MXPA00003462A - Tissue paper having a substantive anhydrous softening mixture deposited thereon - Google Patents

Abstract

Strong, soft, and low dusting tissue paper webs useful in the manufacture of soft, absorbent sanitary products such as bath tissue, facial tissue, and absorbent towels are disclosed. At least one surface of the tissue papers has uniform discrete surface deposits of a substantively affixed chemical softening mixture comprising a mixture of a quartenary ammonium compound, an emollient, and a sorbitan ester.

Description

TISU PAPER THAT HAS A SUBSIDIZING ANHYDRATION SUBSIDY MIX DEPOSITED ON THE SAME FIELD OF THE INVENTION This invention relates, in general, to tissue paper products. More specifically, it relates to tissue paper products containing chemical softening agents deposited on the surface.

BACKGROUND OF THE INVENTION Sanitary tissue paper products are widely used. These products are presented commercially in custom-made formats for a variety of uses such as facial tissues, bath papers and absorbent towels. All these sanitary products share a common need, specifically to be soft to the touch. Softness is a complex tactile impression caused by a product when it is passed over the skin. The purpose of it being gentle is that these products can be used for cleansing the skin without being irritating. The effective cleaning of the skin is a constant personal hygiene problem for many people. Annoying discharges of urine, menstruation and fecal matter from the perineum area or discharge of otolaryngological mucus do not always occur in the convenient time for someone to perform a thorough cleaning, for example with soap and large amounts of water. As a substitute for thorough cleaning, a wide variety of tissue or towel products are offered to assist in the task of removing the aforementioned discharges from the skin and retaining them for hygienic disposal. Not surprisingly, the use of these products is not focused on the level of cleanliness that can be achieved by more thorough cleaning methods and the manufacturers of tissue and towel products constantly strive to make their products compete more favorably. with thorough cleaning methods. The defects in the tissue products for example cause in many cases that the cleaning is suspended before the skin is completely clean. This behavior is encouraged by the roughness of the "tissue, since rubbing continuously with a rough item can scrape the sensitive skin and cause severe pain.The alternative of leaving the skin partially clean, is chosen even when this often causes bad odors When it emanates and can cause staining of underwear and over time it can also cause irritations.Anal discomforts, for example hemorrhoids, make the perianal area extremely sensitive and cause those suffering from these discomforts to be particularly frustrated by the need to clean the anus without causing irritation. A notable case that causes frustration is blowing your nose continuously, which is necessary when you have a cold. The repeated cycles of blowing and drying can culminate in a sore nose even when the softest handkerchiefs available now are used. Therefore, manufacturing tissue products and soft towels that promote comfortable cleaning without making damaging sacrifices has long been the goal of engineers and scientists dedicated to researching the improvement of tissue paper. There have been numerous! attempts to reduce the abrasive effect, for example, improve the softness of the tissue products. One area that has been exploited in this aspect has been to select and modify morphologies of the cellulosic fibers and to devise paper structures to take advantage of the optimal advantages of the various available morphologies. The technique applicable in this area includes Vinson et al. in U.S. Patent No. 5,228,954 issued July 20, 1993, Vinson et al. in U.S. Patent No. 5,405,499 issued April 11, 1995 and Cochrane et al. in U.S. Patent No. 4,874,465 issued October 17, 1989 and Hermans; et al., in the Regulatory Record of Inventions from the United States, all exposing methods to select or improve fiber sources for tissue and towels with superior properties. The applicable technique is further illustrated by Carstens in the United States Patent 4, 300,981, granted on November 17, 1981, which analyzes how fibers can be incorporated to accommodate paper structures so that they have the greatest possible softness potential. Although such techniques as illustrated in these prior art examples are widely recognized, they can only offer limited potential to make truly efficient and comfortable cleaning tissue articles. Another area that has received considerable attention is the addition of chemical softening agents (also referred to herein as "chemical softeners") to tissue and towel products. In the sense in which it is used in the present, the term "chemical softening agent" refers to any chemical ingredient that improves the tactile sensation perceived by the consumer who takes a particular paper product and rubs it on the skin. Although a little desirable in towel products, softness is a particularly important property for bath and facial tissue. That softness that is felt to the touch can be characterized, in a non-exclusive way, by friction,g. flexibility and homogeneity of surface, as well as subjective descriptions, such as a feeling of lubricity, velvet, silk or flannel, which impart a feeling of lubricity to the tissue. These include, for emplusive purposes only, basic waxes such as paraffin and beeswax and oils such as mineral oil and silicone oil as well as petrolatum and more complex emollients and emollients such as quaternary ammonium compounds with long alkyl chains, functional silicones, fatty acids , fatty alcohols and fatty esters. The field of work in the prior art related to chemical softeners has taken two paths. The first path is characterized by the addition of softeners to the tissue paper web during its formation either by adding an attractive ingredient to the pulp inks that will finally take the form of a tissue paper web, to the pulp as it approaches to the paper machine or to the wet web while it resides in the Fourdrinier fabric or in the dryer fabric in the paper machine. The second path is classified by the addition of chemical softeners to the tissue paper web after the web dries. Applicable processes can be incorporated into the papermaking operation, such as spraying on the dry weft before it is applied. wind up in a coil. The prior art technique related to the first mentioned way classified by adding chemical softeners to the tissue paper prior to its plot formation includes U.S. Patent Number 5,264,082, issued to Phan and Trokhan on November 23, 1993, which considered part of this as a reference. These methods have found wide use in the industry, especially when it is desired to decrease the strength that would otherwise be present in the paper and when the papermaking process, in particular the creping operation, is strong enough to tolerate the incorporation of the agents that inhibit the union. However, there are problems associated with these methods, well known to those skilled in the art. First, the location of the softener is not controlled; This generally extends throughout the paper structure just like the paper fibers to which it is applied. In addition, there is a loss in the strength of the paper that accompanies the use of these additives. Although not linked to the theory, everyone believes that additives tend to inhibit the formation of fiber-to-fiber bonds. There may also be a loss of control of the sheet as it is creped from the Yankee dryer. On the other hand, a widespread theory is that additives interfere with the coating in the Yankee dryer so that the bond between the wet web and the dryer weakens. The prior art such as U.S. Patent Number 5,487,813, issued 3. Vinson, et al., On January 30, 1996, which is considered part of the present by reference, discloses a chemical combination to attenuate the effects previously mentioned on the strength and adhesion to the creping cylinder; however, there still remains a need to incorporate a chemical softener into the paper web in a directed mode with minimal effects on the weft strength and interference with the production process. Another exemplary technique related to the addition of chemical softeners to the tissue paper web during its formation includes U.S. Patent No. 5,059,282 issued to Ampulski, et al. on October 22, 1991, which is considered part of this as a reference. The Ampulski patent discloses a process for adding a polysiloxane compound to a wet tissue web (preferably at a fiber consistency between about 20% and 35%). Such a method represents an advance in some aspects with respect to the addition of chemicals to the pulp tubs that feed the paper machine. For example, this means directs the application to one of the surfaces of the P1045 d Weft instead of distributing the additive in all the fibers of the pulp. However, methods of this type fail to overcome the primary disadvantages of the addition of chemical softeners in the final wet stage of the paper machine, that is, the effects on strength and effects on the coating of the Yankee dryer, which must be used. Because of the above-mentioned effects on the strength and breakdown of the papermaking process, considerable techniques have been devised to apply chemical softeners to already dried tissue paper or in the so-called dry end stage of the paper machine or a separate conversion operation subsequent to manufacturing step. The exemplary technique of this field includes U.S. Patent Number 5,215,626 issued to Ampulski, et al. on June 1, 1993; U.S. Patent Number 5,246,545 issued to Ampulski et al. on September 21, 1993; and U.S. Patent Number 5,525,345, issued to Warner et al. on June 11, 1996, which are considered part of this by reference. Patent 5,215,626 discloses a method for preparing soft tissue paper by applying a polysiloxane to a dry weft. Patent 5,246,545 discloses a similar method using a surface of P1045 hot transfer. Finally, the Warner patent discloses methods of application that include roller coating or extrusion to apply particular compositions to the surface of a dry tissue web. Although each of these references represents advances with respect to the so-called previous wet methods, particularly with respect to the elimination of the degrading effects in the papermaking process, none has the capacity to completely address the effects of absorbency and loss of strength. to the tension that accompanies the application to the dry paper web, due to the migration of the chemical softener. Therefore, there is a need for continuous improvements in the technology of chemical softeners in order to reduce the migration of chemical softeners that are applied to an already dry plot, in order to mitigate the effects of this migration. Achieving a high softening potential without unduly affecting other properties of the weft such as absorbency and strength, has long been an objective of the workers in the field of the present application. Accordingly, it is an object of the present invention to provide a soft tissue paper without making harmful sacrifices for example, in the absorbency or in the strength of the paper.

This and other objects are obtained using the present invention as will be shown in the following discussion.

STATEMENT OF THE INVENTION The invention is a soft tissue product, resistant, consisting of one or more sheets of tissue paper, wherein at least one outer surface of the product has a surface deposit of substantially stable chemical softening agent mixture, which it comprises a quaternary ammonium compound, an emollient and a coupling agent. The preferred embodiment of the present invention employs quaternary ammonium compounds such as dialkyldimethylammonium salts (for example, dimethyl ammonium chloride, dimethyl ammonium methyl sulfate, di (hydrogenated tallow) dimethylammonium chloride, etc.). Particularly preferred variants of these compounds are those which are considered mono or diester variations of the aforementioned dialkyldimethylammonium salts. These include diester dimethyl ammonium diester chloride, distearyl dimethyl ammonium diester chloride, dimethylammonium monoester dimeric chloride, diester methylsulfate di (hydrogenated tallow) dimethylammonium, di (hydrogenated tallow) dimethylammonium chloride, P1045 di (hydrogenated tallow) dimethylammonium and mixtures thereof, diester variations of the di (unhydrogenated tallow) dimethylammonium chloride, di (hydrogenated solid to the touch) dimethylammonium chloride (DEDTHTDMAC) and di (hydrogenated tallow) dimethylammonium chloride (DEDHTDMAC), and mixtures thereof, are especially preferred. themselves, which are especially preferred. Depending on the characteristic requirements of the product, the level of saturation of the design can be designed from a non-hydrogenated saturation (soft to the touch), partially hydrogenated (hard to the touch) or completely hydrogenated (hard). Preferred emollients include mineral oil, petrolatum and silicones, with petrolatum being particularly preferred. - Preferred coupling agents have low HLB values. Particularly preferred coupling agents are fatty acid sorbitan esters, for example sorbitan monoesters as well as monoester mixtures with ethoxylated forms thereof. More preferably, both the ethoxylated sorbitan monostearate and the sorbitan monostearate are present in a proportion of sorbitan monostearate to ethoxylated sorbitan monostearate in the range of about 2: 1 to about 4: 1. The preferred embodiment of the present invention it is characterized by having the uniform surface deposits of the softening agent mixture separated with a frequency between about 5 and 100 tanks per linear inch. With superlative preference, the uniform surface deposits are separated with a frequency between about 5 and 25 tanks per linear inch. The term "frequency" referred to the spacing of chemical softener deposits, in the sense in which it is used herein, is defined as the number of deposits per linear inch, as measured in the direction of the closest spacing. It is recognized that many patterns or arrangements of deposits qualify to be uniform and discrete and the spacing can be measured in several directions. For example, a rectilinear array of deposits would be measured with fewer deposits per inch on a diagonal line than on the horizontal or vertical line. The inventors believe that the minimum spacing direction is the most significant and therefore defines the frequency in that direction. A common engraving pattern is the so-called "hexagonal" pattern in which the hollowed out areas are engraved in the centers that reside in the corners of an equilateral hexagon with an additional hollowed area in the center of the figure in the hexagon. It is recognized that the closest spacing for this arrangement is throughout P1045 of a pair of lines intersecting each other at 60 ° and each intersecting a horizontal line at 60 °. The number of cells per square area in the hexagonal array is thus 1.15 times the square of the frequency. The invention is further characterized by having uniform surface deposits of the chemical softening agent residing predominantly on one or both of the two outer surfaces of the soft tissue paper product. Finally, the invention is characterized by having less than about 50%, more preferably less than about 25% and preferably superlative less than 5% of the surface of tissue covered by the chemical softener. Although they do not wish to link it to the theory, the inventors believe that the combination of geometrical parameters mentioned here makes the smoothed tissue cause a surprising maximum in the tactile response resulting from the spacing of the nerve sensors in human skin. Substantially fixed chemical softening agents comprise quaternary ammonium compounds including, but not limited to, the well-known dialkyldimethylammonium salts (eg, ditallowdimethylammonium chloride, ditallowdimethylammonium methyl sulfate) P1045 (dialkyldimethylammonium methyl sulfate whose alkyl groups are derived from tallow), di (hydrogenated tallow) dimethylammonium chloride (dialkyldimethylammonium chloride whose alkyl groups are derived from hydrogenated tallow), etc.). (Translator's Note: Thereafter, when the term tallow is mentioned as part of the name of a compound, it will be understood that it refers to alkyl groups derived from tallow). Particularly preferred variants of these softening agents are those which are considered mono or diester variations of the aforementioned dialkyldimethylammonium salts. These include so-called diester dimethyl ammonium chloride, distearyl dimethyl ammonium diester chloride, dimethyl ammonium monoester diester chloride, ditallow (hydrogenated) dimethyl ammonium diester, ditallow (hydrogenated) diester ammonium chloride , diester (hydrogenated) dimethyl ammonium monoester chloride and mixtures thereof, with chloride variations being especially preferred for dital (non-hydrogenated) diester, dimethyl ammonium chloride (Dihydrochloride) and DiMethyl Ammonium Chloride (DEDTHTDMAC). Disebo (Hydrogenated) DiMetil Ammonium (DEDHTDMAC) and mixtures thereof. Depending on the characteristic requirements of the product, the saturation level of the design can be adjusted from non-hydrogenated (soft) to P1045 partially hydrogenated (to the touch) or completely hydrogenated (hard). The soft tissue paper of the present invention preferably has a basis weight between about 10 g / m2 and 100 g / m2 and more preferably between about 10 g / m2 and 50 g / m2. It has a density between about 0.03 g / cm3 and 0.6 g / cm3 and more preferably between about 0.05 g / cm3 and 0.2 g / cm3. The soft tissue paper of the present invention also comprises papermaking fibers of both the hard wood type and the softwood type where at least 50% of the paper fibers are hardwoods and at least 10% are wood. soft . The fibers of hardwoods and softwoods are preferably isolated by relegating each to separate layers wherein the tissue comprises an inner layer and at least one outer layer. The tissue paper product of the present invention is preferably creped, i.e., produced in a paper machine which culminates with a Yankee dryer to which a partially dry paper web is adhered and on which it is dried and from which it is removed by the action of a flexible creping blade. Although the characteristics of the creped paper webs are preferred, in particular when the process of P1045 creped is preceded by pattern densification methods, to implement the present invention, the creped tissue paper is also a satisfactory substitute and the practice of the present invention using tissue paper without creping is specifically incorporated within the scope of the invention. present invention. The term "creped tissue paper", in the sense in which it is used herein, refers to tissue paper that dries without compression, preferably superlative by drying by passage of air. The resultant dried air-passing wefts are patterned so that the relatively high density areas are dispersed within a high volume field, including patterned densified tissue where the relatively high density areas are continuous and the High volume field is discrete. To produce uncolored tissue paper webs, an embryonic web is transferred from the foraminous forming carrier on which it is laid to a high-fiber, slowly moving transfer fabric carrier. The weft is then transferred to a drying cloth on which it is dried to final dryness. These webs may offer some advantages of surface uniformity compared to creped paper webs. The techniques to produce paper in this form P1045 Uncreped tissue are shown in the prior art. For example, Wendt, et al., In European Patent Application 0 677 612A2, published October 18, 1995 and which is considered part of the present, as a reference, shows a method for making soft tissue products. without creping. In another case, Hyland, et al., In European Patent Application 0 617 164 Al, published September 28, 1994 and which is considered part of the present, as a reference, shows a method for making smooth sheets without crepar dried by air passage. Finally, Farrington, et al., In U.S. Patent 5,656,132, published August 12, 1997 and incorporated herein by reference, discloses the use of a machine for making air dried, soft tissue without the Use of a Yankee dryer. The tissue paper webs are generally constituted basically of paper fibers. Small amounts of functional chemical agents are often included as wet strength or dry strength binders, retention aids, surfactants, sizing agents, chemical softeners, creping facilitating compositions but these are normally used only in minor amounts. The paper fibers that are most frequently used in tissue papers come from virgin chemical pulps.

P1045 Loading materials may also be incorporated in the tissue papers of the present invention. U.S. Patent 5,611,890, issued to Vinson et al., On March 18, 1997, which is considered part of the present by reference, discloses acceptable load-bearing tissue products as substrates for the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a side elevational view of a printing arrangement illustrating the preferred method for forming the uniform surface deposits of the substantially fixed chemical softening agent of the present invention. The process illustrated in Figure 1 applies the softening agent to a surface of the tissue paper product by an offset printing method. Figure 2 is a side elevational view of a printing arrangement illustrating an alternate method for forming the uniform surface deposits of the substantially fixed chemical softening agent of the present invention. The process illustrated in Figure 2 applies the softening agent to a surface of the tissue paper product by a direct printing method. Figure 3 is a side elevational view of a printing arrangement illustrating another alternate method for forming the uniform surface deposits of the substantially fixed chemical softening agent for the present invention. The process illustrated in Figure 3 applies the softening agent to both surfaces of the tissue paper product by an offset printing method. Figure 4 is a schematic representation that illustrates in detail the recessed areas for use in the printing cylinders illustrated in Figures 1, 2 and 3. Figure 4A provides more details of the preferred recessed areas for use in the present invention illustrating one of the hollowed out areas in a cross sectional view.

DETAILED DESCRIPTION OF THE INVENTION Although this specification concludes with the claims that point in a particular way and that claim in a distinctive way the matter considered as the invention, it is believed that the invention can be better understood from the reading of the following detailed description and of the attached examples. In the sense in which the term "comprising" is used herein means that the various components, ingredients or steps may be used together in putting the present invention into practice. Accordingly, the term "comprising" encompasses more restrictive terms "consisting basically of" and "consisting of". As used herein, the term "water-soluble" refers to materials that are soluble in water by at least 3% by weight at 25 ° C. In the sense in which they are used herein, the terms "tissue paper weft, weft of paper, weft, sheet of paper and paper product" refer to sheets of paper made by a process comprising the steps of making an aqueous pulp, deposit this paste on a foraminada surface, as a Fourdrinier mesh and remove the water from the paste for example by gravity or with drainage aided with vacuum, form an embryonic web, transfer the embryonic web from the forming surface to a transfer surface or fabric, which is further dried using means known in the art, such as drying by air passage. The weft can be further dried to a final dryness, using additional means, such as with a Yankee dryer, after which it is wound. The terms "multi-layer tissue paper web, multilayer paper web, multilayer web, multilayer paper sheet and multilayer paper product" P1045 indistinctly in the art refer to sheets of paper prepared from two or more layers of aqueous pulp preferably comprising different types of fibers, typically relatively long softwood fibers and relatively short hardwood fibers as used in the art. the manufacture of tissue paper. The layers, preferably, they are formed from the deposit of separate flows of fiber pulps diluted on one or more endless foraminous surfaces. If the individual layers are initially formed on separate foraminous surfaces, the layers can then be wet-blended to form a multilayer tissue paper web. In the sense in which the term "single-ply tissue product" is used herein, it means that it is composed of a tissue sheet without creping; the sheet can be almost homogeneous in nature or it can be a multilayer tissue paper web. In the sense in which it is used herein, the term "multi-sheet tissue product" means that it is made up of more than one sheet of tissue. The sheets of a multi-sheet tissue product can be almost homogeneous in nature or can be multilayer tissue paper webs. Other terms are defined in the specification, which were analyzed initially.

P1045 All percentages, ratios and proportions used here are given by weight unless otherwise specified. _ General Description of Soft Tissue Paper The invention in its most general form refers to a soft and resistant tissue paper product, comprised of one or more sheets of tissue paper, wherein at least one external surface of the product has superficial deposits of a substantively fixed chemical softening mixture, comprising a quaternary ammonium compound, an emollient and a coupling agent. The preferred embodiment of the present invention is characterized by having uniform, discrete, surface deposits separated with a frequency between about 1 deposit per linear inch to 100 deposits per linear inch. With superlative preference, the uniform surface deposits are spaced at a frequency between about 5 to 25 deposits per linear inch. The uniform surface deposits of the chemical softening agent are preferably less than about 2700 microns in diameter, more preferably less than about 800 microns in diameter and preferably superlative smaller than P1045 approximately 240 microns in diameter. The present invention is further characterized by having the uniform surface deposits residing predominantly in at least one and more preferably in both, of the two outer surfaces of the tissue paper product.

General Description of the Chemical Softening Mixture It has been found that the chemical softening mixture of the present invention imparts desired lubricity and smoothness to the tissue substrates to which it is applied, while at the same time decreasing the detrimental effects on the absorbency and strength of the fabric. the chemical softening compositions of the prior art. In the sense in which the term "substantially fixed chemical softening mixture" is used herein is defined as a chemical mixture imparting lubricity or emollient properties to tissue paper products and also having permanence with respect to maintaining the fidelity of these deposits without significant migration when exposed to the environmental conditions to which products of this type are usually exposed during their characteristic life cycle. Waxes and oils alone, for example, have the ability to impart lubricity or emollient properties to tissue paper, but P1045 they experience the tendency to migrate because they have little affinity for the cellulose pulps that constitute the tissue papers of the present invention. While not wishing to be bound by theory, it is believed that the substantially fixed chemical softening mixtures of the present invention interact with each other by Van der Waals forces, covalent, ionic or hydrogen bonds, or a combination of these, in order to decrease migration. Applicants have identified particularly desirable compositions comprising a mixture of quaternary ammonium compound, an emollient and a coupling agent that provides this desired lubricity and smoothness, without a substantial migration when the mixtures are applied to a tissue substrate, at all levels described above. Suitable embodiments of these mixtures comprise between about 40% and about 80% of a quaternary ammonium compound; between about 10% and about 30% of an emollient; and between about 10% and about 20% of a coupling agent. Preferred embodiments comprise between about 50% and about 70% of a quaternary ammonium compound, between about 15% and about 25% of an emollient; and between about 12% and about 20% of a coupling agent. A mix P1045 particularly preferred has the composition shown in Table 1.

Table 1 Particularly Preferred Chemical Softener Mixture Component% by Weight Quaternary Ammonium Compound 60 Emollient 22 Coupling Agent _, 18 Each of the components of the chemical softening composition of the present invention is discussed in detail below.

Quaternary Ammonium Compounds Preferably, the quaternary ammonium compounds of the present invention have the formula: (R?) 4-m-N + - [R2] m X-where m is between 1 and 3; each R is an alkyl group hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures thereof; each R2 is a C14-C22 alkyl group, hydroxyalkyl group, hydrocarbyl group or substituted hydrocarbyl group P1045 alkoxylated, benzyl group or mixtures thereof; and X "is any anion compatible with the suitable softener for use in the present invention, Preferably, each Rx is methyl and X" is chloride or methyl sulfate. Preferably, each R2 is C16-C1B alkyl or alkenyl, preferably superlative each R2 is straight chain C18 alkyl or alkenyl. Optionally, the substituent R2 can be derived from vegetable oils. Structures of this type include the well-known dialkyldimethylammonium salts (eg, ditallowdimethylammonium chloride, ditallowdimethylammonium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride, etc.), where Rx are methyl groups, R2 are groups alkyl derived from tallow with varying levels of saturation, and X "is chloride or methyl sulfate." As discussed in Swern, Ed. in Bailey's Industrial Oil and Fat Products, Third Edition, John Wiley and Sons (New York 1964), tallow is an existing material in nature that has a variable composition Table 6.13 in the previous reference edited by Swern indicates that typically 78% or more of tallow fatty acids contain between 16 and 18 carbon atoms. The fatty acids present in sebum are unsaturated, mainly in the form of oleic acid, and synthetic "sebas" as well as natural ones. within the scope of the present invention. It is also known that depending on the characteristic requirements of the product, the saturation level of the design can be adjusted from non-hydrogenated (soft) to partially hydrogenated (soft to touch), or completely hydrogenated (hard). All saturation levels described above are expressly referred to be included within the scope of the present invention. Preferred variants in particular of these softening agents are considered to be mono or diester variations of these quaternary ammonium compounds having the formula: (Rx) 4.m-N + - [(CH2) n - Y - R3] m X - where Y is -0- (0) C- or -C (0) -0- or -NH-C (O ) - or -C (0) -NH-; m is between 1 and 3; n is between 0 and 4; each RL is a C1-C6 alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures thereof; each R3 is a C13-C21 alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures thereof; and X "is any anion compatible with the softener.

P1045 Preferably, Y = -O- (O) C- or -C (0) -0-; m = 2 and n = 2. Each Rx substituent is preferably a C1-C3 alkyl group, with methyl being most preferred. Preferably, each R3 is a C13-C17 alkyl and / or alkenyl, more preferably R3 is a C15-C17 alkyl and / or alkenyl linear chain, C15-C17 alkyl, preferably superlative each R3 is a straight chain C17 alkyl . Optionally, the R3 substituent can be derived from vegetable oil sources. As mentioned above, X "can be any anion compatible with the softener, for example, acetate, chloride, bromide, methyl sulfate, formate, sulfate, nitrate and the like can be used in the present invention. or methyl sulfate. Specific examples of ester-functional quaternary ammonium compounds having the structures mentioned above and which are suitable for use in the present invention include the well-known dialkyl dimethyl ammonium diester salts such as ditallow dimethyl ammonium diester chloride, dimethyl ammonium diabonate, ditallowdimethyl ammonium diester methyl sulfate, ditallow (hydrogenated) dimethyl ammonium diester methyl ester, ditallow (hydrogenated) dimethyl ammonium diester chloride and mixtures thereof. Diester dimethyl ammonium chloride and diester chloride P1045 of (hydrogenated) dimethyl ammonium disodium are particularly preferred. These particular materials are commercially available from Witco Chemical Company Inc., of Dublin, Ohio under the trade name "ADOGEN SDMC". As mentioned above, typically, half of the fatty acids present in sebum are unsaturated, mainly in the form of oleic acid. Synthetic "tallows", as well as natural ones, are within the scope of the present invention. It is also known that depending on the characteristic requirements of the product the saturation level of the design can be adjusted from non-hydrogenated (soft) to partially hydrogenated (soft to the touch) or completely hydrogenated (hard). All saturation levels described above are expressly referred to be included within the scope of the present invention. It will be understood that the substituents Rx, R2 and R3 can optionally be substituted with various groups such as alkoxy, hydroxyl, or they can be branched. As mentioned above, preferably each Rx is methyl or hydroxyethyl. Preferably, each R2 is C12-C18 alkyl and / or alkenyl, preferably superlative each R2 is straight chain C16-C18 alkyl and / or alkenyl, preferably superlative each R2 is straight chain C18 alkyl and / or alkenyl. Preferably R3 is alkyl and / or P1045 C13-C17 alkenyl, more preferably R3 is straight chain C15-C17 alkyl and / or alkenyl. Preferably X "is chloride or methyl sulfate In addition, ester-functional quaternary ammonium compounds may optionally contain up to 10% of the mono (long chain alkyl) derivatives, for example, (R ±) N + ((CH2) 2 OH ) ((CH2) 2OC (0) R3) X ~ as minor ingredients These minor ingredients can act as emulsifiers and are useful in the present invention Other types of quaternary ammonium compounds suitable for use in the present invention are described in U.S. Patent No. 5,543,067, Phan et al., Issued August 6, 1996; U.S. Patent No. 5,538,595, Trokhan et al., Issued July 23, 1996; U.S. Patent No. 5,510,000, Phan et al., Issued April 23, 1996, U.S. Patent No. 5,415,737, Phan et al., Issued May 16, 1995, and European Patent Application No. 0 688 901 A2, assigned to Kimberly-Clark Corporation published on December 12, 1995; each of which is considered part of this, as a reference. Di-quat variations of the quaternary ammonium compounds with ester function can also be used and are understood to be within the scope of the present invention. These compounds have the formula: P1045 O (Rib (l) 2 O 11 I I II Rj - C - O - (CH 2) 2 - N + - (CH 2) n N + - (CH 2) 2 - O - C - R 2X- In the structure mentioned above each R1 is an alkyl or hydroxyalkyl group R3 is a C11-C21 hydrocarbyl group, n is between 2 and 4 and X 'is a suitable anion, such as a halide (for example, chloride or bromide) or methyl sulfate. Preferably, R3 is C3-C17 alkyl and / or alkenyl, preferably superlative each R3 is straight chain C15-C17 alkyl and / or alkenyl and Rx is a methyl. Parenthetically, although not wishing to be bound by theory, it is believed that the ester fraction (s) of the aforementioned quaternary compounds lead to a measure of their ability to biodegrade. Importantly, the ester-functional quaternary ammonium compounds used herein biodegrade more rapidly than conventional dialkyl dimethyl ammonium chemical softeners do. While these quaternary ammonium compounds provide desirable softness to tissue webs, the use of these compounds also results in a reduction in the tensile properties of these P1045 frames. As already noted, this reduction in stress properties is considered to be caused by an inhibition in the formation of fiber-to-fiber hydrogen bonds due to the migration of the quaternary ammonium compound.

Emollient The present invention is further characterized by the presence of an emollient. In the sense that is used herein the term "emollient" refers to a material that softens, smoothes, makes flexible, coats, lubricates or moisturizes the skin. An emollient typically achieves several of these objectives, for example softening, moisturizing and lubricating the skin. Preferred emollients will have either a liquid or liquid temperature at room temperature, ie 20 ° C. This particular consistency of the emollient allows the composition to impart a smooth, lubricating and lotion-like perception. Suitable emollients include linear and branched alkanes and alkenes based on petroleum, which are liquids or solids at a temperature of 20 ° C and at atmospheric pressure. Suitable petroleum-based emollients include hydrocarbons or mixtures of hydrocarbons having chain lengths of 16 to 32 carbon atoms. Petroleum-based hydrocarbons that have P1045 These chain lengths include mineral oil (also known as "liquid petrolatum") and petrolatum (also known as mineral wax, "petroleum jelly" and "mineral jelly"). Mineral oil usually refers to mixtures of less viscous hydrocarbons having from 16 to 20 carbon atoms. Petrolatum usually refers to more viscous mixtures of hydrocarbons having from 16 to 32 carbon atoms. Petrolatum and mineral oil are particularly preferred emollients of the compositions of the present invention. Petrolatum is a particularly preferred emollient as it imparts a highly desirable emolliency to the tissue paper. A suitable material is obtained from Witco, Corp., Greenwich, CT as White Protopet® IS. Other suitable types of emollients that are used in the invention include polysiloxane compounds. In general, the polysiloxane materials that are used in this invention include those having monomeric siloxane units with the following structure: wherein R1 and R2 for each monomeric independent siloxane unit can independently be hydrogen or P1045 any of alkyl, aryl, alkenyl, aralkyl, cycloalkyl, halogenated hydrocarbon or other radical. Any of these radicals can be substituted or unsubstituted. The radicals R1 and R2 of any particular monomer unit may be different from the corresponding functional groups of the contiguous monomer unit. In addition, the radicals may be either a straight chain, or a branched chain or have a cyclic structure. The radicals R.sub.1 and R.sub.2 can also independently be other siliceous functional groups, such as, for example, non-exclusively, siloxanes, polysiloxanes and polysilanes. The radicals R1 and R2 can also contain a variety of organic functional groups, including, for example, alcohol, carboxylic acid and amino functional groups. Exemplary alkyl radicals are methyl, ethyl, propyl, butyl, methyl, hexyl, octyl, decyl, octadecyl and the like. Exemplary alkenyl radicals are vinyl, allyl and the like. Exemplary aryl radicals are phenyl, diphenyl, naphthyl and the like. Exemplary alkaryl radicals are toyl, xylyl, ethylphenyl and the like. The aralkyl radicals for example are benzyl, alpha-phenylethyl, beta-phenylethyl, alpha-phenylbutyl and the like. The cycloalkyl radicals P1045 Examples are cyclobutyl, cyclopentyl, cyclohexyl and the like. Exemplary halogenated hydrocarbon radicals are chloromethyl, bromoethyl, tetrafluoroethyl, fluoroethyl, trifluoroethyl, trifluorothioyl, hexafluoroxylyl and the like. Preferred polysiloxanes include straight chain organopolysiloxane materials with the following general formula: wherein each radical Rx-R9 can independently be any unsubstituted Cj ^ -C ^ or aryl alkyl radical and R10 any substituted aryl C-L-C ^ O alkyl radical. Preferably each radical Rx-R9 is independently any unsubstituted C ^^ alkyl group. Those skilled in the art will recognize that technically there is no difference if, for example, R9 or R10 is the substituted radical. Preferably the molar ratio of b to (a + b) is between 0 and about 20%, more preferably between 0 and about 10% and with P1045 Superlative preference between approximately 1% and 5%. In a particular preferred embodiment, R? -R9 are methyl groups and R10 is a substituted or unsubstituted alkyl, aryl or alkenyl group. This material will be described here in general as polydimethylsiloxane with a particular functional group as is suitable in that particular case. Exemplary polydimethylsiloxane includes, for example, polydimethylsiloxane having a hydrocarbon alkyl radical R 10 and polydimethylsiloxane having one or more amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, thiol and / or other functional groups including Alkyl and alkenyl analogs of such functional groups. For example, an alkyl group with amino function such as R 10 can be a polydiethylsiloxane with amino functional group or aminoalkyl functional group. Listing these polydimethylsiloxanes in an exemplary way does not imply that others that are not specifically listed are excluded. The viscosity of the polysiloxanes useful for this invention can vary as widely as the viscosity of the polysiloxanes generally varies, so long as the polysiloxane is present in a form in which it can be applied to the tissue paper product herein. This includes, but is not limited to, viscosity as low as approximately 25 centistokes to P1045 approximately 20,000,000 or even greater. Although one does not wish to be bound by the theory, it is believed that the efficiency in the tactile benefit is related to the average molecular weight and that the viscosity is also related to the average molecular weight. Accordingly, due to the difficulty in directly determining the molecular weight, viscosity is used here as the obvious operational parameter with respect to imparting softness to the tissue paper. References that disclose polysiloxanes include U.S. Patent No. 2,826,551, issued March 11, 1958 to Geen; U.S. Patent Number 3,964,500, issued June 22, 1976 to Drakoff; U.S. Patent No. 4,364,837, issued December 21, 1982 to Pader; U.S. Patent No. 5,059,282 issued to Ampulski; U.S. Patent No. 5,529,665 issued June 25, 1996 to Kaun; U.S. Patent 5,552,020 issued September 3, 1996 to Smithe et al .; and British Patent 849,433 published September 28, 1960 in the name of Wooston. All these patents are considered part of this, as a reference. It is also considered part of the present, as reference Si1icone Compounds, p. 181-217, distributed by Petrach Systems, Inc., which P1045 contains an extensive list and description of polysiloxanes in general.

Coupling Agent While petrolatum provides desirable emolliency to tissue paper, when used alone, it can have detrimental effects on absorbency. Also, as already mentioned, the migration of quaternary ammonium compounds can cause a loss in tensile properties. In addition, it tends to migrate easily over time. As already mentioned, the softening mixture is preferably provided in separate surface deposits. These separate surface deposits are directed to the absorbency effects of hydrophobic emollients, such as petrolatum, as long as the emollient does not migrate. Resistance resins can also be used to mitigate the loss in stress properties due to the migration of a quaternary ammonium compound. Applicants have found that, by providing a coupling agent that is associated with both the quaternary ammonium compound and the emollient of the present invention, the migration of the quaternary ammonium compound and the emollient can be substantially reduced. The applicants consider P1045 that there is a synergistic result between the ratio of the quaternary ammonium compound, the emollient and the coupling agent. The total composition has the desired properties of each component, while any negative property of them decreases. While not wishing to be bound by theory, the applicants consider that the polar head group of a suitable coupling agent can be alienated with the polar nitrogen center of a quaternary ammonium compound that produces a non-migratory mixture (in order to reduce the loss of tension properties) and concentrating their respective alkyl chains in a configuration that can entrap the emollient, preventing it from migrating while retaining its lubricating capacity. Suitable coupling agents are waxy or solid surfactant materials, or mixtures of these materials having an HLB value of between about 2 and about 8. Preferably, the HLB value is between about 3 and about 7. Most preferably, the value HLB is between about 3.5 and about 6. Coupling agents suitable for the present invention can comprise polyhydroxy fatty acid esters. Due to the sensitivity of the skin to paper products to which the P1045 softener mixture, these esters should also be relatively soft and non-irritating to the skin. Suitable polyhydroxy fatty acid esters which are used in the present invention will have the formula: wherein R is a C5-C31 hydrocarbyl group, preferably straight-chain C7-C19 alkyls or alkenyl, more preferably straight-chain C8-C17 alkyl or alkenyl, still more preferably straight chain Clx-C17 alkyl or alkenyl, or mixtures thereof. Y is a polyhydroxyhydrocarbyl entity having a hydrocarbyl chain with at least 2 free hydroxyls directly connected to the chain; and n is at least 1. Suitable Y groups can be derived from polyols such as glycerol, pentaerythritol, sugars such as raffinose, maltodextrose, galactose, sucrose, glucose, xylose, fructose, maltose, lactose, mannose and erythrose; sugar alcohols such as erythritol, xylitol, malitol, mannitol and sorbitol, and sugar alcohols anhydrides as they sorbit. Suitable coupling agents may be selected from diglycerol or glyceryl monoesters of linear saturated C 14 -C 24 fatty acids such as for example glyceryl monopalmitate, glyceryl monobehenate, diglycerol monomyristate, diglycerol monostearate and diglycerol monoesters of tallow fatty acids; sorbitan monoesters of linearly saturated C 14 -C 24 fatty acids, for example sorbitan monomiristate, sorbitan monostearate and sorbitan monoesters derived from tallow fatty acids; diglycerol monoaliphatic ethers of saturated, linear C14-C24 alcohols, and mixtures of these emulsifying components. Other classes of polyhydroxy fatty esters that are used herein include some fatty acid esters of sucrose, preferably sucrose esters of C 12 -C 22 saturated fatty acid. Sucrose monoesters are particularly preferred which include sucrose monolaurate and sucrose monostearate. The diglycerol monoesters of saturated linear fatty acids which are useful as coupling agents in this invention can be prepared by esterifying diglycerol with fatty acids, using procedures well known in the art. Refer, for example, to the method for preparing esters of P1045 polyglycerol which is set forth in U.S. Patent No. 5,387,207 (Dyer et al.) issued on February 7, 1995, which is incorporated herein by reference. Diglycerol can be obtained commercially or can be separated from polyglycerols that have a high diglycerol content. Saturated linear fatty acids can be obtained commercially. The mixed ester product of the esterification reaction can be fractionally distilled in vacuo, one or more times to provide distillation fractions having a high content of diglycerol monoesters. The sorbitan esters of linear and saturated fatty acids can be obtained commercially or prepared using methods known in the art. See, for example, United States Patent No. 4,103,047 issued to Zaki et al on July 25, 1978, the disclosure of which is incorporated by reference. The mixed sorbitan ester product which can be fractionally distilled in vacuo to give compositions having a high content of sorbitan monoesters. A particularly preferred class of coupling agents are the fatty acid esters of sorbitan.

Where R1 is a C14-C24 hydrocarbyl group R2 is a hydroxyl or a C14-C2 hydrocarbyl group And R3 is hiroxyl or a C14-C hydrocarbyl group Representative examples of suitable sorbitan esters include sorbitan palmitates (for example SPAN 40), sorbitan stearates (for example SPAN 60) and sorbitan behenates, comprising one or more of the mono-di and triester versions of these sorbitan esters, for example mono, di and tripalmitate of sorbitan, mono, di and sorbitan tristearate, sorbitan mono, di and tribehenate, as well as mixtures of tallow fatty acid sorbitan mono, di, di-triesters. Mixtures of the different sorbitan esters can also be used, for example sorbitan palmitates with sorbitan stearates. Preferred sorbitan steres are sorbitan stearates, typically a mixture of mono, di and triesters (plus some tetraesters), for example SPAN 60, and sorbitan stearate sold under the tradename GLYCOMUL-S by Lonza, Inc. Although these sorbitan esters typically contain mixtures of mono, di and triesters, some tetraesters, mono and diesters are usually predominant species in these mixtures. A particularly preferred sorbitan ester is the P1045 sorbitan mono-stearate (R1 = C18 hydrocarbyl, R2 = hydroxyl and R3 = hydroxyl). The ethoxylated forms of the sorbitan fatty acid esters can also be added. They have the general formula: Wherein: R1 is a C14-C24 hydrocarbyl group; and w + x + y + z has an average value of between about 5 and about 30. These ethoxylated sorbitan fatty acid esters are preferably mixed with one or more preferred low HLB materials, such as those mentioned above, for formulating the coupling agent compositions that can be designed to more closely match the properties of the quaternary ammonium compound and the emollient. The ethoxylated sorbitan ester can contain any number of ethylene oxide units, with the most preferred range being between about 5 and about 30 moles per mole of ethoxylated sorbitan ester. It preferred particularly the sorbitan monostearate which has been ethoxylated with an average of 20 moles of ethylene oxide. An exemplary and commercially available material of this type is Tween 60 which is available from the ICI surfactants of Wilmington, DE. When present, the ethoxylated sorbitan ester is preferably used as a relatively small fraction, such that the proportion of sorbitan ester to ethoxylated sorbitan ester is between about 2: 1 and about 4: 1.

Tissue Paper The tissue paper webs made according to the present invention have a basis weight between 10 g / m2 and approximately 100 g / m2, more preferably, between approximately 10 g / m2 and 50 g / m2. It has a density of approximately 0.03 g / cm3 and 0.6 g / cm3 and preferably superlative between approximately 0.05 g / cm3 and 0.2 g / cm3. The preferred embodiment of the tissue paper of the present invention further comprises paper fibers of both hardwood and softwood, where at least about 50% of the paper fibers are hardwood and at least about 10% are of soft wood Hardwood and softwood fibers are more preferably isolated by relegating each layer to layers P1045 you separate where the tissue comprises an inner layer and at least one outer layer. The tissue paper product of the present invention is preferably creped, that is, it is produced in a paper machine culminating with a Yankee drying to which the partly dried paper web is adhered and on which it is dried and from which it is removed by the action of a flexible creping blade. Creping is a means to mechanically compact the paper in the machine direction. The result is an increase in the basis weight (mass per unit area) as well as a dramatic change in many of the physical properties, particularly when measured in the machine direction. Creping is generally achieved with a flexible blade, called a doctor blade, against a Yankee dryer in an operation on the machine. A Yankee dryer is a large cylinder generally 8 to 20 feet in diameter, which is designed to be pressurized with steam to provide a hot surface to complete the drying of paper wefts at the end of the papermaking process. The paper web that first forms on a foraminated forming carrier, for example the Fourdrinier mesh, where it is released from the excess water that is needed for the dispersion of the fibrous pulp, in general is transferred to a cloth or felt in a section called pressing, where the drainage of water is continued either by mechanical compaction of the paper or by some other method of drainage, for example drying by passage of hot air , before it is finally transferred, being in a semi-dry condition, to the surface of the Yankee to complete the drying. While the characteristics of the creped paper webs, particularly when the creping process is preceded by densification methods by pattern, are preferred to practice this invention, tissue without creping is also a satisfactory substitute and the practice of the present invention using tissue paper without creping is specifically incorporated within the scope of the present invention. Uncreped tissue paper, a term used herein, refers to a tissue paper that has not been compressively dried, but preferably by air passage. The resulting air-dried plots have densified patterns so that areas of relatively high density are dispersed within a bulk can field, including densified pattern tissue where the areas of relatively high density are continuous and the high-density field. Bulkyness is discreet.

To produce uncolored tissue paper webs, an embryonic web is transferred from the foraminated forming carrier on which it lies, to a cloth carrier for the transfer of the high fiber carrier, and which moves slowly. The web is then transferred to a drying cloth on which it is dried to a final degree of drying. These plots can offer certain advantages in the smoothness of the surface compared to creped paper webs. Techniques for producing tissue without creping are shown in the prior art. For example, Wendt, et. to the. in European Patent Application 0 677 612A2, published October 18, 1995 and incorporated herein by reference, shows a method for the manufacture of soft tissue products without creping. In another case, Hyland, et. to the. in the European Patent Application 0 617 164 Al, published on September 28, 1994 and which is incorporated herein by reference, shows a method for the preparation of flat sheets not creped dried with air passage. Finally, Farrington, et al. U.S. Patent 5,656,132 published August 12, 1997, and which is incorporated herein by reference, discloses the use of a machine for making soft, air dried tissue without the use of a Yankee. The tissue paper webs in general are P1045 comprised essentially of paper fibers. Frequently small amounts of chemical functional agents are included, for example wet strength and dry strength binders, retention aids, surfactants, sizing agents, chemical softeners, creping facilitating compositions, but these are typically used in minor amounts. The paper fibers most frequently used in tissue papers are virgin pulps of chemical wood. It is anticipated that wood pulp in all its varieties will typically comprise the tissue papers that are useful in this invention. However, other fibrous cellulose pulps such as cotton wool, bagasse, rayon, etc., may be used and none of them is excluded. Useful wood pulps here include chemical pulps such as sulphite and sulfate pulps (sometimes called Kraft pulps) as well as mechanical pulps including, for example, crushed wood, thermochemical pulp (TMP) and chemo-thermochemical pulp (CTMP). Pulps derived from deciduous trees and conifers can also be used. Softwood pulps and hardwood pulps as well as combinations thereof may be used as paper fibers for the tissue paper of the present invention. The term "hardwood pulps" which is used herein refers to fibrous pulp derived from P104S woody substance of deciduous trees (angiosperms), while "soft wood pulps" are fibrous pulps derived from coniferous woody substance (gymnosperms). Mixtures of hardwood kraft pulp, especially eucalyptus and northern softwood kraft pulp (NSK) are particularly suitable for the manufacture of tissue webs of the present invention. A preferred embodiment of this invention comprises the use of tissue webs in layers where, more preferably, hardwood pulps such as eucalyptus are those used for the outer layer or layers and where the wood Kraft pulps Soft North are used for layer or inner layers. Fibers derived from recycled paper, which may contain any of the above categories of fibers, also apply to the present invention.

Application of the softening chemical mixture Figures 1-4 is provided as an aid to describe the present invention. Figure 1 is a side elevational view of a printing arrangement illustrating the preferred method for forming the uniform surface deposits of the substantially fixed guyline softening agent of the present invention. The process illustrated in Figure 1 applies the softening agent to a surface of the tissue paper product by a printing method P1045 in offset. In Figure 1, the liquid chemical softener 6, preferably hot by means not shown, is contained in a tray 5, so that the rotary engraver cylinder 4, also preferably hot by means not shown, is submerged partially in the liquid chemical softener 6. The engraving cylinder 4 has a plurality of recessed areas that are substantially empty of content when they enter the tray 5, but which are filled with the chemical softener 6 as the engraver cylinder 4 is submerged partially in the fluid in the tray 5 during the rotation of the cylinder. The engraving cylinder 4 and its pattern of recessed areas is illustrated below in Figure 4 so that the detailed description is postponed until it is provided when reference is made to that figure. Still referring to Figure 1, the excess chemical softener 6 that is taken from the tray 5 but not retained in the recessed areas is removed by a flexible scraper blade 7, which contacts the engraver cylinder 4 on its surface outside, but that does not have the capacity to significantly deform recessed areas. Therefore, the chemical softener remaining in the engraving cylinder 4 resides almost exclusively in the recessed areas of the P1045 engraving cylinder 4. This remaining chemical softener is transferred in the form of discrete uniform reservoirs to an applicator cylinder 3. The applicator cylinder 3 may have any of a variety of surface covers as long as they suit the purpose of the process. The most common is that the cylinder has a metal cover. The engraving cylinder 4 and the applicator cylinder 3 will normally operate with interference since having a loading pressure will aid in the extraction of the liquid chemical softener from the recessed areas of the engraving cylinder 4 as they pass successively through the area 8 formed by the interference of the engraving cylinder 4 and the applicator cylinder 3. Usually an interference or actual contact between the surfaces of the cylinder in the area 8 is preferred, but it can be imagined that certain combinations of shape and size of the recessed areas and of the characteristics of the Chemical fluid softener can allow satisfactory transfer by simply having the two cylinders passing in close proximity. The chemical softener extracted in the area 8 of the engraving cylinder 4 to the applicator cylinder 3 takes the form of surface deposits corresponding in size and spacing to the pattern of recessed areas of the engraving cylinder 4. The deposits of chemical softener in the applicator cylinder 3 are transferred to the paper plot P1045 tissue 1, which is directed towards the area 9, an area defined by the point at which the applicator cylinder 3, the paper web 1 and the impression cylinder 2 are in reciprocal proximity. The printing cylinder 2 can have any of a variety of surface covers as long as they suit the purposes of the process. Most commonly, the cylinder is covered with a compressible shell such as an elastomeric polymer such as natural or synthetic rubber. The impression cylinder 2 and the applicator cylinder 3 will normally operate without interfering. It is only necessary that the cylinders pass sufficiently close to each other so that when the tissue web is present in the area 9, the tissue web comes into contact with the outgoing deposits of the chemical softener in the applicator cylinder 3 sufficiently to cause that these are transferred at least partially from the applicator cylinder 3 to the tissue web 1. Since the loading pressure between the applicator cylinder 3 and the impression cylinder 2 will tend to compress the tissue web 1, the spaces must be avoided too small between the two cylinders to preserve the thickness or volume of the tissue web 1. Interference or actual contact between the surfaces of the cylinders (through the tissue web 1) in area 9 is not usually necessary, but you can imagine that certain combinations of P1045 Patterns and characteristics of the fluid chemical softener will require that the two cylinders be operated by making contact between the two. The tissue paper web 1 leaves the area 9 with the side 11 containing uniform surface deposits of substantially fixed softening agent according to the pattern of the engraving cylinder 4. Figure 2 is a side elevational view of a printing arrangement illustrating an alternative method to form the uniform surface deposits of the substantially fixed chemical softening agent of the present invention. The process illustrated in Figure 2 applies the softening agent to a surface of the tissue paper product by a direct printing method. In Figure 2, a liquid chemical softener 15, preferably hot by means not shown, is contained in a tray 14, so that the rotary engraver cylinder 13, also preferably hot by means not shown, is submerged partially in the liquid chemical softener 15. The engraving cylinder 13 has a plurality of recessed areas that are practically empty of content when they enter the tray 14, but which are filled with the chemical softener 15 while immersing in the tray 14 as the engraving cylinder 13 is partially submerged P104S turn. The engraving cylinder 13 and its pattern of recessed areas are illustrated below in Figure 4, so a detailed description is deferred until it is provided by referring to that figure. Again with reference to Figure 2, the excess chemical softener 15 that is taken from the tray 14 but not retained in the recessed areas, is removed by a flexible scraper blade 16, which makes contact with the engraving cylinder 13 in its interior. outer surface, but which has no capacity to significantly deform recessed areas. Therefore, the chemical softener remaining in the engraving cylinder 13 resides almost exclusively in the recessed areas of the engraving cylinder 13. This remaining chemical softener is transferred in the form of uniform surface deposits to a tissue paper web 1, which it is directed towards the area 17. The transfer occurs because the tissue web 1 is brought to the vicinity of the chemical softener present in the recessed areas due to the coercion of the impression cylinder 12 relative to the engraving cylinder 13 in the area 17. The printing cylinder 12 can have a variety of surface covers as long as they suit the purposes of the process. The most common is that the cylinder is covered with a compressible cover as an elastomeric polymer like natural or synthetic rubber.

P1045 The engraving cylinder 13 and the printing cylinder 12 will normally operate with interference, that is, it will be in contact through the tissue paper web 1, since having a loading pressure will assist in the extraction of the liquid chemical softener from the recessed areas of the engraving cylinder 13 as it passes through the area 17 formed by the interference of the engraving cylinder 13, the tissue paper web 1 and the impression cylinder 12. Usually an interference or a real contact between the surfaces of the cylinders is preferred. transmitted through the tissue paper web 1 in area 17, but it can be imagined that certain combinations of size and shape of the recessed areas and the characteristics of the fluid chemical softener would allow satisfactory transfer by simply making the two cylinders and the web confined tissue pass with close proximity. The tissue paper web 1 leaves the area 17 with the side 18 containing discrete uniform superpositional deposits of substantially fixed softening agent according to the pattern of the engraving cylinder 14. Figure 3 is a side elevational view of a printing arrangement illustrating another alternating method for forming the uniform surface deposits of the substantially fixed chemical softening agent of the present invention. The process illustrated in Figure 3 applies P1045 the softening agent to both surfaces of the tissue paper product by an offset printing method. In Figure 3, the liquid chemical softener 26, preferably hot by means not shown, is contained in trays 27, so that the rotary engraver cylinders 25, also preferably hot by means not shown, are partially submerged. in the liquid chemical softener 26. The engraving cylinders 25 have a plurality of recessed areas that are substantially empty of content when they enter their respective trays 27, but which are filled with the chemical softener 26 while immersing in the trays 27 as they the engraving cylinders 25 are partially immersed in them when rotating. The engraving cylinders 25 and their pattern of recessed areas are illustrated below in Figure 4 so that the detailed description is deferred until it is provided by reference to that figure. The engraving cylinders 25 of Figure 3 will generally be similar in design, but may also be deliberately varied in particular with respect to the pattern of recessed areas. The differences can be used to adjust the characteristics of the product from one side to the other. Still with reference to Figure 3, the excess chemical softener 26 that is taken from the trays P104S 27 but which is not retained in the recessed areas is removed by flexible scraper blades 28, which contact the engraving cylinders 25 on their outer surfaces, but which do not have the capacity to significantly deform the recessed areas. Therefore, the chemical softener remaining in the engraving cylinder 25 resides almost exclusively in the recessed areas of the engraving cylinders 25. This remaining chemical softener is transferred in the form of discrete uniform reservoirs to applicator cylinders 23. The applicator cylinders 23 can have any of a variety of surface covers as long as they suit the purpose of the process. The most common is that the cylinder is covered with compressible covers as an elastomeric polymer like synthetic or natural rubber. Usually, cylinders 23 will be similar in nature, but may also be different to create different product characteristics from one side to the other. Each pair of engraving cylinders 25 with their respective applicator cylinders 23 will normally operate in interference since having a loading pressure between the pairs of cylinders will assist in the extraction of the liquid chemical softener from the recessed areas of the engraving cylinders 25 as they pass successively through their respective areas of interference 24 formed by the interference of P1045 recording cylinders 25 with their respective applicator cylinders 23. Usually an interference or actual contact between the surfaces of the cylinder in one or both of the areas 24 is preferred, but it can be imagined that certain combinations of shape and size of the recessed areas and the characteristics of the fluid chemical softener will allow satisfactory transfer by simply passing one or more of the pairs of cylinders in close proximity. The chemical softener removed in the areas 24 from the engraving cylinders 25 to the applicator cylinders 23 takes the form of surface deposits corresponding in size and spacing to the pattern of recessed areas of the engraving cylinders 25. The deposits of chemical softener in the applicator cylinders 23 are transferred to the tissue paper web 1, which is directed towards the areas 22, as the chemical softener deposits pass through the area 22. The area 22 is formed by the applicator cylinders 23 at their closest point with the tissue paper web 1 passing between the applicator cylinders 23. The applicator cylinders 23 will normally operate without interfering, ie without touching each other. Provided the cylinders pass sufficiently close to each other so that when the tissue web is present in the area 22 it contacts the chemical softener deposits in each of the applicator cylinders 23 sufficient to at least partially transfer the reservoirs from the applicator cylinders 23 to the tissue web 1. Since the loading pressure between the applicator cylinders 23 will tend to compress the tissue web 1, they should be avoided the excessively small spaces between the two cylinders to preserve the thickness or volume of the tissue web 1. Interference or actual contact between the surfaces of the cylinders (through the tissue web 1) in the area is not usually necessary. 22, but it can be imagined that certain combinations of patterns and characteristics of the fluid chemical softener will require that the two cylinders be operated in contact between the two, with movement transmitted through the tissue web 1. The tissue paper web 1 it leaves the area 22 with both sides 29 having uniform discrete surface deposits of substantially fixed softening agent according to the n of the engraving cylinders 25. Figure 4 is a schematic representation illustrating the detail of the recessed areas for use in the printing cylinders illustrated in Figures 1, 2 and 3, i.e. the engraving cylinder 4 of Figure 1, the engraving cylinder 13 of Figure 2 and the engraving cylinders 25 of Figure 3. With reference to Figure 4, the engraving cylinder 31 has a plurality of areas P1045 cupped sometimes called cells. The recessed areas 33 exist in a cylinder surface 32 that would otherwise be smooth. The cylinder 31 can be constituted of a variety of materials. In general, it will be relatively non-compressible in nature as a metallic or ceramic roller, although elastomeric roller covers are also possible. With superlative preference, the surface of the cylinder 31 is ceramic like aluminum oxide. This allows the creation of the plurality of recessed areas when recording them by directing an intense laser beam on the surface as is well known in the processes of the printing industry. An alternate means for creating the recessed areas in the cylinder 31 is to record them electromechanically using an electronically controlled oscillation of a diamond-tipped cutting tool. When this method is selected, it is more convenient to coat the roller surface with copper until it is etched and then deposit a fine chrome finish to protect the smooth copper layer. Another alternate means for creating the recessed areas in the cylinder 31 is to etch them chemically using a labile roller surface protected by a chemically resistant mask secured over the surface of the cylinder.

P1045 the rollers to prevent the engraving in the areas that are not destined to become the recessed areas 33. When this method is selected, it is again more convenient to coat the roller with copper until it is engraved and then deposit a fine finish. Chrome to protect the soft copper layer. Finally, an alternate means for creating the recessed areas in the cylinder 31 is to record them mechanically using a fluted cutting tool. This method allows the widest variety of construction materials for the cylinder but suffers from the small variation possible in the workable patterns. The separation distance 34 of the recessed cells 33 in the cylindrical surface 32 varies from five recessed areas per inch to 100 recessed areas per inch. The geometry of each of the recessed cells is hemispherical. Figures 4 and 4A provide further details of the recessed areas 33 preferred for use in the present invention illustrating one of the recessed areas 33 in a cross-sectional view. In Figure 4A, a recording cylinder surface 32 contains a hemispherical recessed area 33 with a diameter 42 ranging from about 50 microns to about 500 microns, preferably from about one hundred thirty microns P1045 up to approximately four hundred ten microns. As shown in Figure 4, there is a plurality of these areas 33 throughout the surface 32 of the cylinder 31.

Optional Papermakers Components v Weft Structures Papermaking Components Other materials can be added to the aqueous pulp or embryonic web to impart other characteristics to the product or to improve the papermaking process as long as they are compatible with the chemistry of the substantially fixed softening agent and do not affect significantly and unfavorably the softness, strength or low dust character of the present invention. The following materials are expressly included, but their inclusion is not offered so that all are included. Other materials may also be included as long as they do not interfere or counteract the advantages of the present invention. It is common to add species that polarize cationic charges in the papermaking process to control the zeta potential of the aqueous pulp as it is supplied to the papermaking process. These materials are used because most solids by nature have negative surface charges, including the surfaces of cellulose and fine fibers and most inorganic fillers.

P1045 One of the species that polarize cationic charge that is traditionally used is alum. More recently in the art, biasing of charges is made by the use of cationic synthetic polymers of relatively low molecular weight, preferably having a molecular weight of not more than about 500,000 and more preferably not more than about 200,000 or even about 100,000. . The charge densities are such low molecular weight cationic synthetic polymers are relatively high. These charge densities vary between about 4 and 8 equivalents of cationic nitrogen per kilogram of polymer. One example material is Cypro 514®, a product of Cytec, Inc. of Stamford, CT. The use of materials of this type is expressly permitted in the practice of the present invention. The use of high anionic, high surface area microparticles has been shown in the art for the purpose of improving formation, drainage, strength and retention. See, for example, U.S. Patent 5,221,435, issued to Smith on June 22, 1993, which is considered part of the present, as a reference. Common materials for this purpose are colloidal silica or bentonite clay. The incorporation of such materials is expressly included within the scope of the present invention.

P1045 If permanent wet strength is desired, the group of chemicals: including polyamide-epichiorhydrin, polyacrylamides, styrene-butadiene latex; insolubilized polyvinyl alcohol; urea-formaldehyde; polyethyleneimine; Chitosan polymers and mixtures thereof can be added to the pulp or the embryonic web. Polyamide-epichiorhydrin resins are cationic wet strength resins which have been found to be of particular utility. Suitable types of these resins are described in U.S. Patent No. 3,700,623 issued October 24, 1972 and No. 3,772,076 issued November 13, 1973, both granted to Keim and which are considered part of this. as reference . A commercial source of useful polyamide-epichlorohydrin resins is Hercules, Inc. of Willmington, Delaware, which markets those resins under the tradename Kymene 557H®. Many paper products must have limited wet strength due to the need to dispose of them through the toilet in septic and sewer systems. If wet strength is imparted to these products, it is preferred that it be fleeting wet strength characterized by a decrease in part or all of its potency in the presence of water. If desired wet-fugitive resistance, the binder materials can be selected from the group consisting of dialdehyde starch or other aldehyde functional group resins such as Co-Bond 1000® offered by National Starch and Chemical Company, Parez 750® offered by Cytec of Stamford, CT and the resin which is described in U.S. Patent No. 4,981,557 issued January 1, 1991 to Bjorkquist and which is considered part of the present by reference. If increased absorbency is needed, surfactants can be used to treat the tissue paper webs of the present invention. The level of surfactant, if used, is preferably between about 0.01% and 2.0% by weight, based on the dry fiber weight of the tissue paper. The surfactants preferably have alkyl chains with eight or more carbon atoms. Exemplary anionic surfactants are linear alkyl sulfonates and alkylbenzene sulphonates. Exemplary nonionic anionic surfactants are alkyl glycosides including alkyl glycoside esters such as Crodesta SL-40® available from Croda, Inc. (New York, NY); alkyl glycoside ethers as described in United States Patent 4,011, 389, issued to W.K. Langdon, et al. March 8, 1977; and alkyl polyethoxylated esters such as Pegosperse 200 ML available from Glyco Chemicals, Inc.

(Greenwich, CT) and IGEPAL RC-520® available from Rhone Poulenc Corporation (Cranbury, NJ). Although the essence of the present invention is in the presence of a substantially fixed chemical softening composition deposited in the form of discrete and uniform deposits on the surface of the tissue paper web, the invention also expressly includes variations in which the chemical softening agents they are added as part of the papermaking process. Acceptable chemical softening agents include the well known dialkyldimethylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethyl ammonium methyl sulfate, ditallow (hydrogenated) dimethylammonium chloride; ditallow (hydrogenated) dimethylammonium methyl sulfate being preferred. This particular material is commercially available from Witco Chemical Company Inc. of Dublin, Ohio under the trade name Varisoft 137®. Biodegradable mono and diester variations of the quaternary ammonium compounds can also be used and are within the scope of the present invention. Loading materials may also be incorporated into the tissue papers of the present invention. U.S. Patent 5,611,890, issued to Vinson et al., On March 18, 1998, the disclosure of which is P1045 incorporated herein by reference, discloses acceptable tissue paper products acceptable as substrates for the present invention. The above listings of optional chemical additives are intended to be merely exemplary and are not intended to limit the scope of the invention.

Weft Structures The tissue paper webs made according to the present invention can have a basis weight of between g / m2 and approximately 100 g / m2 In its preferred embodiment, the tissue paper made by the present invention has a basis weight of between about 10 g / m2 and about 100 g / m2 and, more preferably, between about 10 g / m2 and approximately_ 50 g / m2. The tissue paper webs prepared by the present invention have a density of about 0.60 g / cm 3 or less. In its preferred embodiment, the tissue paper of the present invention has a density between about 0.03 g / cm3 and about 0.6 g / cm3 and, more preferably, between about 0.05 g / cm3 and 0.2 g / cm3. The present invention is also applicable to the production of multilayer tissue paper webs. The P1045 Multilayer tissue structures and methods for forming multilayer tissue structures are described in U.S. Patent 3,994,771, Morgan, Jr. Et al. granted on November 30, 1976, U.S. Patent No. 4,300,981, Carstens, issued November 17, 1981, U.S. Patent No. 4,166,001, Dunning et al., Issued August 28, 1979 and European Patent Publication No. 0 613 979 Al, Edwards et al., Published September 7, 1994, which is considered hereby incorporated by reference. Preferred layers are made up of different types of fibers, the fibers typically being relatively long soft woods and relatively short hardwoods as used in the manufacture of multilayer tissue paper. The multilayer tissue paper webs resulting from the present invention comprise at least two superimposed layers, an inner layer and at least one outer layer contiguous with the inner layer. Preferably the multilayer tissue papers comprise three superposed layers, an inner or central layer and two outer layers, with the inner layer placed between the two outer layers. The two outer layers preferably comprise a primary filament constituent of relatively short papermaking fibers having an average fiber length between about 0.5 and 1.5.

P1045 mm, preferably less than about 1.0 mm. These short papermaking fibers usually comprise hardwood fibers, preferably Kraft fibers from hardwoods and preferably superlatives derived from eucalyptus. The inner layer preferably comprises a primary filament constituent of relatively long paper fibers having an average fiber length of at least 2.0 mm. These long paper fibers are usually softwood fibers, preferably Kraft fibers from soft northern woods. Preferably, most of the particulate filler of the present invention is contained in at least one of the outer layers of the multilayer tissue paper web of the present invention. More preferably, most of the particulate filler of the present invention is contained in the two outer layers. Tissue paper products made from multilayer or monolayer uncoated tissue paper webs can be single sheet tissue products or multi-sheet tissue products. In typical practice of the present invention, a low consistency pulp is provided in a pressurized inlet box. The entrance box has an opening to supply a thin deposit of pulp on the surface of a Fourdrinier mesh for P1045 form a wet weave. The web is then normally dewatered to a fiber consistency between about 7% and 25% (based on the total weight of the web) by vacuum dewatering. To make the tissue paper products useful in the present invention, an aqueous pulp is deposited on a foraminous surface to form an embryonic web. The scope of the invention also includes the processes for making tissue paper product by forming multiple layers of paper in which two or more layers of pulp are preferably formed from the deposit of separate streams of diluted fibrous pulps for example in a muiti-ribbed entry box. Preferred layers are constituted by different types of fibers, the fibers typically being relatively long soft woods and relatively short hardwoods as used in the manufacture of multilayer tissue paper. If the individual layers are initially formed in separate meshes, the layers are subsequently combined when they are wet to form a multilayer tissue paper web. The paper fibers are preferably made of different types of fibers, the fibers typically being relatively long soft woods and relatively short hardwoods. More preferably, P1045 the hardwood fibers comprise at least about 50% and the softwood fibers comprise at least 10% of the paper fibers. The term "strength" in the sense in which it is used herein refers to the specific total stress resistance, the determination method for this measurement is included in a later section of this description. The tissue paper webs according to the present invention are strong. This usually means that their resistance to the specific total stress is at least about 200 meters, more preferably more than about 300 meters. The terms "fluff" and "powder" are used interchangeably herein and refer to the tendency of a tissue paper web to release fibers or particulate fillers as measured in a controlled abrasion test, the methodology of which is detailed in a later section of this description. Fluff and dust are related to the resistance since the tendency to release Eibras or particles is directly related to the degree to which those fibers or particles are anchored in the structure. As the total anchor level increases, the resistance will increase. However, it is possible to have a level of resistance that is considered acceptable but have an unacceptable level of release from fluff and dust. This is because the release of dust or lint can be localized. For example, the surface of a tissue paper web may be prone to release lint or release dust, while the degree of attachment below the surface may be sufficient to raise the total level of resistance to fully acceptable levels. In another case, the strength may be derived from a relatively long fiber bundle, while the fine fibers or the particulate filler may be insufficiently bonded within the structure. The tissue paper webs of the present invention are relatively low in fluff. Lint levels of less than about 12 and more preferably less than 10 are preferable. The multilayer tissue paper webs of the present invention can be used in any application where absorbent, soft multilayer tissue paper webs are required. Particularly advantageous uses of the multilayer tissue paper web of this invention are in bath tissue and facial tissue products. Both single and multi-sheet tissue paper products can be produced from the plots of the present invention.

Test Procedures P1045 Density The density of multilayer tissue paper, in the sense in which that term is used in the present, is the average density calculated as the basis weight of that paper divided by the caliber, with the appropriate conversions of incorporated units. The caliper of multilayer tissue paper, in the sense in which it is used in the present, is the thickness of the paper when it is subjected to a compressive load of 95 g / in2 (15.5 g / cm2).

Measurement of Tissue Paper Fluff The amount of fluff generated from a tissue product is determined with a Sutherland Rub Tester (Sutherland Friction Tester). This tester uses a motor to rub 5 times a heavy felt on a stationary facial tissue. The L Color Hunter value is measured before and after the friction test. The difference between these two L values of Color Hunter is calculated as fluff.

SAMPLE PREPARATION: Prior to the friction test for lint, the paper samples to be tested should be conditioned according to the TAPPI Method # T402OM-88. Here, the samples are preconditioned 24 hours at a relative humidity level between 10 and 35% and in a temperature range between 22 and 40 ° C. After this step of preconditioning, the samples should be conditioned for 24 hours at a relative humidity between 48 and 52% and in a temperature range between 22 and 24 ° C. This friction test must be carried out within the limits of the room at constant temperature and humidity. The Sutherland Friction Tester can be obtained from Testing Machines, Inc. (Amityville, NY, 11701). The tissue is first prepared by removing and discarding any product that has been shaved-with handling, for example, on the outside of the roll. For the finished multi-sheet product, three sections are removed, each containing two sheets of multi-sheet product and placed on the top of the table. For single sheet product, six sections are removed, each containing two sheets of single sheet product and placed on top of the table. Each sample is then folded in half so that the fold runs along the direction transverse to the machine (CD) of the tissue sample. For the multi-blade product, make sure that one of the sides facing outward is the same side facing outward after the sample is bent. In other words, do not break the blades together and test the friction with the sides facing each other inside the P1045 product. For the single sheet product, make 3 samples with the side facing the mesh out and 3 with the side not facing the mesh out. Keep record of which samples correspond to the ones on the side facing the mesh outward and which ones on the side not facing the mesh out. Get a 30"X 40" piece of Crescent Cardboard # 300 from Cordage, Inc. of Cincinnati, OH. Using a paper cutter, cut six pieces of cardboard with dimensions of 2.5"X 6". Make two perforations in each of the six pieces by forcing the cardboard over the fastening bolts of the Sutherland Friction Tester. If working with a single sheet finished product, center and carefully place each of the 2.5"X 6" cardboard pieces on top of the six previously folded samples. Make sure that the 6"dimension of the cardboard runs parallel to the machine direction (MD) of each of the tissue samples.When working with multi-sheet finished product, only three pieces of 2.5" X 6 cardboard are required. Carefully center and place the cardboard pieces on top of the three previously folded samples, once again making sure that the 6"dimension of the cardboard runs parallel to the machine direction (MD) of each the samples of tissue.

P1045 Fold one edge of the exposed portion of the tissue sample over the back of the carton. Securing this edge to the cardboard with adhesive tape obtained from 3M Inc. (3/4"wide Scotch Brand, St. Paul, MN) Carefully hold the other edge of the protruding tissue and fold it neatly over the back of the cardboard. While maintaining a perfect fit of the paper on the cardboard, stick this second edge with adhesive tape to the back of the cardboard Repeat this procedure for each sample Turn each sample and stick to the cardboard with adhesive tape the edge with direction transverse to the tissue paper machine One half of the adhesive tape should be in contact with the tissue paper while the other half will be adhered to the cardboard Repeat this procedure for each of the samples If the tissue sample breaks, tears or frays at any time in the course of this sample preparation procedure, discard it and make a new sample with a new sample strip of tissue. or multi-sheet, there will now be 3 samples in the carton. For the single-sheet finished product, there will now be 3 samples with the mesh-oriented side facing out in the cardboard and 3 samples with non-oriented side in the cardboard.

P1045 FELT PREPARATION: Obtain a 30"X 40" piece of Crescent # 300 cardboard from Cordage Inc. of Cincinnati, OH. Using a paper cutter, cut six pieces of cardboard with dimensions of 2.25"X 7.25". Draw two lines parallel to the short dimension and lower 1,125"from the top and bottom most of the edges on the white side of the carton, carefully mark the length of the line with a razor using a ruler as a guide Mark with an incision at a depth of approximately half a way through the thickness of the blade This marking allows the cardboard / felt combination to fit snugly around the weight of the Sutherland Friction Tester Draw an arrow running parallel to the length dimension of the cardboard on this marked side of the cardboard Cut six pieces of black felt (F-55 or New England Gasket equivalent, 550 Broad Street, Bristol, CT 06010) in dimensions of 2.25"X 8.5" X 0.0625" Place the felt on top of the unmarked green side of the cardboard so that the edges of both the felt and cardboard are parallel and aligned. Make sure that the side of the felt that has lint is facing up. Also let approximately 0.5"protrude from the top and bottom of the P1045 most edges of the cardboard. Perfectly fold the two edges of the felt that protrude over the back of the cardboard with Scotch adhesive tape. Prepare a total of six of these felt / cardboard combinations. For best reproducibility, all samples must be run with the same batch of felt. Obviously, there are times when a single batch is completely exhausted. In those cases in which a new batch must be obtained, a correction factor for the new batch of felt must be determined. To determine the correction factor, obtain a representative sample of single tissue of interest and enough felt to make 24 cardboard / felt samples for the new and old lots. As described below and before any friction is performed, obtain the Hunter L readings for each of the 24 cardboard / felt samples of the new and old batches of felt. Calculate the averages for both the 24 carton / felt samples from the vejo lot and the 24 cardboard / felt samples from the new lot. Then, make the friction test to the 24 cardboard / felt cartons of the new batch and to the 24 cardboard / felt cartons of the old batch as described below. Make sure that the same tissue lot number is used for each of the 24 samples for the P1045 old and new lots. In addition, the paper must be sampled in the preparation of the cardboard / tissue samples so that new and old batches of felt are exposed as representative as possible to the tissue sample. For the case of the 1-sheet tissue product, discard any product that may be damaged or frayed. Then, get 48 strips of tissue every two usable units (also called leaves) long. Place the first strip of two usable units on the far left side of the laboratory table and the last of the 48 samples on the far right side of the table. Mark the sample from the far left with the number "1" in an area of 1 cm by 1 cm in the corner of the sample. Continue marking the samples consecutively to 48 so that the last sample in the far right part is numbered 48. Use the 24 odd-numbered samples for the new felt and the 24 samples with even numbers for the old felt. Sort the samples with odd number from least to highest. Sort the samples with even number from least to highest. Now mark the smallest number of each group with the letter "W". Mark the next highest number with the letter "N". Continue marking the samples with this alternating pattern "W" / "N". Use the "W" sample for the analysis of lint on the side facing the mesh out and the samples "N" for the fluff analyzes of the side not oriented to the mesh out. For the 1-sheet product, there are now a total of 24 samples for the new felt batch and the old felt batch. Of these 24, twelve are for the analysis of fluff from the side facing the mesh outward and 12 for the analysis of fluff from the side not oriented to the mesh out. Perform the friction and determine the Hunter Color L values for the 24 samples of the old felt as described below. Record the 12 Hunter Color L values on the mesh-oriented side for the old felt. Average the 12 values. Record the 12 Hunter Color L values on the non-mesh oriented side for the old felt. Average the 12 values. Subtract the average initial Hunter Color L reading for the felt without friction to the average Hunter Color L reading for the friction samples corresponding to the mesh oriented side. This is the average delta difference for the samples corresponding to the mesh-oriented side. Subtract the average initial Hunter Color L reading for the felt without friction to the average Hunter Color L reading for the friction samples corresponding to the non-mesh oriented side. This is the average delta difference for the samples corresponding to the side not oriented to the mesh. Calculate the sum of the average delta difference P1045 for the mesh-oriented side and the average delta difference for the non-mesh oriented side and divide this sum by 2. This is the uncorrected fluff value for the old felt. If there is a current felt correction factor for the old felt, add it to the uncorrected fluff value for the old felt. This value is the Lint Value corrected for the old felt. Perform the friction and determine the Hunter Color L values for the 24 samples of the new felt as described below. Record the 12 Hunter Color L values on the mesh-oriented side for the new felt. Average the 12 values. Record the 12 Hunter Color L values on the non-mesh oriented side for the new felt. Average the 12 values. Subtract the average initial Hunter Color L reading for the felt without friction to the average Hunter Color L reading for the friction samples corresponding to the mesh oriented side. This is the average delta difference for the samples corresponding to the mesh-oriented side. Subtract the average initial Hunter Color L reading for the felt without friction to the average Hunter Color L reading for the friction samples corresponding to the non-mesh oriented side. This is the average delta difference for the samples corresponding to the side not oriented to the mesh. Calculate the sum of the average delta difference P1045 for the mesh-oriented side and the average delta difference for the non-mesh oriented side and divide this sum by 2. This is the uncorrected fluff value for the new felt. Take the difference between the corrected Lint Value of the old felt and the uncorrected lint value for the new felt. This difference is the felt correction factor for the new felt batch. Adding this felt correction factor to the uncorrected lint value for the new felt should be identical to the corrected Lint Value for the old felt. The same type of procedure is applied to the two-sheet tissue product with 24 samples run for the old felt and 24 runs for the new felt. But, only the outer layers of the sheets used by the consumer are tested for friction. As noted above, make sure samples are prepared so that a representative sample is obtained for old and new felts.

CARE OF THE 4-POLE WEIGHT The four-pound weight has four square inches of effective contact area that provides a P104S Contact pressure of one pound per square inch. Since the contact pressure can be changed by modifying the rubber pads that are mounted on the face of the weight, it is important to use only the rubber pads supplied by the manufacturer (Brown Inc., Mechanical Services Department, Kalamazoo, MY) . These pads should be replaced if they become hard, frayed or loose pieces. When not in use, the weight should be placed so that the pads are not supporting the total weight of the weight. It is better to keep the weight on its side.

CALIBRATION OF THE FRICTION TESTING INSTRUMENT: The Sutherland Friction Tester should be calibrated first before use. First flip the Sutherland Friction Tester moving the tester switch to the "cont" position. When the tester arm is in the position closest to the user, change the tester switch to the "auto" position. Adjust the tester to perform 5 runs by moving the pointer arm on the large dial to the "five" setting position. A run is a single and complete movement of the weight forward and in reverse. The end of the friction block must be in the position closest to the operator at the beginning and end of each test.

P1045 Prepare a tissue paper in a cardboard sample as described above. In addition, prepare a felt in a cardboard sample as described above. Both samples will be used for calibration of the instrument and will not be used to obtain data for the real samples. Place this sample of tissue for calibration on the base plate of the tester by sliding the perforations of the cardboard over the fastening bolts. The fastening bolts prevent the sample from moving during the test. Hold the felt / cardboard sample for calibration on the four-pound weight with the cardboard side making contact with the weight pads. Make sure that the cardboard / felt combination is resting fully against the weight. Hook this weight on the arm of the tester and place the tissue sample little by little under the weight / felt combination. The end of the dumbbell closest to the operator should be on the cardboard of the tissue sample and not the tissue sample itself. The felt should rest completely on the tissue sample and should be in 100% contact with the tissue surface. Activate the tester by pressing the "push" button. Keep an account of the number of runs and observe and make a mental note of the start and stop position of the weight covered with felt in relation to the sample. If the total number of runs is P104S five and if the end closest to the operator of the weight covered with felt is above the cardboard of the tissue sample at the beginning and end of this test, the tester is calibrated and ready to be used. If the total number of runs is not five or if the end closest to the operator of the weight covered with felt is on the actual tissue sample either at the beginning or the end of the test, repeat this calibration procedure until counted 5 runs the end closest to the operator of the weight covered with felt is located on the cardboard both at the beginning and at the end of the test. During the actual testing of the samples, monitor and observe the run count and the start and stop point of the weight covered with felt. Recalibrate if necessary.

CALIBRATION OF THE HUNTER COLOR METER Adjust the Hunter Color Difference Meter for the black and white standard plates according to the procedures described in the instrument operation manual. Also run the stability check for normalization as well as the daily color stability if this has not been done in the previous eight hours, In addition, the zero reflectance must be checked and readjusted P1045 if necessary. Place the white standard plate on the sample platform under the instrument port. Release the sample platform and let the sample plate rise below the sample port. Using the normalization knobs "LY", "aX" and "bZ", adjust the instrument to read the values of the White Pattern Plate "L", "a" and "b" when the "L", "a" buttons "and" b "each one is pressed in turn.

MEASURING THE SAMPLES The first step in the measurement of the lint is to measure the Hunter color values of the black felt / cardboard samples before they are rubbed on the toilet paper. The first step in this measurement is to lower the white pattern plate below the instrument port of the Hunter color instrument. Center a cardboard covered with felt, with the arrow pointing to the back of the color meter, on top of the pattern plate. Release the sample platform, let the plate shows rise below the sample port. Since the width of the felt is only slightly larger than the diameter of the observation area, make sure that the felt completely covers the observation area. After confirming full coverage, press the P1045"L" button and wait for it to stabilize to read. Read and record this value for the unit closest to 0.1. If a D25D2A head is in use, lower the cardboard covered with felt and the plate, rotate the felt-covered cardboard 90 degrees so that the arrow points to the right side of the meter. Then, release the sample platform and check once more to make sure that the observation area is completely covered with the felt. Press the L button. Read and record this value for the unit closest to 0.1. For the D25D2M unit, the registered value is the L Color Hunter value. For the head D25D2A where a reading of the sample that was rotated is also recorded, the Hunter Color L value is the average of the two recorded values. Measure the Hunter Color L values for all felt-covered cartons using this technique. If all Hunter Color L values are less than 0.3 units apart, take the average to obtain the initial L reading. If the Hunter Color L values are not all less than 0.3 units apart, discard the felt / cardboard combinations that are out of bounds. Prepare new samples and repeat the Hunter Color L measurements until all samples are less than 0.3 units apart.

P1045 For the measurement of the actual tissue / cardboard combinations, place the sample combination of tissue / cardboard on the base plate of the tester by sliding the perforations of the cardboard over the fastening bolts. The fastening bolts prevent the sample from moving during the test. Attach the felt / cardboard calibration sample on the four-pound weight with the cardboard side making contact with the weight pads. Make sure that the cardboard / felt combination is fully supported against the weight. Hook this weight on the arm of the tester and place the tissue sample little by little under the weight / felt combination. The end of the dumbbell closest to the operator should be on the cardboard of the tissue sample and not the tissue sample itself. The felt should rest completely on the tissue sample and should be in 100% contact with the tissue surface. Then, activate the tester by pressing the "push" button. At the end of the five runs the tester will stop automatically. Observe the stop position of the weight covered with felt in relation to the sample. If the end of the weight covered with felt towards the operator is on the sample, the tester is working properly. If the end of the weight covered with felt towards the operator is on the sample, discard this measurement and recalibrate as indicated above in the Calibration section of the Sutherland Friction Tester. Remove the weight with the cardboard covered with felt. Inspect the tissue sample. If it rips, discard the felt and tissue and start again. If the tissue sample is intact, remove the cardboard covered with felt from the weight. Determine the Hunter Color L value on the felt-covered cardboard as described above for the white felts. Record the Hunter Color L readings for the felt after rubbing. Friction, measure and record the Hunter Color L values for all remaining samples. After all the tissue papers have been measured, remove and discard all the felts. Felt strips are not used again. Cardboards are used until they are twisted, torn, soft or no longer have a smooth surface.

CALCULATIONS: Determine the delta L values by subtracting the average initial L reading found for the unused felts from each of the measured values for the side facing the mesh and for the non-oriented side of the sample mesh. Remember, only one side of the paper will be rubbed on the mui-lamina-sheet product. So, P1045 the three delta values for the multi-sheet product will be obtained. Average the three delta values and subtract the felt factor from this final average. This final result is called the lint for the product of 2 sheets. For the simple sheet product in which both the measurements of the side oriented towards the mesh and the non-oriented side are obtained, subtract the average initial L reading found for the unused felts at each of the three readings L of the side facing the mesh and each of the three readings L on the side not oriented towards the mesh. Calculate the average delta for the three values on the side not oriented towards the mesh. Subtract the felt factor from each of these averages. The final results are called the fluff value for the side not oriented towards the mesh and the fluff value for the side facing the mesh of the single sheet product. Taking the average of these two values, a last fluff value is obtained for the complete single-sheet product.

Measurement of Softness of Tissue Papers by a Panel Ideally, before the softness test, the paper samples to be tested should be conditioned according to the TAPPI Method # T402OM-88. Here, the samples are P1045 precondition for 24 hours at a relative humidity level between 10 and 35% and in a temperature range between 22 and 40 ° C. After this step of preconditioning, the samples should be conditioned for 24 hours at a relative humidity between 48 and 52% and in a temperature range between 22 and 24 ° C. Ideally, the softness panel test should be carried out in the limits of a quarter at constant humidity and temperature. If this is not feasible, all samples, including controls, should experience identical environmental exposure conditions. The softness test is carried out as a pairwise comparison in a manner similar to that described in "Manual of Sensory Testing Methods," ASTM Special Technical Publication 434, published by the American Society for Testing and Materials 1968 and considered part of this, as a reference. Softness is evaluated through subjective tests using the so-called Paired Difference Test. The method employs a pattern external to the test material itself. For the softness by tactile perception two samples are presented in such a way that the subject can not see them and it is required that he himself choose one of them based on the tactile smoothness. The result of this test P1045 it is reported in what is called the Panel Rating Unit (PSU). With respect to the softness test to obtain the softness data in PSU reported here, several softness panel tests were performed. In each test ten gentle expert judges were asked to rank the relative softness of three groups of samples in pairs. The pairs of samples are evaluated one at a time by each judge: one sample of each pair is designated as X and the other as Y. Briefly, each sample X is graded against its sample Y pair as follows: 1. it is given a rating of plus one if you evaluate that X can be a little softer than Y; and a score of minus one is given if it is judged that Y may be a little softer than X; 2. a rating of plus two is given if it is evaluated that X is surely a little softer than Y; and a rating of minus two is given if it is evaluated that Y is surely a little softer than X; 3. a grade of plus three is given if it is evaluated that X is much softer than Y; and a rating of minus one is given if it is evaluated that Y is much softer than X; and finally 4. a grade of four is given if it is evaluated that X is much softer than Y; and a rating of minus four is given if it is evaluated that Y is P1045 much softer than X; The ratings are averaged and the resulting value is in units of PSU. The resulting data is considered the results of the panel test. If more than one pair of samples is evaluated then all the pairs of samples are put in order according to their ratings by statistical analysis of the pairs. Then the classification is shifted up or down in value as required to give a zero_ ^ PSU zero with respect to which some sample is selected to be the zero base standard. The other samples then have values more or less as determined by their relative ratings with respect to the zero base standard. The number of panel tests performed and averaged is such that approximately 0.2 PSU represents a significant difference in subjectively perceived softness.

Tissue Paper Strength Measurement Dry stress resistance: The tensile strength is determined in one inch strips of sample using a Thwing-Albert Intelect II Standard Tensile Tester, available from Thwing-Albert Instrument Co. , of Philadelphia, PA. This method is intended for use in paper products finished, coil samples and non-converted material.

CONDITIONING AND PREPARATION OF THE SAMPLE Before the stress test, the paper samples to be tested must be conditioned according to the TAPPI Method # T402OM-88. Before the test, all cardboard and plastic packaging materials should be carefully removed from the paper samples. The paper samples should be conditioned for at least 2 hours at a relative humidity between 48 and 52% and in a temperature range between 22 and 24 ° C. The preparation of the sample and all aspects of the stress test should also be performed within the limits of a room with constant temperature and humidity. For the finished product, discard any product that is damaged. Then, remove 5 strips of four usable units (also called leaves) and put them on top of each other to form a large set with matching perforations between the sheets. Identify sheets 1 and 3 for voltage measurements in the machine direction and sheets 2 and 4 for voltage measurements in the cross machine direction. Then, cut through the drill line using a paper cutter (JDC-1-10 or JDC-1-12 with safety cap available from Thwing-Albert P1045 Instrument Co., of Philadelphia, PA to make 4 separate groups. Make sure that sets 1 and 3 are still identified for the machine direction test and sets 2 and 4 for the cross machine direction test. Cut two 1"wide strips in the machine direction from sets 1 and 3. Cut two 1" wide strips in the cross machine direction from sets 2 and 4. There are now four strips 1"wide for the test in the direction of the machine and four strips 1" wide for the test in a direction perpendicular to the machine. For these samples of finished product, the eight 1"wide strips are five usable units (also called sheets) of thickness For samples of unconverted and / or coil material, cut a 15" by 15"sample be 8 sheets thick from an area of interest of the sample using a paper cutter (JDC-1-10 or JDC-1-12 with "safety cap from Thwing-Albert Instrument Co., of Philadelphia, PA Make sure that one of the 15"cuts runs parallel to the direction of the machine while the other runs parallel to the direction transverse to the machine.Make sure that the sample is conditioned for at least 2 hours at a relative humidity between 48 and 52% and in P104S a temperature range between 22 and 24 ° C. The preparation of the sample and all aspects of the stress test should be done within the limits of a quarter at constant temperature and humidity. From this preconditioned sample of 15"by 15" which is 8 sheets thick, cut four strips of 1"by 7" with the long dimension of 7"running parallel to the machine direction Note these samples as coil samples or uncut material in machine direction Cut four additional 1" strips by 7"with the long dimension of 7" running parallel to the cross machine direction. Record these samples as coil samples or material without converting in cross direction to the machine. Make sure all previous cuts are made using a paper cutter (JDC-1-10 or JDC-1-12 with safety cover by Thwing-Albert Instrument Co. , of Philadelphia, PA). There are now a total of eight samples: four strips of 1"by 7" which are 8 sheets of thickness with the dimension of 7"running parallel to the direction of the machine and four strips of 1" by 7"which is 8 sheets of thickness with the dimension of 7" running parallel to the direction transverse to the machine .

OPERATION OF THE TENSION TESTER; P1045 For the actual measurement of the tensile strength, use a Thwing-Albert Intelect II Standard Tensile Tester (Thwing-Albert Instrument Co., of Philadelphia, PA). Insert the flat-faced clamps into the unit and calibrate the tester according to the instructions given in the operating manual of the Thwing-Albert Intelect .II. Set the crosshead speed of the instrument to 4.00 inches / min and the Ia and 2 to gauge length to 2.00 inches. The breaking sensitivity should be set at 20.0 grams and the sample width should be set at 1.00"and the sample thickness at 0.025". A load cell is selected so that the predicted stress result for the sample to be tested is between 25% and 75% of the range in use. For example, a 5000 gram load cell can be used for samples with a predicted voltage range of 1250 grams (25% of 5000 grams) and 3750 grams (75% of 5000 grams). can be set in the 10% interval with the 5000 gram load cell so that samples with predicted voltages between 125 grams and 375 grams can be tested.Take one of the tension strips and place one end of it in one of the Tension tester clamps Place the other end of the paper strip in the other clamp Make sure that the long dimension of the P1045 strip runs parallel to the sides of the voltage tester. Also make sure that the strips do not protrude from either side of the two clamps. In addition, the pressure of each of the clamps must be in complete contact with the paper sample. After inserting the test paper strip into the two clamps, the tension of the instrument can be monitored. If it shows a value of 5 grams or more, the sample is too tight. Conversely, if a period of 2-3 seconds passes after the test begins before any value is recorded, the tension strip is too loose. Start the voltage tester as described in the manual of the voltage tester instrument. The test is completed after the crosshead automatically returns to its initial starting position. Read and record the voltage load in units of grams from the scale of the instrument or meter of the digital board as the nearest unit. If the reset condition is not performed automatically by the instrument, make the necessary adjustment to fix the clamps of the instrument in their initial starting positions. Insert the next paper strip into the two clamps as described above and obtain a voltage reading in P1045 units of grams. Obtain tension readings of all paper strips for testing. It should be noted that the readings should be rejected if the strip slips or breaks at the edges of the clamps while the test is being carried out.

CALCULATIONS: For the four strips of finished product 1"wide in the machine direction, add the four individual voltage readings recorded Divide this sum by the number of strips tested.This number should normally be 4. Also divide the sum of the tensions recorded between the number of usable units per strip for tension This is normally five for both the 1-sheet product and the 2-sheet product Repeat this calculation for the finished product strips in the cross-machine direction. For samples of unconverted material or coil cut in the machine direction, add the four individual voltage readings recorded Divide this sum by the number of strips tested.This number should normally be four.Similarly divide the sum of voltages recorded between the number of usable units per voltage strip, which normally is P1045 eight. Repeat this calculation for the unconverted or coil paper strips in the direction transverse to the machine. All results are in units of grams / inch.

EXAMPLES The following examples are given to illustrate the practice of the present inven. These examples are intended to assist in the description of the present inven, but in no way should they be construed as limitations on the scope thereof. The present inven is limited only by the appended claims.

Example 1 This example illustrates the use of an offset rotogravure printer for preparing two-layered foil paper having discrete and uniform deposits of a substally fixed chemical softening agent mixture on one of its outer surfaces. The agents used in the preparation of the softening solution are: 1. Quaternary chloride ammonium compound P1045 of bait diester (ADOGEN SDMC) available from WITCO Chemical Company of Greenwich, CT. 2. Petrolatum (White Protopet®) from WITCO Chemical Company of Greenwich, CT. 3. Sorbitan monostearate (Span 60 from ICI Surfactants, Inc. of Wilmington, DE). 4. Ethoxylated sorbitan monostearate (Tween 60 from ICI Surfactants, Inc. of Wilmington, DE). The softening composition is prepared by weighing the appropriate amounts of each of the materials ideied above, melting them and mixing them in a constant temperature vessel maintained at 140 ° F to prepare a composition comprising 60% diester diester chloride quaternary ammonium compound. bait, 22% petrolatum, 14% sorbitan monostearate and 4% sorbitan monostearate ethoxylate. The softening composition is then fed to an engraving tray which allows the softening composition to fill the recessed areas of the rotating engraving cylinder. The construction of the engraving cylinder includes a central void area suitable for circulation of a hot fluid to maintain the roll surface at approximately 140 ° F. The surface of the engraving cylinder is coated with a ceramic aluminum oxide in which the hollowed areas are engraved by a laser technique.

P1045 The recessed areas are formed hemisphere type; each area has a diameter of approximately 400μ and therefore a depth of approximately 200μ. The pattern of the recessed areas is hexagonal and the frequency of the recessed areas is 10 per linear inch, so there are 115 areas per square inch. The resulting percentage of the total area covered by recessed areas is approximately 2.2%. The excess softening solution is scraped from the surface of the engraving cylinder by a flexible scraper blade of polytetrafluoroethylene. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 300 feet per minute. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 300 feet per minute. The engraving cylinder is operated in contact with an applicator cylinder. The applicator cylinder has a rubber cover with 50 P &J hardness. The two cylinders are loaded in interference so that the width of the contact area of the two cylinders due to the deformation of the rubber cover in the applicator cylinder is 5/32 of an inch. The softening solution is thus transferred from the engraving cylinder to the applicator cylinder.

The applicator cylinder is operated in proximity to a prig cylinder. The prig cylinder is made of steel. The cylinders are loaded to stops so that there is a gap of 7 mils between the two cylinders. A two-layered bath paper web consisting of a densified pattern sheet that is approximately 15.5 mils thick is combined with a convenally compressed tissue sheet having a thickness of approximately 7.5 mils., forms a two-ply tissue paper web. The tissue paper web passes through the space formed between the applicator cylinder and the impression cylinders where the softening solution is transferred from the applicator cylinder to the tissue paper web. The tissue web leaving the space formed between the applicator cylinder and the impression cylinder contains approximately 1.5% by weight of uniformly set softener corresponding to the recessed areas of the recording cylinder. The resulting two-sheet tissue paper web is converted into toilet paper rolls.

Example 2 This example illustrates the use of a printer P1045 offset rotogravure to prepare a two-layered bath paper having discrete and uniform deposits of a substantially fixed chemical softening agent mixture. The chemical softening agent mixture is applied to both outer surfaces of the two-layered tissue paper product. The agents used in the preparation of the softening solution are: 1. Bacterial diester chloride-quaternary ammonium compound (ADOGEN SDMC) available from WITCO Chemical Company of Greenwich, CT. 2. Petrolatum (White Protopet®) from WITCO Chemical Company of Greenwich, CT. 3. Sorbitan monostearate (Span 60 from ICI-Surfactants, Inc. of Wilmington, DE). 4. Ethoxylated sorbitan monostearate (Tween 60 from ICI Surfactants, Inc. of Wilmington, DE). The softening composition is prepared by weighing the appropriate amounts of each of the materials identified above, melting them and mixing them in a constant temperature vessel maintained at 140 ° F to prepare a composition comprising 60% diester diester chloride quaternary ammonium compound. bait, 22% petrolatum, 14% sorbitan monostearate and 4% sorbitan monostearate ethoxylate. The composition The softener is then fed to an engraving tray which allows the softening composition to fill the recessed areas of the rotating engraving cylinder. The construction of the engraving cylinder includes a central void area suitable for circulation of a hot fluid to maintain the roll surface at approximately 140 ° F. The surface of the engraving cylinder is coated with a ceramic aluminum oxide in which the hollowed areas are engraved by a laser technique. The recessed areas are formed hemisphere type; each area has a diameter of approximately 400μ and therefore a depth of approximately 200μ. The pattern of the recessed areas is hexagonal and the frequency of the recessed areas is 10 per linear inch, so there are 115 areas per square inch. The resulting percentage of the total area covered by recessed areas is approximately 2.2%. The excess softening solution is scraped from the surface of the engraving cylinder by a flexible scraper blade of polytetrafluoroethylene. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 300 feet per minute. The offset printer is operated so that the surface speed of its cylinders and so P1045 both the frame rate is 300 feet per minute. The engraving cylinder is operated in contact with an applicator cylinder. The applicator cylinder has a rubber cover with 50 P &J hardness. The two cylinders are loaded in interference so that the width of the contact area of the two cylinders due to the deformation of the rubber cover in the applicator cylinder is 5/32 of an inch. The softening solution is thus transferred from the engraving cylinder to the applicator cylinder. The applicator cylinder is operated in proximity to a printing cylinder. The printing cylinder is made of steel. The cylinders are loaded to stops so that there is a space of 11 mils between the two cylinders. A two-layered bath paper web comprising two densified pattern sheets each having a thickness of about 13 mils, are combined to form a two-ply tissue paper web. The tissue paper web passes through the space formed between the applicator cylinder and the impression cylinders where the softening solution is transferred from the applicator cylinder to the tissue paper web. The tissue paper web leaving the space formed between the applicator cylinder and the impression cylinder contains approximately 0.8% by weight of fixed softener P1045 uniformly corresponding to the recessed areas of the engraving cylinder. The resulting two-layered tissue paper tissue web is converted to a roll and passed through the printing operation again in the same way. In the second pass the tissue is oriented to apply a measure of softener to the surface that was not printed on the first pass. The tissue web that leaves the space formed between the applicator cylinder and the impression cylinder contains a total of approximately 1.3% by weight of uniformly fixed softener corresponding to the recessed areas of the engraving cylinder. The resulting two-ply tissue web is passed through an opposite calender contact point to further reduce its thickness; then it turns into toilet paper rolls. The essential properties of the resulting tissue are measured and the softness is compared to a product of the same starting tissue without printing. The results of this evaluation are shown in Table 2.

Table 2 Tissue Properties The exhibits of all patents, patent applications (and any patents granted thereon, as well as any corresponding published foreign patent applications) and the publications mentioned in this description are incorporated herein by reference. However, it is not expressly admitted that any of the documents incorporated by reference will show or expose the present invention. While particular embodiments of the present invention have been illustrated and described, it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. Therefore, it is intended to cover all those changes and modifications within the scope of the invention in the appended claims.

P1045

Claims (36)

1. CLAIMS: 1. A soft tissue paper product having one or more sheets, wherein at least one outer surface of the tissue paper has a surface deposit of a substantively fixed chemical softening mixture, comprising a quaternary ammonium compound, an emollient and a coupling agent.
2. 2. The tissue paper according to claim 1, wherein the quaternary ammonium compound has the formula: (R ^^ - N ^ tR2] ^ "where m is 1 to 3, each R1 is a Cx- alkyl or alkenyl group; C6, a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl group, an alkoxylated group, a benzyl group or mixtures thereof, each R2 is an alkenyl or C14-C22 alkyl group, a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl group, a alkoxylated group, a benzyl group or mixtures thereof, and X "is any anion compatible with the softener
3. 3. The tissue according to claim 2, wherein m is 2, R1 is methyl and R2 is alkenyl or C16 alkyl.
4. 4. The tissue paper according to claim 3, in P1045 where X "is chloride or methyl sulfate
5. 5. The tissue according to claim 1, wherein the quaternary ammonium compound has the formula: (R1) 4.m-N + - [(CH2) nY-R3] m X-in where Y is -0- (0) C-, or -C (0) -0-, or -NH-C (O) -, or -C (0) -NH-; m is 1 to 3; n is 0 to 4, each R1 is a C ^ Cg alkyl or alkenyl group, a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl group, an alkoxylated group, a benzyl group or mixtures thereof, each R3 is an alkenyl or C13 alkyl group C21, a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl group, an alkoxylated group, a benzyl group or mixtures thereof, and X "is any anion compatible with the softener.
6. 6. The tissue according to claim 5, wherein m is 2, n is 2, R1 is methyl, R3 is alkenyl or C15-C17 alkyl and Y is -0- (0) C-, or -C (0) -0-.
7. 7. The tissue paper according to claim 6, wherein X "is chloride or methyl sulfate
8. 8. The tissue paper according to claim 1, wherein the emollient is selected from the group consisting of mineral oil, petrolatum and polysiloxane compounds. P1045
9. 9. The tissue paper according to claim 8, wherein the emollient is petrolatum.
10. The tissue paper according to claim 1, wherein the coupling agent has an HLB value of between about 2 and about 8.
11. The tissue paper according to claim 1, wherein the coupling agent is an ester of polyhydroxy acid. fatty.
12. 12. The tissue paper according to claim 11, wherein the coupling agent is a fatty acid ester of sorbitan.
13. 13. The tissue paper according to claim 12, wherein the sorbitan fatty acid ester is a C16-C22 saturated fatty acid ester.
14. 14. The tissue paper according to claim 13, wherein the sorbitan fatty acid ester is an ester of sorbitan stearate.
15. 15. The tissue paper according to claim 9, wherein the coupling agent is an ester of polyhydroxy fatty acid. ~~~
16. 16. The tissue paper according to claim 15, wherein the coupling agent is a fatty acid ester of sorbitan.
17. 17. The tissue paper according to claim 16, wherein the fatty acid ester of sorbitan is an ester of P1045 saturated fatty acid C1S-C22.
18. 18. The tissue paper according to claim 17, wherein the sorbitan fatty acid ester is a sorbitan stearate ester.
19. The tissue paper according to claim 18, wherein the chemical softening mixture further comprises an ethoxylated sorbitan monostearate having a ratio of sorbitan monostearate to ethoxylated sorbitan monostearate of between about 2: 1 and about 4: 1.
20. The tissue paper of claim 18, wherein the ethoxylated sorbitan monostearate contains from about 10 to about 50 moles of ethylene oxide per mole of ethoxylated sorbitan monostearate.
21. 21. The tissue paper according to claim 19, wherein the quaternary ammonium compound has the formula: (R ^ -N ^ UCH ^ -Y-R3], X "where Y is -0- (0) C- , or -C (0) -0-, or -NH-C (O) -, or -C (0) -NH-, m is 1 to 3, n is 0 to 4, each R1 is an alkenyl group or I rent a hydroxyalkyl group, a hydrocarbyl or substituted hydrocarbyl, an alkoxylated group, a benzyl group or mixtures thereof; P1045 each R3 is an alkenyl or C13-C21 alkyl group, a hydroxyalkyl group, a substituted hydrocarbyl or hydrocarbyl group, an alkoxylated group, a benzyl group or mixtures thereof; and X "is any anion compatible with the softener;
22. 22. The tissue according to claim 21, wherein m is 2, n is 2, R1 is methyl, R3 is alkenyl or C1S-C17 alkyl and Y is -0- ( 0) C-, or -C (0) -0-
23. 23. The tissue paper according to claim 22, wherein X "is chloride or methyl sulfate.
24. 24. The tissue paper according to claim 1, wherein the paper has a densified pattern.
25. 25. The tissue paper according to claim 7, wherein the paper has a densified pattern.
26. 26. The tissue paper according to claim 9, wherein the paper has a densified pattern.
27. 27. The tissue paper according to claim 19, wherein the paper has a densified pattern.
28. 28. The tissue paper according to claim 1, wherein the paper is a non-creped, air-dried paper.
29. 29. The tissue paper according to claim 1, wherein the chemical softening mixture comprises from about 0.1% to about 10% by weight of the paper. P1045
30. 30. The tissue paper according to claim 7, wherein the chemical softening agent comprises from about 0.1% to about 10% by weight of the paper.
31. 31. The tissue paper according to claim 19, wherein the chemical softening agent comprises from about 0.1% to about 10% by weight of the paper.
32. 32. The tissue paper according to claim 1, wherein the surface deposits are uniform, discrete and are spaced apart at a frequency of between about 1 area per linear inch and about 100 areas per linear inch.
33. 33. The tissue paper according to claim 1, wherein the surface deposits are uniform, discrete and are spaced apart at a frequency of between about 1 area per linear inch and about 100 areas per linear inch.
34. 34. The tissue paper of claim 7, wherein the surface deposits are uniform, discrete, and spaced apart at a frequency of between about 1 area per linear inch and about 100 areas per linear inch.
35. 35. The tissue paper according to claim 31, wherein the surface deposits are uniform, discrete P1045 and they are separated at a frequency of between about 1 area per linear inch and about 100 areas per linear inch.
36. 36. The tissue paper according to claim 35, wherein the surface deposits are uniform, discrete and are spaced apart at a frequency of between about 5 areas per linear inch and about 25 areas per linear inch. P1045