AU1730500A - Multi-ply tissue, and process for the manufacture of multi-ply tissue - Google Patents
Multi-ply tissue, and process for the manufacture of multi-ply tissue Download PDFInfo
- Publication number
- AU1730500A AU1730500A AU17305/00A AU1730500A AU1730500A AU 1730500 A AU1730500 A AU 1730500A AU 17305/00 A AU17305/00 A AU 17305/00A AU 1730500 A AU1730500 A AU 1730500A AU 1730500 A AU1730500 A AU 1730500A
- Authority
- AU
- Australia
- Prior art keywords
- fibres
- ply tissue
- tissue
- ply
- region
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 239000011122 softwood Substances 0.000 claims description 8
- 239000013043 chemical agent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011121 hardwood Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 2
- 239000000123 paper Substances 0.000 description 37
- 239000000126 substance Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 230000001815 facial effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- -1 methylol groups Chemical group 0.000 description 8
- 244000166124 Eucalyptus globulus Species 0.000 description 6
- 238000004049 embossing Methods 0.000 description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000009172 bursting Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003974 emollient agent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 235000013912 Ceratonia siliqua Nutrition 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000003212 astringent agent Substances 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical group C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 229940084106 spermaceti Drugs 0.000 description 1
- 239000012177 spermaceti Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H1/00—Paper; Cardboard
- D21H1/02—Multi-ply material finished plies
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
- D21F11/006—Making patterned paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
- D21F11/14—Making cellulose wadding, filter or blotting paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
Landscapes
- Paper (AREA)
- Sanitary Thin Papers (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a multi-ply tissue comprising at least two plies, the tissue having a surface area in one plane, and a thickness orthogonal to the plane, wherein the thickness is at caliper of at least 0.35 mm, and wherein the tissue has an unembossed wiping surface over a major part of the surface area of the tissue, and wherein the multi-ply tissue has an average basis weight of at least 40 g/m<2> and has a wet burst strength of at least 150g; and to a process for making the multi-ply tissue.
Description
WO 00/31340 PCT/US99/27232 5 MULTI-PLY TISSUE, AND PROCESS FOR THE MANUFACTURE OF MULTI PLY TISSUE 10 15 The present invention relates to multi-ply tissue, and in particular to facial tissue, and disposable handkerchiefs. Paper webs or sheets, sometimes called tissue or paper tissue webs or sheets, find extensive use in modern society. Such items as facial and toilet 20 tissues are staple items of commerce. It has long been recognised that four important physical attributes of these products are their strength, their softness, their absorbency, including their absorbency for aqueous systems; and their lint resistance. Research and development efforts have been directed to the improvement of each of these attributes without seriously affecting the others as 25 well as to the improvement of two or three attributes simultaneously. Softness is the tactile sensation perceived by the consumer as he/she holds a particular product, rubs it across his/her skin, or crumples it within his/her hand. This tactile sensation is a combination of several physical properties. One 30 of the more important physical properties related to the softness is generally considered by those skilled in the art to be the stiffness of the paper tissue from WO 00/31340 PCT/US99/27232 2 which the product is made. Stiffness, in turn, is usually considered to be directly dependent on the dry tensile strength of the web. Strength is the ability of the product to maintain physical integrity and to 5 resist tearing, bursting, and shredding under use conditions. Absorbency is the measure of the ability of a product to absorb quantities of liquid, particularly aqueous solutions or dispersions. Overall absorbency as perceived by the human consumer is generally considered to be a combination of 10 the total quantity of a liquid a given mass of tissue paper will absorb at saturation as well as the rate at which the mass absorbs the liquid. Lint resistance is the ability of the fibrous product, and its constituent webs, to bind together under use conditions, including when wet. In other words, 15 the higher the lint resistance is, the lower the propensity of the web to lint will be. W095/11343, published on 27 April 1995, discloses a process for making layered paper tissues. Example 3 discloses a two-ply facial tissue having a basis weight of about 32 g/m 2 (20 lbs/3000 sq. ft.) The tissue of this example 20 comprises 0.475% of a wet strength resin. US-A-4 481 243, issued on 6 th November 1984 discloses facial tissues which comprise multiple plies secured together by embossing only along the margins of the tissue. 25 Disposable paper products having high wet burst strength are known, for example BountyTM, sold by The Procter & Gamble Company, has a wet burst strength which is greater than 200 g. However such kitchen towels are embossed over the whole surface which results in a surface texture which is rough and does 30 not provide a suitably smooth wiping surface for blowing the nose.
WO 00/31340 PCT/US99/27232 3 Facial tissues are commercially available comprising at least two plies, the tissue having a surface area in one plane, and a thickness orthogonal to the plane, wherein the thickness is a caliper of at least 0.35mm, and wherein the tissue has an unembossed wiping surface over a major part of the surface area 5 of the tissue. However the rather low wet burst strength of today's facial tissues often results in tearing or bursting which in turn results in contamination of the user's hand with mucus or other bodily fluids. The object of the present invention is to provide a multi-ply facial tissue 10 having the at least the desired softness and absorbency of known facial tissues, but also providing enhanced protection against tearing or bursting when used, in particular when used for blowing the nose. Summary of the Invention 15 The object of the invention is achieved by a multi-ply tissue having an average basis weight of at least 40 g/m 2 , and preferably at least 45 g/m 2 , and having a wet burst strength of at least 150g, preferably at least 200g. It is also preferred that the multi-ply tissue has a caliper of at least 0.4 mm. In one 20 embodiment of the invention at least one of the plies comprises first and second regions, the first region comprising a macroscopically monoplanar, continuous network having a high density and low basis weight relative to the second region, the second region being composed of discrete domes having low densities relative to the first region, essentially all of the domes being dispersed 25 throughout, encompassed by, and isolated one from another by said network region. Furthermore it is preferred that the ratio of the average basis weight of the first network region to the average basis weight of the domes of the second region is greater than 0.8, and less than 1.0. 30 The invention also relates to a process for the manufacture of the multi-ply tissue, wherein the process comprises the steps of: WO 00/31340 PCT/US99/27232 4 - mechanically refining a first slurry of fibres wherein the fibres have an average length of at least 2mm, preferably the first slurry comprises a substantial proportion of softwood fibres, such as Nothern Softwood Kraft fibres; 5 - mixing the refined slurry with a second slurry of fibres, the average length of the fibres of the second slurry being shorter than the average length of the fibres of the first slurry, preferably the second slurry comprises a substantial proportion of hardwood fibres, such as eucalyptus fibres; 10 - providing a embryonic web upon a foraminous surface, the composition of fibres in the embryonic web being substantially homogeneous throughout the thickness of the web; - removing water from the embryonic web to form a ply; and - juxtaposing at least two plies to form the multi-ply tissue. 15 Most preferably, the ratio of long softwood fibres to shorter hardwood fibres is greater than 60:40, and preferably about 70:30. Detailed Description of the Invention 20 The present invention may contain, as a highly preferred component, up to about 3.0%, preferably at least 0.5%, and more preferably at least 0.8% by weight, on a dry fiber weight basis, of wet strength chemical agent, such as water-soluble permanent and temporary wet strength resin. 25 Wet strength resins useful herein can be of several types. For example, Westfelt described a number of such materials and discussed their chemistry in Cellulose Chemistry and Technology, Volume 13, at pages 813-825 (1979). Usually, the wet strength resins are water-soluble, cationic materials. That 30 is to say, the resins are water-soluble at the time they are added to the papermaking furnish. It is quite possible, and even to be expected, that subsequent events such as cross-linking will render the resins insoluble in water.
WO 00/31340 PCTIUS99/27232 5 Further some resins are soluble only under specific conditions, such as over a limited pH range. Wet strength resins are generally believed to undergo a cross linking or other curing reactions after they have been deposited on, within, or among the papermaking fibres. Cross-linking or curing does not normally occur 5 so long as substantial amounts of water are present. Of particular utility are the various polyamide-epichlorohydrin resins. These materials are low molecular weight polymers provided with reactive functional groups such as amino, epoxy, and azetidinium groups. The patent lb literature is replete with descriptions of processes for making such materials,including US-A-3 700 623, issued to Keim on October 24th 1972, and US-A-3 772 076, issued to Keim on November 13 1973. Polyamide-epihydrochlorin resins sold under the trademarks Kymene 15 557H and Kymene LX by Hercules Inc. of Wilmington, Delaware, are particularly useful in this invention. These resins are generally described in the aforementioned patents to Keim. Base-activated polyamide-epichlorohydrin resins useful in the present 20 invention are sold under the Santo Res trademark, such as Santo Re 31, by Monsanto Company of St. Louis, Missouri. These types of materials are generally described in US-A-3 855 158 issued to Petrovich on December 17th 1974; US-A-3 899 388 issued to Petrovich on August 12 th 1975; US-A-4 129 528 issued to Petrovich on December 12 1978; US-A-4 147 586 issued to Petrovich 25 on April 3 rd 1979; and US-A-4 222 921 issued to Van Eenam on September 16 t 1980. Other water-soluble cationic resins useful hererin are the polyacrylamide resins such as those sold under the Parez trademark, such as Parez 631NC, by 30 American Cyanamid Company of Sandford, Connecticut. These materials are generally described in US-A-3 556 932 issued to Coscia et al on January 19th 1971; and US-A3 556 933 issued to Williams et al on January 19 th 1971.
WO 00/31340 PCTIUS99/27232 6 Other types of water-soluble resins useful in the present invention include acrylic emulsions and anionic styrene-butadiene latexes. Numerous examples of these types of resins are provided in US-A3 844 880. Meisel Jr et al, issued 5 October 291h 1974. Still other water-soluble cationic resins finding utility in this invention are the urea formaldehyde and melamine formaldehyde resins. These polyfunctional, reactive polymers have molecular weights on the order of a few thousand. The more common functional groups include nitrogen containing groups such as amino groups and methylol groups attached to the nitrogen. 10 Although less preferred, polyethylenimine type resins find utility in the present invention. More complete descriptions of the aforementioned water-soluble resins, including their manufacture, can be found in TAPPI Monograph Series No. 29, 15 "Wet Strength in paper and Paperboard, Technical Association of the Pulp and Paper Industry (New York; 1965). Temporary wet strength agents, such as modified starch may also, optionally, be used. Combinations 20 of permanent and temporary wet strength agents may be used. The present invention may contain dry strength chemical agents, preferably at levels up to 3% by weight, more preferably at least 0.1% by weight, on a dry fiber weight basis. A highly preferred dry strength chemical agent is 25 carboxymethyl cellulose. Other suitable dry strength chemical agents include polyacrylamide (such as combinations of Cypro T M 514 and Accostrength T M 711 produced by American Cyanamid of Wayne, N.J.); starch (such as corn starch or potato starch); polyvinyl alcohol (such as Airvol T M 540 produced by Air Products Inc. of Allentown, PA); guar or locust bean gums; and polyacrylate latexes. 30 Suitable starch materials may also include modified cationic starches such as those modified to have nitrogen containing groups such as amino groups and WO 00/31340 PCT/US99/27232 7 methylol groups attached to nitrogen, available from National Starch and Chemical Company (Bridgewater, NJ). Chemical softening compositions, comprising chemical debonding agents 5 are optional components of the present invention. US-A-3 821 068, issued June 28t, 1974 teaches that chemical debonding agents can be used to reduce the stiffness, and thus enhance the softness, of a tissue paper web. US-A-3 554 862, issued on January 12th 1971 discloses suitable chemical debonding agents. These chemical debonding agents include quaternary ammonium salts. 10 Preferred chemical softening compositions comprise from about 0.01% to about 3.0% of a quaternary ammonium compound, preferably a biodegradable quaternary ammonium compound; and from about 0.01% to about 3.0% of a polyhydroxy compound; preferably selected from the group consisting of glycerol, 15 sorbitols, polyglycerols having an average molecular weight of from about 150 to about 800 and polyoxyethylene glycols and polyoxypropylene glycols having a weight average molecular weight from about 200 to 4000. Preferably the weight ratio of the quaternary ammonium compound to the polyhydroxy compound ranges from about 1.0:0.1 to 0.1:1.0. It has been discovered that the chemical 20 softening composition is more effective when the polyhydroxy compound and the quaternary ammonium compound are first premixed together, preferably at a temperature of at least 40 0 C, before being added to the papermaking furnish. Either additionally, or alternatively, chemical softening compositions may be applied to the substantially dry tissue paper web, for example by means of a 25 printing process (N.B. all percentages herein are by weight of dry fibres, unless otherwise specified). Examples of quaternary ammonium compounds suitable for use in the present invention include either unmodified, or mono- or di- ester variations of : 30 well-known dialkyldimethylammonium salts and alkyltrimethyl ammonium salts. Examples include the di-ester variations of di(hydrogenated tallow)dimethyl ammonium methylsulphate and di-ester variations of di(hydrogenated WO 00/31340 PCT/US99/27232 8 tallow)dimethyl ammonium chloride. Without wishing to be bound by theory, it is believed that the ester moity(ies) lends biodegradability to these compounds. Commercially available materials are available from Witco Chemical Company Inc. of Dublin, Ohio, under the tradename "Rewoquat V3512". Details of 5 analytical and testing procedures are given in W095/11343, published on 2 7 th April, 1995. Examples of polyhydroxy compounds useful in the present invention include polyoxyethylene glycols having a weight average molecular weight of 10 from about 200 to about 600, especially preferred is "PEG-400". The tissue paper of the present invention may be made by common methods well-known to the person skilled in the art, such as by dewatering suitable pulp using, for example, one or more papermakers felts and/or belts. 15 In one embodiment of the present invention, at least one ply of the tissue paper has two primary regions. The first region comprises an imprinted region which is imprinted against the framework of the papermaking belt. The imprinted region preferably comprises an essentially continuous network. The continuous 20 network of the first region of the paper is made on the essentially continuous framework of the belt and will generally correspond thereto in geometry and be disposed very closely thereto in position during papermaking. The second region of the paper comprises a plurality of domes dispersed 25 throughout the imprinted network region. The domes generally correspond in geometry, and during papermaking in position, to the deflection conduits in the belt. The domes protrude outwardly from the essentially continuous network region of the paper, by conforming to the deflection conduits during the papermaking process. By conforming to the deflection conduits during the 30 papermaking process, the fibers in the domes are deflected in the Z-direction between the paper facing surface of the framework and the paper facing surface of the reinforcing structure. Preferably the domes are discrete.
WO 00/31340 PCTIUS99/27232 9 Without being bound by theory, it is believed the domes and essentially continuous network regions of the paper may have generally equivalent basis weights. By deflecting the domes into the deflection conduits, the density of the 5 domes is decreased relative to the density of the essentially continuous network region. Moreover, the essentially continuous network region (or other pattern as may be selected) may later be imprinted as, for example, against a Yankee drying drum. Such imprinting increases the density of the essentially continuous network region relative to that of the domes. 10 The paper according to the present invention may be made according to any of commonly assigned U.S. Patents: 4,529,480, issued July 16, 1985 to Trokhan; 4,637,859, issued Jan. 20, 1987 to Trokhan; 5,364,504, issued Nov. 15, 1994 to Smurkoski et al.; and 5,529,664, issued June 25, 1996 to 15 Trokhan et al. and 5,679,222 issued Oct. 21, 1997 to Rasch et al., the disclosures of which are incorporated herein by reference. If desired, the paper may be dried and made on a through-air drying belt not having a patterned framework. Such paper will have discrete, high density 20 regions and an essentially continuous low density network. During or after drying, the paper may be subjected to a differential vacuum to increase its caliper and dedensify selected regions. Such paper, and the associated belt, may be made according to the following patents: 3,301,746, issued Jan. 31, 1967 to Sanford et al.; 3,905,863, issued Sept. 16, 1975 to Ayers; 3,974,025, issued Aug. 10, 1976 25 to Ayers; 4,191,609, issued March 4, 1980 to Trokhan; 4,239,065, issued Dec. 16, 1980 to Trokhan; 5,366,785 issued Nov. 22, 1994 to Sawdai; and 5,520,778, issued May 28, 1996 to Sawdai, the disclosures of which are incorporated herein by reference. 30 In yet another embodiment, the reinforcing structure may be a felt, also referred to as a press felt as is used in conventional papermaking without through-air drying. The framework may be applied to the felt reinforcing structure WO 00/31340 PCT/US99/27232 10 as taught by commonly assigned U.S. Patents 5,549,790, issued Aug. 27, 1996 to Phan; 5,556,509, issued Sept. 17, 1996 to Trokhan et al.; 5,580,423, issued Dec. 3, 1996 to Ampulski et al.; 5,609,725, issued Mar. 11, 1997 to Phan; 5,629,052 issued May 13, 1997 to Trokhan et al.; 5,637,194, issued June 10, 5 1997 to Ampulski et al.; 5,674,663, issued Oct. 7, 1997 to McFarland et al.; 5,693,187 issued Dec. 2, 1997 to Ampulski et al.; 5,709,775 issued Jan. 20, 1998 to Trokhan et al., 5,814,190 issued Sept. 29, 1998 to Van Phan; and 5,817,377 issued October 6, 1998 to Trokhan et al. the disclosures of which are incorporated herein by reference. 10 If desired, in place of a belt having the patterned framework described above, a belt having a jacquard weave may be utilized. Such a belt may be utilized as a forming wire, drying fabric, imprinting fabric, transfer clothing etc. A jacquard weave is reported in the literature to be particularly useful where one 15 does not wish to compress or imprint the paper in a nip, such as typically occurs upon transfer to a Yankee drying drum. Illustrative belts having a jacquard weave are found in U.S. Pat. Nos. 5,429,686 issued July 4, 1995 to Chiu et al. and 5,672,248 issued Sept. 30, 1997 to Wendt et al. 20 Two or more plies of tissue paper are combined to form the multi-ply tissue. The plies may, optionally, be attached together by means, for example, of gluing or embossing. Gluing is less preferred because it tends to result in a stiffer, less soft product. Indeed it is preferred that no glue is used to attach the plies. Embossing may be used to attach the plies together, for example, as 25 disclosed in EP-A-0 755 212, published on 29th January 1997. According to the present invention the tissue has an unembossed wiping surface over a major part of the surface area of the tissue. As used herein, this means that the tissue has one or more unembossed regions and, optionally, one or more embossed regions, and that the unembossed region is at least 50%, and as much as 100%, 30 of the surface area of the tissue. As used herein an embossed region is a region of the tissue having a plurality of embossed points. Most commonly the embossed regions lie close to the edge of the tissue (for example along two or WO 00/31340 PCT/US99/27232 11 four edges); and embossed regions may also be used for decorative purposes (for example to create a pattern or to spell out a logo or brand name). The unembossed region is the continuous region between and/or around the embossed regions. 5 One or both surfaces of the tissue may, optionally, be further treated with a lotion. The lotion may comprise softening/debonding agents, emollients, immobilizing agents and mixtures thereof. Suitable softening/debonding agents include quaternary ammonium compounds, polysiloxanes, and mixtures thereof. 10 Suitable emollients include propylene glycol, glycerine, triethylene glycol, spermaceti or other waxes, petrolatum, fatty acids, fatty alcohols and fatty alcohol ethers having from 12 to 28 carbon atoms in their fatty acid chain, and mixtures thereof. Suitable immobilizing agents include polyhydroxy fatty acid esters, polyhydroxy fatty acid amides and mixtures thereof. Other optional 15 components include perfumes, antibacterial actives, antiviral actives, disinfectants, pharmaceutical actives, film formers, deodorants, opacifiers, astringents, solvents and the like. Particular examples of lotion components include camphor, thymol and menthol. 20 "Long fibres" as defined herein are considered to be of an average fibre length of at least 2.0 mm. These long paper making fibres are typically softwood fibres, preferably Northern Softwood Kraft. "Short fibres" as defined herein are considered to have an average fibre 25 length of less than 2.0 mm, preferably from 0.2mm to 1.5mm. These short papermaking fibres are typically hardwood fibres, preferably Eucalyptus fibres. Alternatively low cost sources of short fibres such as sulfite fibres, thermomechanical pulp, Chemi-ThermoMechanical Pulp (CTMP) fibres, recycled fibres, and mixtures thereof can also be used. 30 Test Methods WO 00/31340 PCT/US99/27232 12 The wet burst strength is measured using an electronic burst tester and the following test conditions. The burst tester is a Thwing-Albert Burst Tester Cat. No. 177 equipped with a 2000 g load cell. The burst tester is supplied by Thwing 5 Albert Instrument Company, Philadelphia, PA 19154, USA. Take eight paper tissues and stack them in pairs of two. Using scissors, cut the samples so that they are approximately 228 mm in the machine direction and approximately 114 mm in the cross-machine direction, each two finished 10 product units thick. First age the samples for one to two hours by attaching the sample stack together with a small paper clip and "fan" the other end of the sample stack to separate the sheets, this allows circulation of air between them. Suspend each 15 sample stack by a clamp in a 1070C (± 3C) forced draft oven for 5 minutes (± 10 seconds). After the heating period, remove the sample stack from the oven and cool for a minimum of three minutes before testing. Take one sample strip, holding the sample by the narrow cross direction 20 edges, dipping the centre of the sample into a pan filled with about 25mm of distilled water. Leave the sample in the water four (4.0 ± 0.5) seconds. Remove and drain for three (3.0 ± 0.5) seconds holding the sample so the water runs off in the cross direction. Proceed with the test immediately after the drain step. Place the wet sample on the lower ring of the sample holding device with the 25 outer surface of the product facing up, so that the wet part of the sample completely covers the open surface of the sample holding ring. If wrinkles are present, discard the sample and repeat with a new sample. After the sample is properly in place on the lower ring, turn the switch that lowers the upper ring. The sample to be tested is now securely gripped in the sample holding unit. Start the 30 burst test immediately at this point by pressing the start button. The plunger will begin to rise. At the point when the sample tears or ruptures, report the maximum reading. The plunger will automatically reverse and return to its original starting WO 00/31340 PCTIUS99/27232 13 position. Repeat this procedure on three more samples for a total of four tests, i.e., 4 replicates. Report the results, as an average of the four replicates, to the nearest gram. 5 Caliper of the multi-ply tissue paper, as used herein, is the thickness of the paper when subjected to a compressive load of 14.7 g/m 2 . Preferably, caliper is measured using a low load Thwing-Albert micrometer, Model 89-11, available from the Thwing-Albert Instrument Company of Philadelphia, Pa. 10 Example An aqueous slurry comprising 3% by weight of Nothern Softwood Kraft (NSK) fibres was prepared in a conventional re-pulper. The NSK slurry was refined gently and a 2% solution of the permanent wet strength resin (KymeneTM 15 557H) was added to the NSK stock pipe at a rate of 1% by weight of the dry fibres. The absorption of the permanent wet strength resin onto the NSK fibres is enhanced by an in-line mixer. A 1% solution of the dry strength resin (carboxymethyl cellulose) is added to the NSK stock before the fan pump at a rate of 0.15% by weight of the dry fibres. The NSK slurry was diluted to about 20 0.2% consistency at the fan pump. A chemical softening composition was prepared comprising di-hard tallow diethyl ester dimethyl quaternary ammonium chloride and polyoxyethylene glycol, having an average molecular weight of 400 (PEG-400). The PEG-400 was 25 heated to about 66 0 C, and the quat was dissolved into the molten PEG-400 so that a homogeneous mixture was formed. An aqueous slurry comprising 3% by weight of eucalyptus fibres was prepared in a conventional re-pulper. A 1% solution of the chemical softening 30 composition was added to the Eucalyptus stock pipe at a rate of 0.15% by weight of the dry fibres. The Eucalyptus slurry was diluted to about 0.2% consistency at the fan pump.
WO 00/31340 PCT/US99/27232 14 The two slurries were combined so that the ratio of NSK to eucalyptus fibres was 70:30 and the resulting slurry was deposited, by means of a single layer headbox onto a Fourdrinier wire to form an embryonic web. Dewatering 5 occured through the Fourdrinier wire and was assisted by a deflector and vacuum boxes. The Fourdrinier wire was a 5-shed, satin weave configuration having 3.3 machine-direction and 3.0 cross-machine direction monofilaments per millimeter respectively. 10 The embryonic web was transferred from the Fourdrinier wire, at a fibre consistency of about 20% at the point of transfer, to a photo-polymer fabric having 0.87 Linear Idaho cells per square millimeter (562 cells per square inch), 40% knuckle area, and 0.2 mm of photo-polymer depth. Further dewatering was accomplished by vacuum assisted drainage until the web has a fiber consistency 15 of about 28%. The patterned web is predried by air blow-through to- a fibre consistency of about 65% by weight. The web was then adhered to the surface of a Yankee dryer with a sprayed creping adhesive comprising 0.25% aqueous solution of Polyvinyl Alcohol (PVA). The fibre consistency was increased to an estimated 96% before dry creping the web with a doctor blade. The doctor blade 20 had a bevel angle of about 250 and is positioned with respect to the Yankee dryer to provide an impact angle of about 810. The Yankee dryer was operated at about 4 m/s and the dried paper was formed into a roll at a reel. The dry web comprised Kymene T M at a level of 0.7%, carboxymethyl 25 cellulose at a level of 0.11%, chemical softening composition at a level of 0.05%, all by weight of dry fibre. The web is converted into a two ply tissue paper product, having overall dimension of 210 mm square. The tissue paper product was folded and 30 packaged without embossing.
WO 00/31340 PCT/US99/27232 15 In a second example the same two-ply tissue paper product was subjected to an embossing step before folding. The margin of the tissue paper product, extending about 15mm in from the edge was embossed following the process described in W095/27429, published on 19th October 1995. The major 5 part of the surface area of the tissue paper product (i.e. all of the surface area within the 15mm margin) was unembossed. In a third example the product of the previous example was taken and decorated by embossing the brand name over a small area of the previously 10 unembossed area. Alternatively four decorative leaf patterns where embossed in the previously unembossed area. Each decorative pattern being about 30mm square. The process of the previous examples was repeated and the paper was 15 calandared either at the reel; or during combining of the plies; or during converting; or calandared two or three times by combination of these steps. The two-ply tissue paper product of these examples has a caliper of 0.45mm, an average basis weight of 50g/m 2 and a wet burst strength of 250 g.
Claims (10)
1. A multi-ply tissue comprising at least two plies, the tissue having a surface area in one plane, and a thickness orthogonal to the plane, wherein the thickness is at caliper of at least 0.35 mm, and wherein the tissue has an 10 unembossed wiping surface over a major part of the surface area of the tissue, and characterised in that the multi-ply tissue has an average basis weight of at least 40 g/m 2 and has a wet burst strength of at least 150g.
2. A multi-ply tissue according to claim 1 wherein the multi-ply tissue has an 15 average basis weight of at least 45 g/m 2 and has a wet burst strength of at least 200g.
3. A multi-ply tissue according to either of claims 1 or 2 wherein the thickness of the multi-ply tissue is a caliper least 0.4mm. 20
4. A multi-ply tissue according to any of the previous claims wherein at least one of the plies comprises first and second regions, the first region comprising a macroscopically monoplanar, continuous network having a high density and low basis weight relative to the second region, the 25 second region being composed of discrete domes having low densities relative to the first region, essentially all of the domes being dispersed throughout, encompassed by, and isolated one from another by said network region. 30
5. A multi-ply tissue comprising at least one ply according to claim 4 wherein the ratio of the average basis weight of the first, network region to the WO 00/31340 PCT/US99/27232 17 average basis weight of the domes of the second region is greater than 0.8, and less than 1.0.
6. A multi-ply tissue according to any of the previous claims, comprising at 5 least 0.5% by weight of a wet strength chemical agent (% by weight of total dry fibres).
7. A multi-ply tissue according to claim 6 wherein the wet strength chemical agent is selected from the group consisting of polyamide-epihydrochlorin 10 resins, polyacrylamide resins, or mixtures thereof, and/or the dry strength chemical agent is carboxymethyl cellulose.
8. A process for making the multi-ply tissue according to any of the previous claims comprising the steps of : 15 - mechanically refining a first slurry of fibres wherein the fibres have an average length of at least 2mm; - mixing the refined slurry with a second slurry of fibres, the average length of the fibres of the second slurry being shorter than the average length of the fibres of the first slurry; 20 - providing a embryonic web upon a foraminous surface, the composition of fibres in the embryonic web being substantially homogeneous throughout the thickness of the web; - removing water from the embryonic web to form a ply; and - juxtaposing at least two plies to form the multi-ply tissue. 25
9. A process according to claim 8 wherein the fibres of the first slurry comprises a substantial proportion of softwood fibres, and the fibres of the second slurry comprises a substantial proportion of hardwood fibres. 30
10. A process according to claim 9 wherein the ratio of long softwood fibres to shorter hardwood fibres is greater than 60:40, and preferably about 70:30.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98122328 | 1998-11-24 | ||
EP98122328A EP1004703A1 (en) | 1998-11-24 | 1998-11-24 | Multi-ply tissue, and process for its manufacture |
PCT/US1999/027232 WO2000031340A1 (en) | 1998-11-24 | 1999-11-17 | Multi-ply tissue, and process for the manufacture of multi-ply tissue |
Publications (1)
Publication Number | Publication Date |
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AU1730500A true AU1730500A (en) | 2000-06-13 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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AU17305/00A Abandoned AU1730500A (en) | 1998-11-24 | 1999-11-17 | Multi-ply tissue, and process for the manufacture of multi-ply tissue |
Country Status (10)
Country | Link |
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EP (2) | EP1004703A1 (en) |
JP (1) | JP2002530170A (en) |
KR (1) | KR20010080517A (en) |
CN (1) | CN1143916C (en) |
AT (1) | ATE234963T1 (en) |
AU (1) | AU1730500A (en) |
CA (1) | CA2351369C (en) |
DE (1) | DE69906143T2 (en) |
ES (1) | ES2190671T3 (en) |
WO (1) | WO2000031340A1 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6649025B2 (en) * | 2001-12-31 | 2003-11-18 | Kimberly-Clark Worldwide, Inc. | Multiple ply paper wiping product having a soft side and a textured side |
JP4762842B2 (en) * | 2006-09-27 | 2011-08-31 | 大王製紙株式会社 | Sanitary tissue paper |
KR100821355B1 (en) * | 2006-11-22 | 2008-04-11 | 주식회사 쌍용씨앤비 | Manufacturing method of tissue added with functional substance |
WO2009151544A2 (en) * | 2008-05-27 | 2009-12-17 | Georgia-Pacific Consumer Products Lp | Ultra premium bath tissue |
US8034463B2 (en) | 2009-07-30 | 2011-10-11 | The Procter & Gamble Company | Fibrous structures |
US9648874B2 (en) | 2010-12-07 | 2017-05-16 | Kimberly-Clark Worldwide, Inc. | Natural, multiple use and re-use, user saturated wipes |
US8445032B2 (en) | 2010-12-07 | 2013-05-21 | Kimberly-Clark Worldwide, Inc. | Melt-blended protein composition |
US10821085B2 (en) | 2010-12-07 | 2020-11-03 | Kimberly-Clark Worldwide, Inc. | Wipe coated with a botanical composition having antimicrobial properties |
US8524264B2 (en) | 2010-12-07 | 2013-09-03 | Kimberly-Clark Worldwide, Inc. | Protein stabilized antimicrobial composition formed by melt processing |
US9832993B2 (en) | 2010-12-07 | 2017-12-05 | Kimberly-Clark Worldwide, Inc. | Melt processed antimicrobial composition |
US9149045B2 (en) | 2010-12-07 | 2015-10-06 | Kimberly-Clark Worldwide, Inc. | Wipe coated with a botanical emulsion having antimicrobial properties |
JP5903219B2 (en) * | 2011-03-31 | 2016-04-13 | 大王製紙株式会社 | Degreased paper |
CN102179960B (en) * | 2011-03-31 | 2012-10-03 | 维达纸业(广东)有限公司 | Equipment for manufacturing point-to-point printed paper towels |
US8481133B2 (en) | 2011-09-21 | 2013-07-09 | Kimberly-Clark Worldwide, Inc. | High bulk rolled tissue products |
US8574628B2 (en) | 2011-12-19 | 2013-11-05 | Kimberly-Clark Worldwide, Inc. | Natural, multiple release and re-use compositions |
EP2692948B2 (en) | 2012-08-03 | 2023-04-19 | Sca Tissue France | Multi-ply tissue paper product and method for manufacturing the same |
CN103233380B (en) * | 2013-05-07 | 2016-08-03 | 金红叶纸业集团有限公司 | The preparation technology of paper |
US10040265B2 (en) | 2015-03-31 | 2018-08-07 | Kimberly-Clark Worldwide, Inc. | Smooth and bulky rolled tissue products |
JP6188855B1 (en) * | 2016-03-31 | 2017-08-30 | 大王製紙株式会社 | Tissue paper |
CN107313284B (en) * | 2016-04-27 | 2019-04-19 | 上海东冠纸业有限公司 | A kind of suede sense of touch face tissue and preparation method thereof |
CN109137618A (en) * | 2017-06-15 | 2019-01-04 | 金红叶纸业集团有限公司 | Paper for daily use of high bulk and preparation method thereof |
CN110409212B (en) * | 2019-07-19 | 2021-09-03 | 王洲 | Sandwich type hand towel and production process thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US5679222A (en) * | 1990-06-29 | 1997-10-21 | The Procter & Gamble Company | Paper having improved pinhole characteristics and papermaking belt for making the same |
US5397435A (en) * | 1993-10-22 | 1995-03-14 | Procter & Gamble Company | Multi-ply facial tissue paper product comprising chemical softening compositions and binder materials |
US5667637A (en) * | 1995-11-03 | 1997-09-16 | Weyerhaeuser Company | Paper and paper-like products including water insoluble fibrous carboxyalkyl cellulose |
-
1998
- 1998-11-24 EP EP98122328A patent/EP1004703A1/en not_active Withdrawn
-
1999
- 1999-11-17 EP EP99960415A patent/EP1144758B1/en not_active Revoked
- 1999-11-17 CA CA002351369A patent/CA2351369C/en not_active Expired - Fee Related
- 1999-11-17 AT AT99960415T patent/ATE234963T1/en not_active IP Right Cessation
- 1999-11-17 ES ES99960415T patent/ES2190671T3/en not_active Expired - Lifetime
- 1999-11-17 WO PCT/US1999/027232 patent/WO2000031340A1/en not_active Application Discontinuation
- 1999-11-17 DE DE69906143T patent/DE69906143T2/en not_active Revoked
- 1999-11-17 JP JP2000584140A patent/JP2002530170A/en not_active Abandoned
- 1999-11-17 CN CNB998136387A patent/CN1143916C/en not_active Expired - Fee Related
- 1999-11-17 KR KR1020017006371A patent/KR20010080517A/en not_active Ceased
- 1999-11-17 AU AU17305/00A patent/AU1730500A/en not_active Abandoned
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DE69906143T2 (en) | 2003-09-11 |
WO2000031340A1 (en) | 2000-06-02 |
CA2351369A1 (en) | 2000-06-02 |
CN1328610A (en) | 2001-12-26 |
EP1004703A1 (en) | 2000-05-31 |
CN1143916C (en) | 2004-03-31 |
CA2351369C (en) | 2005-07-12 |
KR20010080517A (en) | 2001-08-22 |
EP1144758B1 (en) | 2003-03-19 |
EP1144758A1 (en) | 2001-10-17 |
JP2002530170A (en) | 2002-09-17 |
ES2190671T3 (en) | 2003-08-01 |
DE69906143D1 (en) | 2003-04-24 |
ATE234963T1 (en) | 2003-04-15 |
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