MXPA99011549A - Modified cellulosic fibers and fibrous webs containing these fibers - Google Patents

Abstract

Disclosed are modified cellulosic fibers having a dry zero span tensile index that is substantially less than the dry zero span tensile index of the corresponding unmodified cellulosic fibers. Fibers having reduced dry zero span tensile may provide fibrous structures having improved hand feel compared with fibers prepared from unmodified fibers. In particular, such modified fibers provide fibrous structures with improved flexibility, which is perceived as improved softness. The reduced dry zero span tensile is preferably achieved by reacting the fibers with one or more cellulase enzymes and one or more debonders. The invention also relates to a fibrous structure having a density of not more than about 0.4 g/cc, wherein the fibrous structure comprises modified cellulosic fibers having a dry zero span tensile index that is at least about 15%less than the dry zero span tensile index of the corresponding unmodified cellulosic fibers;and wherein the fibrous structure has a bending modulus per unit dry tensile that is at least about 30%less than the bending modulus per unit dry tensile of a fibrous structure prepared from corresponding unmodified fibers.

Description

MODIFIED CELLULOSE FIBERS AND FIBROUS TRACES CONTAINING THESE FIBERS CROSS REFERENCE OF RELATED REQUESTS This application claims the benefits of the Provisional application of the United States No. 60 / 049,457 filed on June 12, 1997.

FIELD OF THE INVENTION The present invention relates to fibrous structures useful in disposable products such as paper towels, facial tissues, toilet paper and the like. These fibrous structures provide improved tactile perfection as well as improved softness without sacrificing tensile strength in a wet and dry environment.

BACKGROUND OF THE INVENTION Cellulosic fiber structures, for example paper, are well known in the art. These fibrous structures are commonly used today in paper towels, toilet paper, facial tissues, etc. For 'meet the needs of the consumer, these fibrous structures must balance several interests that are in competition. For example, the fibrous structure must have sufficient tensile strength to prevent the fibrous structure from tearing or crumbling during normal use or when relatively small tensile forces are applied. The cellulosic fibrous structure must also be absorbent, so that the liquids are absorbed quickly and are completely retained by the cellulosic fibrous structure. The cellulosic fibrous structure must also exhibit sufficient softness so that it is pleasant to the touch and does not scratch during use. Against this range of competing interests, the fibrous structure must be economical, so that it can be manufactured and sold obtaining a profit, and still be affordable for the consumer. The resistance to tension, one of the properties already mentioned, is the ability of the fibrous structure to retain its physical integrity during use. As analyzed by D.H. Page, "A Theory for the Tensile Strength of Paper", TAPPI, Vol 52 (4), p. 674-82 (1969), the tensile strength is controlled by two primary factors: tensile strength of the fiber with an extension of zero and fiber-fiber bonding (affected by, for example, resistance of pure fiber, area of relative union, length of the fiber, area of the fiber in cross section and average perimeter of the cross section of the fiber). With towel and tissue products and the like, tensile strengths of the fiber with an extension of zero are generally in the order of at least 10 times greater than the general tensile strength of the sheet or sheet. This in turn indicates that the factors influencing the fiber-to-fiber (i.e., interfiber) linkage control the tensile strength of the web and that the zero extension strength for the fiber (i.e., interfiber resistance) can be reduced without adversely affecting it. the general resistance of the product. Softness is the ability of the fibrous structure to impart a particularly desirable tactile sensation to the user's skin. In general, the softness is inversely proportional to the ability of the fibrous structure to resist deformation in a direction perpendicular to the plane of the structure. Softness is influenced by the volume, surface texture (frequency creping, size of various regions and smoothness), the coefficient of surface friction of stick-slip and flexural rigidity or casing (also referred to as a manual perception. A or more properties may be affected by fiber flexibility, fiber morphology, bond density, unsupported length of fiber and the like, it is not surprising that considerable efforts have been expended to improve the tensile strength (wet and / or dry fibrous substrates, the patent literature reflects this effort. examples of prior art to increase the tensile strength are the addition of chemicals to impart wet strength and dry, binding fibers or binders, such as, for example, bicomponent fibers, latex binders and the like. Similarly, considerable effort has been expended in providing substrates that improve manual perception or softness. Examples include the addition of chemical softeners, surface modifying agents, debonding agents and the like. Other examples include mechanical treatment such as creping, Clupak®, Micrex®, wet micro-tension and the like. It is generally accepted that the strength of a fibrous substrate (typically measured in terms of wet and / or dry tensile strength) and that the softness of the substrate is dependently related, at least to some degree. That is, efforts directed at improving the smoothness of the substrate will typically result in a reduction in substrate strength. Indeed, many attempts have been made to improve the smoothness of the substrate and these have focused on modifying (reducing) the fiber to fiber bonds by chemical and / or mechanical treatments such as creping. While softness benefits have been achieved, the reduction in interfiber bonding results in a reduction in the tensile strength of the substrate and an increase in the production of lint from the product. Therefore, there is a continuing need for means to decouple the relationship between the softness of the substrate and the strength. In particular, there is a need for fibrous products that have improved manual perception without sacrificing wet strength. Accordingly, an object of the invention is to provide a fibrous web comprising fibers based on cellulose, exhibiting improved smoothness without having a negative impact on the resistance, to a significant degree. This is achieved by preparing wefts using modified cellulosic fibers having reduced tensile strength with zero extension (ie reduced intrafiber strength) as opposed to reducing the level of interfiber bonding (ie interfiber resistance). Of the plot. More specifically, applicants have discovered that a measurable reduction in dry tensile strength, with zero extension of the fibers typically provides a structure exhibiting better flexibility (measured in terms of a reduction in the "flexural modulus"). per unit of tension in dry "). While a reduction in dry tensile strength with zero extension does not always provide improvements in the flexibility of the structure, this reduction is considered necessary to achieve more flexible structures according to the present invention. An object of the present invention is to provide the modified cellulosic fibers described above as well as a process for obtaining same.

SUMMARY OF THE INVENTION In one aspect, the present invention relates to modified cellulosic fibers having a dry tensile index with zero extension that is at least about 35% less than the dry tensile index with zero extension (also referred to as hereinafter "DZST" for its acronym in English, dry zeró span tensile) of the corresponding unmodified cellulosic fibers. In a further aspect, the invention relates to a fibrous structure having a density not greater than about 0.4 g / cc, wherein the fibrous structure comprises modified cellulosic fibers having a dry tensile index with zero extension which is at least about 15% less than the dry tension index with zero extension of the corresponding unmodified cellulosic fibers, and wherein the fibrous structure has a modulus of flexion per unit tension in dried which is at least about 30% smaller to the flexural modulus per unit of dry tension of a fibrous structure prepared from the corresponding unmodified fibers. Preferably, the modified fibers that form this fibrous structure, when they form a test sheet consisting only of those modified fibers, will have a dry stress index (also referred to as "DT" for its acronym in English, dry tensile) that is at least as large as the dry stress index of a test sheet made with the corresponding unmodified fibers. The terms dry strain index, dry tension index with zero extension and flexural modulus per unit dry tension as well as the methods for determining these parameters are described in more detail below. In summary, the dry tension index of a fibrous web corresponds to the strength of the composite. In contrast, the dry tension index with zero extension, although measured on a fibrous substrate, is a comparative measure of the intrinsic strength of the individual fibers that make up the dry weft. Although the zero continuous wet tension index is generally recognized as a measure of the intrinsic strength of the fibers, the applicants consider that the value of the P952 dry stress with zero extension is more predictive of relative fiber and number flexibility and, therefore, of the smoothness of a substrate formed with those fibers. The modulus of flexion per unit of tension in dry is a measure of the rigidity per unit of gauge and of the tension of the fibrous structure in question. As mentioned above, previous attempts have been made to improve wet softness and have typically resulted in a decrease in wet tensile strength due to a lower fiber to fiber bond. In contrast, the fibrous structures of the present invention comprise fibers that are sufficiently weak in their intrinsic nature to provide flexibility and softness when they form a dry web, but maintain the level of interfiber bonding to provide an overall wet tensile strength equal to or higher. In one aspect, the present invention relates to a method for preparing modified cellulosic fibers, the method comprising combining one or more cellulase enzymes and cellulosic fibers and allowing the combination to react for a sufficient period to reduce the dry strength with zero extension of the fibers by at least 15% compared to the zero extension dry strength of the corresponding unmodified fibers. In a preferred embodiment, a chemical softener or debonder is used in the processing of the modified fibers.

DETAILED DESCRIPTION OF THE INVENTION I. Definitions In the sense used here the term "dry stress index" refers to the tensile strength of a fibrous structure, measured according to the TAPPI standard T220 om-88 and T494 om-88 using an electronic voltage tester as is described in the Test Methods, Divided by the base weight of the sample (weight of the sample per unit area). In the sense used herein, the term "dry tensile index with zero extension" refers to the tensile strength of individual fibers forming a fibrous structure, measured using a combined electronic / compressed-air type tester described in FIG. Test Methods section, divided by the base weight of the sample (sample weight per unit area). While the measurement of the zero extension stress index uses a fibrous substrate as the test sample, it is accepted that the resulting stress index is a relative measure of the fiber's intrinsic strength. This is achieved by providing essentially zero space between the jaws of the tester, compared to a space of 4.

P952 _ _ ^ and inches in the dry stress resistance test. As used herein, the term "wet tensile index with zero extension" refers to the intrinsic strength of wet fibers forming a fibrous structure, measured using the combined electronic / compressed-air type tester described in the section of test methods. In the sense used herein the term "modulus of flexion per unit ratio of dry tension" refers to the stiffness of a fibrous structure per unit of tension, as described in the section on test methods. The measurements of dry and wet tension index with zero extension, as well as the modulus of flexion by dry tension bond, are made on sculptures of low density test sheets produced according to the description established in the Methods section test. In the sense used herein the term "modified fibers" refers to fibers that have been modified according to the present invention, so that the index to the dry tension with zero extension is reduced by the indicated percentage (for example, less 15%, at least 35%, etc.) in relation to the starting fibers. In the sense used herein, the term "unmodified fibers" refers to fibers that may have been processed by one or more operations that are commonly practiced in the industry, for example repulping, blanching, refining, frotopulping and the like, but not have been modified according to the teachings of this specification. In the sense used here the term "soft wood" refers to wood derived from coniferous trees.

II. Modified Fibers and Fibrous Structures "In one aspect, this invention relates to modified cellulosic fibers that have a tensile strength index with zero extension that is at least about 35% smaller, preferably at least about 40% smaller and more preferably at least about 45% smaller, and preferably superlative at least about 50% smaller, and still more preferably at least about 55% smaller than the dry stress resistance index with zero extension of The corresponding unmodified cellulosic fibers Typically, the DZST index of the modified fibers will be from about 35 to about 65% lower than the DZST index of the corresponding unmodified fibers In another aspect, the invention relates to modified cellulosic fibers having a wet tensile strength index with P952 zero extent (also referred to below as "WZST" for its acronym in English, wet zero span tensile) which is at least about 70% less, preferably at least 75% less than the resistance index to the zero tension wet tension of the corresponding unmodified cellulosic fibers. In still another aspect, the invention relates to modified cellulosic fibers exhibiting a ratio between the dry tensile strength index of zero extension and the zero tensile strength tensile strength index of between about 1.5 to about 3. , typically between about 1.7 and about 3, more typically between about 2 and about 3. In still another aspect, the present invention relates to a fibrous structure having a density of no more than about 0.4 g / cc, preferably from about 0.04 g / cc to about 0.4 g / cc, more preferably from about 0.05 to about 0.3 g / cc, wherein the fibrous structure comprises modified cellulosic fibers having a dry tensile strength index with zero extension which is at least about 15% lower than the dry tensile strength rating of e zero stress for the corresponding unmodified fibers, and in P952 where the fibrous structure has a modulus of flexion per unit of dry tension that is at least about 30%, preferably, at least about 35%, more preferably at least about 40% less than the modulus of bending per unit of dry tension of a fibrous structure prepared from the corresponding unmodified fibers. "For the purposes of this invention the density is measured on a dry fibrous structure and is calculated on the basis of the air drying weight of the structure divided by the thickness or gauge of the structure, the weight based on air drying and The caliber is measured in a conditioned room where the temperature is 73 ° F ± 4 ° F (22.8 ° C ± 2.2 ° C) and the relative humidity is 50% ± 10% .The caliber of the structure is measured according to to the TAPPI standard Test Method T 411 om-89, with the modification that the test foot of the gauge tester exerts a pressure of 0.2 psi Preferably, the fibrous structure comprises modified cellulosic fibers having an index of resistance to dry tension with zero extension that is about 20% smaller, more preferably at least about 25% smaller, still more preferably at least about 30% smaller and preferably superlative at least 35% less than the index resistance to dry tension with extension P952 zero of the corresponding unmodified cellulosic fibers. It is understood that the density range described herein refers to the density of the fibrous structure in its final form (including any binder, strength agents, additives, softeners, surface modifying agents, debonding agents and the like, as well as mechanical treatments. such as wet and dry creping, wet and dry microcontension and the like). In contrast, the tension index with zero extension, the dry tension index and the flexural modulus per unit of tension in dry are all measurements that are made in low density test sheets that are formed with the fibers (modified or unmodified) only, as described in the Test Methods section of this description. In relation to the fibrous structures, these structures will preferably comprise modified fibers which, when the modified fibers form a test sheet comprising only those fibers (ie without additives, etc.) have a dry stress resistance index ( also referred to as "DT" - dry tensile) which is at least as large as the dry tensile strength index of a test sheet made from the corresponding unmodified fibers. In the sense P952 herein used, the term "at least equal or so large" refers to the test sheet comprising the modified tests having a dry stress resistance index which is at least about 90% the index of dry stress strength of a similar test sheet (in terms of density, basis weight, etc.) prepared from unmodified fibers. It is even more preferred when the test sheet formed with the modified fibers has a dry tensile strength index which is higher than that of a test sheet made with the corresponding unmodified fibers, for example of at least about 5% and more preferably at least about 15% higher in terms of the dry stress resistance index. Applicants have discovered that a measurable reduction in dry tensile strength with zero extension of the fibers typically provides a fibrous structure exhibiting improved flexibility (measured in terms of a reduction in "modulus of flexion per unit of tension in dry") and smoothness. While a reduction in dry tension with zero extension does not always provide improvements in the flexibility of the structure, it is considered that this reduction is necessary to achieve more flexible structures according to the present invention, in particular, applicants have P952 discovered that an enzymatic treatment of the fibers provides fiber morphologies that result in greater flexibility. Although one does not wish to be limited by a theory, it is considered that this greater flexibility of the fiber is related to reduced values in the dry tension with zero extension. In addition, because the ability of the modified fibers to bind with others has not been significantly reduced, the tensile strength of the frames signed with these fibers is not adversely affected to the extent expected. Indeed, applicants have found that the wet tensile strength can effectively increase relative to the webs formed from corresponding untreated fibers. Therefore, in a preferred embodiment of this invention, in addition to the dry tension with zero extension and the flexural modulus that have already been mentioned above, the fibrous substrates that are prepared from these modified fibers will have a stress index property. dry approximately equal to or greater than the dry tension index of a weft made from corresponding untreated fibers.

A. Fibers to be Modified Fibers of diverse natural origin are applicable to the invention as long as they are P952 susceptible to enzymatic activity. The fibers digested with cellulose from soft wood (derived from coniferous trees), from hardwood (derived from deciduous trees, from cotton or cotton wool), may be used: fibers from esparto, bagasse, hemp, flax and other sources of Lignative and cellulose fibers may be used as raw materials of the invention The optimum source of starting fibers will depend on the particular end use contemplated.In general, wood pulps will be used.The useful wood pulps here include both sulfite pulps as sulphate, as well as mechanical, thermomechanical and chemo-thermo-mechanical pulps derived from virgin or recycled fibrous sources, all of which are known to those skilled in the paper industry.The preferred wood pulps include chemical pulps such as wood kraft pulp soft from the north, south and tropical (ie sulphate); kraft pulp from north, south and tropical woods, including eucalyptus (for example Eucalyptus grandis, Eucalyptus saligna, Eucalyptus urophilia, Eucalyptus globulus); sulphite pulps (including hardwood and soft wood from the north, south and tropical); and the like. Fully bleached, partially bleached and unbleached fibers are applicable. Frequently you want to use pulp P952 bleached to give a higher brightness and better acceptance by the customer. Also useful in this invention are fibers derived from recycled paper which can contain any of the above categories as well as other non-fibrous materials such as fillers and adhesives which are used to facilitate the production of original paper. The paper products formed from the modified fibers of the present invention may also contain non-cellulosic fibrous material, for example glass fibers and synthetic polymer fibers. Synthetic polymeric fibers useful herein include polyolefins, particularly polyethylenes, polypropylene and copolymers having at least one olefinic constituent. Other materials co or polyesters, nylons, copolymers thereof and combinations of any of the foregoing will be suitable as fibrous polymeric materials. Mixtures of the above fibers can also be used.

B. Enzymes It is recognized that during the reading of the applicant's specification, any of the known cellulase enzymes and / or cellulase enzyme preparations (among which other enzymes, for example hemicellulases, may be included for the present invention) may be used for the present invention. pectinases and amylases, etc.). Of the P952 cellulases, various endoglucanases and exoglucanases are known and can be used, individually or in combination, according to the invention. The enzymes must be active and stable to the conditions especially of pH and temperature, which prevail during the process of treatment of the pulp. Representative examples of suitable enzymes are those which are derived from microorganisms mentioned in Tables A and Table B.

Table A; Examples of cellulase-producing fungi Agaricus bisporus Ascoboulus furfuraceus Aspergillus aculeatus, A. fumigatus, A. niger, A. phoenicis, A. terreus and A. wentii Botryodiploida theobromae Chaetomium cellulolytlicum, C. globosum and C. thermophi1e Chrysosporium lignorum Cladosporium cladosporioides Coriolus versicolor Dichomitus squalens Eupenicillium avanicum Fomes famentarium Fusarium moniliforme, F solani and Fusarium spp. Humicola grísea and H. insolens P952 Hypocapra merdaria Irpex lacteus Lenzites trabea Mycellophtora thermophila Myriococcum albomyces Myrothecium verrucaria Neocallimastix frontalis Neurospora crassa Paecilomyces fusisporus and P. variotly Papulaspora thermophilia Pellicularia filamentosa Penicillium chrysogenum, P. citrioviride, P. funicolosum, P. notatum, P. pinophilium, P. variabile and P. verruculosum Phanerochaete chrysosporium Pestalotiopsis versicolor Phialophora malorum _ Phoma hibernica Physarum polycephalum Pleurotus ostreatus and P. sajor-caju Podospora deciplens Poyporus schweinitzil and P. versicolor Poria placenta Poronia punctata Pyricularia orzyzae Saccobolus Sclerotinia libertiana trunctatus Schizophyllum commune Sclerotium rolfsii Sordaria fimicola Scytalidium lignicola Sporotrichum pulverulentu and S. thermophile Stereum sanguinolentum Talaromyces emersonii Thermoascus aurantiacus Thrausiotheca clavata Thermophile torula Trichoderma koningii, T. pseudokoningii and T. reesei Trichurus spiralis Verticillium albo-atrum Volvariella volvacea Table B; Examples of cellulase producing bacteria -'- Cellulomonas flavigena, C. biazotea, C. cellasea, C. fimi, C. gelada, C. curtae, C. uda and C. turbata Bacillus brevis, B. firmus, B. lichenformis, B. pumilus, B. subtilis, B. polymyxa and B. cereus Serrata marcescens' Pseudomonas fluorescens var. cellulose '' Cellvibrio viridus, C. flavescens, C. ochraceus, C. fulvus, C. vulgaris and C. gilvus 'Cytophaga hutchinsonii, C. aurantiaca, C. rubra, C. tenulssima, C. winogradskii and C. krzemienlewskoe Herpetosiphon geysericolus Sprorcytophaga myxococcoides Streptomyces flavogriseus' Thermoactinomyces sp. 'Thermomonospora curvata 1 Bacteria with a premium sign are not validly classified.

The fungi and bacteria listed above are only examples. Currently the microorganisms of the strain Humicola (for example, E. insolens) and Trichoderma (for example, T _; _ reesei) are considered particularly suitable for the production of the enzymes useful herein, but the scope of the invention is not limited to the use of the named microorganisms. It is quite possible that other enzyme producing microorganisms suitable for the present invention already exist or that they are developed using the mutation and selection or genetic manipulation method. It is also likely that the enzyme-producing abilities of an existing microorganism can be further enhanced through genetic engineering.

P952 _ _ _ - - _ A preferred cellulase enzyme useful herein is Celluclast®, an enzyme sold by Enzyme Process Division, Bioindustrial Group, Novo Nordisk A / S, Bagsvaerd, Denmark. Celluclast® is derived from the Trichoderma reesei fungus. Celluclast® 1.5 L is a liquid cellulase preparation that has an activity of 1500 NCU / g. The activity is determined based on Units of Cellulasa Novo (or "NCU" for its acronym in English Novo Cellulase Units). An NCU is the amount of enzyme that degrades carboxymethylcellulose in reducing carbohydrates with a reducing power corresponding to lxl0 ~ 6 moles of glucose per minute, under standard conditions of 40 ° C, pH 4.8 and with a reaction time of 20 minutes. A more detailed description of the activity measurement is delineated in the Novo Nordisk Analytical Method No. AF 187.2 (available from Novo Nordisk). Another preparation of the preferred cellulase useful herein is Celluzyme® sold by Enzyme Process Division, bioindustrial Group, Novo Nordisk A / S, Bagsvaerd, Denmark. Celluzyme® 0.7 T is a granular cellulase preparation that has enzymatic activities of approximately 700 Cellulase Viscosity Units / g and is derived from Humicola insolens. The activity is determined based on the Viscosity Units of Cellulase (abbreviated by its acronym in English CEVU-Cellulase P952 Viscosity Units) under conditions specified in World Patent Publication No. WO 91/17243, dated November 14, 1991 d3 by Rasmussen et al. (whose disclosure is incorporated herein by reference) and the Novo Nordisk Analytical Method AF No. 253 (available from Novo Nordisk). Yet another preferred cellulase preparation useful herein is Pergolase® sold by Ciba, Greensboro, NC. Pergolase® A40 is a liquid cellulase preparation having an active protein content of approximately 140 g / L as measured by the Lowrey Method and derived from Trichoderma reesei. Pergolase® A40 is a mixture of endo and exocellulases, xylanases and mannases. Yet another preferred cellulase chosen for economic reasons is a product sold under the Carezyme® brand of Novo Nordisk A / S. Carezyme® 5.0 L is a liquid cellulase preparation that has an enzyme activity of approximately 5,000 CEVU / g. The activity is determined based on the Cellulase Viscosity Units (CEVU) under specified conditions delineated in World Patent Publication No. WO 91/17243, published November 14, 1991 by Rasmussen et al. and the Novo Nordisk Analytical Method No. AF 253. Carezyme® is composed primarily of the endoglucanase family, EG V (molecular weight -43,000 kD) or homologs thereof, derived from Humicola insolens as P952 describes in WO 91/17243. Variants of the endoglucanase family 45 are found in Carezyme® and are described in World Patent Publication No. WO 94/07998 published April 14, 1994 by M. Schulein, et al. (the disclosure is incorporated herein by reference) and is considered useful for modifying the fibers according to the present invention. In the sense used herein an enzyme of the "family 45" is an enzyme described in Henrissat, B. et al., Biochem. L., Vol. 293, p. 781-788 (1993), the exhibition of which is incorporated herein by reference. It is generally accepted that the endoglucanase found in Carezyme® does not degrade highly crystalline cellulose, but degrades amorphous cellulose mainly to cellobiose, cellotriose and celotetraose. Celluclast®, Celluzyme® and Pergolase® on the other hand are combinations of endo and exoglucanases and / or hemicellulases. As shown in the following examples, acceptable reductions in dry stress are found with zero extension with all enzyme preparations, suggesting that a wide range of exo / endo cellulitic activities can be used to reduce dry stress of zero extension according to the present invention. It will be recognized that the addition of enzymes to the fibers can be done by an isolated enzyme preparation. Alternatively, the microorganisms that P952 contain or produce cellulose degrading enzymes or cellulase can be combined directly with the fibers to be modified.

C__ Preparation of Modified Fibers and_ Corresponding Fibrous Structures i. Modified Fibers In general, the enzymatic treatment of the fibers to obtain the modified fibers of the invention is achieved by adding the cellulase-containing enzyme preparation to an aqueous fiber slurry, stirring the mixture for a sufficient period to allow the enzyme to act to modify the morphology of fibers. After mixing the fibers and the enzyme preparation, the mixture preferably, although not necessarily, is combined with a debonder or chemical softener (collectively referred to as "debonding agent") which is considered to preserve the modifications of fiber morphology resulting from enzymatic action. In order to obtain fibrous structures having the properties suitable for the desired end uses, such as for example paper towels, facial tissues and toilet paper and the like, it is preferred that the length of the fiber is not reduced to a considerable degree during the process of P952 modification. The skilled artisan will recognize that the treatment conditions of the fiber may vary depending on, for example the nature of the fiber to be treated, the enzyme or enzymes used and the like. In this way, the following description may be modified accordingly, depending on the specific materials to be used. In general, the disintegrated pulp of the desired fibers is diluted with water to make a fibrous paste before combining it with the enzyme. The pulp preferably has a pulp consistency of at least about 0.5%, more preferably at least about 1%, still more preferably at least about 2%. In the sense used here "pulp consistency" refers to the mass of the dry fibers divided by the total mass of the pulp. Preferably, the pulp consistency will be no greater than about 40% to facilitate the mixing of the enzyme and the pulp. Of course, pulps of greater consistency may be used to practice this invention. In general, a separate enzymatic solution is also prepared before the combination with the fibers. The concentration of the enzyme solution can vary widely and will be determined by the relative activity of P952 the enzymes used, the fibers to be treated, the degree of stress reduction in dry extension of zero, the time and temperature of reaction and other related conditions. The pH of the fibrous pulp / enzyme mixture is adjusted, if necessary, to the appropriate level of the enzyme used. The pH adjustment, if necessary, may occur before, during or after the combination of the enzyme with the fibrous pulp. The pH of the resulting mixture can be controlled using several buffers or several acids or bases. In a particularly preferred embodiment using Carezyme® and / or Celluzyme®, a pH of between about 5 and about 9 is preferred. For other enzymes, such as for example Celluclast® and Pergolase®, a pH of about 4 to 6 was preferred. After combining the fibrous pulp, the enzyme and any optional pH adjustment, the mixture is preferably reacted with stirring, for a period sufficient to reduce the intrinsic strength of the fiber according to the present invention. The temperature of the mixture is preferably controlled between about 80 and 160 ° F, more preferably between 100 and 140 ° F, and still more preferably between about 120 and 140 ° F. Normally the mixture will react for a period of at least about P952 0.25 hours, preferably at least about 0.5 hours and most preferably at least about 1 hour. Typically the mixture will react for a period not greater than 4 hours, and preferably not more than about 3 hours. Once again, the skilled artisan will recognize that different reaction conditions, concentrations, etc. may be required. to achieve the desired modification of the fiber, depending on the fibers to be treated, the enzyme or enzymes used, the reaction temperature, the reaction time, the degree of reduction of the dry stress of zero extension desired, the type of agitation employed and the like. The determination of how the variables can be adjusted is within the skill level of the expert. Applicants have found that while the intrafiber beneficial weakening in the wet fibers can be measured after the enzymatic reaction (for example wet tensile strength with zero extension, reduced) a certain amount of the reduced strength of the fiber is lost. during the drying thereof (ie resistance to dry tension with zero extension). (See Tables 1 to 9 below.) However, by adding a debonding agent to the enzymatically modified wet fibers, an additional reduction in dry stress can be achieved with extension P952 zero in relation to the fibers treated with the enzyme alone. Applicants have found that while certain debonding agents do not provide a significant reduction in the DZST of the fibers, they do provide fibrous structures of improved flexibility without having a detrimental impact on the dry tensile strength of the structures. Thus, in a particularly preferred embodiment, after the required reaction of the pulp slurry and the enzyme solution, a debonding agent is added to the mixture and allowed to react, typically for at least 30 seconds and preferably for at least 5 minutes and more preferably for at least 30 minutes to 60 minutes approximately, with constant agitation. It will be recognized that the debonding agent can be added to the fibers before or during the combination with the enzyme, as long as the debonding agent does not interfere with the activity of the enzyme used. Any debonding agent (or softener) known in the art may be used in this preferred embodiment. Examples of useful agents are tertiary amines and derivatives thereof; amine oxides; quaternary amines; silicone-based compounds, saturated and unsaturated fatty acids and salts of fatty acids; alkenyl succinic anhydrides; alkenylsuccinic acids and P952 the corresponding alkenyl succinate salts; mono-, di- and tri-esters of sorbitan, including, but not limited to, sorbitan esters of stearate, palmitate, oleate, myristate and behenate, and particularly debonding agents such as clay and silicate fillers. Useful debonding agents are described in, for example, U.S. Patent No. 3,395,708 (issued August 6, 1968 to Hervey et al.), U.S. Patent No. 3,554,862 (issued January 12, 1971 to Hervey et al.), U.S. Patent No. 3,554,863 (issued January 12, 1971 to Hervey et al.), U.S. Patent No. 3,775,220 (issued August 28, 1973 to Freimark et al. al.), U.S. Patent No. 3,844,880 (issued October 29, 1974 to Meisel et al.), U.S. Patent No. 3,916,058 (issued October 28, 1975 to Vossos et al.), U.S. Patent No. 4,028,172 (granted June 7, 1977 to Mazzarella et al.), U.S. Patent No. 4,069,159 (issued January 17, 1978 to Hayek), U.S. Patent No. 4,144,122 (issued March 13, 1979 to Emanuelsson et al.), United States Patent No. 4,158,594 (issued June 19, 1979 to Becker et al.), U.S. Patent No. 4,255,294 (issued March 10, 1981 to Rudy et al.), U.S. Patent No. 4,314,001 (issued 2 P952 of February 1982), U.S. Patent No. 4,377,543 (issued March 22, 1983 to Strohbeen et al.), U.S. Patent No. 4,432,833 (issued February 21, 1984 to Bréese et al. ), U.S. Patent No. 4,776,965 (issued October 11, 1988 to Nuesslein et al.), U.S. Patent No. 4,795,530 (issued January 3, 1989 to Soerens et al.), U.S. Pat. United States No. 4,937,008 (issued June 26, 1990 to Yamamura et al.), United States Patent No. 4,950,545 (issued August 21, 1990 to Walter et al.), United States Patent No. 5,026,489 (issued June 25, 1991 to Snow et al.), U.S. Patent No. 5,051,196 (issued September 24, 1991 to Blumenkopf et al.), U.S. Patent No. 5,529,665 (issued on June 25, 1996 to Kaun et al.), U.S. Patent No. 5,552,020 (issued September 3, 1996 to Smith et al.), Patent No. 5,558,873 (issued September 24, 1996 to Funk et al.), United States Patent No. 5,580,566 (issued December 3, 1996 to Syverson et al.), PCT Publications Nos. WO 97/01470 (published by Kryzysik on February 6, 1997), WO 97/04171 (published by W. Schroeder et al. on February 6, 1997) and WO 96/04424 (published by Vinson on February 15, 1996), the exhibition of which is incorporated P952 here for reference. Preferred debonding agents which are used herein are cationic materials such as quaternary ammonium compounds, imidazolinium compounds and other compounds with aliphatic, saturated or unsaturated carbon chains. The carbon chains can be unsubstituted or one or more of the chains can be substituted, for example with hydroxyl groups. Non-limiting examples of quaternary ammonium cleavage agents useful herein include hexamethonium bromide, tetraethylammonium bromide, lauryl trimethylammonium chloride and dimethyl ammonium methyl sulfate dihydrogenated bait. Other preferred debonding agents which are used here to improve the flexibility of the fibrous structure are the alkenylsuccinic acids and their corresponding alkenyl succinate salts. Non-limiting examples of the alkenyl succinic acid compounds are n-octadecenylsuccinic and n-dodecenylsuccinic acid and their corresponding succinate salts. The ion-quenching of the alkenyl succinates with multivalent metal salts or cationic debonding agents is particularly useful in a further reduction of the flexural modulus per unit of dry tension of the fibrous structure. Although it is not desired to be limited by any theory, it is believed that the debonding agent maintains the "damage" to the fiber that P952 caused the enzymatic attack. That is, after the enzyme alters the morphology of the fiber, the debonding agent prevents "repair" of the fiber, at least to some degree, which would otherwise take place during drying. This in turn increases the flexibility of the resulting fibrous web while retaining or improving fiber-to-fiber bonding. In this regard, other materials can perform the same function to improve dry stress reduction with zero extension and flexibility. The debonding agent will preferably be added at a level of at least about 0.1%, preferably at least about 0.2%, more preferably at least about 0.3% based on the dry fiber. Typically, the debonding agent will be added at a level between about 0.1 to about 6%, more typically between about 0.2 and about 3%, of active material based on the dry fiber. The percentages provided for the amount of debonding agent are given as an amount added to the fiber, and not as a quantity actually retained by the fiber. The applicants have found that the degree of agitation during the treatment of the fibers according to the invention is also an important variable that affects the degree of dry stress reduction with P952 zero extension. While agitation is not necessarily necessary according to the invention, agitation generally increases the reduction of dry tension of zero extension, the other conditions being the same. Indeed, as shown in Example 1 and in particular in samples 10 and 1P, when the treatment of a paste with 10 to 13.3% consistency is carried out using a high intensity laboratory mixer, tension fibers are provided in dry with zero extension less than those obtained using a mixture with a low intensity arrow (Sample 1E) of a paste of smaller consistency, the rest of the variables being the same. The high intensity laboratory mixer used in Example 1 is generally recognized to represent the mixing intensity found in medium consistency pumps and high shear mixers that are used in industrial practice. The skilled artisan will recognize that the parameters that affect the degree of agitation include, but are not limited to, consistency of the mixture, speed of mixing and size and geometry of the reaction vessel and the mixing device. ii. Fibrous Structures After enzymatic treatment and P952 treatment with the preferred debonder, the modified fibers form a fibrous structure using any known method for making a weft. These fibrous structures can comprise any conventional sheet or web having a basis weight, a gauge (thickness), absorbency and strength characteristics suitable for the intended end use. A fibrous structure of the present invention can generally be defined as a bonded fibrous product in which the enzyme-modified fibers are randomly distributed as in "air laying" processes or in certain "wet laying" processes or with a degree of orientation, as in certain processes of "wet laying" or "carded". The fibers may optionally be bonded together with a polymeric binder resin. Conventionally, the fibrous structures of this invention are made with wet laying processes. In these processes, a web is formed into an aqueous pulp comprising whole or partially modified fibers with enzymes of the present invention, depositing this pulp on a foraminous surface, for example a Fourdrinier mesh, and then removing the water from the pulp. paper, for example by gravity, by vacuum assisted drying and / or P952 by evaporation, with or without pressing, in order to form a fibrous structure of the desired fiber consistency. In many cases, the papermaking apparatus is adapted for the rearrangement of the fibers in the pulp as the drainage is carried out, in order to form wefts of a strength, tactile perception, volume, appearance, absorbency. , etc. which are particularly desirable. The pulp used to form the preferred fibrous structures comprises essentially an aqueous slurry of modified fibers of the present invention and optionally can contain a wide range of chemical agents, for example wet strength resins, surfactants, pH controlling agents, additives of softness, unlocking agents and the like. Various processes for papermaking have been developed and utilize a papermaking apparatus that forms wefts with particularly useful or desirable fiber configurations. These configurations can serve to impart characteristics to the paper web such as improved volume, absorbency and strength. One of these processes uses a printing fabric in the papermaking process that serves to impart a knurling pattern to areas of high density and low density to the paper web. A process of P952 this type and the papermaking apparatus for carrying out the process are described in more detail in U.S. Patent 3,301,746 (Sanford et. Al.), Issued January 31, 1967, which is incorporated herein by reference. as reference. Another papermaking process that is carried out with a special papermaking apparatus is that which provides a paper web having a continuous and distinctive network region formed by a plurality of "domes" scattered throughout the region of the network on the substrate. These domes are formed by the compression of an embryonic web that is formed during the papermaking process and is carried to a foraminous deflection member having a network surface with a pattern, formed by a plurality of isolated and discrete deflection conduits in the web. surface of the deflection member. Such a process and the apparatus for carrying out the process are described in greater detail in U.S. Patent 4,529,480 (Trokhan), issued July 16, 1985; U.S. Patent 4,637,859 (Trokhan) , granted on January 20, 1987, and United States Patent 5,073,235 (Trokhan), issued December 17, 1991, all of which are incorporated herein by reference.Another type of papermaking process and apparatus to carry out the same and that is considered appropriate for P952 preparation of paper substrates of composite layers is described in United States Patent 3,994,771 (Morgan et al.), Issued November 30, 1976, which is incorporated by reference. Still another papermaking process that can utilize the fibers of the invention is that which provides a paper web having a continuous network region with a high basis weight surrounding several discrete regions with a low basis weight. The wefts are formed using a forming band having zones of different flow resistances disposed in a particular proportion of flow resistances. In general, the basis weight of a specific region is inversely proportional to the flow resistance of the corresponding zone of the forming band. Such a process and apparatus for carrying out the process are described in greater detail in U.S. Patent 5,245,025 (Trokhan et al.), Issued September 14, 1993; U.S. Patent 5,503,715 (Trokhan et al.), Issued April 2, 1996; and U.S. Patent 5,534,326 (Trokhan et al.), issued July 9, 1996; whose exhibitions are incorporated here as a reference. Yet another process for making paper that can use the fibers of the invention is that which provides a layer of paper in layers having a P952 smooth and velvety surface. The weft is formed using relatively short fibers, wherein the upper surface of the weft is processed so that the interfiber links break to provide free fiber ends that improve tactile perception. A process of this type is described in detail in U.S. Patent No. 4,300,984 (Carstens), issued in November 17, 1981, whose exposition is incorporated here as a reference. Another papermaking process employs a through-drying fabric which has raised print knurls above the plane of the fabric. These impressions create projections on the through-drying sheet and provide the sheet with elasticity in the direction transverse to the machine. A process of this type is described in European Patent Publication No. 677,612A2, published on October 18, 1995 by G. Wendt et al., Which is incorporated herein by reference. Preferred fibrous structures can form a layer of two or more layers that can be laminated together. The lamination is carried out in combination with an etching process to form a plurality of protrusions in the laminated product, and is. described in greater detail in U.S. Patent 3,414,459 (Wells), issued December 3, 1968, which is P952 incorporates here as a reference. These paper substrates preferably have a basis weight of between about 10 g / m ^ and about 65 g / m ^ and a density of about 0.6 g / cc or less. More preferably, the basis weight will be approximately 40 g /? X? or less and the density will be approximately 0.3 g / cc or less. More preferably, the density will be between about 0.04 g / cc and about 0.2 g / cc. Unless otherwise specified, all quantities and weights relative to the substrates of the paper web are given on a dry weight basis.) In addition to the modified fibers of the present invention, the pulp used to make the structures fibrous can have other components or materials that are added to it that are part of the technique or that will later be part of the technique. The type of additives that is desired will depend on the particular end use contemplated for the tissue sheet. For example, in products such as toilet paper, paper towels, facial tissues, baby wipes and other similar products the high wet strength attribute is desired. Therefore, it is usually desired to add to the pulp chemical substances known in the art as "wet strength" resins. A general analysis of the types of resins of P952 wet strength used in the field of paper can be found in the monograph TAPPI series No. 29, Resistance in Moisture in Paper and Cardboard, Technical Association for the Pulp and Paper Industry (New York, 1965). The most useful wet strength resins in general have a cationic character. For the permanent generation of wet strength the polyamide-epichlorohydrin resins are cationic wet strength resins which have been found particularly useful. Some types of these resins are described in U.S. Patent No. 3,700,623 (Keim), issued October 24, 1972 and U.S. Patent No. 3,772,076 (Keim), issued November 13, 1973, which they are incorporated here as a reference. A commercial source of a useful polyamide-epichlorohydrin resin is Hercules, Inc. of Wilmington, Delaware, which markets these resins under the trademark Kymene® 557H. Polyacrylamide resins have also been found useful as wet strength resins. These resins are described in U.S. Patent Nos. 3,556,932 (Coscia et al), issued January 19, 1971 and 3,556,933 (Williams et al), issued January 19, 1971, which are incorporated herein by reference . A commercial source of polyacrylamide resins is American Cyanamid Co. from Stamford, P952 Connecticut, which markets one of these resins under the trademark Parez® 631 NC. Still other water-soluble cationic resins which have utility as wet strength resins are the resins of urea formaldehyde and melamine formaldehyde. The most common functional groups of these polyfunctional resins are nitrogen-containing groups, for example amino groups and methylol groups attached to nitrogen. Polyethyleneimine type resins also have utility in this invention.

In addition, temporary wet strength resins such as Caldas 10 (manufactured by Japan Carlit), CoBond 1000 (manufactured by National Starch and Chemical Company) and Parez 750 (manufactured by American Cyanamide Co.) can be used in the invention. It is to be understood that the addition of chemical compounds such as, for example, wet strength and temporary wet strength resins mentioned above to paper pulp is optional and is not necessary for the practice of the invention. In addition to the wet strength additives it may be desirable to include certain dry strength and lint control additives in the papermaking fibers known in the art. In this regard, the starch binders have proved particularly suitable. In addition to reducing lint formation in structures P952 fibrous, low levels of starch binders also impart a modest improvement in dry tensile strength without imparting rigidity that could originate from the addition of high levels of starch. Typically, the starch binder is included in such an amount that it is retained at a level of from about 0.01 to about 2%, preferably between about 0.1 and about 1% by weight of the paper substrate. In general, the starch binders suitable for these fibrous structures are characterized by water solubility and hydrophilicity. While not intended to limit the scope of suitable starch binders, representative starch materials include corn starch and potato starch, and the particularly preferred one is waxy corn starch known industrially as amioca starch. Amioca starch differs from common corn starch because it consists entirely of amylopectin, while common corn starch contains both amylopectin and amylose. Several unique characteristics of amioca starch are described in "Amioca - The Starch From Waxy Corn", H. H. Schopmeyer, Food Industries, December 1945, pp. 106-108 (Vol. Pp. 1476-1478). The starch binder may be in granular or dispersed form, the granulated form is the P952 especially preferred. The starch binder is preferably sufficiently cooked to induce swelling of the granules. More preferably, the starch granules swell, for example by cooking, to a point just before the starch granule is dispersed. These high-grade starch granules are referred to herein as "fully cooked". The dispersion conditions in general may vary depending on the size of the starch granules, the degree of crystallinity of the granules and the amount of amylose present. Fully boiled amioca starch, for example, can be prepared by heating an aqueous solution of a consistency of about 4% starch granules to about 190 ° F (about 88 ° C) for between about 30 and about 40 minutes. Other exemplary starch binders that can be used include modified cationic starches such as those modified to have nitrogen-containing groups, include amino groups and methylol groups attached to nitrogen, available from the National Starch and Chemical Company, (Bridgewater, New Jersey), which previously they had been used as pulp additives in order to increase wet and / or dry strength. The use of other binders such as latex, alcohol P952 polyvinyl, thermoplastic binder fibers and the like may also be useful in the formation of fibrous structures of the present invention.

III. Paper Products The fibrous substrates of this invention are particularly adapted for paper products or paper product components that are to be discarded after use. Accordingly, it is to be understood that the present invention is applied to a variety of paper products including, but not limited to, disposable absorbent paper products such as those used in the home, for the body or for other cleaning applications. Exemplary paper products therefore include tissue paper encompassing toilet paper and facial tissues, paper towels and core materials for absorbent articles such as feminine hygiene items including sanitary napkins, sanitary guards and tampons, diapers, incontinence articles in adults and the like.

IV. Test Methods Section ^ Sample Preparation The following description__ refers to how P952 prepare the. fibrous structures from both modified (i.e. treated according to the present invention) and unmodified (i.e., untreated or control) fibers. These structures are then subjected to physical tests (ie tension with zero extension, dry tension and flexural modulus per unit of dry tension) that are described in the next Section.

Low Density Test Sheets Low density test sheets are made essentially according to the TAPPI T205 standard with the following modifications that are considered to accurately reflect the tissue manufacturing process. (1) tap water is used without any pH adjustment; (2) The embryonic web is formed in a 12 inch by 12 inch test sheet forming apparatus over a monofilament polyester mesh supplied by Appelton Wire Co. , Appelton, Wl with the following specifications: Size: 13.5 inches x 13.5 inches Warp count at 84 1.5 fibers / inch machine direction: P952 Warp count at 76 ± 3.0 fibers / inch cross direction: Warp size / type: 0.17 mm / 9FU Thread size 0.17 mm / WP-110 cross / type: Caliber: 0.016 ± 0.0005 inch Air permeability: 720 ± 25 cubic feet / minute (3) The embryonic web is transferred by vacuum from the monofilament polyester mesh to a monofilament polyester paper web supplied by Appelton Wire Co. , Appelton, Wl and drained by vacuum suction and not by pressing; Fabric specifications: Size: 16 inches x 14 inches Warp count at 36 ± 1 fiber / inch machine direction: Warp count at 30 ± 3 fibers / inch cross direction: Warp size / type: 0.40 millimeters / WP-87-12A-W Yarn size 0.40 millimeters / WP-801-12A-W transversal / type: Caliber: 0.0270 ± 0.001 inch Air permeability: 397 ± 25 cubic feet / minute P952 Leaf side that is onoplanar Details of transfer and drainage: the embryonic web and the paper mesh are placed on top of the fabric so that the embryonic web comes into contact with the fabric. The triple layer (mesh, weft, cloth with the side of the fabric facing down) is then passed longitudinally through a 13 inch by 1/16 inch wide vacuum slot with a 90 degree flare adjusted to a peak meter reading of approximately a vacuum of 4.0 inches of mercury. The speed at which the triple layer passes through the vacuum slot should be uniform at a speed of 16 + 5 inches / second. The vacuum then decreases to achieve a peak meter reading of approximately 9 inches of vacuum mercury and the triple layer is passed longitudinally in the same vacuum slot at the same rate of 16 ± 5 inches / second twice more . Note that the peak meter reading is the amount of vacuum measured when the triple layer passes through the slot. The weft is carefully removed from the mesh to ensure that the fibers do not stick to the mesh. (4) The sheet is then dried in a dryer P952 rotating drum with a drying felt, passing the weft and the fabric between the felt and the drum, the fabric being against the surface of the drum and again with a second step where the weft is against the surface of the drum.

Specifications of the dryer polishing finishing cylinder: stainless steel with internal heating with steam, mounted horizontally. External dimensions: 17 inches long x 13 inches in diameter. Temperature: 230 ± 5 degrees Fahrenheit. Rotation speed 0.90 ± 0.05 revolutions / minute. Felt dryer: Endless, circumference of 80 inches by 16 inches wide, No. 11614, style X225, all wool. Noble and Wood Lab Machine Company, Hoosick Falls, NY. Felt tension As low and uniform as possible without slip between the felt and the dryer drum and uniform tracking. (5i The resulting test sheet is 12 P952 inches x 12 inches with a white base weight resulting in 16.5 ± 1 pound for 3,000 feet ^ and a white density of 0.15 ± 0.06 g / cc, unless otherwise noted. The 12-inch X 12-inch dry test sheet of the fibers is conditioned before testing for a minimum of 2 hours in a conditioned room where the temperature is 73 ° F ± 4 ° F (22.8 ° C ± 2.2 ° C) and_ the relative humidity is 50% ± 10%.

V ^ Test Methods Section ^ _ Physical Tests It will be recognized that the test methods described in this section require the production of test sheets following the specific procedure described above. When a specific product is in a form that includes chemical additives or when the fibrous structure is subjected to mechanical manipulation to generate the product, it must be recognized that the determination of whether the product is within the scope of the present invention is made by forming test sheets according to the present description and measuring the physical properties of those test sheets, not measuring the physical properties of the product itself. That is, the fibers used to build the product are used to make test sheets as described above, no additives or mechanical manipulation should be applied apart from the aforementioned. However, as already stated, the density measurements are made in the final products that have been mechanically treated, and that include the desired chemical additives, etc.

A. Dry Stress Resistance Index This test is performed in strips of one inch by 6 inches (approximately 2.5 cm X 15.2 cm) of paper according to the TAPPI standard T220 om-88 and T494 om-88 in a conditioned room where the temperature is 73 ° F ± 4 ° ~ F (approximately 28 ° C ± 2.2 ° C) and the relative humidity is 50% ± 10%. An electronic voltage tester (Intellect II-STD, Thwing Albert Corp., Philadelphia, PA.) Is used and operated at a transverse speed of 4 inches per minute. (approximately 10 cm per minute) and to a start gauge length of 4 inches (approximately 10 cm).

A minimum of n = 8 tests are performed on each paper sample. The resulting tensile strength values are recorded in g / inches and are divided by the average base weight of the sample and converted to achieve the corresponding index values at the tension in N * m / g.

B. Zero Extension Tension Resistance Index The test is performed in strips of 1 inch by 4 P952 inches (approximately 2.5 cm X 10.2 cm) of paper (including paper from test sheets as described above, as well as other sheets of paper) in a conditioned room where the temperature is 73 ° F ± 4 ° F (approximately 28 ° C ± 2.2 ° C) and the relative humidity is 50% ± 10%. A combination of electronic / compressed air tester (Troubleshooter, Pulmac Instruments International, Montpelier, VT) is used and operates at a 100 psi air supply pressure. The clamps of the tester are 15 mm wide and are loaded with a clamp pressure of 80 psi. The pressure required to break the strip width of 15 mm with an initial clamp gap of zero is recorded in units of psi. (If the pressure reading is below 9 psi, two sheets of the test material are combined and tested for measurements within the capabilities of the instrument.) The pressure at break minus the zero pressure on the instrument it is divided by the average base weight of the sample and converted to obtain the value of dry tensile strength index with zero extension in units of N * m / g. A minimum of n = 8 tests are performed on each pulp sample.

C. Wet Tension Resistance Index with Zero Extension This test is carried out in a similar way to the Dry Tension Resistance procedure with Zero Extension with the following modifications: The dry strip of 1 inch X 4 inches of paper is inserted between two Wet Sample Inserts supplied with the instrument containing three notch cuts. The paper strip is moistened by the central notch cut with a flask filled with distilled water at 73 ° F ± 4 ° F (approximately 28 ° C ± 2.2 ° C), rubbing a small amount of water very close to the notch and allowing it to drain into the central notch (avoiding making too much pressure spray and touch the sample with the tip of the peephole. The sample and the inserts are then placed on the head of the unit with the notches aligned with the teeth of the clamp and the test run as described. The pressure of the rupture minus the zero pressure of the instrument is divided by the average base weight of the sample and converted to obtain the value of the wet tensile strength index with zero extension in units of N * m / g. A minimum of n = 8 tests are performed on each pulp sample.

P952 D. Bending Stiffness (Cantilever Bending Method) This test is performed on paper strips of 1 inch by 6 inches (approximately 2.5 cm X 15.2 cm) according to the following description in a conditioned room where the temperature it is 73 ° F ± 4 ° F (approximately 28 ° C ± 2.2 ° C) and the relative humidity is 50% ± 10% for a minimum of 2 hours before the test. The Cantilever Bending Tester, as described in ASTM D 1388 (Model 5010, Instrument Marketing Services, Fairfield, NJ.) Can be used and operated at a ramp angle of 41.5 ± 0.5 ° and a sample slip velocity of 0.5 ± 0.2 inches per second (approximately 1.3 ± 0.5 cm per second). A minimum of n = 16 tests are performed on each paper sample of n = 8 sample strips. i. Sample Preparation From a test sheet, four 1-inch-wide strips of the sample and 6.0 ± 0.1 inches in length in the "MD" direction are carefully cut. From a second test sheet in the same sample set, four 1-inch-wide strips of the sample are carefully cut by 6.0 ± 0.1 inches in length in the "CD" direction. It is important that the cut be exactly perpendicular in the longitudinal dimension of the strip. The P952 strip should also be free of wrinkles or excessive mechanical manipulation that might have impact on flexibility. The direction in one of the ends is marked very lightly, maintaining the same surface of the sample upwards in all the strips. Subsequently, the strips will be flipped for testing, therefore it is important that a surface of the strip is clearly identified, however, there is no difference in the surface of the sample being designated as the top surface. ii. Operation The tester should be placed on a bench or table that is relatively free of vibration, excessive heat and blasts of air. The platform is adjusted horizontally as indicated by the leveling bubble and it is verified that the bend angle is at 41.5 ± 0.5 °. Remove the slide bar of the sample from the top of the tester platform _ flexion bending tester. Place one of the sample strips on the horizontal platform, taking care to align the strip parallel to the mobile slide. Align the sample exactly level with the vertical edge of the tester, where the angular ramp is attached or where it is engraved to the zero line mark of the P952 tester. Carefully place the sample slider on top of the sample strip in the tester. The sample slider should be placed carefully so that the strip does not wrinkle or move from its initial position. Move the sample and the sample slider at a rate of approximately 0.5 ± 0.2 inches per second (approximately 1.3 ± 0.5 cm per second) to the end of the tester to which the ramp is attached. This can be achieved with either a manual or automatic tester. Make sure there is no slip between the sample and the mobile slider. As the sample slide bar and sample strip project over the edge of the tester, the sample strip will begin to bend or flex downward. Stop moving the sample slide bar at the moment when the leading edge of the sample strip falls off the level with the edge of the ramp. Read and record the length of the section that hangs on the linear scale with an accuracy of 0.5 millimeters. Record the distance that the sample slider bar has moved, in centimeters, as the length of the hanging section. The sequence of the test is carried out on the face and back part of each sample strip for a total of two readings per sample. This in turn gives a total of sixteen readings for each paper sample that P952 comprises 8 MD readings and 8 CD readings. iii. Calculations The average length that hangs is determined by averaging 16 results obtained in the paper sample. Average hanging length = sum of 16 results 16 Bending length is calculated by dividing the average hanging length by two. Bending length = general length sue hangs 2 Flex Stiffness Calculate the stiffness of flexion (G): G = 0.1629 x W x C3 where W is the base weight of the sample in pounds / 3000 square feet and C is the length of flexion in centimeters. The results expressed in milligrams force * cm, the constant 0.1629 is used to compete the basis weight of English units to metric units.

Bending module In general, the rigidity of bending (rigidity) depends to a great extent on the thickness of the sample (caliber). In order to compare samples of unequal caliber, the P952 flex module is used as the means of comparison. Q = G I where G is the rigidity of the "sample flexion (top) and I is the moment of inertia." Using the standard techniques of plate theory, the above equation can be manipulated to give a more useful relation: Q = = 732 x G 1 / 12A t Where Q is the modulus of flexion in Kg-force / cm, G is the Bending Stiffness (above in mg-force * cm) t is the thickness of the sample (caliber) in thousandths of an inch (1/1000 inches) and 732 is a conversion constant.

Relationship of the modulus of flexion / tension in dry The rigidity of the leaf is also related in a dependent manner with the resistance to the dry tension of the fibrous structure. Since it is desired to produce samples with a lower stiffness without a corresponding decrease in the strength of the sheet, the ratio of the flexural modulus per dry unit of tension is reported. This allows samples of unequal tensile strengths and unequal calibers to be compared, where P952 - "-has a greater softness potential when the ratio is lower." The relationship is shown below: M = 0 * 1000 dry tension where M is the ratio of Flexion / Dry Stress Module in units of 1 / cm , Q is the Bending Module in Kg-force / cm and the dry tension is in grams-force units.

SAW. Examples A. Starting fibers North Softwood Kraft Pulp (NSK): Standard Reference Material 8495, Bleached Kraft Pulp of Softwoods of the North (US Department of Commerce, National Institute of Standards and Technology, Gaithersburg, MD 20899 ), in dry form. Eucalyptus Pulp (Euc): Standard Reference Material 8496 Hardwood Kraft Bleached Pulp Eucalyptus (Department of Commerce of the United States, National Institute of Standards and Technology, Gaithersburg, MD 20899), in the form of a dry envelope. North Hardwood Sulfite Pulp (NHS): Acid bisulfite pulp of hardwood, mixed, bleached, P952 without drying (The Procter and Gamble Paper Products Company of Mehoopany, PA). Bleached totally chlorine-free by EOP bleaching to a color of 93.7, - 0.5, 6.4 Hunter L, a, b. Southern Softwood Kraft Pulp (SSK): Buckeye Cellulose Corporation Memphis, TN type FF (Foley Fluff) fully bleached pulp comprised of Slash and Loblolly pine in the form of a flat envelope.

B ^ _ Pulp Disintegration After determining the consistency of the pulp, the previous pulps were divided into multiple batches of approximately 30 grams of pure dry fiber each and diluted to 2,000 mL with distilled water at room temperature. The fibers and water were disintegrated by 50,000 revolutions in a TAPPI Standard Pulp Disintegrator (Model D-III, Testing Machines Incorporated, Iceland, New York). After disintegration, the pulp paste is transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting pulp cake is separated from filter paper and the filter paper is rinsed on the cake to have the foreign fiber. The pulp cake is refrigerated until the additional tests mentioned below, for a maximum of one week.

P952 C. Enzymatic preparation The concentrated and cooled liquid enzyme was diluted to 1 or 2% concentration (vol / vol) in an 80/20 mixture of distilled water and 1,2-propanediol and refrigerated until use: Carezyme® 5.0 L or Celluclast® 1.5 L or Celluzyme® 0.7 T, all are obtained from Novo Nordisk, Bagsvaerd, Denmark or Pergolase A40, which is obtained from Ciba, Greensboro, NC EXAMPLE 1 Treatment of NSK Fibers with Carezyme® Northern Softwood Kraft pulp (NSK) cakes from section B above are treated and 18 samples of low density test sheet (6 sheets per sample) are formed using the procedure aforementioned. The control NSK pulp is left unmodified and diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a TAPPI Standard Disintegrator prior to the development of the test sheets.

The sample IA is a NSK pulp treated without enzymes: The fibers are treated at a consistency of about 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of P952 hexamethonium bromide (active chemical agent at 1% w / w dry fiber basis weight) for approximately 15 seconds with a Lightnin'® laboratory mixer (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F by a microwave oven and then added to the debonder / water mixture. The mixing speed of the Lightnin'® mixer is increased to achieve a continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp paste is quantitatively transferred and rinsed with approximately 500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting pulp cake is diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to the manufacture of the test sheets.

Sample IB is an NSK pulp treated without enzymes: The fibers are treated to a consistency of about 3%. First, distilled water preheated to 120 ° F is mixed with 90 mL of a 3% solution of tetraethylammonium bromide (active chemical agent at 1% w / wt dry fiber basis) for approximately 15 seconds with a Lightnin 'laboratory mixer. ® P952 (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F by a microwave oven and then added to the debonder / water mixture. The mixing speed of the Lightnin'® mixer is increased to achieve a continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp paste is quantitatively transferred and rinsed with approximately 500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 1C is a NSK pulp not treated with enzymes: The fibers are treated to a consistency of about 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of 1% lauryl trimethyl ammonium chloride (Sherex Chemical Co., Witco Corp., Greenwich, CT) (active chemical agent at 1% w / w dry fiber base) ) for approximately 15 seconds with a Lightnin'® laboratory mixer (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to approximately 120 ° F with a P952 microwave oven and then added to the debonding / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp paste is quantitatively transferred and rinsed with approximately 500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting pulp cake is diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to the development of the test sheet.

The ID sample is an NSK pulp without enzyme treatment: The fibers are treated at a consistency of about 3%. First, distilled water preheated to 120 ° F is mixed with 10 mL of an N-decyl-N oxide., 3% N-dimethylamine (Barlox® IOS-Lonza, Inc. Fairlawn, NJ) (1% by weight of N-decyl-N, N-dimethylamine oxide / dry fiber basis weight) for approximately 15 seconds with a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the debonder / water mixture. The mixing speed of the mixer P952 Lightnin® increases to achieve continuous replenishment and agitation of the pulp and is allowed to react for approximately 1 hour. At the end of the hour, the pulp paste is quantitatively transferred and rinsed with approximately 500 L of distilled water and drained in a Buchner funnel with filter paper. The resulting pulp cake is diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to the manufacture of the test sheets.

Sample 1E is made of NSK pulp that is modified with the following process: The fibers are treated to a consistency of "approximately 3%." First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme. ® (1% volume / weight addition of Carezyme® 5.0 L in pure dry pulp) for approximately 15 seconds with a Lightnin'® laboratory mixer (Lightnin ', Rochester, NY) in a 120 ° F water bath. "The unmodified pulp cake is preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and is allowed to react by P952 approximately 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox®, (available from The Clorox Co., Oakland, CA.) in 2,000 mL of distilled water), mixed and it is left to react for a minimum of 5 minutes at room temperature to stop any enzymatic reaction with cellulose After stopping the reaction, the modified pulp is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained A Buchner funnel with filter paper The resulting modified pulp cake is then diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 1F is made from NSK pulp that is modified with the following process: The fibers are treated to a consistency of approximately 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (2% volume / weight addition of Carezyme® 5.0 L in pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin'® (Lightnin ', P952 Rochester, NY) in a water bath at 120 ° F_. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox, in 2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to stop any additional enzymatic reaction with cellulose. After stopping the reaction, the modified pulp is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

P952 The 1G sample is made of NSK pulp that is modified by the following process: The fibers are treated to a starting consistency of about 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin'® (Lightnin ', Rochester, NY) in a water bath at 120 ° F. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water is added to the enzyme mixture. / pulp paste to achieve a 1% addition level (active chemical weight / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber paste is converted directly into low density test sheets without filtering, reaction cooling or disintegration.

P952 Sample 1H is made from NSK pulp that is modified by the following process: The fibers are treated to a starting consistency of approximately 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (2% volume / weight addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin® (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water is added to the enzyme mixture. / pulp paste to achieve - an addition level of 1% (active chemical agent weight / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber paste is converted directly into low density test sheets without filtering, cooling P952 for the reaction or disintegration.

Sample II is made from NSK pulp that is modified by the following process: The fibers are treated to a starting consistency of about 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% "" in volume / weight of addition of Carezyme® 5.0 L of pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of tetraethylammonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 14,002-3) in distilled water is added to the enzyme mixture. / pulp paste to achieve an addition level of 1% (weight of active chemical agent / dry fiber base weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the pulp is quantitatively transferred and drained P952 in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to stop any additional enzymatic reaction with cellulose. After stopping the reaction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 1J is made from pulp that has been modified with the following process: The pulp is treated at a starting consistency of approximately 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L in pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin® (Lightnin ', Rochester, NY) in a 120 ° F water bath. The "unmodified pulp cake is preheated to approximately 120 ° F P952 with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the pulp / enzyme paste increases to achieve continuous replenishment and stirring and is allowed to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of lauryl trimethyl ammonium chloride (Sherex Chemical Co., Witco Corp., Greenwich, CT) in distilled water is added to the enzyme / pulp mixture to achieve a level of 1% addition (weight of active chemical agent / weight on dry fiber basis) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the pulp paste is transferred quantitatively and drained in a Buchner funnel with filter paper. The modified pulp cake is added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mix and let it react for a minimum of 5 minutes at room temperature to stop any further enzymatic reaction with cellulose. After stopping the reaction, the modified pulp is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is diluted to 2,000 mL with tap water and disintegrates for 3,000 revolutions in a standard TAPPI disintegrator prior to P952 preparation of the test sheets.

The 1K sample is made from pulp that has been modified with the following process: ~~ The pulp is treated at a starting consistency of about 3%. First, distilled water preheated to 120 ° F is mixed with 30 L of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L in pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin® (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the pulp / enzyme paste increases to achieve continuous replenishment and stirring and is allowed to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of triethanolamine (Dow Chemical Co, Midland MI) in distilled water is added to the enzyme / pulp mixture to achieve a level of 1% addition (weight of active chemical agent / weight on dry fiber basis) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The pulp cake Modified P952 is added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to stop any additional enzymatic reaction - with cellulose. After stopping the reaction, the modified pulp is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 1L is made from pulp that has been modified with the following process: The pulp is treated at a starting consistency of approximately 3%. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L in pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin® (Lightnin ', Rochester, NY) in a 120 ° F water bath. Unmodified pulp cake is preheated to approximately 120 ° F with a microwave oven and then added to the mixture P952 enzyme / water. The mixing speed of the pulp / enzyme paste increases to achieve continuous replenishment and stirring and is allowed to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste mixture is adjusted to pH 7.5 with the addition of 0.01 N NaOH. 10 mL of a 3% solution (weight / volume of sodium oxide) is added. N-decyl-N, N-dimethylamine (Barlox® IOS, Lonza, Inc. Fairlawn, NJ) in distilled water to the enzyme / pulp mix to achieve an addition level of 1% (weight of active chemical / weight on a dry fiber basis) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp is acidified to a pH of 3.8 with HCl.The modified pulp pulp is quantitatively transferred and It is rinsed with approximately 500 mL of distilled water and drained in a Buchner funnel with filter paper The resulting modified pulp cake is diluted to 2,000 mL under running water and disintegrates for 3,000 revolutions in a standard TAPPI disintegrator prior to the preparation of the test sheets.

The 1M sample is made from pulp that has been modified with the following process: The pulp is treated at a starting consistency of approximately 3%. First, distilled water is mixed P952 preheated to 120 ° F with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L in pure dry pulp) for approximately 15 seconds using a Lightnin'® laboratory mixer ( Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the pulp / enzyme paste increases to achieve continuous replenishment and stirring and is allowed to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of lauryl trimethyl ammonium chloride (Sherex Chemical Co., Witco Corp., Greenwich, CT) in distilled water is added to the mixture. enzyme / pulp paste to achieve an addition level of 1% (weight of active chemical / weight on a dry fiber basis) and mixing is continued for 55 minutes at 120 ° F. After mixing the lauryl trimethyl ammonium chloride and the modified pulp, add 15 mL of a 2% solution of carboxymethyl cellulose (Aqualon Company, Wilmington, DE) (1% by weight of active chemical / weight basis). of dry fiber) and mixing continues for 5 minutes. The modified fiber pulp is processed directly in low density test sheets, without filtering, quenching or disintegration.

P952 The IN sample is made from pulp that has been modified with the following process: Three unmodified pulp cakes prepared in section B above are treated to a consistency of approximately 5% in a Quantum Mark III high density laboratory mixer . First, distilled water preheated to 120 ° F is mixed with 135 mL of a 2% solution of Carezyme® (1.12% volume / weight addition of Carezyme® 5.0 L pure dry pulp) for approximately 10 seconds and transferred to the container of mixing that has been programmed to maintain a temperature of 120 ° F. Unmodified pulp cakes are preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. After the lid is secured to the top of the container, the arrow on the mixer engages to mix at a rate of approximately 1,200 RPM (high density mixing) for 10 seconds and then stops. For the rest of the hour, mixing at 1,200 RPM for 10 seconds occurs every 10 minutes. At the end of the reaction period with the enzyme, the pulp paste is quantitatively transferred and drained in a Buchner funnel with a gauze fabric to retain as much material as possible. The resulting pulp cake is separated from the gauze fabric and then P952 adds to approximately 6,000 of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixes and is allowed to react for a minimum of 5 minutes at room temperature to stop any further enzymatic reaction with cellulose. After stopping the reaction, the pulp is quantitatively transferred and drained in a Buchner funnel with a gauze fabric to retain as much material as possible. The cake is rinsed with approximately 5,000 mL of distilled water and drained. The resulting pulp cake is separated from the gauze fabric and a sample corresponding to 30 grams of pure and dry sample is diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the samples. test sheets.

Sample 10 is made from pulp that has been modified with the following process: Six unmodified pulp cakes prepared in section B above are treated to a consistency of approximately 5% in a Quantum Mark III high density laboratory mixer . First, distilled water preheated to 120 ° F is mixed with 90 mL of a 2% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L of pure dry pulp) for approximately 10 seconds and P952 is transferred to the mixing vessel that has programmed to maintain a temperature of 120 ° F. Unmodified pulp cakes are preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. After the lid is secured to the top of the container, the arrow on the mixer engages to mix at a rate of approximately 1,200 RPM (high density mixing) for 10 seconds and then stops. For the remainder of the hour, mixing at 1,200 RPM for 10 seconds occurs every 10 minutes for a total of 70 seconds. At the end of the reaction period with the enzyme, the pulp paste is quantitatively transferred and drained in a Buchner funnel with a gauze fabric to retain as much material as possible. The resulting pulp cake is separated from the gauze fabric and then added to approximately 6,000 of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to stop any further enzymatic reaction with cellulose. After stopping the reaction, the pulp is quantitatively transferred and drained in a Buchner funnel with a gauze fabric to retain as much material as possible. The cake is rinsed with approximately 3,500 mL of distilled water and drained.

P952 The resulting pulp cake is separated from the gauze fabric and a sample corresponding to 30 grams of pure and dry sample is diluted to 2,000 mL with tap water and disintegrated by 3,000 revolutions in a standard TAPPI disintegrator prior to the preparation of the test sheets.

The 1P sample is made from pulp that has modified with the following process: Eight unmodified pulp cakes prepared in section B above are treated to a consistency of about 5% in a Quantum Mark III high density laboratory mixer. First, distilled water preheated to 120 ° F is mixed with 45 mL of a 2% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L of pure dry pulp) for approximately 10 seconds and transferred to the container of mixing that has programmed to maintain a temperature of 120 ° F. Unmodified pulp cakes are preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. After the lid is secured to the top of the container, the arrow on the mixer engages to mix at a rate of approximately 1,200 RPM (high density mixing) for 10 seconds and then stops. For the rest of the P952 hour, mixing at 1,200 RPM for 10 seconds occurs every 10 minutes. At the end of the reaction period with the enzyme, the pulp paste is quantitatively transferred and drained in a Buchner funnel with a gauze fabric to retain as much material as possible. The resulting pulp cake is separated from the gauze fabric and then added to approximately 3,000 of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to stop any further enzymatic reaction with cellulose. After stopping the reaction, the pulp is quantitatively transferred and drained in a Buchner funnel with a gauze fabric to retain as much material as possible. The cake is rinsed with approximately 1,500 mL of distilled water and drained. The resulting pulp cake is separated from the gauze fabric and a sample corresponding to 30 grams of pure and dry sample is diluted to 2,000 mL with tap water and disintegrates for 3,000 revolutions in a standard TAPPI disintegrator prior to the preparation of the test sheets.

Sample 1Q is made from pulp that has modified with the following process: Six unmodified pulp cakes prepared in P952 the section B above are treated to a consistency of about 5% in a Quantum Mark III high density laboratory mixer. First, distilled water preheated to 120 ° F is mixed with 90 mL of a 2% solution of Carezyme® (1% by volume / weight of addition of Carezyme® 5.0 L of pure dry pulp) for approximately 10 seconds and transferred to the container of mixing that has been programmed to maintain a temperature of 120 ° F. Unmodified pulp cakes are preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. After the lid is secured to the top of the container, the mixer arrow engages to mix at a rate of approximately 1,200 RPM (high density mixing) for 10 seconds. After the initial high-intensity mixing step, a low-intensity mixing at 120 RPM is performed for 10 seconds every 2 minutes for the rest of the hour, except at times 25, 40 and 50 minutes where mixing is carried out. high intensity of 1200 RPM with durations of 20 seconds. At the end of the reaction period with the enzyme, a combination of 40 mL of 4% (w / v) emulsion (0.9% addition to the dry fibers) of dihydrogenated dimethyl ammonium methyl sulfate is added (Sherex Chemical Co. Witco Corp., Greenwich, CT) in distilled water and 50 mL of 4% solution P952 (weight / volume) (1.1% addition to dry fibers) of lauryl trimethyl ammonium chloride (Sherex Chemical Co., Witco Corp., Greenwich, CT) in distilled water and added to the enzyme / pulp paste to achieve total level of addition of 2% (active chemical agent weight / dry fiber weight basis). After the lid is secured back to the top of the container, the arrow on the mixer engages to mix at approximately 1200 RPM (high intensity mixing) for 10 seconds and then stops. For the next 30 minutes, mixing at a rate of approximately 1,200 RPM for 10 seconds occurs every 3 minutes. At the end of the treatment period, the pulp is quantitatively transferred and drained in a Buchner funnel with a gauze fabric to retain as much material as possible. The cake is rinsed with approximately 3,000 L of distilled water and drained. The resulting pulp cake is stripped off of the gauze fabric and a sample corresponding to 30 grams pure dry is diluted in 2,000 mL with tap water and disintegrates for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheet. Table 1 gives the results of the density, dry stress index, dry and wet stress resistance index with an extension of zero, and the DT / DZST ratios of the leaf samples P952 processed low density test. It can be seen from the table that the enzymatic modification of the fibers with Carezyme® results in a substantial reduction of the dry tension index with zero extension (DZST) of the NSK fibers, while maintaining or improving the overall stress index in dry (DT) of the sheet compared to the test sheet sample produced from the unmodified control fibers. The addition of chemical debonders to the enzyme modified fibers further reduces DZST. In addition, the high intensity mixing combined with the enzymatic treatment as well as the steps of enzyme treatment and debonding, result in even higher reductions in DZST without having a negative impact on the leaf tension.

P952 TABLE 1 P952 *: CZ = Carezyme® 5.0 L HNB = hexamethonium bromide TEAB = tetraarylammonium bromide LTAC = lauryl trimethylammonium chloride TEA = triethanolamine BIOS = Barlox® IOS CMC = carboxymethyl cellulose HIM = high intensity mixing k = consistency DTDMAMS = methyl sulfate of dihydrogenated bait dimethylammonium **: It is not an example of the present invention.

EXAMPLE 2 Treatment of NSK fibers with Celluclast® Northern Softwood Kraft pulp (NSK) cakes from section B above are treated and 4 samples of low density test sheet (6 sheets per sample) are formed using the procedure aforementioned. The control NSK pulp is the same as for Table 1 Sample 2A is an NSK pulp treated without enzymes: The fibers are made of NSK pulp that was modified with the following processes: The fibers were treated at approximately 3% starting consistency in P952 a buffer solution 50 millimolar of sodium acetate and acetic acid of pH 4.7. _ Buffer or buffer solution, preheated to 120 ° F, is first mixed with 30 mL of a 1% solution of Celluclast® (1% volume / weight addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a Lightnin'® mixer (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F by a microwave oven and then enzyme / buffer is added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL "of a 100 ppm NaOCl solution. (4 mL of Clorox® in 2,000 mL of distilled water), mix and let it react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is P952 dilutes to 2,000 mL under running water and disintegrates for 3,000 revolutions in a standard TAPPI disintegrator prior to the preparation of the test samples.

Sample 2B was made from NSK pulp that was modified by the following process: The fibers were made of NSK pulp that was modified with the following "processes: The fibers were treated at approximately 3% starting consistency in a buffer solution. 50 millimolar sodium acetate and acetic acid of pH 4.7 Buffer or buffer solution, preheated to 120 ° F, is first mixed with 60 L of a 1% solution of Celluclast® (2% volume / weight addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a Lightnin® mixer (Lightnin ', Rochester, NY) in a water bath at 120 ° F. The unmodified pulp cake is preheated to approximately 120 ° F by a Microwave oven is then added to the enzyme / buffer mixture.The mixing speed of the Lightnin'® mixer is increased to achieve continuous replenishment and stirring of the pulp and allowed to react for approximately 1 hour. To finish the time, the pulp paste is transferred quantitatively and drained in a Buchner funnel with filter paper. The modified pulp cake is then added P952 'to approximately 1, 000 mL of a NaOCl solution of 100 ppm (4 mL of Clorox® in 2,000 mL of distilled water), mix and allow to react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to the preparation of the test samples.

The 2C sample was elaborated from the NSK pulp that was modified by the following process: The fibers are made of NSK pulp that was modified with the following processes: The fibers were treated at approximately 3% of starting consistency in a buffer solution 50 millimolar of sodium acetate and acetic acid of pH 4.7. Buffer or buffer solution, preheated to 120 ° F, is first mixed with 30 mL of a 1% solution of Celluclast® (1% volume / weight addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a Lightnin'® mixer (Lightnin ', Rochester, NY) in a water bath P952 120 ° F. The unmodified pulp cake is preheated to about 120 ° F by a microwave oven and then enzyme / buffer is added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the reaction period with the enzyme, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water was added to the enzyme mixture. pulp paste to achieve an addition level of 1% (weight of active chemical agent / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp was used to directly process low density test sheets without filtering, quenching or disintegrating.

The 2D sample is made of NSK pulp that is modified by the following process: The fibers are made of NSK pulp that was modified with the following processes: The fibers were treated at approximately 3% starting consistency in a 50 millimolar buffer solution. sodium acetate and acetic acid of pH 4.7. Buffer or buffer solution, P952 preheated to 120 ° F, first mixed with 60 mL of a 1% solution of Celluclast® (2% volume / weight addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a Lightnin'® mixer ( Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F by a microwave oven and then enzyme / buffer is added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the reaction period with the enzyme, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water was added to the mixture.

- Enzyme / pulp paste to achieve an addition level of 1% (weight of active chemical agent / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp was used to directly process low density test sheets without filtering, quenching or disintegrating. Table 2 gives the results of the density, dry tension index, dry and wet tension indexes with an extension of zero, and the relationships P952 DT / DZST of the processed low density test sheet samples. It can be seen from the table that the enzymatic modification of the fibers with Celluclast® results in a considerable reduction in the dry tension index with zero extension (DZST) of the NSK fibers, while maintaining or improving the tension index in General dry (DT) of the sheet compared to the test sheet sample produced from the unmodified control fibers. The addition of chemical debonders to the enzyme modified fibers further reduces DZST.

TABLE 2 *: CC = Celluclast® 1.5 L * HMB = hexamethonium bromide **: It is not an example of the present invention.

P952 EXAMPLE 3; Treatment of NSK Fibers with Celluzvme® or Pergolase® The North Softwood Kraft pulp (NSK) of section B above is treated and processed 2 samples of low density test sheet (6 sheets per sample) using the procedure mentioned above. The control NSK pulp is the same as for Table 1.

Sample 3A is made from NSK pulp that was modified by the following process: The fibers were treated at approximately 3% consistency. First, distilled water preheated to 120 ° F was added, which was mixed with 1.89 g of Celluzyme® 0.7 T (6% weight / weight of addition of Celluzyme® 0.7 T on pure dry pulp) for approximately 15 seconds using a Lightnin 'laboratory mixer. ® (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / water was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to extinguish any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to the preparation of the test sheets.

Sample 3B is made from NSK pulp that was modified by the following process: The fibers are treated at approximately 3% consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 30 mL of a 1% solution of Pergolase® (1% volume / weight addition of Pergolase® A40 on pure dry pulp) for approximately 15 seconds using a mixer.

P952 Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / water was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mix and let it react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets. Table 3 provides the results of the density, dry stress index, dry and wet tensile indexes with an extension of zero, and the DT / DZST ratios of the processed low density test sheet samples. It can be seen from the table that the enzymatic modification of the fibers with Celluzyme® and Pergolase® result in a considerable reduction of the dry tensile index with zero extension (DZST) of the NSK fibers, while maintaining or improving the overall index of dry tension (DT) of the sheet compared to the test sheet sample produced with unmodified control fibers.

TABLE 3 Sample Density DZST% reduction DT Ratio ZST (description *) (g / cc) Nm / g) DZST (Nm / g) DZST / DT (Nm / g) Control NSK ** 0.174 138.9 - 16.3 8.5 121.0 EXAMPLE 4; Treatment of Eucalyptus Fibers with Carezvme® The eucalyptus pulp cakes (Euc) of section B above are treated and with them 5 samples of low density test sheet (6 sheets per sample) are made using the aforementioned procedure. The control eucalyptus pulp is left unmodified and diluted to 2,000 mL with tap water and disintegrates by P952 3,000 revolutions in a TAPPI Standard Disintegrator before the development of the test sheets.

Sample 4A is made from eucalyptus pulp that is modified by the following processes: The fibers are treated at approximately 3% consistency. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L of pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin® (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin 'mixer is increased to achieve a continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in_2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to extinguish any additional enzymatic reaction with cellulose.

P952 After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 4B is made from eucalyptus pulp that is modified by the following process: The fibers are treated at approximately 3% consistency. "First, distilled water preheated to 120 ° F is mixed with 60 mL of a 1% solution of Carezyme® (2% volume / weight of addition of Carezyme® 5.0 L of pure dry pulp) for approximately 15 seconds using a mixer. Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath Unmodified pulp cake is preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture The mixing speed of the Lightnin'® mixer is increased to achieve a continuous replenishment and stirring of the pulp paste and allowed to react for about 1 hour.At the end of the hour, the pulp paste is quantitatively transferred and drained in a P952 Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature. extinguish any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 4C is made of NSK pulp that is modified by the following process: The fibers are treated at approximately 3% consistency. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L of pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin® (Lightnin ', Rochester, NY) in a 120 ° F water bath. Unmodified pulp cake is preheated to approximately 120 ° F P952 with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve a continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the reaction period with the enzyme, 30 mL of a 1% t (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water was added to the enzyme mixture. / pulp paste to achieve an addition level of 1% (weight of active chemical agent / dry fiber base weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp is directly processed into low density test sheets without filtration, quenching or disintegration.

The 4D sample is made from eucalyptus pulp that is modified by the following processes: The fibers are treated at approximately 3% consistency. First, distilled water preheated to 120 ° F is mixed with 60 mL of a 1% solution of Carezyme® (2% volume / weight addition of Carezyme® 5.0 L of pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin® (Lightnin ', Rochester, NY) in a 120 ° F water bath. The cake of P952 unmodified pulp is preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin 'mixer is increased to achieve a continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the reaction period with the enzyme, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water was added to the enzyme / pulp mixture to achieve an addition level of 1% (weight of active chemical agent / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp is processed directly to low density test sheets without filtration, quenching or disintegration.

The sample 4E is made from eucalyptus pulp that is modified by the following processes: The fibers are treated at approximately 3% consistency. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L of pure dry pulp) for approximately 15 seconds using a laboratory mixer Lightnin'® (Lightnin ', P952 Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to approximately 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin 'mixer is increased to achieve a continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the reaction period with the enzyme, 30 mL of a 1% (w / v) solution "of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water was added to the enzyme mixture. / pulp paste to achieve-an addition level of 1% (active chemical agent weight / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, - the Modified fiber pulp is made directly from low density test sheets without filtration, reaction extinction or disintegration Table 4 gives the results of the density, dry tension index, dry and wet tension indexes with an extension of zero, and the DT / DZST ratios of the processed low density test sheet samples It can be seen from the table that the enzymatic modification of the fibers with Carezyme® results in a substantial reduction in the dry stress index with extens zero ion (DZST) of the fibers of P952 wood eucalyptus, while maintaining or improving the overall dry tension (DT) index of the sheet compared to the test sheet sample produced with the unmodified control fibers. The addition of chemical debonders to the enzyme modified fibers further reduces DZST.

TABLE 4 *: Cz = Carezyme® 5.0 L HMB = hexamethonium bromide TEAB = tetraethylammonium bromide **: It is not an example of the present invention.

P952 EXAMPLE 5: Treatment of Eucalyptus Fibers with Celluclast® The eucalyptus pulp cakes (Euc) of section B above are processed and processed 4 samples of low density test sheet (6 sheets per sample) using the procedure above mentioned. The pulp of eucalyptus control is elaborated as in Table 4.

Sample 5A is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 30 mL of a 1% solution of Celluclast® (1% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. When finishing the P952 hour, the pulp paste is transferred quantitatively and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature. extinguish any additional enzymatic reaction with cellulose. After the extinction, the modified pulp • is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 5B is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 60 mL of a 1% solution of Celluclast® (2% volume / weight of addition of Celluclast® 1.5 L on pulp Pure Dry P952) for approximately 15 seconds using a Lightnin'® laboratory mixer (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to extinguish any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

P952 Sample 5C is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 30 mL of a 1% solution of Celluclast® (1% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the reaction period with the enzyme, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water was added to the enzyme mixture. pulp paste to achieve an addition level of 1% (weight of active chemical agent / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the P952 second hour, the modified fiber pulp is directly processed low density test sheets without filtration, quenching or disintegration.

The 5D sample is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a buffer solution 50 millimolar sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 60 mL of a 1% solution of Celluclast® (2% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the reaction period with the enzyme, 30 mL of a 1% (w / v) solution of hexamethonium bromide was added.

(Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water to the enzyme / paste mixture.

P952 pulp to achieve an addition level of 1% (active chemical agent weight / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp is made directly from low density test sheets without filtration, quenching or disintegration. Table 5 gives the results of the density, dry stress index, dry and wet tensile indexes with an extension of zero, and the DT / DZST ratios of the processed low density test sheet samples. It can be seen from the table that the enzymatic modification of hard eucalyptus fibers with Celluclast® results in a substantial reduction in the dry tensile index with zero extension (DZST) of the NSK fibers, while maintaining or improving the index general dry tension (DT) of the sheet compared to the test sheet sample produced from • unmodified control fibers. The addition of chemical debonders to the enzyme modified fibers further reduces DZST.

P952 TABLE 5 *: CC = Celluclast® 1.5 L HMB = hexamethonium bromide **: It is not an example of the present invention.

EXAMPLE 6: Treatment of Eucalyptus Fibers with Celluz me® Eucalyptus pulp cakes (Euc) from section B above are treated and with them low density test sheet samples (6 sheets per sample) are formed using the procedure aforementioned. The eucalyptus control pulp is the same as for Table 4.

Sample 6A is made from eucalyptus pulp that is modified by the following processes: The fibers are treated at approximately 3% P952 consistency. First, distilled water preheated to 120 ° F was mixed with 1.89 g of Celluzyme® 0.7 T (6% weight / weight of addition of Celluzyme® 1.7 T on pure dry pulp) for approximately 15 seconds using a Lightnin'® laboratory mixer ( Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / water was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake was added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose. After the extinction, the modified pulp paste was quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was diluted to 2,000 mL with tap water and disintegrated by 3,000 revolutions in a standard TAPPI disintegrator before P952 of the development of the test sheets.

TABLE 6 **: It is not an example of the present invention.

EXAMPLE 7; Treatment of North Hardwood Sulfite Pulp (NHS) with Carezyme® Hardwood Sulfite Pulp Cakes North (NHS) from section B above are processed and processed with low-density test sheet samples (6 sheets per sample) using the aforementioned procedure. The control NHS pulp was left unmodified and diluted to 2,000 mL with tap water and disintegrated by 3,000 revolutions in a standard TAPPI disintegrator prior to the manufacture of the test sheets.

Sample 7A is made from eucalyptus pulp that is modified by the following processes: P952 The fibers are treated at approximately 3% consistency. First, distilled water preheated to 120 ° F was mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds with a mixer. Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to extinguish any enzymatic reaction with cellulose. After the extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated by P952 3,000 revolutions in a standard TAPPI disintegrator before the development of the test sheets.

The sample 7B is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% consistency. First, distilled water preheated to 120 ° F was mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds with a mixer. Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake is preheated to about 120 ° F with a microwave oven and then added to the enzyme / water mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water is added to the enzyme mixture. / pulp paste to achieve a 1% addition level (active chemical weight / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the P952 modified fiber pulp was used to directly produce low density test sheets without filtering, extinguishing or disintegrating. Table 7 gives the results of the density, dry stress index, dry and wet tensile indexes with an extension of zero, and the DT / DZST ratios of the processed low density test sheet samples. It can be seen from the table that the enzymatic modification of the fibers with Carezyme® results in a substantial reduction in the dry tension index with zero extension (DZST) of the NHS fibers, while maintaining or improving the overall stress index dry (DT) of the sheet compared to the test sheet sample produced from unmodified control fibers. The addition of chemical debonders to the enzyme modified fibers further reduces DZST.

TABLE 7: P952 *: Cz = Carezyme® 5. O L HMB = hexamethonium bromide **: Not an example of the present invention.

EXAMPLE 8: Treatment of North Hard Wood Sulfite Pulp with Celluclast® North Hard Wood Sulfite (NHS) pulp cakes from section B above are processed and processed 4 samples of low density test sheet ( 6 sheets per sample) using the aforementioned procedure. The control NHS pulp is the same as for Table 7.

The sample 8A is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 30 mL of a 1% solution of Celluclast® (1% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The pulp cake does not Modified P952 was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mix and let it react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 8B is made from NHS pulp that is modified by the following processes: P952 The fibers are treated at approximately 3% consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 60 mL of a 1% solution of Celluclast® (2% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to extinguish any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL P952 distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 8C is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 30 mL of a 1% solution of Celluclast® (1% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the reaction period of the enzyme, 30 mL of a P952 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water to the enzyme / pulp mix to achieve an addition level of 1% (weight of active chemical agent / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp was used to directly process low density test sheets without filtering, extinguishing or disintegrating.

The 8D sample is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 60 mL of a 1% solution of Celluclast® (2% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. Mixing speed of Lightnin'® mixer increased to achieve replacement P952 continued stirring the pulp and allowed to react for about 1 hour. At the end of the enzyme reaction period, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water is added to the enzyme mixture. / pulp paste to achieve a 1% addition level (active chemical weight / dry fiber basis weight) and mixing is continued for a second hour at 120 ° F. At the end of the second hour, the modified fiber pulp was used to directly process low density test sheets without filtering, extinguishing or disintegrating. Table 8 gives the results of the density, dry stress index, dry and wet stress indices with an extension of zero / and the DT / DZST ratios of the processed low density test sheet samples. It can be observed from the table that the enzymatic modification of the fibers with Celluclast® results in a substantial reduction in the dry tensile index with zero extension (DZST) of the NHS fibers, while maintaining or improving the general index of tension in the fibers. dry (DT) of the sheet compared to the test sheet sample produced with unmodified control fibers The addition of chemical debonders to the enzyme-modified fibers further reduces the P952 - _ "_ -DZST TABLE 8: *: CC = Celluclast® 1.5 L HMB = hexamethonium bromide **: It is not an example of the present invention.

EXAMPLE 9; Southern Softwood Kraft Fiber Treatment with Carezyme® South Softwood Kraft pulp (SSK) from section B above is treated and processed 3 samples of low density test sheet (6 sheets per sample) using the aforementioned procedure. The control SSK pulp is left unmodified and diluted to 2,000 mL with tap water and disintegrates for 3,000 revolutions in a standard TAPPI disintegrator before the P952 preparation of the test sheets.

The sample 9A is made from SSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 30 mL of a 1% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzymatic reaction period, 30 mL of a 1% (w / v) solution of hexamethonium bromide (Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water is added to the enzyme / pulp mixture to achieve a level of 1% addition (active chemical agent weight / dry fiber base weight) and mixing is continued for a second hour at 120 ° F. At the end of "the second hour, the modified fiber pulp is used P952"" to directly process low density test sheets without filtering, extinguishing or disintegrating.

The sample 9B is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 60 mL of a 1% solution of Carezyme® (2% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzymatic reaction period, 30 mL of a 1% (w / v) solution of hexamethonium bromide is added.

(Aldrich Chemical Company Milwaukee, WL Catalog No. 21,967-3) in distilled water to the enzyme / pulp paste mixture to achieve an addition level of 1% (active chemical weight / dry fiber base weight) and mixing is continued for a second hour at 120 ° F. At the end of the P952 second hour, the modified fiber pulp is used to directly process low density test sheets without filtering, extinguishing or disintegrating. Table 9 gives the results of the density, dry stress index, dry and wet tensile indexes with zero extension, and DT / DZST ratio of the elaborated low density test sheet. of the table that the enzymatic modification of the fibers with Carezyme® followed by debonding treatment results in a considerable reduction of the dry tension index with zero extension (DZST) of the SSK fibers, while maintaining a general improved index of tension dry (DT) of the sheet compared to the test sheet sample produced with unmodified fibers.

TABLE 9; *: Cz = Carezyme® 5.0 L HMB = hexamethonium bromide P952 **: It is not an example of the present invention.

EXAMPLE 10 i Treatment of NSK Fibers and Fibrous Structures Having Improved Flexibility The Northern Softwood Kraft Pulp Cakes "(NSK) of section B above are processed and processed 15 samples of low density test sheet (6 sheets) per sample) using the aforementioned procedure.The NSK control pulp is left unmodified and diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

The sample 10A is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 7.5 mL of a 2% solution of Carezyme® (0.5% volume / weight addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then added to the mixture P952 enzyme / buffer The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox®, available from The Clorox Co., Oakland, CA) in 2,000 mL of distilled water, mixed and left react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose After the extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper The resulting modified pulp cake is then diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 10B is made from NSK pulp which is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water is mixed P952. - _. _ preheated to 120 ° F with 22.5 mL of a 2% solution of Carezyme® (1.5% volume / weight addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin'® laboratory mixer ( Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox, in 2,000 mL of distilled water), mix and let it react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a disintegrator P952 standard TAPPI before the development of the test sheets.

Sample 10C is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% start consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 7.5 mL of a 2% solution of Celluclast® (0.5% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a Lightnin'® laboratory mixer (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL of distilled water), mixed P952 and allowed to react for a minimum of 5 minutes at room temperature to quench any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Sample 10D is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% consistency in a 50 millimolar buffer solution of sodium acetate and acetic acid of pH 4.7. The buffer solution, preheated to 120 ° F, is first mixed with 22.5 mL of a 2% solution of Celluclast® (1.5% volume / weight of addition of Celluclast® 1.5 L on pure dry pulp) for approximately 15 seconds using a mixer of Lightnin'® laboratory (Lightnin ', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then added to the mixture P952 enzyme / buffer The mixing speed of the Lightnin® mixer was increased to achieve continuous replenishment and stirring of the pulp and allowed to react for about 1 hour. At the end of the hour, the pulp is quantitatively transferred and drained in a Buchner funnel with filter paper. The modified pulp cake is then added to approximately 1,000 mL of a 100 ppm NaOCl solution (4 mL of Clorox® in 2,000 mL distilled water), mixed and allowed to react for a minimum of 5 minutes at room temperature to extinguish any additional enzymatic reaction with cellulose. After extinction, the modified pulp paste is quantitatively transferred and rinsed with approximately 1,500 mL of distilled water and drained in a Buchner funnel with filter paper. The resulting modified pulp cake is then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a standard TAPPI disintegrator prior to making the test sheets.

Preparation of n-Dodecenylsuccinate Disodium Salt: 500 g of distilled water were mixed with 3500 g of n-Dodecenylsuccinic anhydride (98% concentration, Milliken Chemical Company, Inman, SC) at 70 degrees P952 - - - - - -centigrade for approximately 16 hours. After the 16 hour reaction period, 3070 g of a 1% sodium sulfate solution was added and mixed for an additional hour and removed from the heat. 1000 g of a 50% solution of sodium hydroxide was slowly added to the emulsion with constant mixing to form a 49% concentration of monosodium salt of n-Dodecenylsuccinic acid. From this a representative mixture was obtained and diluted to a concentration of 6% with distilled water and the pH adjusted to 9 with sodium hydroxide solution to form the n-Dodecenylsuccinate Disodium Salt.

Preparation of n-Octadecenylsuccinate Disodium Salt: 500 g of n-Octadecenylsuccinate anhydride (100% concentration, Milliken Chemical Company, Inman, SC) was melted at 70 degrees centigrade or then mixed with 50 g of distilled water for approximately 16 hours . After the 16 hour reaction period, the emulsion was removed from the heat and 218 g of a 50% sodium hydroxide solution was mixed with 2000 g of distilled water to form the n-Octadecenylsuccinic Disodium Salt. The emulsion was then mixed at room temperature for another 20 hours and then mixed with 100 g of sodium sulfate crystals and 400 g of distilled water. From this a mixture was obtained P952 representative and diluted to a 6% concentration with distilled water.

Sample 10E is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the mixer -Lightnin'® increases to achieve the continuous replenishment and stirring of the pulp and is allowed to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide. After a pH adjustment, 25 mL was added to a 6% (w / v) solution of n-Dodecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp paste mixture to achieve an addition level of 5%. % (weight of active chemo agent / weight P952 dry fiber base) and allowed to continue mixing for 30 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Dodecenylsuccinate paste was adjusted to pH 7 with 1 normal sulfuric acid. After pH adjustment, 1.75 g of calcium chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Dodecenylsuccinate paste and mixed for another 5 minutes at room temperature. 120 ° F. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a TAPPI Standard Disintegrator prior to the preparation of the test samples.

The 10F sample is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F P952 with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide. After a pH adjustment, 5 mL was added to a 6% (w / v) solution of n-Dodecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp mixture to achieve an addition level of 1. % (weight of active chemo agent / dry fiber base weight) and allowed to continue mixing for 30 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Dodecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After adjusting for pH, 0.43 g of zinc chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Dodecenylsuccinate paste and mixed for another 5 minutes. 120 ° F. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL with tap water and disintegrated by 3,000 revolutions in a TAPPI Standard Disintegrator before P952 of the development of the test samples.

The 10G sample is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer ® (Lightnin ', Rochester, NY) in a "water bath at 120 ° F. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour At the end of the enzyme reaction period, the pH of the enzyme / paste combination pulp was adjusted to approximately 10 with 0.1 normal sodium hydroxide.After a pH adjustment, 25 L was added to a 6% (w / v) solution of n-Dodecenylsuccinate Disodium Salt (preparation described above) to the mixture enzyme / pulp pa to achieve an addition level of 5% (weight of active chemo agent / dry fiber base weight) and let continue mixing by A0 P952 minutes more at 120 ° F. "After 30 minutes of mixing, the pH of the enzyme / pulp / n-Dodecenylsuccinate paste was adjusted to pH 7 with normal sulfuric acid 1. After adjusting for pH, 2.15 g of zinc chloride (JT Baker, Phillipsburg, NJ) in 20 mL of distilled water and added to the enzyme / pulp / n-Dodecenylsuccinate paste and mixed for another 5 minutes at 120 ° F. At the end of the treatment, the paste The pulp was quantitatively transferred and drained in a Buchner funnel with filter paper The resulting modified pulp cake was then diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a TAPPI Standard Disintegrator prior to the preparation of the samples. proof.

The sample 10H is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then added to the mixture P952 ~ "~~ Enzyme / buffer The mixing speed of the Lightnin'® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide.After a pH adjustment, 5 mL was added to a 6% (w / v) solution of disodium salt of n- Octadecenyl succinate (preparation described above) to the enzyme / pulp paste mixture to achieve an addition level of 1% (weight of active chemo agent / dry fiber base weight) and allowed to continue mixing for a further 30 minutes at 120 ° F. After 30 minutes of mixing, the pH "of the enzyme / pulp / n-Octadecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After pH adjustment, 0.27 g of calcium chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Octadecenyl succinate paste and mixed for another 5 minutes at room temperature. 120 ° F .. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a TAPPI Standard Disintegrator prior to making the samples of P952 test.

The sample 101 is made from NSK pulp which is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide. After a pH adjustment, 25 mL was added to a 6% (w / v) solution of n-Octadecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp mixture to achieve an addition level of 5%. % (weight of active agent uimio / dry fiber base weight) and allowed to continue mixing for 30 minutes.

P952 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Octadecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After pH adjustment, 1.36 g of calcium chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Octadecenylsuccinate paste and mixed for another 5 minutes at room temperature. 120 ° F. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL with tap water and disintegrated for 3,000 revolutions in a TAPPI Standard Disintegrator prior to the preparation of the test samples.

Sample 10J is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F P952 with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide. After a pH adjustment, 5 mL was added to a 6% (w / v) solution of n-Dodecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp mixture to achieve an addition level of 1. % (weight of active agent guimio / dry fiber base weight) and allowed to continue mixing for 30 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Dodecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After the pH adjustment, 0.35 g of calcium chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 L of distilled water and added to the enzyme / pulp / n-Dodecenylsuccinate paste and mixed for another 5 minutes at room temperature. 120 ° F. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL with tap water and disintegrated by 3,000 revolutions in a TAPPI Standard Disintegrator before P952 of the development of the test samples.

The 10K sample is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide. After a pH adjustment, 5 mL was added to a 6% (w / v) solution of n-Octadecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp paste mixture to achieve an addition level of 1. % (weight of active chemo agent / dry fiber base weight) and allowed to continue mixing for 30 minutes.

P952 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Octadecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After pH adjustment, 0.33 g of zinc chloride "(JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Octadecenyl succinate paste and mixed for another 5 minutes. at 120 ° F. At the end of the treatment, the pulp was quantitatively transferred and drained in a Buchner funnel with filter paper The resulting modified pulp cake was then diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a TAPPI Standard Disintegrator before the development of the test samples.

Sample 10L is made from NSK pulp which is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F P952 with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide. After a pH adjustment, 25 mL was added to a 6% (w / v) solution of n-Octadecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp mixture to achieve an addition level of 5%. % (weight of active chemo agent / dry fiber base weight) and allowed to continue mixing for 30 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Octadecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After the pH adjustment, 1.66 g of zinc chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Octadecenyl succinate paste and mixed for another 5 minutes. 120 ° F. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL with tap water and disintegrated by 3,000 revolutions in a Disintegrator.

P952 Standard TAPPI before the preparation of the test samples.

The 10M sample is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin® mixer is increased to achieve continuous replenishment and stirring of the pulp and left to react for about 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide.After a pH adjustment, 25 mL was added to a 6% solution ( weight / volume) of n-Dodecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp mixture to achieve an addition level of 5% (weight of active chemo agent / weight P952 dry fiber base) and allowed to continue mixing for 30 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Dodecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After adjusting for pH, 2.15 g of zinc chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Dodecenylsuccinate paste and mixed for another 5 minutes. 120 ° F. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL under running water and disintegrated for 3,000 revolutions in a TAPPI Standard Disintegrator prior to the preparation of the test samples.

The ION sample is made from NSK pulp that is modified by the following processes: The fibers are treated at approximately 3% starting consistency. First, distilled water preheated to 120 ° F is mixed with 15 mL of a 2% solution of Carezyme® (1% volume / weight of addition of Carezyme® 5.0 L on pure dry pulp) for approximately 15 seconds using a Lightnin laboratory mixer '® (Lightnin', Rochester, NY) in a 120 ° F water bath. The unmodified pulp cake was preheated to approximately 120 ° F P952 with a microwave oven and then enzyme / buffer was added to the mixture. The mixing speed of the Lightnin'® mixer increases to achieve the continuous replenishment and stirring of the pulp and is allowed to react for approximately 1 hour. At the end of the enzyme reaction period, the pH of the enzyme / pulp paste combination was adjusted to approximately 10 with 0.1 normal sodium hydroxide. After a pH adjustment, 25 mL was added to a 6% (w / v) solution of n-Dodecenylsuccinate Disodium Salt (preparation described above) to the enzyme / pulp paste mixture to achieve an addition level of 5%. % (weight of active chemo agent / dry fiber base weight) and allowed to continue mixing for 30 more minutes at 120 ° F. After 30 minutes of mixing, the pH of the enzyme / pulp / n-Dodecenylsuccinate paste was adjusted to pH 7 with 1 standard sulfuric acid. After pH adjustment, 1.75 g of calcium chloride (JT Baker, Phillipsburg, NJ) was dissolved in 20 mL of distilled water and added to the enzyme / pulp / n-Dodecenylsuccinate paste and mixed for another 5 minutes at room temperature. 120 ° F. At the end of the treatment, the pulp was transferred quantitatively and drained in a Buchner funnel with filter paper. The resulting modified pulp cake was then diluted to 2,000 mL with tap water and disintegrated by. 3,000 revolutions in a TAPPI Standard Disintegrator before P952"" "" "of the preparation of the test samples Table 10 gives the results of the dry tension indexes with zero extension, the relationship between the flexural modulus and the dry tension, the dry tension" and the tension index, the caliber and the base weights of the samples of low density test sheets that were made. It can be seen from the table that the enzymatic modification of the fibers with Carezyme® followed by the debonder and the addition of salt results in a considerable reduction in the dry tensile index with zero extension (DZST) of the NSK fibers, while maintaining or improves the overall dry tension (DT) index of the sheet compared to the test sheet sample produced from unmodified control fibers. In addition, the sheets produced from the modified fibers exhibit substantially reduced modulus of flexion / tension ratios against those shown by the control sample. The average of the dry bending / tension modulus ratio for the test sheets produced from Carezyme® and the debonder and the enzyme-only fibers are 564 cm "2 and 673 cm" 2, respectively, which corresponds at an average reduction of 30.5% and 17.1%. These reductions indicate improved flexibility of smoothness at an equal caliber and a resistance to dry stress P952 with the combination of Carezyme® and debonder being preferred, TABLE 10 P952 *: CZ = Carezyme® 5. O L CC = Celluclast® 1.5 L DDS = Disodium salt of n-Dodecenylsuccinate ODS = N-Octadecenylsuccinate Disodium Salt ZnCl2 = zinc chloride CaCl2 = calcium chloride **: Not a. example of the present invention.

P952

Claims (15)

1. CLAIMS i 1. Modified cellulosic fibers having a dry tensile strength index with zero extension that is at least 35% less than the dry tensile strength with zero extension of the corresponding unmodified cellulosic fibers.
2. 2. Modified cellulosic fibers that exhibit a ratio between the dry tensile strength index of zero extension and the wet tensile strength index of zero extension of between 1.5 and 3.
3. 3. Modified cellulose fibers according to the claim 1 or 2, which has a dry tensile strength index of zero extension that is at least 40% smaller, preferably at least 45% less than the zero tensile strength index of the fibers corresponding unmodified cellulose.
4. 4. The modified cellulosic fibers according to claim 1, characterized in that the fibers are selected from the group consisting of softwood kraft pulp from the north, south and tropical, preferably from the group consisting of modified kraft fibers of softwood North, Modified Kraft fibers from southern softwood and mixtures thereof, modified Kraft pulp from northern, southern and tropical hardwood; modified sulphite pulps P952 hardwood from the north, south and tropical; Modified sulphite pulps of soft wood from the north, south and tropical, and mixtures thereof.
5. 5. The modified cellulosic fibers according to any of claims 1 to 4, characterized in that the modified fibers are prepared by combining one or more cellulase enzymes and cellulosic fibers and allowing the combination to react for a sufficient time to reduce the resistance index to the cellulose fibers. Zero extension dry tension of the fibers by at least 35%.
6. 6. A fibrous structure having a density of not more than 0.4 g / cc, characterized in that the fibrous structure comprises modified cellulose fibers having a dry tensile strength index with zero extension that is at least 15% lower to the dry tensile strength index of zero extension of the corresponding unmodified cellulosic fibers; and further characterized in that the fibrous structure has a modulus of flexion per unit of tensile strength in dry which is at least 30% less than the modulus of flexion per unit of tension in dry of a fibrous structure prepared from the fibers not corresponding modifications.
7. 7. The fibrous structure according to claim 6, characterized in that the structure P952"fibrous comprises modified cellulosic fibers having a dry tensile strength index with zero extension that is at least 20% smaller, preferably at least 25% less than the extended dry tensile strength index zero of the corresponding unmodified cellulosic fibers, and which is further characterized in that the fibrous structure has a flexural modulus per dry unit of tension that is at least 35% smaller, preferably at least 40% smaller than the modulus of bending by dry tension unit of a fibrous structure prepared from the corresponding unmodified fibers 8.
8. The fibrous structure according to claim 6 or 7, characterized in that the modified fibers are selected from the group consisting of modified kraft pulps of soft northern, southern and tropical wood, modified kraft pulp from northern, southern and tropical hardwoods, modified sulfite pulp e hard wood from the north, south and tropical; Modified sulphite pulp from soft wood from north, south and tropical; and mixtures thereof.
9. The fibrous structure according to any of claims 6 to 8, characterized in that the test sheet consists essentially of modified cellulosic fibers having an index of resistance to P952 dry strength which is at least 90% the dry tensile strength index of a corresponding test sheet consisting essentially of corresponding unmodified cellulosic fibers, preferably a dry tensile strength index which is at least 5% higher than the dry tensile strength index of a corresponding test sheet consisting essentially of corresponding unmodified cellulosic fibers.
10. 10. A method for preparing modified cellulosic fibers, the method comprising combining one or more cellulase enzymes and cellulosic fibers and allowing the combination to react for a sufficient period to reduce the dry tensile strength index with zero extension of the fibers by at least 35% compared to the dry tensile strength index of zero extension of the corresponding unmodified fibers.
11. The method according to claim 10, characterized in that the detaching agent also reacts with the fibers.
12. 12. The method according to claim 10 or 11, characterized in that one or more enzymes belong to the family 45 of the cellulase class and are combined with cellulosic fibers, preferably one or more enzymes are P952 - selected from the group consisting of endoglucanase EGV, Celluclast®, Celluzyme®, Pergolase® and mixtures thereof. The method according to claim 11, characterized in that one or more of the debonding agents is mixed with the cellulosic fibers after the fibers are reacted with one or more enzymes. The method according to claim 11 or 13, characterized in that one or more debonding agents is combined with the fibers at a level of at least 1%, based on the dry weight of the modified fibers. The method according to claim 11, 13 or 14, characterized in that one or more debonding agents is selected from the group consisting of saturated and unsaturated fatty acids and salts of fatty acids, alkenyl succinic anhydrides; alkenylsuccinic acids; alkenyl succinate salts; mono-, di- and tri-esters of sorbitan; tertiary amines and derivatives thereof, amine oxides, quaternary amines; silicone-based compounds; particulate clays; particulate silicates and mixtures thereof. P952 SUMMARY OF THE INVENTION [0002] Modified cellulosic fibers having a tensile strength index with zero extension that is essentially lower than the tensile strength index with zero extension of the corresponding unmodified cellulosic fibers are exposed. Fibers having a dry tension with zero extension can provide fibrous structures that have better tactile perception compared to fibers prepared from unmodified fibers. In particular, these modified fibers provide fibrous structures with improved flexibility that is perceived as improved smoothness. The dry tensile strength with reduced zero extension is preferably achieved by reacting the fibers with one or more cellulase enzymes and one or more debonders. The invention also relates to a fibrous structure having a density of not more than about 0.4 g / cc, wherein the fibrous structure comprises modified cellulosic fibers having a dry tensile strength of zero extent which is at least about 15% less than the dry tensile index of zero extension of the corresponding unmodified cellulosic fibers and wherein the fibrous structure has a modulus of flexion per dry unit of tension that is at least about 30% less than P952, «\ 158 modulus of flexion per unit of dry tension of a fibrous structure prepared from the corresponding unmodified fibers. P952