TISSUE PRODUCTS WITH IMPROVED SOFTNESS

Abstract: The softness of tissues is improved by a topical treatment with a formulation containing a hydrophilic solvent and a surface modifying component, which includes quaternary ammonium compounds, quaternized protein compounds, phospholipids, silicone quaternaries, hydrolyzed wheat protein/polydimethylsiloxane phosphocopolyol copolymer, quaternized lanolin derivatives and silicone emulsions.

Description: Tissue products with Improved softness. Background of the Invention In the field of tissue development and production, considerable efforts have been directed toward improving the softness of the tissue. This has been approached in a variety of ways, generally by either improving the tissue basesheet or by adding chemicals to the tissue to provide improved feel. The addition of mineral oil or polysiloxanes, for example, are chemicals which provide a more smooth feel to the surface of the tissue. However, further improvements to softness can be attained, as well as providing other benefits such as skin moisturization, through the identification and appropriate application of certain ingredients. Summary of the Invention It has now been discovered that topically treating the tissue with certain softening chemical compositions renders the surface of the tissue especially soft and smooth. In general, the invention resides in a tissue which has been topically treated with a hydrophilic softening composition comprising one or more of propylene glycol, polyethylene glycol, polypropylene glycol, and/or other hydrophilic solvents and one or more organic surface modifiers (hereinafter defined). More specifically, the invention resides in a tissue comprising from about 0.5 to about 30 dry weight percent, based on the weight of fiber, of a softening composition comprising one or more hydrophilic solvents selected from the group consisting of water, propylene glycol, polypropylene glycol and polyethylene glycol, and one or more surface modifiers selected from the group consisting of quaternary ammonium compounds, quaternized protein compounds, phospholipids, silicone quaternaries, hydrolyzed wheat protein/polydimethyl siioxane, phosphocopolyol copolymer, quaternized lanolin derivatives, and silicone emulsions. Suitabl e quaternary ammonium compounds have the fol l owi ng structures : CH, . * CH, -N-R wherein X = chloride, methyl sulfate, or other compatible counterion; and R = aliphatic, saturated or unsaturated C 8 - C 22 ; and CH 3 R-N-R. R wherein X = chloride, methyl sulfate, or other compatible counterion; R = aliphatic, saturated or unsaturated C 8 - C 22 ; and R,= benzyl or epoxy group; and wherein X = methyl sulfate or other compatible counterion; and R = aliphatic, saturated or unsaturated C 8 -C 22 . and wherein X = methyl sulfate, chloride, or other compatible counterion; R = aliphatic, normal, saturated or unsaturated, C 8 - C 22 ; and R 1 = 2-hydroxyethyl or 2-hydroxypropyl ; and wherein R = aliphatic, normal or branched, saturated or unsaturated, C 8 - 22' X = chloride, methyl sulfate, ethyl sulfate, or other compatible counterion; R'= 2-hydroxyethyl or polyethoxyethanol ; and n = 1 to 50; and 0 CH, 0 u . 3 it R-C-0-CH 2 -CH 2 -N-CH 2 -CH 2 -0-C-R CH ? i 2 CH,-OH wherein R = C 8 - C 22 ; and X = methyl sulfate, chloride, or other compatible counterion; and CH, i CH_ -N-R . CH, wherein R = aliphatic, saturated or unsaturated, C 8 - C 22 ; or allyl-; or R'-0-CH 2 -CH 2 -CH 2 . where R'= normal or branched, C - C 18 ; and X = chloride, sulfate or any other compatible counterion; and wherein R = aliphatic alkyl, normal or branched, saturated or unsaturated, C 8 - C 22 ; and X = chloride, methyl sulfate, or other compatible counterion. Suitable quaternized protein compounds include the following structures: 0 CH, OH II . 3 R C-NH-(CH 2 )-N-CH 2 -CH-CH 2 -R. CH, wherein R 1 = fatty acid radical, saturated or unsaturated, C 12 - C 22 ; R 2 = hydrolyzed soy protein, hydrolyzed silk protein, hydrolyzed wheat protein, collagen moiety, or keratin moiety; and X = chloride, lactate, or other compatible counterion; and CH, i 3 R«-N-CH,-CH-CH,-R \ CH, OH wherein R, = fatty acid radical, saturated or unsaturated, C 12 - C 22 ; R 2 = hydrolyzed collagen or keratin moiety X = chloride, lactate, or other compatible counterion. Suitable phospholipids include, without limitation, those having the following structures: O wherein x = 1 to 3; x + y = 3; a = 0 to 2; B = 0 ' or OM; A = an anion; M = a cation; and R, R 1 & R 2 can be the same or different, are alkyl, substituted alkyl, alkyl aryl or alkenyl groups of up to 16 carbon atoms and the total carbon atoms of R + R., + R 2 = 10 to 24; and + xA + aM wherein X = 1 to 3; X + y = 3; a = 0 to 2; B = 0 " or 0M; A = an anion; M = a cation; R 5 , R, may be the same or different, are alkyl, hydroxyalkyl, carboxyalkyl of up to C 6 , or polyoxyalkylene of up to C 10 ; or R R 6 and the nitrogen they are attached to may represent an N- heterocycle; and R 7 = an amidoamine moiety of the formula: O R 3 R 4 -C-N-(CH 2 ) n - wherein n = 2 to 6; R 3 = hydrogen or alkyl , hydroxyalkyl or alkenyl of up to 6 carbons; or cycloalkyl of up to 6 carbon atoms, or polyoxyalkylene of up to 10 carbon atoms; and al kyl , al kenyl , al koxy or hydroxyal kyl , C- '21 ' or aryl or alkaryl of up to C 20' and 0 ++ If R-N-CH,-CH-CH,-0- P-0-CH„-CH-CH- -N-R 2A I 2 i 2 \ \ \ R, OH OM OH R. wherein A = an anion; M = a cation; R, R 1 & 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 1 + R 2 = 10 to 24; and R 1 is an amidoa ine moiety of the structure: wherein n = 2 to 6; R 3 = hydrogen or alkyl , hydroxyalkyl 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 ,- CH, wherein n = 3 or greater; p = 1 to 1000; q = 1 to 25. Suitable silicone quaternaries include those having the following structure: H, CH, ,H, CH, ++ R-N-Z-(Si-O) -Si-Z-N-R 2X " CH, CH, CH, CH, wherein R = alkyl group, C 12 - C 18 ; Z = -CH 2 -CH 2 -CH 2 -0-(CH 2 ) 3 -; X = alkoxy, chloride or other compatible counterion; and n = 1 to 50. Suitable organoreactive polysiloxanes include the following structures: CH, CH, CH, CH, i 3 i 3 I 3 CH,-Si-0-(Si-0) -(Si-O) Si-CH, I I r ' \ 3 CH CH CHCH, CH, v 3 CH- i ' R and R-(CH 2 ) n - (CH 2 ) n - and R -(CH 2 ) n - wherein R = amine, carboxy, hydroxy, or epoxy; n = 3 or greater; x = 1 to 1000; and y = 1 to 25. The add-on amount of the hydrophilic softening composition containing the surface modifier(s) and the hydrophilic solvent(s) can be from about 0.5 to about 30 dry weight percent based on the weight of the tissue, more specifically from about 1 to about 10 dry weight percent. Water can be added to the formulation to reduce the viscosity of the composition and to make the formulation more suitable for application. The amount of the surface modifier in the hydrophilic softening composition can be from about 0.2 to about 80 weight percent, more specifically from about 0.5 to about 50 weight percent, and still more specifically from about 1 to about 20 weight percent. The amount of the silicone emulsion, if included in the hydrophilic softening composition, can be from about 1 to about 80 percent, more specifically from about 5 to about 50 percent, and still more specifically from about 5 to about 20 percent. Other optional ingredients include aloe, humectants, skin protectants, preservatives, and feel modifiers. Suitable humectants, include lactic acid and its salts, sugars, glycerin, ethoxylated glycerin, ethoxylated lanolin, corn syrup, hydrolyzed starch hydrolysate, urea, and sorbitol. Suitable skin protectants include allentoin, kaolin, aliantoin and zinc oxide. Suitable preservatives include Quaternium-15, organic acids, parabens, DMDM hydantoin, diazolidinyl urea, ethylchloroisothiazoline, methyl isothiazolin, sodium hydroxymethyl glycinate, imidazolidinyl urea, and the like. Suitable feel modifiers include corn starch, oat flour, talc, boron nitride, and cyclodextrin. The hydrophilic softening composition, which can be in the form of a solution or suspension, can be applied to the dry tissue surface by any suitable means, such as spraying or printing. The tissue to which the hydrophilic formulation is applied can be any tissue useful as facial tissue, bath tissue, or towels. Such can be produced by throughdrying or wet-pressing tissue making processes and can be creped or uncreped, layered or blended (not layered). The finished tissue product can be one-ply, two-ply or three or more plies. Either the dryer side or the air side of the tissue can be oriented outwardly in the final tissue product. EXAMPLES Example 1 A hydrophilic solution consisting of 50 parts by weight propylene glycol, 28.5 parts by weight of a softener/debonder composition (quaternary imidazolinium, fatty acid alkoxylate and polyether with 200- 800 molecular weight, identified as DPSC 5299-8, Witco Corporation) and 21.5 parts by weight water. The propylene glycol and DPSC 5299-8 were mixed together until uniform. Then the water was added and the mixture stirred until a homogeneous solution was achieved. Using a gravure printing method, the resulting hydrophilic solution was applied to the outer surfaces of the two outer plies of a three-ply, blended, wet- pressed creped tissue having a basis weight of 41.6 grams per square meter. The furnish of each ply consisted of a blend of 50 percent eucalyptus hardwood, 14 percent northern hardwood kraft, and 36 percent northern softwood kraft fibers. The add-on amount was about 1 dry weight percent based on the total weight of the three-ply tissue. The resulting tissue had a fuzzy softness. Example 2 A hydrophilic solution consisting of 90 parts by weight propylene glycol and 10 parts by weight DPSC 5299-8 was prepared. The propylene glycol and the DPSC 5299-8 were mixed together until a homogeneous solution was achieved. The resulting hydrophilic solution was applied to the outer surfaces of the two outer plies of a three-ply, blended, wet- pressed creped tissue (as described in Example 1) having a basis weight of 41.6 grams per square meter using a gravure printing method. The add¬ on amounts were about 1, 3, and 10 dry weight percent based on the total weight of the tissue. The resulting tissues had a fuzzy softness, with the higher add-on tissues feeling softer. Example 3 A hydrophilic solution was prepared consisting of 80 parts by weight propylene glycol and 20 parts by weight of a quaternary ammonium compound (stearalkonium chloride, 25 percent active, identified as Mackernium SDC- 25, Mclntyre Group, LTD.). The propylene glycol and the Mackernium SDC- 25 were mixed together and stirred until homogeneous. The resulting Example 3 A hydrophilic solution was prepared consisting of 80 parts by weight propylene glycol and 20 parts by weight of a quaternary ammonium compound (stearalkonium chloride, 25 percent active, identified as Mackernium SDC- 25, Mclntyre Group, LTD.). The propylene glycol and the Mackernium SDC- 25 were mixed together and stirred until homogeneous. The resulting hydrophilic solution was applied to the outer surfaces of the two outer plies of a three-ply, wet-pressed creped tissue as described in Example 1 having a basis weight of about 41.6 grams per square meter using a gravure printing method. The add-on amounts were about 1, 3, and 10 dry weight percent based on the weight of the tissue. The resulting tissue had a fuzzy softness, with the higher add-on tissues being softer. Example 4 A hydrophilic solution was prepared consisting of 70 parts by weight propylene glycol, 10 parts by weight DPSC 5299-8 and 20 parts by weight of a second quaternary ammonium compound (olealkonium chloride, 50 percent active, identified as Mackernium KP, Mclntyre Group, LTD.). The propylene glycol and the DPSC 5299-8 were mixed together. The Mackernium KP was added and stirred until homogeneous. Using a gravure printing method, the resulting hydrophilic solution was applied to the outer surfaces of the two outer plies of a three-ply blended, wet-pressed creped tissue as described in Example 1 and a three-ply layered, wet- pressed creped tissue having a basis weight of about 41.6 grams per square meter. Each of the plies of the layered tissue contained three layers. The dryer side outer layer consisted of eucalyptus fibers. The inner layer contained 28 percent northern hardwood kraft and 72 percent northern softwood kraft fibers. The air side outer layer contained northern hardwood kraft and northern softwood kraft fibers. Kymene 557H (Hercules, Inc.) was added at 0.16 - 0.34 weight percent based on dry fiber in all layers. A wet strength agent (Parez 631NC from Cytec Industries, Inc.) was added at 0.45 - 0.55 weight percent based on dry fiber in the inner layer and the airside layer. The three-ply tissue was plied together such that the two outer surfaces were dryer side layers. The add-on amounts of the hydrophilic solution were about 1 and 2 dry weight percent based on the total weight of the tissue. The resulting tissue products were very soft, with the higher add-on tissues being softer. Example 5 A hydrophilic solution was prepared consisting of 50 parts by weight propylene glycol, 20 parts by weight DPSC 5299-8 and 30 parts by weight Mackernium KP. The propylene glycol and the DPSC 5299-8 were mixed together. The Mackernium KP was added and stirred until homogeneous. Using a gravure printing method, the resulting hydrophilic solution was applied to the outer surfaces of the two outer plies of a three-ply, blended, wet-pressed creped tissue as described in Example 1 and a three- ply layered, wet-pressed creped tissue as described in Example 4. The add-on amounts were about 1 and 2 dry weight percent based on the weight of the tissue. The resulting tissue products were very soft, with the higher add-on tissues being softer. Example 6 A hydrophilic solution consisting of 80 parts by weight propylene glycol, 10 parts by weight of DPSC 5299-8 and 10 parts by weight of an organoreactive polysiloxane (identified as FTS-226, 40 percent active, OSi Specialties, Inc.). The propylene glycol and DPSC 5299-8 were mixed together until uniform. Then the FTS-226 was added and the mixture stirred until a homogeneous solution was achieved. Using a gravure printing method, the resulting hydrophilic solution was applied to the outer surfaces of the two outer plies of a three-ply, blended, wet- pressed creped tissue as described in Example 1. The add-on amount was about 1 and 5 dry weight percent based on the weight of the tissue. The resulting tissue had a flannelly softness. Example 7 A hydrophilic solution consisting of 40 parts by weight propylene glycol, 10 parts by weight DPSC 5299-8 and 50 parts by weight FTS-226. The propylene glycol and the DPSC 5299-8 were mixed together until uniform. Then the FTS-226 was added and the mixture stirred until a homogeneous solution achieved. Using a gravure printing method, the resulting hydrophilic solution was applied to a blended three-ply, wet- pressed creped tissue as described in Example 1 and a layered, three- ply, wet-pressed creped tissue as described in Example 4. The add-on amount was about 1 and 2 dry weight percent based on the weight of the tissue. The resulting tissues had a flannelly softness. Example 8 A hydrophilic solution consisting of 55 parts by weight propylene glycol, 20 parts by weight DPSC 5299-8 and 25 parts by weight FTS-226. The propylene glycol and the DPSC 5299-8 were mixed together until uniform. The FTS-226 was added and the mixture stirred until a homogeneous solution achieved. Using a gravure printing method, the resulting hydrophilic solution was applied to both a blended, three-ply, wet-pressed creped tissue as described in Example 1 and a layered, three- ply, wet-pressed creped tissue as described in Example 4. The add-on amount was about 1 and 2 dry weight percent based on the weight of the tissues. The resulting tissues had a flannelly softness with the higher add-on tissue being softer. Example 9 A one-ply, uncreped, through-air-dried tissue was made using a layered headbox. The two outer layers contained bleached eucalyptus hardwood kraft pulp processed through a Maule shaft disperser with a power input of 80 kilowatts at a consistency of about 34 percent and at a temperature of 184 * F. The two outer layers made up 70 percent of the tissue sheet by weight of fiber. The remaining 30 percent of the tissue web constituted the middle layer and consisted of bleached northern softwood kraft pulp. The total basis weight of the sheet was 33.9 grams per square meter of air-dried tissue. The inner layer was refined to obtain sufficient dry strength in the final product. A wet strength agent, Parez 631NC, was metered into the inner layer at a rate of 5 kg. per tonne or 0.5 percent of the weight of fiber. A softener/debonder (DPSC-5299-8) was added to the hardwood thick stock at 0.525 percent of the total fiber weight. After drying, the one-ply tissue was printed with a formulation consisting of about 12 percent Mackernium SDC, about 30 percent glycerin, about 50 percent polypropylene glycol and about 8 percent water. The resulting tissue contained about 0.5 weight percent DPSC-5299-8 and approximately 4 weight percent of the printed formulation based on fiber. The resulting tissue had a smooth, silky, surface feel. It will be appreciated that the foregoing examples, given for purposes of illustration, are not to be construed as limiting the scope of the invention, which is defined by the following claims and all equivalents thereto.

Claims: 97/04170 We claim: 1. A tissue comprising from about 0.5 to about 30 dry weight percent, based on the weight of fiber, of a softening composition comprising one or more hydrophilic solvents selected from the group consisting of water, propylene glycol, polypropylene glycol and polyethylene glycol, and one or more surface modifiers selected from the group consisting of quaternary ammonium compounds, quaternized protein compounds, phospholipids, silicone quaternaries, hydrolyzed wheat protein/polydimethylsiloxane phosphocopolyol copolymer, quaternized lanolin derivatives, and silicone emulsions. 2. The method of Claim 1 wherein at least one of the surface modifiers is a quaternary ammonium compound having the following structure: CH, i 3 CH,-N-R 3 \ wherein X = chloride, methyl sulfate, or other compatible counterion; and R = aliphatic, saturated or unsaturated C a - C 72 . 3. The method of Claim 1 wherein at least one of the surface modifiers is a quaternary ammonium compound having the following structure: CH, R-N- I wherein X = chloride, methyl sulfate, or other compatible counterion; R = aliphatic, saturated or unsaturated C 8 '22' and R^ benzyl or epoxy group. The method of Claim 1 wherein at least one of the surface modifiers is a quaternary ammonium compound having the following structure: wherein X = methyl sulfate or other compatible counterion; and R = aliphatic, saturated or unsaturated C 8 -C 22 . The tissue of Claim 1 wherein at least one of the softener/debonders is a quaternary ammonium compound having the following structure: wherein X = methyl sulfate, chloride, or other compatible counterion; R = aliphatic, normal, saturated or unsaturated, C 8 r • *-22' R, = 2-hydroxyethyl or 2-hydroxypropyl ; The tissue of Claim 1 wherein at least one of the softener/debonders is a quaternary ammonium compound having the following structure: wherein R = aliphatic, normal or branched, saturated or unsaturated, X = chloride, methyl sulfate, ethyl sulfate, or other compatible counterion; R'= 2-hydroxyethyl or polyethoxyethanol ; and n = 1 to 50. 7. The tissue of Claim 1 wherein at least one of the softener/debonders is a quaternary ammonium compound having the following structure: wherein R = C 8 - C 22 ; and X = methyl sulfate, chloride, or other compatible counterion. 8. The tissue of Claim 1 wherein at least one of the softener/debonders is a quaternary ammonium compound having the following structure: CH 3 CH,-N-R 3 I CH, wherein R = aliphatic, saturated or unsaturated, C 8 - C 22 ; or allyl- or R'-0-CH 2 -CH 2 -CH 2 . where R'= normal or branched, C 4 - C 18 ; and X = chloride, sulfate or any other compatible counterion. The tissue of Claim 1 wherein at least one of the softener/debonders is a quaternary ammonium compound having the following structure: CH, CH, -N-R I CH, wherein R = aliphatic alkyl, normal or branched, saturated or unsaturated, C 8 - C 22 ; and X = chloride, methyl sulfate, or other compatible counterion. 10. The method of Claim 1 wherein at least one of the surface modifiers is a quaternized protein compound having the following structure: 0 CH, OH li i 3 l -C-NH-(CH 2 )-N-CH 2 CH-CH 2 -R 2 CH, wherein R 1 = fatty acid radical, saturated or unsaturated, C 12 - C 22' R 2 = hydrolyzed soy protein, hydrolyzed silk protein, hydrolyzed wheat protein, collagen moiety, or keratin moiety; and X = chloride, lactate, or other compatible counterion. 11. The method of Claim 1 wherein at least on of the surface modifiers is a quaternized protein compound having the following structure: CH, R,-N-CH,-CH-CH,-R / CH, OH wherein R, = fatty acid radical, saturated or unsaturated, C 12 - C 22 ; R 2 = hydrolyzed collagen or keratin moiety; and X = chloride, lactate or other compatible counterion. 12. The tissue of Claim 1 wherein at least one of the softener/debonders is a phospholipid having the following structure: + xA + aM wherein x = 1 to 3; x + y = 3; a = 0 to 2; B = 0 ' or 0M; A = an anion; M = a cation; and R, R, & R 2 can be the same or different, are alkyl, substituted alkyl, alkyl aryl or alkenyl groups of up to 16 carbon atoms and the total carbon atoms of R + R t + R 2 = 10 to 24. 13. The tissue of Claim 1 wherein at least one of the softener/debonders is a phospholipid having the following structure: 0 .. R,-N-CH, 2 -CTH-CH, 2 -0 -P-(B1 + xA + aM R_ OH wherein x = 1 to 3; x + y = 3; a = 0 to 2; B = 0 ' or OM; A = an anion; M = a cation; R 5 , R 6 may be the same or different, are alkyl, hydroxyalkyl, carboxyalkyl of up to C 6 , or polyoxyalkylene of up to C 10 ; or R 5 , R 6 and the nitrogen they are attached to may represent an N- heterocycle; and R, = an amidoamine moiety of the formula: wherein n = 2 to 6; R 3 = hydrogen or alkyl , hydroxyalkyl 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, = alkyl , alkenyl , alkoxy or hydroxyalkyl , C 5 '21' or aryl or alkaryl of up to C 20 * 14. The tissue of Claim 1 wherein at least one of the softener/debonders is a phospholipid having the following structure: 0 ++ ti R-NI-CH , 2-CiH-CH2, 0-P-0-CH,-CH-CH,-N-R 2A \ \ R, OH OM OH R- wherein A = an anion; M = a cation; R, R, & 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, + R 2 = 10 to 24; and R * is an amidoamine moiety of the structure: 0 R, If ι 3 R 8 -C-N-(CH 2 ) n - wherein n = 2 to 6; R 3 = hydrogen or alkyl, hydroxyalkyl 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: wherein n = 3 or greater; p = 1 to 1000; and q = 1 to 25. 15. The method of Claim 1 wherein at least one of the surface modifiers is a silicone quaternary having the following structure: R- 2X " wherei n R = al kyl group , C 12 - C 18 ; Z = -CH 2 -CH 2 -CH 2 -0- (CH 2 ) 3 - ; and n = 1 to 50. 16. The method of Claim 1 wherein at least one of the surface modifiers is a organoreactive polysiloxane having the following structure: wherein R = amine, carboxy, hydroxy, or epoxy; n = 3 or greater; x = 1 to 1000; and y = 1 to 25. 17. The method of Claim 1 wherein at least one of the surface modifiers is an organoreactive polysiloxane having the following structure: wherein R = amine, carboxy, hydroxy, or epoxy; n = 3 or greater; and x = 1 to 1000. 18. The method of Claim 1 wherein at least one of the surface modifiers is an organoreactive polysiloxane having the following structure: CH, CH, CH, I 3 R- (CH 2 ) n -Si -0- (Si -0) χ -Si CH 3 CH, CH, CH, wherein R = amine, carboxy, hydroxy, or epoxy; n = 3 or greater; and x = 1 to 1000. 19. A tissue comprising from about 1 to about 10 dry weight percent, based on the weight of fiber, of a topically-applied softening composition comprising propylene glycol and one or more of a quaternary ammonium compound selected from the group consisting of methyl-1-al yl amidoethyl-2-alkyl imidazol inium methylsulfate, stearalkonium chloride, and olealkonium chloride. 20. The tissue of Claim 19 wherein the softening composition further comprises an organoreactive polysiloxane.

Inventors: COLMAN CHARLES WILSON, GOULET MIKE THOMAS, KRZYSIK DUANE GERARD, RADOVANOVICH PETER MICHAEL, SCHROEDER WEN ZYO, SMITH MICHAEL JOHN, COLMAN, CHARLES, WILSON, GOULET, MIKE, THOMAS, KRZYSIK, DUANE, GERARD, RADOVANOVICH, PETER, MICHAEL, SCHROEDER, WEN, ZYO, SMITH, MICHAEL, JOHN
Applicants: KIMBERLY CLARK CO, KIMBERLY-CLARK CORPORATION
Application year: 1996
Main classification: D21H21
IPC codes: D21H17, D21H21