JP2006525433A - Cationic silicone polymer-containing fibrous structure - Google Patents

Abstract

Provided is a fibrous structure comprising a cationic silicone polymer comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties, and a method for producing such a fibrous structure. . In addition, a sanitary tissue product comprising the fibrous structure is also provided.

Description

  The present invention relates to a fibrous structure comprising a cationic silicone polymer comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties, such fibrous structure and such The present invention relates to a method for producing a sanitary tissue product including a fibrous structure.

  It is well known in the art that the flexibility of a structured sanitary tissue product is inversely proportional to the total tensile strength of the structured sanitary tissue product. It is also well known in the art that the smoothness of a structured sanitary tissue product is inversely proportional to the thickness of the structured sanitary tissue product.

  One attempt by formulators to overcome these inverse proportions, particularly the relationship between softness and total tensile strength, is that cations on sanitary tissue products and / or the fibrous structures that make up such products The addition of functional silicone was included. See, for example, U.S. Pat. No. 5,059,282 by Ampulski et al.

  However, such prior art sanitary tissue products and references include one or more polysiloxane units, one or more non-pendant quaternary nitrogen moieties, and one or more alkylene oxide units, ring-opening epoxide units. And a fibrous structure incorporating a cationic silicone polymer that includes alternating units with divalent organic moieties containing quaternary nitrogen.

  Further, in the prior art, the fiber structure is a fiber furnish layer and a cationic silicone polymer layer that is separate from the fiber furnish layer, wherein the cationic silicone polymer is Alternation of one or more polysiloxane units, one or more non-pendant quaternary nitrogen moieties, and one or more divalent organic moieties containing alkylene oxide units, ring-opening epoxide units, or quaternary nitrogen There is no teaching of a fibrous structure comprising the cationic silicone polymer layer comprising units.

  The present invention overcomes the disadvantages associated with the prior art by providing a novel fibrous structure incorporating a cationic silicone polymer.

  In one embodiment of the invention, the fiber furnish layer and the fiber furnish layer are separate cationic silicone polymer layers, wherein the cationic silicone polymer comprises one or more cationic silicone polymers. There is provided a fibrous structure comprising: a cationic silicone polymer layer comprising: a polysiloxane unit; and one or more non-pendant quaternary nitrogen moieties.

In another aspect of the invention,
a. Fiber furnishings,
b.
i. A cationic silicone polymer comprising one or more polysiloxane units, one or more non-pendant quaternary nitrogen moieties, and one or more alkylene oxide units;
ii. A cationic silicone polymer comprising one or more polysiloxane units, one or more non-pendant quaternary nitrogen moieties, and one or more ring-opening epoxide units;
iii. Cationic silicones comprising alternating units of a) a polysiloxane comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties, and b) a divalent organic moiety comprising quaternary nitrogens. A polymer, and iv. A fibrous structure is provided comprising a cationic silicone polymer selected from the group consisting of these mixtures.

In yet another aspect of the invention,
a. Preparing a fiber furnish;
b. Depositing the fiber furnish on a porous surface for paper layer formation to form an initial fiber web;
c. Drying the initial fiber web such that a fibrous structure is formed;
d. Applying a cationic silicone polymer comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties to the initial fibrous web and / or the fibrous structure;
A method for producing a fibrous structure comprising

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

  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 ("NS)), sulfite pulp, and sulfate pulp, and 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 ), Locust, Sycamore, Beech, Catalpa, Sassafras, Gmeli selected from the group consisting of na), Albizia, Anthocephalus, Magnolia, Bagasse, Flax, Cannabis (Hemp), Kenaf, and mixtures thereof However, chemical pulp may be preferred because tissue sheets made from chemical pulp are imparted with excellent tactile flexibility, and deciduous trees (hereinafter "hardwoods"). May also be used, particularly pulp from both tropical hardwoods and cones (hereinafter also referred to as “conifers”). 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.).

  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 product” means wiping device (toilet paper) for urination and post-defecation cleaning, wiping device for otorhinolaryngolical excretion A soft, low-density web (ie, less than about 0.15 g / cm ³ ) useful as a (face tissue and / or handkerchief) and for multi-functional use (absorbent towels) for absorption and cleaning means.

  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.

  The fibrous structure and / or sanitary tissue product using the fibrous structure of the present invention has the following one or more and / or two and / or three or more parameters measured by experiment: Characterized by being contained within multiple parameter domains, defined by a range of: 1) caliper; 2) smoothness; 3) slip and stick coefficient; 4) total tensile strength; 5 6) Flexibility; 7) Absorption; 8) Compressive properties; 9) Basis weight; 10) Wet burst strength; 11) Friction coefficient; and / or 12) WABY coefficient.

  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 Primus 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).

  “Slip stick coefficient of friction” (S & S COF) is defined as the average deviation of the coefficient of friction. Like the coefficient of friction, the slip-stick 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 the Measurement of the Measurement of the Tissue Paper” by Ampulski et al., Page 19 of the 1991 International Paper Physics Conference. Mechanical Properties of Tissue Paper), which is incorporated herein by reference.

  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, “absorbency” and / or “hydrophilicity” includes two factors: 1) absorption capacity and 2) absorption rate. Absorption capacity is a measure of the ability of the fibrous structure and / or sanitary tissue product containing the fibrous structure to retain liquid while held horizontally. Absorption rate is a measure of the rate at which a fibrous structure and / or sanitary tissue product using the fibrous structure absorbs liquid by wicking action. Procedures for measuring absorbency are known in the art. For example, the procedure is described in US Pat. No. 5,908,707.

  As used herein, “compressive properties” means a collection of properties that describe the behavior of the fibrous structure and / or sanitary tissue product of the present invention during pressurization and subsequent relaxation of unloading. Non-limiting examples of compression characteristics include bulkiness, richness, energy required for compression and elasticity of fibrous structures and / or sanitary tissue products. The compression property can be measured by a KES-FB3 compressibility analyzer commercially available from Kato Tekko Co.

  As used herein, “wet burst strength” refers to fibrous structure and / or paper when the fibrous structure and / or paper product surface is wet and deformed in the vertical direction. A measure of the ability of a sanitary tissue product incorporating the product to absorb energy. The wet burst strength can be measured using the Swing-Albert Burst Tester Cat.

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.

  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 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.

  As used herein, “flexibility” refers to a KES-FB2 Pure flex tester commercially available from Kato Tekko Co. for fibrous structures and / or sanitary tissue products. Use to measure.

  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. For example, for a fibrous structure and / or sanitary tissue product of the present invention that stretches 10% (ie, 0.1 cm / cm length) with a force of 20 grams per cm sample width (0% elongation, 0 force) and The secant passing through (elongation 10%, force 20) is 2.0 using the following equation. :

本明細書で使用する時、「総柔軟性」は、機械方向柔軟性及び機械横方向柔軟性の幾何平均を意味する。数学的にはこれは、ｃｍあたりのグラムで表した機械方向柔軟性及び機械横方向柔軟性の積の平方根である。

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.

  In short, the perceived softness in a tissue paper sample 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, “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).

  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 have been pressed and / or felt pressed as usual; patterns with patterned forming wires and / or patterned fibers / resin belts Mention may be made of densified tissue paper; high bulk, non-compressed tissue paper; and creped or non-creped tissue paper. The tissue paper may have a homogeneous structure and / or a single layer structure or a multi-layer structure, and the tissue paper product made therefrom may have a single-ply structure or a multi-ply structure.

  Furthermore, the fibrous structure and / or sanitary tissue product comprising the same of the present invention 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 fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures have 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 It may have a basis weight of 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 .

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 39 g / cm, and / or greater than about 59 g / cm, and / or from about 63 g / cm to about 1575 g / cm. cm and / or from about 78 g / cm to about 985 g / cm, and / or from about 78 g / cm to about 394 g / cm, and / or from about 98 g / cm to about 335 g / cm. Typically, a single-ply fibrous structure has a total dry tensile strength of about 39 g / cm to about 590 g / cm.

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 10 g / cm, and / or from about 12 g / cm to about 394 g / cm, and / or from about 13 g / cm It may have a wet burst strength of about 197 g / cm, and / or about 15 g / cm to about 197 g / cm, and / or about 15 g / cm to about 78 g / cm.

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 0.007, and / or from about 0.007 to about 0.055, and / or from about 0.008 to The slip stick coefficient of friction may be about 0.050, and / or about 0.008 to about 0.035.

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 0.1 and / or from about 0.1 to about 0.90 and / or from about 0.1 It may have a coefficient of friction of about 0.85, and / or about 0.1 to about 0.65, and / or about 0.15 to about 0.60.

The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 7.84 × 10 ⁻⁵ N * cm ² / cm and / or about 7.84 × 10 ^−5. N * cm ² / cm to about 1.47 × 10 ⁻³ N * cm ² and / or about 9.81 × 10 ⁻⁵ N * cm ² / cm to about 1.37 × 10 ⁻³ N * cm ² / Cm flexibility.

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 0.03 mm, and / or from about 0.03 mm to about 0.5 mm, and / or from about 0.05 to It may have a bulkiness (initial thickness-final thickness) of about 0.4 mm.

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 0.5, from about 0.5 to about 1, and / or from about 0.55 to about 0.85. It can have abundance (linearity of the compression curve).

The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 1.96 × 10 ⁻⁴ N * cm / cm ² and / or about 1.96 × 10 ^−4. N * cm / cm ² to about 1.27 × 10 ⁻³ N * cm / cm ² and / or about 2.45 × 10 ⁻⁴ N * cm / cm ² to about 1.18 × 10 ⁻³ N * It may have an energy required for compression of cm / cm ² .

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 35%, and / or from about 35% to about 75%, and / or from about 40% to about 65%. Of elasticity (% elasticity).

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 500, and / or about 500 to about 1200, and / or about 600 to about 1000, and / or about 650. It may have a smoothness (PSS) as measured with a surface meter of about 850. Alternatively, the fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 0.5 μm and / or from about 0.5 μm to about 5 μm and / or from about 0.6 μm to It may have a smoothness (SMD) of about 5 μm and / or about 0.7 μm to about 4 μm as measured with a Kato Surface Tester KES-FB4.

  The fibrous structures of the present invention and / or sanitary tissue products comprising such fibrous structures are greater than about 0.02 cm, and / or from about 0.02 cm to about 0.15 cm, and / or from about 0.0254 cm. It can have caliper (4 ply) of about 0.114 cm.

  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)
The fiber furnish of the present invention comprises one or more fibers and usually one or more optional ingredients.

(Cationic silicone polymer)
The cationic silicone polymer of the present invention is one or more polysiloxane units, preferably polydimethylsiloxane units having the formula — {(CH ₃ ) ₂ SiO} _c —, preferably 1-1000, preferably A polydimethylsiloxane unit having a degree of polymerization c of 20 to 500, more preferably 50 to 300, most preferably 100 to 200, and an organosilicone-free unit comprising at least one diquaternary unit. Including. In one preferred embodiment of the invention, the selected cationic silicone polymer is 0.05 to 1.0 mole fraction, more preferably 0.2 to 0.95 mole fraction, most preferably 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 selected cationic silicone polymer is also 0-0.95 mole fraction, preferably 0.001-0.5 mole fraction, more preferably 0.05-0. It can contain 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 a C ₁₁ -C ₈₈ alkylene amine residue; a is 2-4, b is 0-100. 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 are obtained by incorporating into the silicone polymer structure a compound such as that sold by Huntsman Corporation under the trade name Jeffamine®. Can do. 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 + (wherein R is alkyl, hydroxyalkyl, Or phenyl). These units can be thought of as end caps.

In addition, the selected cationic silicone polymer generally has an anion selected from inorganic and organic anions, and more preferably saturated and unsaturated C _1- to balance the quaternary moiety charge. Contains anions selected from C ₂₀ carboxylates and mixtures thereof, and thus 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 surface energy. Conveniently considered as non-crosslinked or “linear” block copolymers including “and fabric-substantive“ hooks ”. One preferred class of cationic polymers selected (represented below by Structural Formula 1) is considered to include one loop and two hooks; another highly preferred one is more than one , Preferably 3 or more “loops”, and 2 or more, preferably 3 or more “hooks” (hereinafter represented by structural formulas 2a and 2b), and yet another (hereinafter referred to as structure) (Represented by Equation 3) includes two “loops” 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 the selection of 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. Is 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, a certain proportion 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 selected cationic silicone polymers, provided that they do not interfere.

  More particularly, the cationic silicone polymers herein have one or more polysiloxane units and one or more quaternary nitrogen moieties, including cationic silicones. Polymers where the polymer has the 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なる群から独立して選択され；
−Ｒ²は、１つ以上の酸素原子を含んでもよい二価の有機部分（該部分は、好ましくは、ＣとＨ、又はＣ、Ｈ、及びＯからなる）からなる群から独立して選択され；
−Ｘは、開環エポキシドからなる群から独立して選択され；
−Ｒ³は、次式で示されるポリエーテル基から独立して選択され；
−Ｍ¹（Ｃ_aＨ_2aＯ）_b−Ｍ²
式中、Ｍ¹は、ニ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、陽イオン性シリコーン・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。

Where
-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 selected one or more oxygen atoms may contain a divalent organic moiety (the moiety, preferably, C and H, or C, H, and consist O) independently from the group consisting of Is;
-X is independently selected from the group consisting of ring-opening epoxides;
-R ³ is independently selected from polyether groups represented by the following formula;
-M ¹ (C _a H _2a O) _b -M ²
Wherein, M ¹ is located in the 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;

式中、
−Ｒ¹²、Ｒ¹³、Ｒ¹⁴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；
−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なる群から選択され；及び、ｅは１〜６である。

Where
-R ^12, R ^13, R ¹⁴ 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) 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 identical or different, H, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, C ₁ ~ ₂₂ hydroxyalkyl, polyalkyleneoxide , (Poly) alkoxyalkyl, 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 a cation. Polymers having the following formula: (Structure 2a)
Structure 2a: a 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.

Selection In the preferred cationic silicone polymer, R ¹ is, C ₁ ~ ₂₂ alkyl, C ₂ ~ ₂₂ alkenyl, C ₆ ~ ₂₂ alkylaryl, aryl, cycloalkyl, and independently from the group consisting of mixtures Is;
-R ² are independently selected from the group consisting of one or more organic moieties also may bivalent contain an oxygen atom; X is independently selected from the group consisting of ring-opened epoxides; R ³ is Independently selected from the polyether groups represented by 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 ~ Independently selected from the group consisting of ₂₂ 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 between 100 and 200; and d is between 0 and 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, where polysiloxane (i) represented by the formula above in structure 2a In combination with a cationic divalent organic moiety (ii) selected from the group consisting of:

（ｉｉｉ）任意で、次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であり、好ましくは、Ｃ₁₁〜Ｃ₈₈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、ランダム又はブロック様式で、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構成されてもよく；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陽イ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, be a C ₁₁ -C ₈₈ alkylene amine residue; a is an 2 to 4; b is 0-100 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; and (Iv) a cationic monovalent organic moiety used as a terminal group, optionally selected from the group consisting of:

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選択され；あるいは、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；
ここで、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時、陽イ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、陽イ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、陽イ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, 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 components 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
Here, when expressed as a fraction of the total number of moles of organosilicone-free part, the cationic divalent organic part (ii) is preferably 0.05 to 1.0 mole fraction, more preferably 0. Present in a proportion of .2 to 0.95, and most preferably in a proportion of 0.5 to 0.9; polyalkylene oxide amine (iii) is present in a proportion of 0.0 to 0.95, preferably Can be present in 0.001-0.5 mole fraction, more preferably 0.01-0.2 mole fraction; when present, the cationic monovalent organic moiety (iv) is Present in 0-0.2 mole fraction, preferably 0.001-0.2 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 a cationic Polymers having the following formula: (Structure 3)

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なる群から独立して選択され；
−Ｒ²は、１つ以上の酸素原子を含み得る二価有機部分からなる群から独立して選択され；
−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、次式で示されるポリエーテル基から独立して選択され：
−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；
−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；
−Ｗは、少なくとも１個の四級化窒素原子を含む二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、陽イオン性シリコーン・ポリマーに関連した正電荷の数で、１つ以上であり；Ａは、一価の陰イオン、換言すれば、好適な対イオンである。

Where
-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 the polyether group represented by 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 ~ Independently selected from the group consisting of ₂₂ hydroxyalkyl, 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 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 less than 300; Most preferably 100 to 200; d is 0 to 100; n is the number of positive charges associated with the cationic silicone polymer and is one or more; A is a monovalent anion In other words, it is 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、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；あるいは、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, 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 components of a bridged alkylene group; and —Z ¹ and Z ² have at least two carbon atoms, and optionally one The same or different divalent hydrocarbon groups containing hydroxy groups, 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 at the same time and / or after the one or more dried fibrous structures are processed into sanitary tissue products, and / or Alternatively, 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 prior to winding into roll paper. And / or 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 fibers Mention may be made of transfer (especially by gravure transfer) onto sex structures and / or sanitary tissue products.

  The cationic silicone polymer is 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. Can do.

  Cationic silicone polymers can be produced during or after production in a paper machine (in other words, wet (ie, from initial to final drying) or dry (ie, after final drying). ))) And 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, U.S. Pat. No. 3,301,746. Referring to a general construction papermaking machine, the cationic silicone polymer is applied either before the predryer, after the predrying, or after the Yankee dryer / creping condition. The aqueous mixture containing is sprayed onto the initial fiber web and / or sanitary tissue product while the aqueous mixture is flowing through the papermaking machine.

  The cationic silicone polymer can be applied to the initial fibrous web in an aqueous solution, emulsion, or suspension. Cationic silicone polymers can also be applied in solutions containing suitable non-aqueous solvents (eg, hexane) in which the cationic silicone polymer is dissolved or the cationic silicone polymer is miscible can do. 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 process, 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 an initial fibrous web wetted at a fiber concentration greater than about 15% in the case of normal press tissue paper manufacture, and the newly formed initial fibrous web is Initial fiber wetted at a fiber concentration of about 20% to about 35% when making tissue paper on a paper machine transferred from a fine mesh paper machine to a relatively coarse stamp / support fabric and / or belt. Can be applied to the 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 a liquid containing a cationic silicone polymer onto an initial fibrous web and / or dried fibrous structure and / or sanitary tissue product include, for example, Mention may be made of external mixing air atomizing nozzles such as 2 mm nozzles 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. be able to.

  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 effect of the cationic silicone polymer is 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 (see all these patents). 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 the sanitary tissue product obtained by incorporating the fibrous structure have a cationic silicone polymer on the surface. Cationic silicone polymers can be applied to one or both sides of the body and / or sanitary tissue product.

  In one embodiment, the cationic fibrous silicone and the fibrous structure, and / or the sanitary tissue product are both present on the surface such that the cationic silicone is present on the initial fibrous web, and / or Alternatively, the dried fibrous structure and / or sanitary tissue product can be passed through the initial silicone web of the present invention and / or the dried fibrous structure and / or sanitary tissue. It can be applied to one aspect of the product.

  The fibrous structures of the present invention and / or sanitary tissue products incorporating such fibrous structures may contain about 0.0001 cationic silicone polymer per 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 0.005% to about 1.5% may be included.

  Reference may also be made to the following patents and patent applications that also disclose cationic silicone polymers suitable for use in the present invention: PCT International Patent WO02 / 06 403, PCT International Patent WO02. / 18528, EP1 199 350, DE OS 100 36 533, PCT International Publication Patent WO00 / 24853, PCT International Publication Patent WO02 / 10259, PCT International Publication Patent WO02 / 10257, and PCT International Publication Patent WO02 / 10256.

  Synthetic Examples-Unless otherwise known or particularly commercially available, the cationic silicone polymers herein can be prepared by conventional techniques disclosed in PCT International Publication No. WO 02/18528. it can.

(Optional component)
In addition to the cationic silicone polymer, the fibrous structure of the present invention comprises a permanent wet strength improving resin, a chemical softener other than the cationic silicone described above, a temporary wet strength improving resin, and a dry strength improvement. Optional ingredients selected from the group consisting of resins (dry strength resins), wetting agents, lint resisting agents, absorption enhancers, fixing agents, in particular emollient lotion compositions, including organic acids Antiviral 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 to dry fiber after application of cationic silicone. It can be applied to 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.

The 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. can do. 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, a 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.

(Non-limiting examples)
The following examples use the cationic silicone polymer of the present invention. Cationic silicone polymers are usually used in the form of an emulsion containing an amine oxide, a nonionic surfactant, ethanol, and water. In one embodiment, the emulsion is prepared as follows: 24.39 g of cationic silicone solution (80% cationic silicone polymer / 20% ethanol) is added using a normal laboratory blade mixer. Mix with 05 g of C12-15 E03 (4). After 10 minutes, 6.7 g of ethanol is added. 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 One embodiment of a facial tissue of the present invention 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. A 1% dispersion of Hercules sponge 557 LX (Hercules' Kymene 557 LX) is prepared to deliver and release about 0.8% sponge 557 LX (Kymene 557 LX) based on the dry weight of the final sanitary tissue paper Is added to the NSK stock pipe at a sufficient rate. Absorption of the permanent wet strength resin is improved by passing the treated slurry through an in-line mixer. A 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, after the in-line mixer Add to NSK stock pipe. The aqueous slurry of NSK fibers is passed through a centrifugal stock pump to aid CMC distribution. A 1% strength by weight ditallow dimethyl ammonium methyl sulfate (DTDMAMS) aqueous dispersion (170 ° F./76.6° C.) was added to about 0.1% by weight 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 aqueous slurry of eucalyptus bleached kraft fiber pulp fiber (obtained from Aracruz-Brazil, Brazil) was prepared using a conventional repulper and applied to the head box of a long net paper machine. Pass through the dough pipe. This eucalyptus furnish is mixed with the NSK slurry at the fan pump and combined, where both are diluted with white water to a concentration of about 0.2%.

  An aqueous slurry of about 3% by weight eucalyptus-derived bleached kraft fiber pulp fibers (obtained from Aracruz-Brazil, Brazil) is prepared using a conventional repulper. The eucalyptus slurry is passed through a second fan pump where it is diluted with white water to a concentration of about 0.2%.

  NSK / eucalyptus and eucalyptus slurries 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 go. A headbox consisting of three chambers is used. The eucalyptus slurry containing 48% of the dry weight of the final sanitary tissue paper is directed to the chamber leading to the layer in contact with the wire, while the NSK / eucalyptus containing 52% of the dry weight of the final paper The slurry (27-35% NSK and 17-25% Eucalyptus) is directed to the chamber leading to the center and inner layers. NSK / eucalyptus and eucalyptus slurry are mixed at the time of discharging 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 with 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 0.20 mm (8 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 , a 1-ply total dry tensile strength of 98-146 g / cm, a 1-ply wet burst strength of 13-26 g / cm, and a 2-ply caliper of about 0 0.038-0.05 cm. The resulting tissue is then combined with a similar sheet so that the eucalyptus fibers face the outside to form a two-ply, creped, imprinted tissue, and then two smooth Applicable to the calendering process between steel calender rolls. The cationic silicone polymer is then added at about 0.8 to 1.0 g / m ² of emulsion add-on per side (based on the total weight of the fiber per ply at the total add-on level). (Corresponding to 0.7-1.0% by weight silicone)) slot extrusion 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 two-ply tissue has a) a basis weight of about 39-50 g / m ² ; b) a two-ply total dry tensile strength of 177-276 g / cm; c) a two-ply wet burst of 39-51 g / cm Strength; d) 4-ply caliper of about 0.05-0.09 cm; e) slip-stick friction coefficient of about 0.010-0.018; f) about 0.01-0.04 g · cm ² / cm Flexural rigidity (B); and g) A lint of about 10-12 lint units.

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

  Example 2-In one embodiment of the facial tissue of the present invention, prepared according to Example 1, replacing Eucalyptus fibers with acacia fibers (obtained from PT Tel-Indonesia, Indonesia).

  Example 3 One embodiment of a normal, wet pressed and dry creped tissue handkerchief of the present invention is made as follows.

The paper web is composed of about 40% Northern Softwood Kraft and 60% Eucalyptus, about 15.4 g / m ² basis weight, about 0.36 mm 4-ply caliper, about 768 g / cm. It has a total dry tensile strength and a wet burst strength of about 225 g. The paper web is about 0.9% by weight dry fiber of wet strength resin (Kymene 617®, available from Hercules, Wilmington, Del.), 0.14 Dry fiber of weight percent dry strength improving resin (carboxymethylcellulose, available from Hercules, Wilmington, Del., USA), and about 0.05 wt% wet end softener (di-cured tallow diethyl (Esterdimethylammonium chloride) containing dry fibers.

  After conventional papermaking, where the paper web is wet pressed and dry creped, the four sheets of paper web are combined together in an off-line combination process. The pre-combined 4-ply parent roll is then processed into a 4-ply tissue product. The 4-ply parent roll is unwound and subjected to a calendering process between two smooth steel calender rolls, and then the ply is bonded by high pressure embossing. Most tissue papers remain unembossed.

The cationic silicone polymer emulsion is then transferred onto a 4-ply tissue web using the rotogravure method. About 1.5 g / m ² of emulsion is deposited on each side of the 4-ply product. This amount, in total, corresponds to a silicone add-on of 0.5% by weight of the tissue.

  The transfer station is composed of two engraved anilox rolls facing each other in a horizontal arrangement, and a gap is formed while a four-ply tissue web is flowing. The shape is set so that the roll touches the paper web and the lotion moves macroscopically and evenly on both surfaces of the 4-ply paper web, but the web does not wrap either of the two anilox rolls. The anilox roll is recessed to provide a cell volume of about 3 mL per square meter, and the lotion is supplied from a closed supply chamber designed to fill the recess with the lotion. The gap between the two rolls is adjusted so that an add-on level is achieved.

  The tissue is cut into approximately 21 cm × 21 cm sheets and folded.

The 4-ply paper tissue product obtained by the above method has a basis weight of approximately 61 g / m ² , a thickness of 0.27 mm, an MD strength of 504 g / cm, a CD strength of 240 g / cm, and a burst strength when wet of 200 g. Have. The product contains about 0.5% by weight of the cationic silicone polymer of the tissue.

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

Example 4 One embodiment of the tissue handkerchief of the present invention, except that 1.5 g / m ² of the cationic silicone polymer emulsion was transferred to each side of the tissue (1% by weight of the tissue weight Equivalent to the total add-on level of cationic silicone polymer). The 4-ply paper tissue product has a basis weight of approximately 62 g / m ² , a thickness of 0.27 mm, an MD strength of 469 g / cm, a CD strength of 220 g / cm, a wet burst strength of about 200 g.

  The resulting tissue paper is judged to be softer than a tissue sample treated with 0.5% by weight of tissue by a panel of experts.

  Example 5 One embodiment of the sanitary tissue product of the present invention is performed according to Example 3, except that the cationic silicone emulsion is applied to the web using a variety of application methods.

  The emulsifying softener is sprayed onto the tissue using a rotating disk spray device (commercially available from Weitmann & Konrad GmbH & Co KG, Leinfelden, Germany). This device has 5 rotors per applicator and is designed to cover a web width of 448 mm. Each rotor is composed of two disks stacked on top of each other. Each disc is supplied with an equal amount of cationic silicone polymer. The distance between the center of the rotor and the web is about 154 mm. The disc has a diameter of about 80 mm and is operated at a speed of about 3600 rpm. The disks are evenly spaced at a distance of 11.2 cm and cover the entire width of 448 mm. Under the influence of centrifugal force generated by the rotating rotor, the liquid is dispersed in droplets. A 72 ° (equivalent to 20%) spray generated around the disc is deposited on the web and the remainder is collected and returned to the applicator through the recirculation line. Spraying with each rotor covers a web of about 224 cm, except that the first and last rotor cover only about 11.2 cm of the web. At either position, the spray patterns of the two rotors overlap.

The added-on emulsion is adjusted to be about 1.5 g / m ² for each face.

The resulting 4-ply tissue product has a basis weight of about 61 g / m ² and contains about 0.5% by weight of the cationic silicone polymer of the tissue weight.

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

  All documents cited in the best mode for carrying out the invention are incorporated herein by reference in the relevant part, and any citation of any document is said to be prior art to the present invention. Should not be considered acceptable.

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. A fiber furnish layer;
b. A cationic silicone polymer layer separate from the fiber furnish layer, wherein the cationic silicone polymer comprises one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties. Including:
A fibrous structure comprising:   The fibrous structure of claim 1, wherein the cationic silicone polymer comprises at least two or more polysiloxane units and at least two or more quaternary nitrogen moieties.   A single-ply or multi-ply sanitary tissue product selected from the group consisting of facial tissue products, handkerchiefs, toilet paper products, paper towel products, and mixtures thereof comprising the fibrous structure of claim 1. . a. With fiber furnish;
b.
i. A cationic silicone polymer comprising one or more polysiloxane units, one or more non-pendant quaternary nitrogen moieties, and one or more alkylene oxide units;
ii. A cationic silicone polymer comprising one or more polysiloxane units, one or more non-pendant quaternary nitrogen moieties, and one or more ring-opening epoxide units;
iii. a cationic silicone comprising alternating units of a) a polysiloxane comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties; and b) a divalent organic moiety comprising quaternary nitrogens. A polymer; and iv. A cationic silicone polymer selected from the group consisting of:
A fibrous structure comprising:   A single-ply or multi-ply sanitary tissue product selected from the group consisting of facial tissue products, handkerchiefs, toilet paper products, paper towel products, and mixtures thereof comprising the fibrous structure of claim 4 . a. Preparing a fiber furnish;
b. Depositing the fiber furnish on a porous surface for paper layer formation to form an initial fiber web;
c. Drying the initial fiber web such that a fibrous structure is formed;
d. A cationic silicone polymer comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties, the fiber furnish and / or the initial fiber web and / or the fibrous structure; A step of applying to
The manufacturing method of the fibrous structure containing this.   The manufacturing method according to claim 6, wherein the manufacturing method includes a step of processing the fibrous structure into a single-ply and / or multi-ply sanitary tissue product.   The manufacturing method according to claim 7, wherein the step of applying the cationic silicone polymer to the fibrous structure is performed before and / or simultaneously with and / or after the processing step.   A fibrous structure produced by the production method according to claim 6. A single-ply or multi-ply sanitary tissue product selected from the group consisting of facial tissue products, handkerchiefs, toilet paper products, paper towel products, and mixtures thereof comprising the fibrous structure of claim 9 .