JP2002527641A - How to make soft tissue paper - Google Patents

Abstract

(57) Abstract: A composition for softening a cellulose structure by a wet method is disclosed. A particularly preferred structure is an absorbent tissue. Furthermore, a tissue structure softened using the present composition is also disclosed. The composition comprises an effective amount of a softening active ingredient; a dispersion medium in which the softening active ingredient is dispersed; an electrolyte dissolved in the dispersion medium; and a bilayer breaking agent. The electrolyte and the bilayer-breaking agent act in concert to make the composition less viscous than the softening active ingredient dispersion dispersed in the dispersion medium alone. Preferably, softening active ingredient has the formula _{(R 1) 4-m -N} + [(CH 2) n -Y-R 3] m X - in quaternary ammonium compounds having; dispersant in water; electrolyte Is calcium chloride; the bilayer-breaking agent is a non-ionic surfactant. Also disclosed is a method of using the compound by adding the compound to the wet end of a papermaking process at a certain working concentration.

Description

DETAILED DESCRIPTION OF THE INVENTION

This application is based on pending US patent application Ser. No. 60 / 104,371 (Vinson et al. 1998).
(Filed on October 15, 2012).

[0001] Technical Field The present invention relates generally to softening of the cellulose structure by cationic debonding compounds, and more specifically to compositions having easily rheological properties which can be used to enhance the flexibility . Most particularly, the present invention relates to softening tissue paper webs and methods of making such softened webs.

BACKGROUND sanitary paper tissue products of the invention are widely used. Such articles can be used in a variety of applications, such as cosmetic tissues, hand-washing tissues and absorbent towels
It is commercially available in a form adapted to.

[0003] These sanitary products all have common required characteristics, and are particularly required to have a soft touch. Softness is the complex tactile sensation provided by the product when stroking the skin therewith. The purpose of softening is without irritating the skin,
The purpose is to be able to cleanse the skin with these products. Effective cleansing of the skin is a persistent personal hygiene problem for many people. Unpleasant drainage of urine, menstrual bleeding and feces from the perineum or drainage of mucus in the otolaryngeal organs does not always occur when it is convenient to carry out a thorough cleansing, for example with soap and large amounts of water. I can't. As an alternative to thorough cleaning, a great variety of tissue and towel products are provided to help remove such effluents from the skin and retain them for disposal in a hygienic manner. Not surprisingly, the use of these products makes it impossible to reach the level of purification that can be achieved with more complete purification methods, and tissue and towel product manufacturers have turned their products into complete purification methods. We are always striving to better match.

A disadvantage of tissue products is that, for example, many people stop cleansing before the skin can be completely cleansed. Such behavior is facilitated by a rough tissue. This is because rubbing with a rough object rubs sensitive skin, causing severe pain. Another option is to partially cleanse the skin, which often emits odors, stains the underwear and, over time, causes skin irritation.

[0005] Disorders of the anus, such as hemorrhoids, make the perianal area extremely sensitive, and people with such disorders are particularly frustrated by the desire to purify the anus without promoting inflammation.

[0006] Another case of increasing dissatisfaction is when it becomes necessary to repeatedly blow the nose when catching a cold. By repeated swabbing of the nose, the sores of the nose peak even with the soft tissue currently available.

[0007] Thus, producing soft tissue and towel products that promotes comfortable purification without compromising performance has been a long-standing technician and researcher focused on research to improve tissue paper. It was a goal. Many attempts have been made to reduce the abrasive effect, i.e. to improve the softness of tissue products.

One area that has been studied in this regard has been to select and modify the morphology of the cellulose fibers and to devise paper structures to optimally utilize the various available morphologies. . Techniques available in this area include: US Patent No. 5,228,954 (Vinson et al. July 20, 1993); US Patent No. 5,40.
No. 5,499 (Vinson et al. Apr. 11, 1995), US Pat. No. 4,874,465 (Cochrane et al. Oct. 17, 1989), and US Statutory Invention Registration (US Statu
tory Invention Registration) H1672 specification (Hermans et al. August 5, 1997). All of these documents disclose the choice of fiber materials or methods of upgrading tissues and towels with superior properties. Available technologies are further
4,300,981 (Carstens et al., November 17, 1981),
This considers how to incorporate the fibers into a paper structure so that the fibers exhibit maximum flexibility. While the techniques detailed by these prior art examples are widely known, they only provide limited performance to make tissues truly effective and comfortable cleaning tools.

[0009] Another area that has received a great deal of attention is the addition of chemical softeners (also referred to herein as "chemical softeners") to tissue and towel products.

[0010] As used herein, the term "chemical softener" refers to any chemical component that improves the tactile sensation felt by a consumer who grasps and rubs an individual paper product. Although somewhat desirable for towel products, softness is a particularly important property for cosmetic and hand wash tissues. The softness that can be felt as such a tactile sensation is characterized by (but not limited to) friction, suppleness, and smoothness, as well as a more subjective keyword, such as a slippery velvet, silk or flannel-like feel And Suitable materials include those that impart a smooth feel to the tissue. Such substances include:
By way of example, besides basic waxes (eg paraffin and beeswax) and oils (eg mineral oil and silicone oil), petrolatum and more complex lubricants and wetting agents (eg quaternary ammonium compounds with long-chain alkyl, functional groups) Silicones, fatty acids, fatty alcohols, and fatty esters).

[0011] There have been two directions in the prior art area of research relating to chemical softeners. The first direction is characterized by the addition of a softening agent to the tissue paper web during its formation, where the softening agent is of interest to the pulp tank, which is ultimately formed into a tissue paper web. When certain components are added, or when the pulp slurry approaches the paper machine, the components are added to the pulp slurry, or when the wet web is in a fourdrinier cloth or a dryer cloth on the paper machine. To the wet web.

[0012] The second direction is categorized by adding a chemical softener to the tissue paper web after the web has dried. The application step is incorporated into the papermaking operation, for example by spraying the dried web before it is wound up on a paper web.

[0013] Techniques related to the former method ("wet end" addition), which comprises adding a chemical softener before the tissue paper is formed into a web, include US Pat. No. 5,264,082. (Phan & Trokhan, November 23, 1993) and 5,543,0
No. 67 (Phan, Aug. 6, 1996), which are incorporated herein by reference. Such a method has been found to be widely useful industrially. However, such conventional compositions are solids or viscous liquids at room temperature. As a result, such conventional chemical softening compositions need to be heated before being diluted to the working concentration for addition to the papermaking furnish. Such heating complicates the papermaking process and forces new capital investments for the required equipment.

[0014] Furthermore, representative techniques associated with adding a chemical softener to a tissue paper web during its formation include US Pat. No. 5,059,282 (Amp).
ulski et al. Oct. 22, 1991), which is incorporated herein by reference. The patent discloses a method of adding a polysiloxane compound to a wet tissue web (preferably having a fiber concentration of about 20% to about 35%). Such a method represents an advance in several ways compared to adding chemicals to the furnish directed to the paper machine. For example, such means can limit application to one of the web surfaces, rather than distributing the additive throughout the furnish fibers. However, if such a softening composition is used, there will be loss of control of the sheet when peeling the sheet from the Yankee dryer. What is widely believed is that
The additives interfere with the coating of the Yankee dryer, thereby weakening the bond between the wet web and the dryer.

A great many techniques have been aimed at applying the chemical softening agent to the dried paper web at the dry end of the so-called paper machine or in a separate processing step after the paper making step. Representative techniques in this field include US Patent No. 5,215,626 (Amp
ulski et al. June 1, 1993); U.S. Pat. No. 5,246,545 (Ampulski et al. 1993).
US Patent No. 5,525,345 (Warner et al. June 11, 1996) and US Patent Application No. 09 / 053,319 (Vinson et al. Filed April 1, 1998).
These documents are incorporated herein by reference). No. 5,215,626 discloses a method for making soft tissue paper by applying a polysiloxane to a dry web. The 5,246,545 patent discloses a similar method utilizing a heat transfer surface. No. 5,525,345 discloses an application method involving roll coating and extrusion to apply individual compositions to a dry tissue web. Finally, the Vinson et al. Patent application discloses a composition that is particularly suitable for application to the surface of a tissue web.

While each of these references represents an advance over the prior art, the need for soft tissue paper products with good strength properties continues. Furthermore, an improved softening composition that can be applied to such tissue products to provide the required flexibility without adding new complexity and capital expenditures for the manufacture of such tissue products Is also needed.

Such improved products, compositions and methods are provided by the present invention as set forth below.

SUMMARY OF THE INVENTION The present invention provides a structure having improved flexibility by reducing the interfiber bonds of the structure when added to the wet end of a wet process for making cellulosic structures. Disclosed is a softening composition that provides possible strength and absorbency. The softening composition comprises: an effective amount of a softening active ingredient; a dispersion medium in which the softening active ingredient is dispersed; an electrolyte dissolved in the dispersion medium; And a bilayer breaking agent (further reducing the viscosity of the softening composition).

As used herein, the term “cellulosic structure” is defined as a wet-processed fabric, web, or sheet made of fibers containing cellulose. In its broadest sense, such structures are 10
It has a basis weight in the range of g / m ² to about 1 kg / m ² and has a density in the range of about 0.1 g / cc to about 1 g / cc. Preferably, the cellulose structure of the present invention,
At least part of their strength comes from natural inter-fiber bonds, which are formed when the water of a web composed of short cellulosic fibers is removed from an aqueous slurry and dried. Therefore, the so-called wet papermaking method is the most common method utilizing the present invention.

The softening composition of the present invention has a desirable low viscosity at room temperature that can be diluted as part of the papermaking process, and does not require the complexity and additional cost of the heating process.

As used herein, the term “dispersion medium” refers to a liquid that completely dissolves a chemical paper additive, or a liquid that is used to emulsify a chemical paper additive, or Means the liquid used to suspend the papermaking additive. The dispersion medium can also act as a carrier containing the chemical additive or as a carrier to aid in the application of the chemical papermaking additive. All of the above meanings are used interchangeably and are not limiting. Dispersions are liquids containing chemical papermaking additives. As used herein, the term "dispersion" includes intrinsic solutions, suspensions and emulsions. In the present invention, all terms are used interchangeably and are not limiting.

The amount of softening composition added to the cellulosic structure is preferably from about 0.05% to about 10%, based on the total weight of the softening composition, based on the total weight of the resulting cellulosic structure. It is.

The resulting cellulosic structure is preferably a tissue paper, most preferably a tissue paper having a basis weight of about 10 to about 100 g / m ² and a fiber density of less than about 0.6 g / cc. . All percentages, ratios and proportions herein are by weight, unless otherwise specified.

[0024] If Write down detailed description briefly aspect, the present invention provides a composition useful for softening the cellulose structure. Preferably, the composition is added to the wet end of the process for producing a cellulosic structure. Most preferably, the cellulosic structure is a tissue paper. The tissue paper obtained which may comprise the composition of the present invention has enhanced softness perceived as a tactile sensation. The method of making the softening composition, the mixture, and adding it to the wet end of the papermaking process are described.

The composition of the present invention is a dispersion of the softening active ingredient dispersed in a dispersion medium. Importantly, the composition also includes a bilayer breaker, which contains particularly high levels of components that are effective to soften the tissue paper web. And at the same time lower the viscosity at room temperature. Such compositions are particularly desirable for addition at the wet end of the papermaking process, thereby providing a paper having the desired softness made using such a method. Such compositions are particularly preferred for use in the methods used in the manufacture of tissue paper products used for personal cleansing. Tissue Paper The present invention can be generally used with tissue paper including, but not limited to: conventional felt pressed compressed tissue paper; Sanford-Sisson and its High density patterned tissue paper as demonstrated by its successor; and Salbukki (Sa
lvucci) high bulk uncompressed tissue paper as demonstrated by. These tissue papers may have a homogeneous structure or a multilayer structure. Further, the tissue paper products produced therefrom may have a single-ply structure or a (multi-ply) structure. Tissue paper is preferably from about 10g / m ² to about 100g /
It has a basis weight of m ² and a density of about 0.60 g / cc or less. Preferably, the basis weight will be from 10 g / m ² to about 80 g / m ² and the density will be about 0.30 g / cc or less. Most preferably, the density is from about 0.04 g / cc to about 0.2
It will be 0 g / cc.

[0026] Conventionally pressed tissue papers and methods of making such papers are known in the art. Such papers are typically made by depositing papermaking furnish onto a porous paper-forming wire. This forming wire is often referred to in the art as a fourdrinier wire. Once the furnish is deposited on the forming wire, it is called a web. In general, water
Removed from the web by vacuum, mechanical pressing and thermal means. The web is dewatered by pressing the web and drying by high temperature. Specific techniques and typical equipment for producing webs according to the methods described herein are well known to those skilled in the art. In a typical process, a low strength pulp furnish is fed to a pressure headbox. The headbox has an opening that feeds a thin pile of pulp furnish to the fourdrinier wire to form a wet web. Subsequently, the web is dewatered by vacuum dewatering to a fiber concentration of typically from about 7% to about 45% (based on total web weight),
Furthermore, it is dried by a pressing operation. In a compression operation, the web is subjected to pressure created by opposing mechanical units, for example, cylindrical rolls. The dewatering web is then further pressed and dried by a stream drum device known in the art as a Yankee dryer. The pressure can be generated at the dryer section by mechanical means such as a cylindrical drum pressing against the web. Multiple Yankee dryer drums can be used, but this may create new pressurization between the drums. The formed tissue-paper structure is hereinafter referred to as a normally pressed tissue-paper structure. Such a sheet is considered to be tight and tight as substantially all of the web is exposed to mechanical compression when the fibers are wet and subsequently dried under compression. The resulting structures are tough and generally have a single density, but have very little bulk, absorbency and softness.

High-density patterned tissue paper is characterized by relatively high bulk areas having relatively low fiber density and rows of high density zones having relatively high fiber density. The high-bulk area has the characteristics of the field of the pillow-shaped area. The dense zone is otherwise referred to as a knuckle region. The densification zones may be separately spaced within the bulky area or interconnected (fully or partially) within the bulky area. A preferred method of producing a densely patterned tissue web is described in US Pat. No. 3,301,746 (Sanfo).
rd & Sisson, January 31, 1967); U.S. Patent No. 3,974,025 (Ayers, August 1976).
U.S. Pat. No. 4,191,609 (March 4, 1980); and U.S. Pat. No. 4,637,859 (Trkhan Jan. 20, 1987), each of which is incorporated herein by reference. Is).

In general, a web with a high density texture is preferably produced as follows:
The papermaking furnish is deposited on a porous forming wire, such as a fourdrinier wire, to form a wet web, and then the web is transferred from the forming wire to a structure containing a row of supports for further drying. Webs are aligned with the rows of supports as they are being run. The web is pressed against the row of supports, thereby providing a high density zone in the web. This zone occurs at a location that coincides with the point of contact between the row of supports and the wet web. The remainder of the web that is not compressed during this operation is called the bulky area. This bulky area can be further reduced in density by using fluid pressure (e.g., using a vacuum-type device or blow-through dryer) or by mechanically pressing the web against the support rows. The web is dewatered and optionally pre-dried in a manner that substantially avoids compression of the bulky areas. This is preferably a fluid pressure (e.g., a vacuum type device or blow through
By means of a dryer) or by mechanically pressing the web against the support rows (in this case the bulky areas are not compressed). The dewatering (optionally pre-drying) operation and the operation of forming the high density zone may be integrated or partially integrated to reduce the number of processing steps performed. Following formation of the high density zone, dewatering, and optionally pre-drying, the web is completely dried, preferably still avoiding mechanical pressing. Preferably, from about 8% to about 65% of the tissue paper surface includes a high density knuckle, which preferably has a relative density of at least 125% of the density of the high bulk area.

The structure comprising the support row is preferably an indentation carrier fabric having a knuckle-patterned replacement that functions as a support row to facilitate the formation of a high density zone upon pressing. This knuckle pattern constitutes the previously described support row. Indentation carrier fabrics are disclosed in the following documents:
U.S. Pat. No. 3,301,746 (Sanford & Sisson, Jan. 31, 1967); U.S. Pat.
821,068 (Salvucci, Jr. et al. May 21, 1974); U.S. Patent 3,974,025
(Ayers, August 10, 1976); U.S. Pat. No. 3,573,164 (Friedberg et al.)
al. Mar. 30, 1971); U.S. Pat. No. 3,473,576 (Amneus, Oct. 21, 1969).
U.S. Pat. No. 4,239,065 (Trokhan, December 16, 1980); U.S. Pat. No. 4,528,239
(Trokhan, July 9, 1985), each of which is incorporated herein by reference.

Preferably, the furnish is first formed into a wet web on a porous carrier (eg, Fourdrinier wire). The web is dewatered and transferred onto the indentation fabric. Alternatively, the furnish may be first deposited on a porous support carrier which also functions as the impression forming fabric. Once formed, the wet web is dewatered and pre-dried by heat, preferably to a selected fiber concentration of between about 40% and about 80%. Dewatering is preferably performed by blowing, using a suction box or other vacuum device.
It is performed by a through dryer or a combination thereof. The knuckle indents of the indentation fabric are formed in the web as described above prior to completely drying the web. One way to achieve this is by using mechanical pressure.
For example, this involves turning the nip roll supporting the indentation fabric into a drying drum (
For example, it can be achieved by pressing against the surface of a Yankee dryer. In this case, the web is placed between the nip roll and the drying drum. Also, preferably, the web is embossed against the indentation fabric before being completely dried by the application of fluid pressure with a vacuum device such as a suction box or a blow-through drier. Fluid pressure is used to obtain indentations in the high density zone during the initial dehydration, in subsequent separate process steps, or in a process step that combines them.

[0031] Tissue paper structures that are not compressed and do not have a dense pattern are described in US Pat. No. 3,812,000 (Joseph L. Salvucci, Jr. & Pet).
er N. Yiannos, May 21, 1974); and U.S. Pat. No. 4,208,459 (Henry E.
Becker, Albert L. McConnell & Richard Schutte, January 17, 1980), both of which are incorporated herein by reference. Generally, tissue paper structures that are not compressed and do not have a high density pattern are formed by depositing papermaking furnish on a porous forming wire, such as a fourdrinier wire, to form a wet web and drain the web. The water is removed without additional mechanical compression until the fiber concentration of the web is at least 80%, and the web is creped. Water is removed from the web by vacuum dewatering and thermal drying. The resulting structure is a soft but brittle high bulk sheet with relatively uncompressed fibers. Preferably, the binding material is used on a portion of the web prior to creping.

The softening composition of the present invention can also be used on non-creped tissue paper. The term non-creped tissue paper as used herein refers to tissue paper that has been dried without compression, most preferably by through-air drying. The resulting aerated air-dried web has a high density pattern in which relatively dense zones are dispersed in high bulk areas, but relatively dense zones are continuous and high bulk areas are separated. Is included.

To produce a non-creped tissue paper web, the initial web is transferred from a porous forming carrier where the web is settled to a slower moving, high density fiber supporting transfer fabric carrier. Subsequently, the web is transferred to a drying fabric on which the web is dried until final drying. Such webs can offer several advantages in surface smoothness compared to creped paper webs.

Techniques for producing non-creped tissue in this manner are taught in the prior art. For example, US Pat. No. 5,672,248 (Wendt et al., September 30, 1997)
US Pat. No. 5,985,878, which is hereby incorporated by reference, teaches a method for making soft tissue products without creping. In another case, European Patent Application 677164A1 (Hyland et al., Published September 28, 1994), which is hereby incorporated by reference, describes a smooth, non-creped, ventilated air-dried sheet. Is taught. Finally, US Pat. No. 5,656,132 (F
arrington et al., August 12, 1997, which is incorporated herein by reference, discloses the use of a machine to produce soft through-air drying tissue without the use of a Yankee dryer.

[0035] furnish paper fiber: paper fiber used in the present invention usually contain a fiber derived from wood pulp. Other cellulosic fibrous pulp fibers (eg, cotton linters, bagasse, etc.) are also utilized and are included within the scope of the present invention. Synthetic fibers (eg, rayon, polyethylene and polypropylene fibers) can also be used with natural cellulosic fibers. One of the typical available polyethylene fibers is Hercules
es, Inc. (Pulpex), available from Wilmington, Del.

Available wood pulp includes chemical pulp (eg, kraft pulp, sulfite pulp and sulfate pulp) as well as mechanical pulp (eg, groundwood pulp,
Including thermomechanical pulp and chemically modified thermomechanical pulp)
Is included. However, chemical pulp is preferred because it imparts a tactile sensation to tissue sheets made therefrom that exhibits excellent flexibility. Deciduous trees (hereinafter referred to as "hardwood") and trees with conifers (hereinafter referred to as "conifers")
Both species can be used. What can be used in the present invention are fibers derived from recycled paper. The fibers include, in addition to any or all of the above classifications, other non-fibrous materials such as fillers and adhesives used to facilitate the original papermaking process.

Particularly preferred cellulosic pulp are long fibers, such as northern softwood kraft pulp (NSK); short fibers (eg, eucalyptus); and secondary fibers (eg, pre- and used white books, coated book paper). , Office waste). Such fibers may be used in any desired combination and may be multilayer or single layer. Softening composition: In general, the softening composition of the present invention comprises a dispersion of a softening active ingredient dispersed in a dispersion medium. As described herein, such compositions, when dispersed in furnish used to make tissue paper or other fibrous structures, are effective in softening the structure. Preferably, the softening composition of the present invention has properties (eg, components, rheology, p.p.) that allow it to be easily applied on an industrial scale.
H etc.).

It is well known to those skilled in the art that quaternary ammonium compounds containing the preferred active ingredients of the softening compositions of the present invention may not always be readily dispersible in water. Preferred quaternary compounds are solid at room temperature and, when added to water, are difficult to disperse into a uniform dispersion, even with mechanical action. Furthermore, it is also well known that the preferred form for the softening composition is a liquid that can be dispersed in cold water. Previous attempts to resolve this inconsistency have not been entirely satisfactory.

One method has been to use a highly active organic solvent that can solubilize the quaternary ammonium compound in a liquid at room temperature and disperse it in water. For example, a low molecular weight alcohol such as isopropanol can be used. Such methods are undesirable because of increased process safety concerns and environmental concern (VOC) concerns caused by the volatility of such solvents. Less active solvents can be used, but require much larger quantities and have negative cost consequences, as well as environmental consequences.

Another method that has long been used has been to make quaternary ammonium compounds more fluid, for example by introducing more carbon-carbon double bonds into the long alkyl chains of the preferred quaternary ammonium compounds. These materials are typically costly or have problems with undesirable effects, such as, for example, odor.

Quaternary ammonium compounds can also be made more hydrophilic and more dispersible, for example by ethoxylating their alkyl chains. This method reduces the effectiveness of the quaternary ammonium compound as a softening component and requires additional processing costs as well.

The compositions of the present invention are in a highly concentrated form of the preferred softening active ingredient, a quaternary ammonium compound, which can still be easily dispersed in water. In the following, each of the components of the softening composition of the present invention, the properties of the composition, the method of making the composition and the method of applying the composition will be discussed.

[0043] Component softening active ingredient: fourth compound having the following formula are suitable for use in the present _{invention: (R 1) 4-m} -N + - [R 2] m X - wherein, m in 1 to 3; each R ₁ is C ₁ -C ₆ alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylated groups, a benzyl group, or mixtures thereof; each R ₂ is C ₁₄ - C ₂₂ alkyl, hydroxyalkyl, hydrocarbyl or substituted hydrocarbyl, alkoxylated, benzyl, or a mixture thereof; and X ^- is any softener compatible anion. Preferably, each R ₁ is methyl and X ⁻ is chloride or methyl sulfate. Preferably each R ₂ is a C ₁₆ -C ₁₈ straight or branched alkyl or alkenyl, most preferably each R ₂ is a straight C ₁₈ alkyl or alkenyl. Optionally, R ₂ substituent is derived from vegetable oil sources. Several types of vegetable oils (eg, olives, canola, safflower, sunflower, etc.) can be used as fatty acid sources to synthesize quaternary ammonium compounds. Active substances having a branched chain, such as can be derived from equivalent branched chain fatty acids, are also effective. Suitable branched chain fatty acids that serve as a starting point for such quaternary ammonium compounds include 2-
n-heptylundecanoic acid, 2-butyloctanoic acid, 5,7,9-trimethylnonanoic acid, 3,5,7,9-tetramethylnonanoic acid, alpha-heptyldecanoic acid and isostearic acid. Particularly preferred.

Such structures include well-known dialkyl dimethyl ammonium salts (eg, di-tallow dimethyl ammonium chloride, di-tallow dimethyl ammonium methyl sulphate, di (hydrogenated tallow) dimethyl ammonium chloride, etc.). , R ₁ is a methyl group, R ₂ is a tallow group saturated to various levels, and X ⁻
Is chloride or methyl sulfate.

References (Bailey's Industrial Oil and Fat Products, Swern, Ed.
Tallow, as discussed in John Wiley and Sons (New York 1964)), is a naturally occurring substance of varying composition. Table 6.13 of the above-referenced book by Swern states that typically 78% or more of the tallow fatty acid contains 16 or 18 carbon atoms. Typically, half of the fatty acids present in tallow are unsaturated,
It exists mainly in the form of oleic acid. Synthetic "tallow" as well as natural "tallow" are included within the scope of the invention. Depending on the requirements of the product properties, the saturation level of beef tallow can be changed from non-hydrogenated (soft) to touch (partially hydrogenated) or completely hydrogenated (
It is also known that it can be adjusted to stiffness). All of the above saturation levels are clearly included within the scope of the present invention.

Particularly preferred variants of these softening active ingredients are those which are considered to be mono- or diester variants of these quaternary ammonium compounds having the formula: (R ₁ ) _4-m -N ⁺ -[ _{(CH 2) n -Y-R} 3] m X - wherein, Y is -O- (O) C- or -C (O) -O- or -NH-C (O) -
Or -C (O) -NH-; m is 1 to 3; n is 0 to 4; each of R ₁ is a C ₁ -C ₆ alkyl group, hydroxyalkyl group, hydrocarbyl or substituted hydrocarbyl group, alkoxylation. Each of R ₃ is a C ₁₃ -C ₂₁ straight or branched alkyl group, a hydroxyalkyl group, a benzyl group, or a mixture thereof;
Hydrocarbyl or substituted hydrocarbyl group, alkoxylated groups, a benzyl group, or mixtures thereof; further, X ^- is any softener-compatible anion.

Preferably, Y is —O— (O) C, or —C (O) —O—; m is 2;
Is 2. Each R ₁ substituent is preferably a C ₁ -C ₃ alkyl group, with methyl being most preferred. Preferably, each R ₃ is C ₁₃ -C ₁₇ alkyl and / or alkenyl, more preferably R ₃ is a linear C ₁₅ -C ₁₇ alkyl and / or alkenyl, C ₁₅ -C ₁₇ alkyl, most preferably each R 3 is ₃ is straight-chain C ₁₇ alkyl. Optionally, R ₃ substituent can be derived from vegetable oil sources. Several types of vegetable oils (eg, olives, canola, safflower, sunflower, etc.) can be used as fatty acid sources to synthesize quaternary ammonium compounds. Preferably, the quaternary ammonium compound is synthesized using olive oil, canola oil, safflower oil high in oleic acid and / or oilseed rape oil high erucic acid.

As mentioned above, X ⁻ is any softener compatible anion, such as acetate, chloride, bromide, methyl sulfate, formate, sulfate,
Nitrate and the like can also be used in the present invention. Preferably, X ^- is chloride or methyl sulfate.

Specific examples of quaternary ammonium compounds having the structure described above and having an ester functionality suitable for use in the present invention include the well-known diester dialkyldimethylammonium salts and their salts as follows: The mixture includes: diester ditallow dimethyl ammonium chloride, monoester ditallow dimethyl ammonium chloride, diester ditallow dimethyl ammonium methyl sulfate, diester di (hydrogenated) tallow dimethyl ammonium methyl sulfate, diester di (hydrogenated) tallow dimethyl ammonium chloride. Diester ditallow dimethylammonium chloride and diester di (hydrogenated) tallow dimethylammonium chloride are particularly preferred. Diester ditallow dimethyl ammonium chloride and diester di (hydrogenated) tallow dimethyl ammonium chloride are commercially available from Witco Chemical Co. Inc., Dublin, Ohio under the trade name ADGEN SDMC.

As mentioned above, typically, half of the fatty acids present in tallow are unsaturated,
It exists mainly in the form of oleic acid. Synthetic "tallow" as well as natural "tallow" are included within the scope of the invention. It is also known that the saturation level of beef tallow can be adjusted from non-hydrogenated (soft) to touch (partially hydrogenated) or fully hydrogenated (hard) depending on the requirements of the product properties. It is expressly intended that all of the above saturation levels fall within the scope of the present invention. At least a minimum level of hydrogenation is preferred, particularly to remove complex unsaturated species (eg, linolenic acid derivatives) that are known to be more susceptible to odor-causing oxidation.

It will be appreciated that the substituents R ₁ , R ₂ , and R ₃ may be optionally substituted or branched by various groups such as alkoxyl, hydroxyl. As mentioned above, preferably each of R ₁ is methyl or hydroxyethyl. Preferably, each of R ₂ is C ₁₂ -C ₁₈ alkyl and / or alkenyl, most preferably each R ₂ is a linear C ₁₆ -C ₁₈ alkyl and / or alkenyl.
Or alkenyl, most preferably each R ₂ is straight-chain C ₁₈ alkyl or alkenyl. Preferably R ₃ is a C ₁₃ -C ₁₇ alkyl and / or alkenyl, most preferably R ₃ is straight chain C ₁₅ -C ₁₇ alkyl and / or alkenyl. Preferably, X ^- is chloride or methyl sulfate. In addition, quaternary ammonium compounds with an ester function can optionally contain as minor components mono (long chain alkyl) derivatives, for example up to about 10% of the formula: (R ₁ ) ₂ -N ⁺ -(( _{CH 2) 2 OH) ((} CH 2) 2 OC (O) R 3) X - these trace components acts as an emulsifier, is useful in the present invention.

Other types of quaternary ammonium compounds suitable for use in the present invention are described below: US Pat. No. 5,543,067 (Phan et al. Aug. 6, 1996); US Pat. No. 5,538,595 US Patent No. 5,510, Trokhan et al. July 23, 1996;
US Patent No. 5,415,737 (Phan et al. April 23, 1996);
Phan et al. May 16, 1995); and EP 688,901 A2 (Kimb
erly-Clark Corp., published December 12, 1995) (each of these references is incorporated herein by reference).

Di-quat variants of quaternary ammonium compounds having an ester function can also be used and are included within the scope of the present invention. These compounds have the formula:

[0054]

Embedded image

In the above structure, each R ₁ is a C ₁ -C ₆ alkyl or hydroxyalkyl group, R ₃ is a C ₁₁ -C ₂₁ hydrocarbyl group, n is 2 to 4, and X ⁻ is a suitable group. An ion, such as a halide (eg, chloride or bromide) or methyl sulfate. Preferably, each R ₃ is C ₁₃ -C ₁₇ alkyl and / or alkenyl, most preferably each R ₃ is a linear C ₁₅ -C ₁₇ alkyl and / or alkenyl, and R ₁ is methyl.

[0062] Additionally, without being bound by theory, it is believed that the ester moiety of the fourth compound described above provides some biodegradability to such compounds. Importantly, quaternary ammonium compounds having an ester function as used herein are degraded by organisms more rapidly than conventional dialkyldimethylammonium softening agents.

The use of the quaternary ammonium component described above is very effectively achieved when a suitable plasticizer is added to said quaternary ammonium component. As used herein, the term plasticizer refers to a component that can lower the melting point and lower the viscosity of the quaternary ammonium component at a given temperature. The plasticizer can be added during the quaternization step in the preparation of the quaternary ammonium component or after the quaternization but before application as a softening active. Plasticizers are characterized by being substantially inert during chemical synthesis and assisting in the synthesis as viscosity reducing agents. Preferred plasticizers are nonvolatile polyhydroxy compounds. Preferred polyhydroxy compounds include glycerol and polyethylene glycol. Polyethylene glycol has a molecular weight of about 200 to about 2000, with polyethylene glycol having a molecular weight of about 200 to about 600 being particularly preferred. When such plasticizers are added during the production of the quaternary ammonium component, they make up from about 5% to about 75% of the product so produced. Particularly preferred mixtures are from about 15% to about 50
% Plasticizer.

Dispersion medium: As used herein, "dispersion medium" is used to dilute the active ingredients of the compositions described herein that form the dispersions of the invention. The dispersion medium dissolves such components (intrinsic solution or micellar solution) or the components are dispersed in the dispersion medium (dispersion or emulsion). The dispersion medium of a suspension or emulsion is typically its continuous phase. That is, the other components of the dispersion or emulsion are dispersed in the dispersion medium at the molecular level or as individually separated particles or molecular aggregates.

In the present invention, one of the purposes of the dispersion medium is to dilute the concentration of the softening active ingredients so that they can be applied effectively and economically. The components so diluted can be more easily diluted to working concentrations without the need for complicated processing equipment.

[0060] Dispersions and softening compositions comprising such dispersions that are particularly useful for rapidly incorporating softening actives into tissue webs on an industrial scale have also been found.

While the softening component can be dissolved in a dispersion medium that forms a solution, materials useful as solvents for suitable softening actives are commercially available for safety and environmental reasons. Not desirable. Thus, to be suitable for use as a dispersion medium for the present invention, the material must be compatible with the softening active described herein and the tissue substrate in which the softening composition of the present invention is used. Should be. In addition, suitable materials should not include ingredients that raise safety concerns (even to tissue product users who use the softening compositions described herein, even in the tissue manufacturing process), and should not be environmentally harmful. It should not create unacceptable risks. Suitable materials for the dispersion medium of the present invention are liquids containing hydroxyl functionality,
Most preferably it consists of water.

Electrolyte : Water is a particularly preferred substance for use as a dispersion medium in the present invention, while water alone is not preferred as a dispersion medium. In particular, when the softening active of the present invention is dispersed in water at an appropriate level for application to a tissue web, the dispersion has an unacceptably high viscosity. Without being bound by theory, it is believed that the combination of water and the softening active of the present invention to form such a dispersion results in the generation of a liquid crystal phase having a high viscosity. Compositions having such high viscosities are difficult to dilute for use in the process of making tissue webs to soften the web.

By simply adding a suitable electrolyte to the dispersion medium, the viscosity of the softened active ingredient dispersion dispersed in water is maintained while maintaining the desired high level of softened active ingredient in the softened composition. It has been found that it can be substantially reduced. Further, while not being bound by theory, it is believed that the electrolyte masks the charge around the bilayer and vesicles, reduces interaction, and further reduces transfer resistance, reducing the viscosity of the system.
Furthermore, without being bound by theory, the electrolyte creates an osmotic pressure difference between the inside and outside of the vacuole wall, thereby draining the internal water through the wall of the vacuole and reducing the size of the vacuole. Could provide more "free" water and again cause a decrease in viscosity.

Any material suitable for use in the dispersion medium of the present invention that meets the general criteria set forth above and that is effective to reduce the viscosity of the dispersion of the softening active ingredient dispersed in water. Are also suitable for use as the dispersion medium of the present invention. In particular, any known water-soluble electrolyte meeting the above criteria can be included in the dispersion medium of the softening composition of the present invention. If used, the electrolyte can be used in an amount up to about 25% by weight of the softening composition, but preferably not more than about 15% by weight of the softening composition. Preferably, the level of the electrolyte is between about 0.1% and about 10% of the weight of the softening composition, based on the anhydrous weight of the electrolyte. More preferably, the electrolyte is used at a level between about 0.3% and about 1.0% by weight of the softening composition. The minimum amount of electrolyte will be sufficient to provide the desired viscosity. Dispersions typically exhibit non-Newtonian rheology and generally have a viscosity of about 10 centipoise (cp) to about 10 centipoise (cp) when measured at 25 ° C. and a shear rate of 100 sec- ¹ using the methods described in the Test Methods section below. Shear thinning with desired viscosity in the range of 1000 cp, preferably from about 10 to about 200 cp. Suitable electrolytes include alkali metal or alkaline earth metal halides, nitrates, nitrites and sulfates as well as the corresponding ammonium salts. Other useful electrolytes include the alkali metal or alkaline earth metal salts of simple organic acids (eg, sodium formate and sodium acetate) as well as the corresponding ammonium salts.
Preferred electrolytes include sodium, calcium and magnesium chloride salts. Calcium chloride is a particularly preferred electrolyte for the softening composition of the present invention. Without being bound by theory, it is believed that the divalent nature of the calcium ion is particularly effective in reducing the viscosity of the microvesicle dispersion of the softening active. If desired, blends of various compatible electrolytes are also suitable.

Double Layer Breaking Agent : Double layer breaking agent is an essential component of the present invention. As indicated above, the dispersion medium, especially the electrolyte dissolved therein, performs an essential function in the production of the cellulosic structures of the present invention, while maintaining the acceptable viscosity of the softening active. It is also desirable to maximize the concentration. As noted above, the addition of the electrolyte allows the concentration of the softening active in the softening composition to be increased without excessively increasing the viscosity. However, if too much electrolyte is used, phase separation will occur. It has been found that by adding a bilayer breaker to the softening composition, a larger amount of softening active can be mixed while maintaining viscosity at an acceptable level. As used herein, a "double layer breaking agent", when mixed with a dispersion of a softening active in a dispersion medium, is compatible with at least one of the dispersion medium or the softening active, and An organic substance that reduces viscosity.

Although not wishing to be bound by theory, it is believed that the bilayer breaking agent functions by penetrating the liquid crystal structure's palisade layer of the dispersion of the softening active in the dispersion medium and disrupting the order of the liquid crystal structure. . It is believed that such disruption reduces interfacial tension at the hydrophobic-water interface and thus promotes flexibility with respect to the resulting viscosity reduction.
As used herein, the term "palisade layer" refers to the region between the hydrophilic groups and the first few carbon atoms of the hydrophobic layer (MJ Rosen, Surfactants an
d interfacial phenomena, Second Edition, pages 125 and 126).

In addition to providing the viscosity reduction benefits discussed above, materials suitable for use as a bilayer breaker must also be compatible with the other components of the softening composition. For example, a suitable material should not react with other components of the softening composition to cause the softening composition to lose its softening ability.

The bilayer-breaking agents useful in the compositions of the present invention are preferably surfactants. Such materials contain both hydrophobic and hydrophilic moieties. Preferred hydrophilic moieties are polyalkoxylated groups, preferably polyethoxylated groups. Such preferred materials are used at a level between about 1% and about 15% of the level of the softening active. Preferably, the bilayer breaker is present at a level between about 2% and about 10% of the level of the softening active.

Particularly preferred bilayer breakers are non-saturated and / or unsaturated primary and / or secondary amines, amides, amine-oxide fatty alcohols, fatty acids, alkylphenols and / or alkylaryl carboxylic acid compounds. Ionic surfactants, each preferably having about 6 to about 22, more preferably about 8 to about 18 carbon atoms in the hydrophobic chain, more preferably an alkyl or alkylene chain, wherein the compound At least one active hydrogen is ethoxylated with up to 50 ethylene oxide components, preferably up to 30, more preferably from about 3 to about 15, even more preferably from about 5 to about 12, with about 6 to about 6 ethylene oxide components. To about 20, preferably about 8 to about 18, more preferably about 10
From about 15 HLB.

Suitable bilayer breakers also include nonionic surfactants with bulky head groups selected from the following ac: a. A surfactant having the following formula: R ¹ -C (O) -Y ′-[C (R ⁵ )] _m —CH ₂ O (R ₂ O) _Z H wherein R ¹ is a saturated or unsaturated hydroxyl group. Selected from the group consisting of primary, secondary or branched alkyl or alkylaryl hydrocarbons; said hydrocarbon chain is from about 6 to about 22
Y ′ is selected from —O—, —N (A) — groups and mixtures thereof; A is the following group: H, R ¹ , — (R ² —O) _Z Selected from —H—, — (CH ₂ ) _X CH ₃ , phenyl or substituted aryl; wherein 0 ≦ x ≦ about 3 and z is about 5 to about 30; each R ² is a group of the following: (CH _{2) n} - and / or - [CH (CH ₃₎ C
H ₂ ] — or a combination thereof; each R ⁵ is selected from —OH and —O (R ² O) _Z —H; and m is from about 2 to about 4.

B. Surfactant having the formula:

[0072]

Embedded image

Wherein Y ″ is N or O; each R^FiveIs independently -H, -OH,-(CH_Two )_XCH_Three, -O (OR^Two)_Z-H, -OR¹, -OC (O) R¹And -CH (CH _Two − (OR^Two)_{Z "}-H) -CH_Two− (OR^Two)_{Z '}-C (O) R¹Selected from; x and
And R1 are as defined above, 5 ≦ z, z ′ and z ″ ≦ 20, more preferably
5 ≦ z + z ′ + z ″ ≦ 20, most preferably the heterocyclic ring is Y ″ = O
A 5-membered ring having one R^FiveIs -H and two R^FiveIs -O- (R^TwoO)_Z-H,
At least one R^FiveHas the following structure -CH (CH_Two− (OR^Two)_{Z "}-H) -CH_Two−
(OR^Two)_{Z '}-C (O) R¹And 8 ≦ z + z ′ + z ″ ≦ 20, and R¹Is 8
Hydrocarbons having from 2 to 20 carbon atoms and no aryl groups.

C. The following equation polyhydroxy fatty acid amide surfactants: in ^{R 2 -C (O) -N (} R 1) -Z wherein each R ¹ is, H, C ₁ -C ₄ hydrocarbyl, C ₁ -C ₄ alkoxy Alkyl,
Or hydroxyalkyl; R ² is a C ₅ -C ₃₁ hydrocarbyl moiety;
A polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain containing at least three hydroxyls directly attached to the chain, or an ethoxylated derivative thereof; each R ¹ is H or a cyclic monosaccharide or polysaccharide, or an alkoxylation thereof. It is a derivative.

Suitable phase stabilizers also include surfactants formed by one surfactant ion neutralized with an oppositely charged surfactant or electrolyte ions suitable for reducing the viscosity of the diluent. Agent complex.

Examples of representative bilayer breaking agents include: (1) Alkyl or alkyl-aryl alkoxylated nonionic surfactants Suitable alkylalkoxylated nonionic surfactants are generally saturated Or from unsaturated primary and secondary fatty alcohols, fatty acids, alkylphenols or alkylarylcarboxylic acids (eg, benzoic acid), wherein the active hydrogen is about 3
It is alkoxylated with 0 or less alkylene, preferably an ethylene oxide component (eg, ethylene oxide and / or propylene oxide). As used herein, these nonionic surfactants preferably have about 6 to about 22 carbon atoms on the alkyl or alkylene chain, have a linear structure, and preferably have about 8 to about 18 carbon atoms. Alkylene oxide is present, preferably in the first position, with an average amount of about 30 moles or less, more preferably about 3 to 15 moles, of alkylene oxide per alkyl chain. Alkylene oxide, most preferably from about 6 to about 12 moles of alkylene oxide. Preferred materials of this class also have pour points below about 70 ° F. and / or do not solidify in these softening compositions. Examples of alkyl alkoxylated surfactants having a straight chain include Shell Neodol® 91-
8, 23-5, 25-9, 1-9, 25-12, 1-9 and 45-13, Plurafac® B-26 and C-17 from BASF.
And the ICI surfactant Briji® 76 and 35. Examples of alkyl-aryl alkoxylated surfactants include Huntsman's Surfonic N-120, Rhone Poulenc's Igepal® CO-620 and C
O-710, Union Carbide Triton (
(Registered trademark) N-111 and N-150, Dowfax from Dow
x) 9N5 (registered trademark) and Lutensol (registered trademark) of Bazfu
AP9 and AP14 are included. (2) Alkyl or alkyl-arylamine or amine oxide nonionic alkoxylated surfactants Suitable alkylalkoxylated nonionic surfactants having an amine function are:
Generally derived from saturated or unsaturated, primary and secondary fatty alcohols, fatty acids, fatty methyl esters, alkyl phenols, alkyl benzoates and alkyl benzoic acids, which are converted to amines, amine oxides and, optionally, secondary alkyl or alkyl. Substituted with aryl hydrocarbons, said hydrocarbons each having up to about 50 moles of an alkylene oxide moiety (eg, ethylene oxide and / or
Or propylene oxide) with one or two alkylene oxides attached to the amine function having one mole per amine. As used herein, an amine, amide or amine-oxide surfactant has from about 6 to about 22 carbon atoms and has a linear or branched structure, but preferably contains one hydrocarbon within the linear structure. Wherein the hydrocarbon has about 8 to about 18 carbon atoms with one or two alkylene oxide chains attached to the amine moiety, and the average amount attached to the amine moiety is about 50 moles per amine moiety The following alkylene oxides, more preferably from about 3 to about 15 moles of alkylene oxide, most preferably having only one alkylene oxide chain on the amine moiety, containing from about 6 to about 12 moles of alkylene oxide per amine moiety . Preferred substances of this class are also about 21 ° C (70 ° C).
F) has a pour point less than and / or does not solidify in these softening compositions. Examples of ethoxylated amine surfactants include Rhone-Poulenc verol (Bero
l) (registered trademark) 397 and 303 and the etzome of Akzo
omeens® C / 20, C / 25, T / 25, S / 20, S / 25 and Ethodumeens® T / 20 and T / 25.

Preferably, the alkyl or alkyl-aryl alkoxylated surfactant and the alkyl or alkyl-aryl amine, amide, and amine-oxide alkoxylated surfactant compound have the following general formula: R ¹ _m -Y- in _{^{[(R 2 -O) Z -H}} ] P wherein each R ¹ is a saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl, - selected from the group consisting of aryl hydrocarbons; said hydrocarbon The hydrogen chain is preferably about 6 to about 22, more preferably about 8 to about 18 carbon atoms in length, even more preferably about 8 to about 15, and is preferably linear and free of aryl moieties; Wherein each R ² is selected from a group of — (CH ₂ ) _n — and / or — [CH (CH ₃ ) CH ₂ ] — or a combination of those groups; about 1 <n ≦ about 3; , -O-, -N (
A) _q- , -C (O) O-,-(O ←) N (A) _q- , -BR ³ -O-, -B-
_{^{R 3 -N (A) q -}} , - B-R 3 -C (O) O -, - B-R 3 -N (→ O) (A) -
And mixtures thereof; wherein A is H, R ¹ ,-(R ² -O) _Z -H,-(
CH ₂ ) _X CH ₃ , selected from phenyl or substituted aryl; 0 ≦ x ≦ about 3;
Is -O -, - N (A) -, - C (O) is selected from O- groups and mixtures thereof, wherein A is as defined above, each R ³ is R ^2, phenyl, or substituted, Selected from aryl. Terminal hydrogen in each alkoxy chain is short chain C ₁ - substituted by _alkyl or aryl group, wherein the alkoxy chain "the lid" can. z
Is about 5 to about 30. p is the number of ethoxylate chains, typically 1 or 2
, Preferably one, m is the number of hydrophobic chains, typically one or two, preferably one, and q is a number that completes the structure, usually one.

Preferred structures are m = 1, p = 1 or 2, and 5 ≦ z ≦ 30, q is 1 or 2, but if p = 2, q must be 0. A more preferred structure is m = 1, p = 1 or 2, and 7 ≦ z ≦ 20, and a still more preferred structure is m = 1, p = 1 or 2, and 9 ≦ z ≦ 12. Preferably y is 0. (3) Alkoxylated and non-alkoxylated nonionic surfactants with bulky head groups Suitable alkoxylated and non-alkoxylated double layer breaking agents with bulky head groups are generally saturated or unsaturated, primary and secondary. Derived from fatty alcohols, fatty acids, alkylphenols and alkylbenzoic acids, which are derived using carbohydrate groups or heterocyclic head groups. The structure can then optionally be further substituted with alkyl or alkyl-aryl alkoxylated or non-alkoxylated hydrocarbons. Heterocyclic or carbohydrate groups have one or more alkylene oxide chains (eg, ethylene oxide and / or propylene oxide)
Each having about 50 per mole of heterocyclic or carbohydrate group.
It has less than about 1 mole, preferably less than about 30 moles, of alkylene oxide chains. Hydrocarbon groups on carbohydrate or heterocyclic surfactants as used herein have about 6
There is one hydrocarbon having from about 8 to about 18 carbon atoms in a linear configuration having from about 22 to about 22 carbon atoms, preferably having one or two alkylene oxide chain carbohydrate or heterocyclic moieties. Each alkylene oxide chain is present in an average amount of no more than about 50 moles, preferably no more than about 30 moles of carbohydrate or heterocyclic moieties, more preferably about 3 to about 15 moles of alkylene oxide per alkylene oxide chain And most preferably about 6 to about 12 moles total of alkylene oxides per surfactant molecule (including both alkylene oxides on the hydrocarbon chain and on the heterocyclic or carbohydrate moieties). Examples of this class of bilayer breakers are Tween® 40, 60, and 80, available from ICI Surfactant.

The alkoxylated and non-alkoxylated nonionic surfactant compounds having a bulky head group preferably have the following general formula: R ¹ -C (O) -Y ′-[C (R ⁵ )] _m -CH ₂ O in (R ₂ O) _Z H formula, R ¹ is a saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl - is selected from the group consisting of aryl hydrocarbons; said hydrocarbon Y 'is selected from -O-, -N (A)-, and mixtures thereof; A is H
, R ¹ , — (R ² —O) _Z —H, — (CH ₂ ) _X CH ₃ , phenyl or substituted aryl; 0 ≦ x ≦ about 3 and z is about 5 to about 30; R ² is - (CH _{2) n} -
And / or _{[CH (CH 3) CH 2} ] - is selected from the group or mixtures thereof; each R ⁵ is selected from -OH and _{^{-O (R 2 O) Z -H}} ; m is from about 2 to about 4.

Another useful general formula for this class of surfactants is:

[0081]

Embedded image

Wherein Y ″ is N or O; each R ⁵ is independently —H, —OH, — (CH ₂ ) _X CH ₃ , — (OR ² ) _Z —H, —OR ¹ , -OC (O) R ¹ and _{-CH 2 (CH 2 - (oR} 2) Z "-H) -CH 2 - is selected from the _{^{(oR 2) Z '-C (}} O) R 1. xR ¹
And R ² are as defined above in section D above, and z, z 'and z
"Is about 20 or less from all about 5 or more. In a particularly preferred form of this structure the heterocyclic ring, Y '= a 5-membered ring of O, one R ⁵ is -H, 2 two R ⁵ is −
O- (R ² O) with _Z -H, at least one R ⁵ has the following structure, CH (CH ₂ - (O
_{^{R 2) Z "-H) -CH}} 2 - (OR 2) Z ' has the ^{-OC (O) R 1, z} + z' + z" is from about 8 or about 20 or less, R ¹ is from about 8 to about It is a hydrocarbon having 20 carbon atoms and no aryl group.

Another group of surfactants that can be used are the polyhydroxy fatty acid amide surfactants of the formula: R ⁶ —C (O) —N (R ⁷ ) —W where each R ⁷ is H , C ₁ -C ₄ hydrocarbyl, C ₁ -C ₄ alkoxyalkyl, or hydroxyalkyl, e.g., 2-hydroxyethyl, etc. 2-hydroxypropyl, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C _2, Alkyl, most preferably C ₁ alkyl (ie methyl) or methoxyalkyl; R ⁶ is a C ₅ -C ₃₁ hydrocarbyl moiety, preferably a linear C ₇ -C ₁₉ alkyl or alkenyl, more preferably a linear C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or mixtures thereof,; W is at least 3 Tsunohi Rokishiru is directly linked linear hydrocarbyl chain polyhydroxy hydrocarbyl moiety having or alkoxylated (preferably ethoxylated or propoxylated) derivatives. W is preferably derived from the reducing sugar of a reductive amination reaction; more preferably W is a glycityl moiety. W is _{preferably, -CH 2 - (CHOH) n} -CH 2 OH, -CH (CH 2 OH)
_{- (CHOH) n -CH 2 OH} , -CH 2 - (CHOH) 2 (CHOR ') (CHO
H) —CH ₂ OH, wherein n is an integer from 3 to 5 (including 3 and 5), and R ′ is H or a cyclic monosaccharide or polysaccharide and alkoxylated derivatives thereof. is there. Most preferred are glycityls, in this case n is 4, particularly -CH ₂ - is (CHOH) ₄ -CH ₂ O. Mixtures of the above W moieties are preferred.

R ⁶ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,
Will be N-butyl, N-isobutyl, N-2-hydroxyethyl, N-1-methoxypropyl, N-2-hydroxypropyl.

R ⁶ —CO—N <may be, for example, cocamide, stearamide, oleamide, lauroamide, myristoamide, capriccoamide, palmitoamide, tallowamide, and the like.

W is 1-deoxyglucityl, 2-deoxyfractityl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymannityl, 1-deoxymaltotrio Such as Chityl. (4) Alkoxylated cationic quaternary ammonium surfactants Alkoxylated cationic quaternary ammonium surfactants suitable for the present invention generally include fatty alcohols, fatty acids, fatty methyl esters, alkyl-substituted phenols,
Derived from alkyl-substituted benzoic acids and / or alkyl-substituted benzoate esters and / or fatty acids, which are converted to amines, which can optionally be reacted with another long-chain alkyl or alkyl-aryl group; The compound is subsequently alkoxylated with one or two alkylene oxide chains, each having up to about 50 moles of an alkylene oxide component (eg, ethylene oxide and / or propylene oxide) per mole of amine. Typical of this class are aliphatic saturated or unsaturated, primary, secondary or branched amines having one or two hydrocarbon chains having from about 6 to about 22 carbon atoms on the amine atom. Products from quaternization that are alkoxylated with one or two alkylene oxide chains, each having less than about 50 alkylene oxide moieties. The amine hydrocarbons used herein have about 6 to about 22 carbon atoms and have a linear or branched structure, preferably one of a linear structure having about 8 to about 18 carbon atoms. Alkyl hydrocarbon groups are present. Suitable quaternary ammonium surfactants are prepared with one or two alkylene oxide chains attached to an amine moiety, the average amount of which is less than about 50 moles of alkylene oxide per alkyl chain, more preferably about 3 to about About 20 moles of alkylene oxide, most preferably about 5 to about 12 moles of alkylene oxide per hydrophobic group (eg, alkyl group). Preferred materials of this class also have a pour point below about 70 ° F. and / or do not solidify in these softening compositions. Suitable double layer breakers of this type include Ethoquad® 18/25, C / 25, and O / 25 from Akzo and Variquat®-66 from Witco (total of about Soft tallow alkyl bis (polyoxyethyl) ammonium ethyl sulfate with 16 ethoxy units) is included.

[0087] Preferably the ammonium alkoxylated cation surfactant compounds having the following general _{^{formula: {R 1 m -Y - [}} (R 2 -O) Z -H] p} + X - wherein, R ¹ and fort R ² is previously defined in the above section D; Y is N ⁺ -
(A) _q ,-(CH ₂ ) _n -N ⁺ -(A) _q , -B- (CH ₂ ) _n -N ⁺ -(A) ₂ ,-
_{^{(Phenyl) -N + - (A) q}} , - (B- phenyl) -N ⁺ - selected from (A) _q;
n is from about 1 to about 4.

Each A is independently the following groups H, R ¹ , — (R ² O) _Z —H, (CH ₂ ) _X C
Selected from H ₃ , phenyl and substituted aryl; 0 ≦ x ≦ about 3; B represents the following groups —O—, —NA—, —NA ₂ —, —C (O) O— and C (O) N (a) - is selected from; R ² is above in as defined; q is 1 or 2; X ^- is a compatible with softening active ingredients and other components of the softening composition anion .

A preferred structure is about 5 ≦ z ≦ about 50 when m is 1 and p is 1 or 2, and a more preferred structure is when about 7 ≦ z ≦ about 20 when m is 1 and p is 1 or 2. The most preferred structure is about 9 ≦ z ≦ about 12 when m is 1 and p is 1 or 2.

(5) Alkylamide alkoxylated nonionic surfactants Suitable surfactants have the formula: RC (O) -N (R ⁴ ) _n -[(R ¹ O) _x ( R ² O) _y R ³ ] _{m wherein} R is C _7-21 linear alkyl, C _7-21 branched alkyl, C _7-21 linear alkenyl, C _7-21 branched Alkenyl and mixtures thereof. Preferably,
R is C _8-18 straight chain alkyl or alkenyl.

R ¹ is —CH ₂ —CH ₂ — and R ₂ is C ₃ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl and mixtures thereof, preferably R ² is -CH (CH ₃₎ -CH ₂
-. A surfactant comprising a mixture of R ¹ and R ² units is preferably about 4
About 12 -CH ₂ -CH ₂ - units from about 1 to about 4 -CH (CH ₃₎ -C
H ₂ - containing together with unit. This unit may be included alternately,
Alternatively, they may be combined in any combination suitable for the manufacturer. Preferably, the ratio of R ¹ units to R ² units is from about 4: 1 to about 8: 1. Preferably, the R ² units (ie, —C (CH ₃ ) H—CH ₂ —) are attached to nitrogen atoms according to the balance of the chain containing about 4 to 8 —CH ₂ —CH ₂ units.

R ³ is hydrogen, C ₁ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.

R ⁴ is hydrogen, C ₁ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl and mixtures thereof, preferably hydrogen. When the index m is 2, the index n must be 0, R ⁴ unit is absent.

Provided that m + n is 2, the index m is 1 or 2 and the index n is 0 or 1; preferably, m is 1 and n is 1, resulting in one-[(R ¹ O ) _X (R ²
O) _y R ^3] unit and R ⁴ are present on the nitrogen. The index x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10. The index y is from 0 to about 10, preferably 0, but when the index y is not 0, y is 1
From about 4. Preferably, all alkyleneoxy units are ethyleneoxy units.

Examples of suitable ethoxylated alkyl amide surfactants are Rewopal® C6 from Witco, Amidox from Stepan.
® C5 and Akzo's Ethomid ® O / 17
And etmid® HT / 60.

Secondary Components of the Softening Composition The dispersion medium may also include secondary components known in the art. These include, for example: mineral acids or buffer systems for pH adjustment (required to maintain the hydrolytic stability of certain softening actives) and antifoaming components (eg Dow = A silicone emulsion available as Dow Corning 2310 from Dow Corning, Corp. Midland, Mich. (Used as a processing aid to reduce foaming when using the softening composition of the present invention in tissue webs) Is).

[0097] Stabilizers can also be used to improve the homogeneity of the dispersion and the shelf life. For example, an ethoxylated polyester, HOES 4060 (available from Clariant Corp., Charlotte, NC) can be mixed for this purpose.

Formation of Softening Composition As noted above, the softening composition of the present invention is a dispersion of the softening active ingredient dispersed in a dispersion medium. Depending on the softening active selected, the level of application desired, and other factors that require a particular level of softening active in the composition, the level of softening active may vary from about 10% of the composition to about 10% of the composition. Will vary between about 50% of the objects. Preferably, the softening active comprises from about 25% to about 45% of the composition. More preferably, the softening active comprises from about 30% to about 40% of the composition. The non-ionic surfactant is present at a level of about 1% to about 15%, preferably about 2% to about 10% of the level of the softening active. Depending on the method used to produce the softening active, the softening composition may also contain from about 2% to about 30%, preferably from about 5% to about 25% of a plasticizer. As noted above, the preferred main component of the dispersion medium is water. Further, the dispersion medium preferably contains an alkali metal or alkaline earth metal halide electrolyte, and may also contain minor components for pH adjustment, foam control, or dispersion stability assistance. In the following, the production of a particularly preferred softening composition of the invention is described.

[0099] A particularly preferred softening composition of the present invention (Composition 1) is prepared as follows.
These substances are more specifically defined in the tables detailing Composition 1 below. The amounts used in each step are sufficient to form the finished compositions detailed in the table above. Heat the appropriate amount of water to about 165 ° F. (additional water can be added to compensate for evaporation loss). Hydrochloric acid (25% solution) and antifoaming agent are added. At the same time, the mixture of softening active, plasticizer, and nonionic surfactant is melted by heating to about 65 ° C (150 ° F). A molten mixture of the softening active, the plasticizer, and the nonionic surfactant is then slowly added to the heated acidic liquid phase with stirring to evenly distribute the dispersed phase throughout the dispersion medium (polyethylene glycol). Water solubility probably moves it to the continuous phase,
This is not essential to the invention, and further, plasticizers that are more hydrophobic and thus remain attached to the alkyl chain of the quaternary ammonium compound are also included within the scope of the invention). Once the softening active is completely dispersed, a portion of the calcium chloride (as a 2.5% solution) is added with intermittent mixing to provide an initial viscosity reduction. The stabilizer is then slowly added to the mixture with continued stirring. Finally, the remainder of the calcium chloride is added with continued mixing (as a 25% solution).

Composition 1 Ingredient Concentration Continuous phase Water Add an appropriate amount to make 100% Electrolyte ¹ 0.6% Anti-fog agent ² 0.2% Double layer breaking agent ^3,5 1.0% Hydrochloric acid ⁴ 0.04% Plasticizer ⁵ 19% Stabilizer ⁶ 0.5% Disperse phase Softening active ingredient ⁵ 40.0% 1. 1. 2.5% aqueous calcium chloride solution from 0.38% and 25% aqueous calcium chloride solution from 0.22% Silicone emulsion (10% active), Dow Corning
(Registered trademark) 2310, commercially available from Dow Corning (Midland, Michigan). A suitable nonionic surfactant is available from Shell Chemical, Houston, TX, under the trade name NEODOL 91-8. J. T. Baker Chemical Co., New Jersey,
4. Available as a 25% solution from Philipsburg) The bilayer breaker, plasticizer and softening active are available as a pre-mix from Witco Chemical Co. Dublin, Ohio (about 2 parts Neodol 91-8, about 29 parts polyethylene glycol 400). And about 6
5. 9 parts tallow diester quaternized substance) The stabilizer was HOES 4060 from Clariant Corp., Charlotte, NC. The resulting chemical softening composition was a milky, low viscosity dispersion suitable for use in cellulosic structures as described below. And provide the desired soft touch to such structures. It exhibits shear thinning non-Newtonian viscosity. Suitably, the composition is prepared at 25 ° C. and 100 s using the methods described in the Test Methods section below.
It has a viscosity of less than about 1 Pa · sec (1000 cp) when measured at a shear rate of ec ⁻¹ . Preferably, the composition has a viscosity of less than about 0.5 Pa · sec (500 cp). More preferably, the viscosity is about 0.3 Pa · sec (300 cp).
).

The present chemical composition is easy to handle as a liquid and has a relatively high active ingredient concentration, so that it can be easily transported from the production site to the point of use. At the point of use, it is easily diluted to the working concentration. This dilution step is necessary for proper metering of the softening active in the papermaking step. That is, in an industrial papermaking process, a fairly large amount of dispersion containing a low concentration of softening active is metered into a suitable process stream. It will be appreciated that the concentration used will depend on several factors, including: That is, the process capacity for the metering process, the need to add a softening activator, the flow rates of the various process streams, and other factors known to those skilled in the art. A suitable concentration range has been found to be from about 0.5% to about 10% (concentrations are expressed as% by weight of softening active). Preferably, the use concentration is about 0.5% to about 5%, more preferably about 0.5% to about 2%. A particularly preferred use concentration is about 1%.

Optional Chemical Additives To impart other desired properties to the product or to improve the papermaking process, other materials may also be added to the aqueous papermaking furnish or initial web as they are added to the softening composition. It can be added as long as it is chemically compatible or does not significantly affect or adversely affect the flexibility or strength properties of the present invention. The following substances are explicitly included, but not all. Other materials may be included as long as they do not interfere with the advantages of the present invention or exhibit the opposite effect.

In order to control the zeta potential of the aqueous papermaking furnish, it is common to add a cationic charge biasing species to the papermaking step when the aqueous papermaking furnish is sent to the papermaking step. . These materials are used because the surface of cellulosic and fine fibers and most of the solids present, including most inorganic fillers, have a negative surface charge. One of the traditionally used cationic charge-deflecting species is the band. More recently, charge deflection in the art is achieved by using cationic synthetic polymers of relatively low molecular weight, preferably having a molecular weight of less than about 500,000, more preferably less than about 200,000 or about 100,000. The charge density of such low molecular weight cationic synthetic polymers is relatively high. These charge densities range from about 4 to about 8 equivalents of cationic nitrogen per kg of polymer. A typical material is Cypro, 514®, a product of Cytec, Inc., Stamford, CT. Use of such materials is clearly within the scope of the present invention.

The use of microparticles with high surface area and strong anionic charge to improve formation, drainage, strength and retention is taught in the art, but is described, for example, in US Pat. No. 5,221,435 ( Smith, June 22, 1993), which is incorporated herein by reference. Common materials for this purpose are silica colloids or bentonite clays. The inclusion of such materials is clearly within the scope of the present invention.

If permanent wet strength is desired, a group of chemicals can be added to the papermaking furnish or initial web, including: polyamide-epichlorohydrin, polyacrylamide, styrene-butadiene latex; insolubilized polyvinyl alcohol; Urea
Formaldehyde; polyethyleneimine; chitosan polymers and mixtures thereof. Preferred resins are cationic wet strength resins, such as polyamide-epichlorohydrin resins. Suitable types of such resins are described in the following references: U.S. Pat. No. 3,700,623 (Kein, Oct. 24, 1972) and 3,772,0
No. 76 (Kein, Nov. 13, 1973) (the disclosures of both documents are incorporated herein by reference). One commercially available source of useful polyamide-epichlorohydrin resins is Hercules, Wilmington, Del.
Such a resin is commercially available as (Kymene) 557H.

Many paper products had to be wet-strength limited in order to dispose of them from the washroom to the sewage or drainage system. When wet strength is imparted to these products, temporary wet strength (characterized by the collapse of all or part of the original strength when present with water) is preferred. If temporary wet strength is desired, the binder is selected from the group consisting of: a dialdehyde starch having aldehyde functionality, such as Co-Bond 100 (National Starch a).
nd Chemical Company, Scarborough, Maine); Parez® (Par)
ez) 750 (Cytec, Stamford, CT); and US Patent No. 4,9.
Nos. 81,557 (Bjorkquist, Jan. 1, 1991), which are known in the art, having the disintegration properties described above, and the resins described therein, which are incorporated herein by reference. Other resin.

When enhanced absorbency is required, the tissue and tissue of the present invention can be treated with a surfactant.
It can process the paper web. The level of surfactant when used is preferably about 0.01% by weight based on the dry fiber weight of the tissue web.
To about 2.0%. The surfactant preferably has an alkyl chain containing 8 or more carbon atoms. Typical anionic surfactants include linear alkyl sulfonates and alkyl benzene sulfonates. Typical nonionic surfactants include alkyl glycosides (Crodesta SL-40 (
Alkyl glycoside esters, such as US Pat. No. 4,011,389 (Langdon et al., Mar. 8, 1977).
Alkyl glycoside ether) and Pegosperse
200 ML (available from Glyco Chemicals, Inc. (Greenwich, Conn.)) And IGEPAL RC-520® (Rhone Poulenc Corporation (Cranbu
ry, NJ)). Alternatively, cationic softening actives with a high frequency of unsaturated (mono and / or poly) and / or branched alkyl groups greatly enhance absorption.

The cellulosic structures of the present invention can include other types of chemical softeners as well. For example, another type of added chemical softener added in the papermaking process includes the well-known organic reactive polydimethylsiloxane component, including the most preferred amino-functionalized polydimethylsiloxane.

Fillers can also be included in the tissue paper of the present invention. U.S. Patent No.
No. 5,611,890 (Vinson, March 18, 1997), which is incorporated herein by reference, discloses a fillerable tissue paper product acceptable as a substrate for the present invention. I have.

[0110] The above list of optional chemical additives is intended for purposes of illustration only and is not intended to limit the scope of the invention.

Addition Method Preparation of Furnish An understanding of the method of preparing the aqueous papermaking furnish can be obtained with reference to FIG. FIG. 2 is a schematic diagram illustrating the preparation of an aqueous papermaking furnish for a creping papermaking operation in which the product of the present invention is manufactured. The following discussion refers to FIG.

The storage container 8 is a storage location for the low viscosity chemical softening composition of the present invention. Pipe 9 provides dilution water to reduce the concentration of the softening active to the appropriate concentration. Pump 10 functions to deliver a dilute vesicle dispersion of the softening active. The dispersion is optionally processed in a mixer 12 to assist in vesicle formation. The resulting dispersion 13 is sent to a point where it is mixed with the selected aqueous dispersion of relatively long fiber papermaking fibers.

Still referring to FIG. 2, a storage vessel 1 is provided for stepping an aqueous slurry of relatively long papermaking fibers. The slurry is pumped by means of a pump 2, but is optionally passed through a refiner 3 to maximize the strength potential of long papermaking fibers. Using a pump 27 located between the pump 2 and the refiner 3, a cationic binding inhibitor is added, if desired, to compensate for the charged microfibers, thereby adding at a later stage in the process. The use of other substances can be minimized. If desired, resin is fed through the addition pipe 4 to provide wet or dry strength to the finished product. Subsequently, the slurry is further processed by the mixer 5 to assist absorption of the resin. After mixing with the small vacuolar dispersion 13 of the softening active ingredient, it becomes an aqueous papermaking slurry 17 predominantly of relatively long fibers. Optionally, the slurry is treated in a mixer 25 to help absorb the softening active. Subsequently, the properly treated slurry is passed through a fan pump 6
It is diluted with the white water 7 therein to produce a slurry 29 of dilute long papermaking fibers. The pipe 20 adds a cationic coagulant to the slurry 29, resulting in a coagulant added slurry 22 of relatively long fibers.

Referring to FIG. 2, the slurry of the relatively short papermaking fiber starts from the storage container 11, is sent from the container to the pipe 49 by the pump 14, and passes through the refiner 15. In the refiner 15 the slurry becomes a refined slurry composed of relatively short papermaking fibers 16. The white water 7 is mixed with the slurry 16 in a fan pump 18 at which point the slurry becomes a diluted aqueous papermaking slurry 19. The pipe 21 guides the cationic flocculant into the slurry 19, which is then made into a relatively short fiber-based papermaking slurry 23 to which the flocculant has been added.
become.

[0115] In one embodiment of the papermaking method, an aqueous papermaking slurry 23 based on relatively short fibers to which a flocculant has been added is directed to the creping papermaking process shown in Figure 1 and split into two approximately equal streams. These are then followed by headbox chambers 82 and 8
3 and is ultimately released to the non-Yankee face layer 75 and the Yankee face layer 71 of the tough and soft creped tissue paper, respectively. Similarly, the aqueous slurry 22 of relatively long papermaking fibers with the addition of a flocculant is preferably directed to the headbox chamber 82b and ultimately discharged into the central layer 73 of tough, soft creped tissue paper. (See FIG. 2).

[0116] creped papermaking process Figure 1 is a schematic diagram illustrating a creped papermaking process for producing a strong and soft creped tissue paper. These preferred embodiments are discussed below with reference to FIG. FIG. 1 is a side view of a preferred paper machine 80 for producing paper according to the present invention. Referring to FIG. 1, the paper machine 80 includes an upper chamber 8
2, including a multi-layer headbox 81 having a central chamber 82b and a lower chamber 83, a slice roof 84, and a fourdrinier wire 85. Fourdrinier wire 85
Surrounds a breast roll 86, a deflector 90, a vacuum suction box 91, a coach roll 92, and a plurality of turning rolls 94. In operation, a first furnish is sent to the upper chamber 82, a second furnish is sent to the central chamber 82b, while a third furnish is sent from the lower chamber 83, and The fourdrinier wire 85 is moved up and down from the slice roof 84.
To form an initial web 88 comprising layers 88a and 88b and 88c on the wire. Dewatering is performed on Fourdrinier wire 85 and is assisted by deflector 90 and vacuum box 91. When the Fourdrinier wire returns in the direction indicated by the arrow, the shower 9 will start before another new pass is started on the breast roll 86.
5 cleans the fourdrinier wire. In the web transfer zone 93, the initial web 88 is applied to the porous carrier fabric 96 by the vacuum transfer box 9
It is transferred by the action of 7. The carrier fabric 96 sends the web from the transfer zone 93 to a vacuum dewatering box 98 and further to a blow-through pre-dryer 100 and two turning rolls 101. Thereafter, the web is transferred to the Yankee dryer 108 by the action of the pressure roll 102. Subsequently, the carrier fabric 96 is washed and dewatered as it passes around yet another turning roll 101, shower 103 and vacuum dewatering box 105 as it completes its loop.
The pre-dried paper web is adhesively secured to the surface of the Yankee dryer 108 by an adhesive applied by a spray applicator 109. Drying is completed on a steam heated Yankee dryer 108 by heated hot air circulating in a drying hood 110 (not shown). Subsequently, the web is peeled off from the Yankee dryer 108 by a doctor blade 111 in a dry state, after which the web is referred to as a paper sheet 70 and the Yankee side layer 71,
A central layer 73 and an anti-Yankee side layer 75 are included. Subsequently, the paper sheet passes between the calender rolls 112 and 113, around the periphery of the reel 115, and from there is taken up by a take-up 116 of a core 117 arranged on a shaft 118.

Referring to FIG. 1, the Yankee side layer 71 of the paper sheet 70 originates from the furnish sent from the lower chamber 83 of the head box 81, and this furnish is supplied to the fourdrinier wire 85. Applied directly, on this Fourdrinier wire it becomes layer 88c of initial web 88. The origin of the central layer 73 of the paper sheet 70 is furnish delivered from the chamber 82b of the head box 81, which furnish forms a layer 88b above the layer 88c. The origin of the anti-Yankee side layer 75 of the paper sheet 70 is the furnish delivered from the upper chamber 82 of the head box 81, which furnish forms a layer 88a above the layer 88b of the initial web 88. . FIG. 1 shows a paper machine 80 with a head box 81 tailored for the production of three-layer webs, but the head box 81 can also be separately adapted for the production of non-layered webs, two-layer webs or other multi-layer webs. You can also.

Further, when the present invention is carried out on the paper machine 80 (FIG. 1) to produce the paper sheet 70, the fourdrinier wire 85 is used to form a short fiber furnish so that a good paper layer can be formed. Requires a fine mesh having a relatively small span relative to the average length of the fibers comprising In addition, the porous carrier fabric 96 has a fine mesh with a relatively small open span relative to the average length of the fibers that make up the long fiber furnish, and the initial webs The fabric side must be substantially prevented from increasing. Still further, as process conditions for the production of a representative paper sheet 70, the paper web preferably has a fiber concentration of about 80% prior to creping, more preferably about 95% fiber.
% Fiber concentration.

The present invention includes, but is not limited to, generally felt compressed creped tissue paper; high bulk densely patterned creped tissue paper; and high bulk uncompressed creped tissue paper. ) Applies to creped tissue paper. Those skilled in the art will appreciate that the above steps are exemplary and other steps are equally within the scope of the present invention. For example, a homogenous furnish can be provided which comprises a mixture of any desired long and short papermaking fibers treated with a vesicle dispersion of a chemical softening active using a process similar to that described above. Methods of providing a two-layer tissue structure (eg, those shown in Examples 3 and 4) are also within the scope of the invention.

Specific Examples Specific Examples 1 This example details preferred production modes of the softening composition of the present invention. The materials used in the preparation of the chemical softening mixture are as follows: Partially hydrogenated tallow diester chloride quaternary ammonium compound premixed with polyethylene glycol 400 and an ethoxylated fatty alcohol nonionic surfactant. This premix contains 69% of the quaternary ammonium compound (
Witco's Adogen SDMC type), 29% PEG400 (J
. T. Baker (available from Philipsburg, NJ))
And 2% nonionic surfactant (available as Neodol 91-8 from Shell Chemical, Houston, Tex.). 2. Calcium chloride pellets (JT Baker, Phillipsburg, NJ). 3. 3. Polydimethylsiloxane: 10% actives emulsion (DC2310) (Dow-Corning, Midland, Mich.) Hydrochloric acid (25% solution) (JT Baker, Phillipsburg, NJ) The stabilizer is HOES 4060 (available from Clariant Corp., Charlotte, NC). These materials are prepared to produce the softening composition of the present invention as follows.

The chemical softening composition is prepared by first heating the required amount of water to about 75 ° C., and then adding polydimethylsiloxane to the heated water. PH of this premixed water
To about 4. Further, the pre-mix of the quaternary compound, PEG 400 and the non-ionic surfactant is heated to about 65 ° C., weighed into the pre-mix of water and stirred until completely homogenous. About half of the calcium chloride is added as a 2.5% aqueous solution with constant stirring. Subsequently, the stabilizer is added with continuous stirring. Final viscosity reduction is achieved by adding the remainder of the calcium chloride as a 25% solution with constant stirring. These components are mixed in sufficient proportions to provide a composition having the following approximate concentrations of each component: 40.1% partially hydrogenated tallow diester chloride quaternary ammonium compound Water 17.2% PEG400 1.1% Neodol 91-8 0.6% Calcium chloride 0.5% Stabilizer 0.02% Polydimethylsiloxane 0.02% Hydrochloric acid After cooling and adding constituent water, this composition Is determined using the method described in the test method section.
When measured at 5 ° C. and a shear rate of 100 sec ⁻¹ , about 0.3 Pa · sec (
300 centipoise).

Example 2 This example demonstrates the effect of a non-ionic surfactant composition on the properties (viscosity) of an essential softening composition. The chemical softening composition is made by first preparing a masterbatch containing all components of the softening composition except for the bilayer breaking agent. The composition of this composition is shown in Table 1.

Table 1 Ingredient Concentration (%) Partially hydrogenated tallow diester chloride quaternary ammonium compound 41 Water 39 PEG400 19 Calcium chloride 0.6 Stabilizer 0.5 Polydimethylsiloxane 0.02 Hydrochloric acid 0.02 1%, 2%, 3% and 4% of a bilayer breaker capable of testing softening compositions
By mixing with the masterbatch at a level of. The viscosity of each of the test softening compositions is measured according to the method described in the Test Methods section below. The viscosity of the masterbatch is also measured. Table 2 lists the test substances, their HLB (a measure of emulsification effectiveness) and the viscosity of each composition prepared.

Table 2 Nonionic surfactant HLB concentration (%) Viscosity (Pa · sec (cp)) Neodol 23-3 ¹ 7.9 0 1.8 × 10 ⁴ (18 × 10 ^{7 *} ) 1 6. 774 (6774) 2 4.375 (4375) 3 1.549 (1549) 4 1.365 (1365) Neodol 23-5 ¹ 10.70 2.150 ^* (2150 ^* ) 1 0.335 (335) 2 0.260 (260) 3 0.644 (644) 4 1.285 (1285) Neodol 91-8 ¹ 13.9 0 1.8 × 10 ^{4 *} (1.8 × 10 ^{7 *} ) 1 0.166 ( 166) 2 1.583 (1583) 3 9 × 10 ² (9 × 10 ⁵ ) 48 8 × 10 ³ (8 × 10 ⁶ ) Sulfonic N-120 ² 14.10 6.103 ^* (6103 ^* ) 1 0.193 (193) 2 0.704 (704) 37 595 (7595) 4 9 × 10 3 (9 × 10 6) Akukonon ^{CC-6 3 0 6.103 * (} 6103 *) 1 0.450 (450) 2 0.421 (421) 3 1.194 (1194) 4 1.7 × 10 (1.7 × 10 ⁴ ) Tween 60 ⁴ 14.9 0 6.4 × 10 ^{4 *} (6.4 × 10 ^{7 *} ) 1 0.215 (215) 2 0.367 (367) 3.) 3 0.652 (652) 4 2.043 (2043) Furafax B25-5 ⁵ 12.00 1.029 ^* (1029 ^* ) 1 0.442 (442) 22.100 (2100) 3 2. 9 × 10 (2.9 × 10 ⁴ ) 4 1.1 × 10 ⁴ (1.1 × 10 ⁷ ) *: Without being bound by theory, Applicants believe that the variability of viscosity is This is thought to be due to the intermittent formation of a stable liquid crystal phase by the softening active ingredient. As noted above, it is believed that the addition of a double layer breaking agent reduces this viscosity by breaking the structure of the liquid crystal phase. 1. 1. Ethoxylated fatty alcohol from Shell Chemical (Houston, TX). 2. Huntsman Corp. (Houston, Tex.) Ethoxylated alkylphenol. 3. Ethoxylated caprin / caprylic glyceride from Abitec Corp. (Columbus, OH) Henkel Corp. (Chart, North Carolina) POE
(20) Sorbitan monostearate Modified oxyethylated linear alcohols from BASF Corp. (Mount Olive, NJ) As can be seen, each of these materials substantially reduced the viscosity of the dispersions from that of the dispersions without them. Let it.

Example 3 The purpose of this example was to use di (hydrogenated) tallow dimethylammonium methyl sulfate (DHTDMAMS) and polyoxyethylene glycol 400 (PEG).
-400) A method using conventional papermaking techniques to produce soft, absorbent tissue paper treated with a (solid) premix and a conventional chemical softening composition containing a wet strength enhancing additive resin. That is to say.

A pilot scale S-lap twin-wire paper machine is used in the practice of the present invention. First, a substantially water-free self-emulsifying chemical softening composition is prepared according to US Pat. No. 5,474,689. In said patent, DHTDMA
A homogeneous premix of MS and solid PEG-400 is dispersed in a conditioned (temperature about 66 ° C.) water tank to form a submicron vesicle dispersion.

Second, a 3% by weight slurry of deinked commercial pulp (DMP) is prepared with a conventional repulper. The DMP slurry is gently refined and a 0.25% solution wet strength resin (eg, Kymene 557H available from Hercules, Wilmington, Del.) Is added to the dry fiber per weight basis. At a rate of 0.72 pounds resin / ton to the DMP stock. Adsorption of the wet strength resin to the DMP fibers is enhanced by an in-line mixer. U.S. Pat. No. 5,474,689 in the form of a chemical softener mixture
HTDMAMS is also used before the stock pump (but after the wet strength resin), about 2.5 lbs / ton dry fiber weight.
125%) to the DNP stock pipe (at a concentration of 1% softening active). The adsorption of the chemical softener mixture to the DMP fibers is enhanced by an in-line mixer. The DMP slurry is diluted with a fan pump to a concentration of about 0.2%.

Third, a 3% by weight eucalyptus fiber slurry is prepared with a conventional repulper. The eucalyptus slurry is diluted with a fan pump to a concentration of about 0.2%.

The slurry of DMP and eucalyptus tree is directed to a multi-channel head box. The head box is suitably equipped with a multi-layered laminar chamber to maintain the flow in separate layers until it is released on the moving S-wrap twin-wire. A head box with three chambers is used. The eucalyptus slurry (containing sufficient solids flow to achieve 34% of the final paper dry weight) is directed into the chamber leading to the forming wire, while 6% of the final paper dry weight.
A DMP slurry containing sufficient solids flow to reach 6% is directed into the remaining two chambers. The DMP and eucalyptus slurry are combined when discharged from the head box to form a composite slurry.

[0130] The composite slurry is discharged to a moving S-wrap twin-wire former and dewatered.
Dehydration is assisted by deflectors and vacuum boxes.

The incipient wet web was transferred to the S-Lap Twin- at a transfer point at a fiber concentration of about 15%.
Transfer from wiremaking section to dry fabric. A suitable dried fabric is Albany Internati as TRIOVENT
onal, Albany, NY). Further dewatering is performed by vacuum assisted drainage until the web has a fiber concentration of about 28%.

Subsequently, the semi-dried web is adhered to the surface of the Yankee dryer by spraying a creping adhesive containing a mixture of polyvinyl alcohol and a polyamide base resin. The creped adhesive is distributed on the Yankee surface at a percentage of adhesive solids of 0.125% based on the dry weight of the web.

The fiber concentration increases to about 96% before the web is peeled dry from the Yankee with a doctor blade.

The doctor blade has an oblique angle of about 20 degrees and is arranged to provide an impact angle of about 76 degrees for the Yankee dryer.

[0135] Percent crepe was measured using a Yankee dryer at about 305 m / min (1000 fp).
m) is adjusted to about 21-25% by operating at a speed of m), and the dried web is formed into a web at a speed of 235 m / min (770 fpm).

This tissue paper has a basis weight of about 16 g / m ² (10 pounds / 3000 ft ² ) and contains about 0.1% of a substantially water-free, self-emulsifying chemical softener mixture and wet strength enhancement. Contains about 0.1% resin. Importantly, the resulting tissue paper is soft and absorbent and is also suitable for use as a cosmetic and / or hand wash tissue.

EXAMPLE 4 The purpose of this example is to produce a soft, absorbent tissue paper treated with a low viscosity chemical softener composition prepared according to Example 1 of the present invention and a wet strength resin. The purpose is to explain the method using ordinary dry papermaking technology. The preparation of the furnish is substantially the same as that used in Example 1, with the only exception that the 2.5% dispersion of the chemical softener mixture of Example 1 is replaced by a conventional chemical softener. It was used in place of the composition.

The separate furnish was directed to a head box, deposited on a twin-wire former and dried in substantially the same manner as described in Example 1 to form a dried tissue.
Form the web.

This tissue paper has a basis weight of about 16 g / m ² (10 pounds / 3000 ft ² ) and contains about 0.05% of a substantially water-free self-emulsifying chemical softener mixture.
And about 0.1% wet strength resin. Importantly, the resulting tissue paper is soft and absorbent and is also suitable for use as a cosmetic and / or hand wash tissue.

Example 5 In this example, the characteristics of the tissue papers of Examples 3 and 4 are compared. Tissue basis weight MD tensile strength CD tensile strength softener holding sample (g / m ² ) (g / cm) (g / cm) (%) Specific example 3 16 62.6 42.5 17.2 Specific example 4 16. 5 75.2 44.8 16.8 Clearly, the tissue papers produced in Examples 3 and 4 have substantially the same physical properties.

Test Methods Softening Active Component Level of Cellulose Fibers The analysis of the amount of softening active component described herein retained on the cellulosic structure can be performed by any of the art accepted methods. These methods are exemplary and are not intended to exclude other methods useful for determining the levels of individual components retained by the tissue paper.

The following method is suitable for determining the amount of a preferred quaternary ammonium compound (QAC) deposited by the method of the present invention. The QAC is titrated with a dimidium bromide indicator using a standard anionic surfactant (sodium dodecyl sulfate, NaDDS) solution.

Preparation of standard solution : The following method can be used for preparing the standard solution used in the present titration method.

Preparation of Dimidium Bromide Indicator : In a 1 liter volumetric flask: A) Add 500 ml of distilled water B) 40 ml of a dimidium bromide-disulfin blue indicator stock solution (
Addition of Gallard-Schlesinger Industries, Inc. (Carl Place, NY)) C) Add 46 ml of 5N sulfuric acid D) Fill distilled water up to the mark on the flask and mix as follows A NaDDS solution is prepared in a 1-liter volumetric flask. A) 0.1154 gram of NaDDS (available from Aldrich Chemical Co., Milwaukee, Wis.) As sodium dodecyl sulfate (special grade) B) Fill up with distilled water to mark and mix to 0.0004N Method for Producing a Solution of Weigh approximately 0.5 grams of cellulosic fibrous structure specimen on an analytical balance. Record the sample weight to the nearest 0.1 mg. 2. The sample is placed in a glass cylinder with a volume of about 150 ml containing a star magnetic stirrer. Using a graduated cylinder, add 20 ml of methylene chloride. 3. Place the cylinder on a hot plate set to low heat with a fume hood. The solvent is brought to a full boil with stirring and 35 ml of the dimidium bromide indicator solution are added. 4. While stirring at high speed, the methylene chloride is again brought to a full boil. Stop heating, but continue to agitate sample. QAC forms a complex with the indicator, forming a blue compound in the methylene chloride layer. 5. Using a 10 ml burette, titrate the sample with a solution of anionic surfactant. Titration is performed by adding a portion of the titrant and rapidly stirring for 30 seconds. Stop the stir plate, allow the layers to separate, and check the blue color depth.
If the color is deep blue, add 0.3 ml of titrant, stir quickly for 30 seconds and stop the stirrer. Check the blue color again. Repeat with an additional 0.3 ml if necessary. If the blue color begins to become very pale, titrant is added dropwise during stirring. The end point is when the faint pink color first appears in the methylene chloride layer. 6. Record the volume of titrant used to the nearest approx. 0.05 ml. 7. Calculate the amount of QAC in the product using the following formula: (milliliters of NaDDS-X) x Y x 2 / weight of sample (grams) =
Pounds / ton QAC where X is the blank correction obtained by titrating a sample without the QACs of the present invention. Y is the milligram of QAC titrating 1.00 milliliter of NaDDS (eg, Y = 0.25 for one particularly preferred QAC (ie, diester di (touch-hydrogenated) tallow dimethyl ammonium chloride).
4) Density As the term "density" is used herein, the density of a cellulosic structure is calculated as the basis weight of the paper divided by calipers and the appropriate unit conversion incorporated therein. Is the average density. As used herein, paper caliper is the thickness of the paper when subjected to a compression load of 15.5 g / cm ² (95 g / in ² ).

Tissue Paper Strength Dry Tensile Strength : This method is intended for use on finished paper products, reel samples, and unprocessed stock. The tensile strength of such products is 2.54 cm
Swing-Albert-Intellect (1 inch) wide sample strip
Thwing-Albert Intelect II Standard Tensile Tester (Thwing-Albert Instrument)
Co., Philadelphia, PA).

Sample Humidification and Preparation : Prior to the tensile test, the paper sample under test must be conditioned for at least 15 minutes in a relative humidity of 48 to 52% and a temperature range of 22 to 24 ° C. All stages of sample preparation and tensile testing must also be performed in a room at constant temperature and humidity.

In the case of a finished product, all damaged products are discarded. Next, five strips containing four usable units (also referred to as sheets) are removed, another strip is superimposed on one strip, and a large bundle is formed so that the perforations between the sheets overlap. make. Sheets 1 and 3
Are specified for the longitudinal tensile measurement, and sheets 2 and 4 are specified for the width direction measurement. Next, a paper cutter (Swing-Albert with safety cover (Th.
wing-Albert Instrument Co. JDC, Philadelphia, PA
Cut along perforations using -1-10 or JDC-1-12) to make four separate stocks. Ensure that bundles 1 and 3 are identified for longitudinal testing and bundles 2 and 3 are identified for width testing.

Bundles 1 and 3 Two strips 1 to 2.54 cm (1 inch) wide are cut in the machine direction. Bundles 2 and 4 are cut in width direction into two strips 1 inch wide from 2.54 cm (1 inch). There are now four 2.54 cm (1 inch) wide strips for the longitudinal tensile test and four 2.54 cm (1 inch) wide strips for the transverse tensile test. For these finished product samples, all eight 2.54 cm (1 inch) wide strips have a thickness of five usable units.

For unprocessed stock and / or reel samples, an eight layer thickness of 38
. A 1 cm x 38.1 cm (15 inch x 15 inch) sample was
Cutter (Thwing-Albert Instru with safety cover)
ment Co. JDC-1-10 or J of Philadelphia, PA)
Using DC-1-12), cut out the sample from the region of interest. One side 38
. Make sure that the cut surface of 1 cm (15 inches) is parallel to the longitudinal direction and the other cut surface is parallel to the width direction. Verify that the sample is conditioned for at least 2 hours in a relative humidity of 48-52% and a temperature range of 22-24 ° C. All steps of sample preparation and tensile testing must be performed in a room at constant temperature and humidity.

From this 15 inch x 15 inch (38.1 cm x 38.1 cm) sample having a thickness of 8 layers pre-humidified, a 2.54 cm x 17.78 cm (1 inch x 15 inch)
Cut out four 7 inch (7 inch) strips. At this time, 38.1 cm (7 inches) long
Are parallel to the longitudinal direction. Mark these samples as longitudinal reels or unprocessed stock samples. In addition, four 2.54 cm x 17.78 cm (1 inch x 7 inch) strips are cut out. At this time, the long dimension of 38.1 cm (7 inches) is parallel to the width direction. Mark these samples as widthwise reels or unprocessed stock samples. All previous cuts were made using a paper cutter (Thing-Albert Instrument C with safety cover).
o. JDC-1-10 or JDC- of Philadelphia, PA)
Confirm that the operation is performed using 1-12). There were now a total of eight samples: 2.54 cm x 38.1 cm (1 in x 7 in) with dimensions of 38.1 cm (7 in) parallel to the machine direction, with a thickness of 8 layers One strip and four strips of 2.54 cm x 38.1 cm (1 inch x 7 inch) with dimensions of 38.1 cm (7 inches) parallel to the width direction with a thickness of 8 layers .

Operation of the tensile tester : To actually measure the tensile strength, a swing-albert-intellect (Th
wing-Albert Intelect) II standard tensile tester (Thwing-Albert Instrument Co.
(Philadelphia, PA) is used. Insert a flat-faced fastener into the unit and set the scale on the tester according to the instructions given in the Swing-Albert-Intellect II operating manual. The instrument cross head speed is set to 10.16 cm / min (4.00 inches / min), and the length of the first and second gauges is set to 5.08 cm (2.00 inches). Brake sensitivity is 2
Set to 0.0 grams, sample width is set to 2.54 cm (1.00 inch) and sample thickness is set to 0.0635 cm (0.025 inch).

The load cell is chosen such that the expected tensile result of the sample under test is between 25% and 75% of the working range. For example, a 5000 gram load cell has an expected tensile range of 1250 grams (25% of 5000 grams) to 3750 grams (25% of 5000 grams).
5000% (75% of 5000 grams). The tensile tester can also be set in the 10% range for a 5000 gram load cell so that samples with an expected tensile of 125 to 375 grams can be tested.

Take one of the pull strips and place one end into one of the fasteners of the pull tester. Place the other end of the strip on another fastener. Make sure the long side of the strip is parallel to the side of the tensile tester. Also make sure that the strip does not hang on either end of the two fasteners. In addition, the pressure of each fastener must be in full contact with the paper sample.

After the test paper strip has been inserted into the two fasteners, the tension in the device can be monitored. If it shows a value of 5 grams or more, the sample is too tight. Conversely, if 2-3 seconds elapse before any value is recorded after the start of the test, the pull strip is too loose.

Start the tensile tester as described in the tensile tester equipment manual. The test is completed after the cross head has automatically returned to its starting position. The tensile load is read and recorded from the instrument scale or digital panel meter to the nearest unit in grams.

If the device does not automatically perform the reset state, perform the necessary adjustments to set the device fasteners to the initial starting position. The next piece of paper is inserted into the two clamps as described above and a tensile reading is obtained in grams. Obtain tensile readings for all test paper strips. It should be noted that if the strip comes off or breaks in or on the fastener, the reading must be discarded while the test is being performed.

Calculations : For four 1 inch wide finished product strips, sum the four individual tensile readings recorded. Divide this total by the number of test strips. The number of strips is usually four. Furthermore, the total recorded pull is divided by the number of usable units per pull strip. This number is usually 5 for both 1-ply and 2-ply products.

[0158] This calculation is repeated for the finished product strip in the width direction.

For unprocessed stock or reel samples cut in the machine direction, sum the four individual tensile readings recorded. Divide this total by the number of test strips. The number of strips should normally be four. Furthermore, the total recorded pull is divided by the number of usable units per pull strip. This is usually 8.

This calculation is repeated for the unprocessed stock or reel sample paper strip in the width direction.

All results are in units of grams / 2.54 cm (inch).

For the purposes of this specification, tensile strength is referred to as “total tensile specific strength”.
otal tensile strength). It is defined as the sum of the tensile strengths measured in the machine direction and the width direction divided by the basis weight and corrected to a value in meters.

Viscosity Overview : The viscosity is measured using a rotational viscometer at a shear rate of 100 (s ^-1 ). The sample is subjected to a linear stress sweep in which a range of stresses are each applied at a constant amplitude.

Apparatus : Viscometer Dynamic Stress Rheometer Model SR500
, This is Rheometrics Scientifi
c, Inc. Sample plate available from Piscataway, NJ Setup using a 25 mm co-directional insulating plate: Gap 0.5 mm Sample temperature 20 ° C. Sample volume at least 0.2455 cm ³ Initial shear stress 10 dynes / cm ² last shear stress 1000 dynes / cm ² stress increase Apply 25 dynes / cm ² every 20 seconds Method : Open gap and place sample on sample plate. Close the gap and operate the rheometer according to the manufacturer's instructions and measure the viscosity between the initial and final shear stress as a function of the shear stress using the stress increase defined above.

Results and Calculations : In the result graph, the log of the shear rate (s ^-1 ) is plotted on the x-axis with the viscosity (Poise (P
)) Is plotted on the left y-axis and stress (dyne / cm ² ) is plotted on the right x-axis. Viscosity values are read at a shear rate of 100 (s ^-1 ). The value of this viscosity is multiplied by 100 to convert P to centipoise (cP).

The disclosures of all patents, patent applications (and any subsequently issued patents and corresponding foreign patent application publications), and publications mentioned herein, are hereby incorporated by reference. However, no admission is made that any document contained herein by reference teaches or discloses the present invention.

While specific embodiments of the present invention have been described in detail, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention. Accordingly, such changes and modifications within the scope of the invention are intended to be included within the scope of the appended claims.

[Brief description of the drawings]

 In the following figures, the same reference numbers refer to the same elements in the figures.

FIG. 1 is a schematic diagram showing a creped papermaking method of the present invention for producing a tough and soft tissue paper containing papermaking fibers using the softening composition of the present invention.

FIG. 2 is a schematic diagram illustrating the steps of preparing an aqueous papermaking furnish for a creped papermaking method according to one of the embodiments of the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZA, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Rice John Ernest United States of America Ohio, Sharonville, Beakley Woods Drive, 3508 (72) Inventor Vinson Kenneth Douglas, Ohio, United States of America Cincinnati, Wyoming Avenue, 303 (72) Inventor McFarland James Robert United States Ohio, Cincinnati, Airesboro Avenue, 3770 (72) Inventor Carl Amy Joe United States Ohio, Cincinnati, Dale Road # 10, 8557 (72) Inventor Whirl Erol Hoffman United States Ohio , Cincinnati, Deershad Lane, 8021 (72) Inventor Frankenbach Gail Marie Ohio, Cincinnati, Voyager Way, 10010 F-term (reference) 4L055 AA01 AC09 AG04 AG34 AG35 AG88 AH29 AH33 FA16

Claims (10)

[Claims] 1. A method for producing a soft tissue paper product comprising the steps of: a) a dispersion medium; a softening active ingredient containing a quaternary ammonium compound; an electrolyte; and a bilayer breaking agent. Providing a chemical softening composition; b) diluting the chemical softening composition to a working concentration; c) providing a papermaking fiber slurry; d) treating the papermaking fiber slurry with the diluted chemical softening composition. E) depositing the treated slurry of the papermaking fibers on a porous paper layer forming wire; f) dewatering the treated slurry by draining from the porous paper layer forming wire to form an initial web. . 2. The method of claim 1, wherein: a) the papermaking fiber slurry comprises a separate slurry, a first slurry of short papermaking fibers, and a second slurry of long papermaking fibers; b) only the second slurry comprises 2. The method of claim 1 wherein the first slurry is treated with a diluted chemical softening composition; and c) the first slurry is deposited between the wire and the second slurry on the porous fabric. 3. The method of claim 1, wherein the softening active is at least about 25% of the composition;
3. The method of any one of claims 1 or 2, wherein the method preferably comprises at least about 35%. 4. The softening active according to claim 1, wherein the softening active comprises a quaternary ammonium compound, preferably wherein the softening composition comprises a quaternary ammonium compound having the formula: Method: embedded image Wherein Y is -O- (O) C- or -C (O) -O- or -NH-C (O)-
Or -C (O) -NH-, wherein preferably Y is -O- (O) C or -C (O)
M is 1 to 3, preferably 2; n is 0 to 4, preferably 2. each R ₁ is a C ₁ -C ₆ alkyl or alkenyl group, a hydroxyalkyl group, a hydrocarbyl or a substituted hydrocarbyl. Group, alkoxylated group, benzyl group,
Or a mixture thereof; each R ₃ is a C ₁₃ -C ₂₁ alkyl or alkenyl group, a hydroxyalkyl group,
A hydrocarbyl or substituted hydrocarbyl group, an alkoxylated group, a benzyl group, or a mixture thereof, preferably R ₃ is C ₁₅ -C ₁₇ alkyl or alkenyl; X ⁻ is any softener compatible anion, preferably X ⁻ is Chloride or methyl sulfate. 5. The composition according to claim 1, wherein the composition further comprises a plasticizer, wherein the plasticizer is selected from the group consisting of polyethylene glycol, polypropylene glycol and mixtures thereof. the method of. 6. The method according to claim 1, wherein the dispersion medium is water, and the electrolyte is a salt selected from the group consisting of chlorides of sodium, calcium, and magnesium. 7. The method of claim 6, wherein said salt is present at a level of about 0.1% to about 20% by weight of said composition. 8. The method of claim 1, wherein the bilayer breaking agent comprises about 2% of the level of the softening active.
The method according to any one of claims 1 to 7, wherein the method is used at a level of from about 15% to about 15%. 9. The method of claim 1, wherein the double layer breaking agent is selected from the group consisting of:
The method according to any one of 1 to 8 above: Saturated and / or unsaturated primary, secondary and / or branched having from about 6 to about 22 carbon atoms in the hydrophobic chain, amines, amides, amine-oxide fatty alcohols, fatty acids, alkylphenols, and / or alkyls A nonionic surfactant derived from an aryl carboxylic acid compound, wherein at least one active hydrogen of said compound is ethoxylated with no more than 50 ethylene oxide moieties to provide an HLB of about 6 to about 20; The non-ionic surfactant having a hydrophobic moiety selected from the group consisting of a fatty alcohol having about 8 to about 18 carbon atoms, and an alkylphenol having about 8 to about 18 carbon atoms. Wherein the hydrophobic moiety is ethoxylated with about 3 to about 15 ethylene oxide moieties. Yl; 2. Nonionic surfactant with a bulky head group selected from the following a and b: a. A surfactant having the following formula: Wherein Y ″ is N or O; and each R ⁵ is independently selected from: —H, —OH, — (CH ₂ ) _X CH ₃ , —O (OR ² ) _Z —H, — OR ¹ , -OC (O
) R ¹ , and —CH (CH ₂ — (OR ² ) _{Z ″} —H) —CH ₂ — (OR ² ) _Z′— C (
O) R ¹ , x and R ¹ are as defined above and additionally 5 ≦ z, z ′ and z
. "It is ≦ 20; and b the following formula polyhydroxy fatty acid amide ^{surfactants: R 2 -C (O) -N} (R 1) in -Z wherein each R ¹ is H, C ₁ -C ₄ hydrocarbyl , C ₁ -C ₄ alkoxyalkyl, or hydroxyalkyl; R ² is a C ₅ -C ₂₁ hydrocarbyl moiety;
Is a polyhydroxyhydrocarbyl moiety having said linear hydrocarbyl chain with at least three hydroxyls directly attached to the linear hydrocarbyl chain, or an ethoxylated derivative thereof; and Cationic surfactants having the _{^{formula: {R 1 m -Y - [}} (R 2 -O) Z -H] P} + X - wherein, R ¹ represents a saturated or unsaturated, first, A di- or branched-chain alkyl or alkyl-aryl hydrocarbon; wherein the hydrocarbon chain has about 6 to about 22 carbon atoms; each R ² is selected from the following groups or combinations of the following groups: CH _{2) n} - and / or _{- [CH (CH 3) CH} 2] -; Y is selected from the following groups: = n ⁺ -
_{(A) q ;-( CH 2)} n -N + - (A) q; -B- (CH 2) n -N + - (A) 2; -
(Phenyl) -N ⁺ -(A) _q ;-( B-phenyl) -N ⁺ -(A) _q ; n is about 1 to about 4, wherein each A is independently selected from the following groups: : H; C _1-5 alkyl; R ¹ ;-(R ² O) _Z -H;-(CH ₂ ) _X CH ₃ ; phenyl and substituted aryl; wherein 0 ≦ x ≦ about 3; Selected from the group: -O-; -NA-;
_{-NA 2; -C (O) O-} ; and -C (O) N (A) -; Total number of 1 per molecule z; this time R ² is as defined above; with q = 1 or 2 Is about 3 to about 50
And X ^- is an anion compatible with the fabric softener active and accessory ingredients. 10. The use concentration is between about 0.5% and about 10%, preferably the use concentration is between about 0.5% and about 5%, most preferably the use concentration is between about 0.5% and about 5%. The method according to any one of claims 1 to 9, which is 1%.