JP3194958B2 - Anhydrous, self-emulsifying chemical softener composition useful for fibrous cellulosic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a substantially anhydrous, self-emulsifying chemical softener composition. More particularly, the present invention relates to a substantially anhydrous, self-emulsifying chemical softener composition useful for treating fibrous cellulosic materials such as tissue paper webs. The treated tissue web can be used in the manufacture of soft absorbent paper products such as towels, napkins, cosmetic and toilet tissue products.

BACKGROUND OF THE INVENTION Paper webs or sheets, sometimes referred to as tissue or paper tissue webs or sheets, are widely used in modern society. Products such as paper towels, napkins, cosmetic and toilet tissues are major commercial products. It has long been recognized that three important properties of these products are their softness, their absorbency, especially their absorbency in aqueous systems, and their strength, especially their wet strength. ing. Research and development efforts are being made to improve each of these properties without seriously affecting the other properties, as well as to improve two or three properties simultaneously.

Softness is the feel that consumers feel when they pick up a particular product, rub it against the skin, and roll it in their hands. This feel is a combination of several physical properties. One of skill in the art considers that one of the most important physical properties related to softness is the stiffness of the paper web from which the product is made. It is believed that the stiffness generally depends directly on the dry tensile strength of the web and the stiffness of the fibers forming the web.

Strength is the ability of the product and its constituent webs to maintain physical integrity under conditions of use, especially when wet, and resist tearing, tearing, and tearing.

Absorbency is the ability of the product and its constituent webs to absorb large amounts of liquids, especially aqueous solutions or dispersions. The overall absorbency perceived by the consumer is generally considered to be a combination of the total amount of liquid a constant mass of tissue paper absorbs to saturation as well as the rate at which the material absorbs the liquid.

The use of wet strength resins to increase the strength of paper webs is widely known. For example, Westfelt is Cellul
Many such materials and their chemical properties are described in ose Chemistry and Technology, Volume 13, pages 813-825 (1979). Freimark et al. In U.S. Pat.
No. 755,220, issued Aug. 28, 1973, states that certain chemical additives, called debinding agents, interfere with the natural fiber-to-fiber bonding that occurs during sheet formation in the papermaking process. I have. Due to this bond reduction, softer,
Alternatively, a paper sheet having a small roughness can be obtained. Freimark et al. Disclose the use of wet strength resins to increase the wet strength of the sheet and offset the undesirable effects of the debinding agent. These debinding agents reduce both dry and wet tensile strength.

Shaw also discloses in U.S. Patent No. 3,821,068, issued June 28, 1974, that a chemical debinding agent can be used to reduce the stiffness of the tissue paper and thereby increase its softness.

Chemical decoupling agents are described in various publications, such as U.S. Pat.
No. 862, issued to Hervey et al. On January 12, 1971. These materials include quaternary ammonium salts such as cocotrimethylammonium chloride, oleyltrimethylammonium chloride, di (hydrogenated) tallowdimethylammonium chloride and stearyltrimethylammonium chloride.

Emanuelsson et al., US Pat. No. 4,144,122, Mar. 1979
Published on March 13, discloses the use of a complex quaternary ammonium compound, such as bis (alkoxy (2-hydroxy) propylene) quaternary ammonium chloride, to soften the web. The authors have also attempted to overcome the loss of absorbency caused by the debinding agent by using nonionic surfactants such as the addition of fatty alcohols ethylene oxide and propylene oxide.

Armak Company of Chicago, Ill.
7 (1977), mention that the use of dimethyl di (hydrogenated) tallow ammonium chloride in combination with a fatty acid ester of polyoxyethylene glycol imparts both softness and absorbency to tissue paper webs. ing.

Representative findings for improving the paper web are described in U.S. Pat. No. 3,301,746, issued Jan. 31, 1967 to Stanford and Sisson. Despite the high quality of the paper webs produced by the process described in this patent, and the products formed from these webs, which have achieved commercial success, Research efforts are continuing.

For example, Becker et al., In U.S. Pat. No. 4,158,594, issued Jan. 19, 1979, describe that the method they alleged formed strong, soft fibrous sheets. More specifically, they report that the strength of a tissue paper web, which may have been softened by the addition of a chemical debinding agent, is such that during processing, one side surface of the web is reduced in a finely patterned arrangement. An adhesive (eg, acrylic latex rubber emulsion, water-soluble resin, or elastomeric adhesive) attached to one surface of the creped surface and the creped surface is adhered to the creped surface in a finely patterned arrangement, and the web is creped. It discloses that it can be strengthened by creping from the surface to form a sheet material.

Conventional quaternary ammonium compounds such as the well-known dialkyldimethylammonium salts (eg, ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di (hydrogenated) tallow dimethyl ammonium chloride, etc.) are effective. It is a chemical debinding agent. Unfortunately, these quaternary ammonium compounds are not hydrophilic. The inventors have discovered that the chemical softener composition of the present invention enhances both the softness and absorbency of fibrous cellulosic materials.

Further, by producing a chemical softener composition comprising these softener compounds in a substantially anhydrous form, product shipping costs are reduced (low weight), packaging material costs are reduced, and chemical softener compositions are reduced. The cost of the machinery required for the processing of the product is saved (fewer equipment is required for the production of the aqueous dispersion). In addition, the present invention provides the advantage of environmental safety as no organic solvents, especially volatile organic solvents commonly used in the production of concentrated softener compositions, are used.

It is an object of the present invention to provide a substantially anhydrous, self-emulsifying chemical softener composition that is effective in treating fibrous cellulosic materials.

Another object of the present invention is to provide a soft absorbent tissue paper product.

Yet another object of the present invention is to provide a method of making a soft absorbent tissue paper product.

These and other objects can be achieved by the use of the present invention, as will be apparent from the description below.

SUMMARY OF THE INVENTION The present invention is effective in treating fibrous cellulosic materials,
A substantially anhydrous, self-emulsifying chemical softener composition is provided. Briefly, an anhydrous, self-emulsifying chemical softener composition comprises: (Wherein each R ₂ substituent is C1~C6 alkyl or hydroxyalkyl group, or mixtures thereof, each R ₁ substituent is C14~C22 hydrocarbyl group or mixtures thereof, X ^- is a suitable And (b) glycerol, a polyglycerol having a weight average molecular weight of about 150 to about 800, and a weight average molecular weight of about 200.
A polyhydroxy compound selected from the group consisting of polyoxyethylene glycol and polyoxypropylene glycol, wherein the weight ratio of quaternary ammonium compound to polyhydroxy compound is from about 1: 0.1 to 0.1: 1. And
The polyhydroxy compound may be miscible with the quaternary ammonium compound at a temperature of at least 40 ° C. The chemical softener composition of the present invention is a stable, homogeneous, solid or viscous fluid at a temperature of about 20 ° C. or higher. This fluid can have a liquid or liquid crystal phase structure. The water content of the substantially self-emulsifying chemical softener composition is less than about 20% by weight, preferably the water content of the chemical softener composition is less than about 10% by weight, more preferably the chemical softener composition The water content of the product is less than about 5% by weight.

Examples of quaternary ammonium compounds suitable for use in the present invention include well-known dialkyl dimethyl ammonium salts such as ditallow dimethyl ammonium chloride (DTDMAC), ditallow dimethyl ammonium methyl sulfate (DTDMAMS), methyl There are di (hydrogenated) tallow dimethyl ammonium sulfate (DHTDMAMS) and di (hydrogenated) tallow dimethyl ammonium chloride (DHTDMAC).

Examples of polyhydroxy compounds useful in the present invention include glycerol, polyglycerol having a weight average molecular weight of about 150 to about 800, and polyoxyethylene glycol having a weight average molecular weight of about 200 to about 4000; About 200-600 polyoxyethylene glycols are preferred.

Briefly, the method of making a tissue web of the present invention comprises forming a paper stock from the above ingredients, depositing the paper stock on a perforated surface, such as a Ford linear wire, and depositing the paper stock. Removing moisture from the stock.

All percentages, ratios and ratios herein are expressed by weight unless otherwise indicated.

BRIEF DESCRIPTION OF THE DRAWINGS The claims at the end of the specification particularly point out the invention,
Although clearly claimed, it is believed that the present invention will be better understood upon reading the following description in conjunction with the accompanying drawings.

FIG. 1 is a phase diagram of dioctadecyldimethylammonium methylsulfate (DODMAMS) and DHTDMAMS.

 FIG. 2 is a state diagram of the DODMAMS / PEG-400 system.

FIG. 3 shows a 6% dispersion of a 2% dispersion formed by diluting a 1: 1 weight ratio solid premix of the system DHTDMAMS and PEG-400.
3 is a cryo-transmission micrograph taken at 3,000 ×.

FIG. 4 shows a 6% dispersion of a 2% dispersion formed by diluting a 1: 1 weight ratio liquid premix of the DHTDMAMS and PEG-400 system.
It is a low-temperature transmission microscope photograph taken at 3,000 times.

FIG. 5 is a cold transmission micrograph taken at 63,000 times of a 2% dispersion formed by diluting a 1: 1 weight ratio liquid premix of DHTDMAC and a mixture of glycerol and PEG-400.

 Hereinafter, the present invention will be described in more detail.

DETAILED DESCRIPTION OF THE INVENTION While the claims at the end of this specification particularly point out and distinctly claim the subject matter of the present invention, it is believed that the present invention will be more accurately understood upon reading the following description and accompanying examples. It is considered understandable.

As used herein, the term “viscous fluid” means a fluid having a viscosity at 20 ° C. of about 10,000 centipoise or greater.

As used herein, the term "homogeneous mixture" refers to a composition in which a quaternary ammonium and a polyhydroxy compound are dissolved or dispersed in one another.

As used herein, the term "self-emulsifying" refers to the minimum shear, heat, dispersing aid, when added to a liquid carrier such as water.
Etc. means a composition which forms a uniform colloidal dispersion.

As used herein, the terms "tissue paper web, paper web, web, paper sheet and paper product" are all used in the process of forming an aqueous paper stock, which is deposited on a perforated surface, such as a Ford linear wire. Means a sheet of paper made by a process comprising the step of removing water from the stock, with or without compression, by gravity or vacuum drainage and evaporation.

The term "aqueous papermaking stock" as used herein is an aqueous slurry of papermaking fibers and the chemicals described below.

The first step of the present invention is the formation of an aqueous papermaking stock. The stock comprises papermaking fibers (hereinafter sometimes referred to as wood pulp), all described below, and a mixture of at least one quaternary ammonium compound and at least one polyhydroxy compound.

All wood pulp is believed to constitute the papermaking fibers used in the present invention. However, other cellulosic fiber pulps, such as cotton liners, bagasse, rayon, etc., can be used, all falling within the scope of the claims. Wood pulp useful herein includes chemical pulp, such as kraft, sulfite and sulfate pulp, and mechanical pulp, including groundwood pulp, thermomechanical pulp, and chemically modified thermochemical pulp (CTMP). Pulp from both deciduous and coniferous trees can be used. From any or all of the above materials, as well as other non-fibrous materials, such as recycled paper that may contain fillers and adhesives used to facilitate the original papermaking operation Fibrous fibers can be used in the present invention. Preferably, the papermaking fibers used in the present invention comprise kraft pulp from northern softwood.

Anhydrous, self-emulsifying chemical softener composition The present invention comprises, as an essential component, a mixture of a quaternary ammonium compound and a polyhydroxy compound. The ratio of the quaternary ammonium compound to the polyhydroxy compound is about
1: 0.1-0.1: 1, preferably the weight ratio of quaternary ammonium compound to polyhydroxy compound is about 1: 0.3-0.1.
3: 1 and more preferably the weight ratio of quaternary ammonium compound to polyhydroxy compound is about 1: 0.7-0.7-1.
However, this ratio depends on the molecular weight of the particular polyhydroxy compound and / or quaternary ammonium compound used.

Each of these types of compounds is described in detail below.

A. Quaternary Ammonium Compound A self-emulsifying chemical softener composition substantially free of water comprises, as an essential component, a compound of the formula A quaternary ammonium compound having the formula:

In the above structure, each R ₁ is a C 14 -C 22 hydrocarbon group, preferably a tallow, R ₂ is a C ₁ -C 6 alkyl or hydroxyalkyl group, preferably a C ₁ -C 3 alkyl, and X ⁻ is a halide. (Eg chloride or bromide) or a suitable anion such as methyl sulfate. Edited by Swern, Bailey's Industrial Oil and Fat Products, No. 3
As described in the edition, John Wiley and Sons (New York 1964), tallow is a naturally occurring substance with various compositions. In the above publication edited by Swern, Table 6.13 indicates that generally more than 78% of the fatty acids of tallow contain 16 or 18 carbon atoms. Generally, half of the fatty acids present in the tallow are unsaturated, mainly in the form of oleic acid. Synthetic as well as natural "tallows" fall within the scope of the present invention. Preferably, each R ₁ is C16~C18 alkyl, most preferably each R ₁ is a linear C18 alkyl. Preferably, R
₂ is methyl and X ^- is chloride or methyl sulfate.

Examples of quaternary ammonium compounds suitable for use in the present invention include well-known dialkyl dimethyl ammonium salts such as ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di (hydrogenated) tallow. There is dimethyl ammonium, but di (hydrogenated) tallow dimethyl ammonium methyl sulfate is preferred. This special substance is available in Sherex, Dublin, Ohio.
Commercially available from Chemical Company Inc. under the trade name "Varisoft ^R 137".

B. Polyhydroxy Compound The chemical softener composition contains a polyhydroxy compound as an essential component.

Examples of polyhydroxy compounds useful in the present invention include glycerol, polyglycerol having a weight average molecular weight of about 150 to about 800, and weight average molecular weight of about 200 to about 4000, preferably about 200 to about 1000, and most preferably about 200 to about 600
Of polyoxyethylene glycol and polyoxypropylene glycol. Weight average molecular weight about 200-
About 600 polyoxyethylene glycols are particularly preferred. Mixtures of the above polyhydroxy compounds can also be used. For example, glycerol and a weight average molecular weight of about 200 to
Mixtures of about 1000, more preferably about 200 to about 600 polyoxyethylene glycols are useful in the present invention. Preferably, the weight ratio of glycerol to polyoxyethylene glycol is about 10: 1 to 1:10.

A particularly preferred polyhydroxy compound is polyoxyethylene glycol having a weight average molecular weight of about 400. This substance is available from Union Carbid in Danbury, Connecticut.
Commercially available from e Company under the trade name "PEG-400".

The anhydrous, self-emulsifying chemical softener composition, ie, a mixture of a quaternary ammonium compound and a polyhydroxy compound, is preferably diluted to a desired concentration to form a dispersion of the quaternary compound and the polyhydroxy compound. It is then added to the aqueous slurry of papermaking fibers, or stock, at the wet end of the papermaking machine at a suitable point prior to the Ford linear wire or sheet forming stage. However, applying the above chemical softener composition after wet tissue web formation and before drying the web also significantly improves softness, absorbency, and wet strength, of course,
It falls within the scope of the present invention.

The chemical softener composition has been found to be more effective when first mixed together with the quaternary ammonium compound and the polyhydroxy compound before being added to the papermaking stock. In a preferred method, the polyhydroxy compound is first heated to about 66 ° C (15 ° C), as described in more detail in Example 1 below.
Heat to a temperature of 0 ° F. and then add the quaternary ammonium compound to the hot polyhydroxy compound to form a homogeneous liquid. The weight ratio of quaternary ammonium compound to polyhydroxy compound is from about 1: 0.1 to 0.1: 1, preferably the weight ratio of quaternary ammonium compound to compound is about 1: 0.
3 to 0.3: 1, and more preferably the weight ratio of quaternary ammonium compound to compound is about 1: 0.7 to 0.7: 1, although the ratio may vary depending on the particular compound used and / or the quaternary ammonium compound. Depends on the molecular weight of The water content of the chemical softener composition is less than about 20% by weight, preferably the water content of the chemical softener composition is less than about 10% by weight, and more preferably the water content of the chemical softener composition is about 5%. % By weight. It is important that the chemical softener composition be stable at a temperature of at least about 20 ° C. and be a homogeneous, solid or viscous liquid.

The substantially anhydrous, self-emulsifying chemical softener composition can be premixed at the drug supplier (eg, Sherex, Dublin, Ohio). By producing a chemical softener composition comprising these softener compounds in a substantially anhydrous form, product shipping costs are reduced (low weight), packaging material costs are reduced, and the chemical softener composition is reduced. Machine costs required for processing are saved (fewer equipment is required for the production of aqueous dispersions). Furthermore, the invention provides the advantage of environmental safety, since no organic solvents, in particular no volatile organic solvents, are used. The end user of the chemical softener composition simply dilutes the mixture with a liquid carrier (ie, water) to form an aqueous dispersion of the quaternary ammonium compound / polyhydroxyl compound mixture, which is then added to the paper stock. Just add it. A homogeneous mixture of a quaternary ammonium and a polyhydroxy compound can exist in a solid or liquid state before being dispersed in an aqueous medium. Preferably, the mixture of quaternary ammonium compound and polyhydroxy compound is diluted with a liquid carrier, such as water, to a concentration of about 0.01 to about 25% by weight of the softener composition before adding to the paper stock. The temperature of the liquid carrier is preferably from about 20C to about 80C. After mixing, the quaternary ammonium compound and the polyhydroxy compound are present as dispersed particles in the liquid carrier, preferably having an average particle size of about 0.01 to 10 microns, most preferably about 0.1 to about 1.0 microns. As shown in FIGS. 3-5, the dispersed particles are present in the form of closed vesicles or open particles.

Unexpectedly, it has been found that the adsorptivity of the polyhydroxy compound on paper is significantly enhanced when the polyhydroxy compound is premixed with the quaternary ammonium compound and added to the paper in the manner described above. . In fact, at least 20% of the polyhydroxy and quaternary ammonium compounds added to the fibrous cellulose are retained, preferably
The retention of the quaternary ammonium compound and the polyhydroxy compound is about 50% to 90% of the amount added.

Importantly, adsorption occurs within a concentration and time frame that is practical for use in papermaking. To elucidate the surprisingly high retention of polyhydroxy compounds on paper, di (hydrogenated) tallow dimethyl ammonium methyl sulfate (DH
The physical science of melt solutions and aqueous dispersions of TMDMAMS) and polyoxyethylene glycol 400 was studied.

Without being bound by theory or limiting the present invention, the following discussion is provided to illustrate how quaternary ammonium compounds promote adsorption of polyhydroxy compounds onto paper.

DHTMDMAMS The physical state of di (hydrogenated) tallowdimethylammonium methylsulfate, R ₂ N ⁺ (CH ₃ ) ₂ , CH ₃ OSO ₃ − and information on DODMAMS are provided by X for commercial mixtures.
Given by line and NMR (nuclear magnetic resonance) data. D
ODMAMS (dioctadecyldimethylammonium methylsulfate, (C ₁₈ H ₃₇ ) ₂ N ⁺ (CH ₃ ) ₂ , CH ₃ OSO ₃ −) is a major component of DHTDMAMS and serves as a model compound for commercial mixtures. It is advantageous to first consider the simpler DODMAMS system and then the more complex commercially available DHTDMAMS mixtures.

Depending on the temperature, DODMAMS provides two polymorphs (Xβ
And Xα), a thin liquid crystal (Lam) liquid crystal, or a liquid phase (FIG. 1).
Xβ crystals are present at below room temperature to 47 ° C. At this temperature X
β converts to polymorphic Xα crystals and at 72 ° C. to the Lam liquid crystal phase. This phase further converts at 150 ° C. to an isotropic liquid. D
HTDMAMS is expected to resemble DODMAMS in its physical behavior, but the temperature of the phase inversion is lower and broader.
For example, the conversion of Xβ to Xα is performed at 47 ° C. in DODMAMS.
Instead, it occurs at 27 ° C. for DHTDMAMS. Further, the calorimetric data show that DHTDMAMS converts to several types of crystal φLam phases instead of one type in DODMAMS. The highest onset temperature for these conversions is 56 ° C., which is in good agreement with the X-ray data.

DODMAC (dioctadecyl dimethyl ammonium chloride)
Is DODMA because the Lam liquid crystal phase is not present in this compound.
Exhibits qualitatively different behavior from MS (Laughlin et al., Journal of Physical Chemistr, incorporated herein by reference).
y, Physical science of dioctadecyldimethylammonium chloride-water system. 1. Equilibrium phase behavior, see 1990, Vol. 94, pp. 2546-2552). However, this difference is not believed to be important for the use of this compound (or its commercially available analog DHTDMAC) in paper processing.

Mixture of DHTDMAMS and PEG400 A 1: 1 weight ratio mixture of these two materials was studied and a valid model for the phase behavior of this system is shown in FIG. The graph shows that DODMAMS and PEG are immiscible at elevated temperatures and coexist as two liquid phases. Cooling the mixture of these two liquids in this area will result in Lam
The phases separate from the mixture. Therefore, this study shows that these two materials are immiscible at high temperatures but not at low temperatures.
It shows that they can be mixed in the Lam liquid crystal phase. At lower temperatures, the crystalline phase separates from the Lam phase and these compounds become immiscible again.

Therefore, these studies show that DHTDMAMS and PE
It shows that to form a good dispersion of G-400, the premix diluted with water should be kept within an intermediate temperature range where the two compounds are miscible.

Mixture of DHTDMAC and PEG400 From these two phase studies using a serial dilution method,
It can be seen that their physical behavior is significantly different from that of DHTDMAMS. No liquid crystal phase is seen. These compounds are miscible within a wide temperature range, suggesting that dispersions can be prepared from these mixtures over a corresponding temperature range. In particular, there is no upper limit of miscibility.

Preparation of Dispersions Dispersions of any of these substances can be prepared by diluting water with a premix maintained at a temperature at which the polyhydroxy compound and the quaternary ammonium salt are miscible. It does not matter whether they are miscible in the liquid crystal phase (as in DHTDMAMS) or in the liquid phase (as in DHTDMAC). Since neither DHTDMAMS nor DHTDMAC is soluble in water, dilution of either dry phase with water precipitates the quaternary ammonium compound as small particles. Regardless of whether the dry solution was liquid or liquid crystal, both quaternary ammonium compounds precipitate as liquid crystal phases in dilute aqueous solution at elevated temperatures. The polyhydroxy compound is soluble in water in all proportions and does not precipitate.

Cryo-electron microscopy shows that the size of the particles present is about 0.1-1.0 micrometer and the structure varies greatly. Some are sheets (curved or flat) and some are closed vesicles. The film of all these particles is a bilayer of molecular size, with groups of heads exposed to water and tails together. PEG is presumed to be associated with these particles. By applying the dispersion thus produced to paper, quaternary ammonium ions adhere to the paper, strongly promoting adsorption of the polyhydroxy compound onto the paper, and improving softness and wettability.

State of the Dispersion Upon cooling the above dispersion, partial crystallization of the material in the colloidal particles may occur. However, it is likely that a long time (perhaps several months) will be required to achieve equilibrium, so the thin film within the particles that interacts with the paper is disordered.

When the fibrous cellulosic material dries, DHTDMAMS and
Vesicles containing PEG are thought to break. When the vesicles break, most of the PEG component penetrates into the interior of the cellulose fibers, where it enhances the flexibility of the fibers. What matters is PE
Part of G is retained on the fiber surface, where it acts to increase the rate of absorption of the cellulose fibers. Due to the ionic interaction, most of the DHTDMAMS remains on the surface of the cellulosic fibers, where it enhances the surface feel and softness of the paper product.

The second step of the method of the present invention is to deposit papermaking stock on a porous surface using the chemical softener composition described above as an additive, and the third step is to deposit such a paperstock. To remove moisture from the paper stock. The techniques and equipment used to accomplish these two processing steps will be apparent to those skilled in the papermaking art. Preferred tissue paper embodiments of the present invention comprise from about 0.05% to about 5.0%, more preferably from about 0.03 to 0.5% by weight, based on dry fiber.
Of the chemical softener compositions disclosed herein.

The present invention can be used for general tissue paper, including regular felt pressed tissue paper, bulky, patterned compacted tissue paper, and bulky, uncompressed tissue paper. However, the present invention is not limited to these.
The tissue paper can have a homogeneous or multi-layered structure, and the tissue paper product produced therefrom can have one or more multi-layered structures. Tissue structures formed from layered paper webs are disclosed in U.S. Pat.No. 3,994,771, Morgan,
Jr. et al., Issued November 30, 1976. In general, the soft, bulky absorbent paper structure of the composite material placed in the wet state is preferably made from two or more plies comprising different types of fibers. These layers are formed by depositing a separate stream of diluted fiber slurry onto one or more infinitely porous screens, where the fibers are commonly used in tissue paper making, A long softwood and relatively short hardwood fiber. The layers are then combined to form a layered composite web. The layer web is then conformed to the surface of the open mesh drying / imprinted fabric by pressing it against the fluidized web and then thermally pre-dried on the fabric as part of a low density papermaking process. The layered web can be sectioned by fiber type or the fiber content of each layer can be substantially equal. Tissue paper, preferably at a basis weight of 10 g / m ² ~ about 65 g / m ^2, density of about 0.60 g / cm ³ or less. Preferably, basis weight of about 35 g / m ² or less, a density of about
0.3 g / cm ³ or less. Most preferably the density is about 0.04 cm ³
~ Is about 0.20cm ^3.

Conventional pressed tissue papers and methods for making such papers are well known in the art. Such papers are generally made by depositing paper stock on perforated formed wire. This formed wire is often referred to in the art as a Ford linear wire. After the stock has been deposited on the forming wire, it is called a web. The web is sent to a dewatering felt where the web is compressed to dewater and dried at elevated temperatures. Techniques and representative equipment for producing webs by the above process are well known to those skilled in the art. In a typical process, a low consistency pulp stock is supplied from a pressurized headbox. The headbox has openings for delivering thin deposits of pulp stock onto Ford linear wire and forming a wet web. The web is then dewatered by vacuum, typically to a consistency of about 7% to about 25%.
The web is dewatered (relative to the total weight of the web) and further dried by a compression operation, wherein the web is pressed by an opposing mechanical member, for example a cylindrical roll.

The dewatered web is then further compressed and dried in a stream drum device, referred to in the art as a Yankee dryer. In a Yankee dryer, the pressure can be generated by mechanical means, such as a cylindrical drum that opposes the web. A vacuum can also be applied to the web as it is pressed against the Yankee surface. Multiple Yankee dryer drums can be used, with additional compression between the drums as desired. The tissue tissue structure formed is hereinafter referred to as a normal, compressed tissue structure. Such a sheet is considered densified because it is subjected to significant mechanical compression while the fibers are wet and then dried in the compressed state.

Tissue paper densified in a pattern is characterized by having a relatively low fiber density, a relatively large bulk surface, and a row of densified areas having a relatively high fiber density. The bulky side is the pillow area
egion). The densified area is also called a knuckle area. The densified areas may be discontinuously spaced in the bulky surface, or may be fully or partially interconnected in the bulky surface. A preferred method of making a patterned densified tissue web is described in U.S. Pat. No. 3,301,746, Jan. 31, 1967, all incorporated herein by reference.
U.S. Pat.No. 3,974,025, issued to anford and Siaaon, 1
Issued on August 10, 976 to Peter G. Ayers, and issued to U.S. Patent No. 4,191,609; issued March 4, 1980 to Paul D. Trokhan; and issued to U.S. Patent No. 4,637,859, issued January 20, 1987 to P.
Published by aul D. Trokhan, disclosed in

Generally, the patterned densified web is preferably formed by depositing paper stock on a perforated forming wire, such as a Ford linear wire, to form a wet web, which is then coated with a row of supports. Place in close proximity to Squeezing the web against the row of supports, thereby geometrically corresponding to the interface between the row of supports and the wet web,
A densified area is formed in the web. The remainder of the web that was not compressed during this operation is called the bulky surface. This bulky surface can be further densified, for example, by applying fluid pressure in a vacuum apparatus or blow dryer, or by mechanically pressing the web against a row of supports. it can. The web is dewatered so that the bulky surface is not substantially pressed and optionally pre-dried. This is preferably done in such a way that the bulky surface is not compressed, for example by fluid pressure in a vacuum-type device or blow-through dryer, or by mechanically pressing the web against a row of supports. The dewatering, optional predrying, and densification zone forming operations can be integrated or partially integrated to reduce the total number of manufacturing steps performed. Following formation of the densified area, dewatering, and optional predrying, dry completely, preferably still avoiding mechanical compression. Preferably, about 8% to about 55% of the tissue paper surface includes densified knuckles having a relative density of at least 125% of the bulk area density.

The row of supports is preferably an imprinted carrier fabric having knuckles arranged in a pattern, which acts as a row of supports that facilitates formation of densified areas when pressed.
ting carrier fabrics). The pattern of knuckles constitutes the row of supports described above. The imprinted carrier fabric is disclosed in U.S. Pat.No. 3,301,746, all of which are incorporated herein by reference.
No. 3, Sanford and Sisson, issued Jan. 31, 1967; U.S. Pat.No. 3,821,068; Salvucci, Jr et al., Issued May 21, 1974; U.S. Pat.No. 3,974,025; Patent No. 3,573,164, Friedberg et al., March 1971.
30th, U.S. Pat.No. 3,473,576, Amneus, 10 October 1969
Issued on March 21, U.S. Pat.No. 4,239,067, Trokhan, 1980
Issued December 16, and U.S. Patent No. 4,528,239, Trokha
n, issued July 9, 1985.

Preferably, the stock is first formed into a wet web on a perforated formed carrier, such as a Ford linear wire. The web is dewatered and conveyed to the imprint fabric. Alternatively, the stock can be first deposited on a perforated support that also acts as an imprint fabric. After molding, the wet web is dewatered and preferably thermally pre-dried to a selected fiber consistency of about 40% to about 80%. Dewatering is preferably performed in a suction box or other vacuum device or blow dryer. Before the web is completely dried, the knuckle imprint of the imprint fabric is pressed into the web as described above. In one method, this is done by applying mechanical pressure, for example by placing a web between a nip roll supporting the imprinted fabric and a drying drum, for example a Yankee dryer, and placing the nip roll on the surface of the drying drum. This can be achieved by pressing. Preferably, the web is formed into a stamped fabric and then completely dried by applying a fluid pressure with a vacuum device such as a suction box or a blow-through dryer. Fluid pressure can be applied during the initial dewatering, in a separate, subsequent step, or a combination thereof, to effect imprinting of the densified area.

Uncompressed, non-patterned densified tissue paper structures are described in U.S. Pat. No. 3,812,000, Joseph L. Salvucci, Jr. and Peter N. Yiannos, May 21, 1974, both of which are incorporated herein by reference. And U.S. Pat.No. 4,208,459, Henry E. Becker, Albert L. McCon
ell and Richard Schutte, issued June 17, 1980. Generally, uncompressed, non-patterned densified tissue paper structures are obtained by depositing papermaking stock onto a perforated forming wire, such as a Ford Linear wire, to form a wet web, and from the web. Manufactured by draining and removing excess water and creping the web without mechanical compression until the fiber consistency of the web is at least about 80%.
Water is removed from the web by vacuum dewatering and thermal drying. The resulting structure is a soft but weak, bulky, relatively uncompressed sheet of fibers. Preferably, the binder is partially applied to the web prior to creping.

The tissue paper web of the present invention can be used in any application where a soft absorbent tissue paper web is required. A particularly advantageous use of the tissue paper web of the present invention is in paper towels, toilet tissue and cosmetic tissue products. See, for example, U.S. Pat. No. 3,414,459, Wells, issued Dec. 3, 1968, incorporated herein by reference.
The two tissue paper webs of the present invention can be embossed and secured with an adhesive in a face-to-face relationship to form a double paper towel, as disclosed in US Pat.

Molecular Weight Measurement A. Introduction A substantial property that distinguishes polymeric materials is the size of their molecules. The properties that allow polymers to be used in a variety of applications derive almost entirely from their polymeric nature. To fully characterize these materials, it is essential to have some means of measuring their molecular weight and molecular weight distribution. While it is more accurate to use the term relative molecular mass rather than molecular weight, the term molecular weight is more commonly used in polymer technology. Measuring the molecular weight distribution is not always practical. However, this is becoming more common using chromatography techniques. Rather, it relies on molecular weight averaging to describe molecular size.

B. Molecular Weight Average Given a simple molecular weight distribution that is representative of the weight fraction (w _i ) of molecules having a relative molecular mass (M _i ), some useful averages can be defined. The average based on the number of molecules (N _i ) having a particular size (M _i ) is the number average molecular weight give.

An important aspect of this definition is that the number average molecular weight in grams includes the Avogadro number of the molecule. This definition of molecular weight is consistent with the molecular weight of monodisperse species, ie, molecules having the same molecular weight. More importantly, n can be easily calculated if the number of molecules in a particular mass of polydisperse polymer can be determined by either method. This is the basis for comprehensive characterization.

The average based on the weight fraction (W _i ) of molecules having a specific mass (M _i ) is the weight average molecular weight give.

w is a more useful means of expressing the molecular weight of the polymer than n because it more accurately reflects properties such as the melt viscosity and mechanical properties of the polymer, and is therefore used in the present invention.

Analytical and Test Procedures The analysis of the amount of treatment chemical used here, ie, retained on the tissue paper web, can be performed by any method employed in the art.

A. Quantitative analysis of quaternary ammonium and polyhydroxy compounds For example, the amount of quaternary ammonium compounds, such as di (hydrogenated) tallowdimethylammonium methylsulfate (DHTDMAMS), retained by tissue paper can be determined by using DHTDMAMS in an organic solvent. Can be measured by anion titration using dimdium bromide as an indicator, and the amount of polyhydroxy compound, e.g., PEG-400, extracted with an aqueous solvent, e.g., water, followed by PE in extracts by gas chromatography or colorimetric techniques
It is determined by measuring the amount of G-400. These methods are examples and do not exclude other methods useful for measuring the amount of a particular component retained on a tissue paper.

B. Hydrophilicity (absorptivity) The hydrophilicity of the tissue paper indicates the tendency of the tissue paper to get wet with water. The hydrophilicity of the tissue paper can be quantified to some extent by measuring the time required for the dried tissue paper to completely wet with water. This time is called the "wetting time". To perform a repeatable test with a constant wetting time, the following procedure can be used for the wetting time measurement. First, a conditioned sample unit sheet of tissue paper (the environmental conditions for testing the paper sample are 23 + 1 ° C. and 50 + 2% RH as specified in TAPPI Method T402), about 4P-3 / 8
Prepare an inch x 4-3 / 4 inch (approximately 11.1 cm x 12 cm).
1.9 cm) to about 1 inch (about 2.5 cm) balls, and thirdly, place the rolled sheet at 23 ± 1 ° C. on an amount of distilled water and simultaneously start the timer, When the rolled sheet is completely wet, stop the timer and read. The completely wet state is visually observed.

The hydrophilicity of the tissue paper embodiment of the present invention can, of course, be measured immediately after manufacture. However, the hydrophobicity may increase significantly after the first two weeks after tissue paper production, i.e. after aging for two weeks after paper production. Therefore, the above wetting time is preferably measured after such two weeks. Therefore, the wet time measured at room temperature after aging for two weeks is referred to as "two week wet time".

C. Density The term used here, tissue paper density,
Is the average density calculated by dividing the basis weight of the paper by the thickness, with the appropriate unit conversions contained therein. The thickness of the tissue paper used here is 95g / in ²
(15.5 g / cm ² ) is the thickness of the paper when a compression load is applied.

Optional Chemical Ingredients Other chemicals commonly used in papermaking do not significantly affect the softening and absorbency of the fibrous material and enhance the action of the chemical softener composition as described herein. Water-free, self-emulsifying, biodegradable chemical softener composition or papermaking stock.

For example, surfactants can be used to treat the tissue paper webs of the present invention. If used,
The surfactant charge is preferably from about 0.01 to about 2.0% by weight based on the dry fiber weight of the tissue paper. Preferably, the surfactant has an alkyl chain having 8 or more carbon atoms. Representative anionic surfactants are linear alkyl sulfonates and alkyl benzene sulfonates. Representative nonionic surfactants are alkyl glycosides, including alkyl glycoside esters, such as Cro, available from Croda, Inc. (New York, NY).
desta SL-40, U.S. Pat.No. 4,011,389, March 8, 1977
Alkyl glycoside ethers, and alkyl polyethoxylated esters, described in WKLangdon, et al., For example, Glyco Chemicals, Inc. (Grrenwich,
Pegosperse 200 ML and Phone Phulenc from CT)
IGEPAL RC- available from Corporation (Cranbury, NJ)
520.

Other types of chemicals that can be added include dry strength additives to increase the tensile strength of the tissue web. Examples of dry strength additives include carboxymethylcellulose and cationic polymers from the Acco family of drugs, such as Acco 771 and Acco 514, with the Acco family of drugs being preferred. The substance is available from Americ, Wayne, NJ
Commercially available from an Cyanamid Company. If used, the amount of dry strength additive is from about 0.01 to about 1.0% by weight based on the dry fiber weight of the tissue paper.

Other types of chemicals that can be added include wet strength additives to increase wet rupture of tissue webs. The present invention provides for the optional use of from about 0.01 to about 3.0% by weight, more preferably from about 0.3 to
It may contain about 1.5% by weight of a water-soluble permanent wet strength resin.

There are several types of permanent wet strength resins useful herein. In general, resins that have been and will continue to be used in the papermaking field are useful here. Numerous examples are provided in Westfelt, supra, which is incorporated herein by reference.

Usually, the wet strength resin is a water-soluble cationic material. That is, these resins are water-soluble when added to papermaking stock. Subsequent treatments, such as cross-linking, make the resin insoluble in water is well possible and even desirable. In addition, certain resins are only soluble under special conditions, for example, within a limited pH range.

Wet strength resins are generally believed to undergo crosslinking or other curing reactions after depositing on, within, or between papermaking fibers. Crosslinking or curing usually does not occur as long as large amounts of water are present.

Various polyamide-epichlorohydrin resins are used in particular. These materials are low molecular weight polymers with reactive functional groups, such as amino, epoxy, and azetidinium groups. The patent literature describes many methods for producing such substances. U.S. Pat.No. 3,700,623, both incorporated herein by reference, Keim, Oct. 24, 1972.
And U.S. Pat.No. 3,772,076, Nov. 13, 1973
Issued to Keim on a date is an example of such a patent.

Hercules Incorpora in Wilmington, Delaware
ted from Kymene ^R 557H and Kymene polyamides are commercially available under the trade name ^R 2064 - epichlorohydrin resins are particularly useful in the present invention. These resins are generally described in the above patent to Keim.

Base-activated polyamide-epichlorohydrin resins useful in the present invention are available from Mons, St. Louis, Mo.
Santo Res trade name from anto Company, e.g. Santo Res
31, sold in. These types of materials are generally described in U.S. Pat.No. 3,855,15, all of which are incorporated herein by reference.
No. 8, issued to Petrovich on December 17, 1974, 3,899,388
Issue, issued to Petrovich on August 12, 1975, No. 4,129,528
Issue No. 4,147,586 issued to Petrovich on December 12, 1978
Issued on April 3, 1979 to Petrovich and 4,222,9
No. 21, issued to Van Eenam on September 16, 1980.

Other water-soluble cationic resins useful herein are the American Cyanamid Company of Stamford, Connecticut.
Is a polyacrylamide resin sold under the trademark Parez, eg, Parez 631NC. These materials are generally described in U.S. Pat.
No. 6,932, issued to Coscia et al. On January 19, 1971, and
3,556,933, issued Jan. 19, 1971 to Williams et al.

Other types of water-soluble resins that are useful in the present invention include acrylic emulsions and anionic styrene-butadiene latex. Many examples of these types of resins are disclosed in U.S. Pat.No. 3,844,880, M
eisel, Jr, et al., Oct. 29, 1974.

Still other water soluble cationic resins that can be used in the present invention are urea formaldehyde and melamine formaldehyde resins. These polyfunctional and reactive polymers have molecular weights on the order of thousands. More common functional groups include nitrogen-containing groups such as amino groups and methylol groups appended to nitrogen.

Although not preferred, polyethyleneimine-type resins can also be used in the present invention.

The water-soluble resins, including their preparation, are described in more detail in TAPPI Monograph Series No. 29, wet strength in paper and cardboard, Pulp and Paper Technical Association (New York; 1965), which is hereby incorporated by reference. Have been. As used herein, the term "permanent wet strength resin" refers to a resin that allows a large portion of its initial wet strength to be maintained for at least more than 2 minutes when the paper sheet is placed in an aqueous medium.

The above-mentioned wet strength additives result in paper products having permanent wet strength, that is, paper products which, when placed in an aqueous medium, retain most of their initial wet strength for a long time. However, the permanent wet strength in certain paper products can be an unwanted and undesirable property. Toilet tissue and the like are discarded after being used for a short time by a purification mechanism or the like. These mechanisms can become clogged if the paper product permanently retains its hydrolysis resistance properties. More recently, temporary wet strength additives have been added to paper products where the wet strength is sufficient for the intended use, but which fades with immersion in water. The decrease in wet strength makes it easier for the paper product to flow through the purification mechanism.

Examples of suitable temporary wet strength resins include modified starch temporary wet strength agents such as National Starch and Chem
There is a National Starch 78-0080 marketed by ical Corporation (New York, New York). This type of wet strength agent can be prepared by reacting dimethoxyethyl-N-methyl-chloroacetamide with a cationic starch polymer. The modified starch temporary wet strength agent is
U.S. Pat.No. 4,675,394, Solar
ek et al., issued June 23, 1987. Preferred temporary wet strength resins include U.S. Patent No. 4,981,557, Bjorkquist, January 1, 1991, which is hereby incorporated by reference.
There is a resin described in, issued on the day.

With respect to both types and embodiments of both permanent and temporary wet strength resins described above, of course, these resins are examples and do not limit the scope of the invention.

Mixtures of compatible wet strength resins can also be used in the practice of the present invention.

The above optional chemical additives are merely examples and do not limit the scope of the invention.

The following examples illustrate, but do not limit, the practice of the invention.

Example 1 The purpose of this example was to provide a substantially anhydrous, self-emulsifying composition comprising a mixture of di (hydrogenated) tallow dimethyl ammonium methyl sulfate (DHTDMAMS) and polyoxyethylene glycol 400 (PEG-400). It is an illustration of a method that can be used to produce a chemical softener composition.

An anhydrous, self-emulsifying chemical softener composition is prepared by the following procedure: 1. Weigh out equivalents of DHTDMAMS and PEG-400 separately, 2. Heat PEG to about 66 ° C (150 ° F), 3.DHTDM
Dissolve AMS in PEG, form a melt at 66 ° C (150 ° F), mix well to form a homogeneous mixture of DHTDMAMS and PEG, and mix the homogeneous mixture of 5. (4). Cool to solid form at room temperature.

The (5) substantially anhydrous, self-emulsifying chemical softener composition can be obtained from a drug supplier (eg, Dublin, Ohio).
Sherex) and then economically transported to the end user of the chemical softener composition, where it can be diluted to the desired concentration.

Example 2 The purpose of this example is to provide a substantially anhydrous, self-emulsifying chemistry comprising a mixture of di (hydrogenated) tallow dimethyl ammonium methyl sulfate (DHTDMAMS) and a mixture of glycerol and PEG-400. It is an illustration of a method that can be used to produce a softener composition.

A substantially anhydrous, self-emulsifying chemical softener composition is prepared by the following procedure: 1.Glycerol and PEG-400.
Of the mixture in a weight ratio of about 75:25, and 2.
AMS and the mixture of (1) are weighed separately and the mixture of (1) is heated to about 66 ° C. (150 ° F.), 4. DHTDMAMS is dissolved in (3), and ) To form a molten solution; 5. Mix well to form a homogeneous mixture of DHTDMAMS and (3); 6. Cool the homogeneous mixture of (5) to a solid form at room temperature.

The substantially anhydrous, self-emulsifying chemical softener composition of (6) can be obtained from a drug supplier (eg, Dublin, Ohio).
(Sherex) and then economically transported to the end user of the chemical softener composition where it can be diluted to the desired concentration.

Example 3 The purpose of this example was to use a blow-through dry papermaking technique to prepare the solid state of di (hydrogenated) tallow dimethyl ammonium methyl sulfate (DHTDMAMS) and polyoxyethylene glycol 400 (PEG-400). FIG. 3 illustrates a method of making a soft absorbent paper towel sheet treated with a substantially anhydrous, self-emulsifying chemical softener composition comprising a premix and a permanent wet strength resin.

The practice of the present invention uses a pilot scale Ford linear paper machine. First, a substantially anhydrous, self-emulsifying chemical softener composition is prepared according to the procedure of Example 1, wherein a solid-state, homogeneous premix of DHTDMAMS and PEG-400 is prepared from water. Tank (pH about 3, temperature about
(66 ° C.) to form a vesicle dispersion of less than 1 micron. The particle size of the vesicle dispersion is measured using light microscopy techniques. Particle size is from about 0.1 to about 0.1 microns.
FIG. 3 is a low-temperature transmission micrograph taken at 63,000 times of a 1: 1 weight ratio vesicle dispersion of DHTDMAMS and PEG-400.
FIG. 3 shows that the particles have one or two bilayer-thick films and their geometry ranges from closed / open vesicles to disc-like structures and sheets.

Second, a 3% by weight aqueous slurry of NSK is prepared in a conventional lee pulper. Gently purify the NSK slurry,
Permanent wet strength resin (ie DE, Wilmington's Herc
A 2% solution of Kymene ^R 557H, commercially available from ules company, is added to the NSK stock pipe in a proportion of 1% by weight of dry fiber. Kymene ^R
Adsorption of 557H to NSK is enhanced by an in-line mixer. After the in-line mixer, a 1% solution of carboxymethylcellulose (CMC) is added to about 0.2% by weight of dry fiber.
To increase the dry strength of the fibrous base material. CMC
Can be enhanced by an in-line mixer. Then, a chemical softener mixture (DHTDMAMS
/ PEG) is added to the NSK slurry in a proportion of 0.1% by weight of dry fiber. Adsorption of chemical softener mixture to NSK fiber is also in-
Can be enhanced by a line mixer. Dilute the NSK slurry to about 0.2% by weight with a fan pump.

Third, a 3% by weight aqueous slurry of CTMP is prepared in a conventional re-pulper. Nonionic surfactant (Pegosp
erse) is added to the repulper in a proportion of about 0.2% by weight of dry fiber. A 1% solution of the chemical softener mixture is added to the CTMP stock pipe in front of the stock pump at a rate of about 0.1% by weight of dry fiber. The adsorption of the chemical softener mixture to CTMP can be enhanced by an in-line mixer. Dilute the CTMP slurry to about 0.2% with a fan pump. The treated stock mixture (NSK / CTMP) is mixed in a headbox and deposited on a Ford linear wire to form a green web. Dewater through Ford linear wire with the aid of baffles and vacuum boxes. Ford linear wire has a monofilament with 84 monofilaments per inch in the machine direction and 76 in the cross machine direction, respectively.
d, has a satin weave structure. The undeveloped wet web was converted from Ford linear wire at approximately 22% fiber consistency at the point of transfer to light with 240 linear Idahocells per square inch, 34% knuckle area and 14 mil photopolymer depth. Transferred to polymer fabric.
The name “Linear Idaho” is due to the fact that the cross section of the conduit from which this pattern originated resembles the shape of a potato in nature. However, since the four side walls of the conduit are generally formed in straight lines, this pattern is referred to as a "linear" Idaho, rather than simply an Idaho pattern. The web is further dewatered by vacuum drainage until the fiber consistency of the web is about 28%. The patterned web is pre-dried by air blow to a fiber consistency of about 65% by weight. The web is then adhered to the surface of a Yankee dryer while spraying a creped adhesive containing a 0.25% aqueous solution of polyvinyl alcohol (PVA). After increasing the fiber consistency to an estimated 96%, the web is dry creped with a doctor blade. The doctor blade has an inclination angle of about 25 degrees,
The Yankee dryer is positioned so that the end angle is about 81 degrees, and the Yankee dryer is operated at about 800 fpm (feet / minute) (about 244 meters / minute). The dried web is formed into rolls at a speed of 700 fpm (214 meters / minute).

The two webs are embossed and laminated together using a PVA adhesive to form a paper towel product. This paper towel weighs approximately 26 # / 3M SqFt, approximately 0.
It has 2% of a substantially anhydrous, self-emulsifying, biodegradable chemical softener mixture and about 1.0% of a permanent wet strength resin.
The resulting paper towel is soft, absorbent and very strong when wet.

Example 4 The purpose of this example is to provide a liquid premix of di (hydrogenated) tallow dimethyl ammonium methyl sulfate (DHTDMAMS) and polyoxyethylene glycol 400 (PEG-400) using blow-through drying and layered papermaking techniques. And a method of making soft absorbent toilet tissue paper treated with a substantially anhydrous, self-emulsifying chemical softener composition comprising a temporary wet strength resin.

The practice of the present invention uses a pilot scale Ford linear paper machine. First, a substantially anhydrous, self-emulsifying chemical softener composition is prepared according to the procedure of Example 1, wherein a solid-state homogeneous premix of DHTDMAMS and a polyhydroxy compound is heated to about 66 ° C. Re-melt at a temperature of (150 ° F). The molten mixture is then dispersed in a conditioned water tank (temperature about 66 ° C.) to form a submicron vesicle dispersion. The particle size of the vesicle dispersion is measured using light microscopy techniques. Particle size is about 0.1-1.0 microns. FIG. 4 is a low-temperature transmission micrograph of a small bubble dispersion of DHTDMAMS and polyhydroxy compound at a 1: 1 weight ratio taken at a magnification of 63,000. FIG. 4 shows that the particles have one or two bilayer-thick films and their geometry ranges from closed / open vesicles to disc-like structures and sheets.

Second, a 3% by weight aqueous slurry of NSK is prepared in a conventional re-pulper. Gently purify the NSK slurry,
Temporary wet strength resins (ie NY, Nati of New York)
National starc commercially available from onal Starch and Chemical
h 78-0080) is added to the NSK stock pipe in a proportion of about 0.75% by weight of dry fiber. NS of temporary wet strength resin
Adsorption to K fibers is enhanced by an in-line mixer. Dilute the NSK slurry with a fan pump to about 0.2% consistency. Third, a 3% by weight aqueous slurry of eucalyptus fibers is prepared in a conventional lee pulper. A 1% solution of the chemical softener mixture is added to the eucalyptus stock pipe before the stock pump at a rate of about 0.2% by weight of dry fiber.
Adsorption of the substantially anhydrous, self-emulsifying chemical softener mixture onto eucalyptus fibers can be enhanced by an in-line mixer. Eucalyptus slurry with a fan pump to about 0.
Dilute to 2% consistency.

The treated stock mixture (30% NSK / 70% eucalyptus) is mixed in a headbox and deposited on a Ford linear wire to form a green web. Dewater through Ford linear wire with the aid of baffles and vacuum boxes. The Ford Linear wire is a 5-shed, satin woven construction having 84 monofilaments per inch in the machine direction and 76 per machine direction. Undeveloped wet web is about 15% at transfer point
From the photopolymer wire that corresponds to the fiber consistency of
562 linear Idaho cells per square inch, 40
% Knuckle area and transferred to a photopolymer fabric having a photopolymer depth of 9 mils. The web is further dewatered by vacuum drainage until the fiber consistency of the web is about 28%. The patterned web is pre-dried by air blow to a fiber consistency of about 65% by weight. The web is then adhered to the surface of a Yankee dryer while spraying a creped adhesive containing a 0.25% aqueous solution of polyvinyl alcohol (PVA). After increasing the fiber consistency to an estimated 96%, the web is dry creped with a doctor blade. The doctor blade has an inclination angle of about 25 degrees, and is placed against the Yankee dryer so that the end angle is about 81 degrees. The Yankee dryer is about 800 fpm (feet minute) / (about 244 meters /
Minutes). 700 fpm (214 meters /
Min) at the speed of the roll.

Web processing of a single tissue paper product. This tissue paper has a basis weight of about 18 # / 3M Sq Ft, about 0.1% chemical softener mixture and about 0.2% temporary wet strength resin. The resulting tissue paper is soft, absorbent and suitable for use as cosmetic and / or toilet tissue.

Example 5 The purpose of this example was to use blow-through drying papermaking technology,
Di (hydrogenated) tallow dimethyl ammonium chloride (DHTDMA
C) and a soft absorbent treated with a substantially anhydrous, self-emulsifying chemical softener composition comprising a premix of a liquid state mixture of a polyhydroxy compound (glycerol / PEG-400) and a dry strength resin. The present invention is to exemplify a method for producing toilet tissue paper.

The practice of the present invention uses a pilot scale Ford linear paper machine. First, a substantially anhydrous, self-emulsifying chemical softener composition is prepared according to the procedure of Example 2, wherein a solid-state homogeneous premix of DHTDMAC and the polyhydroxy compound is added at about 66 ° C. Re-melt at a temperature of (150 ° F). The molten mixture is then dispersed in a conditioned water tank (temperature about 66 ° C.) to form a submicron vesicle dispersion. The particle size of the vesicle dispersion is measured using light microscopy techniques. Particle size is about 0.1-1.0 microns. FIG. 5 is a low-temperature transmission micrograph of a small bubble dispersion of DHTDMAC and polyhydroxy compound at a weight ratio of 1: 1 taken at a magnification of 63,000. FIG. 5 shows that the particles have one or two bilayer-thick films and their geometry ranges from closed / open vesicles to disc-like structures and sheets.

Second, a 3% by weight aqueous slurry of NSK is prepared in a conventional re-pulper. Gently purify the NSK slurry,
Dry strength resin (ie OH, Fairfield Americ
2% of Acco 514, Acco 711) available from an Cyanamid
The solution is added to the NSK stock pipe at a rate of about 0.2% by weight of dry fiber. The adsorption of the dry strength resin to the NSK fiber is enhanced by an in-line mixer. Dilute the NSK slurry with a fan pump to about 0.2% consistency. Third, a 3% by weight aqueous slurry of eucalyptus fibers is produced in a conventional re-pulper. A 1% solution of the chemical softener mixture is placed in a eucalyptus stock pipe, before the stock pump, at about 0.1% of dry fiber.
Add 2% by weight. Adsorption of the substantially anhydrous, self-emulsifying chemical softener mixture onto eucalyptus fibers can be enhanced by an in-line mixer. Dilute the eucalyptus slurry to about 0.2% consistency with a fan pump.

The treated stock mixture (30% NSK / 70% eucalyptus) is mixed in a headbox and deposited on a Ford linear wire to form a green web. Dewater through Ford linear wire with the aid of baffles and vacuum boxes. The Ford Linear wire is a 5-shed, satin woven construction having 84 monofilaments per inch in the machine direction and 76 per machine direction. Undeveloped wet web is about 15% at transfer point
From the photopolymer wire that corresponds to the fiber consistency of
562 linear Idaho cells per square inch, 40
% Knuckle area and transferred to a photopolymer fabric having a photopolymer depth of 9 mils. The web is further dewatered by vacuum drainage until the fiber consistency of the web is about 28%. The patterned web is pre-dried by air blow to a fiber consistency of about 65% by weight. The web is then adhered to the surface of a Yankee dryer while spraying a creped adhesive containing a 0.25% aqueous solution of polyvinyl alcohol (PVA). After increasing the fiber consistency to an estimated 96%, the web is dry creped with a doctor blade. The doctor blade has an inclination angle of about 25 degrees, and is positioned with respect to the Yankee dryer so that the end angle is about 81 degrees. The Yankee dryer is about 800 fpm (feet / minute) (about 244 meters / minute).
Minutes). 700 fpm (214 meters /
Min) at the speed of the roll.

The double web is formed into a tissue paper product and laminated together using a layer bonding technique. This tissue paper has a basis weight of about 23 # / 3M Sq Ft, about 0.1% of a substantially anhydrous, self-emulsifying chemical softener mixture and about 0.1%.
Having a dry strength resin. The resulting tissue paper is soft, absorbent and suitable for use as cosmetic and / or toilet tissue.

Example 6 The purpose of this example was to use conventional dry papermaking technology,
Di (hydrogenated) methyl tallowdimethylammonium sulfate (DHTDMAMS) and polyoxyethylene glycol 400
Producing a soft absorbent toilet tissue treated with a substantially anhydrous, self-emulsifying, biodegradable chemical softener composition comprising a solid state premix of (PEG-400) and a dry strength resin The following is an example of a method.

The practice of the present invention uses a pilot scale Ford linear paper machine. First, a substantially anhydrous, self-emulsifying chemical softener composition is prepared according to the procedure of Example 1, wherein a solid-state, homogeneous premix of DHTDMAMS and PEG-400 is prepared from water. Disperse in a tank (temperature about 66 ° C.) to form a vesicle dispersion of less than 1 micron.
The particle size of the vesicle dispersion is measured using light microscopy techniques. Particle size is about 0.1-1.0 microns. FIG. 3 shows DH
63,00 of a 1: 1 weight ratio of small foam dispersion of TDMAMS and PEG-400 system
It is a low-temperature transmission microscope photograph taken at 0 times. FIG. 3 shows that the particles have one or two bilayer-thick films and their geometry ranges from closed / open vesicles to disc-like structures and sheets.

Second, a 3% by weight aqueous slurry of NSK is prepared in a conventional re-pulper. Gently purify the NSK slurry,
Dry strength resin (ie, Acco 514, Acco 71, available from American Cyanamid, Wayne, NJ)
A 2% solution of 1) is added to the NSK stock pipe at a rate of about 0.2% by weight of dry fiber. The adsorption of the dry strength resin to the NSK fiber is enhanced by an in-line mixer. Dilute the NSK slurry with a fan pump to about 0.2% consistency.
Third, a 3% by weight aqueous slurry of eucalyptus fibers is produced in a conventional re-pulper. 1% of chemical softener mixture
The solution is added to the eucalyptus stock pipe before the stock pump at a rate of about 0.2% by weight of dry fiber. Adsorption of the chemical softener mixture to eucalyptus fibers can be enhanced by an in-line mixer. Dilute the eucalyptus slurry to about 0.2% consistency with a fan pump.

The treated stock mixture (30% NSK / 70% eucalyptus) is mixed in a headbox and deposited on a Ford linear wire to form a green web. Dewater through Ford linear wire with the aid of baffles and vacuum boxes. The Ford Linear wire is a 5-shed, satin woven construction having 84 monofilaments per inch in the machine direction and 76 per machine direction. Undeveloped wet web is about 15% at transfer point
From Ford Linear Wire at Fiber Consistency, Inc. to regular felt. By vacuum drainage
Further dewater the web until the fiber consistency is about 35%. The web is then adhered to the surface of the Yankee dryer. After increasing the fiber consistency to an estimated 96%, the web is dry creped with a doctor blade. The doctor blade has an inclination angle of about 25 degrees, and is positioned with respect to the Yankee dryer so that the end angle is about 81 degrees. The Yankee dryer operates at about 800 fpm (feet / minute) (about 244 meters / minute) I do. The dried web is formed into rolls at a speed of 700 fpm (214 meters / minute).

The double web is formed into a tissue paper product and laminated together using a layer bonding technique. This tissue paper has a basis weight of about 23 # / 3M Sq Ft, about 0.1% of a substantially anhydrous, self-emulsifying, biodegradable chemical softener mixture and about 0.1% dry strength resin. The resulting tissue paper is soft, absorbent and suitable for use as cosmetic and / or toilet tissue.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Trocan, Paul Dennis, Ohio, USA, Hamilton, Wobel, Road, 1356 (56) References JP-A-4-100995 (JP, A) JP-A-63-165597 (JP, A) WO 93/9287 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21H 11/00-27/42

Claims (10)

(57) [Claims] (1) Expression (a) (Wherein each R ₂ substituent is C1~C6 alkyl or hydroxyalkyl group, or mixtures thereof, each R ₁ substituent is C14~C22 hydrocarbyl group or mixtures thereof, X ^- is a suitable (B) glycerol, a polyglycerol having a weight average molecular weight of 150 to 800, and a weight average molecular weight of 200 to 4000.
A mixture of a polyhydroxy compound selected from polyoxyethylene glycol and polyoxypropylene glycol, wherein the weight ratio of the quaternary ammonium compound to the polyhydroxy compound is from about 1: 0.1 to 0.1: 1,
The polyhydroxy compound is mixed with the quaternary ammonium compound at a temperature at which the quaternary ammonium compound and the polyhydroxy compound are miscible, and the composition has a water content of less than 20% by weight. A substantially anhydrous, self-emulsifying chemical softener composition. 2. A substantially anhydrous, self-emulsifying chemical softener according to claim 1, wherein the chemical softener composition is a stable, homogeneous, solid or viscous fluid at a temperature above about 20 ° C. Composition. 3. A substantially anhydrous self-emulsifying composition according to claim 1, wherein the quaternary ammonium compound is di (hydrogenated) tallow dimethyl ammonium chloride or di (hydrogenated) tallow dimethyl ammonium methyl sulfate. Sex chemical softener composition. 4. A substantially anhydrous, self-emulsifying chemical softener according to claim 1, wherein the quaternary ammonium compound is mixed with the polyhydroxy compound at a temperature of at least 40 ° C. Composition. 5. The substantially anhydrous, self-supporting compound according to claim 1, wherein the quaternary ammonium compound is in a liquid crystal state or a liquid state when mixed with the polyhydroxy compound. An emulsifying chemical softener composition. 6. An aqueous dispersion comprising a substantially anhydrous, self-emulsifying chemical softener composition according to any one of claims 1 to 5 and an aqueous medium, wherein said quaternary. An aqueous dispersion wherein the homogeneous mixture of the ammonium compound and the polyhydroxy compound is self-dispersed in the aqueous medium to form a vesicle dispersion of less than 1 micron. 7. The temperature of the aqueous medium is at least 20 ° C.
The aqueous dispersion according to claim 6. 8. The aqueous dispersion according to claim 6, wherein the homogeneous mixture of the quaternary ammonium compound and the polyhydroxy compound is in a solid state before being dispersed in the aqueous medium. 9. The aqueous dispersion according to claim 6, wherein the homogeneous mixture of the quaternary ammonium compound and the polyhydroxy compound is in a liquid state before being dispersed in the aqueous medium. 10. A substantially anhydrous, self-emulsifying chemical softener composition according to claim 1, wherein the chemical softener has a water content of less than 10% by weight.