CN1784524A - Cationic silicone polymer-containing fibrous structure - Google Patents

Abstract

This invention provides a fibrous structure comprising a cationic siloxane polymer, the cationic siloxane polymer comprising one or more polysiloxane units and one or more non-side-group quaternary nitrogen moieties. The invention also provides a method for manufacturing such a fibrous structure. Furthermore, the invention provides a sheet of toilet paper comprising said fibrous structure.

Description

Fibrous structure with cationic silicone polymer

field of invention

The present invention relates to fibrous structures comprising cationic silicone polymers comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties and the manufacture of such fibrous structures and methods of sanitary tissue products incorporating the fibrous structure.

Background of the invention

It is well known in the art that the softness of a structured sanitary tissue product is inversely proportional to the overall 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.

Attempts by formulators to overcome these inverse relationships, particularly the relationship between softness and overall tensile strength, have included the addition of cationic silicones to sanitary tissue products and/or to the fibrous structure with which these products are formulated. See, eg, US Patent 5,059,282 to Ampulski et al.

However, these prior art sanitary tissue products and documents fail to address fibrous structures incorporating cationic silicone polymers comprising one or more polysiloxane units, one or more non-side The quaternary nitrogen moiety of the group and one or more of the following moieties: alkylene oxide units, ring-opening epoxide units, and alternating units of divalent organic moieties comprising quaternary nitrogen.

The prior art fails even to propose a fibrous structure comprising a fiber furnish layer and a cationic silicone polymer layer discrete from the fiber furnish layer, wherein the cationic silicone polymer comprises a One or more polysiloxane units, one or more non-pendant quaternary nitrogen moieties, and one or more of the following moieties: alkylene oxide units, ring-opening epoxide units, and divalent organic compounds containing quaternary nitrogen Alternate units of parts.

Summary of the invention

The present invention overcomes the deficiencies associated with the prior art by providing novel fiber structures incorporating cationic silicone polymers.

In one aspect of the present invention, a fibrous structure is provided comprising a fiber furnish layer and a cationic silicone layer discrete 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.

In another aspect of the present invention, a fibrous structure is provided comprising:

a. Fiber ingredients; and

b. Cationic silicone polymers selected from the group consisting of:

i. a cationic siloxane 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 siloxane 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 silicone polymers comprising alternating units comprising: a) polysiloxanes comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties and b) a divalent organic moiety containing quaternary nitrogen; and

iv. Mixtures thereof.

In another aspect of the present invention, there is provided a method of manufacturing a fibrous structure, the method comprising the steps of:

a. Prepare fiber ingredients;

b. depositing a fiber furnish on a porous forming surface to form a web of embryo fibers;

c. drying the embryo fiber web to form a fibrous structure; and

d. Applying to the embryo web and/or fiber structure a cationic silicone polymer comprising one or more polysiloxane units and one or more non-pendant quaternary nitrogen moieties.

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

Detailed description of the invention

As used herein, "fiber" means an elongated particle whose apparent length substantially exceeds its apparent width, ie, has a length-to-diameter ratio of at least about 10. More specifically, "fiber" as used herein relates to papermaking fibers. The present invention contemplates the use of a variety of papermaking fibers, such as natural fibers or synthetic fibers, or any other suitable fibers, and any combination thereof. Papermaking fibers useful in the present invention include cellulosic fibers commonly referred to as wood pulp fibers. Applicable wood pulps include chemical wood pulps, such as kraft pulps, especially Northern Softwood Kraft ("NSK"), sulfite wood pulps and sulfate wood pulps, and mechanical wood pulps, including, for example, groundwood , thermodynamic wood pulp and chemically modified thermodynamic wood pulp. Non-limiting examples of wood pulp include fibers derived from the group consisting of acacia, eucalyptus, maple, oak, poplar, birch, cottonwood, alder, ash, cherry, elm, hickory, poplar , rubber tree, walnut, locust, sycamore, beech, catalpa, sassafras, catalpa, acacia, tulip, magnolia, bagasse, flax, hemp, kenaf, and mixtures thereof. However, chemical wood pulps may be preferred because of their ability to impart a superior soft feel to facial tissue sheets made from them. Pulps derived from deciduous trees (hereinafter also referred to as "hardwoods"), especially tropical hardwoods, and conifers (hereinafter also referred to as "softwoods"), both may be utilized. Hardwood fibers and softwood fibers may be blended, or alternatively deposited in layers, to provide a laminated web. US Patent 4,300,981 and US Patent 3,994,771 are incorporated herein by reference for the disclosure of layered hardwood fibers and softwood fibers. Also applicable to the present invention are fibers derived from recycled paper, which may contain any or all of the above-mentioned species, as well as other non-fibrous materials such as fillers and binders used to facilitate primary papermaking.

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

Germ fiber webs are typically prepared from aqueous dispersions of papermaking fibers, although liquid dispersions other than water can also be used. The fibers can be dispersed into a carrier liquid to have a consistency of about 0.1% to about 0.3%. It is believed that the present invention is also applicable to wet forming operations wherein the fibers are dispersed into a carrier liquid to have a consistency of less than about 50%, more preferably less than about 10%.

As used herein, "sanitary tissue product" refers to a soft, low density (i.e., less than about 0.15 g/cm ³ ) web that can be used as a wipe (toilet tissue) for post-urination or post-defecation cleansing for ENT excreta (facial tissues and/or handkerchiefs), and multipurpose absorbent and cleansing uses (absorbent wipes).

As used herein, "weight average molecular weight" refers to the weight average molecular weight determined by gel permeation chromatography according to the protocol found in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pp. 107-121.

"Layer" or "multilayer" as used herein means that individual fibrous structures may optionally be placed in substantially contiguous, face-to-face relationship with other layers to form a multi-layered fibrous structure. It is also contemplated that a single fibrous structure may effectively form two or more "layers" such as by being folded upon itself.

The fibrous structure and/or the sanitary tissue product using the fibrous structure of the present invention can be described in a multi-parameter range empirically composed of one or more and/or two or more and/or three or more Defined by a range determined by the following parameters: 1) thickness; 2) smoothness; 3) slip and viscosity coefficients; 4) total tensile strength; 5) flexibility; 6) curvature; 7) absorbency; 8) Properties related to compression; 9) basis weight; 10) wet burst strength; 11) coefficient of friction; and/or 12) WABY factor.

As used herein, "thickness" refers to the macroscopic thickness of a sample. Thicknesses of fibrous structures and/or sanitary tissue product samples according to the present invention were obtained from a VIR Electronic Thickness Tester Model II available from Thwing-Albert Instrument Company, Philadelphia, PA. The thickness measurement can be repeated and recorded at least five (5) times, whereby an average thickness can be calculated. The results are reported in millimeters.

"Smoothness" and/or "physiological surface smoothness" as used herein is a factor (hereinafter referred to as PSS factor and/or SMD factor) derived from profilometer scanning of longitudinal fiber structures with a diamond stylus and and/or samples of sanitary tissue products with the profilometer installed in a surface testing device such as described in the 1991 International paper Physics Conference. TAPPI Book 1, Ampulski et al. entitled "Methods for the Measurement of the Mechanical Properties of Tissue Paper" paper, found at page 19, and/or described in US Patent 5,059,282 to Ampulski et al., both of which are incorporated herein by reference. The smoothness and/or the inverse of smoothness (i.e., roughness) can also be measured using Kato Surface Tester KES-FB4, which is available from Kato Tekko Co., LTD., Karato-Cho, Nishikiyo, Minami-Ku, Koyota, Japan. Alternatively, the smoothness of the fibrous structure and/or sanitary tissue product according to the present invention can be determined using a commercially available Primos Optical Profiler/3D Surface Analyzer from GF Messtechnik, Berlin, Germany.

The "Slip and Viscous Coefficient of Friction" (S&S COF) is defined as the average deviation of the stated coefficient of friction. Like the coefficient of friction stated, it is dimensionless. The test was performed on a KES-FB4 Surface Analyzer from Kato Tekko Co. using a modified friction probe. The probe readhead is a two centimeter diameter, 40-60 micron glass frit from Ace Glass Company. The normal force of the probe is 19.6 grams. Details of the procedure are described in Ampulski et al., "Methods for the Measurement of the Mechanical Properties of Tissue Paper", 1991 International Paper Physics Conference, p. 19, 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 determined as follows. A one (1 ) inch by five (5) inch (2.5 cm x 12.7 cm) tape of the fibrous structure and/or a paper product comprising such a fibrous structure is prepared. Place the strip in an electronic tensile tester (Model 1122, available from Instron Corp. Canton, Massachusetts). The tensile tester had a crosshead speed of 2.0 inches per minute (about 5.1 cm/minute) and a gauge length of 4.0 inches (about 10.2 cm). The TDT is the arithmetic sum of the MD and CD tensile strengths of the tape.

As used herein, "absorbency" and/or "hydrophilicity" include two factors: 1) absorbency and 2) speed of absorption. The absorbent capacity is a measure of the ability of a fibrous structure and/or a sanitary tissue product comprising a fibrous structure to retain liquid in a horizontally supported state. The absorption rate is a measure of the rate at which the fibrous structure and/or the sanitary tissue product using the fibrous structure acquires liquid by wicking. Procedures for determining absorbency are known in the art. For example, the procedure described in US Patent 5,908,707.

As used herein, "compression-related properties" refers to a set of properties that describe the behavior of the fibrous structures and/or sanitary tissue products of the present invention under increasing pressure followed by unloading reduced pressure. Non-limiting examples of properties related to compression include bulk, bulk, compression, and energy necessary to spring (ie, resiliency) of the fibrous structure and/or sanitary tissue product. Properties related to compression were determined by KES-FB3 Compressibility Analyzer, commercially available from Kato Tekko Co.

As used herein, "wet burst strength" refers to a measure of the ability of a fibrous structure and/or paper product incorporating the fibrous structure to absorb energy when wetted and subjected to deformation perpendicular to the plane of the fibrous structure and/or paper product. Wet burst strength can be measured using a Thwing-Albert Burst Tester Cat. No. 177 equipped with a 2000 g load cell, available from Thwing-Albert Instrument Company, Philadelphia, PA.

As used herein, "basis weight" is the weight of a sample per unit area, reported in ^lbs /3000ft2 or g/ ^m2 . The basis weight is determined by preparing one or more samples with a defined area (m ² ) and then weighing the fibrous structure according to the invention and/or a product comprising such a fibrous structure on a top-loading balance with a minimum resolution of 0.01 g. Samples of paper products. The balance is protected from drafts and other disturbances using a draft hood. The weight is recorded when the reading on the balance is constant. Calculate the average weight (g) and the average area (m ² ) of the samples. The basis weight (g/m ² ) was calculated by dividing the average weight (g) by the average area (m ² ) of the sample.

As used herein, "machine direction" or "MD" refers to the direction parallel to the flow of the fibrous structure on a paper machine and/or product manufacturing equipment.

As used herein, "cross direction" or "CD" refers to the direction perpendicular to the machine direction within the same plane of the fibrous structure and/or paper product comprising the fibrous structure.

"Apparent density" or "density" as used herein refers to the basis weight of a sample divided by thickness, using the appropriate conversions incorporated herein. The unit of apparent density used herein is g/cm ³ .

As used herein, "total tensile strength" means the geometric mean of the breaking strengths in the machine and transverse directions expressed in grams per cm of sample width. Arithmetically, this is the square root of the product of the longitudinal and transverse breaking strengths expressed in grams per cm of sample width.

As used herein, "bending properties" are determined for fibrous structures and/or sanitary tissue products using a KES-FB2 Pure Bending Tester available from Kato Tekko Co.

As used herein, "flexibility" refers to the slope of the secant line obtained from a plot of force versus percent stretch, the secant passing through the origin (0% stretch, 0 force) and passing through the force per centimeter of width on the plot for the 20 g point. For example, for a sample of a fibrous structure and/or sanitary tissue product of the present invention stretched 10% (i.e., 0.1 cm/cm length) at 20 grams force per cm sample width, the penetration (0% Stretch, 0 force) and (10% stretch, 20 force) have a slope of 2.0:

As used herein, "total flexibility" refers to the geometric mean of the longitudinal and transverse flexibility. Arithmetically, this is the square root of the product of longitudinal flexibility and transverse flexibility expressed in grams per cm.

As used herein, "WABY factor" refers to the ratio of total flexibility to total tensile strength. The measured WABY factor is the factor that characterizes embodiments of the invention as being tough yet having high bulk volume softness. This ratio is therefore called the WABY factor. For example, a sample having an overall flexibility of 20 g/cm and an overall tensile strength of 154 g/cm has a WABY factor of 0.13.

Briefly, the softness of touch of a tissue paper is inversely proportional to its WABY factor. Also, note that the WABY factor is dimensionless since both flexibility and total tensile strength as defined above have units of g/cm and their ratios are dimensionless.

As used herein, "lint" is determined according to the procedure set forth in commonly assigned US Patent 5,814,188, issued September 29, 1998 to Vinson et al., which is incorporated herein by reference.

The article "a" as used herein (eg, "an anionic surfactant" or "a fiber" as used herein) is understood to mean one or more of such material as claimed or described.

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

Unless otherwise indicated, all component or composition levels refer to the active level of that component or composition and do not include impurities, such as residual solvents or by-products, which may be present in commercially available raw materials.

fiber structure

The fibrous structures and/or tissue papers of the present invention can be made by different methods. Non-limiting examples of fibrous structure types and/or tissue types include conventional pressed and/or felted tissues; patterned densified tissues with patterned wires and/or patterned fabric/resin Webbing; high bulk, uncompacted tissue and creped or uncreped tissue. The tissue paper may be of homogeneous and/or single-ply or multi-ply construction; and the tissue paper article produced therefrom may be of single-ply or multi-ply construction.

Additionally, the fibrous structures of the present invention and/or sanitary tissue products incorporating the same fibrous structures may be creped or uncreped.

Additionally, sanitary tissue products incorporating the fibrous structures of the present invention may also incorporate dry fibers by air-laying and/or latex binders by wet-laying.

Conventional manufacturing processes can be used to convert dry rolls of fibrous structures according to the present invention into single-ply and/or ply sanitary tissue products. Non-limiting examples of such manufacturing processes include embossing, including high pressure embossing, dry creping, ply bonding, calendering, and/or other mechanical treatments of the fibrous structure.

The fibrous structure can be produced from a fiber furnish for producing a single-layer germ fiber web or a fiber furnish for producing a multi-layer germ fiber web.

The fibrous structures of the present invention and/or sanitary tissue products comprising such fibrous structures may have a basis weight of from about 12 g/ ^m to about 120 g/m ^and /or from about 14 g/ ^m to about 80 g/ ^m and/or from about 17 g/m ² to about 70 g/m ² and/or from about 20 g/m ² to about 60 g/m ² . Typically, a single layer of said 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 can have a total dry tensile strength 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 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 layer of said fibrous structure has an overall dry tensile strength of from 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 can have a total wet burst strength greater than about 10 g/cm and/or from about 12 g/cm to about 394 g/cm and/or about 13 g/cm to 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 can have slip and viscous coefficients of friction greater than about 0.007 and/or about 0.007 to about 0.055 and/or about 0.008 to 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 can have a coefficient of friction of greater than about 0.1 and/or from about 0.1 to about 0.90 and/or from about 0.1 to about 0.85 and/or from about 0.1 to about 0.65 And/or from about 0.15 to about 0.60.

The fibrous structures of the present invention and/or sanitary tissue products comprising such fibrous structures can have a curvature of greater than about 0.008 gf ^{* cm2} /cm and/or from about 0.008 gf ^{* cm2} /cm to about 0.15 gf ^{* cm2} /cm and/or from about 0.01 gf ^* cm ² /cm to about 0.14 gf ^* cm ² /cm.

The fibrous structures of the present invention and/or sanitary tissue products comprising such fibrous structures can have a bulk (initial caliper - final caliper) of greater than about 0.03 mm and/or about 0.03 mm to about 0.5 mm and/or about 0.05 mm to about 0.4mm.

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

The fibrous structures of the present invention and/or sanitary tissue products comprising such fibrous structures may have a necessary energy for compression of greater than about 0.02 gf ^* cm/cm ^and /or from about 0.02 gf ^* cm/ ^cm to about 0.13 gf ^* cm /cm ² and/or about 0.025gf ^* cm/cm ² to about 0.12gf ^* cm/cm ² .

The fibrous structures of the present invention and/or sanitary tissue products comprising such fibrous structures may have an elasticity (percent rebound) of greater than about 35% and/or from about 35% to about 75% and/or from about 40% to about 65% %.

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

The fibrous structures of the present invention and/or sanitary tissue products comprising such fibrous structures can have a thickness (4-ply) of 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 to about 0.114 cm cm.

The properties described herein can be applied to said fibrous structures in a single ply and/or to a single ply sanitary tissue product, and/or to a multiply sanitary tissue product incorporating at least one ply comprising the fibrous structure of the present invention .

Fiber Ingredients

The fiber furnishes of the present invention comprise one or more fibers and typically one or more optional ingredients.

cationic silicone polymer

The cationic silicone polymers of the present invention comprise one or more polysiloxane units and organosiloxane-free units comprising at least one diquaternary ammonium unit, wherein the polysiloxane units are preferably polydimethylsiloxane The oxane unit has the formula -{( _CH3 ) _2SiO } _c- , which has a degree of polymerization c of 1 to 1000, preferably 20 to 500, more preferably 50 to 300, most preferably 100 to about 200. In a preferred embodiment of the present invention, the cationic silicone polymer is selected to have from 0.05 to 1.0 mole fraction, more preferably from 0.2 to 0.95 mole fraction, most preferably from 0.5 to 0.9 mole fraction of organosiloxane-free unit selected from divalent cationic organic moieties. The divalent cationic organic moiety is preferably selected from N,N,N',N'-tetramethyl-1,6-hexanediamine units.

The selected cationic silicone polymer also comprises 0 to 0.95 mole fraction, preferably 0.001 to 0.5 mole fraction, more preferably 0.05 to 0.2 mole fraction, based on the total number of organosiloxane-free units, of a polyepoxide having the formula Alkylamine:

[-YO(-C _a H _2a O) _b -Y-]

wherein Y is a divalent organic group, including a _secondary or tertiary amine, preferably a C to C _alkylene amine residue; a is 2 to 4, and b is 0 to 100. The polyalkylene oxide block can be composed of ethylene oxide (a=2), propylene oxide (a=3), butylene oxide (a=4) and mixtures thereof in a random or block manner .

Such polyalkyleneoxide-containing units can be obtained by introducing compounds such as those sold under the tradename Jeffamine ^(R ) by Huntsman Corporation into the structure of the silicone polymer. A preferred Jeffamine is Jeffamine ED-2003.

The selected cationic silicone polymer may also contain from 0 to 0.2, preferably from 0.001 to 0.2 mole fraction of the total number of organosiloxane-free units _-NR3 +, where R is alkyl, hydroxyalkyl or phenyl. These units can be considered as capping groups.

In addition, to balance the charge of the quaternary ammonium moiety, the selected cationic silicone polymer typically contains anions selected from inorganic and organic anions, more preferably from saturated and unsaturated _C1 - _C20 carboxylates, As well as mixtures thereof, the cationic silicone polymers thus also include such anions that balance the charge ratio of the quaternary ammonium.

Conceptually, the cationic silicone polymers selected here can be usefully thought of as non-crosslinked or "linear" block copolymers comprising "rings" composed of polysiloxane units that are not fabric entities but are surface energy modified. ” and the “hook” of the fabric entity. A preferred class of selected cationic polymers (illustrated by Structural Formula 1 below) can be considered to contain one "loop" and two "hooks"; another highly preferred class contains two or more, preferably three or More "rings" and two or more, preferably three or more "hooks" (illustrated by Structural Formulas 2a and 2b below), and yet another class (illustrated by Structural Formula 3 below) Two "rings" suspended from a single "hook".

In the selected cationic silicone polymers of the present invention, it is especially important that the "hooks" contain no silicone and that each "hook" contains at least two quaternary nitrogen atoms.

In the preferred cationic silicone polymers selected for the present invention, it is also important that the quaternary nitrogen is preferentially located on the "backbone" of the "linear" polymer, as opposed to alternative but less preferred structures in which the quaternary nitrogen The nitrogen is incorporated in one or more moieties which form "branch" or "side group" structures off the "backbone".

The structure is closed by capping moieties which can be uncharged or charged. Additionally, there may be a proportion of moieties free of non-quaternary ammonium siloxanes, such as the [-YO(-C _a H _2a O) _b -Y-] moieties described above.

Of course, the conceptual model presented is not intended to limit other moieties, such as linking moieties, that may be present in the selected cationic silicone polymer, provided that such moieties do not substantially destroy the intended function as a tissue benefit agent.

In more detail, the cationic silicone polymers herein contain one or more polysiloxane units and one or more quaternary nitrogen moieties, comprising polymers wherein said cationic silicone polymer has the formula:

Structural formula 1

in:

-R ^is independently selected from: C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkyl aryl, aryl, cycloalkyl, and mixtures thereof;

-R ^is independently selected from: divalent organic moieties, which may contain one or more oxygen atoms (such moieties preferably consist essentially of C and H, or C, H and O);

-X is independently selected from ring-opened epoxides;

^{-R3 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 independently selected from H, C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkyl aryl, aryl, cycloalkyl, C _1-22 hydroxyalkyl, polyalkylene oxide, (poly)alkoxyalkyl, and mixtures thereof;

-Z is independently selected from monovalent organic moieties comprising at least one quaternized nitrogen atom;

-a is 2 to 4; b is 0 to 100; c is 1 to 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 said cationic silicone polymer, greater than or equal to 2; and A is a monovalent anion.

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

(v) a monovalent aromatic or aliphatic heterocyclic group, substituted or unsubstituted, containing at least one quaternized nitrogen atom;

in:

-R ¹² , R ¹³ , R ¹⁴ may be the same or different, and are selected from: C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkylaryl, aryl, cycloalkyl, C _1-22 hydroxyalkyl groups, polyalkylene oxides, (poly)alkoxyalkyl groups, and mixtures thereof;

-R ¹⁵ is -O- or NR ¹⁹ ;

-R ¹⁶ is a divalent hydrocarbon residue;

-R ¹⁷ , R ¹⁸ , R ¹⁹ are the same or different, and are selected from: H, C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkylaryl, aryl, ring Alkyl, C _1-22 hydroxyalkyl, polyalkylene oxide, (poly)alkoxyalkyl, and mixtures thereof; and e is 1 to 6.

In a highly preferred embodiment, the cationic silicone polymers herein contain one or more polysiloxane units and one or more quaternary nitrogen moieties, comprising polymers in which the cationic silicone polymers The compound has the chemical formula: (structural formula 2a)

Structural formula 2a: a cationic siloxane polymer composed of alternating units, the alternating units include:

(i) polysiloxanes having the formula

and

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

Note that Formula 2a includes alternating combinations of both polysiloxanes of said formula and said divalent organic moieties, and said divalent organic moieties are organosiloxane-free corresponding to the preferred "hook" above .

In this preferred cationic silicone polymer, R ^is independently selected from: C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkyl aryl, aryl, cycloalkyl, and mixtures thereof; ^-R2 is independently selected from: divalent organic moieties which may contain one or more oxygen atoms; X is independently selected from ring-opened epoxides; ^R3 is independently selected from poly Ether group:

-M ¹ (C _a H _2a O) _b -M ²

Wherein M ¹ is a divalent hydrocarbon residue; M ² is independently selected from H, C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkyl aryl, aryl, cycloalkyl, C _1-22 hydroxyalkyl, polyalkylene oxide, (poly)alkoxyalkyl, and mixtures thereof; a is about 2 to 4; b is about 0 to 100; c is about 1 to 1000, preferably greater than 20 , more preferably greater than 50, preferably less than 500, more preferably less than 300, most preferably about 100 to 200; and d is about 0 to 100.

In an even more highly preferred embodiment of the cationic silicone polymer of formula 2a, the cationic silicone polymer is of formula 2b, wherein the polysiloxane (i) having the formula described above in formula 2a appears in structural formula 2b together with a divalent cationic organic moiety (ii) selected from:

(d) a divalent aromatic or aliphatic heterocyclic group, substituted or unsubstituted, containing at least one quaternized nitrogen atom; and

(iii) Optionally, a polyalkylene oxide amine having the formula:

[-YO(-C _a H _2a O) _b -Y-]

-Y is a divalent organic group, including secondary or tertiary amines, preferably C ₁ to C ₈ alkylene amine residues; a is 2 to 4; b is 0 to 100; the polyalkylene oxide block may consist of ethylene oxide (a=2), propylene oxide (a=3), butylene oxide (a=4) and mixtures thereof in a random or block fashion; and

(iv) Optionally, the monovalent cationic organic moieties to be used as end groups are selected from:

(v) a monovalent aromatic or aliphatic heterocyclic group, substituted or unsubstituted, comprising at least one quaternized nitrogen atom;

in:

-R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ can be the same or different, and are selected from: C _1-22 alkyl, C _2-22 alkenyl, C _{6 -22} alkylaryl, aryl, cycloalkyl, C _1-22 hydroxyalkyl, polyalkylene oxide, (poly)alkoxyalkyl, 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 may be bridged alkylene moieties;

-R ¹² , R ¹³ , R ¹⁴ may be the same or different, and are selected from: C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkylaryl, C _1-22 hydroxyalkyl, Polyalkylene oxides, (poly)alkoxyalkyl groups, and mixtures thereof; and

-R ¹⁵ is -O- or NR ¹⁹ ;

-R ¹⁶ and M ¹ are the same or different divalent hydrocarbon residues;

-R ¹⁷ , R ¹⁸ , R ¹⁹ can be the same or different, and are selected from: H, C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkyl aryl, aryl, cycloalkyl , C _1-22 hydroxyalkyl, polyalkylene oxide, (poly)alkoxyalkyl, and mixtures thereof; and

- ^Z and ^Z are identical or different divalent hydrocarbon groups containing at least 2 carbon atoms, optionally containing hydroxyl groups, and may be interrupted by one or several ether, ester or amide groups;

wherein, expressed as fractions of the total moles of said organosiloxane-free moieties, said divalent cationic organic moiety (ii) is preferably present in an amount of from 0.05 to 1.0 mole fraction, more preferably from 0.2 to 0.95 mole fraction, and Most preferably 0.5 to 0.9 mole fraction; the content of the polyalkylene oxide amine (iii) is 0.0 to 0.95 mole fraction, preferably 0.001 to 0.5 mole fraction, and more preferably 0.01 to 0.2 mole fraction; if present The monovalent cationic organic part (iv), then its content is 0 to 0.2 mole fraction, preferably 0.001 to 0.2 mole fraction;

-e is 1 to 6; m is the number of positive charges associated with the organic moiety of the divalent cation, which is greater than or equal to 2; and A is an anion.

Note that Formula 2a includes alternating combinations of both polysiloxanes of said formula and said divalent organic moieties, and said divalent organic moieties are organosiloxane-free corresponding to the preferred "hook" above . In addition, the optional polyalkyleneoxy and/or end group moieties may or may not be present in the embodiments encompassed by structure 2b.

In yet another embodiment, the cationic silicone polymers herein contain one or more polysiloxane units and one or more quaternary nitrogen moieties, comprising polymers in which the cationic silicone polymers The substance has the chemical formula: (structural formula 3)

Structural formula 3

in:

-R ^is independently selected from: C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkyl aryl, aryl, cycloalkyl, and mixtures thereof;

-R ^is independently selected from: a divalent organic moiety which may contain one or more oxygen atoms;

-X is independently selected from ring-opened epoxides;

^-R3 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 independently selected from H, C _1-22 alkyl, C _2-22 alkenyl, C _6-22 alkyl aryl, aryl, cycloalkyl, C _1-22 hydroxyalkyl groups, polyalkylene oxides, (poly)alkoxyalkyl groups, and mixtures thereof;

-X is independently selected from ring-opened epoxides;

-W is independently selected from divalent organic moieties comprising at least one quaternized nitrogen atom;

-a is 2 to 4; b is 0 to 100; c is 1 to 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, which is greater than or equal to 1; and A is a monovalent anion, a suitable counterion.

In preferred cationic silicone polymers of Formula 3, W is selected from:

(d) a divalent aromatic or aliphatic heterocyclic group, substituted or unsubstituted, containing at least one quaternized nitrogen atom; and

in:

-R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ can be the same or different, and are selected from: C _1-22 alkyl, C _2-22 alkenyl, C _{6 -22} alkylaryl, aryl, cycloalkyl, C _1-22 hydroxyalkyl, polyalkylene oxide, (poly)alkoxyalkyl, and mixtures thereof; or wherein, R ⁴ and R ⁶ , Either R ⁵ and R ⁷ , or R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ may be a bridged alkylene moiety; and

- ^Z1 and ^Z2 are identical or different divalent hydrocarbon radicals containing at least 2 carbon atoms, optionally containing hydroxyl groups, and may be interrupted by one or several ether, ester or amide groups.

The cationic silicone polymer may be applied to the germ fiber web and/or to the dry fibrous structure, and/or prior to and/or simultaneously with the conversion of one or more dry fibrous structures into a sanitary tissue product Or thereafter, the cationic silicone polymer is applied to the germ fiber web and/or to the dry fiber structure. A non-limiting example of a suitable method of applying the cationic silicone polymer to the fibrous structure includes spraying (using, but not limited to using a spray disc) onto the fibrous structure prior to winding it into a paper roll. onto the germ web and/or dry fiber structure; extrusion, especially by slot extrusion onto said germ web and/or dry fiber structure; and/or by printing, especially gravure printing onto said germ web and and/or on dry fibrous structures and/or tissue hygiene paper products.

The cationic silicone polymer may be applied to the germ web and/or dry fiber structure and/or hygiene tissue product in a uniform and/or patterned and/or non-uniform manner.

The cationic silicone polymer can be applied to the germ web and/or dry fibrous structure and/or hygiene tissue product of the present invention while it is being made on a paper machine or after: or when it is wet (i.e. , before final drying) or dried (ie, after final drying).

In one embodiment, the aqueous mixture comprising said cationic silicone polymer is sprayed onto said embryonic web and/or fibrous structure and/or hygiene tissue product as it passes through a papermaking machine: for example, but Not to be limiting, with reference to the paper machine of general configuration disclosed in U.S. Patent 3,301,746, the spray is either before predrying, or after predrying, or even after the Yankee dryer/creping station, although the fiber structure Creping preferably follows application of the cationic silicone polymer.

The cationic silicone polymer can be applied to the germ fiber web in an aqueous solution, emulsion or suspension. The cationic silicone polymer may also be applied in a solution comprising a suitable non-aqueous solvent in which the cationic silicone polymer is soluble or which the cationic silicone polymer is readily miscible with: For example, hexane. The cationic silicone polymers can be supplied neat or preferably emulsified with suitable surfactant emulsifiers. The cationic silicone polymer may be applied after the formation of the germ web has been achieved. In a typical process, the embryonic web is formed and then dehydrated prior to application of the cationic silicone polymer in order to minimize loss of the cationic silicone polymer due to expulsion of free water. The cationic silicone polymers may be applied to a damp web of germ fibers at a fiber consistency of greater than about 15% in the manufacture of conventional pressed tissue paper; The web is transferred from a fine mesh fourdrinier to a relatively coarse print/carrier fabric and/or belt, and the cationic silicone polymer can be applied to the wet germ fiber web at a fiber consistency of between about 20% and about 35%.

Methods of applying the cationic silicone polymer to the germ web and/or dry fiber structure and/or hygiene tissue product include spraying, slot extrusion and gravure printing. Other methods include depositing the cationic silicone polymers onto forming wires or fabrics or belts, these cationic silicone polymers are then bound by the embryo web and/or the dry fiber structure and/or the sanitary tissue product. Apparatus suitable for spraying cationic silicone polymer-containing liquids onto germ fiber webs and/or dry fibrous structures and/or sanitary tissue products, including external mixing, air atomizing nozzles, such as 2 mm nozzles, available from V.I.B. Systems, Inc., Tucker, Ga. Apparatus suitable for printing liquids containing cationic silicone polymers onto embryonic webs and/or dry fibrous structures and/or sanitary tissue products, including rotogravure printers.

The cationic silicone polymer can be applied uniformly to the germ web and/or dry fiber structure and/or sanitary tissue product. Uniform distribution is desired so that substantially the entire sheet benefits from the contact effect of the cationic silicone polymer. Both sequential dispensing and patterned dispensing are within the scope of the invention and meet the above criteria.

The methods of application of the cationic silicone polymers described herein can be used in dry or wet embryonic webs and/or fibrous structures and/or sanitary tissue products.

Exemplary techniques involving the addition of silicone materials thereto during formation of the fibrous structures include US Patent 5,059,282 to Ampulski et al., issued October 22, 1991, which is incorporated herein by reference. Said Ampulski patent discloses the addition of silicone compounds to wet tissue webs ("fibrous structures"), preferably having a fiber consistency of between about 20% and about 35%. This method represents an improvement in some respects compared to adding chemicals to the slurry vat feeding the paper machine. For example, such methods target application to one surface of the web, as opposed to distributing additives to all fibers of the furnish.

Quite a number of techniques have been devised to apply silicone and/or other chemical softeners to the already dried paper web ("fibrous structure"), either at the so-called dry end of the paper machine or after the papermaking step carried out in a separate converting operation. Exemplary technologies in this area include: U.S. Patent 5,215,626 issued June 1, 1993 to Ampulski et al; U.S. Patent 5,246,545 issued September 21, 1993 to Ampulski et al; Patent 5,525,345, all patents are incorporated herein by reference. US Patent 5,215,626 discloses a process for making soft tissue paper by applying polysiloxanes to a dry web ("fibrous structure"). US Patent No. 5,246,545 discloses a similar approach utilizing a heated transfer surface. Finally, the Warner patent discloses an application process involving roll coating and extrusion for applying specific compositions to the surface of a dry tissue web ("fibrous structure").

The cationic silicone can be applied to one or both sides of the germ web and/or the dry fibrous structure and/or the sanitary tissue product such that one or both outer surfaces of the resulting sanitary tissue product incorporating the fibrous structure The cationic silicone polymer is present on.

In one embodiment, the cationic silicone may be applied to the germ web and/or the dry fibrous structure and/or a surface of the hygiene tissue product such that the cationic silicone passes through the germ web and/or Or dry fibrous structure and/or sanitary tissue product such that the cationic silicone is present on both surfaces of the germ web and/or fibrous structure and/or sanitary tissue product.

The fibrous structures of the present invention and/or sanitary tissue products incorporating such fibrous structures may comprise from about 0.0001% to about 10% and/or about 0.001% by dry weight of said fibrous structure or sanitary tissue products to about 5%, and/or about 0.005% to about 3%, and/or about 0.005% to about 2%, and/or about 0.005% to about 1.5% of said cationic silicone polymer.

References are made to the following patents and patent applications which also disclose cationic silicone polymers suitable for use in the present invention: WO 02/06403; WO 02/18528, EP 1 199350; DE OS 100 36 533; WO 00 /24853; WO 02/10259; WO 02/10257 and WO 02/10256.

Synthesis Examples - When not otherwise known or commercially available, the cationic silicone polymers herein can be prepared by conventional techniques as disclosed in WO 02/18528.

optional ingredients

The fibrous structures of the present invention, in addition to the cationic silicone polymers, also comprise optional ingredients selected from the group consisting of permanent wet strength resins, chemical softeners other than the cationic silicones described above, Temporary wet strength resins, dry strength resins, wetting agents, anti-lint agents, absorption enhancers, fixatives (especially in combination with body lotion compositions), antiviral agents (including organic acids), antibacterial agents , polyol polyester, anti-migration agent, polyhydroxyl plasticizer, filler (clay), wetting agent, and their mixtures. Such optional ingredients may be added to the fiber furnish, the germ fiber web and/or the dry fiber structure. Such optional ingredients may be present in the fibrous structure in any amount based on the dry weight of the fibrous structure.

The optional ingredients may be applied to the fibrous furnish and/or germ fiber web and/or dry fibrous structure and/or hygiene tissue product of the present invention. In addition, optional ingredients such as other chemical softeners, more specifically dew agents, especially transferable dew agents, can be added after the cationic silicone is applied to the dry fibrous structure and/or sanitary tissue product applied there.

The optional ingredients may be present in the fibrous structures and/or sanitary tissue products of the present invention at levels of from about 0.001% to about 50% by weight on the dry fibrous structure or sanitary tissue product substrate and/or about 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% to about 3% and/or about 0.05% to about 2% and/or From about 0.1% to about 1%.

Method of the present invention :

The fibrous structures of the present invention may be produced by any suitable papermaking process.

Non-limiting examples of suitable papermaking processes for making the fibrous structures of the present invention are described below.

In one embodiment, the fiber furnish is prepared by mixing one or more fibers with water. One or more additional optional ingredients may be added to the fiber furnish. The fiber furnish may then be fed to the headbox of the paper machine, which may be a layered headbox. The fiber furnish is then deposited on the foraminous surface to form a single or multilayer web of embryo fibers. The cationic silicone polymer and/or optional ingredients may be added to the embryo by spraying and/or extrusion and/or printing and/or any other suitable method known to those of ordinary skill in the art. Fiber web. The germ web can then be transferred to an air drying belt and/or a Yankee dryer so that the germ web is dried by means of an air drying and/or Yankee dryer. The fibrous structure may be transferred from the through-air drying belt (if one is present) to a Yankee dryer. The fibrous structure may be transferred from the Yankee dryer to a rewinder to form rolls of dry fibrous structure. During this transfer step, the cationic silicone polymer and/or optional ingredients may be applied to the dry fibrous structure. The fibrous structure can be converted into various paper products, especially sanitary tissue products, in single-ply and/or multi-ply form. During this converting step, the cationic silicone polymer can be applied to the fibrous structure. Thus, the cationic silicone polymer can be applied before and/or simultaneously with and/or after the converting step.

non-limiting example

The following examples use cationic silicone polymers according to the invention. The cationic silicone polymers are typically used in the form of emulsions comprising amine oxides, nonionic surfactants, ethanol and water. In one embodiment, the emulsion is formed by mixing 24.39 g of a cationic silicone solution (80% cationic silicone polymer/20% ethanol) with 6.05 g of C12- 15 E03(4) mixed. After 10 minutes, 6.7 g of ethanol was added. After a further 10 minutes, 8.71 g of a 31% active substance aqueous solution of C12-14 alkyldimethylamine oxide (2) were added. After a further 10 minutes, 54.2 g of demineralized water were quickly added to the mixture with continuous stirring. The pH of the emulsion was adjusted to pH 7.5 with 0.8 g of 0.1 M HCl. The emulsion may be diluted to a concentration of about 10% to 20% cationic silicone polymer.

Example 1 - An embodiment of a facial tissue according to the present invention was prepared as follows.

An aqueous slurry of Northern Softwood Kraft (NSK) pulp of approximately 3% consistency was made using a conventional pulping machine and sent to the headbox of the fourdrinier paper machine through a main pipe. A 1% dispersion of Hercules' Kymene 557 LX was prepared and added to the NSK master tube at a rate sufficient to deliver approximately 0.8% Kymene 557 LX based on final hygiene tissue dry weight. The absorbency of the permanent wet strength resin is enhanced by passing the treated slurry through an in-line mixer. Next, carboxymethyl cellulose (CMC) was dissolved in water and diluted to a 1% solution concentration in water, and added to the NSK main pipe immediately after the in-line mixer at a ratio based on the dry weight of the final hygiene tissue paper. About 0.1% CMC by weight. The aqueous slurry of NSK fibers is passed through a centrifugal feed pump to help disperse the CMC. Aqueous dispersion (170°F/76.6°C) of ditallow dimethyl ammonium methyl sulfate (DTDMAMS), added to the NSK parent pipe at a concentration of 1% by weight at a rate of about 0.1% DTDMAMS by weight, Based on the dry weight of the final hygiene tissue paper.

An aqueous slurry of approximately 1.5% by weight of eucalyptus bleached kraft fiber (available from Aracruz-Brazil) was prepared using a conventional secondary pulper and sent to the headbox of the fourdrinier machine through a main pipe. The eucalyptus furnish was added to the NSK slurry at the fan pump where the two were diluted with white water to a consistency of about 0.2%.

An aqueous slurry of approximately 3% by weight eucalyptus bleached kraft fiber (available from Aracruz-Brazil) was prepared using a conventional secondary pulper. The eucalyptus slurry was sent to a second fan pump where the slurry was diluted with white water to a consistency of about 0.2%.

The NSK/eucalyptus and eucalyptus slurries are directed into a multi-slot headbox suitably fitted with layered vanes to maintain the slurry flow in separate layers until discharge onto the moving Fourdrinier wire. Use a three-chamber headbox. A eucalyptus slurry containing 48% of the dry weight of the final hygiene tissue paper was introduced into the chamber leading to the layer in contact with the wires, while a slurry containing 52% of the dry weight of the final paper (27% to 35% NSK and 17% to 25% eucalyptus ) of NSK/eucalyptus slurry into the chamber leading to the center and inner layers. The NSK/eucalyptus slurry was combined with the eucalyptus slurry at the discharge of the headbox to form a composite slurry.

The composite slurry is discharged onto a moving fourdrinier wire and dewatered assisted by deflectors and vacuum boxes.

The wet embryonic web was transferred from the fourdrinier wire to a patterned dry fabric at a fiber consistency of about 17% by weight. The dry fabric is designed to produce a densely patterned tissue with discrete low density deviated regions arranged within a continuous network of high density (knuckle) regions. The dry fabric is formed by casting an impermeable resin surface on a fabric supporting a mesh of fibers. The support fabric is a 48 x 52 filament, double mesh. The resin casting was about 8 mils thicker than the support fabric. The joint area is about 35% to 50%, and the frequency of open cells is maintained at about 10/cm ² to 87/cm ² .

Further dewatering was accomplished by vacuum assisted drainage until the fiber consistency of the web was about 23% to 27%.

While remaining in contact with the patterned forming fabric, the patterned web was air-dried to a fiber consistency of about 60% by weight.

The semi-dry web was then adhered to the surface of the Yankee dryer using a spray creping adhesive comprising 0.250% polyvinyl alcohol in water. The creping adhesive was delivered to the Yankee surface at a rate of 0.1% adhesive solids based on the dry weight of the web. The fiber consistency was increased to about 98% before the web was dry-creped on the Yankee with a doctor blade. After the doctor blade, the web was calendered across its entire width with a steel-to-rubber calender roll operating under a load of 2 MPa to 3.5 MPa.

The resulting tissue has a basis weight of about 20 g/ ^m2 to 25 g/ ^m2 ; a 1 ply total dry tensile strength between 98 g/cm and 146 g/cm and a 1 ply wet burst strength between 13 g/cm and 26 g /cm, and the thickness of the 2-layer sheet is about 0.038cm to 0.05cm. The resulting tissue was then combined with the same sheet to form a two-ply, creped pattern dense tissue with the eucalyptus fibers facing outwards, and calendered between two smooth steel calender rolls. The cationic silicone polymer emulsion is then extruded through slots to both sides in contact with human skin, and the amount added is about 0.8g/m ² to 1.0g/m ² of emulsion per side, and the silicone of each layer sheet The total addition of oxanes is equal to 0.7% to 1.0%, based on the total weight of the fibers. The product plies are then bonded using a mechanical ply bonding wheel to ensure that the two plies stick together. The resulting two-ply tissue has a) a total basis weight of about 39 g/ ^m2 to 50 g/ ^m2 ; b) a 2-ply total dry tensile strength between 177 g/cm and 276 g/cm; c) a 2-ply Wet burst strength between 39 g/cm and 51 g/cm; d) 4-ply thickness of about 0.05 g/cm and 0.09 cm; e) slip-viscous friction coefficient of about 0.010 to 0.018; f) stiffness (B ) from about 0.01 g.cm ² /cm to 0.04 g.cm ² /cm; and g) from about 9 to 12 lint units of lint.

The resulting tissue was judged by an expert panel to be softer than the untreated tissue samples.

Example 2 - An embodiment of a facial tissue according to the invention was prepared according to Example 1, wherein the eucalyptus fibers were replaced with acacia fibers (available from PT Tel-Indonesia).

Example 3 - An embodiment of a wet pressed, dry creped conventional tissue handkerchief according to the present invention was prepared as follows.

A web comprising a composition of about 40% northern softwood kraft pulp and 60% eucalyptus had a basis weight of about 15.4 g/ ^m2 , a 4-ply sheet thickness of about 0.36 mm, and a total dry tensile strength of about 768 g/cm, And the wet burst strength is about 225g. It contains approximately 0.9% by weight of the dry fibers of a wet strength resin (Kymene 617 ^™ , available from Hercules Incorporated of Wilmington, DE, USA) and 0.14% by weight of the dry fibers of a dry strength resin (carboxy Methylcellulose, available from Hercules Incorporated of Wilmington, DE, USA), and contains about 0.05% wet end softener (dihard tallow diethyl ester dimethyl chloride) by weight of the dry fiber ammonium).

Following wet-pressed, dry-creped conventional papermaking of the web, the four webs were combined in an off-line combining operation. The preassembled 4-ply master roll was then converted into a 4-ply tissue product. The 4-ply master roll is unwound and calendered between two smooth steel calender rolls followed by high pressure embossing to complete the ply bonding. The greater part of the tissue paper remains unembossed.

The cationic silicone polymer emulsion was then printed onto the surface of the 4-ply tissue web using a web gravure printing process. About 1.5 g/ ^m2 of emulsion was transferred to each side of the 4-ply product with a total silicone addition equal to 0.5% by weight of the tissue weight.

The printing station consisted of two engraved bast fiber rolls placed face to face in a horizontal row with a gap formed in the middle through which the 4-ply tissue web was run. The geometry is arranged in such a way that the rolls are in contact with the web and visibly and uniformly transfer dew to both surfaces of the 4-ply web, but the web does not wrap the web. Either of the two bast fiber rolls. The bast fiber roll was engraved with a unit volume of about 3 ml per square meter, fed with dew from a closed supply chamber designed to fill the engraved volume with dew. Adjust the gap between the two rollers to achieve the target addition amount.

The tissue paper was cut into approximately 21 cm x 21 cm sheets and folded.

The 4-ply tissue paper product obtained by the above method had a basis weight of about 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 wet burst strength of about 200 g. It contained about 0.5% by weight of the tissue weight of the cationic silicone polymer.

The resulting tissue was judged by an expert panel to be softer than the untreated tissue samples.

Example 4 - An embodiment of a tissue handkerchief according to the invention is manufactured according to Example 3, except that 1.5 g/ ^m of the cationic silicone polymer emulsion is printed onto each outer face of the tissue , a total addition equal to 1% of said cationic silicone polymer by weight of said tissue weight. The 4-ply tissue product has a basis weight of about 62 g/ ^m2 , a thickness of 0.27 mm, a MD strength of 469 g/cm, a CD strength of 220 g/cm, and a wet burst strength of about 200 g.

The resulting tissue was judged by a panel to be softer than the tissue samples treated with 0.5% by weight of the tissue of the cationic silicone polymer.

Example 5 - An embodiment of a sanitary tissue product according to the present invention was made according to Example 3, except that the cationic silicone emulsion was applied to the web using a different application method.

The emulsified softener was sprayed onto the tissue using a rotating disk spray device (commercially available from Weitmann & Konrad GmbH & Co KG, Leinfelden, Germany). Equipped with 5 rotors per applicator, the equipment is designed to cover a web width of 448mm. Each rotor consists of two discs stacked on top of each other. An equal amount of the cationic silicone emulsion was added to each pan. The distance between the center of the rotor and the web is about 154 mm. The disc is about 80 mm in diameter and runs at about 3600 rpm. The discs are spaced evenly at a distance of 11.2 cm to cover a total width of 448 mm. Under the action of the centrifugal force generated by the rotating rotor, the liquid is dispersed into small droplets. 72° generated around the disc, equal to 20% of the spray, was deposited onto the web, while the remainder was withdrawn and re-introduced to the applicator through the recirculation line. The spray from each rotor covered about 224 mm of the web, except for the first and last rotors which only covered about 11.2 cm of the web. In any position, the spray patterns of the two rotors overlap.

On each side, the emulsion addition was adjusted to approximately 1.5 g/m ² .

The resulting 4-ply tissue paper product had a basis weight of about 61 g/ ^m2 and contained about 0.5% by weight of the tissue weight of the cationic silicone polymer.

The resulting tissue was judged by an expert panel to be softer than the untreated tissue samples.

All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art to the present invention.

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. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (10)

1. fibre structure, described fibre structure comprises:

A. fiber furnish layer; With

B. with the cationic silicone polymeric layer of described fiber furnish layer scattering, wherein said cationic silicone polymer comprises the quaternary nitrogen part of one or more polysiloxane unit and one or more non-side groups.

2. fibre structure as claimed in claim 1, wherein said cationic silicone polymer comprise at least 2 kinds or wide variety of silicone unit and at least 2 kinds or multiple quaternary nitrogen part.

3. a single or multiple lift approaches the page or leaf sanitary tissue products, and described thin page or leaf sanitary tissue products is selected from tissue product, tissue, sanitary tissue products, towel products and their mixture, and described thin page or leaf sanitary tissue products comprises fibre structure as claimed in claim 1.

4. fibre structure, described fibre structure comprises:

A. fiber furnish; With

B. cationic silicone polymer, described cationic silicone polymer is selected from:

I. comprise the quaternary nitrogen part of one or more polysiloxane unit, one or more non-side groups and the cationic silicone polymer of one or more alkylene oxide units;

Ii. comprise the quaternary nitrogen part of one or more polysiloxane unit, one or more non-side groups and the cationic silicone polymer of one or more open loop epoxides unit;

Iii. comprise the cationic silicone polymer of alternate cells, described alternate cells comprises: the polysiloxanes that a) comprises the quaternary nitrogen part of one or more polysiloxane unit and one or more non-side groups; And b) contains the divalence organic moiety of quaternary nitrogen; With

Iv. their mixture.

5. a single or multiple lift approaches the page or leaf sanitary tissue products, and described thin page or leaf sanitary tissue products is selected from tissue product, tissue, sanitary tissue products, towel products and their mixture, and described thin page or leaf sanitary tissue products comprises fibre structure as claimed in claim 4.

6. method of making fibre structure said method comprising the steps of:

A. prepare fiber furnish;

B. described fiber furnish is deposited on porous and forms the surface upward to form the embryo fiber web;

C. dry described embryo fiber web, thus described fibre structure formed; With

D. to described fiber furnish and/or described embryo fiber web and/or described fibre structure application cationic silicone polymer, described cationic silicone polymer comprises the quaternary nitrogen part of one or more polysiloxane unit and one or more non-side groups.

7. method as claimed in claim 6, wherein said method also comprise the step that described fibre structure conversion is become individual layer and/or multi-layer thin page or leaf sanitary tissue products.

8. method as claimed in claim 7 wherein appears at described cationic silicone polymer applications to the step of described fibre structure before the described conversion step and/or simultaneously and/or afterwards.

9. fibre structure, described fibre structure is made according to method as claimed in claim 6.

10. a single or multiple lift approaches the page or leaf sanitary tissue products, described thin page or leaf sanitary tissue products is selected from tissue product, tissue, sanitary tissue products, towel products and their mixture, and described thin page or leaf sanitary tissue products comprises fibre structure as claimed in claim 9.