II O q = 1-6; r, s = 0 - 6; and Ri6, Rι 7 = C 8 - C 24 aliphatic. 12. The tissue of claim 1 further comprising a softener/debonder selected from the group consisting of quaternary ammonium compounds, bis-imidazolinium compounds, di-quaternary ammonium compounds, polyammonium compounds, phospholipids, silicone debonders, silicone betaines, organoreactive polysiloxanes and silicone glycols. 13. The tissue of claim 12 wherein the amount of the softener/debonder is from about 0.01 to about 10 weight percent, based on fiber. 14. A method for making a soft tissue comprising: (a) forming an aqueous suspension of papermaking fibers and from about 0.01 to about 10 weight percent, based on fiber, of a silicone quaternary compound; (b) forming a tissue web by depositing the aqueous suspension of papermaking fibers onto a forming fabric; and (c) dewatering and drying the tissue web. 15. The method of Claim 14 comprising topically applying to the tissue web from about 0.01 to about 10 weight percent, based on fiber, of a silicone quaternary compound. 16. The method of claim 14 or 15 wherein from about 0.01 to about 10 weight percent, based on fiber, of a softener/debonder is included in the aqueous suspension of papermaking fiber. 17. The method of claim 14 or 15 wherein from about 0.01 to about 10 weight percent, based on fiber, of a softener/debonder is topically applied to the tissue web. 18. A method for making a soft tissue comprising: (a) forming an aqueous suspension of papermaking fibers; (b) forming a tissue web by depositing the aqueous suspension of papermaking fibers onto a forming fabric; (c) dewatering and drying the tissue web; and (d) topically applying to the tissue web from about 0.01 to about 10 weight percent, based on fiber, of a silicone quaternary compound. 19. The method of claim 18 further comprising topically applying from about 0.01 to about 10 weight percent, based on fiber, of a softener/debonder to the tissue web. 20. The method of claim 18 further comprising including from about 0.01 to about 10 weight percent, based on fiber, of a softener/debonder in the aqueous suspension of papermaking fibers.

Inventors: SCHROEDER WEN ZYO, SHANKLIN GARY LEE, SCHROEDER, WEN, ZYO, SHANKLIN, GARY, LEE
Applicants: KIMBERLY CLARK CO, KIMBERLY-CLARK WORLDWIDE, INC.
Application year: 1997
Main classification: D21H21
IPC codes: C08G77, D21H17, D21H21