JP2006525432A - Flexible fibrous structure - Google Patents

Abstract

Fibrous structures exhibiting a slip-stick friction coefficient of less than about 0.023 and a B compressibility of about 15 to about 50, in particular, fibrous structures dried by ventilation, and / or slip-stick friction of less than about 0.0175. Provided is a fibrous structure exhibiting a modulus, especially a fibrous structure that is air-dried.

Description

  The present invention relates to fibrous structures, particularly through-air-dried fibrous structures exhibiting a slip-stick coefficient of friction of less than about 0.023 and a B compressibility of about 15 to about 50, and / or Or a fibrous structure exhibiting a slip-stick coefficient of friction of less than about 0.0175, particularly a ventilated and dried fibrous structure.

  It is well known in the art that the flexibility of a fibrous structure or sanitary tissue product, particularly an air-dried sanitary tissue product incorporating the fibrous structure, is inversely proportional to the total tensile strength of the fibrous structure or sanitary tissue product. is there. In addition, the flexibility of fibrous structures or sanitary tissue products, especially air-dried sanitary tissue products incorporating the fibrous structure, is inversely proportional to the caliper (thickness) of the fibrous structure or sanitary tissue product. It is well known in the field.

  The attempt by formulators to overcome these inverse proportions, particularly the relationship between flexibility and total tensile strength, is that the cationic nature of the sanitary tissue product and / or the fibrous structure that constitutes such product Silicone addition was included. See, for example, U.S. Pat. No. 5,059,282 by Ampulski et al.

  Formulators attempted to attach a softener, such as a silicone material, to the outer surface of the fibrous structure to achieve the flexibility and / or smoothness desired by the consumer. Such prior art fibrous structures exhibited a coefficient of friction of about 0.72 to about 1.07, or a slip-stick coefficient of friction of at least 0.0207, or a B compressibility of 17 or less.

  Previous formulators have found that fibrous structures exhibiting a slip-stick coefficient of friction of less than about 0.023 and a B compressibility of about 15 to about 50, particularly fiber-dried fiber structures, and / or about 0.0175. No fibrous structure exhibiting a slip-stick friction coefficient of less than that, particularly a fiber structure that has been air-dried, has not been developed. Thus, less than about 0.023 slip-fibrous structures exhibiting a coefficient of sticking friction and a B compressibility of about 15 to about 50, in particular ventilated fibrous structures, and / or less than about 0.0175 slip- It has long been desired to provide a fibrous structure exhibiting a sticking friction coefficient, in particular a fiber structure that is air-dried.

  The present invention provides a fibrous structure that exhibits a slip-stick coefficient of friction of less than about 0.023, and optionally exhibits a B compressibility of about 15 to about 50, in particular an air-dried fibrous structure, This fulfills the above requirements.

  In one aspect of the invention, a fibrous structure is provided that exhibits a slip-stick coefficient of friction of less than about 0.023 and / or less than about 0.021 and / or less than about 0.0190 and / or less than about 0.0175. Is done.

  In another aspect of the invention, a fibrous structure is provided that exhibits a slip-stick coefficient of friction of less than about 0.023 and a B compressibility of about 15 to about 50.

  In yet another aspect of the invention, a single ply sanitary tissue product or a multi-ply sanitary tissue product comprising the fibrous structure of the invention is provided.

  Accordingly, the present invention provides a fibrous structure that exhibits a slip-stick friction coefficient of less than about 0.023, a fibrous structure that exhibits a slip-stick friction coefficient of less than about 0.023 and a B compressibility of about 15 to about 50. And a single-ply sanitary tissue product or a multi-ply sanitary tissue product comprising the fibrous structure of the present invention.

  As used herein, “fiber” means an elongated microparticle having an apparent length much greater than its apparent width, ie, a length to diameter ratio of at least about 10. More specifically, as used herein, “fiber” refers to papermaking fiber. The present invention contemplates the use of a variety of papermaking fibers, such as natural or synthetic fibers, or any other suitable fiber, and any combination thereof. Papermaking fibers useful in the present invention include cellulose fibers commonly known as wood pulp fibers. Available wood pulps include chemical pulps such as kraft pulp (especially Northern Softwood Kraft ("NSK")), sulfite pulp, and sulfate pulp, as well as, for example, groundwood pulp, thermomechanical pulp, And mechanical pulps such as chemically modified thermomechanical pulps. Non-limiting examples of wood pulp include Acacia, Eucalyptus, Maple, Oak, Aspen, Birch, Cottonwood, Alder, Ash, Cherry, Elm, Hickory, Poplar, Gum, Walnut, False Acacia, Sycamore, Beech, Catalpa, Sassafras, Gmelina, Albizia, Anthocephalus, Magnolia, Bagasse, Flax, Hemp, Kenaf ), And fibers derived from a fiber source selected from the group consisting of mixtures thereof. However, chemical pulp may be preferred because tissue sheets made from chemical pulp are provided with excellent tactile flexibility. Pulp derived from both deciduous trees (hereinafter also referred to as “broadleaf trees”), in particular tropical broadleaf trees, and cones (hereinafter also referred to as “coniferous trees”) may be used. Hardwood fibers and coniferous fibers can be mixed or laminated in layers to provide a layered web. U.S. Pat. Nos. 4,300,981 and 3,994,771 are incorporated herein by reference for the purpose of disclosing hardwood and coniferous fiber stratification. Also, fibers derived from recycled paper that may contain any or all of the above classifications, as well as other non-fibrous materials such as fillers and adhesives used to facilitate initial papermaking. Can be used in the present invention.

  In addition to various wood pulp fibers, other cellulosic fibers such as cotton linters, rayon and bagasse can be used in the present invention. Synthetic fibers such as polymer fibers can also be used. Elastomeric polymers, polypropylene, polyethylene, polyester, polyolefin and nylon can be used. The polymeric fibers can be made by spunbonding, meltblown, and other suitable methods known in the art. One exemplary polyethylene fiber that can be used is Pulpex® available from Hercules, Inc. (Wilmington, Del.).

  In addition to the above, fibers and / or long fibers made from polymers, specifically hydroxyl polymers, may be used in the present invention. Non-limiting examples of suitable hydroxyl polymers include polyvinyl alcohol, starch, starch derivatives, chitosan, chitosan derivatives, cellulose derivatives, gums, arabinans, galactans, and mixtures thereof.

  The initial fiber web can generally be made from an aqueous dispersion of papermaking fibers, although dispersions in liquids other than water can also be used. The fibers can be dispersed in the carrier liquid to have a concentration of about 0.1% to about 0.3%. It is also contemplated that the present invention may be applicable to wet paper forming operations where the fibers are dispersed in a carrier fluid and have a concentration of less than about 50%, more preferably less than about 10%.

As used herein, “sanitary tissue products” refers to wiping tools (toilet paper) for urination and post-defecation cleaning, wipes for otolaryngological secretions (facial tissue) And / or handkerchief) and a soft, low density (ie, less than about 0.15 g / cm ³ ) web useful as a multi-functional use for absorption and cleaning (absorbent towels). Those properties and values described herein for the fibrous structures described herein may also appear in sanitary tissue products that incorporate the fibrous structures.

  As used herein, “weight average molecular weight” refers to “Colloids and Surfaces A. Physico Chemical & Engineering Aspects”, Volume 162, 2000, pages 107-121. By weight-average molecular weight determined using gel permeation chromatography according to the protocol found.

  As used herein, “ply” or “plies” are arbitrarily placed in a face-to-face relationship substantially in contact with other plies to form a multi-ply fibrous structure. Means a fibrous structure. It is also believed that a single fibrous structure can effectively form two “plies” or multiple “plies”, for example by folding on itself.

  As used herein, “caliper” means the macroscopic thickness of a sample. A caliper of a sample of the fibrous structure and / or sanitary tissue product of the present invention is available from Swing-Albert Instrument Company (Philadelphia, PA). Obtained by VIR Electronic Thickness Tester Model II. The caliper measurement can be repeated and recorded at least 5 times so that an average caliper can be calculated. Results are recorded in millimeters.

  As used herein, “smoothness” and / or “physiological surface smoothness” is obtained from a machine-direction scanning of a fibrous structure and / or sanitary tissue product sample by a surface gauge having a diamond needle. Coefficient (hereinafter referred to as PSS coefficient and / or SMD coefficient). The surface gauge at this time is attached to the surface test apparatus as described in, for example, the 1991 International paper Physics Conference. In addition, smoothness and / or the opposite of smoothness (ie, roughness) is determined by Kato Tekko Co., LTD. (Karato-Cho, Kyoto, Japan) It can also be measured using a Kato Surface Tester KES-FB4 available from Nishikiyo, Minami-Ku, Koyota, Japan)). Alternatively, the smoothness of the fibrous structure and / or sanitary tissue product of the present invention is determined by the Primos optical surface meter / three-dimensional available from GF Messtechnik (Berlin, Germany). It can be measured using a surface analyzer (Primos Optical Profiler / 3D Surface Analyzer). The smoothness of the fibrous structure and / or sanitary tissue product comprising the fibrous structure is greater than about 500 and / or from about 500 to about 1200, and / or from about 550 to about 1000, and Desirably, it is from about 600 to about 950 and / or from about 650 to about 900.

  “Slip Stick Coefficient of Friction” (S & S COF) is defined as the average deviation of the friction coefficient. Similar to the coefficient of friction, the sliding-fixed coefficient of friction is dimensionless. This test is performed using a KES-FB4 surface analyzer from Kato Tekko Co., LTD. With an improved friction probe. The probe sled is a glass frit with a diameter of 2 centimeters and 40-60 μm obtained from Ace Glass Company. The vertical resistance of the probe is 19.6 grams. For details of the above procedure, see “Methods for measuring the mechanical properties of tissue paper” by Ampulski et al, 1991, International Paper Physics Conference, page 19. Measurement of the Mechanical Properties of Tissue Paper), which is incorporated herein by reference.

  In one embodiment, the fibrous structure has a slip-stick coefficient of friction of about 0.010 to about 0.021 and / or about 0.0135 to about 0.0190 and / or about 0.0135 to about 0.0175. Show.

  The “total dry tensile strength” or “TDT” of a fibrous structure and / or a sanitary tissue product comprising such a fibrous structure is measured as follows. A 2.5 cm × 12.7 cm (1 inch × 5 inch) fibrous structure and / or a strip of paper product containing such fibrous structure is provided. The strips were placed in a conditioned room at a temperature of about 28 ° C. ± 2.2 ° C. (73 ° F. ± 4 ° F.) and 50% ± 10% relative humidity in Instron Corp. (Canton)) is placed on an electronic tensile tester model 1122 commercially available. The tensile tester has a crosshead speed of about 5.1 cm / min (2.0 inches / min) and a gauge length of about 10.2 cm (4.0 inches). TDT is the arithmetic sum of the MD and CD tensile strength of the strip.

  As used herein, “wet burst strength” refers to a fibrous structure and / or paper when the fibrous structure and / or paper product is wetted and deformed vertically. A measure of the ability of a sanitary tissue product incorporating the product to absorb energy. Wet burst strength is Swing Albert Burst equipped with a 2000g load cell, commercially available from Thwing-Albert Instrument Company (Philadelphia, PA). It can be measured using a tester catalog number 177 (Thwing-Albert Burst Tester Cat. No. 177). In one embodiment, the wet burst strength of the fibrous structure of the present invention and / or sanitary tissue products comprising the fibrous structure is greater than about 10 g / cm and / or from about 12 g / cm to about 394 g / cm. cm, and / or from about 13 g / cm to about 197 g / cm, and / or from about 15 g / cm to about 197 g / cm, and / or from about 15 g / cm to about 78 g / cm.

As used herein, “basis weight” is the weight per unit area of a sample reported in lbs / 3000 ft ² or g / m ² . The basis weight is 0.01 g of one or more samples having a specific area (m ² ), which is a fibrous structure according to the present invention and / or a paper product containing such a fibrous structure. It is measured by weighing with a pan balance having a minimum sensitivity of. The balance is protected from airflow and other disturbances by using a windshield. When the balance display stabilizes, the weight is recorded. The average weight (g) and the average area (m ² ) of the sample are calculated. The basis weight (g / m ² ) is calculated by dividing the average weight (g) by the average area (m ² ) of the sample. In one embodiment, the basis weight of the fibrous structure of the present invention and / or sanitary tissue product comprising the fibrous structure is about 12 g / m ² to about 120 g / m ² , and / or about 14 g / m ^2. To about 80 g / m ² , and / or about 17 g / m ² to about 70 g / m ² , and / or about 20 g / m ² to about 60 g / m ² . Typically, a single ply fibrous structure has a basis weight of from about 12 g / m ² to about 50 g / m ² .

  As used herein, “machine direction” or “MD” means a direction parallel to the flow of fibrous structures through a paper machine and / or product manufacturing equipment.

  As used herein, “cross-machine direction” (“CD”) means the direction perpendicular to the machine direction in the same plane of the fibrous structure and / or paper product containing the fibrous structure.

As used herein, “apparent density” or “density” means the basis weight of a sample divided by caliper using the appropriate degree of processing incorporated into the sample. Apparent density used herein is expressed in units of g / cm ³ .

  As used herein, “total dry tensile strength” means the geometric mean of the breaking strength in the machine direction and the cross machine direction in grams per cm width of the sample. Mathematically, this is the square root of the product of the machine direction and the cross machine direction fracture strength in grams per cm width of the sample. In one embodiment, the fibrous structure of the present invention and / or the sanitary tissue product comprising the fibrous structure has a total dry tensile strength of greater than about 39 g / cm and / or greater than about 59 g / cm, and / Or about 63 g / cm to about 1575 g / cm, and / or about 78 g / cm to about 985 g / cm, and / or about 78 g / cm to about 394 g / cm, and / or about 98 g / cm to about 335 g / cm. It is. Typically, a single-ply fibrous structure has a total dry tensile strength of about 39 g / cm to about 590 g / cm.

  As used herein, “flexibility” means the slope of the secant of a graph curve derived from force data for percent elongation, which secant passes through the origin (0% elongation, zero force) and is a centimeter wide. Pass through a point on the graph curve where the force per meter is 20 grams.

  As used herein, “total flexibility” means the geometric mean of machine direction flexibility and machine direction flexibility. Mathematically this is the square root of the product of machine direction flexibility and machine direction flexibility in grams per cm.

  As used herein, “WABY coefficient” means the average of the ratio of total flexibility to total tensile strength. The Waveby coefficient is measured as a coefficient characterizing embodiments of the present invention that have high strength but high bulk flexibility. For this reason, this ratio is referred to as a WABY coefficient. For example, a sample having a total flexibility of 20 g / cm and a total tensile strength of 154 g / cm has a WABY coefficient of 0.13. The fibrous structure and / or sanitary tissue product comprising the fibrous structure is less than about 0.2 and / or from about 0.05 to about 0.15 and / or from about 0.06 to It is desirable to have a WABY factor of about 0.13 and / or about 0.06 to about 0.11.

  In short, the perceived softness of tissue paper is related to its WABY factor. Also note that this WABY coefficient is dimensionless. This is because, as defined above, the flexibility and total tensile strength are both g / cm, and the proportions are dimensionless.

  As used herein, “B compressibility” refers to the intercept of a curve that results from plotting weight versus thickness obtained in a compression test.

  As used herein, “Lint” is Vinson et al., US Pat. No. 5,814,188, issued September 29, 1998, assigned to the assignee. (This patent document is incorporated herein by reference).

  The fibrous structure of the present invention and / or a sanitary tissue product using the fibrous structure may include one or more of the following experimentally measured parameter ranges and / or two or more and / or Characterized as being contained within a multi-parametric domain defined by three or more: 1) caliper; 2) physiological surface smoothness; 3) slip-stick friction coefficient; 4) total tensile strength; 5) flexibility; 6) basis weight; 7) wet burst strength; 8) coefficient of friction; 9) WABY coefficient; and / or 10) B compressibility.

  Surprisingly, the fibrous structure and sanitary tissue product incorporating the fibrous structure have a coefficient of friction of about 0.65 to about 0.6, in addition to having a sliding-stick coefficient of friction of less than about 0.023. 0.83 and / or about 0.65 to about 0.81 and / or about 0.71 to about 0.81 and / or B compressibility of about 15 to about 50 and / or about 20 to about 40. Thus, it has been found that it exhibits higher flexibility and / or smoothness than known fibrous structures.

  As used herein, the articles “a” and “an” as used herein, eg, “an anionic surfactant” or “a fiber”. Is understood to mean one or more of the claimed or described substances.

  All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.

  Unless otherwise stated, all concentrations of a component or composition relate to the activity level of the component or composition and exclude impurities, such as residual solvents or byproducts, that may be present in commercial sources. The

(Fibrous structure)
The fibrous structure and / or tissue paper of the present invention can be produced by various methods. Non-limiting examples of fibrous structure types and / or tissue paper types include tissue papers that are normally pressed and / or felt pressed; patterned forming wires and / or patterned fibers / resin belts And densified tissue paper; high bulk uncompressed tissue paper; and creped or non-creped tissue paper. The tissue paper may be of a homogeneous structure and / or a single layer structure or a multilayer structure, and the tissue paper product made therefrom may be a single ply structure or a multi-ply structure.

  Furthermore, the fibrous structure of the present invention and / or the sanitary tissue product comprising it may be creped or not creped.

  Furthermore, sanitary tissue products incorporating the fibrous structure of the present invention may include dry fibers from an airlaid process and / or latex binders from a wet laid process.

  Using conventional processing methods, the fibrous structure dry roll of the present invention can be processed into single-ply and / or multi-ply sanitary tissue products. Non-limiting examples of such processing methods include embossing, including high pressure embossing, dry creping, ply bonding, calendering, and / or other mechanical processing to fibrous structures. Can be mentioned.

  The fibrous structure may be made using a fibrous furnish that creates a single layer initial fibrous web or a fibrous furnish that creates a multilayer initial fibrous web.

  The properties described herein may be for a single-ply fibrous structure and / or a single-ply sanitary tissue product and / or at least one ply comprising the fibrous structure of the present invention. It may be for an incorporated multi-ply sanitary tissue product.

(Fibre finished paper)
In one embodiment, the fibrous structure is made from a fiber furnish. In another embodiment, the fibrous structure is made by a meltblown method and / or a spunbond method and / or a rotary die method. The fiber furnish of the present invention comprises one or more fibers and usually one or more optional ingredients.

(Optional component)
The fibrous structure of the present invention comprises a permanent wet strength improving resin; a chemical softener such as silicone, particularly cationic silicone, and / or a quaternary ammonium compound; a temporary wet strength improving resin; dry strength resins); wetting agents; lint resisting agents: absorption enhancers; optional ingredients selected from the group consisting of immobilizing agents, in particular emollient lotion compositions, antivirals comprising organic acids Agents, antibacterial agents, polyol polyesters, antimigration agents, polyhydroxy plasticizers, fillers (clays), humectants, and mixtures thereof may be included. Such optional ingredients can be added to the fibrous furnish, the initial fibrous web, and / or the dried fibrous structure. Such optional ingredients may be present in the fibrous structure in any concentration based on the dry weight of the fibrous structure.

  The optional ingredients can be applied to the fibrous furnish, and / or the initial fibrous web, and / or the dried fibrous structure, and / or the sanitary tissue product of the present invention. In addition, the optional ingredients (eg other chemical softeners, more specifically lotions, especially transferable lotions) can be applied after application of cationic silicones. , May be applied to dried fibrous structures and / or sanitary tissue products.

  The optional ingredient is about 0.001% to about 50% by weight and / or about 0% in the fibrous structure and / or sanitary tissue product of the present invention, based on the dry fibrous structure or sanitary tissue product. 0.001% to about 30%, and / or about 0.001% to about 22%, and / or about 0.01% to about 5%, and / or about 0.03% by weight It may be present at a concentration of about 3%, and / or about 0.05% to about 2%, and / or about 0.1% to about 1% by weight.

(Chemical softener)
Non-limiting examples of suitable chemical softeners include silicones, particularly cationic silicones, more preferably one or more polysiloxane units, preferably of the formula — {(CH ₃ ) ₂ SiO} _c —. Organosilicone comprising polydimethylsiloxane units (with a degree of polymerization c of 1-1000, preferably 20-500, more preferably 50-300, most preferably 100-200) and at least one diquaternary unit Examples include cationic silicones containing non-containing units. In one preferred embodiment of the present invention, the cationic silicone polymer selected is from 0.05 to 1.0 mole fraction, more preferably from 0.2 to 0.95 mole fraction, most preferably from 0.00. It has 5 to 0.9 mole fraction of organosilicone-free units selected from cationic divalent organic moieties. The cationic divalent organic moiety is preferably selected from N, N, N ′, N′-tetramethyl-1,6-hexanediammonium units.

The cationic silicone polymer selected is also from 0 to 0.95 mole fraction of the total organosilicone-free unit, preferably from 0.001 to 0.5 mole fraction, more preferably from 0.05 to 0.2. Mole fractions of polyalkylene oxide amines of the formula:
[—Y—O (—C _a H _2a O) _b —Y—]
Wherein, Y is a divalent organic group containing a secondary or tertiary amine, preferably the C ₁ -C ₈ alkylene amine residue; a is 2 to 4, b is 0 to 100 is there. The polyalkylene oxide block may be composed of ethylene oxide (a = 2), propylene oxide (a = 3), butylene oxide (a = 4), and mixtures thereof in a random or block fashion.

  Such polyalkylene oxide amine-containing units can be obtained by introducing into the silicone polymer structure a compound such as that sold by Huntsman Corporation under the trade name Jeffamine®. Obtainable. A preferred Jeffamine is Jeffamine ED-2003.

The cationic silicone polymer selected is also 0, preferably 0.001-0.2 mole fraction of —NR ₃ + (where R is alkyl, hydroxyalkyl, or Phenyl). These units can be thought of as end caps.

Furthermore, the selected cationic silicone polymer is generally an anion selected from inorganic and organic anions, more preferably saturated and unsaturated C ₁ -C to balance the quaternary charge. _It contains anions selected from ₂₀ carboxylates and mixtures thereof, so the cationic silicone polymer also contains such anions in proportions that balance the charge of the quaternary moieties.

  Conceptually, the selected cationic silicone polymers herein are non-fabric-substantive "loops composed of polysiloxane units that change the surface energy but not the fabric. "And fabric-substantive" hooks "conveniently considered as non-crosslinked or" linear "block copolymers. One preferred class of selected cationic polymers (represented below by Structural Formula 1) is considered to include one loop and two hooks; another highly preferred one is more than one, Preferably comprises three or more “loops” and two or more, preferably three or more “hooks” (represented by structural formulas 2a and 2b below), and yet another (hereinafter structural formulas). 3) includes two “loops” that are pendant from one “hook”.

  Of particular importance in this selection of cationic silicone polymer is that “hooks” do not contain silicone and each “hook” contains at least two quaternary nitrogen atoms.

  Also important in selecting the preferred cationic silicone polymers in the present invention is that the quaternary nitrogen is preferentially located in the “main chain” of the “linear” polymer, In contrast to alternative less preferred structures in which the quaternary nitrogen is incorporated into one or more parts that form a “pendant” or “sag” structure from the “backbone”.

The structure is completed by a terminal portion, which can be an uncharged portion or a charged portion. In addition, certain proportions of non-quaternary silicone-free moieties may also be present, for example, the aforementioned [—Y—O (—C _a H _2a O) _b —Y—] moiety.

  It goes without saying that the conceptual model presented is not intended to limit other parts, such as the connector part, which substantially function as intended as a tissue benefit agent. It can be present in the selected cationic silicone polymers provided it does not interfere.

  More particularly, the cationic silicone polymers herein have one or more polysiloxane units and one or more quaternary nitrogen moieties, including cationic silicone polymers. Include polymers having the following formula:

式中：
−Ｒ¹は、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、
Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、及びこれらの混合物から成る群より独立して選択され；
−Ｒ²は、１個以上の酸素原子を含有しうる二価の有機部分（このような部分は好ましくはＣとＨ、又はＣとＨとＯから構成される）から成る群より独立して選択され；
−Ｘは、開環エポキシド類からなる群から独立して選択され；
−Ｒ³は、次式：
−Ｍ¹（Ｃ_aＨ_2aＯ）_b−Ｍ²
式中、Ｍ¹は、二価の炭化水素残基であり；Ｍ²は、Ｈ、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル、及びこれらの混合物からなる群から独立して選択され；
−Ｚは、少なくとも１個の四級化窒素原子を含む一価の有機部分からなる群から独立して選択され；
−ａは、２〜４であり；ｂは、０〜１００であり；ｃは、１〜１０００、好ましくは２０より大きく、より好ましくは５０より大きく、好ましくは５００より小さく、より好ましくは３００より小さく、最も好ましくは１００〜２００であり；
−ｄは、０〜１００であり；ｎは、カチオン性シリコーン・ポリマーに付随する正電荷の数であって、２つ以上であり；及びＡは、一価の陰イオンである。

In the formula:
-R ¹ is, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl,
C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, and are independently selected from the group consisting of mixtures thereof;
-R ² is independently from the group consisting of divalent organic moieties which may contain one or more oxygen atoms, such moieties preferably consisting of C and H, or C, H and O. Selected;
-X is independently selected from the group consisting of ring-opened epoxides;
-R ³ is selected from the group consisting of:
-M ¹ (C _a H _2a O) _b -M ²
Wherein, M ¹ is a divalent hydrocarbon residue; M ² is H, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, C ₁ ~ Independently selected from the group consisting of ₂₂ hydroxyalkyl, polyalkylene oxide, (poly) alkoxyalkyl, and mixtures thereof;
-Z is independently selected from the group consisting of monovalent organic moieties containing at least one quaternized nitrogen atom;
-A is 2-4; b is 0-100; c is 1-1000, preferably greater than 20, more preferably greater than 50, preferably less than 500, more preferably greater than 300. Small, most preferably 100-200;
-D is 0-100; n is the number of positive charges associated with the cationic silicone polymer and is 2 or more; and A is a monovalent anion.

  In a preferred embodiment of the structure 1 cationic silicone polymer, Z is independently selected from the following group:

から成る群より独立して選択され；
前記式中：
−Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、同一又は異なって、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル、及びこれらの混合物から成る群より選択され；
−Ｒ¹⁵は、−Ｏ−又はＮＲ¹⁹であり；
−Ｒ¹⁶は、二価の炭化水素残基であり；
−Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹は、同一又は異なって、Ｈ、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル、及びこれらの混合物から成る群より選択され；そしてｅは１〜６である。

Independently selected from the group consisting of:
In the above formula:
-R ^12, R ^13, R ¹⁴ are the same or different, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, C ₁ ~ ₂₂ hydroxyalkyl, polyalkyleneoxide , (Poly) alkoxyalkyl, and mixtures thereof;
-R ¹⁵ is an -O- or NR ^19;
-R ¹⁶ is a divalent hydrocarbon residue;
-R ^17, R ^18, R ¹⁹ are the same or different, H, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, C ₁ ~ ₂₂ hydroxyalkyl, poly Selected from the group consisting of alkylene oxides, (poly) alkoxyalkyls, and mixtures thereof; and e is 1-6.

In one highly preferred embodiment, the cationic silicone polymers herein have one or more polysiloxane units and one or more quaternary nitrogen moieties, including cationic The silicone polymer includes polymers having the following formula: (Structure 2a)
Structure 2a: Cationic silicone polymer consisting of the following alternating units:
(I) a polysiloxane of the formula

及び
（ｉｉ）少なくとも２個の四級化された窒素原子を含む二価の有機部分。

And (ii) a divalent organic moiety comprising at least two quaternized nitrogen atoms.

  Structure 2a comprises an alternating combination of both a polysiloxane of the formula described and a divalent organic moiety, the divalent organic moiety being an organosilicone-free moiety corresponding to the preferred “hook” in the foregoing description. Note that there are.

In this preferred cationic silicone polymer, R ¹ is, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, and are independently selected from the group consisting of mixtures ;
-R ² are independently selected from the group consisting of organic moieties of the or divalent optionally containing one or more oxygen atoms; X is independently selected from the group consisting of ring-opened epoxides; R ³ is independently selected from polyether groups having the formula:
-M ¹ (C _a H _2a O) _b -M ²
(Wherein, M ¹ is a divalent hydrocarbon residue; M ² is, H, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, C ₁ ~ ₂₂ is independently selected from the group consisting of hydroxyalkyl, polyalkylene oxide, (poly) alkoxyalkyl, and mixtures thereof); a is 2-4; b is 0-100; c is 1- 1000, preferably greater than 20, more preferably greater than 50, preferably less than 500, more preferably less than 300, most preferably 100 to 200; and d is 0 to 100.

  In an even more preferred embodiment of the cationic silicone polymer of structure 2a, the cationic silicone polymer is represented by formula structure 2b, in which case the polysiloxane (i) represented by the formula above in structure 2a is Included with a cationic divalent organic moiety (ii) selected from the group consisting of:

（ｉｉｉ）任意で、以下の式で表されるポリアルキレンオキシドアミン：
［−Ｙ−Ｏ（−Ｃ_aＨ_2aＯ）_b−Ｙ−］
−Ｙは、二級又は三級アミンを含む二価の有機基、好ましくはＣ₁〜Ｃ₈アルキレンアミン残基であり；ａは、２〜４であり；ｂは０〜１００であり；ポリアルキレンオキシドブロックは、エチレンオキシド（ａ＝２）、プロピレンオキシド（ａ＝３）、ブチレンオキシド（ａ＝４））及びこれらの混合物からランダム又はブロック様式で構成されていてよく；及び
（ｉｖ）任意で、以下からなる群から選択される、末端基として使用されるカチオン性一価有機部分：

(Iii) optionally a polyalkylene oxide amine represented by the following formula:
[—Y—O (—C _a H _2a O) _b —Y—]
-Y is a divalent organic group comprising a secondary or tertiary amine, preferably the C ₁ -C ₈ alkylene amine residue; a is an 2 to 4; b is 0 to 100; poly The alkylene oxide block may be composed of ethylene oxide (a = 2), propylene oxide (a = 3), butylene oxide (a = 4)) and mixtures thereof in a random or block manner; and (iv) optionally A cationic monovalent organic moiety used as a terminal group selected from the group consisting of:

式中、
−Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹は同一又は異なり：Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル、及びこれらの混合物から選択され；或いは、式中、Ｒ⁴とＲ⁶、又はＲ⁵とＲ⁷、又はＲ⁸とＲ¹⁰、又はＲ⁹とＲ¹¹は、架橋アルキレン基の構成成分であり得る；
−Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、同一又は異なり、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル基、及びこれらの混合物から選択され；
−Ｒ¹⁵は、−０−又はＮＲ¹⁹であり；
−Ｒ¹⁶及びＭ¹は、同一又は異なる二価の炭化水素残基であり；
−Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹は、同一又は異なり、Ｈ、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル、及びこれらの混合物から選択され；
−Ｚ¹及びＺ²は、少なくとも２個の炭素原子を有し、任意に、１個のヒドロキシ基を含有する、同一又は異なる二価の炭化水素基であり、これらは、１個又は複数個のエーテル、エステル、又はアミド基によって割り込まれてもよく；
この場合、オルガノシリコーン遊離部分の総モル数に対する分数として表現したとき、カチオン性二価有機部分（ｉｉ）は、好ましくは、０．０５〜１．０モル分率、より好ましくは、０．２〜０．９５モル分率、及び最も好ましくは、０．５〜０．９モル分率で存在し；ポリアルキレンオキシドアミン（ｉｉｉ）は、０．０〜０．９５モル分率、好ましくは、０．００１〜０．５モル分率、より好ましくは、０．０１〜０．２モル分率で存在することができ；存在する場合、カチオン性一価有機部分（ｉｖ）は、０〜０．２モル分率、好ましくは、０．００１〜０．２モル分率で存在し；
−ｅは、１〜６であり；ｍは、カチオン性二価有機部分に付随する正電荷の数であって、２つ以上のものであり；及びＡは、陰イオンである。

Where
^{-R 4, R 5, R 6} , R 7, R 8, R 9, R 10, R 11 are the same or different: C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkyl, aryl, cycloalkyl, C ₁ ~ ₂₂ hydroxyalkyl, polyalkyleneoxide, (poly) alkoxy alkyl, and mixtures thereof; or wherein, R ⁴ and R ^6, or R ⁵ and R ^7, or a R ⁸ R ¹⁰ or R ⁹ and R ¹¹ can be a component of a bridged alkylene group;
-R ^12, R ^13, R ¹⁴ are the same or different, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, C ₁ ~ ₂₂ hydroxyalkyl, polyalkyleneoxide, (poly) alkoxyalkyl Selected from groups, and mixtures thereof;
-R ¹⁵ is an -0- or NR ^19;
-R ¹⁶ and M ¹ are the same or different divalent hydrocarbon residues;
-R ^17, R ^18, R ¹⁹ are the same or different, H, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, C ₁ ~ ₂₂ hydroxyalkyl, polyalkylene Selected from oxides, (poly) alkoxyalkyls, and mixtures thereof;
-Z ¹ and Z ² are the same or different divalent hydrocarbon groups having at least 2 carbon atoms and optionally containing one hydroxy group, these being one or more May be interrupted by an ether, ester, or amide group of
In this case, when expressed as a fraction relative to the total number of moles of the organosilicon free part, the cationic divalent organic part (ii) is preferably 0.05 to 1.0 mole fraction, more preferably 0.2. Present in a ˜0.95 mole fraction, and most preferably in a 0.5 to 0.9 mole fraction; the polyalkylene oxide amine (iii) is in a 0.0 to 0.95 mole fraction, preferably 0.001 to 0.5 mole fraction, more preferably 0.01 to 0.2 mole fraction can be present; when present, the cationic monovalent organic moiety (iv) is 0 to 0 .2 mole fraction, preferably present in 0.001 to 0.2 mole fraction;
-E is 1-6; m is the number of positive charges associated with the cationic divalent organic moiety and is 2 or more; and A is an anion.

  Structure 2b includes an alternating combination of both polysiloxane and divalent organic moieties of the formulas described, wherein the divalent organic moiety is an organosilicone-free moiety corresponding to the preferred “hook” in the foregoing general description. Note that there are. Structure 2b further includes embodiments in which any polyalkyleneoxy moiety and / or end group moiety is present or absent.

  In yet another embodiment, the cationic silicone polymers herein have one or more polysiloxane units and one or more quaternary nitrogen moieties, including cationic silicones. The polymers include polymers having the following formula: (Structure 3)

前記式中：
−Ｒ¹は、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、
Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、及びこれらの混合物から成る群より独立して選択され；
−Ｒ²は、１個以上の酸素原子を含有しうる二価の有機部分から成る群より独立して選択され；
−Ｘは、開環エポキシド類から成る群より独立して選択され；
−Ｒ³は、以下の式で表されるポリエーテル基から独立して選択され；
−Ｍ¹（Ｃ_aＨ_2a０）_b−Ｍ²
式中、Ｍ¹は二価の炭化水素残基であり；Ｍ²はＨ、Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル、及びこれらの混合物から成る群より独立して選択され；
−Ｘは、開環エポキシド類から成る群より独立して選択され；
−Ｗは、少なくとも１個の四級化窒素を含む二価の有機部分からなる群より独立して選択され；
−ａは２〜４であり；ｂは０〜１００であり；ｃは１〜１０００、好ましくは２０より大きく、より好ましくは５０より大きく、好ましくは５００未満、より好ましくは３００未満、最も好ましくは１００〜２００であり；ｄは０〜１００であり；ｎはカチオン性シリコーン・ポリマーに付随する正電荷の価数であって、１つ以上であり；及びＡは一価の陰イオン、換言すれば、好適な対イオンである。

In the above formula:
-R ¹ is, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl,
C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, and are independently selected from the group consisting of mixtures thereof;
-R ² are independently selected from the group consisting of divalent organic moieties that may contain one or more oxygen atoms;
-X is independently selected from the group consisting of ring-opened epoxides;
-R ³ is independently selected from polyether groups represented by the following formula;
-M ¹ (C _a H _2a 0) _b -M ²
Wherein, M ¹ is a divalent hydrocarbon residue; M ² is H, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, C ₁ ~ ₂₂ hydroxy Independently selected from the group consisting of alkyl, polyalkylene oxide, (poly) alkoxyalkyl, and mixtures thereof;
-X is independently selected from the group consisting of ring-opened epoxides;
-W is independently selected from the group consisting of divalent organic moieties comprising at least one quaternized nitrogen;
-A is 2-4; b is 0-100; c is 1-1000, preferably greater than 20, more preferably greater than 50, preferably less than 500, more preferably less than 300, most preferably D is 0 to 100; n is the positive charge valence associated with the cationic silicone polymer and is one or more; and A is a monovalent anion, in other words For example, a suitable counter ion.

  In a preferred Structure 3 cationic silicone polymer, W is selected from the following group:

式中、
−Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹は、同一又は異なり、及び：Ｃ₁〜₂₂アルキル、Ｃ₂〜₂₂アルケニル、Ｃ₆〜₂₂アルキルアリール、アリール、シクロアルキル、Ｃ₁〜₂₂ヒドロキシアルキル、ポリアルキレンオキシド、（ポリ）アルコキシアルキル、及びこれらの混合物からなる群から選択され；或いは、式中、Ｒ⁴とＲ⁶、又はＲ⁵とＲ⁷、又はＲ⁸とＲ¹⁰、又はＲ⁹とＲ¹¹は、架橋アルキレン基の構成成分であり得る；及び
−Ｚ¹及びＺ²は、少なくとも２個の炭素原子を有し、任意に、１個のヒドロキシ基を含有する、同一又は異なる二価の炭化水素基であり、これらは、１個又は複数個のエーテル、エステル、又はアミド基によって割り込まれてもよい。

Where
^{-R 4, R 5, R 6} , R 7, R 8, R 9, R 10, R 11 are the same or different, and: C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl , aryl, cycloalkyl, C ₁ ~ ₂₂ hydroxyalkyl, polyalkyleneoxide, (poly) alkoxy alkyl, and mixtures thereof; or wherein, R ⁴ and R ^6, or R ⁵ and R ⁷ , or R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ , can be a component of a bridged alkylene group; and —Z ¹ and Z ² have at least 2 carbon atoms and are optionally 1 Identical or different divalent hydrocarbon groups containing one hydroxy group, which may be interrupted by one or more ether, ester or amide groups.

  The cationic silicone polymer can be applied to the initial fibrous web before and / or simultaneously and / or after the one or more dried fibrous structures are processed into sanitary tissue products, and / or It can be applied to a dried fibrous structure. Non-limiting examples of suitable methods for applying the cationic silicone polymer to the fibrous structure include, but are not limited to, an initial fibrous web using a spray disc and before being wound into roll paper. Spraying onto the dried fibrous structure; extrusion onto the initial fibrous web and / or dried fibrous structure (especially by slot extrusion); initial fibrous web and / or dried fibrous Transfer (especially by gravure transfer) onto structures and / or sanitary tissue products can be mentioned.

  The cationic silicone polymer may be applied to the initial fibrous web and / or dried fibrous structure and / or sanitary tissue product in a homogeneous and / or patterned and / or heterogeneous manner. it can.

  The cationic silicone polymer is being produced on the papermaking machine or thereafter (in other words, in a wet state (ie, from initial to final drying) or in a dry state (ie, after final drying). Any of the above) can be applied to the initial fibrous web and / or fibrous structure and / or sanitary tissue product of the present invention.

  In one embodiment, it is preferred to crepe the fibrous structure after applying the cationic silicone polymer, but it is described in, for example, but not limited to, US Pat. No. 3,301,746. Referring to a general construction papermaking machine, containing a cationic silicone polymer either before predrying, after predrying, or even after Yankee dryer / creping conditions The aqueous mixture is sprayed onto the initial fibrous web and / or sanitary tissue product while the aqueous mixture is flowing through the papermaking apparatus.

  The cationic silicone polymer can be applied to the initial fibrous web in the form of an aqueous solution, emulsion, or suspension. The cationic silicone polymer may also be applied in a solution containing a suitable non-aqueous solvent (eg, hexane) in which the cationic silicone polymer is dissolved or the cationic silicone polymer is miscible. it can. The cationic silicone polymer may be provided in neat form, or preferably emulsified with a suitable surfactant emulsifier. The cationic silicone polymer can be applied after the initial fiber web formation has taken place. In a typical method, an initial fibrous web is formed and then dehydrated prior to application of the cationic silicone polymer to reduce loss of the cationic silicone polymer due to drainage of free water. The cationic silicone polymer can be applied to the initial fibrous web wetted at a fiber concentration higher than about 15% in the case of normal press tissue paper manufacture, and the newly formed initial fibrous web A paper machine that is transported from a fine mesh paper machine to a relatively coarse stamping carrier fabric and / or belt, wetted at a fiber concentration of about 20% to about 35% when producing tissue paper Can be applied to any initial fiber web.

  Methods of applying the cationic silicone polymer to the initial fibrous web, and / or dried fibrous structure, and / or sanitary tissue product include spraying, slot extrusion, and gravure transfer. Other methods can include depositing a cationic silicone polymer onto a forming wire or fabric or belt, and after deposition, an initial fibrous web, and / or a dried fibrous structure, And / or contact with sanitary tissue products. Suitable devices for spraying the liquid containing the cationic silicone polymer onto the initial fibrous web, and / or dried fibrous structure, and / or sanitary tissue product include, for example, Mention may be made of an external mixing air atomizing nozzle such as a 2 mm nozzle available from VIBSystems, Inc. (Tucker, Ga.). Suitable apparatus for transferring a liquid containing a cationic silicone polymer to an initial fibrous web and / or dried fibrous structure and / or sanitary tissue product includes a rotogravure transfer apparatus. Can do.

  The cationic silicone polymer can be uniformly applied to the initial fibrous web, and / or the dried fibrous structure, and / or the sanitary tissue product. A uniform distribution is desirable so that the tactile effects of the cationic silicone polymer are received from substantially the entire sheet. Both continuous and patterned distributions are within the scope of the present invention and meet the above conditions.

  The application methods described herein for cationic silicone polymers can be used on dry or wet initial fiber webs, and / or fibrous structures, and / or sanitary tissue products.

  Representative techniques for adding silicone materials to fibrous structures during formation include those in US Pat. No. 5,059,282 issued Oct. 22, 1991 to Ampulski et al. Which are described (which is hereby incorporated by reference). The Ampleski et al. Patent describes a method for adding a polysiloxane compound to a wet tissue web ("fibrous structure"), preferably at a fiber concentration of between about 20% to about 35%. Disclosure. The above method represents several advantages with respect to adding chemicals into a slurry vat for feeding to a paper machine. For example, the method is intended for application to one web surface as opposed to distributing additive material over all of the furnish fibers.

  Silicone and / or other chemical softeners are already dried paper paper (“fibrous structures”) either at the end of the so-called drying of the paper machine or at another processing operation following the paper making process. A considerable number of techniques have been devised to apply to Representative techniques in this area include Ampulski et al., US Pat. No. 5,215,626 issued June 1, 1993; Ampulski issued September 21, 1993. U.S. Pat. No. 5,246,545; Warner et al. U.S. Pat. No. 5,525,345, issued June 11, 1996, all of which are incorporated by reference. Are incorporated herein by reference). US Pat. No. 5,215,626 discloses a method for producing soft tissue paper by applying polysiloxane to a dry web (“fibrous structure”). U.S. Pat. No. 5,246,545 discloses a similar method utilizing a heated transfer surface. Finally, the Warner patent discloses an application method, including roll coating and extrusion, for applying a specific composition to the surface of a dry tissue web (“fibrous structure”). .

  An initial fibrous web and / or a dried fibrous structure such that one or both outer surfaces of a sanitary tissue product obtained by incorporating the fibrous structure have a cationic silicone polymer on the surface And / or a cationic silicone polymer can be applied to one or both sides of the sanitary tissue product.

  In one embodiment, the cationic silicone is removed from the initial fibrous web, and / or the fibrous structure, and / or the sanitary tissue product so that the cationic silicone is present on the surface. The cationic silicone of the present invention is passed through the fibrous structure and / or sanitary tissue product in a dried state, and the initial fibrous web and / or the dried fibrous structure and / or sanitary tissue product. Can be applied to two aspects.

  The fibrous structures of the present invention and / or sanitary tissue products incorporating such fibrous structures have a cationic silicone polymer of about 0.0001% by dry weight of the fibrous structure or sanitary tissue product. To about 10%, and / or about 0.001% to about 5%, and / or about 0.005% to about 3%, and / or about 0.005% to about 2%, and / or about 0.1%. 005% to about 1.5% may be included.

  Reference is made to the following patents and patent applications which also disclose cationic silicone polymers suitable for use in the present invention: PCT International Publication No. WO 02/06403; WO 02/18528, European Patent No. 1199350; German published patent DE OS 10030533; PCT International Publication WO 00/24853; WO 02/10259; WO 02/10257, and WO 02/10256.

  Synthetic Examples-If not known or not commercially available, the cationic silicone polymers herein can be prepared by conventional techniques disclosed in PCT International Publication No. WO 02/18528.

  Other silicone compounds than the aforementioned cationic silicones may be used as chemical softeners. Non-limiting examples of such other silicone compounds suitable for the present invention include silicone emulsions, particularly aminosilicones. Suitable aminosilicones are those available under the trade name AF2130, which is commercially available from Wacker Silicones.

(Method of the present invention)
The fibrous structure of the present invention can be produced by any suitable papermaking method.

  Non-limiting examples of suitable papermaking methods for producing the fibrous structure of the present invention are described below.

  In one embodiment, the fibrous furnish is made by mixing one or more fibers and water. One or more additional optional ingredients may be added to the fibrous furnish. The fibrous furnish may then be placed in a paper machine head box (which may be a layered head box). The fibrous furnish can then be deposited on the porous surface to form a single or multilayer initial fibrous web. The cationic silicone polymer and / or optional ingredients are added to the initial fibrous web by spraying and / or extruding and / or transfer, and / or any other suitable method known to those skilled in the art. be able to. The initial web can then be transferred to an air-pass drying belt and / or Yankee dryer in order to dry the initial fiber web with an air-pass drying and / or Yankee dryer. From the air-pass drying belt, the fibrous structure, if present, can be transferred to a Yankee dryer. From the Yankee dryer, the fibrous structure can be transferred to a rewinder to form a dry fibrous structure roll. During this transfer step, the cationic silicone polymer and / or optional ingredients can be applied to the dry fibrous structure. Fibrous structures can be processed into various paper products, in particular sanitary tissue products (single-ply and / or multi-ply types). During this processing step, a cationic silicone polymer can be applied to the fibrous structure. Thus, the cationic silicone polymer can be applied before and / or simultaneously and / or after the processing step.

(Test method)
(A) Coefficient of Friction Coefficient of friction is the title “Methods for the Measurement” by Ampulski et al of the 1991 International Paper Physics Conference TAPPI press. of the Mechanical Properties of Tissue Paper) obtained using a KES-4BF surface analyzer equipped with an improved friction probe, which is hereby incorporated by reference.

  The substrate used for friction evaluation is a handmade paper prepared for experimentation, as disclosed herein, which is TAPPI standard T-205 (this document is incorporated herein by reference). It is prepared according to Friction is measured on a smooth surface of handmade paper (this surface is dried in contact with a metal plate according to the method described above).

  The substrate is advanced for measurement at a constant speed of 1 mm / sec and the friction probe is changed from a standard instrument probe to a 2-60 cm diameter 40-60 micron glass frit.

  The friction coefficient is calculated by dividing the friction force by the normal force when using 19.6 g normal force for the probe and the aforementioned translation rate for the substrate. Frictional force is the lateral force on the probe being scanned and is the output of the device.

  The average coefficient of friction obtained by one scan in the forward direction and one scan in the opposite direction is recorded as the coefficient of friction of the specimen.

(B) Physiological Surface Smoothness As used herein, physiological surface smoothness is a coefficient obtained from scanning in the machine direction of a tissue paper sample by a surface gauge having a diamond needle (hereinafter referred to as PSS coefficient). Here, the surface gauge is, for example, Kato Tekko Co., LTD. (Karato-Cho, Nishikiyo, Minami-Ku, Koyota, Kyoto, Japan) , Japan)) is mounted on a surface tester KES-FB-4 (Surface Tester KES-FB-4). In this test apparatus, a tissue sample is attached to a motorized drum and the needle is gravity biased toward the drum in the 12 o'clock direction. The drum is rotated to give a sample speed of 1 mm / sec and the sample is moved 2 cm relative to the probe. In this way, the probe scans a 2 cm long sample. The surface gauge includes means for balancing the needles to provide a normal force of 270 mg. Basically, the device senses the vertical displacement (mm) of the needle when a 2 cm long sample is scanned with a probe of a surface meter. After digitizing the obtained needle-amplitude point versus needle-scan distance data, SAS Institute Inc. (Post Office Box, 27605 Raleigh, North Carolina, USA, Post Office Box 10066) 10066, Raleigh, NC 27605)), by performing a Fourier transform using the Proc Spectra standard program available to convert to needle-amplitude point versus frequency spectrum. This identifies the spectral constituents in the topography of the sample, after which the frequency spectral data is obtained from the Verillo (Ronald T. Verrillo), titled “Conformation at the Vibrotactile Threshold”. As quantified and reported by "Effect of Contractor Area on the Vibrotactile Threshold"), The Journal of the Accoustical Society of America, 35, 1962 (1963). , Adjusted according to the sensitivity perceived by humans. Here, the Verillo data is a value in the time domain (that is, the number of cycles per second), and the physiological surface smoothness is related to the relative sample velocity. -type) data is converted to the spatial domain (ie, cycles per mm) using the standard finger-to-sample velocity factor of 65 mm / sec. Finally, this data is integrated from 0 cycle to 10 cycles / mm. This result is the PSS coefficient. According to the chart, the PPS coefficient is a region from 0 cycle / mm to 10 cycles / mm below the Verillolo-adjusted frequency (cycle / mm) vs. needle amplification point curve. Preferably, the PPS coefficient is an average value obtained by scanning a plurality of samples (for example, 10 samples) in the forward direction and the reverse direction thereof.

  More specifically, the above-mentioned surface gauge is a Gould Surfanalyzer Equipment Controller product number 21-1330-20428, a probe product number 21-3100-465, a diamond stylus tip (0 .0127 mm diameter) product number 21-0120-00 and needle tip extender product number 22-0129-00, both of which are federal products (Providence, Rhode Island, USA) Providence, RI)). The surface gauge probe assembly is equipped with a counterbalance and is assembled as shown in FIG. 22 of US Pat. No. 4,300,981 (referenced earlier herein).

(C) Sliding-sticking friction coefficient The sliding-sticking friction coefficient (hereinafter referred to as S & S COF) is defined as the average deviation of the friction coefficient. This coefficient is dimensionless. This factor is calculated, for example, by the Kato Surface Tester described above equipped with a needle (eg, a molten glass disk) that is shaped and arranged to move over the surface of the sample to be scanned. ) And other commercially available test equipment. When a sample is scanned as described above, the device senses a force transverse to the needle as the sample moves (ie, is scanned) under that condition. This lateral force is called a frictional force, and the ratio of the frictional force to the needle weight is the friction coefficient, COF. The instrument then calculates and records the S & S COF for each sample scan.

(D) B Compressibility test A 2.55-inch diameter circular sample (single ply or multi-ply) of the fibrous structure and / or sanitary tissue product to be tested was taken from Swing Albert (Thwing). -Albert) will be placed on the Swing-Albert Compressibility Tester. A weight of up to 1500 g is placed on the sample at a test speed according to the test apparatus.

  Measure / record sample thickness per gram of weight. The data (weight (X) vs. thickness (Y)) is then written to the XY graph using the Microsoft Excel Program.

After creating the XY graph, the logarithmic trend line is expressed as:
Y = Mln (X) + B
Where M is the slope of the curve and B is its intercept. B is the B compressibility of the fibrous structure of the present invention and / or a sanitary tissue product incorporating the fibrous structure.

(Non-limiting examples)
The following non-limiting examples use the cationic silicone polymers of the present invention. Cationic silicone polymers are typically used in the form of emulsions containing amine oxides, nonionic surfactants, ethanol, and water. In one embodiment, the emulsion is formed as follows: 24.39 g of a cationic silicone solution (80% cationic silicone polymer / 20% ethanol) is added to a C12-15 EO3 (in a vertical laboratory blade mixer). 4) Mix with 6.05 g. After another 10 minutes, 8.71 g of C12-14 alkyldimethylamine oxide 31% active aqueous solution (2) is added. After another 10 minutes, 54.2 g of demineralized water is quickly added to the mixture with continued stirring. Bring the pH of the emulsion to pH 7.5 with 0.8 g of 0.1 M HCl. The emulsion can be diluted to a cationic silicone polymer concentration of about 10-20%.

  Example 1 A non-limiting embodiment of a fibrous structure of the present invention, such as facial tissue, is prepared as follows.

  An approximately 3% concentration of Northern Softwood Kraft (NSK) aqueous slurry is made using a conventional pulper and sent through a stock pipe to the headboard of a long net paper machine. Prepare 1% dispersion of Hercules sponge 557 LX (Hercules' Kymene 557 LX) and deliver about 0.8% sponge 557 LX (Kymene 557 LX) based on the dry weight of the final sanitary tissue paper Add to the NSK stock pipe at a rate sufficient to do so. Absorption of the permanent wet strength resin is improved by passing the treated slurry through an in-line mixer. After the in-line mixer, an aqueous solution of carboxymethylcellulose (CMC) dissolved in water and diluted to a solution concentration of 1%, then at a rate of about 0.1 wt% CMC, based on the dry weight of the final sanitary tissue paper Add to the NSK stock pipe. The aqueous slurry of NSK fibers is passed through a centrifugal stock pump to aid CMC distribution. A 1 wt% concentration of ditallow dimethyl ammonium methyl sulfate (DTDMAMS) in water dispersion 76.6 ° C. (170 ° F.) was added to about 0.1 wt% DTDMAMS based on the dry weight of the final sanitary tissue paper. Add to the NSK stock pipe at the rate of

  About 1.5% by weight of an aqueous slurry of acacia pulp fiber (obtained from PT Tel, Indonesia) was prepared using a conventional repulper, and the head box of a long net paper machine Pass through the stock pipe to the front. This Acacia derived furnish is mixed and combined with the NSK slurry at the fan pump location, where both are diluted with white water to a concentration of about 0.2%.

  An aqueous slurry of approximately 3% by weight of acacia derived pulp fiber (obtained from PT Tel, Indonesia) is prepared using a conventional repulper. This acacia slurry is passed through a second fan pump where it is diluted with white water to a concentration of about 0.2%.

  NSK / Acacia and Acacia slurry in a multi-channel headbox, suitably equipped with stratified leaves to maintain flow as separate layers until discharged onto a running paper machine wire To face. A headbox consisting of three chambers is used. The acacia slurry containing 48% of the final sanitary tissue paper dry weight is directed to the chamber leading to the layer in contact with the wire, while NSK containing 52% of the final paper dry weight. Acacia slurry (NSK 27-35% and Acacia 17-25%) is directed to the chamber leading to the center and inner layers. A slurry of NSK / Acacia and Acacia is mixed at the discharge of the head box to form a composite slurry.

  The composite slurry is discharged onto a running paper machine wire and dehydrated with the aid of a deflector and vacuum box.

The initial wet web is transferred from the wire of a long paper machine to the patterned dry fabric at a fiber concentration of about 17% by weight at the time of transfer. The dry fabric is designed to provide a high density patterned tissue having discontinuous low density deflection areas within a continuous network of high density (knuckle) areas. This dry fabric is formed by casting an impermeable resin surface onto a fiber mesh support fabric. The support fabric is a double layer mesh made of 48 x 52 filaments. The thickness of the resin cast is about 0.23 mm (9 mils) on the support fabric. Knuckle area is about 35% to 50% and the open cells remain at a frequency of about 10-87 / cm ^2.

  Further dewatering is achieved by drainage with the aid of vacuum until the web is at a fiber concentration of about 23-27%.

  While in contact with the patterned forming fabric, the patterned web is pre-dried to a fiber concentration of about 60% by weight by aeration.

  The semi-dried web is then bonded to the surface of the Yankee dryer with a sprayed creping adhesive containing a 0.250% aqueous solution of polyvinyl alcohol. The creping adhesive is supplied to the Yankee surface at a rate of 0.1% adhesive solids based on the dry weight of the web. Before the web is dry creped from a Yankee with a doctor blade, the fiber concentration increases to about 98%. After the doctor blade, the web is calendered over the entire width using a steel to rubber calender at a load of 2 to 3.5 MPa.

The resulting tissue has a basis weight of about 20-25 g / m ² , 1 ply total dry tension (strength) 225 to 300 g / cm, 1 ply wet burst (strength) 30 to 65 g / cm, and 2 plies Caliper of about 0.035 to 0.05 cm. The resulting tissue is then combined with a similar sheet with the acacia fibers facing the outside to form a two-ply, creped, dense patterned tissue, followed by two pieces It is subjected to a cannling process between smooth steel calender rolls. The cationic silicone polymer is then added at about 0.8 to 1.0 g / m ² emulsion add-on per side (based on the total weight of the fiber, 0 per ply at the total add-on level). (Corresponding to 7-1.0% by weight of silicone)) slot extruded onto both sides in contact with human skin. The ply is then bonded using a mechanical ply bond wheel to ensure that both plies are held together. The resulting 2-ply tissue has a) a total basis weight of about 39-50 g / m ² ; b) a 2-ply total dry tensile strength of 450-550 g / cm; c) a 2-ply wet burst (Strength) is 55-120 g / cm; d) 4-ply caliper is about 0.05-0.09 cm; e) slip-stick friction coefficient (MMD) is about 0.0146-0.0172. Yes; f) Coefficient of friction (MIU) of about 0.734 to 0.742; g) B compressibility of 29 to 31; h) Calculated WABY coefficient of about 0.0786 to .0. I) PAA is about 720-770; and j) Fluff (Lint) is about 9-12 lint units.

  The resulting tissue paper is judged to be more flexible than an untreated tissue sample by a panel of experts.

  All documents cited in “Best Mode for Carrying Out the Invention” are incorporated herein by reference in the relevant part, and any citation of any document is prior art to the present invention. Should not be regarded as an admission.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (10)

  A fibrous structure exhibiting a slip-stick coefficient of friction of less than 0.023.   2. The fibrous structure according to claim 1, wherein the fibrous structure exhibits a slip-stick friction coefficient of 0.010 to 0.021, preferably 0.0135 to 0.0190, more preferably 0.0135 to 0.0175. Fibrous structure.   The fibrous structure according to any one of claims 1 or 2, wherein the fibrous structure exhibits a B compressibility of 15 to 50, preferably 20 to 40.   4. The fiber structure according to any one of claims 1 to 3, wherein the fibrous structure exhibits a coefficient of friction of 0.65 to 0.83, preferably 0.65 to 0.81, more preferably 0.71 to 0.81. The fibrous structure according to Item.   5. The fiber structure according to any one of claims 1 to 4, wherein the fibrous structure comprises hardwood fibers, preferably tropical hardwood fibers, more preferably tropical hardwood fibers comprising acacia fibers and / or eucalyptus fibers. The fibrous structure described.   The fibrous structure according to any one of claims 1 to 5, wherein the fibrous structure includes coniferous fibers.   The fibrous structure is a chemical softener, preferably a chemical softener selected from the group consisting of silicone compounds, quaternized ammonium compounds and mixtures thereof, more preferably one or more polysiloxane units and one or more. A fibrous structure according to any one of the preceding claims comprising a silicone compound comprising a cationic silicone polymer comprising a non-pendant quaternary nitrogen moiety.   The fibrous structure according to any one of claims 1 to 7, wherein the fibrous structure exhibits a WABY coefficient of less than 0.2.   The fibrous structure according to any one of claims 1 to 8, wherein the fibrous structure exhibits a smoothness exceeding 500. Use of the fibrous structure according to any one of claims 1 to 9 in a single-ply sanitary tissue product or a multi-ply sanitary tissue product.