MXPA99006149A - Soft tissue paper having a surface deposited softening agent - 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 agent.

Description

SOFT TISSUE PAPER THAT HAS A SOFTENING AGENT DEPOSITED ON THE SURFACE FIELD OF THE INVENTION This invention relates, in general, to tissue paper products. More specifically, it relates to tissue paper products that contain chemical softening agents.

BACKGROUND OF THE INVENTION Tissue tissue paper products are widely used. These products are presented commercially in tailored 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 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 at a 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 above-mentioned discharges from the skin and retaining them for hygienic disposal. Not surprisingly, the use of these products does not come close to 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 article can scrape the sensitive skin and cause severe pain. The alternative of leaving the skin partially clean, is chosen even when this often causes odors to emanate and can cause staining of underwear and over time can also cause irritation. Disorders in the anus, for example hemorrhoids, make the perianal area extremely sensitive and make those who suffer from these discomforts particularly frustrated by the need to clean the anus without causing irritation. A notable case that causes frustration is the continuous blowing of the nose needed 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, to 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 all disclosing methods for selecting or improving fiber sources for tissue and towels with superior properties. The applicable technique is further illustrated by Carstens in U.S. Patent 4,300,981, issued November 17, 1981, which analyzes how fibers can be incorporated to accommodate the paper structures so that they have the greatest potential for smoothness. 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 herein, 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 tissues. This softness that is perceived by touch can be characterized, in a non-exclusive way, by friction, flexibility and surface homogeneity, 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 exemplary 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 interesting ingredient to the pulp tubs that will finally take the form of a tissue paper web, to the pulp as it approaches the tissue. The papermaking machine or the wet weft machine resides in the fourdrinier fabric or in the dryer fabric in the papermaking machine. The second path is classified by the addition of chemical softeners to the tissue paper web after the web is dried. Applicable processes can be incorporated into the papermaking operation, such as spraying on the dry weft before it is wound on a reel. The exemplary technique related to the first mentioned path classified by adding chemical softeners to the tissue paper prior to its weft formation includes U.S. Patent Number 5,264,082, issued to Phan and Trokhan on November 23, 1993, which is considered a form part of the present as 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 theory that all believe that the additives interfere with the coating in the P828 Yankee dryer so that the connection between the wet screen and the dryer weakens. The prior art, such as U.S. Patent Number 5,487,813, issued to Vinson, et al., On January 30, 1996, which is considered part of the present by reference, discloses a chemical combination to attenuate the aforementioned effects. on the resistance 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 vats that feed the papermaking machine. For example, this means directs the application to one of the surfaces of the weft instead of distributing the additive in all the fibers of the pulp. However, such a method fails to overcome the primary disadvantages of the addition of chemical softeners in the final wet stage of the papermaking machine, that is, the effects on strength and effects on the coating of the Yankee dryer. , dryer that should be used. Because of the aforementioned effects on the strength and rupture of the papermaking process, considerable techniques have been devised to apply chemical softeners to already dried tissue paper webs or to the so-called dry end stage of the machine of papermaking or in 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 hereby incorporated by reference, The 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 method P828 similar using a hot transfer surface. 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 represent 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 ability to completely direct the loss of the tensile strength. that accompanies the application to the dry paper web. One of the most important physical properties related to smoothness generally considered by those skilled in the art is the strength of the weft. The resistance is the ability of the product and the frames that constitute it, to maintain physical integrity and resist tearing, explosion and defibering under the conditions of use. For a long time it has been the object of the specialists in the field of the present invention to achieve a high potential for smoothness without degrading the strength. Accordingly, it is an object of the present invention to provide a soft tissue paper without making harmful sacrifices for example, on the strength of the paper. This and other objects are obtained using the present invention as will be shown in the following discussion.

SUMMARY OF THE INVENTION The invention is a soft, strong tissue paper product constituted of one or more sheets of tissue paper, wherein at least one outer surface of the product has discrete uniform surface deposits of a substantively fixed chemical softening agent. The preferred embodiment of the present invention is characterized by having the uniform surface deposits 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 7 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 along 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.

P828 Although they do not wish to link it to the theory, the inventors believe that the combination of geometrical parameters mentioned here makes the softened tissue cause a surprising maximum in the tactile response that results 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 (dialkyldimethylammonium chloride whose alkyl groups are derived from tallow), methyl sulfate of dialkyldimethylammonium (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 the so-called diester dimethyl ammonium chloride, distearyl dimethyl ammonium diester chloride, chloride P828 of dimethyl ammonium diester monoester, diester methyl ester (hydrogenated) dimethyl ammonium dichloride, ditallow (hydrogenated) dimethyl ammonium chloride, ditallow (hydrogenated) dimethyl ammonium monoester chloride and mixtures thereof, especially preferred are chloride diester diester (non-hydrogenated) dimethyl ammonium, Disodium Chloride (Hydrogenated to the Touch) DiMetil Ammonium (DEDTHTDMAC) and Dihydrate Ammonium Dihydrate (Hydrogenated) Chloride (DEDHTDMAC) and mixtures thereof. Depending on the characteristic requirements of the product, the level of saturation of the design can be adjusted from non-hydrogenated (soft) to touch, partially or completely hydrogenated (hard). The use of quaternary ammonium ingredients as described herein is more efficiently carried out if these are accompanied by a suitable plasticizer. The plasticizer can be added during the quaternization step in the manufacture of the quaternary ammonium ingredient or it can be added later. The plasticizer is characterized as being practically inert during chemical synthesis, but acts as a viscosity reducer to aid in the synthesis and subsequent handling, for example, in the application of the quaternary ammonium compound to the tissue paper product. The preferred plasticizers are constituted by a P828 combination of a non-volatile polyhydroxy compound and a fatty acid. Preferred polyhydroxy compounds include glycerol and polyethylene glycols having a molecular weight between about 200 and 2000, with polyethylene glycol having a molecular weight between 200 and 600 being particularly preferred. Preferred fatty acids include linear or branched C6-C23 analogs and saturated or unsaturated, with isetheraic acid being the most preferred. An alternate embodiment of a substantially fixed chemical softening agent comprises the well-known organo-reactive polydimethyl siloxane ingredients, most preferably including the amino functional polydimethyl siloxane. One of the most preferred forms of the substantially fixed softening agent is to combine the organo-reactive silicone with a suitable quaternary ammonium compound. In this embodiment it is preferred that the organofunctional silicone is an amino polydimethyl siloxane and is used in an amount ranging from 0 to about 50%, with the preferred use being in the range between about 5% and 15%. The previous percentages represent by weight of the polysiloxane relative to the total weight of the substantially fixed softening agent. The soft tissue paper of the present invention of P828 preference has a basis weight between approximately 10 2 2 g / m and 50 g / m and more preferably, between approximately 10 g / m 2 and 30 g / m2. It has a density between about 0.03 g / cm and 0.6 g / cm and more preferably between about 0.1 g / cm 3 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, ie produced in a papermaking machine that 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 dried. 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 creping process is preceded by pattern densification methods, to implement the present invention, the P828 tissue paper 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. 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 resulting air-dried patches 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 unwound tissue paper webs, an embryonic web is transferred from the foraminous forming carrier on which it is laid to a transfer carrier with high fiber support, which moves slowly. The weft is then transferred to a drying cloth on which it is dried to final dryness.These wefts may offer some advantages of surface uniformity as compared to creped paper webs The techniques for producing uncreped tissue paper in this form 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 paper without creping. In another case, Hyland, et. to the. in European Patent Application 0 617 164 Al, published on September 28, 1994 and which is considered part of the present, as a reference, shows a method for making flat sheets without creping dried by air passage. 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, compositions that facilitate creping but are normally used only in minor amounts. The paper fibers that are most often used in tissue papers come from virgin chemical pulps. Loading materials may also be incorporated in the tissue papers of the present invention. The U.S. Series No. 08 / 418,990, Vinson et al., Filed April 7, 1995, which is considered part of the present, as a reference, discloses acceptable load-bearing tissue products as substrates for the present invention.

P828 BRIEF DESCRIPTION OF THE DRAWINGS OR FIGURES Figure 1 is a side elevational view of a printed 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 printed 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 printed arrangement illustrating another alternate 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 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 P828 3. Figure 4A provides more details of the preferred recessed areas for use in the present invention illustrating one of the recessed areas in a cross-sectional view.

DETAILED DESCRIPTION OF THE INVENTION Although this specification concludes with claims that point out in a particular way and claim differently the subject matter considered as the invention, it is believed that the invention can be better understood from the reading of the following detailed description and 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" embraces the 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 foraminada surface to a transfer surface traveling at a lower speed than the forming surface. The weft is then transferred to a cloth on which it is dried by passing air to a final dryness after which it is wound. The terms "multilayer tissue paper web, multilayer paper web, multilayer web, multilayer paper web, and multilayer paper product" used interchangeably in the art refer to paper webs prepared from two or more layers of aqueous pulp. which preferably comprises different types of fibers, typically being relatively long softwood fibers and relatively short hardwood fibers as used in the manufacture of tissue paper. Preferred layers are formed from the deposit of separate streams of fiber pulps diluted on one or more endless foraminous surfaces. If the individual layers are initially formed on P828 separated foraminous surfaces, the layers can then be combined wet to form a multilayer tissue paper web. In the sense in which the term "single-sheet tissue product" is used herein, it means that it consists of a sheet of tissue 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 consists of more than one sheet of tissue without creping. The sheets of a multi-sheet tissue product can be almost homogeneous in nature or can be multilayer tissue paper webs. The invention in its most general form is a soft, strong tissue paper product comprising one or more sheets of tissue paper, wherein at least one outer surface of the product has uniform surface deposits of a substantially fixed chemical softener. In the sense in which the term "substantially fixed chemical softening agent" is used herein, it is defined as a chemical agent that imparts lubricity or emollient properties to tissue paper products and also has permanence with respect to maintaining the fidelity of these deposits without migration P828 when exposed to the environmental conditions to which products of this type are usually exposed during their characteristic life cycle. Waxes and oils, for example, have the ability to impart lubricity or emollient properties to tissue paper, but experience the tendency to migrate because they have little affinity for the cellulose pulps constituting the tissue papers of the present invention. While not wishing to be bound by theory, it is believed that the substantially fixed chemical softening agents of the present invention interact with cellulose by means of covalent, ionic or hydrogen bonds, of which either is powerful enough to halt migration in the normal environmental conditions. The preferred embodiment of the present invention is characterized by having the uniform surface deposits separated with a frequency between about 5 and 100 tanks per linear inch. With superlative preference, the uniform surface deposits are spaced at a frequency between about 7 and 25 tanks per linear inch. 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 less than about 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. Preferably, the substantially fixed chemical softening agents comprise quaternary ammonium compounds. The quaternary ammonium compounds that are preferred have the formula: (R1) 4_m-N - [R2] m X "wherein m is between 1 and 3, each Rx is a Cx-C6 alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures of the Each R2 is a C14-C22 alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures thereof, and X any anion compatible with the softener suitable for use in the present invention. preference, each R-, is methyl and X ~ is chloride P828 or methyl sulfate. Preferably, each R2 is C16-C18 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.), wherein R are methyl groups, R 2 are alkyl groups Sebum derivatives 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. Typically, half of the fatty acids present in sebum are unsaturated, mainly in the form of oleic acid. Synthetic "sebs" 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 level of saturation of the design can be adjusted from non-hydrogenated (soft) to touch, P828 partially or completely hydrogenated (hard). All the 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: (R?) 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 R- is a C1-C6 alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures thereof; R3 is a C13-C2 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, preferably Y = -0- (0 ) C-, or -C (0) -0-, m = 2, and n = 2. Each R? Substituent is preferably a CLC alkyl group with methyl being the most preferred, preferably each R3 is an alkyl and / or C13-C17 alkenyl, with P828 greater preference R3 is a linear alkyl chain and / or C15-C17 alkenyl, 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 diester monochloride, dimethyl ammonium diester methyl sulfate, ditallow (hydrogenated) dimethyl ammonium diester methyl ester, ditallow (hydrogenated) dimethyl ammonium diester chloride, and mixtures thereof. Dimethyl ammonium and diester chloride (hydrogenated) dimethyl ammonium are particularly preferred. are commercially available from Witco Chemical Company Inc., of Dublin, Ohio under the trade name "ADOGEN SDMC".

P828 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 level of saturation of the design can be adjusted from non-hydrogenated (soft) to touch, partially or completely hydrogenated (hard). All the saturation levels described above are expressly referred to be included within the scope of the present invention. It will be understood that the substituents R1 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 C13-C17 alkyl and / or 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?) 2-N - ((CH2) 20H) ((CH2) 20C (O ) R3) X as minority 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. published on August 6, 1996; U.S. Patent No. 5,538,595, Trokhan et al., Published July 23, 1996; U.S. Patent No. 5,510,000, Phan et al., Published April 23, 1996.; U.S. Patent No. 5,415,737, Phan et al., Published 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: P828 (Rlb (Rib O I Rj-C-O- (CH2) 2-N + - (CH2) n N + - (CH2) 2-O-C-R3 2X " In the structure mentioned above each R is an alkyl or hydroxyalkyl group ^ Cg, 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 C13-C17 alkyl and / or alkenyl, preferably superlative each R3 is straight chain C15-C17 alkyl and / or alkenyl and R- | _ is a methyl. Parenthetically, although it is not desired to limit it to 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. The use of quaternary ammonium ingredients such as those described above is carried out more efficiently if the quaternary ammonium ingredient is accompanied by a suitable plasticizer. The plasticizer can be added during the quaternization step in the manufacture of the quaternary ammonium ingredient or it can be added later to the quaternization but before application as a chemical softening agent. The plasticizer is characterized as being practically inert during chemical synthesis, but acts as a viscosity reducer that aids in the synthesis and subsequent handling, for example, in the application of the quaternary ammonium compound to the tissue paper product. Preferred plasticizers are comprised of a combination of non-volatile polyhydroxy compounds and a fatty acid. Preferred polyhydroxy compounds include glycerol and polyethyl-glycols having a molecular weight between about 200 and 2000, with polyethylene glycol having a molecular weight between about 200 and 600 being particularly preferred. Preferred fatty acids comprise C6 analogs -C23 linear or branched and saturated or unsaturated, with isostearic acid being the most preferred. Although not wishing to be bound by theory, the applicants believe that a synergism results in the mixture from the ratio between the polyhydroxy compound and the fatty acid. Although the polyhydroxy compound performs the essential function in reducing the viscosity, it can be quite mobile after it becomes hindered by one of the objects of the present invention, for example, that the deposited fabric softener must be substantially fixed.

P828 The inventors have now found that the addition of small amounts of the fatty acid can stop the mobility of the polyhydroxy compound and further reduce the viscosity of the mixture to increase the processability of the compositions of a given fraction of a quaternary ammonium compound. An alternate embodiment of preferred substantially fixed chemical softening agents comprises the well known polydimethyl siloxane organo-reactive ingredients, among which the polydimethyl siloxane with amino function is most preferred. One of the most preferred forms of the substantially fixed softening agent is to combine the organo-reactive silicone with a suitable quaternary ammonium compound. In this embodiment it is preferred that the organofunctional silicone is an amino polydimethyl siloxane and is used in an amount ranging from 0 to about 50% of the composition by weight, the preferred use being in the range between about 5% and 15% by weight based on the weight of the polysiloxane relative to the substantially fixed softening agent. The soft tissue paper of the present invention preferably has a basis weight between about 10 g / m and 50 g / m and more preferably between 2 about 10 g / m and 30 g / m. It has a density between P828 3 3 approximately 0.03 g / cm and 0.6 g / cm and with greater 3 3 preference, between approximately 0.1 g / cm and 0.2 g / cm. 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 insulated 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, ie produced in a papermaking machine that 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 dried. 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 dramatic changes in many physical properties, particularly when measured in the machine direction. Creping is usually carried out with a flexible blade, the so-called scraper blade, against a Yankee dryer in a machine operation. A Yankee dryer is a large diameter cylinder, usually between 8 and 20 feet that is designed to be pressurized with steam to provide a hot surface to complete the drying of the paper webs at the end of the papermaking process. The paper web that is first formed on a foraminous forming carrier, such as a Fourdrinier mesh, where it is released from the plentiful water that is needed to disperse the fibrous pulp is generally transferred to a felt or cloth in a so-called press section where the dewatering is continued either by compacting the paper mechanically or by some other dewatering methods such as hot air drying, before finally being transferred in semi-dry condition to the surface of the Yankee so that the drying is complete. Although the characteristics of the creped paper webs are preferred, in particular when the creping process is preceded by pattern densification methods, to implement the present invention, the non-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 present invention. Tissue paper without creping, a term that in the sense in which it is used in the P828 present refers to tissue paper that is dried without compression, preferably superlative, dried by passage of air. The resulting air-dried slits are patterned so that 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 field high volume is discreet. To produce unwound tissue paper webs, an embryonic web is transferred from the foraminated forming carrier on which it is laid to a slowly moving, high fiber support web transfer 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 for producing uncreped tissue paper in this way are shown in the prior art. For example, Wendt, et.al. in European Patent Application 0 677 612A2, published on October 18, 1995 which is considered part of the present, as a reference, shows a method for making soft tissue paper without creping. In another case, Hyland, et. to the. in European Patent Application 0 617 164 Al, published on 28 P828 September 1994 which is considered part of the present, as a reference, shows a method for making smooth sheets without creping dried by passage of air. 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, compositions that facilitate creping but are normally used only in minor amounts. The paper fibers that are most often used in tissue papers come from virgin chemical pulps. Loading materials may also be incorporated in the tissue papers of the present invention. The U.S. Series No. 08 / 418,990, Vinson et al., Filed April 7, 1995, which is considered part of the present, as a reference, discloses acceptable load-bearing tissue products as substrates for the present invention. Modes of the present invention wherein the substantially fixed softening agent comprises a quaternary ammonium compound further comprises between about 1% and 50% of a polyhydroxy compound and between about 0.1% and 10% of a fatty acid, each as a percentage of the weight of the quaternary ammonium compound. The polyhydroxy compounds useful in this embodiment of the present invention include polyethylene glycol, polypropylene glycol and mixtures thereof. The fatty acids useful in this embodiment of the present invention comprise linear, branched, saturated or unsaturated C6-C23 analogues. The most preferred form of these fatty acids is isostearic acid. A particularly preferred chemical softening agent contains between about 0.1% and 70% of a polysiloxane compound. The polysiloxanes which are applicable to the chemical softening compositions of the present invention include polymeric, oligomeric, copolymeric and other monomeric siloxane materials.

As used herein, the term "polysiloxane" will include all of these polymeric, oligomeric, copolymeric, and other monomeric multiple materials. In addition, the polysiloxane may be straight chain, branched chain or have a cyclic structure. Preferred polysiloxane materials include those having monomeric siloxane units with the following structure: P828 wherein R and R2 for each monomeric siloxane unit can independently be 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 can be either a linear chain, or a branched chain or have a cyclic structure. The radicals Rx and R2 can also be independently other silicone functional groups, such as, but not limited to, siloxanes, polysiloxanes and polysilanes. The radicals Rx and R2 may also contain a variety of organic functional groups including, for example, alcohol, carboxylic acid and amino functional groups. Organophosphoric, reactive silicones, especially amino functional silicones are particularly preferred for the present invention. Preferred polysiloxanes include straight chain organopolysiloxane materials with the following general formula: wherein each radical Rx-R9 can independently be any unsubstituted C 1 -C 4 alkyl aryl radical and R 10 any C 1 -C 4 alkyl or substituted aryl radical. Preferably each radical R ± -R9 is independently any Ci-C alkyl group? without replacing Those skilled in the art will recognize that technically there is no difference if, for example, Rg 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 preferably superlative between about 1% and 5%. In a particular preferred embodiment, 1-R9 are methyl groups and R10 is an alkyl, aryl or P828 substituted or unsubstituted alkenyl. 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, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, thiol and / or other functional groups including alkyl analogues and alkenyl 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 manner does not imply that others 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 about 25 centistokes to about 20,000,000 or even higher. The high viscosity polysiloxanes which are themselves resistant to flow can be deposited efficiently by emulsification with a surfactant or solution in a vehicle, such as hexane, mentioned for exemplary purposes only. Although it is not desired to link to 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; Patent of the United States No. 5,059,282 granted to Ampulski; United States Patent? 5,529,665 issued on 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 by Wooston. All these patents are considered part of this, as a reference. It is also considered part of the present, as a reference Silicone Compounds, p. 181-217, distributed by Petrach Systems, Inc., which contains an extensive list and description of polysiloxanes in general. Figures 1-4 is provided as an aid to describe the present invention. Figure 1 is a side elevational view of a printed 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. In Figure 1, the liquid chemical softener 6, preferably hot by means which are not shown, is contained in a tray 5, so that the rotary engraver cylinder 4, also preferably hot by means which are not shown, is partially immersed in the softener liquid guímico 6. The engraving cylinder 4 has a plurality of recessed areas that are practically empty of content when they enter the tray 5, but which are filled with the chemical softener 6 as the engraving cylinder 4 is partially submerged in the fluid on the tray 5 during cylinder rotation. 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.

P828 when referring to that figure. Still with reference 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 engraving cylinder 4. This remaining chemical softener is transferred in the form of uniform discrete deposits to an applicator cylinder 3. The applicator cylinder 3 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 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 applied 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 P828 shape and size of the recessed areas and the characteristics of the fluid chemical 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 tissue paper web 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 may 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.

P828 to cause these to be 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, they should be avoid excessively small gaps between the two cylinders to preserve the thickness or volume of the tissue web 1. Commonly no interference or actual contact between the surfaces of the cylinders (through the tissue web 1) in the area 9, 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 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 printed 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. In Figure 2, a liquid chemical softener 15, P828 preferably hot by means which are not shown, is contained in a tray 14, so that the rotary engraving cylinder 13, also preferably hot by means not shown, is partially immersed in the liquid chemical softener 15. The cylinder Recorder 13 has a plurality of recessed areas that are substantially 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 at turning. The engraving cylinder 13 and its pattern of recessed areas are illustrated later 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 does not have the 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.

P828 to a tissue paper web 1, which is directed towards the area 17. The transfer occurs because the tissue web 1 is brought into proximity to the chemical softener present in the recessed areas due to the coercion of the impression cylinder 12 in relation 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. 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 an actual 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 P828 confined tissue pass with close proximity. The tissue paper web 1 leaves the area 17 with the side 18 containing uniform discrete surface deposits of substantially fixed softening agent according to the pattern of the engraving cylinder 14. Figure 3 is a side elevational view of a printed arrangement illustrating another alternate method to form the uniform surface deposits of the substantially fixed chemical softening agent of 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. 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 the engraving cylinders 25 are partially immersed in them when rotating. The engraving cylinders 25 and their pattern of recessed areas are illustrated in P828 further 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 referring to Figure 3, the excess chemical softener 26 that is taken from the trays 27 but not retained in the recessed areas is removed by flexible scraper blades 28, which contact the engraving cylinders 25 on their surfaces outside, but that do not have the capacity to significantly deform 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 they 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 such as synthetic or natural rubber.

P828 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 interference areas 24 formed by the interference of the engraving cylinders 25 with their respective applicator cylinders 23. Usually an interference or an actual contact between the surfaces of the cylinder in one or both of the areas 24 is preferred, but you can imagine 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 making one or more of the pairs of cylinders pass 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 P828 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 to 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 that 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 enough to make it at least partially the reservoirs are transferred 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, excessively small gaps between the two cylinders must be avoided to preserve the thickness or volume of the tissue web 1. Commonly no interference or actual contact between the surfaces of the cylinders (through the tissue web 1) in the area 22 is necessary, 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 by making contact between the two, with movement transmitted through the tissue web 1. The tissue paper web 1 leaves the area 22 with both sides --- 29 having uniform discrete surface deposits of substantially fixed softening agent according to the pattern 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 recessed areas sometimes referred to as cells. The recessed areas 33 exist in a cylinder surface 32 that is distinct from the smooth one. 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. An 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 rollers to prevent etching in areas that are not destined to become areas hollowed out 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 chrome finish 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 P828 five recessed areas per inch up to 100 recessed areas per inch. The geometry of each of the recessed cells is hemispherical. Figure 4A provides further details of the preferred recessed areas for use in the present invention illustrating one of the recessed areas in a cross-sectional view. In Figure 4A, a recording cylinder surface 42 contains a hemispherical recessed area with a diameter ranging from one hundred thirty microns to four hundred ten microns. It is to be expected that wood pulp in all its varieties will normally constitute tissue paper with utility in this invention. However, other cellulose fibrous pulps can be used, such as cotton wool, bagasse, mouse, etc., and none are discarded. The wood pulps useful here include chemical pulps such as sulphite and sulphate pulps (sometimes called kraft) as well as mechanical pulps including, for example, mechanical pulps, Thermo-Mechanical Pulp (TMP) and Chemical Pulp Thermo-Mechanical (CTMP). The pulps derived from both deciduous and coniferous can be used. Both hardwood pulp and soft wood pulp as well as combinations of the two can be used as paper fibers for the tissue paper of the P828 present invention. The term "hard wood pulps" in the sense in which it is used herein refers to the fibrous pulp derived from the woody substance of deciduous (angiosperms), while the "soft wood pulps" are fibrous pulps derived from the woody substance of conifers (gymnosperms). Mixtures of hardwood kraft pulp, especially eucalyptus and northern softwood Kraft pulp (NSK) are particularly suitable for making the tissue webs of the present invention. A preferred embodiment of the present invention comprises the use of tissue webs in layers where, preferably superlatively, hard wood pulps are used as eucalyptus for the outer layers and where Kraft pulps of soft northern woods are used for the inner layer (s). Also applicable to the present invention are fibers derived from recycled paper, which may contain some or all of the above fiber classes. In a preferred embodiment of the present invention, which uses multiple pulps, the pulp containing the papermaking fibers that will be in contact with the particulate filler is predominantly of the hardwood type, preferably with a content of at least about 80. % hardwood.

P828 Optional Chemical Additives Other materials may be added to the aqueous pulp or embryo 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 to include them all. 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. One of the species that polarize cationic charge that is traditionally used is alum. More recently in the art, charge polarization is made by the use of relatively low molecular weight cationic synthetic polymers., preferably having a molecular weight not greater than about 500,000 and more preferably not greater 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. If permanent wet strength is desired, the group of chemicals: including polyamide-epichlorohydrin, 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-epichlorohydrin 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 published November 13, 1973, both assigned 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 wet fugitive resistance is desired, 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 P828 Company, Parez 750® offered by Cytec of Stamford, CT and the resin described in U.S. Patent No. 4,981,557 issued January 1, 1991 to Bjorkquist and which is considered part of this, as a 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. The above list of optional chemical additives is intended only to be of an exemplary nature and is not intended to limit the scope of the invention. The tissue paper webs made according to the present invention have a basis weight between 10 g / m and approximately 100 g / m. In its preferred embodiment, the tissue without creping with load made by the P828 present invention has a basis weight between approximately 2 2 10 g / m and 50 g / m and preferably superlative between 2 2 approximately 10 g / m and 30 g / m. The uncolored tissue paper webs prepared by the present invention have a density of about 0.60 g / cm or less. In its preferred embodiment, the uncolored tissue paper of the present invention has a density between about 0. 03 g / cm 3 and 0.6 g / cm3 and preferably superlative between 3 3 approximately 0.05 g / cm and 0.2 g / cm. The present invention is also applicable to the production of multilayer tissue paper webs. 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 the European Patent Publication No. 0 613 979 Al, Edwards et al., Published September 7, 1994, which is considered part of the present, as a 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 tissue paper.

P828 multilayer. 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 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 for supplying a thin deposit of pulp on the surface of a Fourdrinier mesh to form a wet web. 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 multi-ribbed entry box. The preferred layers P828 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, 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. Lint and dust are related to the resistance since the tendency to loose fibers or particles is directly related to the degree to which those fibers or particles are anchored in the structure. As the anchor level increases, the resistance will increase. However, it is possible to have a level of resistance that is considered acceptable but has an unacceptable level of lint and dust release. 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.

P828 The multilayer tissue paper webs of the present invention can be used in any application where soft, absorbent multi-layer 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.

Analytical and Test Procedures A. 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 built-in units. The caliper of the 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 / inch 2 (15.5 g / cm2).

B. 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 P828 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 lint friction test, 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 would have frayed with handling, for example, on the outer side of the roll. For finished multi-sheet product, three sections are removed, each containing two sheets of multi-product P828 foil and put on 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 side 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 product. For the simple sheet product, make 3 samples with the side facing the mesh outwards and 3 with the side not facing the mesh outwards. Keep record of which samples correspond to the ones on the side facing the mesh outwards and which ones on the side not facing the mesh outwards. Obtain a 30"X 40" piece of Crescent # 300 cardboard from Cordage, Inc. (800 E. Ross Road, Cincinnati, Ohio, 45217). 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 you work with finished sheet product P828 simple, 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. 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 P828 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 during the course of this sample preparation procedure, discard it and make a new sample with a new tissue sample strip. If you work with converted multi-sheet product, there will now be 3 samples in the carton. For the single-sheet finished product, there will now be 3 samples with mesh-oriented side facing outward in the cardboard and 3 samples with non-oriented side in the cardboard.

FELT PREPARATION: Obtain a 30"X 40" piece of Crescent # 300 cardboard from Cordage Inc. (800 E. Ross Road, Cincinnati, Ohio, 45217). 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 sheet This marking allows the cardboard / felt combination to fit tightly P828 around the weight of the Sutherland Friction tester. Draw an arrow that runs parallel to the long 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 the top of the green side without marking of the cardboard so that the edges of both the felt and the cardboard are parallel and aligned Ensure that the side of the lint felt is facing upward Also let approximately 0.5"protrude from the top and bottom of the felt. the edges of the cardboard. Perfectly fold the two edges of the felt that protrude over the back of the cardboard with Scotch brand 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 P828 cardboard / felt samples for 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 the same tissue lot number is used for each of the 24 samples for 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 P828 of the samples consecutively to 48 so that the last sample in the far right part is numbered with 48. Use the 24 samples with odd numbers 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 fluff on the side facing the mesh outwards and the "N" samples for the fluff analysis on the non-mesh oriented side outwards. For the product of 1 sheet, there are now a total of 24 samples for the new felt lot and the old felt lot. Of these 24, twelve are for the analysis of fluff on the side facing the mesh outward and 12 for the analysis of fluff on the side not oriented to the mesh outward. Perform the friction and determine the values Hunter Color L 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 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 values Hunter Color L 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 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.

P828 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 FOUR POUNDS: The four-pound weight has four square inches of effective contact area that provides a 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 fragments. 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.

P828 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 unique 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. 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 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 test 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's 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 should be checked and readjusted 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.

MEASUREMENT OF THE SAMPLES The first step in the measurement of the fluff is P828 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 the full coverage, press the "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 P828 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 get 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. 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 nearest dumbbell P828 the operator must 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 button "press". 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 felt-covered weight toward 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, in the multi-blade-sheet product only one side of the paper will be rubbed. So, 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 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 delta P828 average for the three values of 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.

C. Measurement of Tissue Paper Softness 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 preconditioned 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 similar to that described in "Manual of Sensory Testing Methods", ASTM Special Technical Publication 434, published by American Society for Testing and Materials 1968 and which is considered is 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 softness. The result of this test is reported in what is called the Panel Score 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 it is evaluated that X can be a little softer than Y and a rating of minus one is given if it is evaluated that Y can be a little softer than X; 2. a score of plus two is given if it is judged that X is surely a bit softer than Y and a rating of minus two is given if it is judged that Y is surely a little softer than X; 3. a score of plus three is given if it is judged that X is much softer than Y and a rating of minus one is given if it is judged 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 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 value 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 P828 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.

D. Tissue Paper Strength Measurement DRY TENSION RESISTANCE: The tensile strength is determined in one inch strips of sample using a Thwing-Albert Intelect II Standard Tensile Tester (Thwing-Albert Instrument Co., 10960 Dutton RD. , Philadelphia, PA, 19154). This method is intended for use on finished paper products, coil samples and non-converted material.

CONDITIONING AND PREPARATION OF THE SAMPLE: Before the stress test, the paper samples to be tested should be conditioned according to the Tappi Method # T402OM-88. Before the test all cardboard and plastic packing 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 P828 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 lid from Thwing-Albert Instrument Co., 10960 Dutton Road, Philadelphia, PA, 19154) 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 P828 direction perpendicular to the magic. For these finished product samples, 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 one area of interest of the sample using a paper cutter (JDC-1-10 or JDC-1-12 with safety lid from Thwing-Albert Instrument Co., 10960 Dutton Road, Philadelphia , PA, 19154) .Make sure that one of the 15"cuts runs parallel to the machine direction 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 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 15"by 15" sample, which is 8 sheets thick, cut four strips of 1"by 7" with the long dimension of 7"running parallel to the machine direction. Record these samples as coil samples or uncut material in machine direction Cut four additional 1"by 7" strips P828 with the long dimension of 7"running parallel to the cross machine direction, record these samples as coil samples or uncut material in cross direction to the machine, make sure that all previous cuts are made using a paper cutter ( JDC-1-10 or JDC-1-12 with safety cover by Thwing-Albert Instrument Co., 10960 Dutton Road, Philadelphia, PA, 19154) There are now a total of eight samples: four strips of 1"by 7" which is 8 sheets thick with the dimension of 7"running parallel to the direction of the magic and four strips of 1" by 7"which is 8 sheets thick with the dimension of 7" running parallel to the direction transversal to the machine.

OPERATION OF THE TENSION TESTER: For the actual measurement of the tensile strength, use a Thwing-Albert Intelect II Standard Tensile Tester (Thwing-Albert Instrument Co., 10960 Dutton Road, Philadelphia, PA, 19154). 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 2nd gauge length to 2.00 inches. The breaking sensitivity should be set at 20.0 grams and the width of the sample of P828 will set at 1.00"and the thickness of the sample 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). The tension tester can also be set in the 10% range with the 5000 gram load cell so that samples with predicted stresses 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 clamps of the tension tester. Place the other end of the paper strip in the other clamp. Make sure that the long dimension of the strip runs parallel to the sides of the tension 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 start position. Read and record the voltage load in units of grams from the scale of the instrument or digital board meter 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 tension reading in 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.

P828 sum between the number of strips tested. This number should normally be four. Also divide the sum of the voltages recorded between the number of usable units per strip for voltage. This is normally five for both the 1-sheet product and the 2-sheet product. Repeat this calculation for the strips of finished product in the direction transverse to the machine. For samples of unconverted or coil material 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. Also divide the sum of recorded voltages between the number of usable units per strip for voltage. This is usually 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. For the purposes of this description, the tensile strength shall be converted to a "specific total stress resistance" defined as the sum of the tensile strength determined in P828 machine direction and cross machine direction, divided by base weight and corrected in units for a value in meters.

EXAMPLES The following examples are given to illustrate the practice of the present invention. These examples are intended to assist in the description of the present invention, but in no way should they be construed as limitations on the scope thereof. The present invention 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 uniform surface deposits of a substantially fixed chemical softening agent. The agents used in the preparation of the softening solution are: 1. Tallow Diester Chioride Quaternary (ADOGEN SDMC) from WITCO Chemical Company of Greenwich, CT. 2. Polyethylene Glycol 400 by J.T. Baker Company of Phillipsburg, NJ.

P828 3. Isoestearic Acid (Century 1105 from Union Camp Company of Wayne, NJ). The softening solution is prepared by melting and mixing 75% quaternary tallow diester chloride, 20% polyethylene glycol 400 and 5% isetheraic acid in a constant temperature vessel maintained at 140 ° F. The softening solution is then fed to an engraving tray which allows the softening solution to fill the recessed areas of the rotary 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 off the surface of the engraving cylinder by a blade P828 flexible PTFE scraper. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 100 feet per minute. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 100 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 so that there is a space of 13 thousandths of an inch between the two cylinders. A two-layered two-layered bath tissue web passes through the space formed between the applicator cylinder and the impression cylinder where the softening solution is transferred from the applicator cylinder to the tissue web.

The tissue web that leaves the space formed between the applicator cylinder and the impression cylinder contains approximately 1.2% by weight of uniformly set softener corresponding to the recessed areas of the recording cylinder. The resulting two-sheet tissue web is converted to rolls of toilet paper.

Example 2 This example illustrates the use of an offset rotogravure printer for preparing two-layered foil paper having uniform surface deposits of a substantially fixed chemical softening agent. The agents used in the preparation of the softening solution are: 1. Tallow Diester Chioride Quaternary (ADOGEN SDMC) from WITCO Chemical Company of Greenwich, C. 2. Polyethylene Glycol 400 by J.T. Baker Company of Phillipsburg, NJ. 3. Isoestearic Acid (Century 1105 from Union Camp Company of Wayne, NJ). 4. Amino polydimethylsiloxane (SF1921 from GE Silicones of Waterford, NY). The softening solution is prepared by melting and P828 mixing 33.8% quaternary tallow diester chloride, 9% polyethylene glycol 400 and 2.3% isoesteric acid and 55% SF1921 in a constant temperature vessel maintained at 140 ° F. The softening solution is then fed to an engraving tray which allows the softening solution to fill the recessed areas of the rotary 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 off the surface of the engraving cylinder by a flexible PTFE scraper blade. The offset printer is operated in a P828 that the surface speed of its cylinders and therefore the frame speed is 100 feet per minute. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 100 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 so that there is a space of 4 mils between the two cylinders. A two-layered two-layered bath tissue web passes through the space formed between the applicator cylinder and the impression cylinder where the softening solution is transferred from the applicator cylinder to the tissue web. The tissue paper web that comes out of the space formed between the applicator cylinder and the impression cylinder contains P828 about 1.5% by weight of uniformly fixed softener corresponding to the recessed areas of the engraving cylinder. The resulting two-sheet tissue web is converted to rolls of toilet paper.

Example 3 This example illustrates the use of an offset rotogravure printer for preparing two-layered foil paper having uniform surface deposits of a substantially fixed chemical softening agent. The agents used in the preparation of the softening solution are: 1. Tallow Diester Chioride Quaternary (Quaternary Sebum Diester Chloride) (ADOGEN SDMC) from WITCO Chemical Company of Greenwich, CT. 2. Polyethylene Glycol 400 by J.T. Baker Company of Phillipsburg, NJ. 3. Isoestearic Acid (Century 1105 from Union Camp Company of Wayne, NJ). The softening solution is prepared by melting and mixing 76% quaternary tallow diester chloride, % polyethylene glycol 400 and 4% isetheraic acid in a container at a constant temperature maintained at 140 ° F. The softening solution is then fed to a tray of P828 engraving that allows the softening solution to fill the recessed areas of the rotary 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 off the surface of the engraving cylinder by a flexible PTFE scraper blade. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 100 feet per minute. The offset printer is operated so that the surface speed of its cylinders and therefore the frame speed is 100 feet per minute.

P828 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 so that there is a space of 15 thousandths of an inch between the two cylinders. A two-layered two-layered bath tissue web passes through the space formed between the applicator cylinder and the impression cylinder where the softening solution is transferred from the applicator cylinder to the tissue web. The tissue paper web leaving the space formed between the applicator cylinder and the impression cylinder contains approximately 0.7% by weight of uniformly fixed softener corresponding to the recessed areas of the recording cylinder. The resulting two-layered bath paper web is wound onto a coil and passed through P828 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 tissue web of two sheets is converted to rolls of toilet paper. The essential properties of the resulting tissue are measured and the softness is compared to a product of the same starting tissue without printing.

P828

Claims (11)

1. CLAIMS: 1. A tissue paper product having one or more sheets, wherein at least one outer surface of the tissue paper has uniform discrete surface deposits of a substantially fixed chemical softening agent, the chemical softening agent preferably comprising a compound of quaternary ammonium.
2. 2. The tissue paper according to claim 1, wherein the chemical softening agent has the formula: wherein m is between 1 and 3, preferably 2; each Rx is a C-L-Cg alkyl or alkenyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures thereof, Rx is preferably a methyl group; each R2 is a C14-C22 alkyl or alkenyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures thereof, R2 is preferably selected from the group consisting of C16-C18 alkyl groups and alkenyl groups C16-C18; and X ~ is any anion compatible with the softener, the anion compatible with the softener is preferably selected from the group consisting of chloride and methyl sulfate.
3. 3. The tissue paper according to claim 1, wherein the chemical softening agent has the formula: (R1) 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-; Y is preferably selected from the group consisting of -O- (0) C- and -C (0) -0-: m is between 1 and 3, preferably 2, n is between 0 and 4, preferably 2, each Rx is an alkyl or alkenyl group, Cg, hydroxyalkyl group, hydrocarbyl or hydrocarbyl group substituted, alkoxylated group, benzyl group or mixtures thereof, Rx is preferably a methyl group, each R3 is a C13-C21 alkenyl or alkenyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated group, benzyl group or mixtures of R3 is preferably selected from the group consisting of C15-C17 alkyl groups and C15-cl7 alkenyl groups, and X is any anion compatible with the softener, the anion compatible with the softener is preferably selected from the group consisting of chlorur or and methyl sulfate.
4. 4. The tissue paper according to any of the P828 claims from above, wherein the chemical softening agent further comprises a polyhydroxy compound and a fatty acid.
5. The tissue according to claim 4, wherein the polyhydroxy compound is selected from a group consisting of polyethylene glycol, polypropylene glycol and mixtures thereof and the fatty acid comprises linear, branched, saturated or unsaturated C6-C23 homologs, the fatty acid preferably comprises isothermal acid.
6. 6. The tissue paper of claim 1, wherein the chemical softening agent comprises a polysiloxane compound, the polysiloxane compound preferably comprises an amino functional polysiloxane compound.
7. 7. The tissue paper according to claim 2 or 3, wherein the chemical softening agent further comprises a polysiloxane compound, the polysiloxane compound preferably comprises an araino-functional polysiloxane compound.
8. 8. The tissue paper according to any of the preceding claims, wherein the paper is densified with pattern.
9. 9. The tissue paper according to any of the preceding claims, wherein the paper is paper without creping, drying by passage of air.
10. 10. The tissue according to any of the preceding claims, wherein the surface deposits are spaced at a frequency of approximately between 5 areas per linear inch and approximately 100 areas per linear inch. The tissue paper according to any of the preceding claims, wherein the chemical softening agent comprises between about 0.1% and 10% by weight of the paper.